JPH07159925A - Manufacture of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent occurrence of striations and foreign matter by forming a hardened layer containing a polysaccharide non-hardenable by a hardening agent, and a hardening agent between the hardenable layers and applying the hardenable layers and the nonhardenable layer at the same time. CONSTITUTION:The polysaccharide capable of sol-gel conversion and nonhardenable by the hardening agent is used as the inder of the nonhardenable layer containing the immediately effective hardening agent (the hardener supplying layer), thus permitting too early hardening to be restrained and freed of occurrence of striations and foreign matter. The hardening layer is formed between the hardenable layers and sandwiched with the hardenable layers containing gelatin and these layers are applied at the same time, thus permitting the coating films to be high in both of dry film strength and wet film strength. As the sol-gel conversible polysaccharide by change of temperature, xanthan, gum, agarose, carrageenan alginic acid, furcellaran and the like are embodied.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silver halide photographic light-sensitive material containing a so-called fast-acting curing agent, which allows the curing reaction to be completed within a short period of time after the production and allows the product to be used as a final product quickly. It is about.

[0002]

2. Description of the Related Art It is common to use gelatin as a binder in silver halide photographic light-sensitive materials, and various hardeners are used in order to improve the water resistance and mechanical strength during the development process. Known to cure.
Aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Pat. No. 3,288,775.
Reactive halogen-containing compounds described in US Pat. No. 3,642,486, Japanese Patent Publication No. 49
-13563 and other compounds having a reactive ethylenically unsaturated bond, U.S. Pat. No. 3,017,
280, aziridine compounds described in US Pat. No. 3,091,537, epoxy compounds described in U.S. Pat. No. 3,091,537, halogen carboxyl aldehydes such as mucochloric acid, dihydroxydioxane, dichlorodioxane and other dioxane, Alternatively, chromium alum, zirconium sulfate and the like are known as inorganic curing agents.
However, when these known gelatin hardeners are used in photographic light-sensitive materials, they do not have a sufficient hardening effect or have a long-term change in hardening degree called "post-hardening" that occurs due to a slow hardening effect on gelatin. was there. This long-term change in curing degree causes a great change in photographic properties (sensitivity, gradation, density, etc.), and it was necessary to store the product for a considerable period of time until the final properties were reached. Therefore, using a so-called fast-acting curing agent, which cures in a short period of time after production and reaches the final level of product quality, has a great advantage such as shortening the storage period.

For this purpose, a compound having a dihydroquinoline skeleton described in JP-A No. 50-38540, JP-A No. 52-93470, is used as a hardening agent which has a relatively fast hardening reaction to gelatin and little post-hardening. Phosphorus-
Compounds having a halogen bond, JP-A-52-93470
A compound having an N-sulfonyloxyimide group,
Further, compounds having two or more N-acyloxyimino groups in the molecule described in JP-B-53-22089, N-carbamoylpyridinium salts described in JP-B-56-12853 and JP-B-58-32699, 56
2-Sulfonyloxypolydinium salts described in No. 110762 are known. Further, as a curing agent for gelatin which has a remarkably fast curing reaction and a curing agent which gives high use efficiency, haloformamidinium salts described in JP-A-60-225148, and German Patent Publication No. 2,225 , No. 230, No. 2,439,551 and the like. When applying these curing agents to a photographic light-sensitive material, it is common to mix gelatin and the curing agent immediately before coating to minimize the curing reaction in the coating liquid. However, in the case of using the fast-acting curing agent described above, in other words, a curing agent that is fast and ends the curing reaction within 5 days after coating at the end of coating and drying, mix it just before coating. However, the hardening reaction of gelatin occurs in the stagnation portion in the coating die, which causes foreign matter and streaks in continuous coating for a long time.

Various proposals have been made to overcome this problem. For example, as disclosed in JP-A-2-181143, a method of simultaneously or sequentially applying a layer containing a water-soluble binder that does not substantially contain gelatin and does not react with a curing agent and a curing agent as a top layer, and a German patent is published. 3,70
No. 0,727, a method of applying a curing agent layer as a lowermost layer or an uppermost layer using a V-shaped curtain die,
As in US Pat. No. 4,241,171, there is a method of setting a hardener layer as the lowermost layer and a polymer layer which does not react with the hardener thereon. In any of the above methods, it is necessary to use a trace amount of gelatin or a gelatin derivative, or a water-soluble polymer other than gelatin in order to impart a certain degree of viscosity to the hardened layer. Of these, when gelatin is used as a thickening agent, the mechanical strength of the coating film is reduced due to gelatin that has been mixed with a hardening agent and internally cross-linked in advance. It is difficult to suppress the generation of streaks. When a gelatin derivative or a water-soluble polymer other than gelatin is used as a thickener, when the gelatin derivative or polymer appears on the product surface, the mechanical strength of the film surface in the product state or during treatment is often impaired. On the other hand, the method of using the cured layer as the layer adjacent to the support tends to make it difficult to secure the adhesiveness between the polymer and the support. In addition, generally used water-soluble polymers, such as polyacrylamide and polyvinyl alcohol, are liable to dissolve in the processing solution during the development processing and cause contamination of the processing solution. Further, in the case of a polymer that does not gel, flow due to wind occurs in the drying step of removing water after coating, and there are cases where the surface quality is unacceptable.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to use a fast-acting curing agent, to prevent generation of streaks and foreign substances during coating, and to obtain a silver halide photographic light-sensitive material excellent in mechanical strength and processing suitability of products. It is intended to provide a method for producing a high production efficiency.

[0006]

The object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material in which gelatin is used as a binder and the gelatin is hardened by a fast-acting hardener. Characterized in that a hardening layer containing a sol-gel convertible polysaccharide that is not hardened into a solid and a hardening agent is set as a layer sandwiched between hardening layers containing gelatin, and the hardening layer and the hardening layer are simultaneously applied. It was achieved by a method of manufacturing a silver photographic light-sensitive material.

In the present invention, since a sol-gel convertible polysaccharide which is not cured by the curing agent is used as a binder of the curing layer containing the fast-acting curing agent (curing agent supply layer), premature curing in the curing layer. Does not occur. Therefore, there is no risk of foreign matter or streaks. In the present invention, the above-mentioned cured layer is set between the layers to be cured containing gelatin (that is, the layer to be cured is sandwiched between the layers to be cured containing gelatin), and these are simultaneously coated, whereby the wet film strength and the dry film strength are increased. It is possible to obtain a cured coating layer having a high hardness. In the present invention, the hardened layer containing gelatin is a silver halide emulsion layer, an intermediate layer, an antihalation layer,
It may be any of photographic constituent layers using gelatin as a binder such as a protective layer.

In the present invention, the sol-gel changeable polysaccharide which is not hardened by a gelatin hardening agent is a polysaccharide such as xanthan gum, agarose, carrageenan, alginic acid or furceleran, which changes sol-gel with a change in temperature. Κ Carrageenan that forms a weak cross-linked structure with certain gelatin by electrostatic bond and hydrogen bond (eg: Taito Co., Ltd .: K-9F, Nitta Gelatin Co., Ltd.)
Manufacturing: K-15: K-21 to 24, I-3) is preferable, but not limited to this. Even if it is applied at the same time as the layer to be hardened containing gelatin to be hardened by giving viscosity to the hardened layer with these polysaccharides, it can be continuously applied for a long time without the generation of foreign matter or streaks, and gelation. Therefore, the coating film is not deformed by the wind in the drying process. In addition, dissolution into the processing solution during development processing is generally small, and the processing solution is unlikely to be contaminated. These sol-gel changing polysaccharides have little influence on the water resistance and mechanical strength of the product, but further minimize the influence on the mechanical strength of the product surface and the adhesiveness with the support, so that the hardened layer product It is important to set the layer other than the outermost layer and the layer adjacent to the support. When the product has a large number of layers and is to be applied many times before completion, it is sufficient to apply the liquid containing the curing agent to at least one of the applications.

Any coating method such as a slide bead coater, a curtain coater, and an extrusion coater can be used as the coating method used in the present invention as long as it can be coated in multiple layers at the same time. As a coating method particularly suitable for the present invention, a slide bead coater,
A curtain coater can be used. When using a slide bead coater or a curtain coater, a liquid that is not cured by a curing agent (hereinafter referred to as a dummy liquid) is flowed along the coating width regulation plate to prevent aggregation at the edge portion,
Further, suitability for continuous coating for a long time is improved. The dummy liquid may be any liquid as long as it is not hardened by the curing agent, but in order to reduce the influence on the mainstream, a small amount of low-viscosity liquid is used,
It is desirable to flow at 0.5 to 5 cc / minute.

In the present invention, it is preferable to use a surfactant as a curing agent for the cured layer, an improvement in solubility and compatibility of the polysaccharide, or a coating aid. For example, saponin (steroidal), alkylene oxide derivative (for example,
Polyester glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adduct of silicone Non-ionic surfactants such as glycidol derivatives (eg, alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates, alkyl sulfonates , Alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates Carboxyl groups, sulfo groups, such as alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as phospho group, sulfuric acid ester group, phosphoric acid ester group; amphoteric surface such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides Activator: A fluorine-containing surfactant or the like can be used. Among these, an anionic surfactant having a sulfate group as a sulfonic acid group is preferable. Specific compound examples are shown below.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

The fast-acting curing agent in the present invention means that the curing reaction is completed within about 5 days after coating and drying,
Typically, a vinyl sulfone-based curing agent represented by the following general formula (I) and a carboxyl group active type curing agent represented by the general formulas (II) and (VIII) are mentioned. Among them, the curing agent of the general formula (I) is particularly suitable for the production method according to the present invention and has a long-term continuous production suitability, but the application range is not limited to this. General formula _{(I) CH 2 = CH- SO} 2 -C (R) H- (OC (R) H) n -
SO ₂ —CH═CH _{2 In the} formula, R is a hydrogen atom, an alkyl group, an aralkyl group,
Represents an aryl group, which may be substituted. n represents 0 or 1. More specifically,
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, etc.), an aralkyl group having 6 to 20 carbon atoms (for example, a benzyl group, a phenethyl group, etc.), and an aryl group having 5 to 20 carbon atoms ( For example, a phenyl group, a naphthyl group, a pyridyl group, etc.), and these groups may be substituted. Examples of the substituent include a sulfonic acid group, a hydroxyl group, a carboxyl group and the like. Particularly preferred as R is a hydrogen atom. n is 0
Alternatively, it represents 1, and 0 is preferable. Examples of the compound used in the present invention are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 3]

The method of synthesizing the compound represented by formula (I) of the present invention is described in JP-B-47-24259 and JP-A-49-7.
3122, JP-A-63-241539 and the like. When the curing agent represented by the general formula (I) is used, the coating solution for the cured layer has a pH of 3 to 6, preferably 4 to.
By setting it to 5.5, the stability of the coating solution for the cured layer over time and the stability of continuous coating for a long time are guaranteed. General formula (II)

[0016]

[Chemical 4]

In the formula, R ¹¹ and R ¹² are alkyl groups having 1 to 10 carbon atoms (for example, methyl group, ethyl group, 2-ethylhexyl group, etc.) and aryl groups having 6 to 15 carbon atoms (for example, phenyl group and naphthyl group). Etc.) or an aralkyl group having 7 to 15 carbon atoms (eg, benzyl group, phenethyl group, etc.), and they may be the same or different. Also R
It is also preferred that ¹¹ and R ¹² are bonded to each other to form a heterocycle with a nitrogen atom. Examples of forming a ring include a pyrrolidine ring, a piperazine ring, a morpholine ring and the like.
R ¹³ is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, a sulfoamino group, a ureido group,
It represents a substituent such as an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, and a dialkyl-substituted amino group having 2 to 20 carbon atoms. R ¹³ is an alkoxy group, an alkyl group,
When it is a dialkylamino group or an N-alkylcarbamoyl group, those groups may be further substituted, and examples of the substituents include a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, a sulfoamino group and a ureido group. Is mentioned. X ⁻ represents an anion and serves as a counter ion of the N-carbamoylpyridinium salt. When the substituent of R ¹³ contains a sulfo group, a sulfooxy group or a sulfoamino group, it may form an inner salt and X ⁻ may not be present. Preferred examples of the anion, halide ions, sulfate ion, sulfonate ion, ClO ₄ ^-, B
Examples include F ₄ ⁻ and PF ₆ ⁻ . The detailed description of the carbamoyl ammonium salt type curing agent represented by the general formula (II) is described in JP-B Nos. 56-12853 and 58-58.
32699, JP-A-49-51945, 51-5.
No. 9625, No. 61-9641, No. 62-26285.
No. 4, No. 62-264044, No. 63-184741.
And Japanese Patent Laid-Open No. 3-63643. General formula (III)

[0018]

[Chemical 5]

[0019] R ^11, R ^12, R ¹³ and X ^- definition is exactly the same as defined in formula (II), these compounds are familiar to the Belgian Patent No. 825,726. General formula (IV)

[0020]

[Chemical 6]

R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ have 1 to 1 carbon atoms.
20 alkyl groups (eg, methyl group, ethyl group, butyl group, 2-ethylhexyl group, dodecyl group, etc.), aralkyl groups having 6 to 20 carbon atoms (eg, benzyl group, phenethyl group, 3-pyridylmethyl group), or Carbon number 5
20 aryl groups (eg, phenyl group, naphthyl group, pyridyl group, etc.), which may be the same or different. R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may have a substituent, and examples of the substituent include a halogen atom, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. Group, N, N-disubstituted carbamoyl group and the like. It is also preferable that any two of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are bonded to form a ring.
For example, R ¹⁴ and R ¹⁵ , or R ¹⁶ and R ¹⁷ are bonded to each other to form a ring with a nitrogen atom, for example, a pyrrolidine ring,
Examples include the case of forming a piperazine ring, a perhydroazepine ring, a morpholine ring and the like. Examples of R ¹⁴ and R ¹⁶ , or R ¹⁵ and R ^{17 which} are bonded to each other to form a ring with two nitrogen atoms and a carbon atom sandwiched between them are:
The case of forming an imidazoline ring, a tetrahydropyrimidine ring, a tetrahydrodiazepine ring and the like can be mentioned. X
Represents a group capable of splitting off when the compound represented by the general formula (IV) reacts with a nucleophile, and other preferable examples include halogen atom, sulfonyloxy group and the like.

[0022]

[Chemical 7]

Examples include groups represented by: Y ⁻ represents an anion, and is a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^−.
Are preferred. When Y ⁻ represents a sulfonate ion, it may combine with X, R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ to form an inner salt. Regarding the amidinium salt-based curing agent represented by the general formula (IV), JP-A-60-225148.
No. 61-240236, 63-229450
Is there a detailed description in the gazettes such as No. 3, Tokuhyo 3-503103, etc.? General formula (V)

[0024]

[Chemical 8]

Where R¹⁸Is an alkyl group having 1 to 10 carbon atoms
(For example, methyl group, ethyl group, 2-ethylhexyl group
Etc.), a cycloalkyl group having 5 to 8 carbon atoms (for example, cycloalkyl
Hexyl group, etc.), alkoxyalkoxy having 3 to 10 carbon atoms
Group (eg methoxyethyl group) or C7
~ 15 aralkyl groups (eg benzyl, phenethyl)
Group, etc.) R¹⁹Is R¹⁸Represents a group defined in
In addition, -R²⁰-N⁺R ^{twenty one}R^{twenty two}R^{twenty three}X^-The group represented by
preferable. R²⁰Is an alkylene group having 2 to 4 carbon atoms (for example,
Ethylene group, propylene group, trimethylene group, etc.)
Forget R^{twenty one}, R ^{twenty two}Are the same or different
May be an alkyl group having 1 to 6 carbon atoms (for example, a methyl group,
Represents an ethyl group). Also, R^{twenty one}And R^{twenty two}Combined with
Heterocycle with nitrogen atom (eg pyrrolidine ring, piperazi
Ring, morpholine ring, etc.) are also preferred.
R^{twenty three}Is an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ether
Group, but may also be substituted.
preferable. Examples of substituents include substituted or unsubstituted
Luvamoyl group, sulfo group and the like are preferable. X^-Is Yin Io
Represents a halide ion, sulfonate ion
Ion, sulfate ion, ClO_Four ^-, BF_Four ^-, PF₆ ^-Such
Is preferred. Also R^{twenty three}Is replaced by a sulfo group
Forms an inner salt to form X^-Does not have to exist.
Regarding these carbodiimide type curing agents, JP-A-51 is recommended.
For details, refer to Nos. -126125 and 52-48311. General formula (VI)

[0026]

[Chemical 9]

In the formula, R ²⁴ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, butyl group, etc.), an aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group, etc.), or carbon It represents an aralkyl group of the formulas 7 to 15 (eg, benzyl group, phenethyl group, etc.). These groups may be substituted, and examples of the substituent include a carbamoyl group, a sulfamoyl group and a sulfo group. R
²⁵ and R ²⁶ are a hydrogen atom, a halogen atom, an acylamido group,
It represents a substituent such as a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group and an aralkyl group, which may be the same or different. It is also preferable that R ²⁵ and R ²⁶ are bonded to each other to form a condensed ring together with the pyridinium ring skeleton. X represents a group capable of splitting off when the compound represented by the general formula (VI) reacts with a nucleophile, and preferable examples thereof include a halogen atom, a sulfonyloxy group and a group represented by —OPO (OR ²⁷ ) ₂ (R ²⁷ represents an alkyl group or an aryl group),

[0028]

[Chemical 10]

Examples include groups represented by: When X represents a sulfonyloxy group, it is also preferable that X and R ²⁴ are bonded. Y ⁻ represents an anion, which is a halide ion, a sulfonate ion, a sulfate ion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. See also R ²⁴
When is substituted with a sulfo group, it forms an inner salt,
Y ⁻ does not have to exist. Regarding these pyridinium salt type curing agents, JP-B-58-50699, JP-A-57-44140, 57-46538 and 63-
No. 229450, Tokuhyo 3-503103, etc. have detailed description. General formula (VII)

[0030]

[Chemical 11]

[0031] wherein the definition of R ^11, R ¹² is exactly the same in the general formula (II) and the definition of R ^11, R ^12, R ²⁸ represents an alkyl group (e.g. methyl group having 1 to 10 carbon atoms, ethyl Base,
Butyl group), an aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group, etc.), or 7 to 15 carbon atoms
Represents an aralkyl group (eg, benzyl group, phenethyl group, etc.). X ⁻ is an anion, which is a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ ,
BF ₄ ⁻ , PF ₆ ^{− and the} like are preferable. The pyridinium salt-based curing agent represented by the general formula (VII) is described in JP-A-52
-54427. General formula (VIII)

[0032]

[Chemical 12]

In the formula, R ²⁹ is an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), an aryl group having 6 to 15 carbon atoms (eg, phenyl group, naphthyl group, etc.), Alternatively, it represents an aralkyl group having 7 to 15 carbon atoms (eg, a benzyl group, a phenethyl group, etc.), and may be substituted or unsubstituted. As a substituent, a halogen atom, a carbamoyl group, a sulfo group,
Sulfooxy group, ureido group, alkoxy group having 1 to 10 carbon atoms, alkyl group having 1 to 10 carbon atoms, 2 to 20 carbon atoms
Examples include dialkyl-substituted amino groups of Z represents a group of non-metal atoms necessary for completing a nitrogen-containing heteroaromatic ring, and preferable examples thereof include a pyridine ring, a pyrimidine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and a benzo-fused ring thereof. R ³⁰ is a hydrogen atom, a halogen atom, a carbamoyl group, a sulfo group, a sulfooxy group, a ureido group, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a dialkyl-substituted amino group having 2 to 20 carbon atoms, etc. Represents a substituent. When R ³⁰ is an alkoxy group, an alkyl group, a dialkylamino group or an N-alkylcarbamoyl group, those groups may be further substituted, and examples of the substituents include a halogen atom, a carbamoyl group and a sulfo group. , A sulfooxy group, and a ureido group. X ⁻ represents an anion. R ²⁹ ,
When R ³⁰ or a substituent thereof contains a sulfo group or a sulfooxy group, X ⁻ may not be present because it forms an intramolecular salt. Preferred examples of the anion include halide ion, sulfate ion, sulfonate ion, Cl
O ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^{− and the} like can be mentioned. As the curing agent used in the present invention, in addition to the compounds represented by the above general formulas (II) to (VIII), JP-A-50-3
8540, JP-A-52-93470, JP-A-56-
The compounds described in JP-A-43353, JP-A-58-113929, and US Pat. No. 3,321,313 are also preferable. Particularly preferably, the curing agent used in the present invention is a curing agent represented by the general formula (II), the general formula (IV) or the general formula (VI). Specific examples of the compound (curing agent) used in the present invention are listed below, but the present invention is not limited thereto.

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

The amount of the curing agent used in the present invention can be arbitrarily selected. Normally 0.0 for dry gelatin
It can be used in proportions ranging from 1 to 20% by weight. Particularly preferably, it is used in a proportion in the range of 0.05 to 15% by weight.

The curing agent of the present invention may be used alone, or two or more curing agents of the present invention may be mixed and used. Further, it may be used in combination with other curing agents known so far. Known curing agents that may be used in combination include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4, 6-dichloro-1,3,5
-Triazine and others U.S. Pat. No. 3,288,775
No. 2,732,303, British Patent 974,72
No. 3, 1,167,207 and the like, compounds having a reactive halogen, 5-acetyl-1,
3-diacryloylhexahydro-1,3,5-triazine, other U.S. Pat. Nos. 3,635,718, 3,232,763, British Patent 994,869,
JP-B-44-29622, JP-A-47-24259, JP-A-47-25373, JP-A-49-73122, JP-A-49-73122.
Compounds having a reactive olefin described in, for example, 3-241539, N-hydroxymethyl phthalimide, and other U.S. Pat. Nos. 2,732,316 and 2,586,168. N-methylol compounds, isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,
280, 2,983,611 and the like, aziridine compounds, US Pat. No. 2,725,294.
No. 2,725,295, etc., acid derivatives described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. You can Alternatively, as the curing agent for the inorganic compound, there are chromium alum, zirconium sulfate and the like. Those in the form of precursors instead of the above compounds, for example, alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic nitroalcohols, mesyloxyethylsulfonyl compounds, chloroethylsulfonyl. You may use together with a system compound.

When the curing agent of the present invention is used in combination with other curing agents, the ratio of the curing agent of the present invention to be used can be selected arbitrarily according to the purpose and effect. It is preferably 50 mol% or more. Further, the addition layer of the curing agent of the present invention and another curing agent may be the same layer or another layer. It is preferable to add them in separate layers.

A compound that accelerates the hardening of gelatin may be used in combination with the hardening agent of the present invention. For example, the curing agent of the present invention may be used in combination with a polymer having a sulfinic acid group described in JP-A-56-4141 as a curing accelerator. Gelatin to which the hardening agent of the present invention is applied, in the production process thereof, so-called alkali-treated (lime-treated) gelatin dipped in an alkali bath, acid-treated gelatin dipped in an acid bath, and both treatments are performed before gelatin extraction. Either a double-dipped gelatin or an oxygen-treated gelatin that has been used may be used. Further, the hardener of the present invention can be applied to low molecular weight gelatin obtained by heating these gelatins in a water bath or by causing them to act on a protease to partially hydrolyze them.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate, polyethylene naphthalate, polyethylene coated paper and the like can be used. Further, a waterproof layer containing a polyvinylidene chloride-based polymer may be provided for the purpose of so-called dimensional stability improvement in which the size changes due to changes in temperature and humidity or development processing.

In the present invention, JP-A-1-229244 is used.
When drying after coating the hydrophilic colloid layer coating solution described in No.
Based on the dry weight of the binder contained in all the layers formed on the support, 300% or less of water is dried at a relative humidity of 50% or less, and after drying, the silver halide photographic light-sensitive material is absolutely dried. A silver halide photographic light-sensitive material having good dimensional stability is obtained by a method of heat-treating at a temperature of 30 ° C. or higher in an atmosphere of 1% or less in humidity and storing it in an atmosphere of 1% or less in absolute humidity. be able to.

There are no particular restrictions on the various additives and the like used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts can be preferably used. Item This section 1) Silver halide emulsion and JP-A-2-97937, page 20, lower right column 12, its manufacturing line to page 21, left lower column, line 14 and JP-A-2-12236. Page 7, upper right column, line 19 to page 8, lower left column, line 12, Japanese Patent Application No. 3-116573, Japanese Patent Application No. 3-189532. 2) Spectral sensitizing dyes JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8; JP-A 2-39042, page 7, lower right column, line 8 to Page 13, lower right column, line 5. JP-A-2-12236, page 8, lower left column 1, line 3 to lower right column, line 4; JP-A-2-103236, page 16, lower right column, line 3 to page 17, lower left column, line 20; Furthermore, JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application Nos. 3-189532 and 3-4111064. 3) Hydrazine Nucleating Agent JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3 No. 3-17 4143, page 20, lower right column, line 1 to page 27, upper right column, line 20, general formula (II) and compound examples II-1 to II-54. 4) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound example II- 1 No. II-22, the compounds described in JP-A-1-179939.

5) Surfactant From JP-A-2-12236, page 9, upper right column, line 7 From antistatic agent, same as lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column 18, line 18. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. JP-A-4-214551, paragraph numbers “0041” to “0045”. 7) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A-2-5 5349, page 8, lower right column, line 13 From the same page, page 1, upper left column, line 8 8) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A 1-23753 A thiosulfinic acid compound described in JP-B-8. 9) Polyhydroxybenze JP-A-2-55349, page 11, upper left column, page 9 to lower right column, line 17 10) Lubricants, plasticizers, mats JP-A-2-103536, page 19, upper right column, line 6 to agent, page 19 upper right column, line 15 11) Dyes JP-A-2-103536, page 17, lower right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5, Solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 12) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 13) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 14) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 15) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 16) Colloidal silica The compound described in paragraph “0005” of JP-A-4-214551. 17) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8 JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10

[0053]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 On both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm), an undercoat layer having the following composition, the first layer and the second layer were prepared.
The layers were applied. <Undercoat first layer> Core-shell type vinylidene chloride copolymer-15g 2,4-dichloro-6-hydroxy-s-triazine 0.25〃 polystyrene fine particles (average particle size 3µ) 0.05〃 compound- 1 0.20〃 colloidal silica (Sunotex ZL; particle size 70-100 μm, manufactured by Nissan Kagaku Co., Ltd.) 0.12〃 Water added 100〃 Further, 10% by weight KOH was added to adjust pH = 6 The liquid was dried at a temperature of 180 ° C. for 2 minutes and the dry film thickness was 0.
It was applied so as to be 9μ. <Undercoat layer second layer> Gelatin 1 g Methylcellulose 0.05 〃 Compound-2 0.02 〃 C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.02 〃 Compound-3 3.5 × 10 ^-3 〃 acetic acid 0.2 〃 water was added 100 〃 This coating solution was applied at a drying temperature of 170 ° C for 2 minutes so that the dry film thickness would be 0.1µ.

[0055]

[Chemical formula 24]

Next, on one side of this support, the following emulsion first layer and second layer, protective layer lower layer, hardened layer and protective layer upper layer were applied along a coating width regulating plate using a slide bead coater. The dummy liquid was applied at the same time while flowing at the flow rates shown in Table-2. As the dummy liquid, a liquid obtained by removing the hardening agent from the hardened layer was further diluted with water two times.

<Emulsion 1st layer> Liquid I: 300 ml of water, gelatin 9 g Liquid II: AgNO ₃ 100 g, water 400 ml III liquid: NaCl 37 g, (NH ₄ ) ₃ RhCl ₅ 1.1 m
l, 400 ml of water Solution II and solution III were simultaneously added to solution I kept at 45 ° C at a constant rate. Soluble salts were removed from this emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. The emulsion was a monodisperse emulsion having an average grain size of 0.20 μ. The following compounds were added to the emulsion thus obtained. Compound-6 × 10 ^-3 mol / Aglmol Compound-60 mg / m ² Compound-9 mg / m ² Compound-10 mg / m ² Polystyrenesulfonic acid sodium salt 40 mg / m ² N-oleoyl-N-methyltaurine sodium salt 50 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05μ) 0.46g / m ² silver amount 1.3 g / m ² so that the gelatin 0.6 g / m ² Was applied to.

[0058]

[Chemical 25]

<Emulsion Second Layer> Liquid I: 300 ml of water, gelatin 9 g Liquid II: AgNO ₃ 100 g, water 400 ml III liquid: NaCl 37 g, (NH ₄ ) ₃ RhCl ₅ 2.2 m
l, 400 ml of water In the same manner as the emulsion of the emulsion layer 1st layer
The liquid was added simultaneously to prepare an emulsion. This emulsion was a monodisperse emulsion having an average grain size of 0.20μ. The following compounds were added to the emulsion thus obtained. Emulsified Dispersion of Hydrazine Derivative 5 × 10 ⁻³ mol / Aglmol Compound-60 mg / m ² Compound-9 mg / m ² Compound-10 mg / m ² Polystyrenesulfonic Acid Sodium Salt 50 mg / m ² N-oleoyl- N-methyl taurine sodium salt 40 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 0.40 g / m ² silver amount 1.3 g / m ² gelatin 0. It was applied so as to be 65 g / m ² .

[0060]

[Chemical formula 26]

<Method for Preparing Emulsified Dispersion of Hydrazine Derivative> Solution I: Compound-3.0 g Compound- (11) 1.5 g Poly- (N-tert-butylacrylamide) 6.0 g Ethyl acetate 30 ml Sodium dodecylbenzenesulfonate (72% methanol solution) 0.12 g Water 0.12 ml It was heated to 65 ° C. and uniformly dissolved to obtain a solution I. Solution II: Gelatin 12 g Compound-0.02 g Water 108 ml It was heated to 65 ° C. and uniformly dissolved to obtain solution II. With liquid I
Liquid II was mixed and stirred at high speed with a homogenizer (manufactured by Nippon Seiki Seisakusho) to obtain a fine particle emulsion dispersion. After removing ethyl acetate from this emulsion by heating under reduced pressure, water was added to make 250 g. The residual ethyl acetate was 0.2%.

[0062]

[Chemical 27]

<Protective Layer Lower Layer> Gelatin 1.0 g / m ² lipoic acid 5 mg / m ² dodecylbenzenesulfonic acid sodium salt 5 mg / m ² compound-20 mg / m ² polystyrene sulfonic acid sodium salt 10 mg / m ² compound- (10 ) 20 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 200 mg / m ²

[0064]

[Chemical 28]

<Cured layer> To the polysaccharide compounds shown in Table 1, 20 cc of methanol was added, and then 950 cc of H ₂ O was added and mixed by stirring to completely dissolve the mixture at 60 ° C, and then the liquid temperature was lowered to 40 ° C. Next, after adjusting the pH to 5 ± 0.2 with a 2% phosphoric acid aqueous solution, a curing agent and a surfactant were added as shown in Table-1,
After completely dissolved, H ₂ O was added to make 1000 cc. The viscosity of this solution at 40 ° C. was 30 cp. The cured layer was applied so that the coating amount of the curing agent was as shown in Table-1.

[0066]

[Table 1]

<Protective Layer Upper Layer> Gelatin 1.0 g / m ² Silicon dioxide fine powder particles (average particle size 3.5 μ, pore diameter 25 Å surface area 700 m ² / g) 50 mg / m ² dodecylbenzenesulfonic acid sodium salt 20 mg / m ² Perfluorooctane sulfonic acid potassium salt 10 mg / m ² N-perfluorooctane sulfonyl-N-propylglycine potassium salt 3 mg / m ² Polystyrene sulfonic acid sodium salt 2 mg / m ² Poly (degree of polymerization 5) oxyethylene nonyl phenyl ether Sulfate ester sodium salt 20mg / m ² Liquid paraffin (gelatin dispersion) 50mg / m ²

Then, a conductive layer and a back layer shown below were simultaneously coated on the opposite surface of the support. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 300 mg / m ² Gelatin (Ca ⁺⁺ content 30 ppm) 170 〃 compound-7 〃 dodecylbenzene sulfonic acid sodium salt 10 〃 dihexyl -Α-sulfosuccinate sodium salt 40 〃 polystyrene sulfonic acid sodium salt 9 〃 <back layer> gelatin 2.9 g / m ² compound − 300 mg / m ² compound − 50 〃 compound − 50 〃 compound -10 〃 dodecylbenzene sulfonic acid Sodium salt 70 〃 Dibenzyl-α-sulfosuccinate sodium salt 15 〃 1,2-bis (vinylsulfonylacetamido) ethane 150 〃 Ethyl acrylate latex (average particle size 0.05 µ) 500 〃 Perfluorooctane sulfonic acid lithium salt 10 〃 Fine particles of silicon dioxide (average particle size 4 , Pore diameter 170Å, surface area of 300m ² / g) 35 〃

[0069]

[Chemical 29]

(1) Coating suitability All the layers on the emulsion layer side were continuously discharged with a slide bead coater to observe foreign matter and streaks on the slide surface, and the unevenness of the surface when coated on the support (crepe noodles) Shape, streak, etc.) was evaluated. At this time, the coating liquid and the coater were kept warm at 40 ° C., the gap between the coater and the support was 0.2 mm, the bead back pressure of the slide coater was a negative pressure of 200 mPa, and the coating was performed at a speed of 2 m / s. In addition, the sample passed through a cooling zone of 10 ° C after coating and then 25m /
It was dried with a wind of sec and wound up.

(2) Swelling ratio The obtained sample was stored in an atmosphere of 25 ° C. and 50% RH for 2 days and 7 days, and then the thickness (do) before swelling was measured with an electronic micrometer manufactured by Anritsu Electric Co., Ltd. With measuring force of 30 ± 5g, 2
Swelled thickness when immersed in distilled water at 5 ° C for 1 minute (△
d) is measured with a measuring force of 2 ± 0.5 g, and Δd ÷ do × 10
0 = Swelling ratio (%)

(3) Photographic properties The obtained sample was stored in an atmosphere of 25 ° C. and 50% RH for 5 days, and then optically measured by a bright room printer P-617DQ (quartz lamp light source) manufactured by Dainippon Screen Co., Ltd. After exposing through a wedge, a developing solution and a fixing solution having the following compositions were prepared using Fuji Photo Film Co., Ltd. GR-F1 and an automatic developing machine FG.
Processing was performed with -680A (manufactured by Fuji Photo Film Co., Ltd.) under the developing conditions of 38 ° C and 20 seconds. The sensitivity was expressed as a relative value when the sample number -1 was set to 100 as a logarithmic value of the exposure amount giving a density of 3.0. The γ value represents the average gradation degree from density 0.3 to 3.0 of the characteristic curve, and 2.7 is ΔlogE (logarithmic value of exposure amount giving density 3.0 and density 0.3) It is shown by the value obtained by dividing by (difference in logarithm of exposure amount). The larger the value, the higher the contrast of the image characteristics.

<Developer composition> Potassium hydroxide 90.0 g Sodium hydroxide 8.0 g Ethylenediaminetetraacetic acid disodium 1.0 g Boric acid 24.0 g Sodium metabisulfite 65.0 g Potassium bromide 10.0 g Hydroquinone 55.0 g 5-Methylbenzotriazole 0.40 g N-methyl-p-aminophenol 0.50 g 2-Mercaptobenzimidazole-5-sulfonate sodium 0.30 g 3- (5-Mercaptotetrazole) benzenesulfonate sodium 0.20 g N- n-Butyl-diethanol-amine 14.0 g N, N-dimethylamino-6-hexanol 0.20 g sodium toluenesulfonate 8.0 g 5-sulfosalicylic acid 23.0 g potassium hydroxide was added and water was added to make 1 liter. pH Fit to 11.9. 1 liter

The results obtained are shown in Table 2. As is clear from Table 2, it is understood that the samples of the present invention have remarkably good coating suitability and do not impair the fast-acting property and photographic characteristics of the curing agent.

[0075]

[Table 2]

Example 2 Using the cured layer (A) of Example 1, the coating position of the cured layer was changed as shown in Table 3, coating and drying were carried out in the same manner as in Example 1 to obtain a sample. The obtained sample was tested for dry scratch strength and wet scratch strength as shown below, and the results shown in Table 3 were obtained. From Table 3, it can be seen that when the cured layer is the first layer, the wet scratch strength is weak, and when the fifth layer is the dry scratch strength, the dry scratch strength is weak, and it is the best when the second layer to the fourth layer of the present invention are used.

Scratch Strength Test After the sample was stored in an atmosphere of 25 ° C. and 50% for 7 days, the sample was kept as it was in the case of dry scratching strength, and the sample was kept at 38 ° C. in the case of wet scratching strength by Fuji Photo Film Co., Ltd. Made by GRAN
After immersing in SGX-D1 developer for DEX system for 20 seconds, press it onto the sample surface with a sapphire needle with a radius of 0.4 mm, and
The load (g) when the film breaks was measured by continuously changing the load of the needle while moving at a speed of 0 mm / sec.

[0078]

[Table 3]

Example 3 The surfactants in the cured layers (A) and (D) of Example 1 are shown in Table-4.
The long-term coating suitability was evaluated in the same manner as in Example 1 except that the above changes were made, and the swelling ratio and the photographic property of the obtained sample were evaluated in the same manner as in Example 1. The results are shown in Table-4. As is clear from Table 4, the samples of the present invention have excellent long-term application suitability and do not impair the rapid-acting properties and photographic characteristics of the curing agent.

[0080]

[Table 4]

Example 4 Both sides of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) were subjected to corona discharge treatment, and then an undercoat liquid having the following composition was applied to provide an undercoat layer on the high temperature surface side during stretching. . For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and the support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. <Undercoat layer> Gelatin 1 part by weight Distilled water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight p-Chlorophenol 4 parts by weight This undercoating solution is applied at 10 ml / m ^{2 and} dried at 115 ° C. for 2 minutes. did.

A conductive layer, a back layer and a back protective layer shown below were simultaneously coated on one side of this support. (Conductive layer) Gelatin (Ca ⁺⁺ content 30 ppm) 0.1 g / m ² SnO ₂ / Sb (90/10, average particle size 0.25 μ) 200 mg / m ² p-dodecylbenzenesulfonic acid sodium salt 10 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Sodium polystyrene sulfonate 9 mg / m ² Proxel 7 mg / m ² (back layer) Gelatin (Ca ⁺⁺ content 30 ppm) 3.0 g / m ² p-dodecylbenzene sodium sulfonate 40 mg / m ² dibenzyl -α- sulfosuccinates sodium salt 40 mg / m ² 1,2-bis (vinylsulfonyl acetamide) ethane 200 mg / m ² dye following dye (A), (B), (C) , (D) Dye (A) 20 mg / m ² Dye (B) 50 mg / m ² Dye (C) 20 mg / m ² Dye (D) 30 mg / m ² Proxel 10 mg / m ²

[0083]

[Chemical 30]

(Back protective layer) Gelatin (Ca ⁺⁺ content 30 ppm) 1.1 g / m ² Polymethylmethacrylate fine particles (average particle size 3.0 μ) 20 mg / m ² p-dodecylbenzenesulfonic acid sodium salt 15 mg / m ² Dibenzyl-α-sulfosuccinate sodium salt 15 mg / m ² Sodium acetate 60 mg / m ² Proxel 1 mg / m ²

Then, on the opposite side of the support, the bottom layer having the following composition, the emulsion first layer, the intermediate layer, the cured layer (A) of Example 1 (coating agent coating amount 90 mg / m ² ), the emulsion layer having the following composition For the second layer and the protective layer, a slide coater was used as in Example 1, and 1 cc / mm of the same dummy liquid as in Example 1 was applied along the coating width regulating plate.
It was applied simultaneously while flowing at a flow rate of min. <Bottom layer> Gelatin 0.2 g / m ² Polyethyl acrylate latex (particle size 0.05 μ) 0.2 g / m ² <Emulsion layer first layer> (Preparation of hydrazine-containing layer emulsion and coating solution) Silver nitrate 6
Silver nitrate aqueous solution 250cc prepared by dissolving 3g, the _{K 2 Rh (H 2 O)} Cl 6 and K ₃ IrCl ₆ corresponding to 1 × 10 ^-7 mol equivalent to 1 × 10 ^-7 mole per silver mole of the total emulsion 250 cc of an aqueous solution of a halogen salt in which 20 g of potassium bromide and 14 g of sodium chloride are dissolved, and sodium chloride (0.5%) and 1,
3-Dimethyl-2-imidazolithione (0.002%)
And 2% gelatin aqueous solution containing citric acid (0.05%) were added by stirring with a double jet method at 38 ° C. for 12 minutes to obtain silver chlorobromide having an average grain size of 0.20 μm and a silver chloride content of 55 mol%. Nucleation was performed by obtaining particles. Subsequently, 450 cc of a silver nitrate aqueous solution in which 107 g of silver nitrate was dissolved, 28 g of potassium bromide and 28 g of sodium chloride were added.
450 cc of an aqueous solution of halogen salt in which g was dissolved was added by the double jet method over 20 minutes to form particles.

Then, 1 × 10 ⁻³ mol of KI solution was added to 1 mol of silver for conversion, and the product was washed with water by a flocculation method according to a conventional method. Then, 40 g of gelatin was added per mol of silver, and the pH was 6.0, pAg
After adjusting to 7.5, 7 mg of sodium benzenethiosulfonate, 2 mg of sodium benzenesulfinate, 5 mg of sodium thiosulfate and 8 mg of chloroauric acid were added to 1 mol of silver, and the mixture was heated at 60 ° C. for 70 minutes for chemical sensitization. Then, 4-hydroxy-6-methyl-1, as a stabilizer,
150 mg of 3,3a, 7-tetrazaindene and 30 mg of proxel as a preservative were added. The obtained grains were silver iodochlorobromide cubic grains having an average grain size of 0.27 μm and a silver chloride content of 60 mol%. (Variation coefficient 10%)

Silver 1 was added to each of the emulsions as a sensitizing dye.
3 × 10 ⁻⁴ mol of 5- [3- (4-sulfobutyl) -5-chloro-2-benzoxazolidylidene] per mol
Ethylidene-1-hydroxyethoxyethyl-3- (2
-Phenyl) -2-thiohydantoin potassium salt, and 3 x 10 ^-4 mol of 5- [3- (4-sulfobutyl)-
2-benzoxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-phenyl) -2-thiohydantoin potassium salt was added, and 6 × 10 ⁻⁴ mol of the following structural formula (E) was used. Shortwave cyanine dye, 3
× 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole, 6 × 10 ^-4 mol of the mercapto compound represented by the following structural formula (F), and the mercapto compound represented by the following structural formula (G), 3 × 10 ^-4 mol of the triazine compound represented by the following structural formula (H), 3 × 10 ^-4 mol of the compound represented by the following structural formula (I), 6 × 10 ^-4 mol of 5-chloro-8 -Hydroxyquinoline, and as a hydrazine compound, 1 × 10 ⁻³ mol of a compound represented by the following structural formula (J) and 1 × 10 ⁻³ mol of a compound represented by the following structural formula (K) are added, and , N-oleyl-N-methyltaurine sodium salt 30 mg / m ² , colloidal silica (Nissan Chemical's Snowtex C) 500 mg / m ² , polyethyl acrylate dispersion 500 mg / m ² , as applied. Add Hydra To prepare a coating solution for the layer containing. The pH of the coating solution was adjusted to 6.0. This coating liquid is Ag3.5
It was coated so as to have g / m ² and gelatin of 1.7 g / m ² .

[0088]

[Chemical 31]

[0089]

[Chemical 32]

<Intermediate Layer> Gelatin 1.0 g / m ² Proxel 3 mg / m ² Sodium ethanethiosulfonate 5 mg / m ² Dye (L) 100 mg / m ² Hydroquinone 100 mg / m ² Polyethyl acrylate latex (particle size 0. 05μ) 300mg / m ²

[0091]

[Chemical 33]

<Second emulsion layer> (Preparation of redox compound-containing layer emulsion and coating solution)
700 cc of silver nitrate aqueous solution in which 170 g of silver oxide is dissolved, and 1 silver
3 x 10 per mole ^-7Equivalent to mol (NH_Four)₃RhC
l₆Containing 36 g potassium bromide and 4 sodium chloride
700 g of an aqueous solution of halogen salt in which 7 g is dissolved is added to sodium chloride.
Lithium (0.5%) and 1,3-dimethyl-2-imidazo
2% gelatin water solution containing lithion (0.002%)
Double jet method at 45 ° C for 30 minutes while stirring the liquid
Added, average grain size 0.30 μm, silver chloride content
70 mol% of silver chlorobromide grains were obtained. After that, 1 mol of silver
1 x 10^-3Conversion by adding mol KI solution
And wash with water by the flocculation method according to the usual method.
Then, 40 g of gelatin was added to 1 mol of silver to give a pH of 6.
0, pAg 7.5 adjusted to 1
Sodium zenthiosulfonate 7mg and benzene sulfi
Sodium acid salt 2 mg, chloroauric acid 8 mg and sodium thiosulfate
Add 5 mg of thorium and heat at 60 ° C for 60 minutes for chemical sensitization
After application, 4-hydroxy-6-methyl- as a stabilizer
350 mg of 1,3,3a, 7-tetrazaindene and protection
100 mg of proxel was added as a preservative. Particles obtained
Has an average grain size of 0.30 μm and a silver chloride content of 70 mol
It was a% silver chlorobromide cube. (Coefficient of variation 9%)

The emulsion thus obtained was added with 5 × 10 ⁻⁴ mol of 5- [3- (4-sulfobutyl) -5 as a sensitizing dye per 5 mol of silver of the redox compound-containing layer emulsion.
-Chloro-2-benzoxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-phenyl) -2-thiohydantoin potassium salt, and 6 × 1
A mercapto compound represented by the structural formula (F) added to ^0-4 mol of the hydrazine-containing layer coating solution, 3 × 10 ^-4 mol of the triazine compound represented by the structural formula (H), 6 × 10 ^-4
Mol of 5-chloro-8-hydroxyquinoline, 10 mg / m ^{2 of the} dye represented by the following structural formula (M), 60 mg / m ^{2 of the} redox compound represented by the following structural formula (N), and polyethyl acrylate. Dispersion (300 mg / m ² ) was added. This coating solution was Ag 0.3 g / m ² , gelatin 0.3
It was applied so that it became mg.

[0094]

[Chemical 34]

<Protective Layer> Gelatin 0.3 g / m ² matting agent (polymethylmethacrylate fine particles: average particle size 2.5 μm) 40 mg / m ² colloidal silica (Snowtex C manufactured by Nissan Chemical Co., Ltd.) 100 mg / m ² liquid paraffin 50 mg / m ² fluorosurfactant (O) 5 mg / m ² sodium p-dodecylbenzenesulfonate 20 mg / m ²

[0096]

[Chemical 35]

With respect to this sample, suitability for long-term application was evaluated in the same manner as in Example 1. As a result, even after continuous application for 48 hours,
It was good with no occurrence of surface unevenness.

Example 5 A polyethylene terephthalate support (thickness 100 μm) coated with an undercoat layer on both sides of Example 1 was coated with a conductive layer and a back layer having the following compositions on one side. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 77 mg / m ² compound-4 7 mg / m ² dodecylbenzenesulfonic acid Sodium 10 mg / m ² Dihexyl-α-sulfosuccinate sodium 40 mg / m ² Sodium polystyrene sulfonate 9 mg / m ²

[0099] <Back Layer> Gelatin (Ca ⁺⁺ content 30ppm) 2.82g / m ² Compound -4 3 g / m ² Matting agent Table 3 Compound -5 40 mg / m ² Compound -6 80 mg / m ² Compound - 7 80 mg / m ² sodium dodecylbenzene sulfonate 75 mg / m ² dihexyl-α-sulfosuccinate sodium 20 mg / m ² compound-8 5 mg / m ² N-perfluorooctanesulfonyl-N-propylglycine potadium 7 mg / m ² sulfuric acid Sodium 50 mg / m ² Sodium acetate 85 mg / m ² 1,2-bis (vinylsulfonylacetamido) ethane 150 mg / m ²

[0100]

[Chemical 36]

[0101]

[Chemical 37]

Then, on the opposite side of the support, an emulsion layer having the following composition, the cured layer (A) of Example 1 (coating amount of the curing agent: 100 mg /
m ² ), using a slide coater for the lower layer and the upper layer of the following composition in the same manner as in Example 1, while flowing a dummy liquid similar to that in Example 1 at a flow rate of 1 cc / min along the coating width regulating plate, It was applied at the same time. <Emulsion layer> Emulsion preparation Liquid I Water 1000 ml Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 g Sodium benzenesulfonate 6 mg II liquid Water 400 ml Silver nitrate 100 g III liquid Water 400 ml Sodium chloride 30.5 g Bromide Potassium 14g Potassium hexachloroiridium (III) (0.001% aqueous solution) 15ml Ammonium hexabromodium (III) (0.001% aqueous solution) 1.5ml Solution I and solution III kept at pH = 4.5 at 38 ° C The solution was added simultaneously with stirring for 10 minutes to give 0.16
Fine particles of μm were formed. Then, the following IV liquid and V liquid 10
Added over minutes. Further potassium iodide 0.15
g was added to complete the grain formation.

Liquid IV water 400 ml Silver nitrate 100 g V liquid water 400 ml Sodium chloride 30.5 g Sodium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 ⁻⁵ mol / mol Ag Then, according to the conventional method, by the flocculation method, After washing with water, 40 g of gelatin was added.

This emulsion had a pH of 5.3 and a pAg of 7.
Adjusted to 5, sodium thiosulfate 5.2mg, chloroauric acid 1
0.0 mg and 2.0 mg of N, N-dimethylselenourea were added, 8 mg of sodium benzenesulfonate and 2.0 mg of sodium benzenesulfinate were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally A silver iodochlorobromide cubic grain emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was prepared. Then, a sensitizing dye was added at 5 × 10 ⁻⁴ mol / mol Ag for ortho-sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added at 2.5 g per 1 mol of Ag, respectively.
50 mg of colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd., average particle size 0.015 μm) to gelatin, 30
40% by weight of polyethyl acrylate latex (0.05 μm) as a plasticizer, based on gelatin.
added. This coating solution was Ag 3.3 g / m ² , gelatin 1.
It was applied so as to be 5 g / m ² .

[0105]

[Chemical 38]

<Protective layer lower layer formulation> Gelatin per m ² 0.5 g Sodium benzenesulfonate 4 mg 1,5-dihydroxy-2-benzaldoxime 25 mg Polyethyl acrylate latex 125 mg <Protective layer upper layer formulation> Gelatin per m ² 25 g Matting agent (polymethylmethacrylate fine particles; average particle size 2.5 μm) 40 mg Compound-9 (gelatin dispersion of slipping agent) 30 mg Colloidal silica (Snowtex C manufactured by Nissan Chemical Industries) 30 mg Compound-10 5 mg Sodium dodecylbenzenesulfonate 22 mg This The coefficient of dynamic friction of each sample is 0.22 ± 0.03 (2
5 ℃ 60RH, Sapphire needle φ = 1mm, load 100g,
The speed was 60 cm / min).

[0107]

[Chemical Formula 39]

With respect to this sample, the suitability for long-term coating was evaluated in the same manner as in Example 1. As a result, even after continuous coating for 48 hours,
It was good with no occurrence of surface unevenness.

Example 6 In place of the sensitizing dye of the emulsion of Example 5, 100 mg was added per mol of Ag, and then as a supersensitizer and stabilizer,
4,4'-bis (4,6-dinaphthoxy-pyrimidine-
2-ylamino))-stilbene disulfonic acid disodium was added in an amount of 300 mg per mol of Ag to perform panchromatic sensitization. Additionally, antifoggants, colloidal silica, plasticizers added in the same manner as in Example 4, the coating liquid of the emulsion layer was prepared, Ag3.4g / m ^2, was coated so as to be gelatin 1.4 g / m ² . The hardened layer was changed to the hardened layer (D) of Example 1, and the applied amount of the hardener is 100 mg / m ² . The other conductive layers, the back layer, the lower layer and the upper layer of the protective layer were coated with the same composition as in Example 5. The sample was evaluated for suitability for a long time in the same manner as in Example 1. As a result, even if it was continuously applied for 48 hours, no unevenness in the surface condition was generated and it was good.

[0110]

[Chemical 40]

Example 7 A back layer and a back protective layer having the following compositions were simultaneously coated on one side of a polyethylene terephthalate support (thickness: 100 μm) coated with a subbing layer on both sides of Example 4.

<Back Layer> Gelatin 2.5 g / m ² Compound-11 3 mg / m ² Dye-a 35 mg / m ² Compound-b 95 mg / m ² Compound-c 70 mg / m ² Dihexyl-α-sulfosuccinate sodium 25 mg / m ² sodium dodecylbenzene sulfonate 35 mg / m ² acetic acid 10 mg / m ² polyethyl acrylate latex (particle size 0.05 μm) 500 mg / m ² 1,3-divinylsulfonyl-2-propanol 130 mg / m ² <back protection Layer> Gelatin 0.8 g / m ² compound-11 1 mg / m ² polymethylmethacrylate tex (particle size 3.4 μm) 35 mg / m ² dihexyl-α-sulfosuccinate sodium 7 mg / m ² sodium dodecylbenzenesulfonate 10 mg / M ² compound-12 2 mg / m ² sodium acetate 30 mg / m ²

[0113]

[Chemical 41]

Then, on the surface opposite to the support, an emulsion layer having the following composition, Cured Layer-A of Example 1 (a coating amount of the curing agent of 130 mg) was used.
/ M ² ), a protective layer having the following composition was simultaneously applied along a coating width regulating plate using a slide coater as in Example 1, while flowing the same dummy liquid as in Example 1 at a flow rate of 1 cc / min. <Emulsion layer> A 0.13 M silver nitrate aqueous solution, 0.04 M potassium bromide and 0.09 M sodium chloride, and a halogen salt aqueous solution containing ammonium hexachlororhodium (III) acid are added to sodium chloride and 1,8-dihydroxy-
The mixture was added to a gelatin aqueous solution containing 3,6-dithiaoctane by stirring with a double jet method at 45 ° C. for 12 minutes to give an average grain size of 0.15 μm and a silver chloride content of 70.
Nucleation was performed by obtaining mol% silver chlorobromide grains. Then, in the same manner as above, 0.86 M silver nitrate aqueous solution and 0.26
An aqueous solution of halogen salt containing M potassium bromide, 0.65 M sodium chloride, and potassium hexachloroiridium (III) was added by the double jet method over 20 minutes. After that, it was washed with water by the flocculation method according to a conventional method, 40 g of gelatin was added, and the pH was 6.5 and pA.
g 7.5, sodium thiosulfate 5 mg and chloroauric acid 8 mg are added per 1 mol of silver, and the mixture is heated at 60 ° C. for 75 minutes to be chemically sensitized, and then added as a stabilizer to 1,3,3.
150 mg of a, 7-tetrazaindene was added. The obtained particles had Rh of 1.0 × 10 ⁻⁷ mol per mol of silver, Ir
Containing 6.0 × 10 ⁻⁷ mol, an average particle size of 0.2
Cubic silver chlorobromide grains having a particle size of 8 μm (variation coefficient of 10%) and a silver chloride content of 70 mol% were obtained.

0.05 kg of infrared sensitizing dye was added to 1 kg of this emulsion.
% Solution (60 ml) was added, and as a supersensitizer and stabilizer,
4,4'-bis (4,6-dinaphthoxy-pyrimidine-
2-ylamino))-stilbene disulfonic acid disodium salt 70 ml of 0.5% methanol solution and 0.5 of 2,5-dimethyl-3-allyl-benzothiazole iodo salt
90 ml of a% methanol solution was added. Furthermore, hydroquinone 100 mg / m ² and polyethyl acrylate latex (particle size 0.05 μm) as a plasticizer were added to gelatin,
25% by weight added, silver 3.7 g / m ² , gelatin 2.5 g
It was applied so that it would be / m ² .

[0116]

[Chemical 42]

<Protective Layer> Gelatin 0.9 g / m ² compound-13 2 mg / m ² SiO ₂ matting agent (average particle size 3.6 μ) 40 mg / m ² compound-14 30 mg / m ² Dye-C 7 mg / m ² Sodium dodecylbenzene sulfonate 30 mg / m ² Colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) 10 mg / m ² compound-15 2 mg / m ² Hydroquinone 45 mg / m ² 1,5-dihydroxy-2-benzaldoxime 6 mg / m ² Sodium benzenethiosulfonate 4mg / m ²

[0118]

[Chemical 43]

With respect to this sample, the suitability for long-term coating was evaluated in the same manner as in Example 1. As a result, even after continuous coating for 48 hours,
It was good with no occurrence of surface unevenness.

Example 8 On one side of a polyethylene terephthalate support (thickness 100 μm) coated with a subbing layer on both sides of Example 1, an emulsion layer first layer and an emulsion layer second layer having the following compositions were prepared. Cured layer (D) (curing agent coating amount 150 mg / m ² ), protective layer lower layer and upper layer having the following composition were used in the same manner as in Example 1 using a slide coater, and along the coating width regulating plate as in Example 1. The dummy liquid was applied at the same time while flowing at a flow rate of 1 cc / min.

<Emulsion layer 1st layer> Gelatin containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (5 × 10 ⁻³ mol per mol of silver) kept at 40 ° C. An aqueous silver nitrate solution and an aqueous sodium chloride solution containing 2 × 10 ^-5 mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver are simultaneously added in 7 minutes, and the potential between them is controlled to 95 mV. By doing so, 0.12 μm of core particles were prepared. Then, 1.2 x 10 per 1 mol of silver and silver nitrate aqueous solution
^-Sodium chloride aqueous solution containing ⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added simultaneously for 14 minutes, and the potential was controlled to 95 mV during that period to obtain an average particle size of 0.15 μm.
Of silver chloride cubic grains were prepared. To this emulsion, add 6 parts of polyethyl acrylate latex (average particle size 0.05 μm).
A solution of 00 mg / m ² and the following hydrazine compound in a molar ratio of 1: 1 was 2.2 × 10 ⁻⁵ mol / m ² , respectively.
30 mg / m ^{2 of} 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, the following compounds-16 and -1
7 each ^{40mg / m 2, 10mg / m} 2 to become as added silver amount 2.0 g / m ^2, was coated so as to be gelatin 0.9 g / m ^2.

[0122]

[Chemical 44]

<Emulsion Layer Second Layer> 5,6− kept at 40 ° C.
Cyclopentane-4-hydroxy-1,3,3a, 7-
In a gelatin aqueous solution containing tetrazaindene (5 × 10 ⁻³ mol per 1 mol of silver), an aqueous silver nitrate solution and 4 × 10 ⁻⁵ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per mol of silver were added. An aqueous sodium chloride solution containing the same was added at the same time in 3 and a half minutes, and the potential during that period was adjusted to 95
By controlling to mV, the particle in the core is 0.08
μm was prepared. Then, an aqueous silver nitrate solution and an aqueous sodium chloride solution containing 1.2 × 10 ⁻⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver were simultaneously added over 7 minutes, and the potential between them was set to 9
Cubic silver chloride cubic grains having an average grain size of 0.10 µm were prepared by controlling to 5 mV. An emulsion layer similar to the above first emulsion layer except that it was used in this emulsion was coated so that the silver amount was 1.5 g / m ² gelatin and 0.7 g / m ² .

<Lower layer of protective layer> 1-hydroxy-2-benzaldoxime 15 mg / m ² compound-19 80 mg / m ² compound-20 10 mg / m ² polyethyl acrylate latex (average particle size 0.05 μm) 280 mg / m ² <Protective layer upper layer> Gelatin 0.95 g / m ² Irregular matting agent (SiO ₂ , average particle size 3.0 μm) 30 mg / m ² Spherical matting agent (PMMA, average particle size 2.7 μm) 30 mg / m ² Liquid paraffin (Gelatin dispersion) 50 mg / m ² N-perfluorotoctansulfonyl-N-propyl glycine potassium 5 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² * Solid disperse dye A 80 mg / m ² * Solid disperse dye B 40 mg / m ² * Preparation Method of Fine Particle Dispersion of Solid Disperse Dyes A and B The preparation method in the present invention was according to the method of JP-A-63-197943. That is, water (434 ml) and
Triton X-200R Surfactant (TX-200R)
(53 g) (sold by Rohm & Haas) and a 6.7% solution were placed in a 1.5 liter screw cap bottle. To this, 20 g of the dye and a bead of zirconium oxide (ZrO ₂ ) (80
0 ml) (2 mm diameter) was added, the bottle was capped tightly, placed in a mill and the contents crushed for 4 days. 12.5% gelatin aqueous solution (160g)
Was added and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO ₂ beads. If this is left, the average particle size is about 0.3 μm,
Since the particles still contained coarse particles, the particles were classified by a centrifugal separation method so that the maximum particle size was 1 μm or less.

[0125]

[Chemical formula 45]

On the other side of the support, a conductive layer and a back layer having the following compositions were precoated simultaneously before coating the emulsion layer. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ² gelatin (Ca ⁺⁺ content 3000 ppm) 77 mg / m ² compound-6 7 mg / m ² dodecylbenzenesulfonic acid Sodium 10 mg / m ² Dihexyl-α-sulfosuccinate sodium 40 mg / m ² Sodium polystyrene sulfonate 9 mg / m ²

<Back Layer> Gelatin (Ca ⁺⁺ content 30 ppm) 2.82 g / m ² Polymethylmethacrylate fine particles (average particle size 4.7 μ) 54 mg / m ² compound-21 3 mg / m ² compound-22 40 mg / m ² compound-23 40 mg / m ² compound-24 80 mg / m ² compound-25 150 mg / m ² sodium dodecylbenzenesulfonate 75 mg / m ² dihexyl-α-sulfosuccinate sodium 20 mg / m ² compound-26 5 mg / m ² sodium acetate ² sodium sulfate 50mg / m 85mg / m ² 1,2- bis (vinylsulfonyl acetamide) ethane 150 mg / m ²

[0128]

[Chemical formula 46]

[0129]

[Chemical 47]

With respect to this sample, the suitability for long-term coating was evaluated in the same manner as in Example 1. As a result, even after continuous coating for 48 hours,
It was good with no occurrence of surface unevenness. Example 9 A conductive layer and a protective layer having the following formulations were sequentially coated on one side of a 125 μm-thick polyethylene terephthalate support having subbing layers on both sides, in the order close to the support. (1) Conductive layer Julimer ET410 (manufactured by Nippon Pure Chemical KK) 38 mg / m ² (polyacrylic acid ester) SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μ) 216 mg / m ² compound-275 mg / M ² compound-28 5 mg / m ² (2) Protective layer Chemipearl S120 (manufactured by Mitsui Petrochemical KK) 33 mg / m ² (aqueous polyolefin dispersion) Snowtex C (manufactured by Nissan Kagaku KK) 17 mg / m ² compound-27 5 mg / m ² compound-29 5 mg / m ² sodium polystyrene sulfonate 2 mg / m ²

[0131]

[Chemical 48]

Then, on the surface opposite to the support, a dyeing layer having the following composition, an emulsion layer, a cured layer (A) of Example 1 (coating agent coating amount 100 mg / m ² ) and a protective layer having the following composition were implemented. A slide coater was used in the same manner as in Example 1, and the same dummy liquid as in Example 1 was applied at a flow rate of 1 cc / min along the application width regulating plate, and simultaneously applied. (3) Dyeing layer Gelatin 1.5 g / m ^{2 *} Solid disperse dye Refer to Table-6 Compound-30 8 mg / m ² Compound-31 40 mg / m ² Sodium polystyrene sulfonate 25 mg / m ² Sodium dodecylbenzene sulfonate 15 mg / m ² phosphoric acid 15mg / m ²

[0133]

[Chemical 49]

^* Preparation Method of Solid Disperse Dye The preparation method in the present invention was according to the method of JP-A-63-197943. That is, 434 ml of water and Triton X-
53 g of a 6.7% solution of 200R surfactant (TX-200R, sold by Rohm & Haas) was placed in a 1.5 liter screw cap bottle. To this, 20 g of the dye and 80 ml of zirconium oxide (ZrO ₂ ) beads (2 mm diameter) were added, the lid of the bottle was tightly placed and placed in a mill, and the contents were ground for 4 days. The contents were added to 160 g of a 12.5% aqueous gelatin solution and placed on a roll mill for 10 days to reduce foam. The resulting mixture was filtered to remove ZrO ₂ beads. Since the average particle size was 0.3 μm in this state, it still contained coarse particles, so that the particles were classified by the centrifugal separation method so that the maximum particle size was 1 μm or less.

(4) Emulsion Layer Preparation of Emulsion While the following solution A was kept at 65 ° C. and stirred, solution B and solution C were added to 5 times.
Added by the double jet method for minutes. Then 7 minutes 6
After physical aging was performed while maintaining the temperature at 5 ° C, the following D liquid and E
The solution was added over 40 minutes by the controlled double jet method while controlling the pAg to 7.2. The obtained grains were monodisperse cubic silver iodobromide grains having an average grain size of 0.26 μm and a silver iodide content of 1 mol% (variation coefficient: 10%). (Solution A) Gelatin 20 g Potassium bromide 3 g Benzenethiosulfonic acid 5 mg 1,3-Dimethylimidazolidine-2-thione 6 mg Water was added to 900 ml (Solution B) Silver nitrate 18.9 g Water was added to 85 ml (Solution C) Odor Potassium iodide 13.9 g Water added 60 ml (D liquid) Silver nitrate 151 g Water added 680 ml (E liquid) Potassium bromide 106 g Potassium iodide 1.5 g Water added 455 ml Then washed with water according to the conventional method Then, add 41 g of gelatin, pH 6.8, pAg 8.9
Adjusted to. After dissolving and dispersing this emulsion at 35 ° C,
After adding 5 × 10 ⁻⁴ mol / mol Ag of a sensitizing dye, 15
After raising the temperature to 65 ° C. over a period of time, 14 mg of sodium thiosulfate, 4 mg of N, N-dimethylselenourea per mol of silver,
Add 5 mg of chloroauric acid and 7 mg of benzenethiosulfonic acid and add 6
Chemical sensitization was performed for 0 minutes, and 4-hydroxy- was used as a stabilizer.
6-methyl-1,3,3a, 7-tetrazaindene 10
Add 0 mg of phenoxyethanol as preservative to 100
mg was added.

[0136]

[Chemical 50]

Furthermore, 1-phenyl-5-mercaptotetrazole 15 mg / mol Ag, 3- (5-mercaptotetrazole) -sodium benzene sulfonate 100 mg
/ Mol Ag, 4-hydroxy-6-methyl-1,3,3
1.5 g of a, 7-tetrazaindene / mol Ag, 700 mg / mol Ag of potassium bromide and 150 mg / mol Ag of compound-6 were added.

[0138]

[Chemical 51]

Next, 20 mg of sodium polystyrene sulfonate was added as a thickener per 1 g of gelatin, and the pH was adjusted to 5.2 with phosphoric acid. Furthermore, polyethyl acrylate latex as plasticizer (average particle size 0.05 μm)
Was added to gelatin at 30% by weight. This coating liquid is A
g1.4g / m ^2, was coated as a gelatin 1.3g / m ^2. (5) Protective layer Gelatin 0.5 g / m ² Polymethylmethacrylate fine particles (average particle size 0.9 μ) 25 mg / m ² compound-33 (gelatin dispersion) 40 mg / m ² compound-34 8 mg / m ² dodecylbenzene Sodium sulfonate 5 mg / m ² Colloidal silica (Snowtex C manufactured by Nissan Kagaku) 88 mg / m ² Compound-35 5 mg / m ² L-ascorbic acid 10 mg / m ² 1,5-dihydroxy-2-benzaldoxime 5 mg / m ² Sodium acetate 100 mg / m ² Polystyrene sulfonate 15 mg / m ²

[0140]

[Chemical 52]

With respect to this sample, the suitability for long-term coating was evaluated in the same manner as in Example 1. As a result, even after continuous coating for 48 hours,
It was good with no occurrence of surface unevenness.

[Procedure amendment]

[Submission date] February 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

Examples include groups represented by: Y ⁻ represents an anion, and is a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆ ^−.
Are preferred. When Y ⁻ represents a sulfonate ion, it may combine with X, R ¹⁴ , R ¹⁵ , R ¹⁶ or R ¹⁷ to form an inner salt. Regarding the amidinium salt-based curing agent represented by the general formula (IV), JP-A-60-225148.
No. 61-240236, 63-229450
No. 3 to 501033, etc., there are detailed descriptions.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

5) Surfactant From JP-A-2-12236, page 9, upper right column, line 7 From antistatic agent, same as lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column 18, line 18. 6) Polymer latex JP-A-2-103536, page 18, lower left column, lines 12 to 20. JP-A-4-214551, paragraph numbers “0041” to “0045”. JP-A 64-538, page 5, upper left column, line 9 to page 12, upper right column, line 16 7) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1 and JP-A-2-5 5349, page 8, lower right column, line 13 From the same page, page 1, upper left column, line 8 8) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A-1-23753 A thiosulfinic acid compound described in JP-B-8. 9) Polyhydroxybenze JP-A-2-55349, page 11, upper left column, page 9 to lower right column, line 17 10) Lubricants, plasticizers, mats JP-A-2-103536, page 19, upper right column, line 6 to agent, page 19 upper right column, line 15 11) Dyes JP-A-2-103536, page 17, lower right column, lines 1 to 18; JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5; Solid dyes described in JP-A-2-294638 and Japanese Patent Application No. 3-185773. 12) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 20. 13) Black spot inhibitor The compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 14) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143), R-1), (R-2), (R-3), compound examples 1 to 75, and compounds described in Japanese Patent Application Nos. 3-69466 and 3-15648. 15) Monomethine compounds Compounds of general formula (II) described in JP-A-2-287532 (particularly compound examples II-1 to II-26). 16) Colloidal silica The compound described in paragraph “0005” of JP-A-4-214551. 17) Developer and developing method JP-A-2-103536, page 19, upper right column, line 16 to page 21, upper left column, line 8 JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

Then, on the opposite side of the support, the bottom layer having the following composition, the emulsion first layer, the intermediate layer, the cured layer (A) of Example 1 (coating agent coating amount 90 mg / m ² ), the emulsion layer having the following composition For the second layer and the protective layer, a slide coater was used as in Example 1, and 1 cc / mm of the same dummy liquid as in Example 1 was applied along the coating width regulating plate.
It was applied simultaneously while flowing at a flow rate of min. <Bottom layer> Gelatin 0.2 g / m ² Butyl acrylate / acrylic acid / 2-acetoacetoxy ethyl methacrylate (84/6/10 mol%) copolymerized latex (average particle size 0.1 μm) 0.2 g / m ² < Emulsion layer 1st layer> (Preparation of hydrazine-containing layer emulsion and coating solution) Silver nitrate 6
Silver nitrate aqueous solution 250cc prepared by dissolving 3g, the _{K 2 Rh (H 2 O)} Cl 6 and K ₃ IrCl ₆ corresponding to 1 × 10 ^-7 mol equivalent to 1 × 10 ^-7 mole per silver mole of the total emulsion 250 cc of an aqueous solution of a halogen salt in which 20 g of potassium bromide and 14 g of sodium chloride are dissolved, and sodium chloride (0.5%) and 1,
3-Dimethyl-2-imidazolithione (0.002%)
And 2% gelatin aqueous solution containing citric acid (0.05%) were added by stirring with a double jet method at 38 ° C. for 12 minutes to obtain silver chlorobromide having an average grain size of 0.20 μm and a silver chloride content of 55 mol%. Nucleation was performed by obtaining particles. Subsequently, 450 cc of a silver nitrate aqueous solution in which 107 g of silver nitrate was dissolved, 28 g of potassium bromide and 28 g of sodium chloride were added.
450 cc of an aqueous solution of halogen salt in which g was dissolved was added by the double jet method over 20 minutes to form particles.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0087

[Correction method] Change

[Correction content]

Silver 1 was added to each of the emulsions as a sensitizing dye.
3 × 10 ⁻⁴ mol of 5- [3- (4-sulfobutyl) -5-chloro-2-benzoxazolidylidene] per mol
Ethylidene-1-hydroxyethoxyethyl-3- (2
-Phenyl) -2-thiohydantoin potassium salt, and 3 x 10 ^-4 mol of 5- [3- (4-sulfobutyl)-
2-benzoxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-phenyl) -2-thiohydantoin potassium salt was added, and 6 × 10 ⁻⁴ mol of the following structural formula (E) was used. Shortwave cyanine dye, 3
× 10 ^-4 mol of 1-phenyl-5-mercaptotetrazole, 6 × 10 ^-4 mol of the mercapto compound represented by the following structural formula (F), and the mercapto compound represented by the following structural formula (G), 3 × 10 ^-4 mol of the triazine compound represented by the following structural formula (H), 3 × 10 ^-4 mol of the compound represented by the following structural formula (I), 6 × 10 ^-4 mol of 5-chloro-8 -Hydroxyquinoline, and as a hydrazine compound, 1 × 10 ⁻³ mol of a compound represented by the following structural formula (J) and 1 × 10 ⁻³ mol of a compound represented by the following structural formula (K) are added, and , N-oleyl-N-methyltaurine sodium salt 30 mg / m ² , colloidal silica (Nissan Chemical Snowtex C) 500 mg / m ² , butyl acrylate / acrylic acid / 2-acetoacetoxyethyl methacrylate (84 Copolymerized latex (average particle size 0.1 μm) (500 mg / m ² ) was added so as to be coated to prepare a hydrazine-containing layer coating solution. The pH of the coating solution was adjusted to 6.0. This coating liquid is Ag 3.5 g /
m ² and gelatin 1.7 g / m ² were applied.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

<Intermediate layer> Gelatin 1.0 g / m ² Proxel 3 mg / m ² Sodium ethanethiosulfonate 5 mg / m ² Dye (L) 100 mg / m ² Hydroquinone 100 mg / m ² Butyl acrylate / acrylic acid / 2-acetate Acetoxy ethyl methacrylate (84/6/10 mol%) copolymerized latex (average particle size 0.1 μm) 300 mg / m ²

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0093

[Correction method] Change

[Correction content]

The emulsion thus obtained was added with 5 × 10 ⁻⁴ mol of 5- [3- (4-sulfobutyl) -5 as a sensitizing dye per 5 mol of silver of the redox compound-containing layer emulsion.
-Chloro-2-benzoxazolidylidene] ethylidene-1-hydroxyethoxyethyl-3- (2-phenyl) -2-thiohydantoin potassium salt, and 6 × 1
A mercapto compound represented by the structural formula (F) added to ^0-4 mol of the hydrazine-containing layer coating solution, 3 × 10 ^-4 mol of the triazine compound represented by the structural formula (H), 6 × 10 ^-4
Mol of 5-chloro-8-hydroxyquinoline, 10 mg / m ^{2 of the} dye represented by the following structural formula (M), 60 mg / m ^{2 of the} redox compound represented by the following structural formula (N), butyl acrylate / Acrylic acid / 2-acetoacetoxyethyl methacrylate (84/6/10 mol%) copolymerized latex (average particle size 0.1 μm) (300 mg / m ² ) was added. This coating solution was Ag 0.3 g / m ² , gelatin 0.3 mg
Was applied so that

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0104

[Correction method] Change

[Correction content]

This emulsion had a pH of 5.3 and a pAg of 7.
Adjusted to 5, sodium thiosulfate 5.2mg, chloroauric acid 1
0.0 mg and 2.0 mg of N, N-dimethylselenourea were added, 8 mg of sodium benzenesulfonate and 2.0 mg of sodium benzenesulfinate were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally A silver iodochlorobromide cubic grain emulsion containing 80 mol% of silver chloride and having an average grain size of 0.20 μm was prepared. Then, a sensitizing dye was added at 5 × 10 ⁻⁴ mol / mol Ag for ortho-sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added at 2.5 g per 1 mol of Ag, respectively.
50 mg of colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd., average particle size 0.015 μm) to gelatin, 30
% By weight, and butyl acrylate / acrylic acid / 2-acetoacetoxyethyl methacrylate (84
/ 6/10 mol%) Copolymerized latex (average particle size 0.1 μm)
Was added to gelatin in an amount of 40% by weight. This coating solution is A
g3.3g / m ^2, was coated so as to become a gelatin 1.5g / m ^2.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction content]

<Protective Layer Lower Layer Formulation> Per m ² gelatin 0.5 g sodium benzenesulfonate 4 mg 1,5-dihydroxy-2-benzaldoxime 25 mg butyl acrylate / acrylic acid / 2-acetoacetoxy ethyl methacrylate (84/6 / 10 mol%) Copolymerized latex (average particle size 0.1 μm) 125 mg <Protective layer upper layer formulation> Gelatin per m ² 0.25 g Matting agent (polymethylmethacrylate fine particles; average particle size 2.5 μm) 40 mg Compound-9 (sliding agent) Gelatin dispersion) 30 mg Colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) 30 mg Compound-10 5 mg Sodium dodecylbenzenesulfonate 22 mg The dynamic friction coefficient of all the samples is 0.22 ± 0.03 (2
5 ℃ 60RH, Sapphire needle φ = 1mm, load 100g,
The speed was 60 cm / min).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0112

[Correction method] Change

[Correction content]

<Back Layer> Gelatin 2.5 g / m ² Compound-11 3 mg / m ² Dye-a 35 mg / m ² Compound-b 95 mg / m ² Compound-c 70 mg / m ² Dihexyl-α-sulfosuccinate sodium 25 mg / m ² sodium dodecylbenzene sulfonate 35 mg / m ² acetic acid 10 mg / m ² butyl acrylate / acrylic acid / 2-acetoacetoxy ethyl methacrylate (84/6/10 mol%) copolymerized latex (average particle size 0.1 μm) 500 mg / m ² 1,3-divinylsulfonyl-2-propanol 130 mg / m ² <Back protective layer> Gelatin 0.8 g / m ² compound-11 1 mg / m ² Polymethylmethacrylate fine particles (particle size 3.4 μm) 35 mg / m ² dihexyl -α- sulfosuccinates sodium 7 mg / m ² sodium dodecylbenzenesulfonate 10 mg / m ² compound -12 2 mg / m ² acetate Na Potassium 30mg / m ²

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Correction content]

0.05 kg of infrared sensitizing dye was added to 1 kg of this emulsion.
% Solution (60 ml) was added, and as a supersensitizer and stabilizer,
4,4'-bis (4,6-dinaphthoxy-pyrimidine-
2-ylamino))-stilbene disulfonic acid disodium salt 70 ml of 0.5% methanol solution and 0.5 of 2,5-dimethyl-3-allyl-benzothiazole iodo salt
90 ml of a% methanol solution was added. Furthermore, hydroquinone 100 mg / m ² , butyl acrylate / as a plasticizer
Acrylic acid / 2-acetoacetoxyethyl methacrylate (84/6/10 mol%) copolymer latex (average particle size 0.1
μm) was added to gelatin at 25% by weight, and silver 3.7 was added.
g / m ² and gelatin 2.5 g / m ² were applied.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0121

[Correction method] Change

[Correction content]

<Emulsion layer 1st layer> Gelatin containing 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (5 × 10 ⁻³ mol per mol of silver) kept at 40 ° C. An aqueous silver nitrate solution and an aqueous sodium chloride solution containing 2 × 10 ^-5 mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ per 1 mol of silver are simultaneously added in 7 minutes, and the potential between them is controlled to 95 mV. By doing so, 0.12 μm of core particles were prepared. Then, 1.2 x 10 per 1 mol of silver and silver nitrate aqueous solution
^-Sodium chloride aqueous solution containing ⁴ mol of (NH ₄ ) ₂ Rh (H ₂ O) Cl ₅ was added simultaneously for 14 minutes, and the potential was controlled to 95 mV during that period to obtain an average particle size of 0.15 μm.
Of silver chloride cubic grains were prepared. To this emulsion, 600 mg / m ² of butyl acrylate / acrylic acid / 2-acetoacetoxyethyl methacrylate (84/6/10 mol%) copolymerized latex (average particle size 0.1 μm) and the following hydrazine compound were used in a molar ratio. 1: 1 mixed solutions were each added to 2.
2 × 10 ⁻⁵ mol / m ² , 4-hydroxy-6-methyl-
30 mg / m ^{2 of} 1,3,3a, 7-tetrazaindene and 40 mg / m ² , 10 mg / m ² of the following compounds -16 and -17, respectively.
It added which becomes m ^2, the silver amount 2.0 g / m ^2, gelatin 0.9
It was applied so as to be g / m ² .

[Procedure Amendment 12]

[Document name to be amended] Statement

[Correction target item name] 0124

[Correction method] Change

[Correction content]

<Protective Layer Lower Layer> 1-Hydroxy-2-benzaldoxime 15 mg / m ² compound-19 80 mg / m ² compound-20 10 mg / m ² butyl acrylate / acrylic acid / 2-acetoacetoxy ethyl methacrylate (84 / 6/10 mol%) Copolymerized latex (average particle size 0.1 μm) 280 mg / m ² <protective layer upper layer> Gelatin 0.95 g / m ² Irregular matting agent (SiO ₂ , average particle size 3.0 μm) 30 mg / m ² spherical matting agent (PMMA, average particle size 2.7 μm) 30 mg / m ² liquid paraffin (gelatin dispersion) 50 mg / m ² N-perfluorotoctansulfonyl-N-propyl glycine potassium 5 mg / m ² dodecylbenzene sodium sulfonate 10 mg / m ² * solid disperse dye a 80mg / m ² * solid disperse dye B 40 mg / m ² * solid disperse dye a, in the preparation process of the present invention fine particle dispersion B Method of preparation according to the method of JP-A-63-197943. That is, water (434 ml) and
Triton X-200R Surfactant (TX-200R)
(53 g) (sold by Rohm & Haas) and a 6.7% solution were placed in a 1.5 liter screw cap bottle. To this, 20 g of the dye and a bead of zirconium oxide (ZrO ₂ ) (80
0 ml) (2 mm diameter) was added, the bottle was capped tightly, placed in a mill and the contents crushed for 4 days. 12.5% gelatin aqueous solution (160g)
Was added and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO ₂ beads. If this is left, the average particle size is about 0.3 μm,
Since the particles still contained coarse particles, the particles were classified by a centrifugal separation method so that the maximum particle size was 1 μm or less.

Claims (5)

[Claims] 1. A method for producing a silver halide photographic light-sensitive material in which gelatin is used as a binder and the gelatin is hardened by a fast-acting hardener, and a sol-gel convertible polysaccharide which is not substantially hardened by the hardener. A method for producing a silver halide photographic light-sensitive material, characterized in that a hardened layer containing the hardener is set as a layer sandwiched between hardened layers containing gelatin, and the hardened layer and the hardened layer are simultaneously coated. 2. The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein the fast-acting curing agent is represented by formula (I). General formula _{(I) CH 2 = CH- SO} 2 -C (R) H- (OC (R) H) n -
SO ₂ —CH═CH ₂ R represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, or a heterocyclic group, and these groups may be substituted. n represents 0 or 1. 3. The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein the sol-gel convertible polysaccharide is carrageenan. 4. The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein the pH of the hardening layer coating solution is 3 or more and 6 or less. 5. The silver halide photograph according to claim 1, wherein a slide bead coater or a curtain coater is used and coating is performed while flowing a liquid which is not cured by the curing agent along the coating width regulating plate. Manufacturing method of photosensitive material.