JP3610065B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

  The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic material having high sensitivity and excellent storage stability.

  The silver halide photographic light-sensitive material mainly contains a dispersion medium containing photosensitive silver halide grains on a support. Enormous research has been conducted to increase the sensitivity of silver halide light-sensitive materials. In order to increase the sensitivity of silver halide photosensitive materials, it is very important to increase the sensitivity inherent to silver halide grains. Various methods are used to increase the sensitivity inherent to silver halide grains. It has been. For example, high sensitivity by chemical sensitizers such as sulfur, gold and group VIII metal compounds, chemical sensitizers such as sulfur, gold and group VIII metal compounds and additives that promote their sensitization effect Higher sensitivity is achieved by combination, and higher sensitivity is achieved by adding an additive having a sensitizing effect depending on the type of silver halide emulsion. These are described, for example, in Non-Patent Documents 1 and 2 and Patent Documents 1-8. Further, a method of increasing the reduction of silver halide grains is also used as a means for increasing sensitivity. The reduction sensitization of silver halide grains is described in, for example, Patent Documents 9 to 13, and the method of using a reducing agent is described in, for example, Patent Documents 14 to 16. Recently, a sensitization technique using an organic electron donating compound comprising an electron donating group and a leaving group as described in Patent Documents 17 to 22 has been reported. This method is an unprecedented new sensitization technique and is effective in increasing sensitivity. However, using this compound increases sensitivity, but the effect is not sufficient, and at the same time it has the disadvantage that the covering (Dmin) becomes high, and the latent image preservability deteriorates, so the improvement is strong. It was requested. Further, it has been found that when these compounds are used, the fog rises when pressure and heat are simultaneously applied to the photosensitive material.

  Recently, Patent Document 23 discloses a technique for increasing the sensitivity without deteriorating graininess by incorporating a compound having at least three heteroatoms that do not react with the oxidized developing agent into a silver halide photographic material. It is disclosed. However, although the sensitivity is increased by the method described in this publication, the effect is not sufficient only by this technique, and a further sensitivity increasing method has been desired.

As a result of continuous studies to obtain a larger effect, a method for increasing sensitivity preferably using the compound of the general formula (M) or the general formula (C) was found. Although the detailed mechanism is unclear, it is advantageous to have the property of adsorbing to the surface of the emulsion grains without changing the silver ion concentration in the film, and the general formula ( It is presumed that the use of the compound of M) or the general formula (C) is more effective in this respect. However, there is a great demand for sensitivity required for today's light-sensitive materials, and even if these techniques are used, the effect cannot be said to be sufficient, and a method for further increasing sensitivity has been desired.
Research Disclosure, Volume 120, April 1974, 12008 Research Disclosure, Volume 34, June 1975, 13452 US Pat. No. 2,642,361 U.S. Pat. No. 3,297,446 US Pat. No. 3,772,031 US Pat. No. 3,857,711 U.S. Pat. No. 3,901,714 U.S. Pat. No. 4,266,018 U.S. Pat. No. 3,904,415 British Patent 1,315,755 US Pat. No. 2,518,698 US Pat. No. 3,201,254 US Pat. No. 3,411,917 U.S. Pat. No. 3,779,777 US Pat. No. 3,930,867 Japanese Patent Publication No.57-33572 Japanese Patent Publication No.58-1410 JP-A-57-179835 US Pat. No. 5,747,235 US Pat. No. 5,747,236 European Patent No. 786692A1 European Patent No. 893731A1 European Patent No. 893732A1 International publication WO99 / 05570 pamphlet JP 2000-194085 A

  The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a silver halide photographic material having high sensitivity and excellent storage stability.

The object of the present invention can be achieved by the following means.
(1) A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion containing a cyan coupler on the support. layer, and a silver halide color photographic material have a non-photosensitive layer comprises a compound selected from the compound group of the type a and type 1-4 in at least one layer, and an ultraviolet absorbent in at least one layer the silver halide color photographic light-sensitive material characterized that you contain fine particles dispersion containing the agent and a vinyl polymer.
(Type A)
In the compound represented by XY, X represents a reducing group, Y represents a leaving group, and a one-electron oxidant formed by one-electron oxidation of the reducing group represented by X is followed by XY A compound capable of releasing Y by releasing Y with a bond cleavage reaction and releasing another electron therefrom.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit two or more electrons with a subsequent bond cleavage reaction.
(Type 2)
The one-electron oxidant produced by one-electron oxidation is a compound capable of releasing another electron with a subsequent carbon-carbon bond cleavage reaction, and 2 adsorbing groups to silver halide are present in the same molecule. A compound having two or more.
(Type 3)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation process.
(Type 4)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent intramolecular ring-cleaving reaction.

  (2) The compound selected from the compound group of type A and types 1 to 4 is a compound selected from the compound group of general formula (A) and general formulas (1-1) to (4-2) The silver halide color photographic light-sensitive material according to (1).

Formula (A)

In the general formula (A), RED ₀ represents a reducing group, L ₀ represents a leaving group, and R ₀ and R ₁ represent a hydrogen atom or a substituent. RED ₀ and R ₀ , and R ₀ and R ₁ may be bonded to each other to form a ring structure.

General formula (1-1) to general formula (4-2)

In the general formula (1-1), RED ₁₁ represents a reducing group, L ₁₁ represents a leaving group, and R ₁₁₂ represents a hydrogen atom or a substituent. R ₁₁₁ together with carbon atom (C) and RED ₁₁ can form a cyclic structure corresponding to a tetrahydro, hexahydro or octahydro form of a 5- or 6-membered aromatic ring (including aromatic heterocycle). Represents a metal atomic group.

In the general formula (1-2), RED ₁₂ and L ₁₂ each represent a group having the same meaning as RED ₁₁ and L _{11 in} the general formula (1-1). R ₁₂₁ and R ₁₂₂ each represent a hydrogen atom or a substituent that can be substituted with a carbon atom, and this is the same group as R _{112 in} formula (1-1). ED ₁₂ represents an electron donating group. In the general formula (1-2), R ₁₂₁ and RED ₁₂ , R ₁₂₁ and R ₁₂₂ , or ED ₁₂ and RED ₁₂ may be bonded to each other to form a cyclic structure.

In the general formula (2), RED ₂ represents a group having the same meaning as RED _{12 in the} general formula (1-2). L ₂ represents a carboxy group or a salt thereof, and R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent. RED ₂ and R ₂₁ may be bonded to each other to form a ring structure. However, the compound represented by the general formula (2) is a compound having two or more adsorption promoting groups for silver halide in the molecule.

In the general formula (3), RED ₃ represents a group having the same meaning as RED _{12 in the} general formula (1-2). Y ₃ is a reactive group containing a carbon-carbon double bond site or a carbon-carbon triple bond site capable of reacting with a one-electron oxidant formed by one-electron oxidation of RED ₃ to form a new bond. Represents. L ₃ represents a linking group that links RED ₃ and Y ₃ .

In General Formula (4-1) and General Formula (4-2), RED ₄₁ and RED ₄₂ each represent a group having the same meaning as RED _{12 in} General Formula (1-2). R _{40 to} R ₄₄ and R _{45 to} R ₄₉ each represent a hydrogen atom or a substituent. Z ₄₂ in the general formula _{(4-2) -CR 420 R 421 -} , - NR 423 -, or an -O-. Here, R ₄₂₀ and R ₄₂₁ each represent a hydrogen atom or a substituent, and R ₄₂₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  (3) The compound selected from the compound group of type A and types 1 to 4 described above has a partial structure of an adsorptive group or a sensitizing dye in the molecule (1) or (2) Silver halide color photographic light-sensitive material.

(4) The vinyl polymer contains a monomer selected from acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins and vinyl ethers as a forming monomer. The silver halide color photographic material according to any one of 1 to 3.

(5) The vinyl polymer is a copolymer composed of two or more monomers, and at least one of the monomers has a dissociable group, (1) to (4), Silver halide color photographic light-sensitive material.

(6) The silver halide color photographic light-sensitive material as described in (5), wherein the dissociable group of the monomer is sulfonic acid.

(7) The ratio of the monomer having a dissociable group in the copolymer is 0.1 to 3.0 mmol / g with respect to the vinyl polymer, (5) or (6) Silver halide color photographic material.
(8) The silver halide color photographic light-sensitive material as described in any one of (1) to (7), wherein the vinyl polymer has an average molecular weight of 3,000 to 50,000.
(9) The fine particle dispersion containing the ultraviolet absorber and the vinyl polymer is charged with water in the organic solvent phase containing the vinyl polymer and the ultraviolet absorber, or by introducing the organic solvent phase into water. The silver halide color photographic light-sensitive material as described in any one of (1) to (8), which is produced by emulsification.
(10) 50% or more of the total projected area of silver halide grains contained in any one of the light-sensitive silver halide emulsion layers satisfies the following (a) to (d): The silver halide color photographic light-sensitive material as described in 9).
(A) Parallel main plane is (111) plane
(B) The aspect ratio is 2 or more
(C) including at least 10 dislocation lines per particle
(D) A plate-shaped substrate made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%
Silver halide grains
(11) 50% or more of the total projected area of the silver halide grains contained in any one of the light-sensitive silver halide emulsion layers satisfies the following (a), (d) and (e): The silver halide color photographic light-sensitive material according to any one of (1) to (9).
(A) Parallel main plane is (111) plane
(D) A plate-shaped substrate made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%
Silver halide grains
(E) Vertex and / or side surface and / or main plane of hexagonal silver halide grain
Have at least one epitaxial junction per particle in the part
(12) The silver halide color photographic light-sensitive material as described in any one of (1) to (11), wherein the silver halide color photographic light-sensitive material contains the following compound (B).
Compound (B): a compound having at least three heteroatoms, and a photographic sensitivity of the photosensitive material is increased as compared with the case where the compound is not contained
Here, the increase in photographic sensitivity means that the photographic sensitivity increases when processed with the development processing step and processing solution described in Example 1 of the present specification.
(13) The silver halide grains contained in at least one of the light-sensitive silver halide emulsion layers are subjected to reduction sensitization, (1) to (12), Silver halide color photographic material.
(14) The silver halide grains contained in at least one of the photosensitive silver halide emulsion layers are Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Particles of at least one metal ion selected from the group consisting of Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi The silver halide color photographic light-sensitive material as described in any one of (1) to (13), which is contained inside.

Hereinafter, the present invention will be described in more detail.
A compound selected from type A or type 1-4 compounds used in the present invention will be described.

(Type A)
In the compound represented by XY, X represents a reducing group, Y represents a leaving group, and a one-electron oxidant formed by one-electron oxidation of the reducing group represented by X is followed by XY A compound capable of releasing Y by releasing Y with a bond cleavage reaction and releasing another electron therefrom.

(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit two or more electrons with a subsequent bond cleavage reaction.

(Type 2)
The one-electron oxidant produced by one-electron oxidation is a compound capable of releasing another electron with a subsequent carbon-carbon bond cleavage reaction, and 2 adsorbing groups to silver halide are present in the same molecule. A compound having two or more.

(Type 3)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation process.

(Type 4)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent intramolecular ring-cleaving reaction.

  Among the compounds of type A and types 1 to 4 of the present invention, preferred are represented by the following general formula (A) and general formulas (1-1) to (4-2). That is, among the above-mentioned type A compounds of the present invention, preferred compounds are represented by the following general formula (A), and among the above-mentioned type 1 compounds, preferred compounds are represented by the following general formulas (1-1) and (1). -2), among the compounds of type 2 described above, preferable ones are represented by the following general formula (2), and among the compounds of type 3 described above, preferable ones are represented by the following general formula (3). Preferred among the compounds of type 4 are represented by the following general formulas (4-1) and (4-2).

Formula (A)

In the general formula (A), RED ₀ represents a reducing group, L ₀ represents a leaving group, and R ₀ and R ₁ represent a hydrogen atom or a substituent. RED ₀ and R ₀ , and R ₀ and R ₁ may be bonded to each other to form a ring structure.

General formula (1-1) to general formula (4-2)

In the general formula (1-1), RED ₁₁ represents a reducing group, L ₁₁ represents a leaving group, and R ₁₁₂ represents a hydrogen atom or a substituent. R ₁₁₁ together with carbon atom (C) and RED ₁₁ can form a cyclic structure corresponding to a tetrahydro, hexahydro or octahydro form of a 5- or 6-membered aromatic ring (including aromatic heterocycle). Represents a metal atomic group.

In the general formula (1-2), RED ₁₂ and L ₁₂ each represent a group having the same meaning as RED ₁₁ and L _{11 in} the general formula (1-1). R ₁₂₁ and R ₁₂₂ each represent a hydrogen atom or a substituent that can be substituted with a carbon atom, and this is the same group as R _{112 in} formula (1-1). ED ₁₂ represents an electron donating group. In the general formula (1-2), R ₁₂₁ and RED ₁₂ , R ₁₂₁ and R ₁₂₂ , or ED ₁₂ and RED ₁₂ may be bonded to each other to form a cyclic structure.

In the general formula (2), RED ₂ represents a group having the same meaning as RED _{12 in the} general formula (1-2). L ₂ represents a carboxy group or a salt thereof, and R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent. RED ₂ and R ₂₁ may be bonded to each other to form a ring structure. However, the compound represented by the general formula (2) is a compound having two or more adsorption promoting groups for silver halide in the molecule.

In the general formula (3), RED ₃ represents a group having the same meaning as RED _{12 in the} general formula (1-2). Y ₃ is a reactive group containing a carbon-carbon double bond site or a carbon-carbon triple bond site capable of reacting with a one-electron oxidant formed by one-electron oxidation of RED ₃ to form a new bond. Represents. L ₃ represents a linking group that links RED ₃ and Y ₃ .

In General Formula (4-1) and General Formula (4-2), RED ₄₁ and RED ₄₂ each represent a group having the same meaning as RED _{12 in} General Formula (1-2). R _{40 to} R ₄₄ and R _{45 to} R ₄₉ each represent a hydrogen atom or a substituent. Z ₄₂ in the general formula _{(4-2) -CR 420 R 421 -} , - NR 423 -, or an -O-. Here, R ₄₂₀ and R ₄₂₁ each represent a hydrogen atom or a substituent, and R ₄₂₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

  Preferred among the compounds of type A, type 1, type 3, and type 4 are “compounds having an adsorbing group for silver halide in the molecule” or “spectral sensitizing dyes in the molecule”. A compound having a partial structure of More preferred is a “compound having an adsorptive group to silver halide in the molecule”.

  Similarly, among the compounds of the above general formula (A) and general formula (1-1) to general formula (4-2), “a compound having an adsorptive group to silver halide in the molecule” is preferable. Or “a compound having a partial structure of a spectral sensitizing dye in the molecule”. More preferred is a “compound having an adsorptive group to silver halide in the molecule”.

First, the compounds of types 1 to 4 will be described.
In the type 1 compound, “bond cleavage reaction” specifically means cleavage of a carbon-carbon or carbon-silicon bond, which may be accompanied by cleavage of a carbon-hydrogen bond. A type 1 compound is a compound capable of emitting two or more (preferably three or more) electrons for the first time after a one-electron oxidation to form a one-electron oxidant with a bond cleavage reaction. In other words, it is a compound that can be further oxidized by 2 electrons or more (preferably 3 electrons or more).

Among the compounds of type 1, preferred compounds are represented by general formula (1-1) or general formula (1-2), and these compounds are those represented by general formula (1-1) or general formula (1-2). After the reducing group represented by RED ₁₁ or RED ₁₂ is oxidized by one electron, L ₁₁ or L ₁₂ is released spontaneously by bond cleavage reaction, that is, C (carbon atom) -L ₁₁ bond or C This is a compound capable of releasing two or more, preferably three or more electrons, along with the cleavage of the (carbon atom) -L ₁₂ bond.

Hereinafter, the compound represented by formula (1-1) will be described in detail below.
The reducing group capable of being one-electron oxidized represented by RED ₁₁ in the general formula (1-1) is a group capable of forming a specific ring by bonding to R ₁₁₁ described later. Examples thereof include a divalent group obtained by removing one hydrogen atom from a suitable group for ring formation. For example, alkylamino group, arylamino group (anilino group, naphthylamino group etc.), heterocyclic amino group (benzthiazolylamino group, pyrrolylamino group etc.), alkylthio group, arylthio group (phenylthio group etc.), heterocyclic thiol Group, alkoxy group, aryloxy group (phenoxy group, etc.), heterocyclic oxy group, aryl group (phenyl group, naphthyl group, anthranyl group, etc.), aromatic or non-aromatic heterocyclic group Examples include tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydroquinazoline ring, indoline ring, indole ring, indazole ring, carbazole ring, phenoxazine ring, phenothiazine ring, benzothiazoline ring, pyrrole ring, imidazole ring, Thiazoline ring, piperidy Ring describing the pyrrolidine ring, a morpholine ring, a benzimidazole ring, benzimidazoline ring, benzo-oxazoline ring, a 3,4-methylenedioxyphenyl ring, and the like) (hereinafter, for convenience RED ₁₁ as monovalent Name ). These may have a substituent.

  Examples of the substituent include a halogen atom, an alkyl group (including an aralkyl group, a cycloalkyl group, and an active methine group), an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group (regardless of the position of substitution), quaternary A substituted nitrogen atom-containing heterocyclic group (e.g., pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, Acyl carbamoyl group, sulfamoyl carbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group units), aryloxy Group, heterocyclic o Si group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido Group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group , Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or Salts, sulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoric acid amide or a group containing a phosphoric acid ester structure and so forth. These substituents may be further substituted with these substituents.

L ₁₁ in the general formula (1-1) represents a leaving group which leaves by the first bond cleavage after the reducing group represented by RED ₁₁ is one-electron oxidation, specifically the carboxy group or a salt thereof Or a silyl group.

When L ₁₁ represents a salt of a carboxy group, the counter ions forming the salt are specifically alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ etc.), heavy metal ions (Ag ⁺ , Fe ^{2 + / 3 +} etc.), ammonium ions, phosphonium ions and the like. When L ₁₁ represents a silyl group, the silyl group specifically represents a trialkylsilyl group, an aryldialkylsilyl group, a triarylsilyl group, etc., where the alkyl group is a methyl, ethyl, benzyl, t-butyl group. And the aryl group includes a phenyl group.

In the general formula (1-1), R ₁₁₂ represents a hydrogen atom or a substituent that can be substituted with a carbon atom. When R ₁₁₂ represents a substituent substitutable on a carbon atom, the substituent is specifically the same as the example of the substituent when RED ₁₁ has a substituent. However, R ₁₁₂ does not represent the same group as L ₁₁ .

In the general formula (1-1), R ₁₁₁ represents a nonmetallic atomic group capable of forming a specific 5-membered or 6-membered cyclic structure together with the carbon atom (C) and RED ₁₁ . The specific 5- or 6-membered cyclic structure formed by R ₁₁₁ is a ring corresponding to a tetrahydro, hexahydro or octahydro form of a 5- or 6-membered aromatic ring (including aromatic heterocycle). Means structure. Here, the hydro form means a ring structure in which a carbon-carbon double bond (or carbon-nitrogen double bond) inherent in an aromatic ring (including an aromatic heterocycle) is partially hydrogenated, The tetrahydro form means a structure in which two carbon-carbon double bonds (or carbon-nitrogen double bonds) are hydrogenated, and the hexahydro form means three carbon-carbon double bonds (or carbon-nitrogen double bonds). (Bond) means a hydrogenated structure, and the octahydro form means a structure in which four carbon-carbon double bonds (or carbon-nitrogen double bonds) are hydrogenated. By being hydrogenated, the aromatic ring becomes a partially hydrogenated non-aromatic ring structure.

  Specifically, as an example of a monocyclic 5-membered ring, a pyrrolidine ring, an imidazolidine ring, which corresponds to a tetrahydro form of an aromatic ring such as a pyrrole ring, an imidazole ring, a thiazole ring, a pyrazole ring, or an oxazole ring, Examples include a thiazolidine ring, a pyrazolidine ring, an oxazolidine ring, and the like. Examples of 6-membered monocycles include tetrahydro or hexahydro forms of aromatic rings such as pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, such as piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, And piperazine ring. Examples of 6-membered condensed rings include tetrahydro rings, tetrahydroquinoline rings, tetrahydroisoquinoline rings, tetrahydroisoquinoline rings, quinoline rings, isoquinoline rings, quinazoline rings, quinazoline rings, and other aromatic ring tetrahydro compounds. Examples thereof include a quinazoline ring and a tetrahydroquinoxaline ring. Examples of the tricyclic compound include a tetrahydrocarbazole ring of a tetrahydro form of a carbazole ring and an octahydrophenanthridine ring which is an octahydro form of a phenanthridine ring.

These ring structures may be further substituted, and examples of the substituent include the same as those described for the substituent that RED ₁₁ may have. The substituents of these ring structures may be further connected to form a ring, and the newly formed ring is a non-aromatic carbocycle or heterocycle.

Next, the preferable range of the compound represented by the general formula (1-1) of the present invention will be described.
In the general formula (1-1), L ₁₁ is preferably a carboxy group or a salt thereof. The salt counter ions are preferably alkali metal ions or ammonium ions, and alkali metal ions (particularly Li ⁺ , Na ⁺ , K ⁺ ions) are most preferred.

In the general formula (1-1), RED ₁₁ is preferably an alkylamino group, an arylamino group, a heterocyclic amino group, an aryl group, an aromatic or non-aromatic heterocyclic group. Tetrahydroquinolinyl group, tetrahydroquinoxalinyl group, tetrahydroquinazolinyl group, indolyl group, indolenyl group, carbazolyl group, phenoxazinyl group, phenothiazinyl group, benzothiazolinyl group, pyrrolyl group, imidazolyl group, thiazolidinyl group, A benzoimidazolyl group, a benzoimidazolinyl group, a 3,4-methylenedioxyphenyl-1-yl group and the like are preferable. More preferred are an arylamino group (particularly anilino group) and an aryl group (particularly a phenyl group).

Here, when RED ₁₁ represents an aryl group, the aryl group has at least one electron-donating group (the number of electron-donating groups is preferably 4 or less, more preferably 1 to 3). Preferably it is. Here, the electron donating group means a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an acylamino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an active methine group, an electron-rich aromatic heterocyclic ring. A group (for example, indolyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, thiazolyl group, benzthiazolyl group, indazolyl group, etc.), a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom (pyrrolidinyl group, indolinyl group, piperidinyl group, A piperazinyl group, a morpholino group, etc.). Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group means an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl group. A sulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and an imino group are meant. Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure.

When RED ₁₁ represents an aryl group, the substituent of the aryl group is more preferably an alkylamino group, a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an active methine group, a non-aromatic nitrogen-containing group that is substituted with a nitrogen atom A heterocyclic group, more preferably an alkylamino group, a hydroxy group, an active methine group, and a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, most preferably an alkylamino group and a non-aromatic group substituted with a nitrogen atom Group nitrogen-containing heterocyclic group.

In the general formula (1-1), R ₁₁₂ is preferably a hydrogen atom, an alkyl group, an aryl group (such as a phenyl group), an alkoxy group (such as a methoxy group, an ethoxy group, or a benzyloxy group), a hydroxy group, an alkylthio group (a methylthio group). , A butylthio group and the like), an amino group, an alkylamino group, an arylamino group, and a heterocyclic amino group, and more preferably a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group, and an alkylamino group.

In the general formula (1-1), R ₁₁₁ is preferably a nonmetallic atomic group capable of forming the following specific 5-membered or 6-membered cyclic structure together with the carbon atom (C) and RED ₁₁ . That is, a pyrrole ring, which is a monocyclic 5-membered aromatic ring, a pyrrolidine ring corresponding to a tetrahydro form of an imidazole ring, an imidazolidine ring, and the like. A tetrahydro or hexahydro form of a pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, which is a monocyclic 6-membered aromatic ring. For example, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring and the like. Corresponding to the tetrahydro form of the condensed 6-membered aromatic rings naphthalene ring, quinoline ring, isoquinoline ring, quinazoline ring, quinoxaline ring, tetralin ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinazoline ring, and tetrahydro Quinoxaline ring etc. Examples thereof include a tetrahydrocarbazole ring which is a tetrahydro form of a carbazole ring which is a tricyclic aromatic ring and an octahydrophenanthridine ring which is an octahydro form of a phenanthridine ring.

More preferably, the cyclic structure formed by R ₁₁₁ is a pyrrolidine ring, an imidazolidine ring, a piperidine ring, a tetrahydropyridine ring, a tetrahydropyrimidine ring, a piperazine ring, a tetrahydroquinoline ring, a tetrahydroquinazoline ring, a tetrahydroquinoxaline ring, or a tetrahydrocarbazole ring. Particularly preferred are pyrrolidine ring, piperidine ring, piperazine ring, tetrahydroquinoline ring, tetrahydroquinazoline ring, tetrahydroquinoxaline ring and tetrahydrocarbazole ring, and most preferred are pyrrolidine ring, piperidine ring and tetrahydroquinoline ring.

Next, the general formula (1-2) will be described in detail.
In the general formula (1-2), RED ₁₂ and L ₁₂ are groups having the same meanings as RED ₁₁ and L ₁₁ in the general formula (1-1), respectively, and preferred ranges thereof are also the same. However, RED ₁₂ is a monovalent group except for the case where the following cyclic structure is formed, and specific examples include groups having the monovalent group name described in RED ₁₁ . R ₁₂₁ and R ₁₂₂ are groups having the same meaning as R ₁₁₂ in the general formula (1-1), and preferred ranges thereof are also the same. ED ₁₂ represents an electron donating group. R ₁₂₁ and RED ₁₂ , R ₁₂₁ and R ₁₂₂ , or ED ₁₂ and RED ₁₂ may be bonded to each other to form a cyclic structure.

The electron donating group represented by ED ₁₂ in the general formula (1-2) is a hydroxy group, an alkoxy group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, an acylamino group, an alkylamino group. Group, arylamino group, heterocyclic amino group, active methine group, electron-rich aromatic heterocyclic group (for example, indolyl group, pyrrolyl group, indazolyl group), non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen atom (pyrrolidinyl) Groups, piperidinyl groups, indolinyl groups, piperazinyl groups, morpholino groups, etc.), and aryl groups substituted with these electron donating groups (for example, p-hydroxyphenyl group, p-dialkylaminophenyl group, o, p-dialkoxyphenyl) Group, 4-hydroxynaphthyl group, etc.). Here, the active methine group is the same as that described as the substituent when RED ₁₁ represents an aryl group.

ED ₁₂ is preferably a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an alkylamino group, an arylamino group, an active methine group, an electron-rich aromatic heterocyclic group, or a non-aromatic nitrogen-containing heterocycle substituted with a nitrogen atom. A cyclic group, and a phenyl group substituted with these electron-donating groups, and further includes a hydroxy group, a mercapto group, a sulfonamide group, an alkylamino group, an arylamino group, an active methine group, and a non-aromatic group substituted with a nitrogen atom. A nitrogen heterocyclic group and a phenyl group substituted with these electron donating groups (for example, p-hydroxyphenyl group, p-dialkylaminophenyl group, o, p-dialkoxyphenyl group, etc.) are preferable.

In the general formula (1-2), R ₁₂₂ and RED ₁₂ , R ₁₂₂ and R ₁₂₁ , or ED ₁₂ and RED ₁₂ may be bonded to each other to form a cyclic structure. The cyclic structure formed here is a non-aromatic carbocyclic or heterocyclic ring, which is a 5-membered to 7-membered monocyclic or condensed ring, and is a substituted or unsubstituted cyclic structure.

When R ₁₂₂ and RED ₁₂ form a ring structure, specific examples thereof include pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, thiazolidine ring, thiazoline ring, pyrazolidine ring, pyrazoline ring, oxazolidine ring, oxazoline ring, Indane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, indoline ring, tetralin ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydro-1,4-oxazine ring, 2,3 -Dihydrobenzo-1,4-oxazine ring, tetrahydro-1,4-thiazine ring, 2,3-dihydrobenzo-1,4-thiazine ring, 2,3-dihydrobenzofuran ring, 2,3-dihydrobenzothiophene ring Etc.

When ED ₁₂ and RED ₁₂ form a ring structure, ED ₁₂ preferably represents an amino group, an alkylamino group, or an arylamino group, and specific examples of the formed ring structure include a tetrahydropyrazine ring, a piperazine ring, A tetrahydroquinoxaline ring, a tetrahydroisoquinoline ring, etc. are mentioned.

When R ₁₂₂ and R ₁₂₁ form a ring structure, specific examples thereof include a cyclohexane ring and a cyclopentane ring.

Of the compounds represented by the general formula (1-1) of the present invention, more preferred are the following general formulas (10) to (12), and among the compounds represented by the general formula (1-2): More preferred are represented by the following general formulas (13) and (14).

In the general formulas (10) to (14), L ₁₀₀ , L ₁₀₁ , L ₁₀₂ , L ₁₀₃ , and L ₁₀₄ are groups having the same meaning as L ₁₁ in the general formula (1-1), and preferred ranges thereof are also the same. is there. R ₁₁₀₀ and R ₁₁₀₁ , R ₁₁₁₀ and R ₁₁₁₁ , R ₁₁₂₀ and R ₁₁₂₁ , R ₁₁₃₀ and R ₁₁₃₁ , R ₁₁₄₀ and R ₁₁₄₁ are groups having the same meaning as R ₁₂₁ and R ₁₂₂ in the general formula (1-2), respectively. The preferred range is also the same. ED ₁₃ and ED ₁₄ each represent a group having the same meaning as ED ₁₂ of the general formula (1-2), and preferred ranges thereof are also the same.

X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , and X ₁₄ each represent a substituent that can be substituted on the benzene ring, and m ₁₀ , m ₁₁ , m ₁₂ , m ₁₃ , and m ₁₄ each represent an integer of 0 to 3. When there are a plurality of these, the plurality of X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ and X ₁₄ may be the same or different. Y ₁₂ and Y ₁₄ are amino group, alkylamino group, arylamino group, non-aromatic nitrogen-containing heterocyclic group substituted with nitrogen atom (pyrrolyl group, piperidinyl group, indolinyl group, piperazino group, morpholino group, etc.), hydroxy Group represents an alkoxy group.

Z ₁₀ , Z ₁₁ , and Z ₁₂ represent nonmetallic atomic groups that can form a specific ring structure. The specific ring structure formed by Z ₁₀ is a ring structure corresponding to a tetrahydro or hexahydro form of a 5-membered or 6-membered monocyclic or condensed ring nitrogen-containing aromatic heterocycle, specifically, a pyrrolidine ring, Examples include imidazolidine ring, thiazolidine ring, pyrazolidine ring, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinazoline ring, tetrahydroquinoxaline ring and the like. The specific ring structure formed by Z ₁₁ is a tetrahydroquinoline ring or a tetrahydroquinoxaline ring. The specific ring structure formed by Z ₁₂ is a tetralin ring, a tetrahydroquinoline ring, or a tetrahydroisoquinoline ring.

R _N11 and R _N13 are each a hydrogen atom or a substituent that can be substituted with a nitrogen atom. Specific examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and an acyl group, preferably an alkyl group and an aryl group.

Examples of the substituent that can be substituted on the benzene ring represented by X ₁₀ , X ₁₁ , X ₁₂ , X ₁₃ , and X ₁₄ are examples of the substituent that RED ₁₁ of the general formula (1-1) may have. The same thing as is given as a specific example. Preferably, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group, an alkoxy group (a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit). (Including), (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, nitro group, (alkyl, aryl, or Heterocycle) thio group, (alkyl or aryl) sulfonyl group, sulfamoyl group and the like.

m ₁₀ , m ₁₁ , m ₁₂ , m ₁₃ and m ₁₄ are preferably 0 to 2, more preferably 0 or 1.

Y ₁₂ and Y ₁₄ are preferably an alkylamino group, an arylamino group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, a hydroxy group or an alkoxy group, more preferably an alkylamino group or a nitrogen atom. A 5- to 6-membered non-aromatic nitrogen-containing heterocyclic group, which is a hydroxy group, most preferably an alkylamino group (particularly a dialkylamino group) or a nitrogen atom. It is a group.

In the general formula (13), R ₁₁₃₁ and X ₁₃ , R ₁₁₃₁ and R _N13 , R ₁₁₃₀ and X ₁₃ , or R ₁₁₃₀ and R _N13 may be bonded to form a cyclic structure. In the general formula (14), R ₁₁₄₁ and X ₁₄ , R ₁₁₄₁ and R ₁₁₄₀ , ED ₁₄ and X ₁₄ , or R ₁₁₄₀ and X ₁₄ may be bonded to form a cyclic structure. The cyclic structure formed here is a non-aromatic carbocyclic or heterocyclic ring, which is a 5-membered to 7-membered monocyclic or condensed ring, and is a substituted or unsubstituted cyclic structure.

In the general formula (13), when R ₁₁₃₁ and X ₁₃ are bonded to form a cyclic structure, and R ₁₁₃₁ and _{RN 13} are bonded to form a cyclic structure, the same as when no ring structure is formed. Further, preferred examples of the compound represented by the general formula (13).

Specific examples of the ring structure formed by R ₁₁₃₁ and X ₁₃ in the general formula (13) include an indoline ring (in this case, R ₁₁₃₁ represents a single bond), a tetrahydroquinoline ring, a tetrahydroquinoxaline ring, Examples include 2,3-dihydrobenzo-1,4-oxazine ring, 2,3-dihydrobenzo-1,4-thiazine ring, and the like. Particularly preferred are an indoline ring, a tetrahydroquinoline ring and a tetrahydroquinoxaline ring.

Specific examples of the ring structure formed by R ₁₁₃₁ and R _N13 in the general formula (13) include pyrrolidine ring, pyrroline ring, imidazolidine ring, imidazoline ring, thiazolidine ring, thiazoline ring, pyrazolidine ring, pyrazoline ring, oxazolidine Ring, oxazoline ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, indoline ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinoxaline ring, tetrahydro-1,4-oxazine ring, 2,3- Dihydrobenzo-1,4-oxazine ring, tetrahydro-1,4-thiazine ring, 2,3-dihydrobenzo-1,4-thiazine ring, 2,3-dihydrobenzofuran ring, 2,3-dihydrobenzothiophene ring, Etc. Particularly preferred are pyrrolidine ring, piperidine ring, tetrahydroquinoline ring and tetrahydroquinoxaline ring.

In the general formula (14), when R ₁₁₄₁ and X ₁₄ are combined to form a cyclic structure, and when ED ₁₄ and X ₁₄ are combined to form a cyclic structure, the same as when no ring structure is formed Further, preferred examples of the compound represented by the general formula (14). _{Examples of} the cyclic structure formed by combining R ₁₁₄₁ and X ₁₄ in the general formula (14) include an indane ring, a tetralin ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, and an indoline ring. Examples of the cyclic structure formed by combining ED ₁₄ and X ₁₄ include a tetrahydroisoquinoline ring and a tetrahydrocinnoline ring.

Next, the type 2 compound will be described.
A compound of type 2 is a compound that can be oxidized one more electron for the first time after one-electron oxidation to form a one-electron oxidant, accompanied by a carbon-carbon bond cleavage reaction. . Here, the bond cleavage reaction means the cleavage of a carbon-carbon bond, and the cleavage of a carbon-hydrogen bond may accompany this.

A preferred compound of type 2 is represented by the general formula (2). Here, after the reducing group represented by RED ₂ is oxidized by one electron, L ₂ spontaneously leaves by bond cleavage reaction. In other words, it is a compound capable of releasing one more electron in association with the cleavage of the C (carbon atom) -L ₂ bond.

  However, the type 2 compound is a compound having 2 or more (preferably 2 to 6, more preferably 2 to 4) adsorptive groups to silver halide in the molecule. More preferred is a compound having a nitrogen-containing heterocyclic group substituted with two or more mercapto groups as an adsorptive group. The adsorptive group will be described later.

In the general formula (2), RED ₂ represents a group having the same meaning as RED _{12 in the} general formula (1-2), and the preferred range thereof is also the same. L ₂ represents a carboxy group or a salt thereof, and the counter ion forming the salt is the same as described for L _{11 in the} general formula (1-1), and the preferred range is also the same. R ₂₁ and R ₂₂ represent a hydrogen atom or a substituent, and these are groups having the same meaning as R _{112 in the} general formula (1-1), and their preferred ranges are also the same. RED ₂ and R ₂₁ may be bonded to each other to form a ring structure.

  The ring structure formed here is a non-aromatic 5- to 7-membered carbocyclic or heterocyclic ring, which may be a single ring or a condensed ring, and may have a substituent. Specific examples of the ring structure include, for example, indoline ring, 2,3-dihydrobenzothiophene ring, 2,3-dihydrobenzofuran ring, 1,2-dihydropyridine ring, 1,4-dihydropyridine ring, benzo-α-pyran ring, Examples include a benzothiazoline ring, a benzoxazoline ring, a benzimidazoline ring, a 1,2-dihydroquinoline ring, a 1,2-dihydroquinazoline ring, a 1,2-dihydroquinoxaline ring, a chroman ring, and an isochroman ring. Preferably, an indoline ring, 2,3-dihydrobenzothiophene ring, 1,2-dihydropyridine ring, benzothiazoline ring, benzoxazoline ring, benzimidazoline ring, 1,2-dihydroquinoline ring, 1,2-dihydroquinazoline ring, 1,2-dihydroquinoxaline ring and the like. Indoline ring, benzothiazoline ring, benzimidazoline ring and 1,2-dihydroquinoline ring are more preferable, and indoline ring is particularly preferable.

Next, the compound of type 3 will be described.
A compound of type 3 is a compound characterized in that a one-electron oxidant produced by one-electron oxidation can emit one or more electrons after passing through a subsequent bond formation process. The formation process means formation of interatomic bonds such as carbon-carbon, carbon-nitrogen, carbon-sulfur, and carbon-oxygen.

  The compound of type 3 is preferably a one-electron oxidant formed by one-electron oxidation and subsequently reacts with a carbon-carbon double bond site or a carbon-carbon triple bond site present in the molecule to form a bond. After that, the compound is characterized in that it can further emit one electron or more electrons.

  A one-electron oxidant produced by one-electron oxidation of a type 3 compound is a cation radical species, but it may be a neutral radical species with the elimination of protons therefrom. This one-electron oxidant (cation radical species or radical species) forms a chemistry generally called “cycloaddition reaction” at the carbon-carbon double bond site or carbon-carbon triple bond site that coexists in the same molecule. A reaction is caused to form an interatomic bond such as carbon-carbon, carbon-nitrogen, carbon-sulfur, carbon-oxygen, and a new ring structure is formed in the molecule. At this time, one or more electrons are emitted at the same time or after that, which is a characteristic of the type 3 compound.

  In more detail, the compound of type 3 generates a radical species having a new ring structure by this cycloaddition reaction after one-electron oxidation, but directly or with elimination of a proton from this radical species, Further, the second electron is emitted and oxidized.

  Type 3 compounds further have tautomerization of the two-electron oxidant so produced, after undergoing a hydrolysis reaction in some cases and directly in some cases with proton transfer. Those having the ability to cause a reaction, further emit electrons of 1 electron or more, and usually 2 electrons or more therefrom, and be oxidized are included. Alternatively, those having the ability to emit one or more electrons, usually two or more electrons, from the two-electron oxidant directly without going through such a tautomerization reaction and to be oxidized are included. .

The compound of type 3 is preferably represented by the general formula (3).
In the general formula (3), RED ₃ represents a group having the same meaning as RED _{12 in the} general formula (1-2).
RED ₃ is preferably an arylamino group, a heterocyclic amino group, or an aryl group or heterocyclic group substituted with a group selected from the group consisting of a hydroxy group, a mercapto group, an alkylthio group, a methyl group, and an amino group .

When RED ₃ represents an arylamino group, examples include an anilino group and a naphthylamino group. The heterocyclic ring of the heterocyclic amino group is an aromatic or non-aromatic monocyclic or condensed heterocyclic ring, and preferably contains at least one aromatic ring as a partial structure. Here, including an aromatic ring as a partial structure means 1) the hetero ring itself is an aromatic ring, 2) the aromatic ring is condensed to the hetero ring, and 3) the aromatic ring is substituted for the hetero ring. However, 1) or 2) is preferable. Here, the amino group is directly substituted on the aromatic ring contained as a partial structure in the heterocycle. Examples of the heterocycle include a pyrrole ring, an indole ring, an indoline ring, an imidazole ring, a benzimidazole ring, a benzimidazoline ring, a thiazole ring, a benzothiazole ring, a benzothiazoline ring, an oxazole ring, a benzoxazole ring, a benzoxazoline ring, and a quinoline ring. , Tetrahydroquinoline ring, quinoxaline ring, tetrahydroquinoxaline ring, quinazoline ring, tetrahydroquinazoline ring, pyridine ring, isoquinoline ring, thiophene ring, benzothiophene ring, 2,3-dihydrobenzothiophene ring, furan ring, benzofuran ring, 2,3 -Dihydrobenzofuran ring, carbazole ring, phenothiazine ring, phenoxazine ring, phenazine ring and the like.

When RED ₃ represents an arylamino group or a heterocyclic amino group, the amino group of the arylamino group and the amino group of the heterocyclic amino group may be further substituted with an arbitrary substituent. May further form a ring structure with the aryl group or the heterocyclic group. Examples of such include an indoline ring, a tetrahydroquinoline ring, a carbazole ring, and the like.

When RED ₃ represents an aryl group or a heterocyclic group substituted with a hydroxy group, a mercapto group, a methyl group, an alkylthio group or an amino group, the aryl group includes a phenyl group, a naphthyl group, etc. Examples of the heterocyclic ring include the same groups as those described for the “heterocyclic heterocyclic group”. Here, the methyl group may have an arbitrary substituent, and this substituent may form a ring structure with the aryl group or heterocyclic group. Examples of such a ring structure include a tetralin ring and an indane ring. On the other hand, the amino group may have an alkyl group, an aryl group, or a heterocyclic group as a substituent, and these substituents may form a ring structure with the aryl group or the heterocyclic group. Examples of such a ring structure include a tetrahydroquinoline ring, an indoline ring, and a carbazole ring.

RED ₃ is preferably an arylamino group, or an aryl group or heterocyclic group substituted with a hydroxy group, mercapto group, methyl group or amino group, more preferably an arylamino group, mercapto group, methyl group or amino group. An aryl group or a heterocyclic group substituted with a group. RED ₃ is particularly preferably an arylamino group, or an aryl group or heterocyclic group substituted with a methyl group or an amino group.

  As the arylamino group, an anilino group and a naphthylamino group are preferable, and an anilino group is particularly preferable. Examples of the substituent of the anilino group include a chloro atom, an alkyl group, an alkoxy group, an acylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a sulfonamide group, an alkoxycarbonyl group, a cyano group, an alkyl or arylsulfonyl group, and a heterocyclic group. Etc. are preferable.

  Preferred examples of the aryl group or heterocyclic group substituted with a hydroxy group include a hydroxyphenyl group, a 5-hydroxyindoline ring group, and a 6-hydroxy-1,2,3,4-tetrahydroquinoline ring group. A hydroxyphenyl group is particularly preferred.

  The aryl group or heterocyclic group substituted with a mercapto group is preferably a mercaptophenyl group, a 5-mercaptoindoline ring group, a 6-mercapto-1,2,3,4-tetrahydroquinoline ring group, and the like. Of these, a mercaptophenyl group is particularly preferred.

  The aryl group or heterocyclic group substituted with a methyl group is preferably a methylphenyl group, an ethylphenyl group, an isopropylphenyl group, a 3-methylindole ring group, a 3-isopropylindole ring group, a 5-methylindole ring group, Examples include 5-methylindoline ring group, 6-methyl-1,2,3,4-tetrahydroquinoline ring group, 6-methyl-1,2,3,4-tetrahydroquinoxaline ring group and the like.

  The aryl group or heterocyclic group substituted with an amino group is preferably, for example, methylaminophenyl group, octylaminophenyl group, dodecylaminophenyl group, dimethylaminophenyl group, benzylaminophenyl group, phenylaminophenyl group, methylamino Naphthyl group, 5-methylaminotetralin, 1-butylamino-3,4-methylenedioxyphenyl group, 3-methylaminopyrrole ring group, 3-ethylaminoindole ring group, 5-benzylaminoindoline ring group, 2- Examples thereof include an aminoimidazole ring group, a 2-methylaminothiazole ring group, and a 6-phenylaminobenzothiazole ring group. Of these, a phenyl group substituted with an alkylamino group or a phenylamino group is more preferred, and a phenyl group substituted with an alkylamino group is particularly preferred.

  The aryl group or heterocyclic group substituted with a hydroxy group, mercapto group, methyl group or amino group includes chloro atom, alkyl group, alkoxy group, acylamino group, sulfamoyl group, carbamoyl group, ureido group, sulfone. Amide group, alkoxycarbonyl group, cyano group, alkyl or arylsulfonyl group, heterocyclic group, alkylamino group, arylamino group and the like are preferable.

In the general formula (3), the reactive group represented by Y ₃ specifically represents an organic group containing at least one carbon-carbon double bond site or carbon-carbon triple bond site. The carbon-carbon double bond or carbon-carbon triple bond may have a substituent, and as the substituent, the RED ₁₁ of the general formula (1-1) may have a substituent. The same ones as described. Preferred are an alkyl group, an aryl group, an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, and an electron donating group. Here, the electron donating group is an alkoxy group, hydroxy group, amino group, alkylamino group, arylamino group, heterocyclic amino group, sulfonamido group, acylamino group, active methine group, mercapto group, alkylthio group, arylthio group. And an aryl group having these groups as substituents. Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and an imino group are meant. Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure.

When Y ₃ represents a carbon-carbon double bond site, the substituent is more preferably an alkyl group, an alkoxycarbonyl group, a carbamoyl group, an electron donating group, etc., and the electron donating group is preferably an alkoxy group. Group, amino group, alkylamino group, arylamino group, heterocyclic amino group, sulfonamido group, acylamino group, active methine group, mercapto group, alkylthio group, and phenyl group having these electron donating groups as substituents. . In addition, it is also preferable that an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, or the like as a substituent is bonded to each other to form a ring structure containing a carbon-carbon double bond. Specifically, for example, 2,3-dihydro -Γ-pyran ring group, cyclohexene ring group, 1-thia-2-cyclohexen-3-yl group, tetrahydropyridine ring group and the like can be mentioned.

When Y ₃ represents an organic group containing a carbon-carbon double bond site, the substituents may be bonded to each other to form a cyclic structure. The cyclic structure formed here is a non-aromatic 5- to 7-membered carbocyclic or heterocyclic ring. When Y ₃ represents a carbon-carbon triple bond site, the substituent is preferably a hydrogen atom, an alkoxycarbonyl group, a carbamoyl group, an electron donating group, etc., and the electron donating group is preferably an alkoxy group, amino Groups, alkylamino groups, arylamino groups, heterocyclic amino groups, sulfonamido groups, acylamino groups, active methine groups, mercapto groups, alkylthio groups, and phenyl groups having these electron donating groups as substituents.

In the general formula (3), the reactive group represented by Y ₃ is more preferably an organic group containing a carbon-carbon double bond.

In the general formula (3), L ₃ represents a linking group for connecting RED ₃ and Y ₃ , specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, — NR _N —, —C (═O) —, —SO ₂ —, —SO—, —P (═O) — each independently represents a group consisting of a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. The linking group represented by L ₃ may have a substituent. Examples of the substituent include the same as those described as the substituent that RED ₁₁ of the general formula (1-1) may have.

The group represented by L ₃ in the general formula (3) includes a cation radical species generated by oxidation of RED _{3 in the} general formula (3), or a radical species generated from the release of a proton therefrom, When the reactive group represented by Y ₃ in the formula (3) reacts to form a bond, it is preferable that the atomic group involved in this can form a _3- to 7-membered cyclic structure including L _3. .

Preferred examples of L ₃ include a single bond, an alkylene group, an arylene group (particularly a phenylene group), a —C (═O) — group, a —O— group, a —NH— group, a —N (alkyl group) — group, And a divalent linking group comprising a combination of these groups.

Among the compounds represented by the general formula (3), preferable compounds are represented by the following general formulas (I) to (IV).

In the general formulas (I) to (IV), A ₁₀₀ , A ₂₀₀ , A ₃₀₀ , and A ₄₀₀ represent an aryl group or a heterocyclic group, and the preferred range thereof is the same as the preferred range of RED _{3 in} the general formula (3). . L ₃₀₁ , L ₃₀₂ , L ₃₀₃ and L ₃₀₄ each represent a linking group, which represents a group having the same meaning as L _{3 in the} general formula (3), and the preferred range thereof is also the same. Y ₁₀₀ , Y ₂₀₀ , Y ₃₀₀ , and Y ₄₀₀ represent a reactive group, which represents a group having the same meaning as Y _{3 in the} general formula (3), and its preferred range is also the same. R ₃₁₀₀ , R ₃₁₁₀ , R ₃₂₀₀ , R ₃₂₁₀ and R ₃₃₁₀ each represents a hydrogen atom or a substituent. R ₃₁₀₀ and R ₃₁₁₀ are preferably a hydrogen atom, an alkyl group or an aryl group. R ₃₂₀₀ and R ₃₃₁₀ are preferably a hydrogen atom. R ₃₂₁₀ is preferably a substituent, and the substituent is preferably an alkyl group or an aryl group. R ₃₁₁₀ may be bonded to A ₁₀₀ , R ₃₂₁₀ may be bonded to A ₂₀₀ , and R ₃₃₁₀ may be bonded to A ₃₀₀ to form a ring structure. The ring structure formed here is preferably a tetralin ring, an indane ring, a tetrahydroquinoline ring, an indoline ring or the like. X ₄₀₀ represents a hydroxy group, a mercapto group, or an alkylthio group, preferably a hydroxy group or a mercapto group, and more preferably a mercapto group.

Here, the relationship between the general formulas (I) to (IV) and the general formula (3) will be explained. A _{100 in the} general formula (I) is substituted with a methyl group: —CH (R ₃₁₁₀ ) (R ₃₁₀₀ ). Represents an aryl group or a heterocyclic group, and A _{200 in the} general formula (II) represents an aryl group or a heterocyclic group substituted with an amino group: —N (R ₃₂₁₀ ) (R ₃₂₀₀ ); A ₄₀₀ represents an aryl group or heterocyclic group substituted with a hydroxy group, a mercapto group, or an alkylthio group represented by X ₄₀₀ , and is represented by A ₃₀₀ —N (R ₃₃₁₀ ) — in the general formula (III). The group likewise represents an arylamino group or a heterocyclic amino group.

  Among the general formulas (I) to (IV), more preferable compounds are compounds represented by the general formulas (I), (II), and (IV).

Next, the type 4 compound will be described.
A compound of type 4 is a compound having a ring structure substituted with a reducing group, and after the reducing group is oxidized by one electron, one or more electrons are emitted along with the ring structure cleavage reaction. Compound.

Type 4 compounds undergo one-electron oxidation and the ring structure is cleaved. The ring cleavage reaction mentioned here refers to the type represented by the following scheme.

  In the above scheme, compound a represents a type 4 compound. In the compound a, D represents a reducing group, and X and Y represent atoms that form a bond that is cleaved after one-electron oxidation in the ring structure. First, one-electron oxidation of the compound a generates a one-electron oxidant b. From this, the single bond of D—X becomes a double bond, and at the same time, the bond of X—Y is cleaved to produce ring-opened product c. Alternatively, a radical intermediate d may be generated from the one-electron oxidant b with proton desorption, and a ring opening e may be similarly generated therefrom. The compound of the present invention is characterized in that one or more electrons are subsequently released from the ring-opened product c or e thus produced.

  The ring structure possessed by the type 4 compound is a 3- to 7-membered carbocyclic or heterocyclic ring, and represents a monocyclic or condensed, saturated or unsaturated non-aromatic ring. A saturated ring structure is preferable, and a 3-membered ring or 4-membered ring is more preferable. Preferred examples of the ring structure include a cyclopropane ring, a cyclobutane ring, an oxirane ring, an oxetane ring, an aziridine ring, an azetidine ring, an episulfide ring, and a thietane ring. More preferred are cyclopropane ring, cyclobutane ring, oxirane ring, oxetane ring and azetidine ring, and particularly preferred are cyclopropane ring, cyclobutane ring and azetidine ring. The ring structure may have a substituent.

  The compound of type 4 is preferably represented by the general formula (4-1) or (4-2).

In the general formula (4-1) and the general formula (4-2), RED ₄₁ and RED ₄₂ each represent a group having the same meaning as RED _{12 in the} general formula (1-2), and the preferred ranges thereof are also the same. R _{40 to} R ₄₄ and R _{45 to} R ₄₉ each represent a hydrogen atom or a substituent. Examples of the substituent include the same substituents that RED ₁₂ may have. Z ₄₂ in the general formula _{(4-2), -CR 420 R 421 -, -} NR 423 -, or an -O-. Here, R ₄₂₀ and R ₄₂₁ each represent a hydrogen atom or a substituent, and R ₄₂₃ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (4-1), R ₄₀ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Group, alkoxycarbonyl group, acyl group, carbamoyl group, cyano group, sulfamoyl group, more preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, alkoxycarbonyl group, acyl group, carbamoyl group Particularly preferred are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group and a carbamoyl group.

R _{41 to} R ₄₄ are preferably a case where at least one of them is a donor group and a case where R ₄₁ and R ₄₂ , or R ₄₃ and R ₄₄ are both electron withdrawing groups. More preferably, at least one of R _{41 to} R ₄₄ is a donor group. More preferably, at least one of R _{41 to} R ₄₄ is a donor group, and a group that is not a donor group among R _{41 to} R ₄₄ is a hydrogen atom or an alkyl group.

The donor group referred to here is a group selected from the group of hydroxy groups, alkoxy groups, aryloxy groups, mercapto groups, acylamino groups, sulfonylamino groups, active methine groups, or groups preferred as RED ₄₁ and RED _42. . The donor group is preferably an alkylamino group, an arylamino group, a heterocyclic amino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (which may be monocyclic or condensed), and a nitrogen atom. Non-aromatic nitrogen-containing heterocyclic group to be substituted, phenyl group substituted with at least one electron-donating group (here, the electron-donating group is a hydroxy group, an alkoxy group, an aryloxy group, an amino group, an alkylamino group, an aryl group) An amino group, a heterocyclic amino group, or a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom). More preferably, an alkylamino group, an arylamino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (herein, the aromatic heterocyclic ring represents an indole ring, a pyrrole ring, or a carbazole ring), an electron A phenyl group substituted with a donating group (here, specifically, a phenyl group substituted with three or more alkoxy groups, a phenyl group substituted with a hydroxy group, an alkylamino group, or an arylamino group) is used. Particularly preferably, an arylamino group, a 5-membered aromatic heterocyclic group having one nitrogen atom in the ring (in this case, represents a 3-indolyl group), a phenyl group substituted with an electron-donating group (here, particularly Represents a phenyl group substituted with a trialkoxyphenyl group, an alkylamino group or an arylamino group). The electron withdrawing group is the same as that already described in the description of the active methine group.

In the general formula (4-2), a preferable range of R ₄₅ is the same as that of R _{40 in} the general formula (4-1).

R _{46 to} R ₄₉ are preferably a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, hydroxy group, alkoxy group, amino group, alkylamino group, arylamino group, heterocyclic amino group, mercapto Group, arylthio group, alkylthio group, acylamino group, sulfoneamino group, more preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxy group, alkylamino group, arylamino group, heterocyclic amino group . Particularly preferred R _{46 to} R ₄₉ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group when Z ₄₂ is a group represented by —CR ₄₂₀ R ₄₂₁ —, Z ₄₂ is -NR ₄₂₃ - hydrogen atoms to represent a alkyl group, an aryl group, a heterocyclic group, a hydrogen atom when Z ₄₂ represents -O-, an alkyl group, an aryl group, a heterocyclic group It is.

Z ₄₂ is preferably —CR ₄₂₀ R ₄₂₁ — or —NR ₄₂₃ —, more preferably —NR ₄₂₃ —.

R ₄₂₀ and R ₄₂₁ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an amino group, a mercapto group, an acylamino group, a sulfonamino group, and more A hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an amino group are preferable. _R423 preferably represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group, more preferably a methyl group, an ethyl group, an isopropyl group, a t-butyl group, a t-amyl group, a benzyl group or a diphenylmethyl group. Allyl group, phenyl group, naphthyl group, 2-pyridyl group, 4-pyridyl group, 2-thiazolyl group.

When each of R _{40 to} R ₄₉ and R ₄₂₀ , R ₄₂₁ and R ₄₂₃ is a substituent, the total number of carbon atoms is preferably 40 or less, more preferably 30 or less, and particularly preferably The total carbon number is 15 or less. In addition, these substituents may be bonded to each other or may be bonded to other sites in the molecule (RED ₄₁ , RED ₄₂ or Z ₄₂ ) to form a ring.

  The compounds of types 1, 3, and 4 of the present invention are “compounds having an adsorptive group to silver halide in the molecule” or “compounds having a partial structure of a spectral sensitizing dye in the molecule”. It is preferable that A type 2 compound is a “compound having two or more adsorptive groups to silver halide in the molecule”.

  In the compounds of types 1 to 4 of the present invention, the adsorptive group to silver halide is a group that directly adsorbs to silver halide or a group that promotes adsorption to silver halide. Specifically, mercapto A heterocyclic group containing at least one atom selected from a group (or a salt thereof), a thione group (—C (═S) —), a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom, a sulfide group, a cationic group, Or an ethynyl group.

However, the type 2 compound of the present invention does not contain a sulfide group as an adsorptive group.

The mercapto group (or salt thereof) as the adsorptive group means the mercapto group (or salt thereof) itself, and more preferably a heterocyclic group or aryl group substituted with at least one mercapto group (or salt thereof). Or represents an alkyl group. Here, the heterocyclic group is a 5-membered to 7-membered monocyclic or condensed aromatic or non-aromatic heterocyclic group such as an imidazole ring group, a thiazole ring group, an oxazole ring group, or a benzimidazole ring group. , Benzthiazole ring group, benzoxazole ring group, triazole ring group, thiadiazole ring group, oxadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyrimidine ring group, triazine A cyclic group etc. are mentioned. Further, it may be a heterocyclic group containing a quaternized nitrogen atom. In this case, the substituted mercapto group may be dissociated into a meso ion. Examples of such a heterocyclic group include an imidazolium ring group, Examples include a pyrazolium ring group, a thiazolium ring group, a triazolium ring group, a tetrazolium ring group, a thiadiazolium ring group, a pyridinium ring group, a pyrimidinium ring group, and a triazinium ring group. Triazolium-3-thiolate ring group) is preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms. When the mercapto group forms a salt, the counter ion includes a cation such as alkali metal, alkaline earth metal, heavy metal (Li ⁺ , Na ⁺ , K ⁺ , Mg ²⁺ , Ag ⁺ , Zn ^2+, etc.), ammonium ion Examples thereof include a heterocyclic group containing a quaternized nitrogen atom, a phosphonium ion, and the like.

  Further, the mercapto group as the adsorptive group may be tautomerized into a thione group, specifically, a thioamide group (here, —C (═S) —NH— group), and the thioamide group. A group having a partial structure of, ie, a chain or cyclic thioamide group, a thioureido group, a thiourethane group, or a dithiocarbamate group. Examples of cyclic groups include thiazolidine-2-thione group, oxazolidine-2-thione group, 2-thiohydantoin group, rhodanine group, isorhodanine group, thiobarbituric acid group, 2-thioxo-oxazolidine-4-one group Is mentioned.

  The thione group as an adsorptive group cannot be tautomerized to a mercapto group (including a hydrogen atom at the α-position of the thione group), including the case where the mercapto group described above is tautomerized into a thione group. A chain or cyclic thioamide group, thioureido group, thiourethane group, or dithiocarbamate group is also included.

  A heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as the adsorptive group is a -NH- group capable of forming imino silver (> NAg) and a partial structure of the heterocyclic ring A nitrogen-containing heterocyclic group, or a “—S—” group, a “—Se—” group, a “—Te—” group, or a “═N—” group that can coordinate to a silver ion via a coordination bond. A heterocyclic group having a ring partial structure. Examples of the former include benzotriazole group, triazole group, indazole group, pyrazole group, tetrazole group, benzimidazole group, imidazole group, and purine group, and examples of the latter include thiophene. Group, thiazole group, oxazole group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole group, triazine group, Renoazoru group, benz seleno azole group, tellurium azole group, such as benz tellurium azole group. The former is preferred.

  The sulfide group as the adsorptive group includes all groups having a partial structure of “—S—”, preferably alkyl (or alkylene) -S-alkyl (or alkylene), aryl (or arylene) -S—. A group having a partial structure of alkyl (or alkylene), aryl (or arylene) -S-aryl (or arylene). Furthermore, these sulfide groups may form a cyclic structure or may be an -S-S- group. Specific examples in the case of forming a cyclic structure include groups containing a thiolane ring, a 1,3-dithiolane ring or a 1,2-dithiolane ring, a thiane ring, a dithiane ring, a tetrahydro-1,4-thiazine ring and the like. Particularly preferred as the sulfide group is a group having a partial structure of alkyl (or alkylene) -S-alkyl (or alkylene).

  The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, specifically, an ammonio group or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. . Here, the ammonio group is a trialkylammonio group, a dialkylarylammonio group, an alkyldiarylammonio group or the like, and examples thereof include a benzyldimethylammonio group, a trihexylammonio group, and a phenyldiethylammonio group. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, an imidazolio group, and the like. A pyridinio group and an imidazolio group are preferable, and a pyridinio group is particularly preferable. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent, but in the case of a pyridinio group and an imidazolio group, the substituent is preferably an alkyl group, an aryl group, an acylamino group , A chloro atom, an alkoxycarbonyl group, a carbamoyl group, and the like. In the case of a pyridinio group, a phenyl group is particularly preferable as a substituent.

An ethynyl group as an adsorptive group means a —C≡CH group, and a hydrogen atom may be substituted.
The above adsorptive group may have an arbitrary substituent.
Specific examples of the adsorptive group further include those described in the specifications p4 to p7 of JP-A No. 11-95355.

Preferred as the adsorptive group are mercapto-substituted nitrogen-containing heterocyclic groups (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3, 4-oxadiazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.), dimercapto-substituted heterocyclic group (for example, 2,4-dimercaptopyrimidine group) 2,4-dimercaptotriazine group, 3,5-dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3-thiazole group), or imino silver (> NAg) A nitrogen-containing heterocyclic group having a -NH- group as a heterocyclic partial structure (for example, benzotriazole group, benzimidazole) Group, an indazole group). The adsorptive group may be substituted anywhere in the general formulas (A) to (F), but in the general formulas (A) to (D), RED ₁₁ , RED ₁₂ , RED ₂ , RED ₃ In the formulas (E) and (F), RED ₄₁ , R ₄₁ , RED ₄₂ , R _{46 to} R ₄₈ are preferably substituted, and all of the general formulas (A) to (F) are represented by RED ₁₁ to More preferably, RED ₄₂ is substituted.

The partial structure of the spectral sensitizing dye is a group containing the chromophore of the spectral sensitizing dye, and is a residue obtained by removing any hydrogen atom or substituent from the spectral sensitizing dye compound. The partial structure of the spectral sensitizing dye may be substituted anywhere in the general formulas (A) to (F), but in the general formulas (A) to (D), RED ₁₁ , RED ₁₂ , RED ₂ , RED ₃ , in general formulas (E) and (F), RED ₄₁ , R ₄₁ , RED ₄₂ and R _{46 to} R ₄₈ are preferably substituted, and all of general formulas (A) to (F) are preferably substituted. More preferably, RED _{11 to} RED ₄₂ are substituted. Preferred spectral sensitizing dyes are spectral sensitizing dyes typically used in color sensitization techniques such as cyanine dyes, complex cyanine dyes, merocyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, Includes styryl dyes and hemicyanine dyes. Exemplary spectral sensitizing dyes are disclosed in Research Disclosure, Item 36544, September 1994. Those skilled in the art can synthesize these dyes by the procedures described in the Research Disclosure, or FMHamer's The Cyanine dyes and Related Compounds (Interscience Publishers, New yprk, 1964). Further, all the dyes described in the specifications p7 to p14 of JP-A No. 11-95355 (US Pat. No. 6,054,260) are applied as they are.

  The compounds of types 1 to 4 of the present invention preferably have a total carbon number of 10 to 60. More preferably, it is 10-50, More preferably, it is 11-40, Most preferably, it is 12-30.

  The compounds of types 1 to 4 of the present invention are subjected to 1-electron oxidation triggered by exposure of the silver halide photographic light-sensitive material using the compound, and after the subsequent reaction, further 1 electron, or 2 electrons or more depending on the type. Electrons are emitted and oxidized, and the oxidation potential of the first electron is preferably about 1.4 V or less, and more preferably 1.0 V or less. This oxidation potential is preferably higher than 0V, more preferably higher than 0.3V. Accordingly, the oxidation potential is preferably in the range of about 0 to about 1.4V, more preferably about 0.3 to about 1.0V.

  Here, the oxidation potential can be measured by a cyclic voltammetry technique. Specifically, a sample is dissolved in a solution of acetonitrile: water (including 0.1 M lithium perchlorate) = 80%: 20% (volume%). After bubbling nitrogen gas for 10 minutes, a glassy carbon disk was used as the working electrode, a platinum wire was used as the counter electrode, and a calomel electrode (SCE) was used as the reference electrode at 25 ° C. and 0.1 V / Measured at a potential scanning speed of seconds. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave.

  In the case where the compounds of types 1 to 4 of the present invention are one-electron oxidized and further emit one electron after the subsequent reaction, the subsequent oxidation potential is preferably −0.5 V to −2 V. More preferably, it is -0.7V-2V, More preferably, it is -0.9V--1.6V.

  In the case where the compound of types 1 to 4 of the present invention is a compound that is oxidized by one electron and emits two or more electrons after the subsequent reaction and is oxidized, there is no particular limitation on the oxidation potential of this latter stage. Absent. This is because the oxidation potential of the second electron and the oxidation potential of the third and subsequent electrons cannot be clearly distinguished, and it is often difficult to accurately measure and distinguish these actually.

Although the specific example of the compound of the types 1-4 of this invention is enumerated below, this invention is not limited to these.

  The compounds of types 1 to 4 of the present invention are the same as those described in detail in Japanese Patent Application Nos. 2001-234075, 2001-234048, and 2001-250679, respectively. Specific compound examples described in these patent application specifications can also be given as specific examples of the compounds of types 1 to 4 of the present invention.

Next, the compound of type A will be described.
The compound of type A is represented by XY, where X represents a reducing group, Y represents a leaving group, and a one-electron oxidant produced by one-electron oxidation of the reducing group represented by X is This is a compound capable of releasing X by further elimination of Y with subsequent XY bond cleavage reaction to generate an X radical, from which another electron is emitted. The reaction when such a type A compound is oxidized can be expressed by the following formula.

The compound of type A preferably has an oxidation potential of 0 to 1.4V, more preferably 0.3 to 1.0V. The oxidation potential of the radical X · generated in the above reaction formula is preferably −0.7 V to −2.0 V, more preferably −0.9 V to −1.6 V.
The compound of type A is preferably represented by the general formula (A).

In the general formula (A), RED ₀ represents a reducing group, L ₀ represents a leaving group, and R ₀ and R ₁ represent a hydrogen atom or a substituent. RED ₀ and R ₀ , and R ₀ and R ₁ may be bonded to each other to form a ring structure.

RED ₀ represents a group having the same meaning as RED _{12 in} formula (1-2), and the preferred range thereof is also the same. R ₀ and R ₁ are the same groups as R ₂₁ and R _{22 in} the general formula (2), and their preferred ranges are also the same. However, R ₀ and R ₁ do not represent the same group as L ₀ except for a hydrogen atom. RED ₀ and R ₀ may be bonded to each other to form a ring structure. As an example of the ring structure, RED ₂ and R _{21 in} the general formula (2) are linked to form a ring structure. The same example as the case is mentioned, The preferable range is also the same. Examples of the ring structure formed by combining R ₀ and R ₁ with each other include a cyclopentane ring and a tetrahydrofuran ring.

In the general formula (A), the leaving group represented by L ₀ is a carboxy group or a salt thereof, a silyl group, a stannyl group, a germyl group, a triaryl boron atom anion, —C (R ₀ ) (R ₁ ) — RED represents ₀ group or hydrogen atom. Among these, a carboxy group or a salt thereof, and a silyl group have the same meaning as L _{11 in the} general formula (1-1), and a preferred range thereof is also the same.

The stannyl group is preferably a trialkylstannyl group, the germyl group is preferably a trialkylgermyl group, and the triarylboron atom anion is preferably a triphenylboron atom anion, where the phenyl group has a substituent. Also good. When L ₀ represents “—C (R ₀ ) (R ₁ ) —RED ₀ group”, the compound represented by the general formula (A) is a group of —C (R ₀ ) (R ₁ ) —RED ₀ groups. Means a bis-type compound in which is bound.

The leaving group represented by L ₀ in the general formula (A) is preferably a carboxy group or a salt thereof, a silyl group, a —C (R ₀ ) (R ₁ ) -RED ₀ group, and more preferably a carboxy group. A group or a salt thereof, and a hydrogen atom.

When L ₀ represents a hydrogen atom, the compound represented by the general formula (A) preferably has a base moiety in the molecule. By the action of this base, after the compound represented by the general formula (A) is oxidized, the hydrogen atom represented by L ₀ is deprotonated, and “RED ₀ (R ₀ ) (R ₁ ) C” A radical represented by is given, and one electron is emitted therefrom.

Here, the base is specifically a conjugate base of an acid having a pKa of about 1 to about 10. For example, nitrogen-containing heterocycles (pyridines, imidazoles, benzimidazoles, thiazoles, etc.), anilines, trialkylamines, amino groups, carbon acids (active methylene anions, etc.), thioacetic acid anions, carboxylates (- COO ⁻ ), sulfate (—SO ₃ ⁻ ), amine oxide (> N ⁺ (O ⁻ ) −) and the like. Preferably, it is a conjugate base of an acid exhibiting a pKa of about 1 to about 8, more preferably carboxylate, sulfate or amine oxide, particularly preferably carboxylate. When these bases have an anion, they may have a counter cation, and examples thereof are the same as those described as counter ions for forming a salt when L ₀ represents a carboxy group or a salt thereof. .

The position to which these base sites are bonded may be any of RED ₀ , R ₀ , R _{1 in} the general formula (A), preferably R ₁ , for example, a preferable R ₁ group when the base represents a carboxylate. Examples thereof include groups such as — (CH ₂ ) ₃ —COO ⁻ , — (CH ₂ ) ₂ —COO ⁻ and —CH ₂ —COO ⁻ .

  The compound represented by the general formula (A) is “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule”. Preferably there is. More preferred is a “compound having an adsorptive group to silver halide in the molecule”.

  Examples of the adsorptive group to the silver halide of the compound represented by the general formula (A) include the same adsorptive groups that the compounds of types 1 to 4 of the present invention may have. In addition, a selenooxo group (—C═Se—), a tellurium oxo group (—C═Te—), a seleno group (—Se—), a tellurium group (—Te—), or an active methine group may be mentioned. . Here, the selenooxo group (—C═Se—) and the tellurium oxo group (—C═Te—) are Se or Te derivatives of a compound having a thione group (—C═S—), as described for the thione group. In addition, a group containing a selenamide group (—C═Se—NH—) or a telluramide group (—C═Te—NH—) may be used. The seleno group (—Se—) and tellurium group (—Te—) are also Se or Te derivatives of compounds having a sulfide group (—S—), and are Se or Te substitutes of compounds having a sulfide group. Is given as an example. The active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group is an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group. Group, arylsulfonyl group, sulfamoyl group, trifluoromethyl group, cyano group, nitro group, imino group. Here, the two electron withdrawing groups may be bonded to each other to form a cyclic structure.

The adsorption promoting group possessed by the compound represented by the general formula (A) is preferably selected from a mercapto group (or a salt thereof), a thione group (—C═S—), a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom. A heterocyclic group containing at least one atom, a sulfide group, and more preferably a —NH— group capable of forming a mercapto-substituted nitrogen-containing heterocyclic group, a dimercapto-substituted heterocyclic group, or an imino silver (> NAg). These are nitrogen-containing heterocyclic groups having a heterocyclic partial structure, and these are the same as those described for the preferred range of the adsorptive group that the compounds of types 1 to 4 may have. The adsorptive group may be substituted anywhere in the general formula (A), but is preferably substituted with RED ₀ or R ₀ , more preferably with RED ₀ .

  The partial structure of the spectral sensitizing dye that the compound represented by formula (A) may have is the partial structure of the spectral sensitizing dye that the compounds of types 1 to 4 of the present invention may have. Is the same.

Specific examples of the compound represented by formula (A) are shown below, but are not limited thereto.

  As specific examples of the compound represented by the general formula (A), JP-A-9-211769 (compounds PMT-1 to S-37 described in Tables E and F on p28 to p32), JP-A-9- No. 211774, JP-A-11-95355 (Compound INV 1-36), JP-T 2001-500996 (Compounds 1-74, 80-87, 92-122), US Patent 5,747,235, US Patent 5,747,236, European Patent 786692A1 (compound INV 1-35), European Patent 893732A1, US Patent 6,054,260, US Patent 5,994,051, etc. "One-Photon Two-Electron Sensitizer" or "Deprotonated Electron Donor Sensitizer" Examples of compounds referred to as are mentioned as they are.

  The type A or type 1-4 compounds of the present invention may be used at any time during the preparation of the emulsion and during the light-sensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compound of type A or types 1 to 4 of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

The type A or type 1-4 compound of the present invention is preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per 1 mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

Next, the compound (compound (B)) having at least 3 heteroatoms of the present invention will be described. Here, the hetero atom includes any atom other than carbon or hydrogen, but nitrogen, sulfur, phosphorus and oxygen are preferable.
When the compound (B) of the present invention is a heterocyclic ring, three or more heteroatoms are present in the ring system component, or at least one heteroatom is present in the ring system component. On the other hand, it means that there are at least two or more heteroatoms present at a position separated from the ring system by at least one non-conjugated single bond, or at a part of a further substituent of the ring system.

In the present invention, an increase in photographic sensitivity of the light-sensitive material indicates that S _0.2 increases by 0.02 or more, preferably increases by 0.03 or more, and more preferably increases by 0.04 or more. The S _0.2, indicating the logarithm of the reciprocal of the exposure giving a density of fog + 0.2 in the light-sensitive material was developed by developing the method described in Example 1. This value is 0.02 or more higher when it is contained than when it does not contain a compound having at least 3 heteroatoms.

The compound (B) of the present invention may be used for either the silver halide photosensitive layer or the non-photosensitive layer in the photosensitive material, but is preferably used for the silver halide photosensitive layer.
When used for a silver halide photosensitive layer, when the photosensitive layer is divided into a plurality of layers having different sensitivities, it may be used for any sensitive layer, but is preferably used for a highly sensitive layer.
When used for a non-photosensitive layer, it is preferably used for an intermediate layer located between a red-sensitive layer and a green-sensitive layer or between a green-sensitive layer and a blue-sensitive layer.

  The method for adding the compound (B) to the light-sensitive material is not particularly limited, but a method of emulsifying and dispersing together with a high boiling point organic solvent, a solid dispersion, a method of dissolving in an organic solvent such as methanol and adding to a coating solution, a halogen Although there is a method of adding at the time of preparation of a silver halide emulsion, it is preferably introduced into a light-sensitive material by emulsification dispersion.

  A method of introducing the compound (B) into the light-sensitive material as it is is also preferable, but a method of introducing a compound that reacts with an oxidized developer to release a residue of a compound having at least three heteroatoms is also introduced into the light-sensitive material. Preferably, the compound is also included in the range of the compound (B).

There is no particular limitation on the addition amount of compound (B), preferably from 0.1 to 1000 mg / m ^2, more preferably ^{1~500mg / m 2, 5~100mg / m} 2 is particularly preferred.
When used in a light-sensitive silver halide emulsion layer, 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol is preferable, and 1 × 10 ^{−3 to} 5 × 10 ⁻² mol is more preferable per mol of silver in the same layer. .

Although the compound example of the compound (B) of this invention is given to the following, it is not necessarily limited to these.

The compound represented by formula (M) or formula (C) will be described.

In general formula (M), R ₁ represents a hydrogen atom or a substituent. Z represents a group of nonmetallic atoms necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). X represents a hydrogen atom or a substituent.

In General Formula (C), Za represents —NH— or —CH (R ₃ ) —, and Zb and Zc represent —C (R ₄ ) ═ or —N═, respectively. R ₁ , R ₂ and R ₃ each represent an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more and 1.0 or less. R ₄ represents a hydrogen atom or a substituent. However, when two R < ₄ > exists in a formula, they may be same or different. X represents a hydrogen atom or a substituent.

Hereinafter, this compound will be described in detail. Of the skeletons represented by the formula (M), preferred skeletons are 1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4. ] Triazole, each represented by formula (M-1) and formula (M-2).

In the formula, R ₁₁ and R ₁₂ represent a substituent, and X represents a hydrogen atom or a substituent.

The substituents R ₁₁ , R ₁₂ and X in the formula (M-1) or (M-2) will be described in detail.
R ₁₁ is, for example, a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), an alkyl group (having 1 to 60 carbon atoms. For example, methyl, ethyl, propyl, iso-butyl, t-butyl, t-octyl, 1 -Ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (2 to 60 carbon atoms, for example, vinyl, allyl, oleyl), cycloalkyl group (5 to 60 carbon atoms). For example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1-indanyl, cyclododecyl), aryl group (6 to 60 carbon atoms, for example, phenyl, p-tolyl, naphthyl), acylamino group (2 to 60 carbon atoms). For example, acetylamino, n-butanamide, octanoylamino, 2-hexyl Decanamide, 2- (2 ′, 4′-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), sulfonamide group (C1-C60. For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide) ), Ureido groups (2 to 60 carbon atoms, such as decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane groups (2 to 60 carbon atoms, such as dodecyloxycarbonylamino, phenoxycarbonylamino, 2- Ethylhexyloxycarbonylamino), alkoxy group (C1-C60. For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (C6-C60. For example, phenoxy, 2 , 4-Di-t-Ami Phenoxy, 4-t-octylphenoxy, naphthoxy), alkylthio group (1 to 60 carbon atoms, for example, methylthio, ethylthio, butylthio, hexadecylthio), arylthio group (6 to 60 carbon atoms, for example, phenylthio, 4-todecyloxy) Phenylthio), acyl group (having 1 to 60 carbon atoms, for example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (having 1 to 60 carbon atoms, for example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (C1-C60. For example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (C0-60, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, nitro group, Alkylamino group (having 1 to 60 carbon atoms) . For example, methylamino, diethylamino, octylamino, octadecylamino), arylamino group (carbon number 6 to 60. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (carbon number 0 to 60. Preferably, the hetero atom having a ring structure is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably includes a carbon atom in addition to the hetero atom as the ring atom. 8, More preferably, it is 5-6, for example, the group illustrated by the term of X mentioned later), an acyloxy group (carbon 1-60. For example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) etc. are mentioned. .

  Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group.

Among these substituents, preferable R ₁₁ includes an alkyl group, an aryl group, an alkoxy group, and an aryloxy group, and more preferably an alkyl group, an alkoxy group, and an aryloxy group. Particularly preferred is a branched alkyl group.

Examples of R ₁₂ include the substituents exemplified for R ₁₁ , and preferred substituents are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, and an aryloxy group.
More preferred are an alkyl group and a substituted aryl group, and the most preferred group is a substituted aryl group, and compounds represented by general formulas (M-3) and (M-4) are preferred.

In formula, R <_11> , X is synonymous with general formula (M-1) and (M-2), and R < ₁₃ > represents a substituent. Examples of the substituent for R ₁₃ include the substituents enumerated above as R ¹¹ . Preferred examples of the substituent include a substituted aryl group and a substituted or unsubstituted alkyl group. Examples of the substituent in this case include the substituents enumerated above as R ¹¹ .

X represents a hydrogen atom or a substituent, and examples of the substituent include those listed above as R ¹¹ . The substituent for X is preferably an alkyl group, an alkoxycarbonyl group, a carbamoyl group, or a group that is released by reaction with an oxidized form of a developing agent, and the group includes a halogen atom (fluorine, chlorine, bromine, etc.), Alkoxy groups (ethoxy, methoxycarbonylmethoxy, carboxypropyloxy, methanesulfonylethoxy, perfluoropropoxy, etc.), aryloxy groups (4-carboxyphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, 4-methanesulfonyl-3- Carboxyphenoxy, 2-methanesulfonyl-4-acetylsulfamoylphenoxy, etc.), acyloxy groups (acetoxy, benzoyloxy, etc.), sulfonyloxy groups (methanesulfonyloxy, benzenesulfonyloxy, etc.), acylamino groups (f) Tafluorobutyrylamino etc.), sulfonamide groups (methanesulfonamide etc.), alkoxycarbonyloxy groups (ethoxycarbonyloxy etc.), carbamoyloxy groups (diethylcarbamoyloxy, piperidinocarbonyloxy, morpholinocarbonyloxy etc.), alkylthio Groups (such as 2-carboxyethylthio), arylthio groups (such as 2-octyloxy-5-t-octylphenylthio, 2- (2,4-di-t-amylphenoxy) butyrylaminophenylthio), heterocyclic rings Thio group (1-phenyltetrazolylthio, 2-benzimidazolylthio, etc.), heterocyclic oxy group (2-pyridyloxy, 5-nitro-2-pyridyloxy, etc.), 5-membered or 6-membered nitrogen-containing heterocyclic group (1-triazolyl, 1-imidazolyl, 1-pyrazolyl, 5 Chloro-1-tetrazolyl, 1-benzotriazolyl, 2-phenylcarbamoyl-1-imidazolyl, 5,5-dimethylhydantoin-3-yl, 1-benzylhydantoin-3-yl, 5,5-dimethyloxazolidine-2 , 4-dione-3-yl, purine, etc.) and azo groups (4-methoxyphenylazo, 4-pivaloylaminophenylazo, etc.).

  As the substituent for X, an alkyl group, an alkoxycarbonyl group, a carbamoyl group, a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, a 5-membered or 6-membered atom bound to a coupling activity with a nitrogen atom A nitrogen-containing heterocyclic group, particularly preferably an alkyl group, a carbamoyl group, a halogen atom, a substituted aryloxy group, a substituted arylthio group, an alkylthio group, or a 1-pyrazolyl group.

The compounds represented by the general formulas (M-1) and (M-2) and preferably used in the present invention may form a dimer or higher multimer via R ₁₁ and R _12. Further, it may be bonded to a polymer chain. In the present invention, the general formula (M-1) is preferable, and the general formula (M-3) is more preferable.

Next, general formula (C) will be described. Specifically, the general formula (C) of the present invention is represented by the following general formulas (C3) to (C10).

In formula, R < ₁ > -R < ₄ > and X are synonymous with each in general formula (C).

  In the present invention, compounds represented by the general formulas (C3), (C4), (C5), and (C8) are preferable, and a compound represented by (C4) is particularly preferable.

In the general formula (C), the substituent represented by R ₁ , R ₂ and R ₃ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more and 1.0 or less. Preferably, it is an electron withdrawing group having a σp value of 0.2 or more and 0.8 or less. Hammett's rule was established in 1935 by L.L. to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb advocated by Hammet, which is widely accepted today. Substituent constants obtained by Hammett's rule include a σp value and a σm value, and these values are described in many general books. A. Dean ed. "Lange's Handbook of Chemistry" 12th edition, 1979 (McGaw-Hill) and "Chemical area special edition", 122, 96-103, 1979 (Nanedo) Chemical Review, 91, 165-195 Page, detailed in 1991.

In the present invention, R ₁ , R ₂ and R ₃ are defined by Hammett's substituent constant value, but it is not meant to be limited only to substituents having known values described in these documents. Of course, even if the value is unknown, it is included as long as it is included in the range when measured based on the Hammett rule.

Specific examples of electron withdrawing groups having a σp value of 0.2 or more and 1.0 or less include acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, cyano groups, nitro groups, dialkylphosphono groups, diarylphosphones Group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and the like. Among these substituents, the group that can further have a substituent may further have a substituent as described in R ₄ described later.

R ₁ , R ₂ and R ₃ are preferably an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a cyano group or a sulfonyl group, and more preferably a cyano group, an acyl group, an alkoxycarbonyl group or an aryl group. An oxycarbonyl group and a carbamoyl group.
The combination of R ₁ and R ₂ is preferably when R ₁ is a cyano group and R ₂ is an alkoxycarbonyl group.

R ₄ represents a hydrogen atom or a substituent, and examples of the substituent include the substituents listed in R ₁₁ above.
Preferred substituents for R ₄ include alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, aryloxy groups, and acylamino groups. More preferred are alkyl groups and substituted aryl groups, and the most preferred groups are , A substituted aryl group. Examples of the substituent in this case include the substituents listed above.
X is the same as in the general formula (M).

Specific examples of couplers preferably used in the present invention are shown below, but the present invention is not limited thereto.

  The compounds represented by the general formula (M) and general formula (C) of the present invention are, for example, JP-A 61-65245, JP-A 61-65246, JP-A 61-147254, and JP-A-8. It can be easily synthesized by the synthesis method described in No. -122984. The amount of the compound represented by formulas (M) and (C) of the present invention added to the photosensitive material is the same as that for compound B.

  Conventionally known compounds can be used as the vinyl polymer used in the present invention. As the vinyl polymer, either a water-dispersed (self-emulsifying) type or a water-soluble type can be used, but the water-dispersed type is preferable from the viewpoints of easy production of fine particles and dispersion stability.

  The vinyl polymer preferably has a sulfonic acid as a dissociable group. It can also be used in combination with a nonionic dispersible group such as a polyethyleneoxy chain.

  Monomers that form vinyl polymers include acrylic esters, specifically methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, methoxy Benzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate Furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2- Butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate 2,2,2-tetrafluoroethyl acrylate, 1H, 1H, 2H, 2H-perfluorodecyl acrylate and the like. Methacrylic acid esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate , Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate 4-Hido Xylbutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-tetrafluoroethyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate Or the like can be mentioned over door.

  Vinyl esters, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc. ,

Acrylamides such as acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, tert-octyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxymethyl acrylamide, butoxymethyl acrylamide, methoxyethyl acrylamide , Phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide, etc.
Methacrylamide, for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, phenyl Methacrylamide, dimethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-acetoacetoxyethyl) methacrylamide,

Olefins such as dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, styrenes such as styrene, methylstyrene , Dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester, etc.

Vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether,

Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl Ketone, methoxyethyl vinyl ketone, N-vinyloxazolidone, N-vinylpyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyloxy Examples thereof include ethyl phosphate and dioctyl-2-methacryloyloxyethyl phosphate.

  Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkanesulfonic acid (for example, acryloyloxymethanesulfonic acid, acryloyloxyethanesulfonic acid, acryloyloxypropanesulfonic acid, etc.), methacryloyloxyalkanesulfonic acid (for example, Methacryloyloxymethanesulfonic acid, methacryloyloxyethanesulfonic acid, methacryloyloxypropanesulfonic acid, etc.), acrylamide alkanesulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2 -Acrylamide-2-methylbutanesulfonic acid, etc.), methacrylamide alkanesulfonic acid (eg 2-methacrylamido-2-methyl) Ethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid). Among these, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable, and styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 2-acrylamide- are more preferable. 2-methylbutanesulfonic acid.

  Monomers containing nonionic dispersible groups include esters of polyethylene glycol monoalkyl ether and carboxylic acid monomers, esters of polyethylene glycol monoalkyl ether and sulfonic acid monomers, and polyethylene glycol monoalkyl ether and phosphoric acid monomers. Examples thereof include a vinyl group-containing urethane formed from an ester, a polyethylene glycol monoalkyl ether and an isocyanate group-containing monomer, and a macromonomer containing a polyvinyl alcohol structure. The number of ethyleneoxy moiety repeats in the polyethylene glycol monoalkyl ether is preferably 8 to 50, more preferably 10 to 30. The alkyl group of the polyethylene glycol monoalkyl ether preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.

  Monomers (for example, the above-mentioned monomers) used in the polymer of the present invention may be composed of two or more monomers as comonomers according to various purposes (for example, Tg adjustment, solubility improvement, and dispersion stability). May be used.

  When using a monomer having a dissociable group, when the content of the dissociable group is small, the self-emulsifying property of the vinyl polymer is small, and when the content is large, the water solubility becomes high and the UV absorber is dispersed. It becomes inappropriate. The content of the dissociable group is preferably from 0.1 to 3.0 mmol / g, more preferably from 0.2 to 2.0 mmol / g. The dissociable group may be an alkali metal (for example, Na, K, etc.) or a salt of ammonium ion.

Some specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto. The following proportionality represents the mass ratio.
Specific example Polymer type
P-1) Ethyl methacrylate-styrene sulfonic acid copolymer (90:10)
P-2) Isopropyl methacrylate-styrene sulfonic acid copolymer (85:15)
P-3) n-Butyl acrylate-styrene-styrene sulfonic acid copolymer (80: 5: 15)
P-4) Isobutyl methacrylate-styrene sulfonic acid copolymer (85:15)
P-5) Isobutyl acrylate-triethylene glycol monomethacrylate-styrene sulfonic acid copolymer (80:10:10)
P-6) Ethyl acrylate-1H, 1H, 2H, 2H-perfluorodecyl methacrylate-styrene sulfonic acid copolymer (83: 10: 7)
P-7) n-Butyl acrylate-2-butoxyethyl methacrylate-styrene sulfonic acid copolymer (70: 21.5: 8.5)
P-8) Ethyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (90:10)
P-9) Ethyl acrylate-2-butoxyethyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10)
P-10) Isobutyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (92: 8)
P-11) Isobutyl acrylate-ethyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (70:20:10)
P-12) Ethyl acrylate-isopropyl methacrylate-2-acrylamido-2-methylethanesulfonic acid copolymer (60:30:10)
P-13) n-Butylmethacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (90:10)
P-14) Ethyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (93.7: 6.3)
P-15) Ethyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (94.2: 5.8)
P-16) Ethyl acrylate-isopropyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid copolymer (63: 30: 7)
P-17) Ethyl methacrylate-isopropyl methacrylate-2-acrylamido-2-methylpropane sulfonate sodium copolymer (60: 32.3: 7.7)
P-18) tert-Butyl acrylate-tetrahydrofurfuryl acrylate-2-methylpropane sulfonic acid copolymer (50:40:10)
P-19) Isopropyl acrylate-1H, 1H, 2H, 2H-perfluorodecyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
P-20) Methacrylic acid ester-2-acrylamido-2-methylpropanesulfonic acid copolymer of isopropyl acrylate-polyethylene glycol monomethyl ether (ethyleneoxy chain repeat number 23) (60:30:10)
P-21) Isobutyl acrylate-N-vinylpyrrolidone-2-acrylamido-2-methylpropanesulfonic acid copolymer (60:30:10)
P-22) Ethyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid soda copolymer (90.4: 9.6)
P-23) Isopropyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid soda copolymer (98:12)
P-24) Isobutyl methacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (90.4: 9.6)
P-25) Ethyl methacrylate-tert-butyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid soda copolymer (50:35:15)
P-26) Vinylpyrrolidone-isobutylmethacrylate-2-acrylamido-2-methylpropanesulfonic acid soda copolymer (50:35:15)
P-27) n-Butylmethacrylate-2-methacrylamide-2-methylpropanesulfonic acid copolymer (90:10)
P-28) n-Butyl acrylate-Isopropyl methacrylate-2-methacrylamide-2-methylpropanesulfonic acid copolymer (60:30:10)
P-29) Isobutyl acrylate-hydroxymethylacrylamide-2-methacrylamide-2-methylpropanesulfonic acid copolymer (80:10:10)
P-30) Ethyl acrylate-isopropyl methacrylate-vinyl sulfonic acid copolymer (60:30:10)
P-31) Hexyl methacrylate-methyl methacrylate-vinyl sulfonic acid copolymer (40:45:15)
P-32) Ethyl acrylate-isopropyl methacrylate-vinyl sulfonic acid copolymer (60:30:10)
P-33) Ethyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (90:10)
P-34) Isopropyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (90:10)
P-35) Ethyl acrylate-isopropyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (60:30:10)
P-36) Ethyl acrylate-isopropyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid copolymer (60:30:10)
P-37) Ethyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid soda copolymer (90.4: 9.6)
P-38) sec-propyl methacrylate-2-acrylamido-2-methylbutanesulfonic acid soda copolymer (98:12)
P-39) Isobutyl methacrylate-2-acrylamido-2-methylbutane sulfonate copolymer (90.4: 9.6)
P-40) Ethyl methacrylate-isopropyl methacrylate-2-acrylamido-2-methylbutane sulfonate copolymer (50:35:15)
P-41) Ethyl methacrylate-2-methacrylamide-2-methylbutanesulfonic acid copolymer (90:10)

  The molecular weight (Mw) of the vinyl polymer is 1,000 to 100,000, and preferably 3,000 to 50,000. When the molecular weight is less than 1000, it tends to be difficult to obtain a stable dispersion. When the molecular weight is more than 100,000, the solubility in an organic solvent is deteriorated, or the viscosity of the organic solvent solution is increased and it is difficult to disperse. It is not preferable because it is in a tendency.

A method for producing the ultraviolet absorbent-containing fine particle dispersion will be described.
The ultraviolet absorbent-containing fine particle dispersion of the present invention is produced by dispersing ultraviolet absorbent-containing fine particles containing an ultraviolet absorbent and the vinyl polymer in an aqueous medium (an aqueous liquid containing at least water). Specific examples include a co-emulsification dispersion method.

Here, the co-emulsification dispersion method will be described.
The first example of this method is a first step of preparing a vinyl polymer UV absorber solution in which the UV absorber and the self-emulsifiable vinyl polymer are dissolved in an organic solvent, and the vinyl polymer UV absorber solution. And a second step of preparing an ultraviolet absorbent-containing fine particle dispersion by mixing at least water-containing liquid.

  A second example of this method includes a first step of preparing an ultraviolet absorber solution in which the ultraviolet absorber is dissolved in an organic solvent, and a second step of preparing a vinyl polymer solution in which the self-emulsifiable vinyl polymer is dissolved. And a third step of preparing an ultraviolet absorbent-containing fine particle dispersion by mixing the ultraviolet absorbent solution, the vinyl polymer solution and a liquid containing at least water.

  A third example of this method is to prepare an ultraviolet absorbent solution in which the ultraviolet absorbent is dissolved in an organic solvent, and mix the ultraviolet absorbent solution with a liquid containing at least water to obtain an ultraviolet absorbent fine particle dispersion. A first step of preparing a vinyl polymer solution in which the self-emulsifiable vinyl polymer is dissolved, and a vinyl polymer fine particle dispersion is prepared by mixing the vinyl polymer solution and a liquid containing at least water. And a third step of preparing the ultraviolet absorbent-containing fine particle dispersion by mixing the ultraviolet absorbent fine particle dispersion and the vinyl polymer fine particle dispersion.

  A fourth example of this method is a first step of preparing a vinyl polymer solution in which the self-emulsifiable vinyl polymer is dissolved in an organic solvent, and an ultraviolet absorber solution in which the ultraviolet absorber is dissolved. A second step of preparing an ultraviolet absorbent fine particle dispersion by mixing an absorbent solution and a liquid containing at least water, and mixing the vinyl polymer solution and the ultraviolet absorbent fine particle dispersion to obtain an ultraviolet absorbent-containing fine particle. And a third step of preparing the dispersion.

  In the ultraviolet absorbent-containing fine particle dispersion, the use amount of the self-emulsifying vinyl polymer is preferably 10 to 1000 parts by mass, and more preferably 20 to 400 parts by mass with respect to 100 parts by mass of the ultraviolet absorbent.

  If the amount of the self-emulsifying vinyl polymer used is less than 10 parts by mass, fine and stable dispersion tends to be difficult, and if it exceeds 1000 parts by mass, the ultraviolet rays in the ultraviolet absorbent-containing fine particle dispersion There is a tendency that the proportion of the absorbent is reduced, and there is no room for formulation design.

The average particle diameter of the ultraviolet absorbent-containing fine particle dispersion is preferably 1 to 500 nm, and more preferably 10 to 100 nm. The average particle diameter can be adjusted by centrifugation, filtration, or the like.
The addition amount of the ultraviolet absorber is preferably from ^{0.02~2.0g / m 2, 0.2~1.0g / m} 2 is more preferable.

-Organic solvent-
The organic solvent used in producing the ultraviolet absorbent-containing fine particle dispersion is not particularly limited and can be appropriately selected based on the solubility of the ultraviolet absorbent and the vinyl polymer. For example, acetone, methyl ethyl ketone , Ketone solvents such as diethyl ketone, alcohol solvents such as methanol, ethanol, 2-propanol, 1-propanol, 1-butanol and tert-butanol, chlorine solvents such as chloroform and methylene chloride, and fragrances such as benzene and toluene Group solvents, ester solvents such as ethyl acetate, butyl acetate and isopropyl acetate, ether solvents such as diethyl ether, tetrahydrofuran and dioxane, glycol ether solvents such as ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, etc. And the like.

These organic solvents may be used individually by 1 type, and may use 2 or more types together.
The amount of the organic solvent used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 10 to 2000 parts by mass, and 100 to 1000 parts per 100 parts by mass of the self-emulsifiable vinyl polymer. Part by mass is more preferable.

  If the amount of the organic solvent used is less than 10 parts by mass, fine and stable dispersion of the ultraviolet absorber-containing fine particles tends to be difficult, and if it exceeds 2000 parts by mass, the organic solvent is removed. Desolvation and concentration steps are essential, and there is a tendency that there is no room for formulation design.

The organic solvent is removed from the viewpoint of stability of the ultraviolet absorbent-containing fine particle dispersion when the solubility of the organic solvent in water is 10% or less, or when the vapor pressure of the organic solvent is higher than water. Preferably it is done.
The removal of the organic solvent can be performed at 10 to 100 ° C. under normal pressure to reduced pressure conditions, and preferably 40 to 100 ° C. under normal pressure conditions or 10 to 50 ° C. under reduced pressure conditions.

-Additives-
The ultraviolet absorbent-containing fine particle dispersion of the present invention may contain an additive appropriately selected according to the purpose within a range not impairing the effects of the present invention.
Examples of the additive include a neutralizer, a dispersant, and a dispersion stabilizer.

When the self-emulsifiable vinyl polymer has an unneutralized dissociable group, the neutralizing agent is suitable in terms of pH adjustment, self-emulsification adjustment, dispersion stability imparting, etc. of the ultraviolet absorbent-containing fine particle dispersion. Can be used for
Examples of the neutralizing agent include organic bases and inorganic alkalis.

Examples of the organic base include triethanolamine, diethanolamine, N-methyldiethanolamine, and dimethylethanolamine.
Examples of the inorganic alkali include alkali metal hydroxides (for example, sodium hydroxide, lithium hydroxide, and potassium hydroxide), carbonates (for example, sodium carbonate, sodium hydrogen carbonate, and the like), ammonia, and the like.

  From the viewpoint of improving the dispersion stability in the ultraviolet absorbent-containing fine particle dispersion, the neutralizing agent is preferably added so as to have a pH of 4.5 to 10.0, so that the pH becomes 6.0 to 10.0. It is more preferable to add.

  The dispersing agent and dispersion stabilizer may be added to any of the self-emulsifying vinyl polymer dispersion, the self-emulsifying vinyl polymer solution, an ultraviolet absorber solution, a solution containing at least water, and the like. It is preferable to add to the solution containing the self-emulsifiable vinyl polymer, the ultraviolet absorbent solution, and water in the previous step of preparing the fine vinyl polymer and / or ultraviolet absorbent fine particle dispersion.

  Examples of the dispersant and dispersion stabilizer include cation, anion, and nonionic surfactants, water-soluble or water-dispersible low molecular compounds, oligomers, and the like. As addition amount of the said dispersing agent and a dispersion stabilizer, it is 0-100 mass% with respect to the sum total of the said ultraviolet absorber and the said self-emulsifiable vinyl polymer, and 0-20 mass% is preferable.

  Silver halide emulsions that can be used in the silver halide color photographic light-sensitive material of the present invention include silver bromide, silver chloride, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide and the like. preferable. The form of the silver halide grains may be normal crystals such as octahedrons, cubes, and tetradecahedrons, but tabular grains are more preferred.

First, silver iodobromide or chloroiodoodor having a silver chloride content of less than 10 mol%, in which the silver halide grains as the first emulsion that can be used in the light-sensitive material of the present invention are parallel (111) planes. The tabular silver halide grains made of silver halide will be described.
This emulsion consists of opposing (111) main planes and side faces connecting the main planes. The tabular grain emulsion is composed of silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. The silver iodide content is 40 mol% or less, preferably 20 mol% or less.

Regardless of the silver iodide content, the variation coefficient of the distribution of silver iodide content among grains is preferably 20% or less, and particularly preferably 10% or less.
The silver iodide distribution preferably has a structure within the grain. In this case, the structure of silver iodide distribution can be a double structure, a triple structure, a quadruple structure, or even more. Further, the silver iodide content may vary continuously within the grain.

  It is preferable that 50% or more of the total projected area is occupied by grains having an aspect ratio of 2 or more. Here, the projected area and aspect ratio of the tabular grains can be measured from electron micrographs obtained by the carbon replica method in which shadows are applied together with reference latex spheres. Tabular grains are usually hexagonal, triangular, or circular when viewed from the direction perpendicular to the main plane. The value obtained by dividing the diameter of a circle having an area equal to the projected area by the thickness is the aspect ratio. Is the ratio. The shape of the tabular grains is preferably as the hexagonal ratio is high, and the ratio of the lengths of adjacent sides of the hexagon is preferably 1: 2 or less.

  The tabular grains preferably have a projected area diameter of 0.1 to 20.0 μm, more preferably 0.2 to 10.0 μm. The projected area diameter is the diameter of a circle having an area equal to the projected area of the silver halide grains. The thickness of the tabular grain is preferably 0.01 μm or more and 0.5 μm or less, more preferably 0.02 μm or more and 0.4 μm or less. The thickness of the tabular grain is the distance between the two main planes. The equivalent sphere diameter is preferably 0.1 μm or more and 5.0 μm or less, and more preferably 0.2 μm or more and 3 μm or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The aspect ratio is preferably 1 or more and 100 or less, more preferably 2 or more and 50 or less. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.

  The silver halide grains of the present invention are preferably monodispersed. The variation coefficient of the sphere equivalent diameter of all silver halide grains of the present invention is 30% or less, preferably 25% or less. In the case of tabular grains, the variation coefficient of projected area diameter is also important, and the variation coefficient of projected area diameter of all silver halide grains of the present invention is preferably 30% or less, more preferably 25% or less. More preferably, it is 20% or less. Further, the variation coefficient of the thickness of the tabular grains is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The variation coefficient of the projected area diameter is a value obtained by dividing the standard deviation of the distribution of the projected area diameter of each silver halide grain by the average projected area diameter, and the variation coefficient of the thickness is the individual silver halide flat plate. It is a value obtained by dividing the standard deviation of the distribution of the thickness of the shaped particles by the average thickness.

  The tabular grain spacing of the tabular grains of the present invention is 0.012 μm or less as described in US Pat. No. 5,219,720, or the distance between (111) principal planes as described in JP-A-5-249585. / The twin plane spacing may be 15 or more, and may be selected according to the purpose.

  Since the higher the aspect ratio, the more remarkable the effect can be obtained, the tabular grain emulsion is preferably occupied by grains having an aspect ratio of 5 or more at 50% or more of the total projected area. More preferably, the aspect ratio is 8 or more. If the aspect ratio becomes too large, the above-mentioned variation coefficient of the particle size distribution tends to increase. Therefore, the aspect ratio is usually preferably 50 or less.

  The dislocation lines of tabular grains are described in, for example, J. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213, (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

  The number of dislocation lines is preferably an average of 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and clearly, it can be distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

  Dislocation lines can be introduced, for example, in the vicinity of the outer periphery of the tabular grain. In this case, the dislocations are substantially perpendicular to the outer periphery, and dislocation lines are generated starting from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) and reaching the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocation lines start is similar to the particle shape, but is not completely similar and may be distorted. This type of dislocation number is not found in the central region of the grain. The direction of dislocation lines is crystallographically approximately (211) but is often serpentine and sometimes intersects.

  Moreover, even if it has a dislocation line substantially uniformly over the whole region on the outer periphery of a tabular grain, it may have a dislocation line at a local position on the outer periphery. That is, taking hexagonal tabular silver halide grains as an example, the dislocation lines may be limited only to the vicinity of six vertices, or the dislocation lines may be limited to only one of the vertices. Conversely, it is possible that the dislocation line is limited to only the sides excluding the vicinity of the six vertices.

  Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be approximately (211) in terms of crystallography when viewed from the direction perpendicular to the main plane. It may be formed randomly, and the length of each dislocation line is also random, and it may be observed as a short line on the main plane, or it may be observed as reaching a side (periphery) as a long line. is there. Dislocation lines are often straight or meandering. They often cross each other.

  As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining them. That is, it may exist simultaneously on the outer periphery and the main plane.

  The silver iodide content on the surface of the tabular grain emulsion is preferably 10 mol% or less, particularly preferably 5 mol% or less. The silver iodide content on the surface of the grain of the present invention is measured using XPS (X-ray Photoelectron Spectroscopy). Regarding the principle of the XPS method used to analyze the silver iodide content near the surface of silver halide grains, refer to Aihara et al., “Electron Spectroscopy” (Kyoritsu Library-16, published by Kyoritsu Shuppan, Showa 53). can do. The standard XPS measurement method uses Mg-Kα as the excitation X-ray, and iodine (I) and silver (Ag) photoelectrons (usually I-3d5) emitted from silver halide in an appropriate sample form. / 2, Ag-3d5 / 2). To determine the iodine content, several standard samples with known iodine content are used, and a calibration curve of the intensity ratio (intensity (I) / intensity (Ag)) of the photoelectrons of iodine (I) and silver (Ag) is used. Can be obtained and obtained from this calibration curve. In a silver halide emulsion, the XPS measurement must be performed after degrading and removing gelatin adsorbed on the surface of the silver halide grains with a proteolytic enzyme or the like. A tabular grain emulsion having a silver iodide content of 10 mol% or less on the grain surface means an emulsion grain having a silver iodide content of 10 mol% or less when analyzed by XPS of the emulsion grains contained in one emulsion. . In this case, when two or more types of emulsions are clearly mixed, it is necessary to perform analysis on the same type of emulsion after appropriate pretreatment such as centrifugation and filtration.

  As the structure of the tabular grain emulsion of the present invention, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide and a higher order structure higher than that are preferable. The boundary of the silver iodide content between the structures may be clear, or may change continuously and gently. Usually, the measurement of silver iodide content using a powder X-ray diffraction method does not show two distinct peaks with different silver iodide contents, but lies in the direction of high silver iodide content. Such an X-ray diffraction profile is shown.

  The silver iodide content of the layer inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the layer inside the surface is preferably 3 mol% or more, more preferably 5 mol% or more.

  Next, the parallel main plane which is the second emulsion that can be used in the light-sensitive material of the present invention is the (111) plane, and the length of the side having the maximum length with respect to the length of the side having the minimum length. A grain having at least one epitaxial junction per grain at the apex and / or side and / or main plane of hexagonal silver halide grains having a thickness ratio of 2 or less will be described. An epitaxially bonded grain is a grain having a crystal part (that is, an epitaxial part) joined to the grain in addition to the silver halide grain body, and the joined crystal part usually protrudes from the silver halide grain body. The ratio of the bonded crystal part (epitaxial part) to the total silver amount of the grain is preferably 2% or more and 30% or less, and more preferably 5% or more and 15% or less. The epitaxial part may exist in any part of the grain body, but the grain main plane part, grain side part, and grain apex part are preferred. The number of epitaxials is preferably at least one. The composition of the epitaxial portion is preferably AgCl, AgBrCl, AgBrClI, AgBrI, AgI, AgSCN, or the like. When the epitaxial portion exists, dislocation lines may exist inside the grain, but it does not have to exist.

Next, a method for preparing the first emulsion and the second emulsion silver halide grains that can be used in the light-sensitive material of the present invention will be described.
The emulsion preparation process that can be used in the light-sensitive material of the present invention comprises (a) a base grain formation process and a subsequent grain formation process (process (b)). Basically, it is more preferable to perform the step (b) following the step (a), but only the step (a) may be performed. The step (b) may be any of (b1) dislocation introduction step, (b2) apex dislocation limited introduction step, or (b3) epitaxial junction step, and at least one or two or more may be combined. .

  First, (a) the base particle forming step will be described. The base portion is preferably at least 50% or more, more preferably 60% or more, based on the total silver amount used for grain formation. Moreover, the average content of iodine with respect to the amount of silver in the base portion is preferably 0 mol% or more and 30% mol or less, and more preferably 0 mol% or more and 15 mol% or less. The base portion may have a core-shell structure as necessary. At this time, the core part of the base part is preferably 50% or more and 70% or less with respect to the total silver amount of the base part, and the average iodine composition of the core part is preferably 0 mol% or more and 30 mol% or less, and 0 mol% or more and 15 mol or less. % Or less is more preferable. The iodine composition of the shell part is preferably 0 mol% or more and 3 mol% or less.

  As a method for preparing a silver halide emulsion, a method in which after forming silver halide nuclei and further growing silver halide grains to obtain grains of a desired size, the present invention is also the same. There is no change. Further, the formation of tabular grains includes at least nucleation, ripening, and growth steps. This process is described in detail in US Pat. No. 4,945,037. Hereinafter, nucleation, ripening, growth, and each process will be described.

1. Nucleation Step Tabular grain nucleation is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a protective colloid solution containing an alkali halide. A single jet method is used in which a silver salt aqueous solution is added. Moreover, the method of adding aqueous alkali halide solution to the protective colloid solution containing a silver salt as needed can also be used. Furthermore, if necessary, a protective colloid solution, a silver salt solution, and an alkali halide aqueous solution are added to a mixer disclosed in JP-A-2-44335, and immediately transferred to a reaction vessel, whereby the core of tabular grains is obtained. Formation can also be performed. Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. .

  Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin (for example, phthalate) that can be used in the present invention. Gelatinized gelatin, trimellitated gelatin, succinated gelatin, maleated gelatin, esterified gelatin) and low molecular weight gelatin (molecular weight: 3000 to 40,000) are used. Japanese Patent Publication No. 5-12696 can be referred to for the oxidized gelatin, and Japanese Patent Application Laid-Open Nos. 8-82883 and 11-143002 can be referred to for the amino group-modified gelatin. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX.

In the nucleation, the excess halogen salt is preferably Cl ⁻ , Br ⁻ , or I ⁻ , and these may be used alone or in plural. The total halogen salt concentration is 3 × 10 ⁻⁵ mol / liter or more and 0.1 mol / liter or less, preferably 3 × 10 ⁻⁴ mol / liter or more and 0.01 mol / liter or less (hereinafter, the liter is also expressed as “L”). To do.)

The halogen composition in the halide solution added at the time of nucleation is preferably Br ⁻ , Cl ⁻ , or I ⁻ , and these may be used alone or in plural. May be used nucleation such that the chlorine content as described is 10 mol% or more of the amount of silver used in nucleation in JP-A-10-293372, this time Cl ^- concentrations The total halogen salt concentration is preferably 10 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 80 mol% or less.

The protective colloid may be dissolved in the halide solution added at the time of nucleation, or the gelatin solution may be added at the same time as the nucleation separately from the halide solution.
The temperature during nucleation is preferably from 5 to 60 ° C, but more preferably from 5 to 48 ° C when producing fine tabular grains having an average particle size of 0.5 µm or less.
The pH of the dispersion medium is preferably 4 or more and 8 or less when amino group-modified gelatin is used, but preferably 2 or more and 8 or less when other gelatin is used.

2. Aging process In the nucleation, fine particles other than tabular grains (especially octahedral and single twin grains) are formed. Before entering the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.

  Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. At this time, a protective colloid solution may be additionally added. In this case, the concentration of the protective colloid with respect to the dispersion medium solution is preferably 10% by mass or less. As the additional protective colloid used at this time, the above-mentioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer that can be used in the present invention are used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used.

  The aging temperature is 40 to 80 ° C., preferably 50 to 80 ° C., and the pBr is 1.2 to 3.0. The pH is preferably 4 or more and 8 or less when amino group-modified gelatin is present, but is preferably 2 or more and 8 or less for other gelatins.

At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / L or less, and more preferably 0.2 mol / L or less.
Aging in this way leaves almost 100% tabular grains only.

  After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.

(i) In the case of an alkaline silver halide solvent such as NH ₃ , an acid having a large solubility product with Ag ⁺ such as HNO ₃ is added to be invalidated.
(ii) In the case of a thioether-based silver halide solvent, it is invalidated by adding an oxidizing agent such as H ₂ O ₂ as described in JP-A-60-136736.

  In the method for producing an emulsion that can be used in the light-sensitive material of the present invention, the completion of the ripening step means grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes. The time when (regular and single twin particles) disappeared. The disappearance of grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.

  In the ripening step, an over-ripening step described in JP-A-11-174606 may be provided as necessary. The over-ripening step is a step of erasing tabular grains having a slow anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. . When the number of tabular grains obtained in the aging step is 100, the number of tabular grains is preferably reduced to 90 or less, more preferably 60 or more and 80 or less by the over-ripening step. .

  In the method for producing an emulsion that can be used in the light-sensitive material of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, the silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.

3. Growth Process It is preferable to keep pBr in the crystal growth period following the ripening process at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before entering the growth process is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloids may be added during the growth process. The timing of additional addition may be any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably 1 to 10% by mass. As the protective colloid used at this time, the aforementioned alkali-treated gelatin, amino group-modified gelatin, oxidized gelatin, natural polymer, or synthetic polymer that can be used in the present invention are used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present, and 2 to 8 is preferable otherwise. The addition rate of Ag ⁺ and halogen ions in the crystal growth period is preferably 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. In this case, the addition rate of silver ions and halogen ions is increased with crystal growth. In this case, the addition rate of silver salt and halogen salt aqueous solution as described in Japanese Patent Publication Nos. 48-36890 and 52-16364. The concentration of the aqueous solution may be increased.

  When performing the double jet method in which a silver salt aqueous solution and a halogen salt aqueous solution are added simultaneously, in order to prevent the introduction of growth dislocation due to heterogeneous iodine, it is possible to improve the stirring of the reaction vessel and dilute the concentration of the added solution. preferable.

  A method of adding an AgI fine grain emulsion prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is further preferred. At this time, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. The AgI fine grain emulsion to be added may be prepared in advance or may be added while continuously preparing. JP-A-10-43570 can be referred to for the preparation method in this case.

  The average grain size of the added AgI emulsion is 0.01 μm or more and 0.1 μm or less, preferably 0.02 μm or more and 0.08 μm or less. The iodine composition of the base grains can be changed depending on the amount of AgI emulsion to be added.

Further, silver iodobromide fine particles may be added in place of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the base particles having a desired iodine composition can be obtained by making the iodine amount of the fine particles equal to the iodine amount of the desired base particles. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while preparing them continuously. The size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. The temperature during growth is 60 ° C. or higher and 90 ° C. or lower, preferably 70 ° C. or higher and 85 ° C. or lower.
Further, the above ion addition method, AgI fine particle addition method, and AgBrI fine particle addition method may be combined.

  In the present invention, the tabular grains preferably have dislocation lines, but it is preferable that no dislocation lines exist in the base portion in order to reduce pressure desensitization. Dislocation lines of tabular grains are described in, for example, JF Hamilton, Phot. Sci. Eng., 11, 57 (1967), T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213 (1972). It can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

Next, step (b) will be described.
First, step (b1) will be described. The step (b1) includes a first shell step and a second shell step. A first shell is provided on the base described above. The ratio of the first shell is preferably 1% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 20 mol% or more and 100 mol% or less. More preferably, the ratio of the first shell is 1% or more and 20% or less with respect to the total silver amount, and the average silver iodide content thereof is 25 mol% or more and 100 mol% or less. For the growth of the first shell on the substrate, a silver nitrate aqueous solution and a halogen aqueous solution containing iodide and bromide are basically added by the double jet method. Alternatively, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide are added by the double jet method. Alternatively, an aqueous halogen solution containing iodide is added by the single jet method.

  Any of the above methods may be used in combination. As is apparent from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal when the first shell is formed. In either case, normally, silver iodide disappears and all changes to a silver iodobromide mixed crystal when the next second shell is formed.

  As a preferred method for forming the first shell, there is a method in which a silver iodobromide or silver iodide fine grain emulsion is added, ripened and dissolved. Further, as a preferred method, there is a method of adding a silver iodide fine grain emulsion and then adding a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halogen aqueous solution. In this case, dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous silver nitrate solution. The silver content of the added silver iodide fine grain emulsion is used as the first shell, and the silver iodide content is 100 mol%. . Then, the added silver nitrate aqueous solution is calculated as the second shell. The silver iodide fine grain emulsion is preferably added rapidly.

  The rapid addition of the silver iodide fine grain emulsion means that the silver iodide fine grain emulsion is preferably added within 10 minutes. More preferably, it means adding within 7 minutes. This condition may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence / absence, type and concentration of silver halide solvent, but as described above, shorter one is preferable. When adding, it is preferable that substantially no silver salt aqueous solution such as silver nitrate is added. The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

The silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. 100% silver iodide is preferred. Silver iodide may have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, and may be any one subjected to a normal water washing step. What passed through the water washing process of this is used. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0.07 μm. The following is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are obtained by placing the silver iodide fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined by using this equivalent projected area circle diameter. The silver iodide fine particles most effective in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a grain size distribution variation coefficient of 18% or less.

  The silver iodide fine grain emulsion is preferably prepared after the above-described grain formation, by usual water washing described in U.S. Pat. No. 2,614,929, etc., concentration adjustment of protective colloid agents such as pH, pI, gelatin and the like. Density adjustment is performed. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is minimized or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It may be convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to be a value suitable for rapidly adding a silver iodide fine grain emulsion.

  The silver iodide fine grain emulsion is usually dissolved before being added, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used.

  As a more preferable method for forming the first shell, an iodide ion releasing agent described in US Pat. No. 5,496,694 is used in place of the conventional iodide ion supply method (method of adding free iodide ions). Thus, a silver halide phase containing silver iodide can be formed while rapidly generating iodide ions.

  The iodide ion releasing agent releases iodide ions by reaction with an iodide ion release regulator (base and / or nucleophile). Preferred examples of the nucleophilic reagent used in this case include the following chemical species. It is done. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinate, carboxylate, ammonia, amines, Examples include alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, and sulfides.

  The release rate and timing of iodide ions can be controlled by controlling the concentration of the base and the nucleophilic reagent, the addition method, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.

The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used to rapidly generate iodide ions is 1 × 10 ^{−7 to} 20M, more preferably 1 × 10 ^{−5 to} 10M, It is preferably 1 × 10 ^{−4 to} 5M, particularly preferably 1 × 10 ^{−3 to} 2M.

When the concentration exceeds 20M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing agent added is excessively large with respect to the capacity of the particle forming container.
On the other hand, if it is less than 1 × 10 ⁻⁷ M, the iodide ion releasing reaction rate becomes slow, and it becomes difficult to rapidly produce an iodide ion releasing agent, which is not preferable.

A preferable temperature range is 30 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C.
When the temperature is higher than 80 ° C., the iodide ion release reaction rate is generally extremely high, and when the temperature is lower than 30 ° C., the iodide ion release reaction rate is generally extremely low.

When a base is used in releasing iodide ions, a change in solution pH may be used. At this time, the pH range preferable for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably adjusted pH is 7. .5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators.
Further, a nucleophile and a base may be used in combination, and at this time, the pH may be controlled within the above range to control the release rate and timing of iodide ions.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or a part of them may remain without being decomposed.
The second shell is provided on the tabular grain having the base and the first shell described above. The ratio of the second shell is preferably 10 mol% or more and 40 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 5 mol% or less. More preferably, the ratio of the second shell is 15 mol% or more and 30 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 3 mol% or less. The growth of the second shell on the tabular grains having the base and the first shell may be in the direction of increasing or decreasing the aspect ratio of the tabular grains. Basically, the second shell is grown by adding an aqueous silver nitrate solution and an aqueous halogen solution containing bromide by the double jet method. Alternatively, after adding an aqueous halogen solution containing bromide, an aqueous silver nitrate solution may be added by a single jet method. The system temperature, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration can vary widely. As for pBr, in the present invention, it is preferable that pBr at the end of formation of the layer is higher than pBr at the initial stage of formation of the layer. Preferably, pBr at the initial stage of formation of the layer is 2.9 or less, and pBr at the end of formation of the layer is 1.7 or more. More preferably, the pBr at the initial stage of formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, the pBr at the initial stage of formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is from 2.1 to 4.5.

  It is preferable that a dislocation line exists in the part of (b1) process. The dislocation lines are preferably present in the vicinity of the side surface portion of the tabular grain. The vicinity of the side surface portion refers to the outer peripheral portion (side surface portion) of the six sides of the tabular grain and the inner portion thereof, that is, the portion grown in the step (b1). The average number of dislocation lines present on the side surface is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

The tabular grains that can be used in the light-sensitive material of the present invention desirably have a uniform dislocation dose distribution between the grains. In the emulsion which can be used in the light-sensitive material of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%. Particularly preferably 100 to 90%.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

Next, step (b2) will be described.
As a first aspect, a method of dissolving only the vicinity of the apex with iodide ions, as a second aspect, a method of simultaneously adding a silver salt solution and an iodide salt solution, as a third aspect, There is a method of substantially dissolving only the vicinity of the apex using a silver halide solvent, and a fourth embodiment is a method via halogen conversion.

  A method of dissolving with iodide ions according to the first embodiment will be described.

By adding iodide ions to the base particles, the vicinity of each vertex of the base particles is dissolved and rounded. Subsequently, when a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are added simultaneously, the grains further grow and dislocations are introduced near the apex. Regarding this method, JP-A-4-149541 and JP-A-9-189974 can be referred to.

The total amount of iodide ions added in this embodiment is calculated by multiplying the total number of moles of iodide ions by the total number of moles of silver in the base particles and multiplying the value by 100 as I ₂ (mol%). In order to obtain effective dissolution according to the present invention, it is preferable that (I ₂ -I ₁ ) satisfy 0 or more and 8 or less with respect to the silver iodide content I ₁ (mol%) of the base grain, more preferably 0 or more and 4 or less.

In this embodiment, the concentration of iodide ions added is preferably low, specifically, preferably 0.2 mol / L or less, and more preferably 0.1 mol / L.
Further, the pAg at the time of addition of iodide ions is preferably 8.0 or more, and more preferably 8.5 or more.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

  A method of simultaneous addition of a silver salt solution and an iodide salt solution, which is the second embodiment, will be described. By rapidly adding a silver salt solution and an iodide salt solution to the base grain, silver iodide or silver halide having a high silver iodide content can be epitaxially formed at the top of the grain. At this time, the preferable addition rate of the silver salt solution and the iodide salt solution is 0.2 to 0.5 minutes, and more preferably 0.5 to 2 minutes. Since this method is described in detail in JP-A-4-149541, it can be referred to.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

A method using a silver halide solvent which is the third embodiment will be described.
When a silver halide solvent is added to the dispersion medium containing the base grains and then a silver salt solution and an iodide salt solution are added at the same time, silver iodide or silver iodide is contained at the apex of the base grains dissolved by the silver halide solvent. High-rate silver halide will preferentially grow. At this time, the silver salt solution and the iodide salt solution do not need to be added rapidly. Since this method is described in detail in JP-A-4-149541, it can be referred to.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

Next, a method through halogen conversion which is the fourth embodiment will be described.
By adding an epitaxial growth site indicator (hereinafter referred to as a site director), for example, a sensitizing dye described in JP-A-58-108526, or a water-soluble iodide to the base grain, silver chloride is added to the top part of the base grain. In this method, silver chloride is converted to silver iodide or silver halide having a high silver iodide content by adding iodide ions after the formation of the epitaxial layer. As the site director, sensitizing dyes, water-soluble thiocyanate ions, and water-soluble iodide ions can be used, but iodide ions are preferred. Iodide ion is 0.0005 to 1 mol%, preferably 0.001 to 0.5 mol%, based on the base particles. When an optimum amount of iodide ions is added and then a silver salt solution and a chloride salt solution are added simultaneously, a silver chloride epitaxial layer can be formed at the apex of the base grain.

  The halogen conversion by the iodide ion of silver chloride will be described. A silver halide having a high solubility is converted to a silver halide having a low solubility by adding a halogen ion capable of forming a silver halide having a low solubility. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. Silver chloride epitaxially grown on the top of the base is selectively halogen-converted with iodide ions to form a silver iodide phase on the top of the base grain. Details are described in JP-A-4-149541.

  Following the halogen conversion of silver chloride epitaxially grown on the top of the base grain to the silver iodide phase by addition of iodide ions, silver nitrate solution alone, or silver nitrate solution and bromide solution, or silver nitrate solution and bromide solution The mixed solution of iodide solution is simultaneously added to further grow the grains and introduce dislocations near the apex.

  It is preferable that dislocation lines exist in the step (b2). The dislocation line is preferably present in the vicinity of the apex of the tabular grain. The vicinity of the vertex is a three-dimensional area surrounded by the perpendicular and the side when a perpendicular is drawn from the point at the position of x% from the center of the straight line connecting the center of the particle to each vertex. It is a part of. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and less than 100. The average number of dislocation lines present on the side surface is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

The tabular grains that can be used in the light-sensitive material of the present invention desirably have a uniform dislocation dose distribution between the grains. In the emulsion which can be used in the light-sensitive material of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%. Particularly preferably 100 to 90%.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

Next, the step (b3) will be described.
Regarding the epitaxial formation of silver halide on the base grain, as described in US Pat. No. 4,435,501, a site director such as iodide ion, aminoazaindene, or spectral sensitizing dye adsorbed on the base grain surface is used. Shows that silver salt epitaxial can be formed at a selected site, for example, at the side surface or the apex of the base particle. JP-A-8-69069 achieves high sensitization by forming silver salt epitaxials at selected sites of an ultrathin tabular grain base and optimally sensitizing this epitaxial phase.

  Also in the present invention, it is very preferable to enhance the sensitivity of the base particles of the present invention using these methods. As the site director, aminoazaindene or spectral sensitizing dyes may be used, iodide ions or thiocyanate ions may be used, and they may be used properly according to the purpose or may be combined.

  By changing the addition amount of the sensitizing dye amount, iodide ion, and thiocyanate ion, the silver salt epitaxial formation site can be limited to the side surface or apex of the base particle. The amount of iodide ion to be added is 0.0005 to 1.0 mol%, preferably 0.001 to 0.5 mol%, based on the silver amount of the base particles. The amount of thiocyanate ion is 0.01 to 0.2 mol%, preferably 0.02 to 0.1 mol%, based on the silver amount of the base particles. After the addition of these site directors, a silver salt solution and a halogen salt solution are added to form a silver salt epitaxial. In this case, the temperature is preferably 40 to 70 ° C, more preferably 45 to 60 ° C. In this case, the pAg is preferably 7.5 or less, and more preferably 6.5 or less. By using a site director, a silver salt epitaxial layer is formed at the apex or side of the base particle. The emulsion thus obtained may be sensitized by selectively chemically sensitizing the epitaxial phase as disclosed in JP-A-8-69069. However, following the silver salt epitaxial formation, a silver salt solution and a halogen salt solution are added. Further growth may be performed by simultaneous addition. The halogen salt aqueous solution added at this time is preferably a bromide salt solution or a mixed solution of a bromide salt solution and an iodide salt solution. Moreover, the temperature in this case is preferably 40 to 80 ° C, and more preferably 45 to 70 ° C. In this case, the pAg is preferably 5.5 or more and 9.5 or less, and more preferably 6.0 or more and 9.0 or less.

  The epitaxial formed in the step (b3) is basically characterized in that a halogen composition different from the base particles is formed outside the base particles formed in the step (a). The epitaxial composition is preferably AgCl, AgBrCl, AgBrClI, AgBrI, AgI, AgSCN, or the like. It is further preferable to introduce a “dopant (metal complex)” as described in JP-A-8-69069 into the epitaxial layer. The position of the epitaxial growth may be at least a part of the top, side, and main plane portions of the base particle, and may extend over a plurality of locations. It is preferable to take the form of only the apex part, only the side part, or the apex part and the side part.

  (B3) Although dislocation lines do not have to exist in the part of the step, it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the base particle and the epitaxial growth portion or at the epitaxial portion. The average number of dislocation lines present in the junction or epitaxial part is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

It is preferable that a 6-cyano metal complex is doped during the formation of the epitaxial portion. Among the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The addition amount of the metal complex is preferably in the range of 10 ^{−9 to} 10 ⁻² mol per mol of silver halide, and more preferably in the range of 10 ^{−8 to} 10 ⁻⁴ mol per mol of silver halide. preferable. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.

The tabular grains that can be used in the light-sensitive material of the present invention desirably have a uniform dislocation dose distribution between the grains. In the emulsion which can be used in the light-sensitive material of the present invention, silver halide grains containing 10 or more dislocation lines per grain preferably occupy 100 to 50% (number) of all grains, more preferably 100 to 70%. Particularly preferably 100 to 90%.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

  As a protective colloid used in the preparation of an emulsion that can be used in the light-sensitive material of the present invention and as a binder for other hydrophilic colloid layers, gelatin is advantageous, but other hydrophilic colloids are also used. Can do.

  For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used.

  The emulsion which can be used in the light-sensitive material of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. The types of gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin (for example, phthalate) that can be used in the present invention. Gelatinized, trimellitated gelatin, succinylated gelatin, maleated gelatin, esterified gelatin). Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but is preferably selected between 2 and 10. More preferably, it is the range of 3-8. Although pAg at the time of water washing can also be selected according to the objective, it is preferable to select between 5-10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

  At the time of grain formation of the present invention, it was described in, for example, JP-A-5-173268, JP-A-5-173269, JP-A-5-173270, JP-A-5-173271, JP-A-6-202258, and JP-A-7-175147. A polyalkylene oxide block copolymer or a polyalkylene oxide copolymer described, for example, in US Pat. No. 3,089,578 may be present. The time when the compound is present may be any time during the preparation of the particles, but the effect is great when used at an early stage of particle formation.

  The main plane in which the silver halide grains of the third emulsion usable in the light-sensitive material of the present invention are parallel is made of silver iodobromide or silver chloroiodobromide having a (100) plane silver chloride content of less than 10 mol%. The tabular silver halide grains will be described below.

  The {100} tabular grains that can be used in the light-sensitive material of the present invention have an average of 50 to 100%, preferably 70 to 100%, more preferably 90 to 100% of the total projected area of which the main plane is the {100} plane. It consists of tabular grains having an aspect ratio of 2 or more. The particle thickness is 0.01 to 0.10 μm, preferably 0.02 to 0.08 μm, more preferably 0.03 to 0.07 μm, and the aspect ratio is 2 to 100, preferably 3 to 50, more preferably 5 to 30. The variation coefficient of the particle thickness (100% of “standard deviation of distribution / average particle thickness”, hereinafter referred to as COV.) Is 30% or less, preferably 25% or less, more preferably 20% or less. The smaller the COV., The higher the monodispersity of the particle thickness.

  The projected area diameter and thickness of the tabular grains are determined by taking a transmission electron microscope (TEM) photograph by a replica method and calculating the projected area diameter and thickness of each grain. In this case, the thickness is calculated from the length of the shadow of the replica. The measurement of COV. In the present invention is the result of measuring at least 600 particles.

  The composition of {100} tabular grains that can be used in the light-sensitive material of the present invention is silver chloroiodobromide or silver iodobromide having a silver chloride content of less than 10 mol%. Further, other silver salts such as rhodan silver, silver sulfide, silver selenide, silver telluride, silver carbonate, silver phosphate, organic acid silver, etc. are contained as separate grains or as a part of silver halide grains. Also good.

  As a method for examining the halogen composition in the AgX crystal, the X-ray diffraction method is known. The X-ray diffraction method is described in detail in Basic Analytical Chemistry Course 24 “X-ray diffraction” and the like. Typically, the diffraction angle of the AgX (420) plane is determined by a powder method using Cu Kβ rays as a radiation source.

When the diffraction nucleus 2θ is obtained, the lattice constant a is obtained from the Bragg equation as follows.
2 d sinθ = λ
d = a / (h ² + k ² + l ² ) ^1/2
Here, 2θ is the diffraction angle of the (hkl) plane, λ is the wavelength of the X-ray, and d is the surface spacing of the (hkl) plane. Since the relationship between the halogen composition of silver halide solid solutions and the lattice constant a is already known (for example, described in TH James “The Theory of Photographic Process. 4th Ed.” Macmillian New York), the lattice constant is Knowing that, the halogen composition can be determined.

  Any halogen composition structure of {100} tabular grains that can be used in the light-sensitive material of the present invention may be used. For example, grains having a (core / shell) 2 structure in which the halogen composition of the core and the shell are different, and grains having a multiple structure having a core and two or more shells can be mentioned. The composition of the core is preferably silver bromide, but is not limited thereto. The shell composition preferably has a higher silver iodide content than the core.

  The {100} tabular grains that can be used in the light-sensitive material of the present invention preferably have an average silver iodide content of 2.3 mol or more and a surface average silver iodide content of 8 mol% or more. Further, the coefficient of variation of silver iodide content between grains is more preferably less than 20%. The surface silver iodide content can be measured using the XPS described above.

  When {100} tabular grains that can be used in the light-sensitive material of the present invention are classified by shape, the following six can be listed. (1) Particles whose main plane is a right-angled parallelogram. (2) Particles in which one or more, preferably 1 to 4 of the four corners of the right-angled parallelogram are missing non-equivalently. That is, [(the area of the largest missing portion) / the area of the smallest missing portion = particles having K1 of 2 to ∞)], (3) particles in which the four corners are equivalently missing (particles having K1 smaller than 2) (4) Particles in which 5 to 100%, preferably 20 to 100%, of the area of the side surface of the missing portion is the {111} plane. (5) Particles in which at least two opposite sides of the four sides constituting the main plane are curved outwardly convex, (6) one or more of the four corners of the right-angled parallelogram, preferably Is a particle in which 1 to 4 particles are missing in a right-angled parallelogram shape. These can be confirmed by observation using an electron microscope.

  The {100} plane ratio in the crystal habit of the surface of {100} tabular grains that can be used in the light-sensitive material of the present invention is 80% or more, preferably 90% or more. Can be used for statistical estimation. When the {100} tabular ratio of AgX grains in the emulsion is almost 100%, the above estimation can be confirmed by the following method. The method is described in Japanese Chemical Society paper 1984, No. 6, 942p. The amount of the benzothiocyanine dye is changed to a certain amount of the {100} tabular grains at 40 ° C. for 17 hours. The total surface area of all grains per unit emulsion (S) and the total area of {100} planes (S1) are determined by light absorption at 625 nm. Based on these values, the formula: S1 / S This is a method of calculating the {100} plane ratio by × 100 (%).

  The average sphere equivalent diameter of {100} tabular grains that can be used in the light-sensitive material of the present invention is preferably less than 0.35 μm. The estimation of the particle size can be obtained by measuring the projected area and thickness by the replica method.

  The main plane in which the silver halide grains of the fourth emulsion that can be used in the light-sensitive material of the present invention are parallel is the (111) plane or the (100) plane, the aspect ratio is 2 or more, and the chloride is at least 80 mol% or more. The tabular grains containing silver will be described below.

  In order to produce (111) grains with high silver chloride, special measures are required. A method for producing high silver chloride tabular grains using ammonia in US Pat. No. 4,399,215 to Wey may be used. A method for producing high silver chloride tabular grains using thiocyanate in US Pat. No. 5,061,617 of Maskasky may be used. In order to form grains having the (111) face as the outer surface in the high silver chloride grains shown below, a method of adding an additive (crystal phase controlling agent) at the grain formation may be used. It is shown below.

Patent Number Crystal Phase Control Agent Inventor US Pat. No. 4,400,463 Azaindenes + Muscasky
Thioether peptizer
U.S. Pat. No. 4,783,398 2-4-dithiazolidinone Gyoto etc. U.S. Pat. No. 4,713,323 Aminopyrazolopyrimidine Muscasky U.S. Pat. No. 4,983,508 Bispyridinium salt Ishiguro et al. U.S. Pat. No. 5 No. 5,185,239 Triaminopyrimidine Muscasky US Pat. No. 5,178,997 7-azaindole compounds Muscasky US Pat. No. 5,178,998 Xanthine Muscasky JP-A 64-70741 Dye Nishikawa et al. Special Kaihei 3-212439 Aminothioether Ishiguro JP 4-283742 Thiourea derivative Ishiguro JP 4-335632 Triazolium salt Ishiguro JP 2-32 Bispyridinium salt Ishiguro etc. JP 8-227117 Monopyridinium salt Ozeki etc.

  Regarding the formation of (111) tabular grains, methods using various crystal phase controlling agents are known as described in the above table, but the compounds described in JP-A-2-32 (Compound Example 1) are known. To 42) are preferred, and the crystal phase control agents 1 to 29 described in JP-A-8-227117 are particularly preferred. However, the present invention is not limited to these.

  (111) tabular grains are obtained by forming two parallel twin planes. Since the formation of twin planes depends on temperature, dispersion medium (gelatin), halogen concentration, etc., these appropriate conditions must be set. When the crystal phase controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is 0.01 mol / L or more, preferably 0.03 mol / L or more.

  In order to monodisperse the particles, it is disclosed in JP-A-8-184931 that it is preferable not to use a crystal phase controlling agent in nucleation. When the crystal phase controlling agent is not used during nucleation, the gelatin concentration is 0.03% to 10%, preferably 0.05% to 1.0%. The chloride concentration is 0.001 mol / L to 1 mol / L, preferably 0.003 mol / L to 0.1 mol / L. The nucleation temperature may be any temperature from 2 ° C. to 90 ° C., but is preferably 5 ° C. to 80 ° C., particularly preferably 5 ° C. to 40 ° C.

  Tabular grain nuclei are formed in the initial nucleation stage, but immediately after the nucleation, the reaction vessel contains many nuclei other than tabular grains. Therefore, a technique for aging after nucleation, leaving only tabular grains and extinguishing others is required. When normal Ostwald ripening is performed, tabular grain nuclei also dissolve and disappear, so that the number of tabular grain nuclei decreases and the resulting tabular grain size increases. In order to prevent this, a crystal phase controlling agent is added. In particular, by using phthalated gelatin in combination, the effect of the crystal phase controlling agent can be enhanced and dissolution of tabular grains can be prevented. The pAg during aging is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode.

  Next, the formed nucleus is grown in the presence of a crystal phase control agent by physical ripening and addition of a silver salt and a halide. In this case, the chloride concentration is 5 mol / L or less, preferably 0.05 to 1 mol / L. The temperature during grain growth can be selected in the range of 10 ° C to 90 ° C, but the range of 30 ° C to 80 ° C is preferable.

The total amount of the crystal phase controlling agent used is preferably 6 × 10 ⁻⁵ mol or more, particularly 3 × 10 ⁻⁴ mol to 6 × 10 ⁻² mol, per mol of silver halide in the finished emulsion. The timing of adding the crystal phase controlling agent may be any time from the nucleation of silver halide grains to physical ripening and grain growth. Formation of the (111) plane starts after the addition. The crystal phase controlling agent may be added to the reaction vessel in advance, but when forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel together with the grain growth to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to compensate by addition. Preferably 10 g / L to 100 g / L of gelatin is present for growth. As supplementary gelatin, phthalated gelatin or trimellit gelatin is preferable.
The pH at the time of particle formation is arbitrary, but a neutral to acidic region is preferable.

  Next, (100) tabular grains will be described. The (100) tabular grains are tabular grains having the (100) plane as the main plane. The shape of the main plane is a right-angled parallelogram shape, or a 3-5 pentagon shape where one corner of the right-angled parallelogram is missing (the missing shape is the side that forms the corner with the corner as the apex. Or a 4-8 octagonal shape in which two or more and four or less missing portions exist.

  When a right-angled parallelogram shape that compensates for the missing portion is a supplementary quadrilateral, the adjacent side ratio (long side length / short side length) of the right-angled parallelogram and the supplemental quadrilateral is 1 to 6. , Preferably 1 to 4, more preferably 1 to 2.

  (100) As a method of forming tabular silver halide emulsion grains having a main plane, an aqueous silver salt solution and an aqueous halide salt solution are added and mixed in a dispersion medium such as an aqueous gelatin solution while stirring. At this time, for example, in JP-A-6-301129, 6-347929, 9-34045 and 9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is present. And a method of introducing a crystal defect that imparts anisotropic growth such as a screw dislocation by causing distortion in the nucleus due to the difference in the size of the crystal lattice from silver chloride. When the screw dislocation is introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, so that crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocation. Is done. Here, the low supersaturation condition is preferably 35% or less, more preferably 2 to 20% at the time of critical addition. Although the crystal defect is not determined to be a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or the anisotropic growth property is imparted to the particles. In order to make the tabular grains thinner, it is disclosed in Japanese Patent Application Laid-Open Nos. Hei 8-122954 and Hei 9-189777 that the introduced dislocations are preferably retained.

  In addition, in JP-A-6-347928, imidazoles and 3,5-diaminotriazoles are used, and in JP-A-8-339044, polyvinyl alcohols are used to add a (100) surface formation accelerator. A method of forming (100) tabular grains is disclosed. However, the present invention is not limited to these.

High silver chloride grains mean grains having a silver chloride content of 80 mol% or more, and preferably 95 mol% or more is silver chloride. The particles that can be used in the light-sensitive material of the present invention preferably have a so-called core / shell structure comprising a core portion and a shell portion surrounding the core portion. It is preferable that 90 mol% or more of the core portion is silver chloride. The core part may further comprise two or more parts having different halogen compositions. The shell portion is preferably 50% or less, particularly preferably 20% or less of the total particle volume. The shell portion is preferably silver iodochloride or silver iodobromochloride. The shell part preferably contains 0.5 mol% to 13 mol% of iodine, particularly preferably 1 mol% to 13 mol%. The content of silver iodide in all grains is preferably 5 mol% or less, particularly preferably 1 mol% or less.
The silver bromide content is preferably higher in the shell part than in the core part. The silver bromide content is preferably 20 mol% or less, particularly preferably 5 mol% or less.

The average grain size (equivalent volume equivalent sphere diameter) of silver halide grains is not particularly limited, but is preferably 0.1 μm to 0.8 μm, particularly preferably 0.1 μm to 0.6 μm.
The tabular grain of silver halide preferably has a projected area diameter of 0.2 to 1.0 μm. Here, the projected area diameter of silver halide grains refers to the diameter of a circle having an area equal to the projected area of grains in an electron micrograph. The thickness is 0.2 μm or less, preferably 0.1 μm or less, particularly preferably 0.06 μm or less. In the present invention, 50% or more of the projected area of all the silver halide grains is 2 or more in average aspect ratio (diameter / thickness ratio), preferably 5 or more and 20 or less.

In general, a tabular grain has a tabular shape having two parallel planes. Therefore, the “thickness” in the present invention is represented by a distance between two parallel planes constituting the tabular grain.
The grain size distribution of silver halide grains that can be used in the light-sensitive material of the present invention may be polydispersed or monodispersed, but is more preferably monodispersed. In particular, the variation coefficient of the projected area diameter of tabular grains occupying 50% or more of the total projected area is preferably 20% or less. Ideally 0%.

  If the crystal phase controlling agent is present on the particle surface even after the formation of the particles, the adsorption of the sensitizing dye and the development are affected. Therefore, it is preferable to remove the crystal phase controlling agent after forming the particles. However, when the crystal phase controlling agent is removed, it is difficult for the high silver chloride (111) tabular grains to maintain the (111) plane under normal conditions. Therefore, it is preferable to maintain the particle form by substituting with a photographically useful compound such as a sensitizing dye. About this method, JP-A-9-80656, JP-A-9-106026, US Pat. No. 5,221,602, US Pat. No. 5,286,452, US Pat. No. 5,298,387, US Pat. No. 5,298,388, No. 5,176,992, and the like.

Although the crystal phase controlling agent is desorbed from the grains by the above method, it is preferable to remove the desorbed crystal phase controlling agent from the emulsion by washing with water. The washing temperature may be a temperature at which gelatin normally used as a protective colloid does not coagulate. As the water washing method, various known techniques such as a flocculation method and an ultrafiltration method can be used. The washing temperature is preferably 40 ° C. or higher.
In addition, the crystal phase controlling agent is more desorbed than the particles at a low pH. Therefore, the pH of the water washing step is preferably a low pH as long as the particles do not aggregate excessively.

The contents relating to all the emulsions that can be used in the light-sensitive material of the present invention will be described below.
The reduction sensitization preferably used in the present invention is a method of adding a reduction sensitizer to silver halide, a method of growing or ripening silver halide grains in a low pAg atmosphere of pAg 1 to 7 called silver ripening. Any of the methods of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can also be selected. Also, two or more of these methods can be used in combination.

In particular, the method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.
As a reduction sensitizer, stannous salt, ascorbic acid and derivatives thereof, hydroquinone and derivatives thereof, catechol and derivatives thereof, hydroxylamine and derivatives thereof, amines and polyamines, hydrazine and derivatives thereof, paraphenylenediamine and derivatives thereof, form Examples include amidine sulfinic acid (thiourea dioxide), silane compounds, and borane compounds. These reduction sensitizers can be selected and used in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, 3,930, Regarding the method disclosed in No. 867 and the method of using a reducing agent, the methods disclosed in JP-B-57-33572, JP-A-58-1410 and JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, and formamidine sulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver halide is appropriate.
The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.

  Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628, and JP-A-54-1019. (B) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A No. 53-144319, and (d) imidazoles as described in JP-A No. 54-1000071 (E) ammonia, (f) thiocyanate and the like.

Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent used varies depending on the type. For example, in the case of thiocyanate, a preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

Depending on the purpose, it is preferable that a metal ion salt is present at the time of preparation of an emulsion that can be used in the light-sensitive material of the present invention, for example, during grain formation, desalting step, chemical sensitization, and before coating. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. As described above, it is possible to select a method of doping the whole particle and a method of doping only the core part of the particle, only the shell part, or only the epitaxial part. For example, Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydroxide, hexacoordinated complex salt, and tetracoordinated complex salt. For _{example, CdBr 2, CdCl 2, Cd} (NO 3) 2, Pb (NO 3) 2, Pb (CH 3 COO) 2, K 4 [Fe (CN) 6], (NH 4) 4 [Fe (CN) _{6], K 2 IrCl 6,} (NH 4) 3 RhCl 6, K 4 Ru (CN) 6 and the like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one kind of metal compound, but may be used in combination of two or more kinds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before particle formation or can be added during particle formation. Further, it can be added to a water-soluble silver salt (eg, AgNO ₃ ) or an alkali halide aqueous solution (eg, NaCl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

  A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 may be useful. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

  The silver halide grains that can be used in the light-sensitive material of the present invention are sulfur sensitization, chalcogen sensitization such as selenium sensitization and tellurium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. One can be applied in any step of the silver halide emulsion production process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion which can be used in the light-sensitive material of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.

  One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan. 1977, (TH James, The Theory of the Photographic Process, 4th ed, Macmillan, 1977), pages 67-76, and can also be performed using active gelatin. Disclosure, 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3, No. 772,031, No. 3,857,711, No. 3,90 714, 4,266,018 and 3,904,415, and British Patent 1,315,755, pAg 5-10, pH 5-8 and temperature 30 At ˜80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers can be used. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.

The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

  Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion that can be used in the light-sensitive material of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H _{2). O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compound ( For _{example, K 2 [Ti (O 2} ) C 2 O 4] · 3H 2 O, 4K 2 SO 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine Perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferric acid) and thio There is a sulfonate.

  Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).

  Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. These methods can be selected and used in either the particle formation step or the chemical sensitization step.

  The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadrine thione; , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

  The merocyanine dye or the complex merocyanine dye has a ketomethylene structure as a nucleus, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.
Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization.

The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. Spectral sensitization can be performed simultaneously with chemical sensitization, or prior to chemical sensitization as described in JP-A No. 58-113928, and silver halide grains can be precipitated. Spectral sensitization can be started by adding before completion of the production. Further, as taught in U.S. Pat. No. 4,225,666, these compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder is chemically enhanced. It can be added after the sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.
The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

  In the light-sensitive material of the present invention, it is sufficient that at least one light-sensitive layer is provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer is provided on the side away from the support, and a high-sensitivity emulsion is provided on the side close to the support. Layers may be installed.

  As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of.

  Further, as described in Japanese Patent Publication No. 55-34932, it can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they can be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.

In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer. Further, the arrangement may be changed as described above even when there are four or more layers.
In order to improve color reproducibility, main sensitivity layers such as BL, GL, RL and spectral sensitivity distribution described in US 4,663,271, 4,705,744, 4,707,436, JP-A-62-160448, 63-89850 It is preferable to dispose a donor layer (CL) having different multi-layer effects adjacent to or close to the main photosensitive layer.

  A preferred silver halide used in the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. Those having crystal defects of the above or a composite form thereof may be used.
The grain size of the silver halide may be fine grains having a diameter of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

  The silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22 to 23, “I. Emulsion preparation and types”. No. 18716 (November 1979), page 648, No. 307105 (November 1989), pages 863 to 865, and “The Physics and Chemistry of Photography”, published by Paul Monter (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), "Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsion" , Published by Focal Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 1964) and the like.

Also preferred are monodisperse emulsions described in US 3,574,628, 3,655,394 and GB 1,413,748.
Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); US 4,434,226, 4,414,310, 4,433,048, 4,439,520 and GB. It can be easily prepared by the method described in 2,112,157.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, a core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and this preparation method is described in JP-A-59-133542. Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

  As the silver halide emulsion, those subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such a process are described in RD No. 17643, No. 18716 and No. 307105, and the corresponding parts are summarized in the following table.

  In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  US Pat. No. 4,082,553 fogged silver halide grains, US Pat. No. 4,626,498, JP 59-214852, fogged silver halide grains, colloidal silver photosensitive silver halide emulsion layer and It is preferred to apply to / or a substantially light-insensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method thereof is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

  In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized and does not require spectral sensitization. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.
Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer-page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 left column page 873-874 page 7. Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Matte 878-879 pages

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); EP 568,037A A coupler represented by formula (I) in claim 1; a coupler represented by general formula (I) in lines 45 to 55 of column 1 of US 5,066,576; represented by general formula (I) in paragraph 0008 of JP-A-4-74425 Couplers according to claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969A1 (especially Y-1 (page 17), Y-54 (page 41)); couplers represented by formulas (II) to (IV) in columns 7 to 58 of US Pat. No. 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19 )).

  Magenta coupler; JP-A-3-9737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257, A-4 -63 (page 134) ), A-4 -73, -75 (page 139); EP 486,965, M-4, -6 (page 26), M-7 (page 27); EP 571, 959A, M-45 (page 19); (M-1) of Kaihei 5-204106 (page 6); M-22 of paragraph 0237 of JP-A-4-362631.

  Cyan coupler: CX-1,3,4,5,11,12,14,15 (pages 14-16) of JP-A-4-204843; C-7,10 (page 35) of JP-A-4-43345, 34 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385.

Polymer coupler: P-1, P-5 (page 11) of JP-A-2-44345.
As couplers in which the coloring dye has an appropriate diffusibility, those described in US 4,366,237, GB 2,125,570, EP 96,873B, DE 3,234,533 are preferable.

  A coupler for correcting unwanted absorption of the coloring dye is a yellow colored cyan coupler represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), yellow colored magenta coupler ExM-7 described in the EP, page 202, EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 described in US 4,833,069 (Column 8), CC-13 (Column 10), US 4,837,136 (2) (Column 8), colorless masking coupler represented by the formula (A) of claim 1 of WO92 / 11575 (particularly examples on pages 36 to 45) Compound) is preferred.

  Examples of couplers that release a photographically useful group include the following. Development inhibitor releasing compounds: compounds represented by formulas (I), (II), (III), (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (31) Page), T-113 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP 436, 938A2 A compound represented by formula (1) of EP 568,037A (especially (23) (page 11)), a formula described on pages 5-6 of EP 440,195A2 ( Compounds represented by I), (II), (III) (especially I- (1) on page 29); Bleach accelerator releasing compounds: represented by formulas (I), (I ') on page 5 of EP 310,125A2 Compounds (especially (60), (61) on page 61) and compounds of formula (I) in claim 1 of JP-A-6-59411 (especially (7) (page 7); ligand releasing compounds: US 4,555,478) A compound represented by LIG-X according to claim 1 (particularly, a compound in columns 21 to 41 of column 12); a leuco dye-releasing compound: compounds 1 to 6 in columns 3 to 8 of US 4,749,641; a fluorescent dye-releasing compound: US 4,774,181 clay 1 compound represented by COUP-DYE (especially compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: in formula (1), (2) and (3) of column 3 of US 4,656,123 The compounds represented (especially (I-22) in column 25) and ExZK-2 at page 75, lines 36 to 38 of EP 450,637A2; a compound which only releases a group which becomes a dye upon release: according to claim 1 of US 4,857,447 Compounds represented by formula (I) (especially Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: JP-A 62-215272, P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 (140-144) Latex for impregnation of oil-soluble organic compound: Latex described in US 4,199,363; Oxidant scavenger for developing agent: Compound (especially I-, (columns 54-62) of column 2, US 4,978,606 1), (2), (6), (12) (columns 4-5), US Pat. No. 4,923,787, column 2, line 5-10 (especially compound 1 (column 3); stain inhibitor: 4 of EP 298321A Pages 30-33, formulas (I)-(III), especially I-47,72, III-1,27 (pages 24-48); antifading agent: EP 298321A A-6, 7, 20, 21 , 23,24,25,26,30,37,40,42,48,63,90,92,94,164 (pages 69-118), US5,122,444, columns 25-38 II-1 to III-23, Especially III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US 5,139,931, columns 32 to 40, A-1 to 48, especially A-39,42; Or a material that reduces the amount of color mixing inhibitor used: EP 411324A, pages 5 to 24, I-1 to II-15, especially I-4 6; Formalin Scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, in particular SCV-8; Hardener: JP 17,14845, page 17, H-1,4,6,8,14, US Compounds (H-1 to 54) represented by formulas (VII) to (XII) in columns 13 to 23 of 4,618,573, compounds represented by formula (6) at the lower right of page 8 of JP-A-2-148852 -76), in particular compounds according to claim 1 of H-14, US 3,325,287; Development inhibitor precursors: P-24,37,39 (pages 6-7) of JP 62-168139; claim 1 of US 5,019,492 Compounds 28, 29 of column 7; preservatives, fungicides: US Pat. No. 4,923,790, columns 3 to 15, I-1 to III-43, especially II-1,9,10,18, III-25 Stabilizer, antifoggant: US Pat. No. 4,923,793, columns 6-16, I-1 to (14), especially I-1,60, (2), (13), US Pat. 65, in particular 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP 5-40324; dye: a-1 to b-20 on page 15-18 of JP 3-156450, in particular a-1, 12,18,27,35,36, b-5,27 -29 V-1 to 23, especially V-1, EP 445627A, pages 33 to 55, FI-1 to F-II-43, especially FI-11, F-II-8, EP 457153A, pages 17 to 28, III -1 to 36, especially III-1,3, WO 88/04794, 8 to 26, Dye-1 to 124, microcrystalline dispersion, EP 319999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP Compounds D-1 to 87 represented by formulas (1) to (3) of 519306A (pages 3 to 28), compounds 1 to 22 represented by formula (I) of US 4,268,622 (columns 3 to 10), US 4,923,788 Compounds (1) to (31) represented by formula (I) (columns 2 to 9); UV absorbers: Compounds (18b) to (18r), 101 represented by formula (1) in JP-A-46-3335 To 427 (pages 6 to 9), compounds (3) to (66) (pages 10 to 44) represented by formula (I) of EP 520938A and compounds HBT-1 to 10 (page 14) represented by formula (III) ), Compounds (1) to (31) represented by formula (1) of EP 521823A (columns 2 to 9).

  The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or television, color papers, color positive films and color reversal papers. Further, it is suitable for the lens-fitted photo film unit described in JP-B-2-32615 and JP-B-3-39784.

  Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and 307. ing.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed with color developer at 30 ° C for 3 minutes and 15 seconds is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

  In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.

  The light-sensitive material of the present invention is prepared by the usual methods described in the above-mentioned RD. No. 17643, pages 28 to 29, RD. No. 18716, 651, left column to right column, and RD. No. 307105, pages 880 to 881. It can be developed.

Next, the color negative film processing solution used in the present invention will be described.
As the color developer used in the present invention, compounds described in JP-A-4-21739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. In particular, as a color developing agent for rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

  These color developing agents are preferably used in an amount of 0.01 to 0.08 mol, particularly 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol, per liter of color developer (hereinafter also referred to as “L”). Is preferably used. The color developer replenisher preferably contains 1.1 to 3 times the color developing agent of this concentration, and more preferably 1.3 to 2.5 times.

  Hydroxylamine can be widely used as a color developer preservative, but if higher preservability is required, it has a substituent such as an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, or a carboxyalkyl group. Hydroxylamine derivatives are preferred, specifically N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine preferable. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one or more in place of hydroxylamine.

  The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. In the replenisher, it is preferable to contain a preservative at a concentration 1.1 to 3 times that of the mother liquor (processing tank solution), as in the case of the color developing agent.

  In the color developer, sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferably used at a concentration 1.1 to 3 times these.

  The pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher should be set to a high value in the range of 0.1 to 1.0 from these values. preferable. In order to stably maintain such pH, known buffering agents such as carbonate, phosphate, sulfosalicylate, and borate are used.

The replenishment amount of the color developer is preferably 80 to 1300 mL per 1 m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing the environmental pollution load, specifically 80 to 600 mL, more preferably 80 to 400 mL. .

The bromide ion concentration in the color developer is usually 0.01 to 0.06 mol per liter, but for the purpose of suppressing fog and improving discrimination while maintaining sensitivity, and improving graininess. It is preferably set to 0.015 to 0.03 mol per liter. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferable that the replenisher does not contain bromide ions.
C = A-W / V
C: Concentration of bromide ion in color developer replenisher (mol / L)
A: Bromide ion concentration in target color developer (mol / L)
W: The amount (mole) of bromide ions eluted from the light-sensitive material to the color developer when the light-sensitive material of 1 m ² is color-developed.
V: Replenishment amount of color developer replenisher for 1m ² photosensitive material (L)

  In addition, when the replenishment amount is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone is used. It is also preferable to use development accelerators such as thioether compounds typified by pyrazolidones represented by representatives and 3,6-dithia-1,8-octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention.
The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof are those described in JP-A-5-72694 and JP-A-5-173112, particularly 1,3-diaminopropanetetraacetic acid, JP-A-5 A ferric complex salt of the compound of Example 1 on page 7 of No. 173312 is preferred.

  Further, in order to improve the biodegradability of the bleaching agent, the compound ferric complex salt described in JP-A-4-25145, JP-A-4-268552, EP 588,289, 591,934, JP-A-6-208213 is used as a bleaching agent. It is preferable. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of the solution having bleaching ability, and is preferably designed to be 0.1 to 0.15 mol for the purpose of reducing the discharge amount to the environment. Moreover, when the liquid which has bleaching ability is a bleaching liquid, it is preferable to contain 0.2-1 mol of bromide per liter, and it is preferable to contain 0.3-0.8 mol especially.

The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.
CR = CT × (V1 + V2) / V1 + CP
CR: Concentration of component in replenisher CT: Concentration of component in mother liquor (processing tank solution) CP: Concentration of component consumed during processing V1: Replenishment amount of replenisher having bleaching ability for 1 m ² photosensitive material (ML)
V2: Amount brought in from the previous bath by 1m ² photosensitive material (mL)

In addition, it is preferable to contain a pH buffer in the bleaching solution, and it is particularly preferable to contain a dicarboxylic acid with little odor such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. It is also preferable to use a known bleach accelerator described in JP-A-53-95630, RD No. 17129, US 3,893,858.
The bleaching solution is preferably replenished with 50 to 1000 mL of bleach replenisher per 1 m ² of the light-sensitive material, particularly preferably 80 to 500 mL, more preferably 100 to 300 mL. Further, it is preferable to aerate the bleaching solution.

For the processing solution having fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied.
In particular, in order to improve the fixing speed and the preservability, the compounds represented by general formulas (I) and (II) of JP-A-6-301169 are incorporated into a processing solution having fixing ability alone or in combination. It is preferable. Use of sulfinic acid described in JP-A-1-224762 as well as p-toluenesulfinate is also preferable in terms of improving the preservability.
It is preferable to use ammonium as a cation from the viewpoint of improving the desilvering property in a solution having bleaching ability or a fixing ability, but it is preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .

  In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309059.

The replenishing amount of the replenishing solution in the bleach-fixing or fixing step is 100 to 1000 mL, preferably 150 to 700 mL, particularly preferably 200 to 600 mL, per 1 m ² of the light-sensitive material.
In the bleach-fixing or fixing step, it is preferable to collect various silver recovery devices in-line or offline to recover silver. By installing in-line, the amount of replenishment can be reduced as a result of processing with reduced silver concentration in the liquid. It is also preferable to recover silver offline and reuse the remaining liquid as a replenisher.

  The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is cascade-pipe to be a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and it is preferable that the ratio of the processing time in the front tank and the rear tank is in the range of 0.5: 1 to 1: 0.5. The range of 0.8: 1 to 1: 0.8 is particularly preferable.

  In the bleach-fixing solution and the fixing solution, it is preferable that a free chelating agent that is not a metal complex is present from the viewpoint of improving the preservability, but as these chelating agents, the biodegradability described for the bleaching solution is used. It is preferred to use a chelating agent.

Regarding the water washing and stabilization process, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular, in place of formaldehyde, azolylmethylamines described in EP 504,609 and 519,190 and N-methylolazoles described in JP-A-4-362943 are used in place of formaldehyde, or a magenta coupler is converted into two equivalents. It is preferable to use a surfactant solution that does not contain an image stabilizer such as formaldehyde from the viewpoint of maintaining the working environment.
In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizer described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution is preferably 80 to 1000 mL per 1 m ² of the light-sensitive material, particularly 100 to 500 mL, and more preferably 150 to 300 mL, both for ensuring washing function and stabilizing waste and reducing waste for environmental conservation. To a preferable range. In such a replenishing amount, known methods such as thiabendazole, 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one are used to prevent the growth of bacteria and sputum. It is preferable to use water deionized with an antifungal agent, an antibiotic such as gentamicin, an ion exchange resin or the like. It is more effective to use deionized water together with antibacterial agents and antibiotics.

  In addition, the amount of replenishment of the water in the water washing or stabilizing liquid tank is reduced by performing reverse osmosis membrane treatment described in JP-A-3-46652, 3-53246, 3-355542, 3-121448, and 3-12030. The reverse osmosis membrane in this case is preferably a low pressure reverse osmosis membrane.

  In the processing in the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in JIII Journal of Technical Disclosure No. 94-4992. In particular, a method of correcting using the temperature and humidity information of the developing machine installation environment based on (Formula-1) on the second page is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing, in which case deionized water is preferably used as the washing replenishment water.

  As the treating agent used in the present invention, those described in the third page, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. Further, as the developing machine used for this, the film processor described in lines 22 to 28 in the right column on page 3 is preferable.

  Specific examples of a processing agent, an automatic processor, and an evaporation correction method that are preferable for carrying out the present invention are described from the fifth page, right column, line 11 to the seventh page, right column, last line of the above published technical bulletin. .

  The treatment agent used in the present invention may be supplied in any form, such as a solution in the concentration or concentrated form of the working solution, or granules, powders, tablets, pastes, and emulsions. Examples of such treatment agents include a liquid agent stored in a low oxygen permeable container in JP-A-63-17453, powders or granules in vacuum packaging in JP-A-4-19655 and 4-230748, 4- 221951 discloses a granule containing a water-soluble polymer, JP-A-51-61837, JP-A-6-102628 discloses a tablet, JP-T-57-500485 discloses a paste-like treatment agent, both of which are preferred. Although it can be used, it is preferable to use a liquid prepared in advance at a concentration in the state of use from the viewpoint of convenience during use.

In a container for storing these treatment agents, polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, or the like is used alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidized liquid such as a color developer, a low oxygen permeable material is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the processing liquid for the color reversal film used in the present invention will be described.
Regarding processing for color reversal film, publicly known technology No. 6 (April 1, 1991) published by Aztec Co., Ltd., page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, page 2 The contents are described in detail in the lines, and any of the contents can be preferably applied.

  In color reversal film processing, image stabilizers are included in the conditioning bath or the final bath. Examples of such image stabilizers include formaldehyde sodium bisulfite and N-methylol azoles in addition to formalin. From the viewpoint of the working environment, sodium formaldehyde bisulfite or N-methylol azoles are preferred, and N-methylol is preferred. As the azole, N-methyloltriazole is particularly preferable. The contents relating to the color developer, bleaching solution, fixing solution, washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film.

  Examples of preferable processing agents for color reversal films including the above contents include East-6 Kodak E-6 processing agent and Fuji Photo Film Co., Ltd. CR-56 processing agent.

Next, the magnetic recording layer preferably used in the present invention will be described.
The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co-coated ferromagnetic iron oxides such as Co-coated γFe ₂ O ₃ are preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, and particularly preferably 4.0 × 10 ^{4 to} 2.5 × 10 ⁵ mA / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the magnetic particles may be treated on the surface with a silane coupling agent or a titanium coupling agent as described in JP-A-6-61032. Further, magnetic particles having a surface coated with inorganic or organic substances as described in JP-A-4-259911 and 5-81652 can also be used.

  The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product polymer (cellulose) described in JP-A-4-19569. Derivatives, sugar derivatives, etc.) and mixtures thereof. The resin has a Tg of -40 ° C to 300 ° C and a mass average molecular weight of 20,000 to 1,000,000. Examples include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate, cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of isocyanate-based crosslinking agents include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like, and reaction products of these isocyanates with polyalcohol (for example, tolylene diene). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), polyisocyanates formed by condensation of these isocyanates, and the like, for example, are described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin type mill, an annular type mill, etc. are preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15. The magnetic recording layer can be provided on the entire surface or in a stripe shape on the back surface of the photographic support by coating or printing. As a method for applying the magnetic recording layer, an air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extraction, etc. can be used. The coating solution described in 341436 and the like is preferable.

  The magnetic recording layer may have functions such as lubricity improvement, curl adjustment, antistatic, adhesion prevention, head polishing, etc., or another functional layer may be provided to give these functions. An abrasive of non-spherical inorganic particles in which at least one kind of particles has a Mohs hardness of 5 or more is preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide, and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as that for the magnetic recording layer is preferable. Photosensitive materials having a magnetic recording layer are described in US 5,336,589, 5,250,404, 5,229,259, 5,215,874, and EP 466,130.

  Next, the polyester support used in the present invention will be described, but for details including photosensitive materials, processing, cartridges and examples described later, published technical bulletin, public technical number 94-6023 (Invention Association; 1994.3.15. )It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). It is also desirable to devise measures such as preventing knurling of the core part by imparting knurls to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.

  This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

  Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, regarding the undercoating method, a single layer or two or more layers may be used. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. As the gelatin hardener for the undercoat layer, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

  In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.

Most preferred as the antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , V ₂ O _5. The volume resistivity of the seed is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. The particle size is 0.001 to 1.0 μm Crystalline metal oxide or a composite oxide thereof (Sb, P, B, In , S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof. The addition amount to the photographic material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

  The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min against a stainless steel ball with a diameter of 5 mm (25 ° C, 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.

  Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve matting properties, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), polystyrene Examples thereof include particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Furthermore, the cartridge of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine surfactants or polymers can be preferably used. These antistatic cartridges are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, plastic patrone is manufactured using a plastic kneaded with carbon black or pigment to provide light shielding. The patrone size may be the same as the current 135 size. To reduce the size of the camera, it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less. The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less. The mass of the plastic used for the cartridge and the cartridge case is preferably 5 to 15 g.

  Further, a cartridge that feeds a film by rotating a spool may be used in the present invention. Alternatively, the film leading end may be housed in the cartridge main body, and the film leading end may be sent out from the port portion of the cartridge by rotating the spool shaft in the film feeding direction. These are disclosed in US 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development, or may be a developed photographic film. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges.

  The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as AP system), manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film), NEXIA A, NEXIA F, A film that has been processed into an AP system format such as NEXIA H (in order ISO 200/100/400) and stored in a dedicated cartridge can be listed. These AP system cartridge films are used by being loaded into an AP system camera such as the Fuji Film Epion series (Epion 300Z, etc.). The color photographic light-sensitive material of the present invention is also suitable for a lens-equipped film such as a super slim, which is a Fuji color photorun made by Fuji Film.

The film photographed by these is printed through the following process in the minilab system.
(1) Reception (taking the exposed cartridge film from the customer)
(2) Detach process (transfer film from cartridge to intermediate cartridge for development process)
(3) Film development
(4) Rear touch process (return the developed negative film back to the original cartridge)
(5) Print (C / H / P3 type prints and index prints are automatically printed on color paper (preferably Fujifilm SUPER FA8))
(6) Verification / shipment (Cartridge and index print are verified by ID number and shipped together with the print)

  As these systems, FUJIFILM Minilab Champion Super FA-298 / FA-278 / FA-258 / FA-238 and FUJIFILM Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP362B, AL are listed as minilab champion film processors. Fuji Color Just It CN-16L and CN-16Q are recommended treatment chemicals. Examples of printer processors include PP3008AR / PP3008A / PP1828AR / PP1828A / PP1258AR / PP1258A / PP728AR / PP728A, and recommended processing chemicals are Fujicolor Justit CP-47L and CP-40FAII. In the frontier system, the Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP-1000W are used. The detacher used in the detaching step and the rear toucher used in the rear touching step are preferably DT200 / DT100 and AT200 / AT100 made by FUJIFILM respectively.

  The AP system can also be enjoyed with a photo joy system centered on Fujifilm's digital image workstation Aladdin 1000. For example, you can directly load developed AP system cartridge film into Aladdin 1000 or input image information of negative film, positive film, and print using 35mm film scanner FE-550 or flat head scanner PE-550. Digital image data can be easily processed and edited. The data can be output as a print by a digital color printer NC-550AL using a light fixing type thermal color printing system, a pictography 3000 using a laser exposure thermal development transfer system, or by an existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy disk or Zip disk, or to a CD-R via a CD writer.

  On the other hand, at home, you can enjoy photos on a TV simply by loading the developed AP system cartridge film into the Fujifilm photo player AP-1, or you can load it into a PC if you load it into the Fujifilm photo scanner AS-1. Image information can also be captured continuously at high speed. In addition, Fujifilm's Photo Vision FV-10 / FV-5 can be used to input film, prints or three-dimensional objects into a personal computer. In addition, image information recorded on floppy disks, Zip disks, CD-Rs or hard disks can be processed and enjoyed on a personal computer in various ways using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, Fujifilm's digital color printer NC-2 / NC-2D with a light fixing type thermal color printing method is suitable.

  To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, AP-1 Pop L, AP-1 Pop KG or Cartridge File 16 is preferred.

[Example]
Examples of the present invention are shown below. However, the present invention is not limited to this example.
(Example 1)
Silver halide emulsion Em-A1 was prepared by the following production method.
(Em-A1)
42.2 L of an aqueous solution containing 36.7 g of phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15,000 and 31.7 g of KBr was kept at 35 ° C. and stirred vigorously. 1583 ml of an aqueous solution containing 316.7 g of AgNO ₃ (hereinafter, milliliter is also referred to as “mL”) and 1583 ml of an aqueous solution containing 52.7 g of low molecular weight gelatin having a KBr of 221.5 g and a molecular weight of 15000 are obtained by a double jet method. Added over a minute. Immediately after the addition, 52.8 g of KBr was added, and 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by the double jet method. Immediately after the addition, 47.8 g of KBr was added. Then, it heated up to 43 degreeC and fully matured. After completion of aging, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 were added and KBr, 79.2 g, and 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added to the initial flow rate by the double jet method. The flow rate was accelerated to 1.4 times and added over 12 minutes. At this time, the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, pAg, 8.8, 131.8 g of silver equivalent per 1 kg of emulsion, and 64.1 g of gelatin mass to obtain a seed emulsion.

1211 mL of an aqueous solution containing 46 g of phthalated gelatin having a phthalation rate of 97% and 1.7 g of KBr was kept at 75 ° C. and vigorously stirred. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and an aqueous KBr solution are 5.1 times the initial flow rate by the double jet method. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 144.5 g of AgNO ₃ , a mixed solution of KBr and KI containing 410 mL and 7 mol% of KI, the final flow rate is the initial flow rate by the double jet method. The flow rate was accelerated so as to be 3.7 times that of the solution and added over 56 minutes. At this time, the silver potential was kept at −45 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI mass. Immediately after the addition, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 13 and Compound 14 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound were selected from a range of addition amounts of 10 ⁻¹ to 10 ⁻⁸ mol per mol of silver halide.

  As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the periphery of the particles.

(Em-A2 to Em-A16)
Except that 1 × 10 ⁻⁴ mol of a compound selected from type A or types 1 to 4 of the present invention was added per 1 mol of silver halide as shown in Table 2 at the time of chemical sensitization, it was the same as Em-A1. Thus, emulsions Em-A2 to Em-A16 were obtained.

(Em-B) (Emulsion for low sensitivity blue-sensitive layer)
1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin and KBr, 0.9 g was kept at 40 ° C. and stirred vigorously. 37.5 mL of an aqueous solution containing 1.49 g of AgNO ₃ and 37.5 mL of an aqueous solution containing 1.5 g of KBr were added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the mixture was heated to 75 ° C. and aged. After sufficiently ripening, 30 g of trimellitated gelatin having a molecular weight of 100000 having a chemically modified amino group with trimellitic acid was added to adjust the pH to 7. 6 mg of thiourea dioxide was added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added at a flow rate acceleration by a double jet method so that the final flow rate was three times the initial flow rate. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. It was. 96.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 3 minutes by the double jet method. At this time, the silver potential was kept at 0 mV. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 228 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 5 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be + 20mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-C) (low-sensitivity blue-sensitive emulsion)
1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram and 0.97 g of KBr was maintained at 35 ° C. and stirred vigorously. An aqueous solution containing AgNO ₃ , 4.47 g, 42 mL and KBr, an aqueous solution containing 3.16 g, and 42 mL were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C. and fully aged. After completion of aging, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B and NaCl, 18.5 g were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 24 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at an accelerated flow rate so that the silver iodide content was 2.3 mol%, and the silver potential was -20 mV to the saturated calomel electrode. Kept. After adding 10.7 mL of 1N aqueous potassium thiocyanate solution, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 2 minutes and 30 seconds by the double jet method. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. 6.4 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 404 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 45 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be -30mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-D) (Low-sensitivity blue-sensitive emulsion)
In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. Then, the addition at the end of the potential of the aqueous solution 404mL, including the final AgNO _3, 57 g was changed to adjust an aqueous KBr solution to be + 90 mV. Otherwise, it was prepared in substantially the same manner as Em-C.

(Em-E) (magenta color-developing layer having a spectral sensitivity peak at 480 to 550 nm) (layer that gives a multilayer effect to the red-sensitive layer)
1200 mL of an aqueous solution containing 0.2 g of modified silicone oil used in the preparation of low molecular weight gelatin having a molecular weight of 15000, 0.71 g, KBr, 0.92 g, and Em-A1 is maintained at 39 ° C., and the pH is adjusted to 1.8 vigorously. Stir. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% KI were added over 17 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was performed. After fully ripening, 20 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram was added. After adjusting the pH to 5.9, KBr, 2.9 g was added. 288 mL of an aqueous solution containing 28.8 g of AgNO ₃ and an aqueous KBr solution were added over 53 minutes by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After adding KBr, 2.5 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are accelerated over a period of 63 minutes by the double jet method so that the final flow rate is 1.2 times the initial flow rate. did. At this time, the above-mentioned AgI fine grain emulsion was added at the same time with the flow rate accelerated so that the silver iodide content was 10.5 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 609 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 10 minutes. During the initial 6 minutes of addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 56 ° C. After adding 0.0004 mol of the above AgI fine grain emulsion to 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-F) (Emulsion for medium sensitivity green sensitive layer)
Em-E was prepared in substantially the same manner as Em-E, except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times. However, the sensitizing dye of Em-E was changed to sensitizing dyes 15, 16 and 17.

(Em-G) (Low-sensitivity green sensitive layer emulsion)
1,200 mL of an aqueous solution containing 0.70 g of low molecular weight gelatin having a molecular weight of 15000, KBr, 0.9 g, KI, 0.175 g, and 0.2 g of modified silicone oil used in the preparation of Em-A1 was maintained at 33 ° C., and the pH was adjusted to 1. 8 and stirred vigorously. An aqueous solution containing 1.8 g of AgNO ₃ and an aqueous KBr solution containing 3.2 mol% KI were added over 9 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 69 ° C. and aging was performed. After completion of ripening, 27.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 6.3, KBr, 2.9 g was added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, particles prepared by mixing a low molecular weight gelatin aqueous solution having a molecular weight of 15000, an AgNO ₃ aqueous solution and a KI aqueous solution immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570 An AgI fine grain emulsion having a size of 0.008 μm was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV to the saturated calomel electrode. After adding KBr, 2.6 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are accelerated over a period of 49 minutes by the double jet method so that the final flow rate is 3.1 times the initial flow rate. did. At this time, the AgI fine grain emulsion prepared by mixing immediately before the above addition was simultaneously accelerated so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After raising the temperature to 78 ° C. and adjusting the pH to 9.1, KBr was added to bring the potential to −60 mV. 5.73 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, 321 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was kept at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-H) (Low-sensitivity green sensitive layer emulsion)
An aqueous solution containing 17.8 g of ion-exchanged gelatin having a molecular weight of 100,000, KBr, 6.2 g, KI, and 0.46 g was kept at 45 ° C. and stirred vigorously. An aqueous solution containing 11.85 g of AgNO ₃ and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After raising the temperature to 63 ° C., 24.1 g of ion-exchanged gelatin having a molecular weight of 100,000 was added and aged. After fully aging, an aqueous solution containing 133.4 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes so that the final flow rate was 2.6 times the initial flow rate by the double jet method. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. In addition, 0.1 mg of K ₂ IrCl ₆ was added 10 minutes after the start of the addition. After adding 7 g of NaCl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of addition. After the addition of 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-I) (Emulsion for low sensitivity green sensitive layer)
Em-H was prepared in substantially the same manner except that the temperature during nucleation was changed to 38 ° C.

(Em-J) (Emulsion for high sensitivity red-sensitive layer)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g and KBr, 0.99 g was kept at 60 ° C., pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g, KI, and 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. 6.2 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After adding sensitizing dyes 18, 19, 20 and 21, K ₂ IrCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-K) (Emulsion for medium sensitivity red sensitive layer)
1200 mL of an aqueous solution containing 4.9 g of low molecular weight gelatin having a molecular weight of 15000 and 5.3 g of KBr was kept at 60 ° C. and stirred vigorously. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added by a double jet method over 1 minute. After raising the temperature to 77 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2.5 minutes. NH ₄ NO ₃ , 26 g, 1N, NaOH, and 56 mL were sequentially added, followed by aging. After completion of aging, the pH was adjusted to 4.8. 438 mL of an aqueous solution containing 141 g of AgNO ₃ and 458 mL of an aqueous solution containing 102.6 g of KBr were added by a double jet method so that the final flow rate was four times the initial flow rate. After the temperature was lowered to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃ and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. After adding 7.1 g of KBr, 4 mg of sodium benzenethiosulfonate and 0.05 mg of K ₂ IrCl ₆ were added. 177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and 223 mL of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. Washed with water and chemically sensitized in substantially the same manner as Em-J.

(Em-L) (Emulsion for medium sensitivity red sensitive layer)
Em-K was prepared in substantially the same manner except that the temperature during nucleation was changed to 42 ° C.

(Em-M, N, O) (Low-sensitivity red-sensitive emulsion)
Prepared in substantially the same manner as Em-H or Em-I. However, chemical sensitization was carried out in substantially the same manner as Em-J1.

(Em-P) (Emulsion for high sensitivity green sensitive layer)
For Em-J, the sensitizing dye was changed to 15, 16 and 17, and chemical sensitization was optimally performed to obtain Em-P.

The characteristics of the thus obtained silver halide emulsions Em-A1 to P are shown in Table 1.

Moreover, the outline of preparation formulation of the emulsion of this invention is shown below.
A 10% gelatin solution containing a coupler dissolved in ethyl acetate, a high-boiling organic solvent, and a surfactant are added and emulsified using a mixed homogenizer (Nippon Seiki) to obtain an emulsion.

1) Support The support used in this example was prepared by the following method.
100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-shaped die, and stretched 3.3 times at 140 ° C., followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I- 27, II-5) was added in an appropriate amount. Further, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.

2) Coating of undercoat layer The above support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m ² and sodium α-sulfodi-2 on each side. - ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04g / m ^2, p- chlorophenol _{^{0.2g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.012g / m ^2. An undercoat solution of polyamide-epichlorohydrin polycondensate 0.02 g / m ² was applied (10 mL / m ² , using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one side of the support after the undercoating.
3-1) Coating of antistatic layer The specific resistance of the tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm is 0 of a dispersion of fine powder of 5 Ω · cm (secondary aggregated particle diameter of about 0.08 μm) .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02g / m 2, poly (polymerization degree 10) oxyethylene -p- nonylphenol 0. 005 g / m ² and resorcin.

3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m ² / g, (Major axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89Am ² / kg, Fe ⁺² / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide and 2% by mass of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of abrasive aluminum oxide (0.15 μm) treated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C.). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m, the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1) and pouring and dispersing in propylene monomethyl ether at room temperature (10 times the amount). The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum particles (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent It added so that it might become ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. Excellent characteristics.

4) Coating of photosensitive layer Next, on the opposite side to the support of the back layer obtained above, each layer having the following composition was applied in layers to prepare a sample which is a color negative photosensitive material. Samples were made using emulsions, emulsions and couplers as shown in (Table 3), (Table 4), and (Table 5). Emulsions, couplers, high boiling point organic solvents and surfactants were replaced in equal amounts. Moreover, when using two or more, it replaced so that the sum might be equivalent replacement. Specifically, two cases were replaced by 1/3, and three cases were replaced by 1/3.

(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener The chemical formula is mentioned)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

First layer (first antihalation layer)
Black colloidal silver Silver 0.150
0.07 μm surface fogging AgBrI (2) Silver 0.01
Gelatin 0.90
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.004
HBS-2 0.002

Second layer (second antihalation layer)
Black colloidal silver Silver 0.069
Gelatin 0.400
ExM-1 0.055
ExF-1 2.0 × 10 ⁻³
HBS-1 0.079
Solid disperse dye ExF-2 0.018
Solid disperse dye ExF-3 0.024

Third layer (intermediate layer)
0.07 μm AgBrI (2) 0.020
ExC-2 0.022
Cpd-1 0.050
UV-1 0.06
UV-2 0.04
UV-3 0.06
UV-4 0.008
Polyethyl acrylate latex 0.085
HBS-1 0.500
HBS-4 0.500
Gelatin 0.354

4th layer (low sensitivity red sensitive emulsion layer)
Em-M Silver 0.060
Em-N Silver 0.105
Em-O Silver 0.156
ExC-1 0.111
ExC-3 0.047
ExC-4 0.079
ExC-5 0.013
ExC-6 0.005
ExC-8 0.020
Cpd-2 0.025
Cpd-4 0.025
HBS-1 0.17
Gelatin 0.84

5th layer (medium sensitivity red emulsion layer)
Em-K Silver 0.24
Em-L Silver 0.65
ExC-1 0.18
ExC-2 0.024
ExC-3 0.020
ExC-4 0.14
ExC-5 0.016
ExC-6 0.009
ExC-8 0.035
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.19
Gelatin 1.23

6th layer (high-sensitivity red-sensitive emulsion layer)
Em-J Silver 1.60
ExC-1 0.19
ExC-3 0.09
ExC-6 0.049
ExC-8 0.040
Cpd-2 0.043
Cpd-4 0.077
HBS-1 0.25
HBS-2 0.12
Gelatin 2.00

7th layer (intermediate layer)
Cpd-1 0.089
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.83
Gelatin 0.84

Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Em-E Silver 0.510
Cpd-4 0.030
ExM-2 0.090
ExM-3 0.033
ExY-1 0.033
ExG-1 0.007
ExC-8 0.005
HBS-1 0.089
HBS-3 0.004
Gelatin 0.55

9th layer (low sensitivity green emulsion layer)
Em-G Silver 0.36
Em-H Silver 0.24
Em-I Silver 0.32
ExM-2 0.37
ExM-3 0.043
ExG-1 0.005
ExC-8 0.005
HBS-1 0.28
HBS-3 0.01
HBS-4 0.27
Gelatin 1.30

10th layer (medium sensitive green sensitive emulsion layer)
Em-F Silver 0.24
Em-G Silver 0.20
ExC-6 0.011
ExM-2 0.031
ExM-3 0.026
ExY-1 0.005
ExM-4 0.028
ExG-1 0.005
ExC-8 0.010
HBS-1 0.064
HBS-3 2.1 × 10 ^-3
Gelatin 0.43

11th layer (high sensitivity green emulsion layer)
Em-P Silver 1.100
ExC-6 0.004
ExM-1 0.016
ExM-3 0.036
ExM-4 0.020
ExM-5 0.004
ExY-5 0.008
ExM-2 0.013
ExC-8 0.010
Cpd-4 0.007
HBS-1 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.11

12th layer (yellow filter layer)
Yellow colloidal silver Silver 0.047
Cpd-1 0.16
Solid disperse dye ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.082
Gelatin 1.057

13th layer (low sensitivity blue-sensitive emulsion layer)
Em-B Silver 0.19
Em-C Silver 0.23
Em-D Silver 0.05
ExC-1 0.045
ExC-8 0.010
ExY-1 0.032
ExY-2 0.71
ExY-3 0.10
ExY-4 0.005
Cpd-2 0.10
Cpd-3 4.0 × 10 ⁻³
HBS-1 0.26
Gelatin 1.47

14th layer (high sensitivity blue-sensitive emulsion layer)
Em-A1 Silver 0.85
ExC-1 0.016
ExC-8 0.010
ExY-2 0.30
ExY-3 0.05
ExY-6 0.065
Cpd-2 0.075
Cpd-3 1.0 × 10 ⁻³
HBS-1 0.12
Gelatin 0.98

15th layer (first protective layer)
0.07 μm AgBrI (2) Silver 0.30
UV-1 0.21
UV-2 0.13
UV-3 0.20
UV-4 0.025
F-18 0.009
F-19 0.005
HBS-1 0.12
HBS-4 5.0 × 10 ^-2
Gelatin 3.0

16th layer (second protective layer)
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10 ⁻²
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.75

Furthermore, storage stability, processability, pressure resistance, antifungal and antibacterial properties, B-4 to B-6, F-1 to F-18, and iron salts, lead salts, gold salts, platinum salts, as appropriate for each layer , Palladium salts, iridium salts, ruthenium salts and rhodium salts. Further, 8.5 × 10 ⁻³ gram per mole of silver halide was added to the eighth layer coating solution and 7.9 × 10 ⁻³ gram calcium was added to the eleventh layer with a calcium nitrate aqueous solution to prepare a sample. . Further, at least one of W-1, W-6, W-7, and W-8 is contained for improving antistatic properties, and at least one of W-2 and W-5 is used for improving coating properties. Contains.

Preparation of dispersion of organic solid disperse dye The following ExF-3 was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle diameter of the dye fine particles was 0.44 μm.

  Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the dye fine particles was 0.45 μm. ExF-2 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method.
To 2800 g of ExF-6 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-6 having a concentration of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec through the slurry, and the discharge rate was 0.5 l / min for 8 hours. Crushed.

The compounds used for forming each of the above layers are as shown below.

Samples 101 to 116 were prepared in the same manner except that the emulsion of the 14th layer was changed as shown in Table 2. In Samples 117 to 147, as shown in Table 2, the compound (B) of the present invention was added to the 14th layer by emulsifying and dispersing in an amount of 1 × 10 ⁻² mol per 1 mol of silver halide.

  The sample evaluation method is as follows. The film was exposed for 1/100 second through a gelatin filter SC-39 (long wavelength light transmission filter having a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. Development was performed as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, the overflow solution of the bleaching bath was remodeled so as not to flow to the rear bath but to discharge all to the waste liquid tank. This FP-360B is equipped with an evaporation correction means described in Japanese Society of Invention and Innovation technique 94-4992.

The treatment process and the treatment liquid composition are shown below.
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Washing with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C

* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL for a photosensitive material 35 mm width 1.1 m, respectively. 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)

(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

  The said process was performed with respect to the samples 101-147. Photographic performance was evaluated by measuring the yellow density of the processed sample. The sensitivity was determined by comparing the logarithmic value of the reciprocal of the exposure amount giving the minimum density of yellow density +0.1, and the difference with the sample 101 result. Higher values are preferable because of higher sensitivity.

Evaluation of the latent image storage stability was performed as follows.
The sample was exposed by the above method, stored for 2 weeks under a forced deterioration condition of 40 ° C. and 60% RH, and then developed by the above method. The logarithmic value of the reciprocal of the exposure amount giving the lowest density of yellow density +0.5 was obtained.
This result was evaluated by obtaining a difference with respect to the result when not stored under forced deterioration conditions. The closer this value is to 0, the smaller the performance change due to storage after exposure.

The results obtained are shown in Table 2.
From Table 2, it can be seen that a light-sensitive material containing a compound selected from type A or types 1 to 4 and compound B has high sensitivity and is excellent in latent image preservability.

(Example 2)
(Preparation of self-emulsifying vinyl polymer (P-15))
A mixed solution (A) was prepared from 4.6 parts of sodium 2-acrylamido-2-methylpropanesulfonate, 75.4 parts of ethyl methacrylate, 70 parts of isopropyl alcohol and 30 parts of water.

  Next, 30 parts of isopropyl alcohol and 0.4 part of dimethyl 2,2′-azobisisobutyrate were placed in a flask, and the mixture was heated to 80 ° C. with stirring under a nitrogen seal. ) Was added dropwise over 2 hours, and after completion of the dropwise addition, a solution of 0.2 part of dimethyl 2,2′-azobisisobutyrate in 30 parts of isopropyl alcohol was added, and the mixture was further reacted at the same temperature for 5 hours. The resulting polymer solution was concentrated under reduced pressure to obtain 125 parts of the desired self-emulsifying vinyl polymer having a solid content of 35% by mass.

(Preparation of UVPV-1 containing UV absorber-containing fine particle dispersion)
51.4 parts of the self-emulsifiable vinyl polymer solution obtained above, 20 parts of isopropyl alcohol, 3.35 parts of UV-1 3.19 parts of UV-3, 2.07 parts of UV-2, 0.44 of UV-4 Part of the mixture was prepared. The mixture was heated to 80 ° C., and then 300 parts of water was added with stirring. This liquid was concentrated at 40 ° C. under reduced pressure to prepare a UV absorbent-containing fine particle dispersion having a solid content of 14.5%. The dispersion was milky white with paleness, the particle size was 150 nm, and the pH was 6.70.

  The UV-1 to UV-4 of the 15th layer of the sample 118 of Example 1 was added as a dispersion co-emulsified with the high-boiling organic solvents HBS-1 and HBS-2. This was added using the above UVPV-1 so that the addition amount of the ultraviolet absorber was the same as that of the sample 118, thereby preparing a sample 201. At this time, the gelatin coating amount was adjusted so that the dry film thickness was the same as that of the sample 118.

Similarly, samples using UVPV-1 as the fifteenth layer for samples 122, 143, and 145 were prepared and used as samples 202, 203, and 204, respectively.
Moreover, the support body was changed from (a) described in Example 1 to (b), and samples 205 to 212 were produced.

(A) Polyethylene naphthalate film having a magnetic recording layer on the back layer described in Example 1 (a) Cellulose triacetate film The pressure and heat aging fogging of these samples was evaluated by the following method. The sample was cut to 35 mm × 35 mm and then conditioned for 24 hours under conditions of 25 ° C. and 65% RH. 21 sheets of these were stacked, and a 500 g weight was placed thereon and stored for 72 hours under a forced deterioration condition of 60 ° C. and 60% RH. Of the 21 stacked samples, three in the center were developed by the method described in Example 1.

  The yellow density at the center of the sample was measured, and the average value of the three results was obtained. The difference between this result and the case where it was not stored under forced deterioration conditions was determined, and the evaluation of fogging under pressure and heat was performed. The results are shown in Table 3. The evaluation was shown as a relative value to the result of the sample 118.

From Table 3, samples 201-204 and 209- of the present invention using ultraviolet absorbent-containing fine particle dispersions produced by emulsifying water by introducing water into an organic solvent phase containing a vinyl polymer and an ultraviolet absorbent. It can be seen that 212 is preferable because the fogging due to pressure and heat is small. It can also be seen that this effect is more pronounced when (a) is used than when (a) is used as the support.

Claims (14)

A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, a red-sensitive silver halide emulsion layer containing a cyan coupler, and a silver halide color photographic material have a non-photosensitive layer comprises a compound selected from the compound group of the type a and type 1-4 in at least one layer, and a UV absorber in at least one layer vinyl the silver halide color photographic light-sensitive material characterized that you containing fine particle dispersion containing the polymer.
(Type A)
In the compound represented by XY, X represents a reducing group, Y represents a leaving group, and a one-electron oxidant formed by one-electron oxidation of the reducing group represented by X is followed by XY A compound capable of releasing Y by releasing Y with a bond cleavage reaction and releasing another electron therefrom.
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit two or more electrons with a subsequent bond cleavage reaction.
(Type 2)
The one-electron oxidant produced by one-electron oxidation is a compound capable of releasing another electron with a subsequent carbon-carbon bond cleavage reaction, and 2 adsorbing groups to silver halide are present in the same molecule. A compound having two or more.
(Type 3)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation process.
(Type 4)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent intramolecular ring-cleaving reaction.   The compound selected from the type A and type 1-4 compound groups is a compound selected from the following general formula (A) and compound groups represented by general formulas (1-1) to (4-2): The silver halide color photographic light-sensitive material according to claim 1.

  RED in general formula (A) ₀ Represents a reducing group, L ₀ Represents a leaving group, R ₀ And R ₁ Represents a hydrogen atom or a substituent. RED ₀ And R ₀ , And R ₀ And R ₁ And may be bonded to each other to form a ring structure.

  RED in general formula (1-1) ₁₁ Represents a reducing group, L ₁₁ Represents a leaving group, R ₁₁₂ Represents a hydrogen atom or a substituent. R ₁₁₁ Is carbon atom (C) and RED ₁₁ In addition, it represents a nonmetallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form, a hexahydro form, or an octahydro form of a 5-membered or 6-membered aromatic ring (including an aromatic heterocycle).
  RED in general formula (1-2) ₁₂ And L ₁₂ Are respectively RED of the general formula (1-1) ₁₁ And L ₁₁ Represents a group having the same meaning as R ₁₂₁ And R ₁₂₂ Each represents a hydrogen atom or a substituent substitutable on a carbon atom, and this represents R in the general formula (1-1) ₁₁₂ Is synonymous with ED ₁₂ Represents an electron donating group. In the general formula (1-2), R ₁₂₁ And RED ₁₂ , R ₁₂₁ And R ₁₂₂ Or ED ₁₂ And RED ₁₂ And may be bonded to each other to form a cyclic structure.
  RED in general formula (2) ₂ Is RED of general formula (1-2) ₁₂ Represents a group having the same meaning as L ₂ Represents a carboxy group or a salt thereof, R _{twenty one} , R _{twenty two} Represents a hydrogen atom or a substituent. RED ₂ And R _{twenty one} And may be bonded to each other to form a ring structure. However, the compound represented by the general formula (2) is a compound having two or more adsorption promoting groups for silver halide in the molecule.
  RED in general formula (3) _Three Is RED of general formula (1-2) ₁₂ Represents a group having the same meaning as Y _Three RED _Three Represents a reactive group containing a carbon-carbon double bond site or a carbon-carbon triple bond site capable of reacting with a one-electron oxidant produced by one-electron oxidation to form a new bond. L _Three Is RED _Three And Y _Three Represents a linking group for linking.
  RED in general formula (4-1) and general formula (4-2) ₄₁ And RED ₄₂ Are respectively RED of general formula (1-2) ₁₂ Represents a group having the same meaning as R ₄₀ ~ R ₄₄ And R ₄₅ ~ R ₄₉ Each represents a hydrogen atom or a substituent. In general formula (4-2), Z ₄₂ Is -CR ₄₂₀ R ₄₂₁ -, -NR ₄₂₃ -Represents-or -O-. R here ₄₂₀ , R ₄₂₁ Each represents a hydrogen atom or a substituent, and R ₄₂₃ Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.   3. The silver halide color according to claim 1, wherein the compound selected from the group of types A and 1 to 4 has a partial structure of an adsorptive group or a sensitizing dye in the molecule. Photosensitive material.   The vinyl polymer contains a monomer selected from acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins and vinyl ethers as a forming monomer. The silver halide color photographic light-sensitive material according to any one of the above.   The silver halide according to any one of claims 1 to 4, wherein the vinyl polymer is a copolymer composed of two or more monomers, and at least one of the monomers has a dissociable group. Color photographic material.   6. The silver halide color photographic material according to claim 5, wherein the dissociable group of the monomer is sulfonic acid.   The silver halide color photograph according to claim 5 or 6, wherein a ratio of the monomer having a dissociable group in the copolymer is 0.1 to 3.0 mmol / g with respect to the vinyl polymer. Photosensitive material.   The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, wherein the vinyl polymer has an average molecular weight of 3,000 to 50,000.   The fine particle dispersion containing the ultraviolet absorber and the vinyl polymer is emulsified by introducing water into the organic solvent phase containing the vinyl polymer and the ultraviolet absorber, or by introducing the organic solvent phase into water. 9. The silver halide color photographic light-sensitive material according to claim 1, which is produced.   10. The method according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in any one of the light-sensitive silver halide emulsion layers satisfies the following (a) to (d): Silver halide color photographic material.
  (A) Parallel main plane is (111) plane
  (B) The aspect ratio is 2 or more
  (C) including at least 10 dislocation lines per particle
  (D) A plate-shaped substrate made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%
        Silver halide grains   2. 50% or more of the total projected area of silver halide grains contained in any one of the light-sensitive silver halide emulsion layers satisfies the following (a), (d) and (e): The silver halide color photographic light-sensitive material according to any one of? 9.
  (A) Parallel main plane is (111) plane
  (D) A plate-shaped substrate made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%
        Silver halide grains
  (E) Vertex and / or side surface and / or main plane of hexagonal silver halide grain
        Have at least one epitaxial junction per particle in the part The silver halide color photographic light-sensitive material according to any one of claims 1 to 11, wherein the silver halide color photographic light-sensitive material contains the following compound (B).
Compound (B): a heterocyclic compound having at least three heteroatoms in the ring system structure part , and a compound in which the photographic sensitivity of the photosensitive material is increased as compared with the case where the compound is not contained. This means that the photographic sensitivity increases when processed with the following development processing steps and processing solutions.
(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Washing with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing solution and the fixing solution were a countercurrent system from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL, respectively, per photosensitive material 35 mm width 1.1 m, 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
100 cm ² in the color developing solution open area of the processing machine, 120 cm ^2, the other processing solutions in the bleaching solution is about 100 cm ^2.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18
(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0
(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)
(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45
(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.
(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5   The silver halide color according to any one of claims 1 to 12, wherein silver halide grains contained in at least one of the photosensitive silver halide emulsion layers are subjected to reduction sensitization. Photosensitive material.   The silver halide grains contained in at least one of the photosensitive silver halide emulsion layers are Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn Contains at least one metal ion selected from the group consisting of Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi The silver halide color photographic light-sensitive material according to any one of claims 1 to 13, wherein