JP2640126B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a super-high contrast negative type photographic light-sensitive material suitable for a light room light-sensitive material for photolithography for printing. .

(Prior Art) In the field of graphic arts, image formation exhibiting photographic characteristics of ultra-high contrast (especially gamma of 10 or more) in order to improve the reproduction of continuous tone images or the reproduction of line images by halftone images. Need a system.

Conventionally, a special developing solution called a lith developing solution has been used for this purpose. The squirrel developer contains only hydroquinone as a developing agent, and uses a sulfite as a preservative in the form of an adduct with formaldehyde so as not to impair its infectious developability, so that the concentration of free sulfite ions is extremely low (usually 0.1%). Mol / or less). Therefore, the squirrel developer has a serious disadvantage that it is extremely susceptible to air oxidation and cannot withstand storage for more than three days.

U.S. Pat. Nos. 4,224,401 and 4,168,977 for obtaining high contrast photographic characteristics using a stable developer.
No. 4,166,742, No. 4,311,781, No. 4,272,60
No. 6, No. 4,221,857, No. 4,243,739 and the like using a hydrazine derivative.

According to this method, photographic characteristics with ultra-high contrast and high sensitivity are obtained, and the addition of a high concentration of sulfite to the developer is allowed. Dramatically improved.

Further, as a light room light-sensitive material according to this method, a light-sensitive material mainly containing a silver chloride emulsion is disclosed in
−140,339, 61-238,049, Japanese Patent Application 60-221,498, 61
−5715, 61-53461, 61-79,531, 61-99,482.

Further, it is known that various antifoggants and stabilizers are added to silver halide photographic materials for the purpose of preventing fogging during storage or photographic processing or stabilizing photographic performance. I have.

However, if a known combination of an antifoggant or a stabilizer is used in a photosensitive layer containing a silver halide emulsion mainly composed of silver chloride and a hydrazine derivative, serious problems occur in the production and performance of the photosensitive material. did.

That is, as a problem in the production of a photosensitive material, a precipitate is generated in a coating solution and the coated area is deteriorated. As a disadvantage in performance, as a photographic processing solution becomes fatigued, a halftone dot area largely changes.

(Object of the Invention) As a result of intensive studies, the present inventors have solved these problems and made possible a bright room photosensitive material for photolithography for printing utilizing super-curing with a hydrazine derivative.

A first object of the present invention is to provide a photographic material for turning back a bright room, which gives a high quality and stable image.

A second object of the present invention is to provide a photographic light-sensitive material for turning back a bright room, which utilizes a high contrast by a hydrazine derivative.

A third object of the present invention is to provide a photographic material for turning back a bright room with high production stability.

A fourth object of the present invention is to provide a photographic material for turning back a bright room, which has high processing stability.

(Constitution of the Invention) The object of the present invention is to provide at least one silver halide light-sensitive emulsion layer containing at least 80 mol% of silver chloride, wherein the silver halide emulsion layer or another hydrophilic colloid layer is provided. And at least one hydrazine derivative and at least one compound represented by the following general formula (I).

Formula (I) Q-SM In the formula, Q represents a heterocyclic residue in which at least one hydrophilic group is directly or indirectly bonded. M represents a hydrogen atom, an alkali metal, or a quaternary phosphonium.

(Specific description of the invention) The silver halide used in the present invention is silver chloride,
Although any of silver chlorobromide, silver chloroiodide and silver chlorobromoiodide may be used, the silver chloride content in the halogen composition ratio is 80 mol% or more, more preferably 90 mol% or more.
When the content of silver chloride is low, the safety under light in a bright room light, which is important as a light-sensitive material, deteriorates (fogging occurs). For this reason, the workability of handling the light room photosensitive material is reduced, which is a practical obstacle. This is because the lower the silver chloride content, the longer the spectral sensitivity of the light-sensitive material extends to longer wavelengths, and the more sensitive the light is to the room light from which ultraviolet light has been cut, resulting in a deterioration in safety. Can be

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly 0.5 μm.
The following is preferred. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral, and irregular such as spherical and tabular.
It may be one having a simple crystal or a complex of these crystal forms, but a cube is particularly preferred.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention may contain a rhodium salt or a complex salt thereof.

Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium halide complex compound such as hexachlororhodium (III) acid or a salt thereof. (Ammonium salt, sodium salt, potassium salt, etc.).

The addition amount of these water-soluble rhodium salts is 1
It is used in the range of 1.0 × 10 ⁻⁷ mol to 1.0 × 10 ⁻⁴ mol per mol. Preferably it is 5.0 × 10 ^-6 mol to 5.0 × 10 ^-5 mol.

The rhodium salt is preferably added during silver halide grain formation or physical ripening during the preparation of a silver halide emulsion.

In addition to rhodium salts, cadmium salts, sulfites,
A lead salt, a thallium salt, and an iridium salt may coexist.

The compound represented by formula (I) of the present invention will be described in detail.

In the general formula (I), the hydrophilic group of Q is -SO
^{_{3 M, -SO 2 NHR 1,}} -NHCONHR 1, -NHSO 2 R 1, -CO 2 NHR 1,
—NHCOR ¹ , —PO ₃ M, —COOM, or OH are preferred.

Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Specific examples of the heterocyclic residue represented by Q in formula (I) include an oxazole ring, a thiazole ring, an imidazole ring, a zelenazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, an oxadiazole ring, a pentazole ring, and a pyrimidine ring. , A thiadia ring, a triazine ring, a thiadiazine ring or the like, or a ring bonded to another carbon ring or a hetero ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, Represents a zindolizine ring, a diazaindolizine ring, a tetraazaindolizine ring and the like.

Among the mercapto heterocyclic compounds represented by the general formula (I), particularly preferred are the compounds represented by the general formulas (IV) and (V).

General formula (IV) General formula (V) Y and Z in the general formula (IV) are N or CR ¹² (R ¹² represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group) R ¹¹ represents —SO ₃ M, —COOM _{^{, -SO 2 NHR 1, -NHCONHR 1}} , -NH
SO ₂ R ¹ , —CO ₂ NHR ¹ , —NHCOR ¹ , —PO ₃ M or an organic group substituted with at least one of OH, specifically, an alkyl group having 1 to 20 carbon atoms (eg, A methyl group, an ethyl group, a propyl group, a hexyl group, a dodecyl group, an octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (eg, a phenyl group, a naphthyl group, etc.), and an alkyl group or an aryl group having -S-, -O-, -CO -, - SO -, - SO 2 - and the groups formed through a linking group and the like.

These alkyl groups and aryl groups further include a halogen atom (F, Cl, Br, etc.), an alkoxy group (methoxy group, methoxyethoxy group, etc.), an aryloxy group (phenoxy group, etc.), an alkoxy group (R ¹ is an aryl group). ), An aryl group (when R ¹² is an alkyl group), an amide group (such as an acetamido group), a carbamoyl group (such as a methylcarbamoyl group), a sulfonamide group (such as a methanesulfonamide group), and a sulfamoyl group (such as methylsulfur A moyl group), a sulfonyl group (such as a methylsulfonyl group), a sulfinyl group (such as a methylsulfinyl group),
It may be substituted by a substituent such as a cyano group, an alkoxycarbonyl group (such as a methoxycarbonyl group), an aryloxycarbonyl group (such as a phenoxycarbonyl group), and a nitro group.

Here, the substituent of R ¹¹ -SO ₃ M, -COOM, -SO ₂ NHR ¹ ,-
NHCONHR ¹ , —NHSO ₂ R ¹ , —CO ₂ NHR ¹ , —NHCOR ¹ , and —PO ₃ M may be the same or different when there are two or more —OH.

 M has the same meaning as that represented by formula (I).

Next, X in the general formula (V) is a sulfur atom, an oxygen atom, a selenium atom or (R ¹³ is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents a substituted or unsubstituted aryl group)
L is ^{-CONR 14 -, - NR 14 CO} -, - SO 2 NR 14 -, - NR 14 SO 2
-, - OCO -, - COO -, - S -, - NR 14 -, - CO -, -
SO -, - OCOO -, - NR 14 CONR 15 -, - NR 14 COO -, - OCO
R ¹¹ , M represents NR ¹⁴ — or —NR ¹⁴ SO ₂ NR ¹⁵ — (R ¹⁴ and R ¹⁵ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group) Is the same as that represented by formulas (I) and (IV), and n represents 0 or 1.

Further, the alkyl group and the aryl group represented by R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ may be substituted with the substituents of R ¹¹ .

Specific examples of preferred compounds represented by the general formula (I) used in the present invention are shown below.

The compound represented by the general formula (I) can be synthesized by a method described in the following literature.

U.S. Pat.Nos. 2,585,388 and 2,541,924, Japanese Patent Publication No. 42-
21,842, JP-A-53-50,169, UK Patent No. 1,275,701
No., DABerges et.al., “Journal of Heterocyclic C
hemistry "Vol. 15, No. 981 (No. 1978)," The Chemistry
of Heterocyclic Chemistry "I midazole and Deriva
tives part I, pages 336-9, Chemical Abstract, 58 , 7921
No. (1963), p. 394, E. Hoggarth "Journal of Chemical Society" 1160
7 (1949), and SRSandler, W. Karo, “Organic Functioner Group P
reparation "Academic Press, 312-5 (1968), II Kovtunouskaya Levshine, Tr. Ukr. Inst. Eksperim
Endokrinol, 18, 345 (1961), M. Chamdon. Et al., Bull. Chem. Fr., 723 (1954), DAShirley, DWAlley, J. Amer. Chem. Soc., 79 , 4922.
(1954) A. Wchl, W. Marchwald, Ber. (German Chemistry), 22
Vol. 568 (1889) Praphalla Chandra Guha, J. Amer. Chem. Soc., 44 , 1502
1010 (1922) U.S. Patent No. 3,017,270, British Patent No. 940,169, JP-B-49,8,334, JP-A-55-59,463, Advanced in Heterocyclic Chemistry, 9 , 165-209
(1968) Khim. Geterotsikl, Soedin., 7 (7) 905-9, West German Patent No. 2,716,707 The Chemistry of Heterocyclic Compounds imidaz
ole and Derivatives, Vol 1, page 384, Org ,, Synth. IV., 56
9 (1963) LBSebrell.CEBooed, J.Amer.Chem.Soc., 45 , 2390
(1923), JP-A-50-89,034, JP-A-53-28,426, JP-A-55-2
1,007, 57-202531, 57-116340, JP 40-28,49
6 The compound of the present invention represented by the general formula (I) is used in an amount of 1.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻² mol, preferably 1 × 10 ⁻⁴ mol to 5 × 10 ⁻ mol per mol of silver. ³ mol is good. These compounds may be in the form of an aqueous solution or alcohols (eg, methanol, ethanol), ketones (eg, acetone),
It can be added as a solution in an organic solvent such as esters (for example, ethyl acetate). These compounds are added during the production of a silver halide emulsion (for example, during the formation of emulsion grains or during post-ripening) or in a coating solution prepared for coating.

As the hydrazine derivative used in the present invention, there are various known ones. In addition to the hydrazine compounds described in a number of patents mentioned in the section of (prior art), U.S. Pat. No. 4,272,614, JP-A-56-9743, U.S. Pat. No. 4,323,643, JP-A-57-99,635, and 60 −179,734, same
62-948, 61-270,744, 62-160,438, Japanese Patent Application No. 61-2
1,199, 61-175,234, 61-251,482, 61-276,28
3, 62-58,513, 62-67,509, 62-67,510, 62-
130,819 and 62-143,469 can be used.

Particularly preferred hydrazine derivatives have the following general formula (II)
Having a ureido group represented by

General formula (II) In the formula, R ³ and R ⁴ may be the same or different and each represent a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocyclic residue, and R ⁵ is a hydrogen atom or an aliphatic X represents a divalent aromatic residue.

R ² is a hydrogen atom or an alkyl group (C 1
3) or a phenyl group. The phenyl group may have the same substituent as described above.

More specifically, the aliphatic residues represented by R ³ and R ⁴ include linear and branched alkyl groups, cycloalkyl groups and those having a substituent, and alkenyl groups and alkynyl groups. . The linear or branched alkyl group is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and specifically, for example, a methyl group, an ethyl group, an isobutyl group, a 1-octyl group and the like. .

In addition, as the cycloalkyl group, for example, a
10, specifically, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group and the like. Examples of the substituent include an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), a halogen atom (eg, chlorine, bromine, bromine, iodine, etc.) ), An alkoxycarbonyl group, an aryl group (for example, a phenyl group, a halogen-substituted phenyl group, an alkoxyphenyl group, an alkylphenyl group), a hydroxy group, a cyano group, a sulfonyl group, and the like. -Methoxypropyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, p-chlorobenzyl group, 2,
4-dimethylamylphenoxypropyl group and the like can be mentioned. The alkenyl group includes, for example, an allyl group, and the alkynyl group includes a propargyl group.

On the other hand, examples of the aromatic residue represented by R ³ or R ⁴ include a phenyl group, a naphthyl group and a substituent thereof (for example, an alkyl group, an alkoxy group, an acylhydrazino group, a dialkylamino group, an alkoxycarbonyl group, a cyano group, a carboxyl group) Group, nitro group, alkylthio group, hydroxy group,
Sulfonyl group, carbamoyl group, halogen atom, etc.). Specific examples of those having a substituent include, for example, a p-methoxyphenyl group, an o-methoxyphenyl group, a tolyl group, a p-formylhydrazino group, and a p-methoxyphenyl group.
Examples thereof include a chlorophenyl group and an m-fluorophenyl group.

The heterocyclic residue represented by R ³ or R ⁴ is a 5- or 6-membered monocyclic or condensed ring having at least one of oxygen, nitrogen, sulfur, and selenium atoms. Is also good. Specifically, for example, a pyrroline ring,
Pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring,
Residues such as a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring and a naphthoselenazole ring can be exemplified.

These heterocycles have 1 to 1 carbon atoms such as methyl group and ethyl group.
An alkyl group having 4 carbon atoms such as a methoxy group and an ethoxy group;
It may be substituted with an aryl group having 6 to 18 carbon atoms such as an alkoxy group or a phenyl group of 4, a halogen atom such as chloro or bromo, an alkoxycarbonyl group, a cyano group, an amide group or the like.

One of R ³ and R ⁴ is preferably a hydrogen atom.

Examples of the aliphatic residue represented by R ⁵ include a linear or branched alkyl group, a cycloalkyl group, or those having a substituent, an alkenyl group, and an alkynyl group. The linear or branched alkyl group is, for example, an alkyl group having 1 to 18 carbon atoms, preferably 1 to 6 carbon atoms, and specific examples include a methyl group, an ethyl group, and an isopropyl group.
The cycloalkyl group is, for example, one having 3 to 10 carbon atoms, such as a cyclopentyl group and a cyclohexyl group. Examples of the substituent include an alkoxy group (eg, a methoxy group, an ethoxy group, etc.), an alkoxycarbonyl group, an aryl group (eg, a phenyl group, a halogen-substituted phenyl group, an alkoxyphenyl group, an alkylphenyl group, etc.), an amide group , An acyloxy group, and the like. Specific examples of the substituted one include a 3-methoxypropyl group, a benzyl group, a p-chlorobenzyl group, a p-methoxybenzyl group, and a p-methylbenzyl group. The alkenyl group has 3 to 12 carbon atoms, and is preferably, for example, an allyl group or a 2-butenyl group.

R ⁵ is preferably a hydrogen atom.

X represents a divalent aromatic residue, specifically, for example, a phenylene group, a naphthylene group (1,2-, 1,4-, 2,3-, 1,5
-, 1,8-, etc.) and those having a substituent.

Examples of the substituent of the divalent aromatic residue include, for example, those having 1 carbon atom.
To 20 alkyl groups (which may have a branch), an aralkyl group having 1 to 3 carbon atoms in the alkyl portion, an alkoxy group (preferably having 1 to 20 carbon atoms), and a substituted alkoxy group (preferably having 1 carbon atom). To 20), an amino group mono- or di-substituted with an alkyl group or a substituted alkyl group (1 to 20 carbon atoms), an aliphatic acylamino group (preferably 2 to 21 carbon atoms), an aromatic acylamino group, an alkylthio group , A hydroxy group, a halogen atom (such as chlorine) and the like.

 X is more preferably a phenylene group.

 Specific examples of preferred hydrazine derivatives are shown below.

In the present invention, when the compound represented by the general formula (II) is contained in a photographic material, it can be contained in any one or more hydrophilic colloid layers in the photographic material. The compound represented by the general formula (II) is preferably contained in a surface latent image type silver halide photographic emulsion layer, but in other non-photosensitive layers such as a protective layer, an intermediate layer, a filter layer and an antihalation layer. In layers such as layers,
You may make it contain. Specifically, a water-miscible organic solvent such as alcohols (eg, methanol and ethanol), esters (eg, ethyl acetate), and ketones (eg, acetone) is used. Can be added to a hydrophilic colloid solution, or in the case of hydrophobicity, can be added by emulsification dispersion or solid dispersion in an aqueous gelatin solution or another aqueous hydrophilic polymer solution.

When it is added to a photographic emulsion, it may be added at any time after the preparation of the emulsion grains and before coating, but it is preferably added to a coating solution prepared for coating.

The compound represented by formula (II) of the present invention is preferably used in an amount of 10 ^-6 mol to 1 × 10 ^-1 per mol of silver halide.
It is preferred that the compound be contained in a molar amount, particularly 10 ^-5 mol to 4 ×
It is preferable to contain 10 ^-2 mol, but the compound and the content are determined according to the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the containing layer and the photographic emulsion layer, the antifoggant compound. It is desirable to select an optimal amount according to the type of the product.

The compound represented by the general formula (II) of the present invention can be used in combination with a conventionally known hydrazine compound. Various compounds can be used as the hydrazine compound to be used in combination,
Specific examples include JP-A-53-20921 and JP-A-53-16,62.
No. 3, No. 55-52050, No. 55-90940, No. 55-174985
Nos. 59-36788, 61-270744 and 61-21199 can be used.

The ratio used in combination is 0.01 to 100 times, preferably 0.1 to 10 times, the molar ratio of the compound of the formula (II).

The silver halide photographic light-sensitive material of the present invention may contain an organic desensitizer. The organic desensitizer preferably has at least one water-soluble group or alkali-dissociable group.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. A method of measuring the oxidation-reduction potential of a polarograph is described in, for example, US Pat. No. 3,501,307. Specific examples of the water-soluble group present in at least one organic desensitizer include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and the like. These groups include organic bases (eg, ammonia, pyridine, triethylamine). , Piperidine, morpholine, etc.) or alkali metals (eg, sodium, potassium, etc.) and the like.

The alkali dissociable group is defined as the pH of the processing solution (usually pH 9 to pH 1).
Although it is in the range of 3, there may be a treatment solution having a pH other than this. ) At or below the pH,
Refers to a substituent that becomes anionic. Specifically, at least one hydrogen atom bonded to a nitrogen atom by a substituent such as a substituted / unsubstituted sulfamoyl group, a substituted / unsubstituted carbamoyl group, a sulfonamide group, an acylamino group, and a substituted / unsubstituted ureido group. Refers to the substituents and hydroxy groups that are present.

Further, a heterocyclic group having a hydrogen atom on a nitrogen atom constituting the hetero ring of the nitrogen-containing hetero ring is also included in the alkali-dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer, or may have two or more kinds at the same time.

Preferred specific examples of the organic desensitizer used in the present invention,
It is described in Japanese Patent Application No. 61-209169, of which some examples are given below.

The organic desensitizer is contained in the silver halide emulsion layer in an amount of 1.0 × 10 ^{−8 to} 1.0
It is preferred to be present in an amount of × 10 ^-4 mol / m ² , particularly 1.0 × 10 ^{-7 to} 1.0 × 10 ^-5 mol / m ² .

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained as a filter dye or for various purposes such as prevention of irradiation.
As the filter dye, a dye for further lowering the photographic sensitivity, preferably an ultraviolet absorber having a spectral absorption maximum in the inherent sensitivity range of silver halide, and safety against safelight light when handled as a light room photosensitive material Dyes having substantial light absorption mainly in the range of 350 nm to 600 nm are used to increase the light absorption.

These dyes are added to the emulsion layer depending on the purpose,
Alternatively, it is preferred to add and fix together with a mordant to the upper part of the silver halide emulsion layer, that is, the non-photosensitive hydrophilic colloid layer farther from the silver halide emulsion layer with respect to the support.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 50mg~500mg / m ²
It is.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, some of which are as follows.

The dye is dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution.

These dyes can be used in combination of two or more kinds.

The dye of the present invention is used in an amount necessary to enable handling in a bright room.

The amount of the specific dye is generally ^{10 -3 g / m 2 ~1g /} m 2,
In particular it is possible to find the preferred amount in the range of ^{10 -3 g / m 2 ~0.5g /} m 2.

Gelatin is advantageously used as a binder or protective colloid in a photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin with other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sodium alginate;
Sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and various kinds of copolymers such as polyvinylpyrazole. Synthetic hydrophilic polymeric substances can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples are U.S. Patent No. 2,448,060,
It is described in British Patent 618,061 and the like.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin.

As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, Mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaindene) ), Pentaazaindenes; and many other compounds known as antifoggants or stabilizers, such as benzenethiosulfonate, benzenesulfonate, benzenesulfonamide, and the like. Rukoto can. Among these, preferred are benzotriazoles (eg, 5-methyl-benzotriazole) and nitroindazoles (eg, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen Compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholy) carbonyl-3-pyridinio) methanesulfonate, Haloamidinium salts (such as 1- (1-chloro-1-pyridinomethylene) pyrrolidinium and 2-naphthalene sulfonate) can be used alone or in combination. Among them, JP-A-53-41220, JP-A-53-57257, and JP-A-59-16254
6, active vinyl compounds described in JP-A-60-80846 and active halides described in U.S. Pat. No. 3,325,287 are preferred.

The support used in the present invention is glass, cellulose acetate film, polyethylene terephthalate film,
Examples include paper, baryta coated paper, polyolefin (for example, polyethylene, polypropylene, etc.) laminated paper, polystyrene film, polycarbonate film, and metal plates such as aluminum. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating by a known method as necessary.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan ethers, polyalkylene glycol) Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Activator; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, or a phosphate group, such as alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines and amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Examples of development accelerators or accelerators for the nucleation transmission phenomenon suitable for use in the present invention include JP-A-53-77616 and JP-A-54-377.
In addition to the compounds disclosed in Nos. 32, 53-137, 133, 60-140,340, and 60-14959, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

The optimum amount of these accelerators varies depending on the type of the compound, but is 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (H ₂ O), such as alcohols such as methanol and ethanol, acetone, dimethylformamide, and methylcellosolve, and added to the coating solution.

 A plurality of these additives may be used in combination.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use a highly alkaline developer close to pH 13 described in JP-A-975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ion as a preservative, and has a pH of 10.5
With a developer having a pH of from about 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agent that can be used in the method of the present invention, and examples thereof include dihydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-). 3-pyrazolidone), aminophenols (for example, N
-Methyl-p-aminophenol) or the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable to be processed with a developer containing pyrazolidones or aminophenols. Preferably, the developer contains 0.05 to 0.5 mol / dihydroxybenzenes / mol.
, 3-pyrazolidones or aminophenols are 0.
It is used in the range of 06 mol / or less.

Further, as described in U.S. Pat. No. 4,269,929, the development speed can be increased by adding amines to the developer to shorten the development time.

Other developers include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
It can contain a development inhibitor such as iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. If necessary, a water softener, a dissolution aid, a color tone agent, a development accelerator, a surfactant (particularly preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, and prevention of silver staining of the film. Agents (eg, 2-mercaptobenzimidazole sulfonic acids).

As the fixing solution, those having a commonly used composition can be used. As the fixing agent, in addition to thiosulfate and thiocyanate, an organic sulfur compound known to cure as the fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The processing temperature in the process according to the invention is usually chosen between 18 ° C and 50 ° C.

Although it is preferable to use an automatic developing machine for photographic processing, according to the method of the present invention, even if the total processing time from when the photosensitive material is put into the automatic developing machine until it comes out is set to 90 seconds to 120 seconds, Sufficient photographic characteristics of a negative tone with a super-high contrast can be obtained.

The developing solution of the present invention is disclosed in JP-A-56-2 as a silver stain inhibitor.
The compounds described in 4,347 can be used. Compounds described in Japanese Patent Application No. 60-109,743 can be used as a solubilizing agent to be added to the developer. Further, compounds described in JP-A-60-93,433 or compounds described in Japanese Patent Application No. 61-28708 can be used as a pH buffer used in the developer.

 Hereinafter, the present invention will be described in detail with reference to Examples.

 In the examples, a developer having the following formulation was used.

Developer Hydroquinone 45.0 g N-methyl P-aminophenol 1/2 sulfate 0.8 g Sodium hydroxide 18.0 g Potassium hydroxide 55.0 g 5-Sulfosalicylic acid 45.0 g Boric acid 25.0 g Potassium sulfite 110.0 g Disodium ethylenediaminetetraacetate 1.0 g 2-mercaptobenzimitazole 5-sulfonic acid 0.3 g potassium bromide 6.0 g 5-methylbenzotriazole 0.6 g n-butyldiethanolamine 15.0 g 1 (pH = 11.6) by adding water [Comparative Example-1] 5.0 × 10 per mol of silver in gelatin solution
^-6 mol of NH ₄ RhCl _6, an aqueous solution of silver nitrate and an aqueous solution of sodium chloride are mixed at the same time, and then, by a method well-known in the art, a soluble salt is removed, and then gelatin is added. Was added with 2-methyl-4-hydroxy-1,3,3a, 7-tetraazaindene as a stabilizer.
This emulsion was a cubic monodispersed emulsion having an average grain size of 0.15 μm. The following hydrazine compound was added to this emulsion. 1-phenyl-5-mercaptotetrazole 2.6 mg /
m ² , and polyethyl acrylate latex in a solid content of 30 wt% based on gelatin, 1,3-vinylsulfonyl-2-propanol as a hardening agent, and 3.8 g / m ² of Ag on a polyester support. It was applied so as to obtain the amount. Gelatin was 1.8 g / m ² . Gelatin as a protective layer on this
1.5 g / m ² , as a coating aid, the following surfactant, stabilizer,
And a protective layer containing a matting agent and dried.

Surfactant Stabilizer Thioctic acid 2.1 g / m ² matting agent Polymethyl methacrylate (average particle size 2.5 μ) 9.0 g / m ² silica (average particle size 4.0 μ) 9.0 g / m ² [Example-1] In Comparative Example-1 , 1-Phenyl-5-mercaptotetrazole was used in place of the compound of the present invention, and the others were carried out in the same manner as in Comparative Example-1. The types and amounts of the compounds used are shown in Table 1.

An original having a halftone area of 50% was superimposed on this sample, exposed through an optical wedge with a lightning printer p-607 manufactured by Dainippon Screen Co., Ltd., developed at 38 ° C. for 30 seconds, fixed, washed with water,
Dried. As the developing solution, in addition to the fresh solution, the two fatigue solutions described in Table 1 were used.

 Table 1 shows the obtained photographic properties.

Table 1 shows that the sample of the present invention has low sensitivity when treated with the fatigue liquid. That is, it is understood that the sample of the present invention has a great feature that constant performance can be always obtained when the developer is continuously used for a long period of time.

Example-2 When applying the samples in Comparative Example-1 and Example-1, application was performed under the following two conditions. Comparative Example-2
And Example-2. (1) Condition 1 A coating solution for a light-sensitive emulsion layer, after adding an additive, apply immediately (within at most one hour).

Condition 2 In the coating solution for the photosensitive emulsion layer, after adding an additive other than the hardening agent and polyethyl acrylate, and aging at 40 ° C. for 24 hours, the hardening agent and polyethyl acrylate are added, and the coating is performed immediately. .

Table 2 shows the results of evaluating the photographic properties in the same manner as in Example-1.

It can be seen that the sample of the present invention has little change in performance even when the coating solution is aged.

In addition, the filterability of the coating solution was tested. Table 2 shows the test methods and results. Table 2 shows that the comparative examples show that, as the coating solution elapses, a precipitate is formed in the solution and the filter is clogged and cannot be filtered, whereas the sample of the present invention hardly causes clogging. I understand.

As described above, it can be seen that the sample of the present invention is suitable for stably producing a photosensitive material with little performance fluctuation.

Example 3 In Example 1, the hydrazine derivative and the type of the compound of the general formula (I) shown in Table 3 were used.
Made a sample.

As can be seen from Table 3, all of the samples of the present invention have little clogging of filtration, little change in photographic properties,
Extremely excellent in production stability.

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Claims (2)

(57) [Claims] 1. A silver halide emulsion layer comprising at least one silver halide light-sensitive emulsion layer containing at least 80 mol% of silver chloride, wherein said silver halide emulsion layer or another hydrophilic colloid layer comprises
A silver halide photographic material comprising at least one hydrazine derivative and at least one compound represented by the following general formula (I). Formula (I) Q-SM In the formula, Q represents a heterocyclic residue in which at least one hydrophilic group is directly or indirectly bonded. M represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium. 2. The silver halide photographic material according to claim 1, wherein the hydrazine derivative is selected from compounds represented by the following general formula (II). In the formula, R ³ and R ⁴ may be the same or different and each represents a hydrogen atom, an aliphatic residue, an aromatic residue, or a heterocyclic residue, and R ⁵ represents a hydrogen atom or an aliphatic residue. X represents a divalent aromatic residue. R ² is a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms),
Or a phenyl group. The phenyl group may have the same substituent as described above.