JPH07104574B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material.

(Prior Art) Generally, a silver halide color photographic light-sensitive material is basically processed by a color development process and a desilvering process. There is a strong demand, and shortening the desilvering process, which occupies almost half of the processing time, is a major issue.

Heretofore, as a method of increasing the bleaching power for accelerating the desilvering process, a method of adding various bleaching accelerators to a bleaching bath, a bleach-fixing bath or their pre-bath has been proposed. Such bleaching accelerators include, for example, U.S. Patent No. 3,893,858, British Patent No. 1,138,842, and JP-A-53-141623.
Various mercapto compounds as described in Japanese Patent Publication No.
Compounds having a disulfide bond as described in JP-A-53-95630, thiazolidine derivatives as described in JP-B-53-9854, JP-A-53-94927
Isothiourea derivatives as described in JP-B-458506, JP-B-49-26586, and thiourea derivatives as described in JP-A-49-42349. Thioamide compounds such as those described in JP-A-55-2650
Examples thereof include dithiocarbamate salts described in JP-A-6, arylene diamine compounds described in US Pat. No. 4,552,834, and the like. Although some of these bleaching agents certainly have a bleaching promoting effect, they are expensive and have insufficient stability in a bath having a bleaching ability, and further, the bleaching promoting effect itself is not sufficient. It has not been enough to satisfy the practical use.

There is also known a method in which a mercapto compound or a precursor thereof using the above-mentioned bleaching accelerator is present in a light-sensitive material and processed. However, when a nuclear mercapto compound is contained in a light-sensitive material, the influence on photographic properties is large and the reason why the undeveloped silver halide and the mercapto compound in the light-sensitive material form a sparingly soluble salt. However, this method also has many problems.

In contrast, Research Disclosure Item No.
Nos. 24241 and 11449 and JP-A-61-201247 describe a bleach-accelerating compound-releasing coupler.

On the other hand, in recent years, silver halide light-sensitive materials, especially in photographic light-sensitive materials, have a high magnification ratio suitable for ultra-high-sensitivity light-sensitive materials typified by ISO1600 film and small format cameras such as 110 and disk. There is a demand for a light-sensitive material having a high image quality and a high sharpness that are satisfactory for printing.

As a main technique to meet such a demand, it is known to use tabular silver halide grains having a diameter-thickness ratio (aspect ratio) of 8: 1 or more of silver halide grains (see, for example, Japanese Patent Application Laid-Open Publication No. 2000-242242). 58-113934).

Japanese Unexamined Patent Publication (Kokai) No. Sho 61-61 relating to the bleach accelerating compound releasing coupler
-201247 also describes that it is preferable to use tabular silver halide grains, but when the desilvering process was shortened, its desilvering property was not satisfactory.

Further, a water-soluble polymer coupler is known as a specific material for realizing a thin emulsion layer as a means for improving sharpness. For example, a polymer coupler obtained by binding a reactive coupler to a pre-synthesized polymer (acrylic acid homopolymer, p-aminostyrene homopolymer, etc.) or natural polymer compound (gelatin, etc.) is described in US Pat. No. 2,698,
No. 797, No. 2,852,381, No. 2,852,383, No. 2,87
No. 0,712, JP-B-35-16932, JP-A-44-3661, etc., and a coupler synthesized in the form of an ethylenically unsaturated monomer is copolymerized with another polymerizable monomer. The resulting polymer coupler is described in British Patent 880,206.
No., No. 955,197, No. 967,503, No. 967,504,
No. 995,363 and No. 1,104,658. Further, the groups disclosed in U.S. Pat. Water-soluble polymer couplers (for example, hydrophilic polymer couplers having a phenolic hydroxyl group or an active methylene group) are known.

(Problems to be Solved by the Invention) However, although the sharpness is improved by using such tabular grains, the desilvering property is extremely deteriorated because the specific surface area of the grains is increased, and the bleach accelerating compound releasing coupler is used. It has been found that even if is used, it is still insufficient for practical use. In particular, it was found that the deterioration of the desilvering performance was more remarkable when the J band-forming sensitizing dye effective for improving the sensitivity of the tabular emulsion was used.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material capable of satisfying both excellent desilvering performance and excellent sharpness at the same time.

Further, the object of claim (2) is to provide a silver halide capable of satisfying both excellent desilvering performance and excellent freshness at the same time when a J band-forming sensitizing dye which is more effective for improving sensitivity is used. It is to provide a color photographic light-sensitive material.

(Means for Solving Problems) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, and the total projected area of the silver halide emulsion grains. Of at least 50% are tabular silver halide grains having an average aspect ratio of 5: 1 or more, and at least one layer is represented by the following general formula [P-1] and general formula [P-2]. A silver halide color photographic light-sensitive material comprising at least one water-soluble polymer coupler having one or more repeating units.

The general formula [P-1] A A represents a repeating unit having a coupler moiety capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent.

However, the coupler moiety has a repeating site in its coupling-off group.

The general formula [P-2] BB represents a repeating unit that does not undergo a coupling reaction with the oxidation product of the aromatic primary amine developing agent. It has been found that

Next, the tabular silver halide emulsion used in the present invention will be described in detail.

In the tabular silver halide emulsion used in the present invention, the average aspect ratio means the average value of the ratio of the diameter to the thickness of the silver halide grains. That is, it is the average value of the values obtained by excluding the diameter of each silver halide grain by the thickness. Here, the diameter means the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope. Therefore, an average aspect ratio of 5: 1 or more means that the diameter of this circle is 5 times or more the thickness of the grain.

The proportion of the tabular silver halide grains in the projected area of all silver halide grains is 50% or more, preferably 70% or more, particularly preferably 85% or more.

By using such an emulsion, a silver halide photographic light-sensitive material having an excellent sharpness can be obtained. The sharpness is excellent because the light scattering by the emulsion layer using such an emulsion is extremely small as compared with the conventional emulsion layer.
This can be easily confirmed by those skilled in the art by experimental methods that can be routinely used. The reason why the light scattering of the emulsion layer using the tabular silver halide emulsion is small is not clear, but it is considered that the main surface of the tabular silver halide emulsion is oriented parallel to the support surface.

The diameter of tabular silver halide grains is 0.2 to 20.
μ, preferably 0.3 to 10.0 μ, particularly preferably 0.4.
~ 3.0μ. The particle thickness is preferably 0.5μ
It is the following. Here, the tabular silver halide grain diameter means the diameter of a circle having an area equal to the projected area of the grain. The grain thickness is represented by the distance between two parallel grains forming a tabular silver halide grain.

In the present invention, more preferred tabular silver halide grains have a grain diameter of 0.3 μm or more and 10.0 μm or less, a grain thickness of 0.3 μm or less, and an average (diameter / thickness) of 5 or more and 10 or less. . When the amount is more than this, the photographic performance may be abnormal when the light-sensitive material is bent, tightly wound, or touched with a sharp object, which is not preferable. More preferably, in the silver halide photographic emulsion, grains having a grain diameter of 0.4 μm or more and 5.0 μm or less and an average (diameter / thickness) of 5 or more and less than 10 occupy 85% or more of the total projected area of all silver halide grains. This is the case.

The tabular silver halide grains used in the present invention are silver chloride,
Any of silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide may be used, but silver bromide, silver iodobromide containing 30 mol% or less of silver iodide, or 50 mol% or less of silver chloride may be used. Silver chloroiodobromide and silver chlorobromide having a silver iodide content of 2 mol% or less are more preferable, and the composition distribution in the mixed silver halide may be uniform or localized.

The particle size distribution may be narrow or wide.

The tabular silver halide grain agent used in the present invention is Cugn
Ac, Chateau's report and Duffin's “Photographic Emulsio
n Chemistry "(Focal Press, New York 1966) pages 66-72, and APHTrivelli, WF Smith" Phot.Journ "
al " 80 (1940), page 285.
It can be easily prepared by referring to the methods described in Nos. 113927, 58-113928 and 58-127921.

For example, while forming a seed crystal in which tabular grains are present at 40% or more by weight in an atmosphere with a relatively high pAg value of pBr of 1.3 or less, while maintaining the same pBr value, the silver and halogen solutions are added at the same time. Obtained by growing crystals. In this grain growth process, it is desirable to add a silver and halogen solution so that no unfavorable crystal nuclei are generated.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and quality of the solvent, and the addition rate of silver salt and halide used during grain growth.

At the time of producing the tabular silver halide grains of the present invention, a silver halide solvent is optionally used to control the grain size, grain shape (diameter / thickness ratio, etc.), grain size distribution and grain growth rate. You can control.
The amount of the solvent used is preferably in the range of 10 ^{-2 to} 1.0% by weight of the reaction solution, and particularly preferably in the range of 10 ^-2 to 10 ^-1 % by weight. In the present invention, as the amount of solvent used increases, the particle size distribution can be made monodisperse and the growth rate can be promoted, while the thickness of particles also tends to increase with the amount of solvent used.

In the present invention, known silver halide solvents can be used. Examples of silver halide solvents that are often used include ammonia, thioethers, thioureas, thiocyanate salts and thiazoline thiones. Regarding thioethers, US Patent No.
Reference can be made to 3,271,157, 3,574,628 and 3,790,387. Further, regarding thioureas, JP-A-53-82408 and JP-A-55-77737, and regarding thiocyanate salts, U.S. Patent Nos. 2,222,264, 2,448,534 and
No. 3,320,069, regarding thiazoline thiones, JP
3-144319 can be referred to respectively.

In the process of formation or physical ripening of silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together. .

During the production of tabular silver halide grains used in the present invention, a silver salt solution added to accelerate grain growth (for example,
AgNO ₃ aqueous solution) and halide solution (eg KBr aqueous solution)
A method of increasing the addition rate, the addition amount, and the addition concentration of is preferably used. Regarding these methods, for example, U.S. Pat.No. 1,335,925, U.S. Pat.No. 3,650,757, and U.S. Pat.
2,900, 4,242,445, JP-A-55-142329, 55
Reference can be made to the description such as -158124.

The tabular silver halide grain of the present invention can be chemically sensitized if necessary. For chemical sensitization, for example, H.
Frieser edited by “Die Grundlagender Photographischen Proz
esse mit Silberhalogeniden "(AkademischeVerlagsges
ellschaft.1968) p.675-p.735 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, stannous salt, amine) Sensitization using compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds; noble metal compounds (eg, iron complex salts, Pt, I
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as r and Pd) can be used alone or in combination.

These examples refer to US Pat.
4,944, 2,278,947, 2,410,689, 2,7
28,668, 3,656,955, etc., for reduction sensitization method, U.S. Patent Nos. 2,419,974, 2,983,609, 4,054,
U.S. Pat. No. 2,399,083 for precious metal sensitization method such as 458
No. 2,448,060, British Patent No. 618,061 and the like.

From the viewpoint of silver saving, the tabular silver halide grain of the present invention is preferably gold-sensitized or sulfur-sensitized, or a combination thereof.

In the present invention, it is particularly effective to use a sensitizing dye represented by the following general formula (A).

General formula (A) (In the formula, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom or N—R ₅ .

Z ₂ is thiazole, benzothiazole, naphtho [1,2-
d] thiazole, naphtho [2,3-d] thiazole, selenazole, benzoselenazole, naphtho [1,2-d] selenazole, naphtho [2,3-d] selenazole, benzimidazole, naphtho [1,2-d] ] Imidazole, naphtho [2,3-d] imidazole, benzoxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, in addition to the group of nucleating atoms, m is 0; Is a 2-quinoline nucleating atom group, and when m represents 1 and Z ₁ represents N—R ₅ , thiazoline, selenazoline,
Represents an oxazole or 3,3-dialkylindolenine nucleating atom group. These heterocyclic nuclei may be substituted.

R ₅ represents an alkyl group or an alkenyl group having 6 or less carbon atoms which may be substituted with a hydroxyl group, a phenyl group, an alkoxy group, a halogen atom or an alkoxycarbonyl group [eg, sotyl group, ethyl group, propyl group, methoxy group] Ethyl group, ethoxycarbonylmethyl group,
2-fluoroethyl group, phenethyl group, etc.].

R ₁ and R ₂ represent an optionally substituted lower alkyl group or alkenyl group. More preferably a lower alkoxy group, a halogen atom, a carbamoyl group, a carboxy group,
Alkoxycarbonyl group, sulfo group, acylamino group,
Represents a lower alkyl group or a lower alkenyl group having 8 or less carbon atoms which may have a substituent such as a phenyl group or a hydroxy group which may be substituted [eg, methyl group, ethyl group, propyl group, pentyl group, Methoxymethyl group,
Ethoxyethyl group, 2,2,2-trifluoroethyl group, 2,
2,3,3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, carboxymethyl group, carboxyethyl group, 2-sulfoethyl group, 3-sulfoethyl group, 2-sulfobutyl group, 4-sulfobutyl group, phenethyl group, p-sulfophenethyl group, ethoxycarbonylethyl group, 2-hydroxy-3-sulfopropyl group,
2- (2-hydroxyethoxy) ethyl group, 2-acetylaminoethyl group, 2-methylsulfonylaminoethyl group, allyl group and the like].

R ₃ represents a hydrogen atom or R ₁ to form a 5-membered or 6-membered ring.

R ₄ is hydrogen if at least Z ₁ represents NR ₅ or Z ₂ represents benzimidazole, naphtho [1,2-d] imidazole or naphtho [2,3-d] imidazole nucleating atoms. An atom, Z ₁ does not represent N—R ₅ and Z ₂ also does not represent benzimidazole, naphtho [1,2-d] imidazole or naphtho [2,3-d] imidazole nucleating atoms. Group, propyl group, butyl group,
It represents a benzyl group, a phenethyl group or an optionally substituted phenyl group. [The substituent of the phenyl group is preferably a chlorine atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms].

V ₁ represents connecting with a hydrogen atom or V ₂ to form a condensed benzene ring.

V ₂ represents an electron-withdrawing group when Z ₁ represents N—R ₅ [Examples of the electron-withdrawing group include chlorine atom, fluorine atom, cyano group, alkoxycarbonyl group having 5 or less carbon atoms, and carbon number Preferred examples include alkylsulfonyl groups having 4 or less or perfluoroalkyl groups having 4 or less carbon atoms. When Z ₁ represents an oxygen atom, a sulfur atom, or a selenium atom, V ₂ represents a lower alkyl group having a carbon number of 7 or less, which may be branched, a lower alkoxy group having a carbon number of 6 or less, a hydroxy group, and a carbon number of 4 The following acylamino groups,
It represents a halogen atom, an alkoxycarbonyl group having 5 or less carbon atoms, a carboxy group, an optionally substituted phenyl group having 8 or less carbon atoms, or a hydrogen atom.

V ₃ except that represents the same meaning as V _2, also indicates that can form a fused benzene ring by linking with V _2, when Z ₁ represents N-R ₅ also represents a hydrogen atom.

The condensed benzene ring represented by connecting V ₁ and V ₂ or V ₂ and V ₃ may have a substituent, and preferable substituents are an alkyl group having 4 or less carbon atoms and 4 or less carbon atoms. And an alkoxy group, a hydroxy group, a halogen atom, an acylamino group having 4 or less carbon atoms, or an alkoxycarbonyl group having 5 or less carbon atoms.

m represents 0 or 1. X Is an acid anion residue (eg
For example, Cl , Br , I ，▲ C₂H_FiveOSO ₃▼, ▲ PF ₆▼ 、 ▲ BF _Four▼), n
₁Represents 0 or 1.

When the preferable examples of the hetero ring represented by Z ₁ or Z ₂ are listed, for example, thiazoline, 4-methylthiazoline, selenazoline, thiazole, 4-methylthiazole, 5-methylthiazole, 4-ethylthiazole, 4-phenylthiazole, 4,5 -Dimethylthiazole, 4,5-diphenylthiazole, 4-methylselenazole, 4-methyloxazole, 4,5-dimethyloxazole, 4-phenyloxazole, 5-methyl-4-phenyloxazole, benzothiazole, 5-methylbenzo Thiazole, 5-ethylbenzothiazole 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-chlorobenzothiazole, 5-chloro-6-methylbenzothiazole, 5,
6-dimethylbenzothiazole, 5-phenylbenzothiazole, 5-acetylaminobenzothiazole, 6-
Propionylaminobenzothiazole, 5,6-cymethoxybenzothiazole, benzoxazole, 5-methylbenzoxazole, 5-inpropylbenzoxazole, 5-methoxybenzoxazole, 5-ethoxybenzoxazole, 5-chlorobenzoxazole,
5-chloro-6-methylbenzoxazole, 5-phenylbenzoxazole, 5-p-tolylbenzoxazole, benzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 6 -Methylbenzoselenazole, 5-ethylbenzoselenazole, 5-phenylbenzoselenazole, 5-chlorobenzoselenazole, 5-
Chlorobenzimidazole, 5,6-dichlorobenzimidazole, 5-cyanobenzimidazole, 6-chloro-5-cyanobenzimidazole, 6-chloro-5-trifluthiobenzimidazole, 5-butoxycarbonylbenzimidazole, 5-ethoxycarbonyl Benzimidazole, 5-methylsulfonylbenzimidazole, 6-chloro-5-ethoxycarbonylbenzimidazole, naphtho [1,2-d] thiazole, naphtho [2,3-
d] thiazole, naphtho [1,2-d] selenazole, naphtho [2,3-d] selenazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole, 8-methylnaphtho [1, 2-d] oxazole, naphtho [2,3-d]
Imidazole, naphtho [1,2-d] imidazole, 2-
Quinoline, 6-methyl-2-quinoline, 6-hydroxy-2-quinoline, 6-methoxy-2-quinoline, 3,3-
Dimethyl indolenine, 3,3-diallyl indolenine,
Many can be mentioned, such as 3-ethyl-3-phenethylindolenine.

In the general formula (A), a more preferable compound is a compound represented by the following general formula (B) or (C).

General formula (B) In the formula, Z ₂₁ has the same meaning as Z ₁ . Z ₂₂ represents a sulfur atom, a selenium atom, N—R ₂₃ , or —CH═CH, and R ₂₃ has the same meaning as R ₅ .

R ₂₁ and R ₂₂ have the same meaning as R ₁ or R ₂ . More preferably, it may be substituted with a hydroxy group, a fluorine atom, a chlorine atom, a carboxy group, an alkoxycarbonyl group or a sulfo group, and a carbon atom in the chain may be substituted with an oxygen atom or a sulfur atom. It represents an alkyl group or an alkenyl group having a number of 6 or less, or a phenylalkyl group having a total number of carbon atoms of 7 or less, which may have the above-mentioned substituent.

V ₂₁ and V ₂₄ have the same meaning as V ₁ . V ₂₂ when Z ₂₁ represents NR ₅ and V when Z ₂₂ represents NR _23
25 has the same meaning as V ₂ when Z ₁ represents N—R ₅ . V ₂₂ and Z when Z ₂₁ is other than N-R ₅
V ₂₅ when ₂₂ is other than N—R ₂₃ has the same meaning as V ₂ when Z ₁ is other than N—R ₅ . Particularly preferred examples of V ₂₂ when Z ₂₁ represents an oxygen atom include a chlorine atom, an alkyl group having 6 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group or an alkyl group having 4 or less carbon atoms, and a carbon number. 3 or less alkoxy group, chlorine atom, a phenyl group which may be substituted with a hydroxy group and the like, when Z ₂₁ represents a sulfur atom or a selenium atom, particularly preferable V ₂₂ and Z ₂₂ are sulfur atoms, Alternatively, as particularly preferable V ₂₅ when representing a selenium atom, the above-mentioned Z
Substituents or acylamino groups having 2 or less carbon atoms shown as examples of particularly preferable V ₂₂ when ₂₁ represents an oxygen atom,
An alkylcarbonyl group having 5 or less carbon atoms, a carboxy group,
When V represents a hydrogen atom and Z ₂₂ represents a —CH═CH— group, particularly preferable V ₂₅ is an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, or a chlorine atom. And so on.

V ₂₃ when Z ₂₁ represents NR ₅ , V ₂₆ when Z ₂₂ represents NR ₂₃ and V when Z ₂₁ represents other than NR _{5.
When 26} and Z ₂₂ are other than N-R ₂₃ , V ₂₆ is Z respectively.
_It has the same meaning as V ₃ when ₁ represents N—R ₅ and V ₃ when Z ₁ represents something other than N—R ₅ , and particularly preferable examples of the latter include a hydrogen atom and a carbon number of 4 or less. Is an alkyl group, an alkoxy group having 4 or less carbon atoms, a hydroxy group, an alkylcarbonylamino group having 3 or less carbon atoms, a chlorine atom, or the like.

V ₂₂ represents that a fused benzene ring can also be formed by linking with V ₂₁ or V _23, and V ₂₅ represents a link with V ₂₄ or V ₂₆ when Z ₂₂ represents a sulfur atom, a selenium atom or NR _23. It means that a condensed benzene ring can also be formed. These condensed benzene rings may be further substituted with an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, a chlorine atom, or the like.

▲ X _{twenty one}▼ represents an acid anion residue, n_{twenty one}Is 0 or
Represents 1.

General formula (C) In the formula, Z ₃₁ and Z ₃₂ have the same meaning as Z ₁ .

R ₃₁ and R ₃₂ represent the same meaning as R ₂₁ or R _22, may represent a more favorable as defined above for R ₂₁ or R ₂₂ as preferred.

R ₃₃ represents a hydrogen atom or R ₃₁ to form a 5- or 6-membered ring.

At least one of a hydrogen atom in the case of representing the N-R _5, ethyl group if Z ₃₁ and Z ₃₂ both represent non-N-R ₅ for R ₃₄ Z ₃₁ or Z _32, a propyl group, a butyl group , Phenyl group, or phenethyl group, and the latter is particularly preferably ethyl group or propyl group.

V ₃₁ and V ₃₄ have the same meaning as V ₂₁ or V ₂₄ .

V ₃₂ and V ₃₃ are Z ₁ when Z ₃₁ represents NR _5.
There and V ₂ and V ₃ when representing the N-R _5, Z ₃₁ is oxygen atom, in the case of representing a selenium atom or a sulfur atom and V ₂ and V ₃ when Z ₁ represents a non-N-R ₅ They have the same meaning.

V ₃₅ and V ₃₆ are respectively V ₂ and V ₃ when Z ₁ represents N—R ₅ when Z ₃₂ represents N—R ₅ , and Z ₃₂ represents an oxygen atom, a selenium atom or a sulfur atom. When representing
When Z ₁ is other than N-R ₅ , it has the same meaning as V ₂ and V ₃ , respectively. V when Z ₃₁ represents N-R ₅
More preferable examples of V ₃₆ when ₃₃ and Z ₃₂ represent N—R ₅ include a hydrogen atom, a chlorine atom and a trifluoromethyl group, and V ₃₃ when Z ₃₁ represents other than N—R _5. And Z
More preferred V ₃₆ when ₃₂ represents something other than N-R ₅ . Examples thereof include a hydrogen atom, an alkyl group having 6 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, and an alkylcarbonylamino group having 4 or less carbon atoms in total. Also, when Z ₃₁ represents N-R ₅ , V ₃₂ and Z ₃₂ represent N-R ₅
More preferred examples of V ₃₅ when representing are: chlorine atom, fluorine atom, alkylcarbonyl group having 5 or less carbon atoms, alkylsulfonyl group having 3 or less carbon atoms, perfluoroalkyl group having 4 or less carbon atoms, or cyano group. However, particularly preferred examples include a chlorine atom, a trifluoromethyl group, and a cyano group. V ₃₂ when Z ₃₁ represents an oxygen atom
And more preferable examples of V ₃₅ when Z ₃₂ represents an oxygen atom, a chlorine atom, a phenyl group (which may be substituted with a methyl group, an ethyl group, a methoxy group, a chlorine atom or the like), a carbon number of 6 or less. And an alkoxy group having 4 or less carbon atoms, and more preferable examples of V ₃₂ when Z ₃₁ represents a sulfur atom or a selenium atom and V ₃₅ when Z ₃₂ represents a sulfur atom or a selenium atom. Is a chlorine atom, phenyl group (methyl group, ethyl group, methoxy group,
It may be substituted with a chlorine atom or the like), an alkyl group having 6 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, an alkylcarbonylamino group having 4 or less total carbon atoms,
Examples thereof include an alkoxycarbonyl group having a total carbon number of 5 or less, a carboxy group or a hydrogen atom.

Furthermore, V ₃₂ can be linked to V ₃₁ or V _33, and V ₃₅ can be linked to V ₃₄ or V ₃₆ to form a condensed benzene ring, respectively. These condensed benzene rings may further have a substituent. Examples of preferable substituents include an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a hydroxy group, a chlorine atom, or an alkoxycarbonyl group having 3 or less carbon atoms.

▲ X ₃₁▼ represents an acid anion residue, and n₃₁Is 0 or
Represents 1.

Next, specific examples of the compound used in the present invention will be listed.
The present invention is not limited to these.

To incorporate the sensitizing dyes used in the present invention in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water, acetone, methanol, ethanol, propanol, methyl cellosolve, 2 It may be added to the emulsion by dissolving it in a solvent such as 1,2,3,3-tetrafluoropropanol or N, N-dimethylformamide alone or in a mixed solvent. Ultrasonic waves can also be used for dissolution. Further, as a method of adding this sensitizing dye, US Pat.
No. 469,987, a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion.
46-24185 and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion; and JP-B-44-23,389 and JP-B-44- No. 27,555, JP-B No. 57-22,091 and the like, a method of dissolving in an acid and adding the solution to the emulsion, or adding an acid or a base in the form of an aqueous solution to the emulsion; US Pat. No. 3,822,135 As described in U.S. Pat. No. 4,006,025, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion; JP-A-53-102,733.
And a method of directly dispersing in a hydrophilic colloid and adding the dispersion to an emulsion as described in JP-A No. 58-105,141;
As described in JP-A-51-74624, it is possible to use a method in which a compound for red-shifting is dissolved and the solution is added to the emulsion.

The sensitizing dye represented by the general formula (A) may be added to the emulsion at any step of emulsion preparation known to be useful so far. For example, U.S. Pat.
5,766, U.S. Patent 3,628,960, U.S. Patent 4,183,756
No. 4,225,666, JP-A-58-184,142, and JP-A-60-196,749, as disclosed in JP-A-60-196,749, the silver halide grain forming step and / or the timing before desalting; As disclosed in JP-A-58-113,920, it may be added at any time or step immediately before chemical ripening or during the step; after chemical ripening and before coating, before the emulsion is coated. . In addition, U.S. Pat.
As disclosed in the specification of JP-A-58-7,629 and the like, compounds having the same structure alone or in combination with compounds having different structures, for example, during the grain forming step and the chemical aging step or chemical aging It may be added in divided portions such as after completion or before chemical aging or during the process and after completion. Good.

The sensitizing dye represented by the general formula (A) of the present invention may be added in an amount of 4 × 10 ⁻⁶ 8 × 10 ⁻³ mol per mol of silver halide, but a more preferable silver halide When the particle size is 0.2 to 1.2 μm, it is about 5 × 10 ^-5
2 × 10 ⁻³ mol is more preferable.

The tabular silver halide grains of the present invention can be spectrally sensitized with methine dyes other than those mentioned above, if necessary. In addition to the improvement in sharpness described above, a high spectral speed is also a feature of the tabular silver halide grains 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.

Examples of useful sensitizing dyes include German Patent No. 929,080.
U.S. Pat.Nos. 2,493,748, 2,503,776, and 2,
519,001, 2,912,329, 3,656,959, and
3,672,897, 4,025,349, British patent 1,242,588
And those described in JP-B-4414030.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are U.S. Pat.Nos. 2,688,545, 2,977,229, and 3,397,060.
No. 3,522,052, No. 3,527,641, No. 3,617,293
No. 3, No. 3,628,964, No. 3,666,480, No. 3,672,89
No. 8, No. 3,679,428, No. 3,814,609, No. 4,026,7
07, British Patent No. 1,344,281, Japanese Patent Publication No. 43-4936, 5
3-12375, JP-A Nos. 52-109925 and 52-110618.

The water-soluble polymer coupler used in the present invention is 40 ° C.
Is a polymer coupler that dissolves 1.0 wt% or more in distilled water. Those which dissolve in 5% by weight or more, more preferably 10% by weight or more in distilled water at 40 ° C. are advantageous in production.

In the water-soluble polymer coupler having [P-1] and [P-2] as repeating units, the ratio of the coupler part (A) capable of forming a dye to the non-coupler part (B) not forming a dye is a unit area. The amount of coated silver per unit can be arbitrarily changed depending on the amount of coated gelatin per unit area, pH of the coated emulsion, viscosity and the like. Preferably the coupler portion (A) is 5 to 95 mol
%, And the non-coupler portion (B) is 95 to 5 mol%.

The average molecular weight of the water-soluble polymer coupler used in the present invention is preferably 5 × 10 ^{3 to} 1.0 × 10 ⁷ . If the molecular weight is too small, the polymer coupler will tend to move, and if the molecular weight is too large, coating may be hindered. Therefore, the average molecular weight is more preferably 1 × 10 ⁴ to 2 × 10 ₆ . The amount of the polymer coupler in the present invention added per gelatin can also be arbitrarily changed.

Further, the addition amount of the polymer coupler in the present invention is 1 to the conversion silver amount (mole) to the number of moles of the coupler part (A).
It is advantageous in terms of photographic performance to add 200, preferably 5 to 100.

As a method for adding the polymer coupler used in the present invention to the coating liquid, an aqueous solution is added. It is added by dissolving it in a mixed solvent of water and an organic solvent miscible with water such as lower alcohol, THF, acetone and ethyl acetate. It is added after being dissolved in an alkaline aqueous solution or a mixed solution of an alkaline water-containing organic solvent. Etc., and it is also possible to disperse in a gelatin solution or add a small amount of a surfactant.

In any addition method, the water-soluble polymer coupler used in the present invention is not in the form of oil droplets or latices in the coating liquid and the coating film, interacts with the hydrophilic binder, and is compatible to some extent. It seems that there is.
Therefore, the hardness of the film is considered to be considerably harder than that of the oil-soluble (including latex type) polymer coupler.

Preferred examples of the ethylenically unsaturated monomer forming the repeating unit represented by A in the general formula [P-1] are represented by the following general formula [I].

General formula [I] In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and L ¹ is (R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms), —COO—, —NHC
O-, -OCO-, (R ³ and R ⁴ each independently represent hydrogen, hydroxyl, a halogen atom or a substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), (R ² , R ³ and R ⁴ are the same as above), L ₂ represents a linking group connecting L ¹ and Q, m represents 0 or 1, n represents 0 or 1, and Q is oxidized. Represents a coupler residue capable of forming a dye by coupling with an aromatic primary amine developing agent, which is bonded to a moiety other than Q in the general formula [I] at the coupling site.

Linking group represented by L ² is specifically represented by _{^{X 1 J 1 -X 2 p J}} 2 -X 3 q J 3 r s.

J ¹ , J ² , and J ³ may be the same or different, and -CO-,-
SO ₂ −, (R ⁵ is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon atoms), (R ⁵ is as defined above), (R ⁵ is as defined above, R ⁶ is an alkylene group having 1 to about 4 carbon atoms), (R ⁵ and R ⁶ are as defined above, R ⁷ is a hydrogen atom, an alkyl group (having 1 to 6 carbon atoms) or a substituted alkyl group (having 1 to 6 carbon atoms)), —O—, —S—, (R ⁵ and R ⁷ are as defined above), (R ⁵ and R ⁷ are as defined above), -COO-, -COC-, (R ⁵ is as defined above), (R ⁵ is as defined above) and the like.

X ¹ , X ² and X ³ may be the same or different and each represents an alkylene group, a substituted alkylene group, an arylene group, a substituted arylene group, an aralkylene group or a substituted aralkylene group.

p, q, r and s represent 0 or 1.

In the above general formula [I], X ¹ , X ² and X ³ may be the same or different and each represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or a phenylene group, and an alkylene group. The group may be linear or branched.
Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene and m-.
Examples include phenylene and methylphenylene.

Further, X ¹ , X ² , an alkylene group represented by X ³ , a substituent of an aralkylene group or a phenylene group, a halogen atom, a nitro group, a cyano group, an alkyl group, a substituted alkyl group, an alkoxy group, a substituted alkoxy group,- A group represented by NHCOR ⁸ (R ⁸ represents alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl),
-NHSO ₂ R ⁸ (R ⁸ is as defined above), -SOR ⁸ (R ⁸ is as defined above), -SO ₂ R ⁸ (R ⁸ is as defined above), -COR ⁸ (R ⁸ is as defined above) ), A group represented by (R ⁹ and R ¹⁰ may be the same or different from each other and represent a hydrogen atom, alkyl, substituted alkyl, phenyl, substituted phenyl, aralkyl, or substituted aralkyl), (R ⁹ and R ¹⁰ have the same meanings as described above), an amino group (which may be substituted with alkyl), a hydroxyl group or a group which is hydrolyzed to form a hydroxyl group. When there are two or more substituents, they may be the same or different.

Further, examples of the substituents of the above substituted alkyl group, substituted alkoxy group, substituted phenyl group, and substituted aralkyl group include a hydroxyl group, a nitro group, an alkoxy group having 1 to about 4 carbon atoms, and -NH.
SO ₂ R ⁸ (R ⁸ is as defined above), a group represented by —NHCOR ⁸ (R
⁸ is synonymous with the above), (R ⁹ and R ¹⁰ are as defined above), A group represented by (R ⁹ and R ¹⁰ are as defined above), —SO ₂ R ⁸ (R ⁸
Is the same as the above), —COR ⁸ (R ⁸ is the same as the above), a halogen atom, a cyano group, an amino group (which may be substituted with alkyl) and the like.

Next, among the color coupler residues represented by Q in the general formula [I], as cyan color forming coupler residues, phenol type [II], [V] represented by the following general formula,
Alternatively, a naphthol type [III] or [IV] compound (each hydrogen atom other than the hydrogen atom of the hydroxyl group is released to form L ¹
linked to _m L ² _n ) is preferred.

In the formula, R ¹¹ represents a group capable of substituting for a phenol ring or a naphthol ring, and examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxy group, a sulfo group, a cyano group, an aliphatic group, an aromatic group, and a heterocyclic group, Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyloxy group, acyl group, aliphatic oxy group, aliphatic thio group, aliphatic sulfonyl group, aromatic oxy group, aromatic thio group, aromatic Examples thereof include a sulfonyl group, a sulfamoylamino group, a nitro group and an imide group. The carbon number of R ¹¹ is 0 to 30.

R ¹² is _{^{-CONR 14 R 15, -NHCOR 14,}} -NHCOOR 16, -NHSO 2 R
^16, represents -NHCONR ¹⁴ R ¹⁵ or _{^{-NHSO 2 R 14 R 15, R}} 14
And R ¹⁵ is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, methyl, ethyl, butyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, heptafluoropropyl, dodecyloxy). Propyl, 2,4-di-tert-amylphenoxypropyl, 2,4
-Di-tert-amylphenoxybutyl), carbon number 6 to 30
An aromatic group (eg, phenyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 2-chloro-5-dodecyloxycarbonylphenyl), a heterocyclic group having 2 to 30 carbon atoms (eg, 2-pyridyl, 4-pyridyl, 2-furyl, 2-thienyl), R ¹⁶ has 1 to 3 carbon atoms.
0 aliphatic groups (eg, methyl, ethyl, butyl, dodecyl, hexadecyl), 6 to 30 aromatic groups (eg, phenyl, tolyl, 4-chlorophenyl, naphthyl), heterocyclic groups (eg, 4-pyridyl, quinolyl) , 2-frill)
Represents R ¹⁴ and R ¹⁵ are bonded to each other to form a heterocycle (eg,
Morpholine ring, piperidine ring, pyrrolidine ring) may be formed. p'is 0 to 3, s'is 0 to 2, q ',
r'represents an integer of 0 to 4, respectively.

X ⁴ represents an oxygen atom, a sulfur atom or R ¹⁷ N, and R ¹⁷
Represents a hydrogen atom or a monovalent group. When R ¹⁷ represents a monovalent group, examples of R ¹⁷ include an aliphatic group having 1 to 30 carbon atoms (eg, methyl, ethyl, butyl, methoxyethyl, benzyl), an aromatic group having 6 to 30 carbon atoms ( For example, phenyl,
Tolyl), a heterocyclic group having 2 to 30 carbon atoms (eg, 2-pyridyl, 2-pyrimidyl), a carbonamido group having 1 to 30 carbon atoms (eg, formamide, acetamide, N-methylacetamide, benzamide), carbon number 1-30 sulfonamide group (for example, methanesulfonamide, toluenesulfonamide, 4-chlorobenzenesulfonamide), an imide group having 4-30 carbon atoms (for example, succinimide), -OR ¹⁸ , SR ¹⁸ , -COR ¹⁸ , -CONR ¹⁸ R ¹⁹ , -COCOR
¹⁸ , -COCONR ¹⁸ R ¹⁹ , -COOR ²⁰ , -COCOOR ²⁰ , -SO
_{^{2 R 20, -SO 2 OR 20}} , can be mentioned -SO ₂ NR ¹⁸ R ¹⁹ and -NR ¹⁸ R ^19. R ¹⁸ and R ¹⁹ may be the same or different and each is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms (for example, methyl, ethyl, butyl, dodecyl, methoxyethyl, trifluoromethyl, hepta). Fluoropropyl), an aromatic group having 6 to 30 carbon atoms (eg, phenyl,
Tolyl, 4-chlorophenyl, pentafluorophenyl, 4-cyanophenyl, 4-hydroxyphenyl) or a heterocyclic group having 2 to 30 carbon atoms (for example, 4-pyridyl, 3
-Pyridyl, 2-furyl). R ¹⁸ and R ¹⁹ may combine with each other to form a heterocycle (eg, morpholino, pyrrolidino).

Examples of R ²⁰ include the substituents shown for R ¹⁸ and R ¹⁹ excluding a hydrogen atom.

Z ¹ represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Examples of the leaving group are a halogen atom (eg, fluorine, chlorine, bromine, iodine), an aliphatic oxy group having 1 to 30 carbon atoms (eg, methoxy, ethoxy, 2-hydroxyethoxy, carboxymethyloxy, 3-carboxy). Propyloxy, 2-methoxyethoxycarbamoylmethyloxy, 2-methanesulfonylethoxy, 2-carboxymethylthioethoxy, triazolylmethyloxy), an aromatic oxy group having 6 to 30 carbon atoms (for example, phenoxy, 4-
Hydroxyphenoxy, 2-acetamidophenoxy,
2,4-dibenzenesulfonamidophenoxy, 4-phenylazophenoxy), a heterocyclic oxy group having 2 to 30 carbon atoms (for example, 4-pyridyloxy, 1-phenyl-5-tetrazolyloxy), 1 carbon atom To 30 aliphatic thio groups (eg, dodecylthio), aromatic thio groups having 6 to 30 carbon atoms (eg, 4-dodecylphenylthio), 2 to 30 carbon atoms
A heterocyclic thio group (eg, 4-pyridylthio, 1-phenyltetrazol-5-ylthio), an acyloxy group having 2 to 30 carbon atoms (eg, acetoxy, benzoyloxy, lauroyloxy), a carbonamido group having 1 to 30 carbon atoms ( For example, dichloroacetylamide, trifluoroacetamide, heptafluorobutanamide, pentafluorobenzamide), a sulfonamide group having 1 to 30 carbon atoms (for example, methanesulfonamide, toluenesulfonamide), an aromatic azo having 6 to 30 carbon atoms. Group (eg, phenylazo, 4-chlorophenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo), an aliphatic oxycarbonyloxy group having 1 to 30 carbon atoms (eg, ethoxycarbonyloxy, dodecyloxycarbonyloxy) ), Carbon number 6-30 Group oxycarbonyl group (e.g., phenoxycarbonyloxy), a carbon number 1
~ 30 carbamoyloxy groups (eg, methylcarbamoyloxy, dodecylcarbamoyloxy, phenylcarbamoyloxy), heterocyclic groups having 1 to 30 carbon atoms and continuous at the active position of the coupler with a nitrogen atom (eg, succinimide, phthalimide , Hydantoinyl, pyrazolyl,
2-benzotriazolyl) and the like.

Y'represents a group of atoms necessary for forming a 5- to 7-membered ring together with the carbon atom to which it is bonded. More specifically, −
O-, -S-, -N =, = N-, Represents either alone or in combination. R ″ and R each independently represent a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an arylcarbonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, or a cyano group.

Next, examples of the substituents preferably used in the present invention are listed below.

Preferred as R ¹¹ are halogen atom (eg, fluorine, chlorine, bromine, etc.), aliphatic group (eg, methyl, ethyl, isopropyl), carbonamido group (eg, acetamide, benzamide), sulfonamide group (eg,
Methanesulfonamide, toluenesulfonamide) and the like.

Preferred as R ¹² is -CONR ¹⁴ R ¹⁵ , for example, carbamoyl, ethylcarbamoyl, morpholinocarbonyl, dodecylcarbamoyl, hexadecylcarbamoyl, decyloxypropyl, dodecyloxypropyl,
2,4-di-tert-amylphenoxypropyl, 2,4-di-
There is tert-amylphenoxybutyl.

Preferred as X ⁴ is R ¹⁷ N, and further preferred as R ¹⁷ is —COR ¹⁸ (eg, formyl, acetyl, trifluoroacetyl, chloroacetyl, benzoyl, pentafluorobenzoyl, p-chlorobenzoyl), —COOR. ²⁰ (for example, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, methoxyethoxycarbonyl, phenoxycarbonyl), -SO ₂ R ²⁰ (for example, methanesulfonyl, ethanesulfonyl, butanesulfonyl, hexadecanesulfonyl, benzenesulfonyl, toluenesulfonyl) , P
-Chlorobenzenesulfonyl), -CONR ¹⁸ R ¹⁹ (N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N, N
-Dibutylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl, 4-cyanophenylcarbamoyl,
3,4-dichloro-phenylcarbamoyl, ^{_{4-methanesulfonyl-phenylcarbamoyl), - SO 2 NR 18 R}} 19 ( e.g., N, N-dimethylsulfamoyl, N, N-diethyl sulfamoyl, N, N-dipropyl Moyl) is a group represented by. More particularly preferable ones of R ¹⁷ are
It is a group represented by —COR ¹⁸ , —COOR ²⁰ and —SO ₂ R ²⁰ .

Preferred groups as Z ¹ are a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, a heterocyclic thio group and an aromatic azo group.

The coupler represented by the general formula is a dimer or a multimer of the substituents R ¹¹ , R ¹² , X ⁴ or Z ¹ which are bonded to each other through a divalent or higher polyvalent linking group. May be. In this case, the number of carbon atoms shown in each substituent is not limited to this.

The magenta color-forming coupler residue is represented by the general formula [VI],
[VII], [VIII], [IX], [X], [XI] and [X]
II] a coupler residue (Ar, Z ² , R ^{21 to} R ³³ is linked to L ¹ _m L ² _n at any part. In the case of the general formula [V], more preferred is R ²¹ This is the case of directly connecting to the substitution position.).

In the formula, Ar is a substituent of a well-known type at the 1-position of the 2-pyrazolin-5-one coupler, such as an alkyl group, a substituted alkyl group (eg, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), an aryl group or a substituted group. Aryl group [As a substituent, an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, methoxy,
Ethoxy), aryloxy groups (eg phenyloxy), alkoxycarbonyl groups (eg methoxycarbonyl), acylamino groups (eg acetylamino), carbamoyl groups, alkylcarbamoyl groups (eg methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl groups (eg dimethyl). Carbamoyl), arylcarbamoyl group (eg phenylcarbamoyl), alkylsulfonyl group (eg methylsulfonyl), arylsulfonyl group (eg phenylsulfonyl), alkylsulfonamide group (eg methanesulfonamide),
Aryl sulfonamide group (eg phenyl sulfonamide), sulfamoyl, alkyl sulfamoyl group (eg ethylsulfamoyl), dialkylsulfamoyl group (eg dimethylsulfamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio) , A cyano group, a nitro group, and a halogen atom (eg, fluorine, chlorine, bromine, etc.), and when there are two or more substituents, they may be the same or different. Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group. ], A heterocyclic group (eg, triazole, thiazole, benzthiazole, furan, pyridine, quinaldine, benzoxazole, pyrimidine, oxazole, imidazole, etc.).

R ²¹ represents an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido,
Phenylureido), and these substituents include a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradecyl), an alkoxy group (eg, Methoxy, ethoxy, 2-ethylhexyloxy, tetradecyloxy and the like), acylamino group (for example, acetamide, benzamide, butanamide, octanamide, tetradecanamide, α- (2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert-
Amylphenoxy) butyramide, α- (3-pentadecylphenoxy) hexanamide, α- (4-hydroxy-3-tert-butylphenoxy) tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-
5-tetradecylpyrrolidin-1-yl, N-methyl
Tetradecane amide), sulfonamide group (for example, methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide), sulfamoyl group (For example, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, N, N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N- [3- (Dodecyloxy) -propyl] sulfamoyl, N- [4
-(2,4-di-tert-amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl, etc., a carbamoyl group (for example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N- [4- (2,4-di-tert-amylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2,5-dioxo-) 1-
Oxazolidinyl, 3-dodecyl-2,5-dioxo-1
-Hydantoinyl, 3- (N-acetyl-N-dodecylamino) succinimide), alkoxycarbonyl group (e.g. methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl group (e.g. methoxysulfonyl, butoxysulfonyl, octyl). Oxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (eg, phenoxysulfonyl, p-methylphenoxysulfonyl, 2,4-di-tert-amylphenoxysulfonyl, etc.), alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonyl) , Octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl),
An arylsulfonyl group (eg, benzenesulfonyl,
4-nonylbenzenesulfonyl), an alkylthio group (eg, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio, etc.), an arylthio group (eg, phenylthio, p -Tolylthio), an alkyloxycarbonylamino group (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), an alkylureido group (eg, N-methylureido, N, N-dimethylureido) , N-methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido), an acyl group (for example, acetyl, benzoyl, octadecanoyl, p-dodecanoamidobenzoyl), a nitro group, Examples thereof include a ruboxyl group, a sulfo group, a hydroxy group and a trichloromethyl group.

However, among the above substituents, the number of carbon atoms defined as an alkyl group represents 1 to 36, and the number of carbon atoms defined as an aryl group represents 6 to 38.

R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ ,
R ³² and R ³³ are each a hydrogen atom and a hydroxyl group,
Each of them is an unsubstituted or substituted alkyl group (preferably having 1 to 20 carbon atoms, for example, methyl, propyl, t-butyl, trifluoromethyl, tridecyl, etc.) and an aryl group (preferably having 6 to 20 carbon atoms). For example, phenyl,
4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-methoxyphenyl), a heterocyclic group (for example, 2-
Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), alkylamino group (preferably having 1 carbon atom)
~ 20 things. For example, methylamino, diethylamino,
t-butylamino), acylamino group (preferably having 2 to 20 carbon atoms, for example, acetylamino, propylamide, benzamide), anilino group (eg phenylamino, 2-chloroanilino), alkoxycarbonyl group (preferably Having 2 to 20 carbon atoms, such as methoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl), an alkylcarbonyl group (preferably having 2 to 20 carbon atoms, such as acetyl, butylcarbonyl, cyclohexylcarbonyl), arylcarbonyl A group (for example, preferably having 7 to 20 carbon atoms, benzoyl, 4-t-butylbenzoyl), an alkylthio group (preferably having 1 to 20 carbon atoms, such as methylthio,
Octylthio, 2-phenoxyethylthio), arylthio group (preferably having 6 to 20 carbon atoms, for example, phenylthio, 2-butoxy-t-octylphenylthio), carbamoyl group (preferably having 1 to 20 carbon atoms). For example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl, N-N-methyl-N-butylcarbamoyl), sulfamoyl group (preferably having up to 20 carbon atoms. For example, N-ethylsulfamoyl, N, N-diethylsulfamoyl, N, N-dipropylsulfamoyl)
Alternatively, it represents a sulfonamide group (preferably having a carbon number of 1 to 20, for example, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide).

Z ² represents a hydrogen atom or a group capable of splitting off with an oxidized product of an aromatic primary amine developing agent by a coupling reaction. Examples of the group capable of splitting off include a halogen atom (for example, chlorine and bromine), a coupling splitting off group linked by an oxygen atom (for example, acetoxy, propanoyloxy, benzoyloxy,
Ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxy,
4-Methanesulfonamide-phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzoloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyloxy , 2-benzothiazolyloxy), a coupling-off group linked by a nitrogen atom (for example, those described in JP-A-5999437, specifically benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluoro). Butanamide,
2,3,4,5,6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-
Dimethyl-2,4-dioxo-3-oxazolidinyl, 1
-Benzyl-5-ethoxy-3-hydantoinyl, 2-
Oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2-4-triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl, 5-methyl -1,2,3,4-tetrazole-
1-yl, benzimidazolyl), a coupling-off group linked by a sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4-methanesulfonylphenylthio, 4-octanesulfonamidophenyl) Thio, benzylthio, 2
-Cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl). The releasable group is preferably a halogen atom, a coupling-off group linked by an oxygen atom, a coupling-off group linked by a nitrogen atom, and particularly preferably an aryloxy group, a chlorine atom, a pyrazolyl group, an imidazolyl group, triazolyl. It is a base.

The yellow color-forming coupler residue is an acylacetanilide type, particularly a pivaloylacetanilide type [XIII], [XIII '], a benzoylacetanilide type [XIV], [XIV'], [XV] represented by the following general formula. , [XV ′]
Are preferred (in the general formula, the free bond portion is L ¹
_{Connect to m} L ² _n . ) In the formula, R ³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each a hydrogen atom or a well-known substituent of a yellow color forming coupler residue such as an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom or an alkoxycarbamoyl group. ,
Aliphatic amide group, alkylsulfamoyl group, alkylsulfonamide group, alkylureido group, alkyl-substituted succinimide group, aryloxy group, aryloxycarbonyl group, arylcarbamoyl group, arylamide group, arylsulfamoyl group, arylsulfone Amide group, arylureido group, carboxy group, sulfo group,
It represents a nitro group, a cyano group, a thiocyano group or the like, and these substituents may be the same or different.

Z ³ is a hydrogen atom or the following general formula [XVI], [XVII], [XVI
II] or [XIX].

R ³⁸ represents an optionally substituted aryl group or heterocyclic group.

R ³⁹ and R ⁴⁰ are each a hydrogen atom, halogen atom, carboxylic acid ester group, amino group, alkyl group, alkylthio group, alkoxy group, alkylsulfonyl group, alkylsulfinyl group, carboxylic acid group, sulfonic acid group, unsubstituted or substituted. Represents a phenyl group or a heterocycle, which groups may be the same or different.

W ₁ in the formula Represents a non-metal atom required to form a 4-membered ring, 5-membered ring or 6-membered ring.

Of the general formula [XIX], [XX] to [XXII] are preferable.

In the formula, R ⁴¹ and R ⁴² are each a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a hydroxy group, and R ⁴³ , R ⁴⁴ and R ⁴⁵ are each a hydrogen atom, an alkyl group, an aryl group or an aralkyl group. Or, an acyl group and W ₂ represents an oxygen atom or a sulfur atom.

Preferable examples of the ethylenically unsaturated monomer giving the repeating unit represented by B include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid), esters derived from these acrylic acids, or Amides (for example, acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, 2-methoxyethyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, cyclohexyl Xyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, β-alkoxyethyl (meth) acrylate (for example, 2-methoxyethyl acrylate, 2-
Methoxyethyl methacrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-
Ethoxyethyl methacrylate, 2-butoxyethyl acrylate, 2-n-propyloxyethyl methacrylate, 2- (2-methoxy) ethoxyethyl acrylate, etc.), β-sulfonamidoethyl (meth) acrylate, β-carbonamidoethyl (meth ) Acrylate, β-alkoxyethylacrylamide (some alkoxy groups further include a plurality of substituted alkoxy groups), β-sulfonamidoethylacrylamide, β-
Carbonamidoethylacrylamide etc.), vinyl ester (eg vinyl acetate, vinyl laurate) acrylonitrile, methacrylonitrile, dienes (eg butadiene, isoprene), aromatic vinyl compounds (eg styrene, divinylbenzene and its derivatives, eg vinyltoluene) , Vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine. , And 2- and 4-vinylpyridine, ethylene, propylene, 1-butene, isobutene and the like.

Next, typical examples of monomer couplers which give coupler units having a coupler residue capable of forming a dye by coupling with an aromatic primary amine developing agent represented by the general formula [I] which is a color-forming portion are shown below. However, it is not limited to this.

The monomer couplers used in the coupler of the present invention include the following (19) to (28), (34), (53) and (54)
And the others are reference couplers.

The monomer couplers may be used individually or in a combination of several types.

Preferred examples of the ethylenically unsaturated monomer forming the repeating unit represented by B in the general formula [P-2] which does not couple with the oxidation product of the aromatic primary amine developing agent used in the present invention are shown. For example, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester,
Crotonic acid, crotonic acid esters, vinyl ester,
Examples thereof include maleic acid, maleic acid diester, fumaric acid, fumaric acid diester, itaconic acid, itaconic acid diester, acrylamides, methacrylamides, vinyl ethers and styrenes. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions.

More specific examples of these monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, 3-acryloylpropane sulfonic acid, acetoacetoxyethyl acrylate, acetoxy. Examples thereof include ethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, and 2- (2-methoxyethoxy) ethyl acrylate. As the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, te
Examples thereof include rt-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid. Vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl methoxyacetate and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of the itaconic acid diester include diethyl itaconic acid, dimethyl itaconic acid and dibutyl itaconic acid. Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, isopropyl acrylamide, n-butyl acrylamide, hydroxymethyl acrylamide, diacetone acrylamide, acryloylmorpholine, and acrylamido-2-methylpropanesulfonic acid. As methacrylamides, methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide,
Examples thereof include dimethyl methacrylamide and dimethyl methacrylamide. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether. As styrenes, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, esulstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene,
Methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, vinyl benzoic acid methyl ester, 2-methylstyrene, styrene sulfonic acid, vinyl benzoic acid and the like can be mentioned.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocyclic compounds (eg, vinyl pyridine), unsaturated nitriles (eg, acrylonitrile).

Among these monomers, those having high hydrophilicity are particularly preferable.

Further, it is also preferable to use the following monomers B-1 to B-25 as B.

The water-soluble polymer coupler of the present invention is synthesized by a polymerization initiator,
As the polymerization solvent, JP-A-58-120252 and JP-A-58-1459 are used.
44, JP-A-58-111756, JP-A-58-224352, JP-A-59-42543, JP-A-59-271956, JP-A-59-22825.
2, the compounds described in JP-A-60-35732 and JP-A-60-46555 are used.

It is necessary to set the polymerization temperature in relation to the molecular weight of the polymer produced, the type of initiator, etc.
Although the above is possible, polymerization is usually carried out in the range of 30 ° C to 100 ° C.

Synthesis Example (1) Synthesis of water-soluble polymer coupler PC-1 In a 300 ml three-necked flask, 20 g of coupler monomer (1),
Non-color-forming monomer B-7 4.1 g, 2-acrylamide-2
-Sodium methylpropyl sulfonate 14g and DMF16
0 ml was mixed and heated to 80 ° C. under a nitrogen stream, and 5 ml of a DMF solution containing 0.4 g of dimethyl azobisinbutyrate was added to initiate polymerization. After polymerizing for 3 hours, it was cooled and reprecipitated with 1000 ml of acetone. 34.2g of polymer coupler PC after drying
1 was obtained. This polymer is 48.4 according to the determination of chlorine atom.
It was discovered that wt% coupler monomer unit was included.

Synthesis example (2) Synthesis of water-soluble polymer coupler PY-6 18 g of coupler monomer (47) in a 300 ml three-necked flask,
Non-color-forming monomer B-7 2.1 g, 2-acrylamide-2
-Sodium methylpropane sulfonate 11.5 g and DMF
200 ml was mixed and heated to 80 ° C. under a nitrogen stream, and 5 ml of a DMF solution containing 0.4 g of dimethyl tzubisisobutyrate was added to initiate polymerization. Polymerized for 3 hours and cooled, then Sanko Junyaku dialysis membrane 50FT C
Dialysis was performed at -65 for 3 days. 27.5 by freeze-drying
g of polymer coupler PY-6 was obtained.

The polymer was found to contain 55.2 wt% of coupler monomer unit by quantification of chlorine atoms.

Examples of the water-soluble polymer coupler used in the present invention are shown below, but the invention is not limited thereto.

The water-soluble polymer coupler of the present invention has the following C-
4, PC-9, PC-13, PC-15, PM-10, PY-6 to PY10, and others are reference couplers.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers of the emulsion layer and the non-photosensitive layer and the layer order. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to red light, and in a multilayer silver halide color photographic light-sensitive material, the unit light-sensitive layers are generally arranged in order from the support side to the red color-sensitive layer and the green color. The color sensitive layer and the blue color sensitive layer are installed in this order. However, the order of setting may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer, JP-A-61-43748, 59-113438,
No. 59-113440, No. 61-20037, No. 61-20038 may contain a coupler as described in the specification, DIR compounds and the like, and contains a color mixing inhibitor as commonly used. You may stay.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045.
No. 2 of high-speed emulsion layer and low-speed emulsion layer as described in No.
A layer structure can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Further, JP-A-57-112751 and 62-
As described in 200350, 62-206541, 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the lower side of the support.

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) / order, or BH / BL /
It can be installed in the order of GL / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in Japanese Patent Publication No. 55-34932,
It is also possible to arrange the layers in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. In addition, JP-A-56-25738 and 6
It is also possible to arrange the blue-sensitive layer / GL / RL / GH / RH in this order from the side farthest from the support, as described in the specification of 2-63936.

Further, 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. A silver halide emulsion layer having a low degree of sensitization is arranged, and the sensitivities are gradually reduced toward the support.
An example is an array composed of layers. Even in the case of being composed of such three layers having different sensitivities, the method disclosed in JP-A-59-2024
As described in Japanese Patent No. 64, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same photosensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material 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 about 2 mol% to about 25 mol%
Up to silver iodobromide or silver iodochlorobromide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”and ibid. No. 18716 (November 1979), 64
P.Glafkides, Chemic et Phisique Photographi, “Physics and Chemistry of Photography” by Graphide, page 8
Que, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin.
Published by Focal Press (GFDuffin, Photographic Emul
sion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikman et al., VLZnlikman et al. Making and Coating Photograph.
ic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), 14: 248-257 (1970); U.S. Pat. No. 4,434,2
No. 26, No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like can be easily prepared.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add a compound capable of being immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503 to a light-sensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
52, Japanese Patent Publication 58-10739, British Patents 1,425,020, 1,476,760, U.S. Patents 3,973,968, 4,314,02
Those described in No. 3, No. 4,511,649 and European Patent No. 249,473A are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3,725,064, Research Disclosure No. 2422 (June 1984), Japanese Patent Publication No. 60-33552.
Issue, Research Disclosure No. 24230 (June 1984
Month), JP-A-60-43659, JP-A 61-72238, JP-A 60-3573.
No. 0, No. 55-118034, No. 60-185951, U.S. Pat.
Those described in 00,630, 4,540,654, 4,556,630 and the like are particularly preferable.

Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat. Nos. 4,052,212 and 4,1.
No. 46,396, No. 4,228,233, No. 4,296,200, No. 2,
No. 369,929, No. 2,801,171, No. 2,772,162, No.
No. 2,895,826, No. 3,772,002, No. 3,758,308, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,32
9,729, European Patents 121,365A, 249,453A, U.S. Patents 3,446,622, 4,333,999, 4,451,55.
No. 9, No. 4,427,767, No. 4,690,889, No. 4,254,2
Those described in No. 12, No. 4,296,199, and JP-A No. 61-42658 are preferable.

Colored couplers to correct unwanted absorption of colored dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57,39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282,
No. 4,409,320, No. 4,576,910, British patent 2,102,17
It is described in No. 3 etc.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release a development inhibitor are disclosed in the above-mentioned RD 17643, VII to F patents, JP-A-57-151944 and 57-154234.
Nos. 60-184248 and U.S. Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include U.S. Pat. Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP 60-1
85950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252, etc. Dye releasing couplers, U.S. Pat.
Examples thereof include ligand releasing couplers described in JP-A No. 477 and the like.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester Kinds (trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline and the like) hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, a boiling point of about 30 ° C. or higher, preferably an organic solvent of 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, and 2-. Examples include ethoxyethyl acetate and dimethylformamide.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color blur films and color reversal papers.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
Development can be carried out by a usual method described on pages 28 to 29 of 643 and 615, left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β
-Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline and their sulfates, Hydrochloride or p-toluene sulfonic acid salt etc. are mentioned. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, various compounds such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octanes, etc. Preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents typified by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenedia. Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine- Representative examples are N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

When the reversal process is performed, black and white development is usually performed before color development. This black-and-white developer contains hydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or N-methyl-
Known black-and-white developing agents such as aminophenols such as p-aminophenol can be used alone or in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the high temperature and high pH and using the color developing agent as a high concentration.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications; U.S. Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 5, JP-A-53-32736, JP-A-53-57831, and JP-A-53-37418
No. 53-72623, No. 53-95630, No. 53-95631,
53-104232, 53-124424, 53-141623, and
53-28426, Research Disclosure No. 17129
Compounds having a mercapto group or a disulfide group described in JP-A No. 1978/1978; thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-
20832, 53-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamine compounds described in JP-B-45-8836; Other JP-A-49-42,434, 49-59,644, 53-94,927,
The compounds described in Nos. 54-35,727, 55-26,506, and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858
The compounds described in JP-A No. 1,290,812 and JP-A No. 53-95,630 are preferable. Further, the compounds described in US Pat. No. 4,522,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n Engineers Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is a solution,
The method of reducing calcium ion and magnesium ion described in JP-A-62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" It is also possible to use the bactericides described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by The Society of Hygiene Technology, "Encyclopedia of Antibacterial and Antifungal Agents", edited by the Society for Antibacterial and Antifungal Society of Japan.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. -8543, 58-14834, and 60-220345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various breakers of color developing agents. For example, indaniline compounds described in U.S. Pat.No. 3,342,597, No. 3,342,599, Schiff's base type compounds described in Research Disclosures 14,850 and 15,159, aldol compounds described in No. 13,924, metals described in U.S. Pat.No. 3,719,492. Examples thereof include salt complexes and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64339, JP-A-57-144547, and JP-A-58-1.
No. 15438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is described in US Pat.
0,626, JP-A-60-133449, 59-218443, 61
It can also be applied to the photothermographic materials described in, for example, No. 238056 and European Patent 210,660A2.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 An aqueous solution of 30 g of inert gelatin, 6 g of potassium bromide and 1 of distilled water was stirred at 75 ° C. and 5.0 g of silver nitrate was added thereto.
After adding 35CC and 3.2 g of potassium bromide to the aqueous solution in which the above was dissolved, and adding 35CC of an aqueous solution of 0.98 g of potassium iodide for 30 seconds at a flow rate of 70 CC / min, pAg was raised to 10 and aged for 30 minutes, A seed emulsion was prepared.

Subsequently, a predetermined amount of an aqueous solution 1 in which 145 g of silver nitrate was dissolved and an aqueous solution of a mixture of potassium bromide and potassium iodide were added in equimolar amounts at a predetermined temperature and a predetermined pAg at an addition rate close to the demarcation growth rate. A tabular core emulsion was prepared. Further, subsequently, the remaining silver nitrate aqueous solution and an aqueous solution of a mixture of potassium bromide and potassium iodide having a different composition from the preparation of the core emulsion are added in equimolar amounts at an addition rate near the critical growth rate to coat the core. Then, core / shell type silver iodobromide tabular emulsions A to D were prepared.

Aspect ratio control was obtained by selecting pAg during core and shell preparation. The results are shown in Table I-1.

Next, on the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare a multilayer color light-sensitive material 101.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (anti-halation layer) Black colloidal silver …… 0.2 Gelatin …… 1.3 ExM-8 …… 0.06 UV-1 …… 0.1 UV-2 …… 0.2 Solv-1 …… 0.01 Solv-2 …… 0.01 Second Layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.10 Gelatin …… 1.5 UV-1 …… 0.06 UV-2 …… 0.03 ExC-2 …… 0.02 ExF-1 …… 0.004 Solv-1 …… 0.1 Solv-2 …… 0.09 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, spherical equivalent diameter 0.
3μ, variation coefficient of spherical equivalent diameter 29%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Coating silver amount …… 0.4 Gelatin …… 0.6 P-1 …… 3.0 × 10 ^-4 P-2 …… 3.0 × 10 ^-4 ExC-3 ...... 0.06 ExC-4 ...... 0.06 ExC-7 ...... 0.04 ExC-2 ...... 0.03 Solv-1 ...... 0.03 Solv-3 ...... 0.012 4th layer (second red-sensitive emulsion) Layer) Silver iodobromide emulsion (AgI 1.5 mol%, high internal AgI type, equivalent spherical diameter)
0.7μ, coefficient of variation of equivalent spherical diameter 25%, normal crystal, twin mixed particles, diameter / thickness ratio 4) Coating amount of silver …… 0.7 gelatin …… 0.5 P-1 …… 2 × 10 ^-4 P-2… … 2 × 10 ^-4 ExC-3 …… 0.24 ExC-4 …… 0.24 ExC-7 …… 0.04 ExC-2 …… 0.04 Solv-1 …… 0.15 Solv-3 …… 0.02 Fifth layer (3rd red feeling) Emulsion layer) Silver iodobromide emulsion A Coating amount: 1.0 Gelatin: 1.0 P-1: 2 × 10 ^-4 P-2: 2 × 10 ^-4 ExC-5: 0.05 ExC-6: 0.1 Solv-1 …… 0.01 Solv-2 …… 0.05 Sixth layer (intermediate layer) Gelatin …… 1.0 Cpd-1 …… 0.03 Solv-1 …… 0.05 Seventh layer (first green-sensitive emulsion layer) Silver iodobromide Emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent diameter 0.
3μ, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin mixed particles, diameter / thickness ratio 2.5) Coating silver amount… 0.30 ExS-4 …… 5 × 10 ^-4 ExS-6 …… 0.3 × 10 ^-4 ExS-5 …… 2 × 10 ^-4 gelatin …… 1.0 ExM-9 …… 0.2 ExY-14 …… 0.03 ExM-8 …… 0.03 Solv-1 …… 0.5 Eighth layer (second green-sensitive emulsion layer) Iodine Silver bromide emulsion (AgI 4 mol%, internal high AgI type, equivalent spherical diameter of 0.
6μ, coefficient of variation of sphere equivalent diameter 38%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4) Coating silver amount… 0.4 Gelatin …… 0.5 ExS-4 …… 5 × 10 ^-4 ExS-5 …… 2 × 10 ^-4 ExS-6 ・ ・ ・ 0.3 × 10 ^-4 ExM-9 ・ ・ ・ 0.25 ExM-8 ・ ・ ・ 0.03 ExM-10 ・ ・ ・ 0.015 ExM-14 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.2 9th layer (3rd layer) Green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type, spherical equivalent diameter 1.
0μ, coefficient of variation of equivalent spherical diameter 80%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 1.2) Coating silver amount… 0.85 Gelatin …… 1.0 ExS-7 …… 3.5 × 10 ^-4 ExS-8 …… 1.4 × 10 ^-4 ExM-11 …… 0.01 ExM-12 …… 0.03 ExM-13 …… 0.20 ExM-8 …… 0.02 ExY-15 …… 0.02 Solv-1 …… 0.20 Solv-2 …… 0.05 10th layer ( Yellow filter layer) Gelatin …… 1.2 Yellow colloidal silver …… 0.08 Cpd-2 …… 0.1 Solv-1 …… 0.3 11th layer (first blue sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal height) AgI type, sphere equivalent diameter 0.
5μ, coefficient of variation of equivalent sphere diameter 15%, octahedral grain) Coating silver amount… 0.4 Gelatin …… 1.0 ExS-9 …… 2 × 10 ^-4 ExY-16 …… 0.9 ExY-14 …… 0.07 Solv-1… ... 0.2 12th layer (2nd blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent spherical diameter)
1.3μ, variation coefficient of equivalent spherical diameter 25%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 4.5) Coating silver amount… 0.5 Gelatin …… 0.6 ExS-9 …… 1 × 10 ^-4 ExY-16 …… 0.25 Solv-1 ...... 0.07 13th layer (1st protective layer) Gelatin ...... 0.8 UV-1 ...... 0.1 UV-2 ...... 0.2 Solv-1 ...... 0.01 Solv-2 ...... 0.01 14th layer (2nd) Protective layer) Fine silver bromide (average particle size 0.07μ)… 0.5 Gelatin …… 0.45 Polymethylmethacrylate particles (diameter 1.5μ) …… 0.2 H-1 …… 0.4 Cpd-3 …… 0.5 Cpd-4 …… 0.5 In addition to the above components, a surfactant was added to each layer as a coating aid. The sample prepared as described above is sample 101
And

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Solv-1: Tricresyl phosphate Solv-2: Dibutyl phthalate Solv-3: Bis (2-ethylhexyl) phthalate (Preparation of Samples 102 to 130) From Sample 101, the fifth layer emulsion and coupler and the third to fifth samples were prepared.
It was prepared in the same manner as in Sample 101 except that the sensitizing dye in the layer was changed as shown in Table I (changed equimolar). (In the case of the water-soluble polymer coupler, the coupler monomer unit was made to be equimolar.) The water-soluble polymer coupler was added as an aqueous solution of 8.0 wt%, and Solv-1, Solv-
The coating amount of 2 was 1/2.

(Preparation of Samples 201-230) Samples 101-130 were replaced with PY-6 instead of ExY-16 of the 11th layer (the number of moles of the coupler monomer unit and ExY-1.
So that the moles of 6 are equal), the amount of Solv-1 applied is 1
Samples 201 to 230 were prepared in the same manner as Samples 101 to 130 except that the sample was set to / 10.

The comparative coupler (1) in the examples is the following coupler described in JP-A-61-2201247.

After cutting the obtained samples 101 to 130 and 201 to 230 to a width of 35 m / m, a standard subject was photographed, and the following processing step (I) was performed.
Through (II), running tests of 500 m each were performed. After running, samples 101-130 and 201-230
Was exposed to 20 CMS of white light and the following development processing was performed. Further, for evaluation of sharpness, exposure and development were performed through a MTF measurement chart. The sample for MTF measurement was subjected to Fuji Film CN-16 treatment to remove the influence of residual silver, and was measured and evaluated with a micro densitometer.

The results of fluorescent X-ray analysis of the residual silver content of the developer samples are shown in Table I. If the residual silver amount is within 30 mg / m ² , it can be said that it is within a practically acceptable range.

In the above treatment step, the washing with water was a countercurrent washing method from to. Next, the composition of each processing liquid will be described.

<Bleach-fixing solution> Common for mother liquor and replenishing solution Ethylenediaminetetraacetic acid ferric ammonium salt 50.0g Ethylenediaminetetraacetic acid disodium salt 5.0g Sodium sulfite 12.0g Ammonium thiosulfate aqueous solution (70%) 240ml Ammo water is added to pH7.3 water. In addition, 1 <Wash water> As wash water, tap water was passed through a column packed with Na-type strongly acidic cation exchange resin (Diaion SK-1B manufactured by Mitsubishi Kasei Co., Ltd.) to obtain calcium 2 mg / l, magnesium 1.2 mg / l
The water quality was used.

<Washing water> The following three types were used.

(1) Tap water Calcium 26 mg / l Magnesium 9 mg / l pH 7.2 (2) Ion exchange treated water The above tap water was treated with a strong acid cation exchange resin (Na type) manufactured by Mitsubishi Kasei Co., Ltd. did.

Calcium 1.1 mg / l Magnesium 0.5 mg / l pH 6.6 (3) Chelating agent-added tap water To the tap water, 500 mg / l of ethylenediaminetetraacetic acid disodium salt was added.

pH 6.7 It was carried out by the steps and treatment solutions as described above.

As is clear from Table I, when an emulsion having an average aspect ratio of 5 or more is used, the MTF is remarkably improved (up to 20% or more), but the desilvering property is greatly deteriorated. However, it can be seen that this can be improved by using the water-soluble polymer coupler of the present invention together.

Therefore, MTF can be obtained only by using an emulsion having an aspect ratio of 5 or more and by using the water-soluble polymer coupler of the present invention.
It has been found that the desilvering performance can be improved and the practically sufficient desilvering performance can be secured.

It can be seen that when the sensitizing dye of the preferred embodiment of the present invention is used, the above difference becomes remarkable and the sensitivity is further increased.

Further, from the results of Samples 201 to 225, the effect of improving the desilvering property was observed even when the water-soluble polymer coupler was added only to the 11th layer.

Claims (2)

[Claims] 1. In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least 50% of the total projected area of the silver halide emulsion grains has an average aspect ratio of 5: 1 or more. A tabular silver halide grain and having at least one layer each having at least one repeating unit represented by the following general formula [P-1] and general formula [P-2] A silver halide color photographic light-sensitive material containing at least one of the above. The general formula [P-1] A A represents a repeating unit having a coupler moiety capable of forming a dye by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. However, the coupler moiety has a repeating site in its coupling-off group. The general formula [P-2] BB represents a repeating unit that does not undergo a coupling reaction with the oxidation product of the aromatic primary amine developing agent. 2. A sensitizing dye represented by the following general formula (A):
A silver halide color photographic image according to claim 1, which contains
Light material. General formula (A)(In the formula, Z₁Is an oxygen atom, a sulfur atom, a selenium atom or
N-R_FiveRepresents Z₂Is thiazole, benzothiazole, naphtho [1,2-
d] thiazole, naphtho [2,3-d] thiazole, cere
Nazole, benzoselenazole, naphtho [1,2-d] ce
Lenazole, naphtho [2,3-d] selenazole, benz
Imidazole, naphtho [1,2-d] imidazole, naphth
[2,3-d] imidazole, benzoxazole, na
Naphtho [1,2-d] oxazole, naphtho [2,3-d] oxy
In addition to the group of atom forming sazole nuclei, when m is 0
In the case of a 2-quinoline nucleating atom group, m represents 1.
Then Z₁Is N-R_FiveThiazoline and Serena
Zoline, oxazole or 3,3-dialkylindole
It also represents the group of nin-nucleating atoms. Where R_FiveIs a hydroxy
Syl group, phenyl group, alkoxy group, halogen atom or
Is a carbon that may be substituted with an alkoxycarbonyl group
It represents an alkyl group or an alkenyl group having a number of 6 or less. R₁And R₂Is an optionally substituted lower alkyl group or
Represents an alkenyl group. R₃Is a hydrogen atom or R₁Form a 5- or 6-membered ring by connecting with
Show what you can do. R_FourIs at least Z₁Is N-R_FiveRepresents or Z₂Be benzi
Midazole, naphtho [1,2-d] imidazole or na
A field representing a group of fut [2,3-d] imidazole nucleating atoms.
Represents a hydrogen atom, Z₁Is N-R_FiveWithout representing Z₂Also
Benzimidazole, naphtho [1,2-d] imidazole
Or the naphtho [2,3-d] imidazole nucleating atom group
When not represented, ethyl group, propyl group, butyl group,
Benzyl group, phenethyl group or optionally substituted
Represents a phenyl group. V₁Is a hydrogen atom or V₂To form a condensed benzene ring
Indicates to do. V₂Is Z₁Is N-R_FiveRepresents an electron-withdrawing group
You Z₁Represents an oxygen atom, a sulfur atom or a selenium atom
In case V₂Is a lower optionally branched chain having 7 or less carbon atoms
Alkyl group, lower alkoxy group having 6 or less carbon atoms, hydro
Xy group, acylamino group having 4 or less carbon atoms, halogen source
Child, alkoxycarbonyl group having 5 or less carbon atoms, carboxy
Si group, optionally substituted phenyl group having 8 or less carbon atoms
Or represents a hydrogen atom. V₃Is V₂And V₂Condensed benze linked to
Ring also can be formed, Z₁Is N-R_FiveRepresents
In the case where it is represented, it also represents a hydrogen atom. m represents 0 or 1. X Represents an acid anion residue
Then n₁Represents 0 or 1. )