JPH11258722A - Silver halide photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material which is suitable for ultrafast treatment or treatment with a low replenisher amt. and which realizes low pollution, and to provide its treating method, especially to provide a photosensitive material in which enough max. density (Dmax) is obtd. and failure or irregularity in a drying process is hardly caused, and to provide its treating method. SOLUTION: This silver halide photographic sensitive material has at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a supporting body. The silver halide emulsion layer and/or hydrophilic colloid layer contains a developing agent and a latex derived from ethylene type unsatd. monomers having active methylene groups. Or, the silver halide emulsion layer and/or hydrophilic colloid layer may contain a developing agent and a compd. which has electron withdrawing groups and releases iodine ion in an alkaline atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material" or "light-sensitive material"), and a processing method therefor. .

[0002]

2. Description of the Related Art Black-and-white photosensitive materials (for X-rays, printing plate-making,
Micro, negative and the like) have been developed with an alkali developer containing hydroquinone as a developing agent and a 3-pyrazolidone or aminophenol compound as an auxiliary agent. However, hydroquinone has drawbacks in that safety issues are becoming apparent from a biological and toxicological standpoint, and the waste liquid treatment load is high. Further, the treated waste liquid contains hydroquinone and other unfavorable components due to environmental and pollution problems, and cannot be disposed of in a general drainage system, and must be treated as industrial waste. In places where photo processing is performed (for example, hospitals, printing companies, etc.), it is necessary to pay a collection fee to a specialized waste liquid processing company for collection of photographic waste liquid, request collection, and install pollution prevention equipment. I have. Furthermore, the principle of banning the dumping of industrial wastes from the sea was banned in 1996, and wastewater collection involves a large space for storing wastewater and an increase in the cost of collecting wastewater. For example, the necessity of waste liquid treatment is increasing.

[0003] For these reasons, not only the problem of waste liquid recovery but also the development of a method for reducing the amount of waste liquid and a technique for efficiently treating the waste liquid are urgently required. As one means for solving such a problem, a technology in which a developing agent is incorporated in a photosensitive material and processed with an alkaline liquid containing no developing agent is known.
search Disclosure 173 Volume 173
64 (1978), JP-A-50-39928, JP-A-57-84448, JP-A-63-228148, and the like.

However, these techniques cannot provide a sufficient image density, and the amount of silver in the photosensitive material must be increased in order to obtain the image density. In addition, there is a drawback that the processing cannot be performed at a low replenishment rate.

On the other hand, a hydroxyl group such as hydroquinone
It is known that a developing agent having H causes a tanning phenomenon that a crosslinking reaction occurs between the oxide of the main agent and gelatin as a hydrophilic binder to harden a gelatin film. When the tanning phenomenon occurs, it causes a drying unevenness failure due to the ultra-rapid processing.

[0006] The fixing solution used in the ultra-rapid processing is a hardening fixing solution containing a water-soluble aluminum salt for the purpose of shortening the drying time. It is known that the water-soluble aluminum salt changes into a hardly soluble aluminum salt in the fixing solution and becomes a precipitate when the developing solution taken out by the film that has passed through the developing solution is mixed into the fixing solution. In order to prevent this precipitation, a large amount of a boron compound is used, and this boron compound is released into the environment from a fixing waste liquid and a washing waste liquid. Boron compounds are not desirable for environmental protection, and it has been strongly desired to reduce boron compounds contained in waste liquid.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material which is suitable for ultra-rapid processing and low replenishment processing and achieves low pollution and a processing method therefor. In particular, it is an object of the present invention to provide a photosensitive material capable of sufficiently obtaining the maximum density (Dmax) and having less drying unevenness failure, and a processing method therefor.

[0008]

The above objects of the present invention are as follows. In a silver halide photographic material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the silver halide emulsion layer and / or the hydrophilic colloid layer is a developing agent, and A silver halide photographic material comprising a latex derived from an ethylenically unsaturated monomer having an active methylene group,

[0009] 2. In a silver halide photographic material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the silver halide emulsion layer and / or the hydrophilic colloid layer is a developing agent, and A silver halide photographic light-sensitive material comprising a compound having an electron-withdrawing group and releasing iodide ions in an alkaline atmosphere,

[0010] 3. In a silver halide photographic material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the silver halide emulsion layer and / or the hydrophilic colloid layer may contain a developing agent ,
And a silver halide photographic material characterized by containing an oxazoline-based polymer,

4. 3. The silver halide photographic material according to the above 1 or 2, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer contains an oxazoline-based polymer.

5. A silver halide photographic light-sensitive material characterized in that an aqueous resin dispersion of an oxazoline-based polymer containing a developing agent is applied after being added to a silver halide emulsion coating solution and / or a hydrophilic colloid coating solution. ,

6. The silver halide photographic light-sensitive material according to any one of the above items 1 to 4, which is processed with a processing solution having a pH of 8.0 or more containing no developing agent and sulfite and containing an alkaline agent, and then borate Processing method for a silver halide photographic light-sensitive material, characterized by processing with a fixing solution containing no

7. The silver halide photographic light-sensitive material according to any one of the above items 1 to 4, wherein the processing solution containing an alkali agent is prepared by dissolving a solid processing agent formed into tablets by compression molding. Processing method of silver halide photographic light-sensitive material,

[8] 7. The halogenation method according to the above item 5 or 6, wherein the processing solution is replenished in accordance with the processing of the silver halide photographic light-sensitive material, and the replenishment amount is 10 ml or less per four pieces of the silver halide photographic light-sensitive material. Each of the methods for processing a silver photographic light-sensitive material.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

First, a latex derived from an ethylenically unsaturated monomer having an active methylene group will be described. The latex derived from the ethylenically unsaturated monomer having an active methylene group used in the present invention may be any latex having an active methylene group, but a preferred latex is represented by the following general formula (1). Things.

[0018]

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In the formula, D represents a repeating unit derived from an ethylenically unsaturated monomer containing an active methylene group, and A represents a unit other than D and whose homopolymer has a glass transition temperature of 35 ° C. or lower. B represents a repeating unit derived from an ethylenically unsaturated monomer, and B represents a repeating unit derived from an ethylenically unsaturated monomer other than D and A. x, y, and z each represent a weight percentage ratio of each component, and x has a value of 0.5 to 4.0, y has a value of 60 to 99.5 and z has a value of 0 to 50. Furthermore, it represents x + y + z = 100.

More specifically, the ethylenically unsaturated monomer having an active methylene group represented by D is represented by the following general formula (2).

[0021]

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In the general formula (2), R ¹ is a hydrogen atom and has 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl,
n-butyl), or a halogen atom (for example, a chlorine atom,
A bromine atom), preferably a hydrogen atom, a methyl group or a chlorine atom. L represents a single bond or a divalent linking group, and is specifically represented by the following formula.

[0023]

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L ¹ is -CON (R ² )-(R ² represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms), -COO-, -NHCO −,
-OCO-,

[0025]

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(R ³ and R ⁴ each independently represent hydrogen, hydroxyl, halogen atom or substituted or unsubstituted alkyl, alkoxy, acyloxy or aryloxy), and L ² connects L ¹ to X Represents a linking group, m represents 0 or 1, and n represents 0 or 1. L ²
The linking group represented by is specifically represented by the following general formula (3).

[0027]

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J ¹ , J ² and J ³ may be the same or different, and represent —CO—, —SO ₂ — and —CON (R ⁵ ) —.
^{[R 5} is a hydrogen atom, an alkyl group (1-6 carbon atoms), a substituted alkyl group (having 1 to 6 carbon ^{_{atoms)], - SO 2 N (}} R 5) -
(R ⁵ is as defined above), -N (R ⁵ ) -R ^6- (R ⁵ is as defined above, R ⁶ is an alkylene group having 1 to about 4 carbon atoms),
-N (R ⁵ ) -R ⁶ -N (R ⁷ )-[R ⁵ and R ⁶ are as defined above, R ⁷ is a hydrogen atom, an alkyl group (having 1 to 1 carbon atoms)
6) represents a substituted alkyl group (1-6 carbon atoms). ],-
^{O -, - S -, -} N (R 5) -CO-N (R 7) - (R
⁵ and R ⁷ are as defined above), -N (R ⁵ ) -SO ₂ -N
(R ⁷ ) — (R ⁵ and R ⁷ are as defined above), —COO—,
—OCO—, —N (R ⁵ ) CO ₂ — (R ⁵ is as defined above), —N (R ⁵ ) CO— (R ⁵ is as defined above), and the like.

P, q, r, and s represent 0 or 1. X ¹ ,
X ² , X ³ , and X ⁴ may be the same or different from each other, and may be an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or 6 carbon atoms.
Represents a phenylene group of 20 to 20, and the alkylene group may be linear or branched. Examples of the alkylene group include, for example, methylene, methylmethylene, dimethylmethylene, dimethylene,
Examples of trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, and aralkylene groups include benzylidene, and examples of phenylene groups include p-phenylene, m-phenylene, methylphenylene, and chlorophenylene.

X represents a monovalent group containing an active methylene group, and a preferred specific example is R ⁸ —CO—CH ₂ —C
OO- [R ⁸ is a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, n-propyl, n
-Butyl, t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl and the like, and substituted or unsubstituted aryl groups (for example, phenyl, p-methylphenyl, p -Methoxyphenyl, o-chlorophenyl, etc.), alkoxy group (for example, methoxy, ethoxy, methoxyethoxy, n
-Butoxy, etc.), cycloalkyloxy groups (e.g., cyclohexyloxy), allyloxy (e.g., phenoxy, p-methylphenoxy, o-chlorophenoxy, p-
-Cyanophenoxy, etc.), amino group, substituted amino group (for example, methylamino, ethylamino, dimethylamino,
Butylamino, etc.)], NC—CH ₂ —COO—, R ⁸ —
CO—CH ₂ —CO (R ⁸ is as defined above), R ⁸ —CO
—CH ₂ —CONR ⁵ (R ⁵ and R ⁸ are as defined above) and the like.

Hereinafter, in the polymer represented by the general formula (1), an ethylenically unsaturated monomer having an active methylene group represented by D will be exemplified, but the present invention is not limited thereto.

M-1 2-acetoacetoxyethyl methacrylate M-2 2-acetoacetoxyethyl acrylate M-3 2-acetoacetoxypropyl methacrylate M-4 2-acetoacetoxypropyl acrylate M-5 2-acetoacetamidoethyl methacrylate M- 6 2-acetoacetamidoethyl acrylate M-7 2-cyanoacetoxyethyl methacrylate M-8 2-cyanoacetoxyethyl acrylate M-9 N- (2-cyanoacetoxyethyl) acrylamide M-10 2-propionylacetoxyethyl acrylate M-11 N- (2-propionylacetoxyethyl)
Methacrylamide M-12 N-4- (acetoacetoxybenzyl) phenylacrylamide M-13 ethyl acrylolyl acetate M-14 acryloylmethyl acetate M-15 N-methacryloyloxymethyl acetoacetamide M-16 ethyl methacryloyl acetoacetate M-17 N-allyl cyanoacetamide M-18 methyl acryloyl acetoacetate M-19 N- (2-methacryloyloxymethyl) cyanoacetamide M-20 p- (2-acetoacetyl) ethyl styrene M-21 4-acetoacetyl-1-methacryloyl Piperazine M-22 Ethyl-α-acetoacetoxymethacrylate M-23 N-butyl-N-acryloyloxyethylacetoacetamide M-24 p- (2-acetoacetoxy ) Ethyl styrene

The ethylenically unsaturated monomer giving the repeating unit represented by A is a monomer whose homopolymer has a glass transition temperature of 35 ° C. or lower, and specifically, an alkyl acrylate (for example, methyl Acrylate, ethyl acrylate, n-butyl acrylate, n
-Hexyl acrylate, benzyl acrylate, 2-
Ethylhexyl acrylate, n-dodecyl acrylate, etc.), alkyl methacrylate (eg, n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-dodecyl methacrylate, etc.), dienes (eg, butadiene, isoprene, etc.), vinyl esters (For example, vinyl acetate, vinyl propionate, etc.).

More preferred monomers are those having a homopolymer having a glass transition temperature of 10 ° C. or lower, and such monomers include alkyl acrylates having an alkyl side chain having 2 or more carbon atoms (eg, ethyl acrylate, n -Butyl acrylate, 2-ethylhexyl acrylate, etc.), an alkyl methacrylate having an alkyl side chain having 6 or more carbon atoms (e.g., n-hexyl methacrylate, 2-ethylhexyl methacrylate, etc.),
Dienes (eg, butadiene, isoprene) can be mentioned as particularly preferred examples.

Regarding the value of the glass transition temperature of the above-mentioned polymer, see J. Mol. Brandrup E. H. Immeig
ut co-editor "Polymer Handbook" 3rd edition (John Wiley & Son, 1989) V
I / 209 to VI / 277.

The repeating unit represented by B represents a repeating unit other than A, that is, a repeating unit derived from a monomer whose glass transition temperature of the homopolymer exceeds 35 ° C.

Specifically, acrylic esters (for example, t-butyl acrylate, phenyl acrylate,
2-naphthyl acrylate, etc.), methacrylates (e.g., methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, 2-hydroxypropyl methacrylate, phenyl methacrylate, cresyl methacrylate, 4-chlorobenzyl methacrylate, etc.), Vinyl esters (eg, vinyl benzoate, pivaloyloxyethylene, etc.), acrylamides (eg, acrylamide, methylacrylamide, ethylacrylamide,
Propyl acrylamide, butyl acrylamide, te
rt-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, diacetoneacrylamide, etc., methacrylamides (for example, Methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl Meta Rilamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, etc.), styrenes (for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, Chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate), acrylonitrile, methacrylonitrile, N-vinylpyrrolidone, N-vinyloxazolidone, vinylidene chloride, phenyl vinyl ketone, and the like.

The polymers represented by the general formula (1) are described in JP-B-60-15935 and JP-B-45-383.
No. 2, No. 53-28086, U.S. Pat. No. 3,700,4
A monomer having an anionic functional group (for example, a carboxyl group or a sulfonic acid group) as described in No. 56 or the like may be copolymerized for the purpose of improving the stability of the latex.

The following compounds can be mentioned as such monomers. Acrylic acid; methacrylic acid; itaconic acid; maleic acid;
Monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, etc .; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, etc .; citraconic acid; styrene sulfonic acid; vinylbenzyl sulfonic acid; vinyl sulfonic acid; acryloyloxy Alkylsulfonic acids, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, and the like; methacryloyloxyalkylsulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid Acrylamidoalkylsulfonic acid, for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamide 2-methylpropanesulfonic acid, 2-acrylamido-2-methyl butanoic acid, and the like; methacrylamide alkyl sulfonic acids, e.g., 2
Methacrylamide-2-methylethanesulfonic acid, 2
-Methacrylamide-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylbutanesulfonic acid and the like; these acids are alkali metals (for example, Na, K
Etc.) or a salt of ammonium ion.

X, y, and z represent weight percentage ratios of the respective monomer components in the polymer, x is 0.5 to 40, preferably 0.5 to 30, particularly preferably 1 to 20, and y is 6
0 to 99.5, preferably 70 to 99.5, particularly preferably 75 to 99, and z is 0 to 50, preferably 0 to 9
35, particularly preferably 0 to 25.

The above-mentioned monomer having an anionic functional group can be used as required, for example, to impart latex stability, regardless of the glass transition temperature of the homopolymer. The preferred amount when used is 0.5 to 20% by weight, particularly preferably 1 to 20% by weight, based on the total weight of the polymer.
10% by weight.

Preferred compounds of the polymer latex of the general formula (1) are illustrated below. () Indicates the weight percentage of each component in the copolymer. P-1 ethyl acrylate / M-1 / acrylic acid copolymer (85/10/5) P-2 n-butyl acrylate / M-1 / 2-acrylamide-2-methylpropane sodium sulfonic acid copolymer (85 / 10/5) P-3 n-butyl acrylate / M-1 / methacrylic acid copolymer (85/5/10) P-4 2-ethylhexyl acrylate / M-2 / 2
-Acrylamide-2-methylpropanesulfonic acid sodium copolymer (75/20/5) P-5-9 n-butyl acrylate / M-1 / acrylic acid copolymer (x / y / z) P-5x / Y / z = 95/2/3 P-6 x / y / z = 92/5/3 P-7 x / y / z = 89/8/3 P-8 x / y / z = 81/16 / 3 P-9 x / y / z = 72/25/3 P-10 n-butyl acrylate / styrene / M-1
/ Methacrylic acid copolymer (65/20/5/10) P-11 methyl acrylate / M-4 / methacrylic acid copolymer (80/15/5) P-12 n-butyl acrylate / M-5 / acryl Acid copolymer (85/10/5) P-13 n-butyl acrylate / M-7 / methacrylic acid copolymer (85/10/5) P-14 2-ethylhexyl acrylate / M-9 copolymer ( 75/25) P-15 n-butyl acrylate / M-13 / sodium styrene sulfonate copolymer (85/10/5) P-16 n-butyl acrylate / styrene / potassium styrene sulfonate copolymer (75 / 20/5) P-17 n-hexyl acrylate / methoxyethyl acrylate / M-2 copolymer (70/20/10) P-18 2-ethylhexyl acrylate RELAT / M-15
/ Methacrylic acid copolymer (90/5/5) P-19 n-butyl acrylate / M-1 / M-17
/ Acrylic acid copolymer (75/5/15/5) P-20 octyl methacrylate / M-20 / sodium styrene sulfonate copolymer (80/15/5)

The polymer latex derived from the ethylenically unsaturated monomer having an active methylene group used in the present invention is prepared by a generally well-known emulsion polymerization method, and the particle size thereof is preferably in the range of 0.01 to 0.01.
1.0 μm. In the emulsion polymerization method, a monomer is preferably emulsified in water or a mixed solvent of water and an organic solvent miscible with water (for example, methanol, ethanol, acetone, etc.) using at least one emulsifier, and a radical polymerization initiator is formed. Generally from 30 to about 100 ° C, preferably 4 ° C.
The reaction is performed at a temperature of 0 to about 90C. The amount of the organic solvent miscible with water is from 0 to 100%, preferably from 0 to 50%, by volume relative to water.

The polymerization reaction is usually carried out using 0.05 to 5% by weight of a radical polymerization initiator and, if necessary, 0.1 to 10% by weight of an emulsifier based on the monomer to be polymerized.
As the polymerization initiator, azobis compounds, peroxides, hydroperoxides, Redox catalysts and the like, for example, potassium persulfate, ammonium persulfate, tert-
Butyl peroctoate, benzoyl peroxide,
Isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, 2,2′-azobisisobutyrate, 2,2
'-Azobis (2-aminodipropane) hydrochloride and the like.

Examples of the emulsifier include anionic, cationic, amphoteric and nonionic surfactants, as well as water-soluble polymers. For example, sodium laurate, sodium dodecyl sulfate, sodium 1-octoxycarbonylmethyl-1-octoxycarbonylmethanesulfonate, sodium laurylnaphthalenesulfonate, sodium laurylbenzenesulfonate, sodium laurylphosphate, cetyltrimethylammonium chloride, dodecyltrimethyl Ammonium chloride, N-2-ethylhexylpyridinium chloride, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan lauryl ester, polyvinyl alcohol, JP-B-53-6
No. 190, an emulsifier, a water-soluble polymer and the like.

In the emulsion polymerization, depending on the purpose,
It goes without saying that the polymerization initiator, the concentration, the polymerization temperature, the reaction time and the like can be changed widely and easily. In addition, the emulsion polymerization reaction may be carried out by putting all the monomers, surfactants, and media in a container in advance and adding an initiator thereto, or polymerizing while dropping part or all of each component as necessary. May be performed. Regarding the type of the monomer having an active methylene group represented by D in the polymer represented by the general formula (1) and the polymer latex and the method of synthesizing the same, in addition to the above, US Pat. 619, 1
No. 95, No. 3,929,482, No. 3,700,45
No. 6, West German Patent 2,442,165, European Patent 13,
No. 147, JP-A-50-73625 and JP-A-50-146.
No. 331 and the like.

Further, JP-A-8-220669 and JP-A-8-24087 each using a latex derived from the ethylenically unsaturated monomer represented by the general formula (1) of the present invention as a shell.
A polymer latex having a core / shell structure as disclosed in No. 4 may be contained in the silver halide photographic light-sensitive material of the present invention.

The place of addition of the polymer derived from the ethylenically unsaturated monomer having an active methylene group is as follows.
Any of a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, a protective layer and a backing layer may be used, but a silver halide emulsion layer is particularly preferable. The amount of addition is not particularly limited, but is preferably 0.03 to 2.0 g / m ² , especially 0.1 to 2.0 g / m ² .
It is preferably from 1.0 to 1.0 g / m ² . Latex polymers derived from ethylenically unsaturated monomers having active methylene groups are preferably used in combination with gelatin. The preferred mixing ratio for gelatin is 0.5 to 50.
% By weight, in particular 1 to 30% by weight.

Next, the developing agent according to the present invention will be described. The developing agent contained in the silver halide photographic light-sensitive material of the present invention is preferably a reductone represented by the following general formula (4), but may contain the following developing agents. As developing agents other than the reductones represented by the general formula (4), dihydroxybenzenes (for example, hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone, 2,5
-Dimethylhydroquinone, potassium hydroquinone sulfonate, sodium hydroquinone monosulfonate,
Catechols), pyrogallols, 3-pyrazolidones {eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1 -Phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1- Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, and the like; aminophenols (for example, o -Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,
4-diaminophenol, etc.), 1-allyl-3-aminopyrazolines {for example, 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline , 1- (p-amino-m-methylphenyl) -3-aminopyrazoline and the like},
There are pyrazolones (for example, 4-aminopyrazolone) and the like, or a mixture thereof.

Here, the compound represented by formula (4) will be described.

[0051]

Embedded image In the formula, R ₁ and R ₂ each represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group, or an alkylthio group, and X represents R ₁ and R _2. It represents an atomic group necessary for forming a 5- to 6-membered ring together with two substituted vinyl carbon atoms and carbonyl carbon atoms. Here, the compound represented by Formula (4) will be described. In the general formula (4), R ₁ and R ₂ each represent a hydroxyl group or an amino group (substituents include an ethyl group, an n-butyl group, a hydroxyethyl group,
10 to 10 alkyl groups), acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.) ), An alkoxycarbonylamino group (such as a methoxycarbonylamino group), a mercapto group, or an alkylthio group (such as a methylthio group or an ethylthio group). Preferred examples of R ₁ and R ₂ include a hydroxyl group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group. X is a group of atoms necessary for forming a 5- to 6-membered ring, and is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbonyl carbon atom; Constructs a 5- to 6-membered ring together with an atom. Specific examples of X include -O-, -C
_{(R 3) (R 4)} -, - C (R 5) =, - C (= O)
_{-, - N (R 6)} -, - N =, constructed by combining. However, R ₃ , R ₄ , R ₅ , and R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may be substituted (a substituent may be a hydroxyl group, a carboxyl group, or a sulfo group. ), Hydroxyl group and carboxyl group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred 5
Examples of the six-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.
The compound represented by the general formula (4) may form a salt with lithium, sodium, potassium, ammonium and the like.

Specific examples of the compound represented by formula (4) are shown below, but the present invention is not limited thereto.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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Of these, ascorbic acid or erythorbic acid (stereoisomer) (4-1) or a salt thereof is preferred.

The amount of the developing agent added to the silver halide photographic light-sensitive material of the present invention is not fixed depending on factors such as the halogen composition of the emulsion and the amount of coated silver, but is 5 × 10 ⁻⁴ per mol of silver halide. Preferably in the range of 1 to 10 mol.
The range of 10 ^{−4 to} 5 × 10 ⁻¹ mol is more preferred.

Next, the oxazoline-based polymer will be described. Oxazoline-based polymer latex The oxazoline-based polymer latex (hereinafter referred to as oxazoline latex polymer) used in the present invention is a polymer having a monomer represented by the following general formula (5) as a repeating unit.

[0061]

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Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl, and R ⁵ is a noncyclic ring having an addition-polymerizable unsaturated bond. Organic group. As specific examples, (a) 2-vinyl-2-oxazoline (b) 2-vinyl-4-methyl-2-oxazoline (c) 2-vinyl-5-methyl-2-oxazoline (d) 2-iso Propenyl-2-oxazoline (e) 2-isopropenyl-4-methyl-2-oxazoline (f) 2-isopropenyl-5-ethyl-2-oxazoline, and one or more selected from these groups or Mixtures of two or more can be used.

The amount of the monomer represented by the general formula (5) is not particularly limited, but is preferably 5% by weight or more in the monomer mixture used for obtaining the oxazoline latex polymer.

The polymer latex containing an oxazoline group can be obtained, for example, by polymerizing the monomer represented by the above general formula (5) alone or by copolymerizing the monomer represented by the general formula (5) with the monomer. It can be obtained by copolymerizing with one or more ethylenically unsaturated monomers. Such monomers include, for example, acrylates, methacrylates, vinyl esters, olefins, dienes, acrylamides,
Methacrylamides, vinyl ethers, and other various ethylenically unsaturated monomers can be used, and a monomer having two or more ethylenically unsaturated groups can also be preferably used. More specific examples include acrylic acid esters, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, Amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylamino Ethyl acrylate, benzyl acrylate, methoxybenzyl acrylate,
2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5
-Hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro -2-ethoxyethyl acrylate and the like. Examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate , Phenylmethac Rate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3
-Methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2
-Butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, allyl methacrylate and the like. Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caprolate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like. Can be mentioned. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, and 2-ethyl-
1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-
Methyl-1,3-pentadiene, 1-phenyl-1,3
-Butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 1-chloro Butadiene, 2-fluoro-1,3-
Butadiene, 2,3-dichloro-1,3-butadiene,
1,1,2-trichloro-1,3-butadiene and 2-
Cyano-1,3-butadiene and the like can be mentioned.
In addition to the above monomers, acrylamides such as acrylamide, ethylacrylamide, tert
-Butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, diacetone acrylamide, etc .; methacrylamides, for example, methacrylamide, ethyl methacrylamide, tert-butyl methacrylamide, benzyl methacrylamide , Hydroxymethyl methacrylamide, phenyl methacrylamide,
Dimethyl methacrylamide and the like; olefins, for example,
Ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride and the like; styrenes such as styrene, methylstyrene, ethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene,
Chlorostyrene, dichlorostyrene, bromostyrene,
Vinyl benzoic acid methyl ester, etc .; vinyl ethers,
For example, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like; as others, for example, butyl crotonate,
Hexyl crotonic acid, dimethyl itaconate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalononitrile , Vinylidene chloride, acrylic acid,
Examples thereof include methacrylic acid, itaconic acid, maleic acid, maleic anhydride, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and styrenesulfonic acid. Further, in the latex of the present invention, a monomer having at least two copolymerizable ethylenically unsaturated groups can be used. Examples of such monomers include divinylbenzene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate,
Examples include trivinylcyclohexane, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol methacrylate, pentaerythritol tetraacrylate, and pentaerythritol tetramethacrylate. One of the above-listed monomers may be used alone, or two or more monomers may be copolymerized. Further, from the viewpoint of easiness of polymerization, among the above-mentioned monomer groups, acrylates, methacrylates, vinyl esters, conjugated dienes, styrenes, two or more ethylenic esters are preferably used. It is a monomer having an unsaturated group.

The oxazoline latex polymer in the present invention can be produced by a conventionally known polymerization method.
Most preferably, it is an emulsion polymerization method.

In the emulsion polymerization method, a known polymerization catalyst and a surfactant can be used, and can be synthesized by a method such as a so-called monomer dropping method, a multistage polymerization method, or a pre-emulsion method.

The aqueous resin dispersion of the oxazoline latex polymer according to the present invention can be obtained by the method described in Reference Example 1 of JP-A-2-99537.

The compositions of the oxazoline-based polymer latex according to the present invention include those shown in Table 1, but the present invention is not limited to these compositions.

[0069]

[Table 1]

MA: methyl acrylate, EA: ethyl acrylate, BA: butyl acrylate, MMA: methyl methacrylate, AN: acrylonitrile, St: styrene, (a) to (f): addition polymerizability described above Oxazoline monomer Further specific examples of the oxazoline-based polymer latex of the present invention include Epocross K-1010E and K-102.
0E, K-1030E, K-2010E, K-2020
E, K-2030E (manufactured by Nippon Shokubai Co., Ltd.).

Oxazoline-Containing Water-Soluble Polymer The oxazoline-containing water-soluble polymer (hereinafter referred to as polymer A) used in the present invention comprises an addition-polymerizable oxazoline (a) and optionally at least one other monomer. It is obtained by polymerizing (b). In the present invention, the addition-polymerizable oxazoline (a) is represented by the general formula (5).

The amount of the addition-polymerizable oxazoline (a) is not particularly limited, but is preferably 5% by weight or more in the monomer mixture used for obtaining the polymer A. In the present invention, the other monomer (b) is not particularly limited as long as it does not react with the oxazoline group and is copolymerizable with the addition-polymerizable oxazoline (a). For example, methyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth)
Methoxy polyethylene glycol acrylate, (meth)
(Meth) acrylates such as 2-hydroxyethyl acrylate, 2-aminoethyl (meth) acrylate and salts thereof; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) ) Acrylamide, N- (2-hydroxyethyl)
Unsaturated amides such as (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate: vinyl ethers such as methyl vinyl ether and ethyl vinyl ether: α-olefins such as ethylene and propylene;
Halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; α, β-unsaturated aromatic monomers such as styrene, α-methylstyrene, sodium styrenesulfonate; And one or a mixture of two or more of these can be used.

The polymer A is prepared by subjecting an addition-polymerizable oxazoline (a) and, if necessary, at least one other monomer (b) to solution polymerization in an aqueous medium by a conventionally known polymerization method. Can be manufactured. The aqueous medium that can be used is not particularly limited as long as it can be mixed with water. For example, water: or water and methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, ethylene glycol, ethylene glycol A mixed solution of monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol, acetone, methyl ethyl ketone and the like can be mentioned.

In order to impart water solubility to the polymer A, it is preferable that 50% by weight or more of the constituent monomers are hydrophilic monomers. Specific examples of the hydrophilic monomer include 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate / -2-aminoethyl (meth) acrylate and salts thereof, (meth) acrylamide, N-methylol (meth) acrylamide, N- (2
-Hydroxyethyl)-(meth) acrylamide, (meth) acrylonitrile, sodium styrenesulfonate and the like.

Specific examples of the oxazoline-containing water-soluble polymer of the present invention include Epocross WS-300 and WS-50.
0 (all manufactured by Nippon Shokubai Co., Ltd.).

Next, the compounds used in the present invention that release iodine ions in an alkaline atmosphere will be described. The alkaline atmosphere may be a condition generally called alkaline having a pH of 8.0 or more.
H value is 9.0 or more. In the present invention, the compound that releases iodide ions in an alkaline atmosphere is a compound that reacts with a base in an alkaline solution, preferably a solution having a pH value of 9.0 to 11.0, and releases iodide ions. Preferably, the iodide ions are rapidly released in the alkaline solution. The iodide ion release rate of the compound of the present invention is preferably within 10 seconds, more preferably within 5 seconds, until 50% of all iodide ions in the compound are released. The release rate of iodide ions can be preferably changed depending on the structure of the compound. The compound is preferably a compound having an electron-withdrawing group having a Hammett's substituent constant σ _p value of 0.20 or more and releasing iodide ions in an alkaline atmosphere, more preferably an electron having a σ _p value of 0.40 or more. It is a compound having an attractive group.

Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative.
In 1935 L. P. The rules of thumb proposed by Hammett are widely accepted today. The substituent constants determined by the Hammett's rule include σ _p values and σ _m , and these values are described in many general books. A. Dean ed. "Lange '
s Handbook of Chemistry "1st
2nd edition, 1979 (McGraw-Hill) and "Chemical Area Special Edition", No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, the electron-withdrawing group is defined by the Hammett's substituent constant σ _p value. Even if the document is unknown, when it is measured based on the Hammett's rule, it is of course included as long as it is included in the range.

Specific examples of the electron-withdrawing group having a σ _p value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, a dialkylphosphono group ,
Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide group,
Halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with another electron-withdrawing group having a σ _{p of} 0.20 or more, heterocyclic group, halogen atom, azo Or a selenocyanate group. Among these substituents, a group that can have a substituent may further have a substituent.

[0079] In more detail, as the sigma _p value of 0.20 or more electron-withdrawing group, an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxy benzoyl), an acyloxy group (e.g., Acetoxy), carbamoyl group (for example, carbamoyl,
N-ethylcarbamoyl, N-phenylcarbamoyl,
N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N- (4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4- Di-t-amylphenoxy) propyl @ carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), an aryloxycarbonyl group (for example, Phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (for example, dimethylphosphono), diarylphosphono group (for example, diphenylphosphono), diarylphosphinyl group (for example, diphenylphosphinyl) An alkylsulfinyl group (eg, 3-phenoxypropylsulfinyl), an arylsulfinyl group (eg, 3-pentadecylphenylsulfinyl), an alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), an arylsulfonyl group (eg, benzenesulfonyl, Toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy,
Toluenesulfonyloxy), acylthio group (for example,
Acetylthio, benzoylthio), sulfamoyl group (for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N , N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide group (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy group (eg, Fluoromethyloxy), a halogenated aryloxy group (for example, pentafluorophenyloxy), a halogenated alkylamino group (for example, N, N-di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoro Methylthio, 1,1 2,2-tetrafluoroethane ethyl thio), an aryl group which sigma _p value is substituted with 0.20 or more other electron-withdrawing groups (e.g., 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, Pentachlorophenyl), a heterocyclic group (eg, 2-benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), a halogen atom (eg, a chlorine atom) , A bromine atom), an azo group (for example, phenylazo) or a selenocyanate group.

Preferred as the electron-withdrawing group having a σ _p value of 0.20 or more are acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, aryl Substituted with a sulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a halogenated alkyl group, a halogenated alkyloxy group, a halogenated alkylthio group, a halogenated aryloxy group, a halogenated aryl group, and two or more nitro groups Aryl groups and heterocyclic groups. More preferred are an acyl group, an alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group.

[0081] Further specific examples of sigma _p value of 0.20 or more electron withdrawing groups, an anilino group (e.g., phenylamino, 2-chloroanilino, 2-chloro-5-tetradecane amino anilino, 2-chloro - 5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4-hydroxyphenoxy) dodecanamido} anilino), ureido group (for example, phenylureido, methyl Ureido, N, N-dibutylureido), sulfamoylamino group (for example,
N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
Tetradecanamidophenylthio), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 2-methoxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N
-Dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- (3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (for example, , N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl Groups (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy groups (eg,
1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo) , An acyloxy group (eg, acetoxy),
A carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, , N-succinimide, N-phthalimide,
3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole-6-thio, 2-
Pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl,
3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, 3-phenylpropanoyl) Benzoyl, 4-dodecyloxybenzoyl) and an azolyl group (eg, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl).

As a specific compound, the following general formula (6)
The compound represented by is preferably used. In the formula, I represents an iodine atom, and L represents an alkylene having 1 to 3 carbon atoms. X is an acyl group, an acyloxy group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfinyl group, an alkylsulfonyl group, a sulfonyloxy group, a thiocarbonyl group, a thiocyanate group, a halogenated alkyl group, and a substitution product thereof, or of the electron withdrawing group is a complex, sigma _p value is preferably from 0.20 or more.

Next, specific examples of the general formula (6) according to the present invention will be described, but the present invention is not limited thereto.

6-1 ICH ₂ COOH 6-2 ICH ₂ CONH ₂ 6-3 ICH ₂ CN 6-4 I (CH ₂ ) ₂ COOH 6-5 I (CH ₂ ) ₃ COOH

[0085]

Embedded image 6-7 ICH ₂ COCH ₃ 6-8 ICH ₂ SCN 6-9 I (CH ₂ ) ₂ OCOCH ₃ 6-10 I (CH ₂ ) ₂ SO ₂ CH ₃ 6-11 ICH ₂ NO ₂ 6-12 I (CH ₂ ) ₂ SO ₂ CH ₂ CONH ₂

[0086]

Embedded image 6-14 ICH ₂ CH = C (CN) ₂ 6-15 I (CH ₂ ) ₂ SO ₂ NH ₂

[0087]

Embedded image

The above compounds can be easily synthesized, for example, according to the method described below. J. Am. Che
m. Soc. 76, 3227-8 (1954); O
rg. Chem. 16, 798 (1951), Che
m. Ber. 97, 390 (1946), Org. Sy
nth. V, 478 (1973); Chem. So
c. 1951, 1851, J.I. Org. Chem. 1
9, 1571 (1954); Chem. Soc. 1
955, 1383, Chem. Commu, 1971,
1112.

Next, the developer of the present invention will be described. The developer according to the present invention does not contain a developing agent and a sulfite. The developer of the present invention contains an alkali agent. The alkaline agent is dissolved in a developer to adjust the pH of the developer to 8.0.
Any of the above compounds may be used, but sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and sodium phosphate having a buffering action Potassium acid, sodium salicylate, potassium salicylate and the like are used.

Other additives that may be contained include dissolution aids (eg, polyethylene glycols and esters thereof), pH adjusters (eg, organic acids such as citric acid), and sensitizers (eg, quaternary). Ammonium salts, etc.), development accelerators, hardeners (eg, dialdehydes such as glutaraldehyde), surfactants, and azole organic antifoggants as antifoggants (eg, indazole, imidazole, benz) Imidazole type, triazole type, benztriazole type, tetrazole type, thiadiazole type), concealing agent for shielding calcium ions mixed in tap water used for treatment liquid, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, and further Diethylenetriamine pentaacetate, ethylenediaminetetraacetate, etc.

In the present invention, silver stain inhibitors, for example, compounds described in JP-A-56-24347 can be used. Further, the pH of the developer used in the present invention is preferably 8.0 or more, more preferably 9.0 to 9.0.
It is in the range of 12.5. Further, an amino compound such as an alkanolamine described in JP-A-56-106244 can be used in the developer used in the present invention.

In addition, the developing solution used in the present invention includes:
L. F. A. Meson, Photographic Processing Chemistry, Published by Focal Press (19
66), pp. 22-229, U.S. Pat.
No. 5,2,592,364, JP-A-48-6493.
No. 3 may be used.

Next, the fixing solution used in the present invention will be described. The fixer according to the present invention does not contain boric acid. The fixing agent preferably contains a thiosulfate.
The thiosulfate is specifically used as a salt of lithium, potassium, sodium, or ammonium. Preferably, a fixing solution having a high fixing speed can be obtained by using ammonium thiosulfate and sodium thiosulfate.

In addition, iodide salts, thiocyanates and the like can also be used as fixing agents. The fixing solution used in the present invention may contain a sulfite. Examples of the sulfite include lithium, potassium, sodium, and ammonium salts.

The fixing solution may contain a water-soluble chromium salt or a water-soluble ammonium salt. Examples of the water-soluble chromium salt include chromium alum, and examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride.

The fixer according to the present invention may contain acetate ions. The type of acetate ion is optional, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution, but lithium, potassium, sodium, ammonium salts of acetic acid or acetate are preferably used, and particularly, Sodium salts and ammonium salts are preferred.

Further, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof may be contained. These salts (e.g., potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium bitartrate, potassium bitartrate, potassium tartrate, sodium bitartrate, sodium tartrate, ammonium bitartrate, ammonium potassium tartrate, Lithium, potassium represented by sodium potassium tartrate, sodium malate, ammonium malate, sodium succinate, ammonium succinate, etc.
Sodium and ammonium salts are preferred.

Among the above compounds, more preferred are citric acid, tartaric acid, succinic acid, acetic acid and salts thereof. Examples of other acids include salts of inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, and organic acids such as formic acid, propionic acid, oxalic acid, and malic acid.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof. Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric activity. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include a thiourea derivative, an alcohol having a triple bond in the molecule, and a thioether. The fixing solution according to the present invention has p
H3.8 or more, preferably 4.2 to 5.5.

Further, the replenishment rate during the processing of the present invention is important to reduce the amount of waste liquid to 10 ml / 4 or less for both the alkali developing solution and the fixing solution, and more preferably 7 ml / cut.
Less than 4 pieces. By setting the replenishing amount within this range, the effect of the present invention becomes more remarkable. The treatment agent as described above,
It is preferable to prepare a solid processing agent, dissolve it, and use it as a processing liquid. The treatment agent according to the present invention is preferably made into a tablet by compression molding.

Here, the solidification (solidification) of the photographic processing agent will be described. In order to solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent (raw material) and a water-soluble binder are kneaded and molded, or a water-soluble binder is temporarily attached to the surface of the photographic processing agent. Any means such as forming a coating layer by spraying an agent can be adopted (Japanese Patent Laid-Open No. 4-29136).
Nos. 4-85535, 4-85536, 4-
No. 85533, No. 4-85534, No. 4-17234
No. 1).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated, granulated, and then compression-molded to form a tablet. As a granulation method for tablet molding, known methods such as tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. it can. For tablet molding, the average particle size of the obtained granules is such that when the granules are mixed and pressed and compressed in the tableting process, non-uniformity of components, so-called segregation is unlikely to occur. It is preferable to use one having a thickness of 100 to 800 μm, more preferably 200 to 750 μm. Further, the particle size distribution is such that 60% or more of
Those that are within μm deviation are preferred. Next, when compressing the obtained granules under pressure in the tableting step, a known compressor,
For example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, and a pre-kitting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but a cylindrical tablet is preferred from the viewpoint of productivity and handling, or from the problem of dust when used on the user side. Further, at the time of granulation, for each component, for example,
Separation and granulation of an alkali agent, a reducing agent, a preservative, and the like can also be preferably performed.

The method for producing a tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent No. 1,213,808 and the like.
For example, Japanese Unexamined Patent Publication Nos.
No. 3, 3-39735 and 3-39939 can be produced. Further, the powder treating agent may be prepared by a method as described in, for example, JP-A-54-133332, British Patents 725,892 and 729,862, and German Patent 3,733,861. Can be manufactured.

Next, a preferred structure of the photosensitive material will be described. The thickness of the silver halide emulsion layer (also simply referred to as emulsion layer) of the light-sensitive material according to the present invention is preferably in the range of 0.5 to 3.5 μm, more preferably in the range of 1.0 to 3.0 μm. In the case where the emulsion layer is provided on both sides of the support, the thickness of the emulsion layer referred to herein means the thickness of one emulsion layer on one side,
When there are multiple emulsion layers on one side, this refers to the thickness of all the layers. The thickness of the photosensitive material can be measured by leaving it in an atmosphere of 23 ° C. and 50% RH for at least 2 hours and cutting a cross section of this photosensitive material perpendicular to the support from an electron microscopic photograph.

The silver halide emulsion used for the light-sensitive material can be produced by a known method. Crystal habit is cubic, 1
Surfaces such as tetrahedron, octahedron and (111) plane and (100) plane may be arbitrarily mixed, for example, may have a spherical shape. The crystal structure of the silver halide may be different from the silver halide composition inside and outside. For example, internal high iodine type monodisperse particles disclosed in JP-A-2-85846 and the like can be mentioned.

Further, the silver halide emulsion particularly preferably used in the present invention is tabular grains having an average aspect ratio of more than 1, preferably 3 to 20. Here, the aspect ratio refers to the ratio of the diameter (particle diameter) of the main plane of the tabular grains to the thickness. Here, the diameter of the main plane of the silver halide grain refers to the diameter of a circle having an area equal to the projected area of the main plane. In the present invention, the diameter of the main plane of the tabular silver halide grains is preferably from 0.3 to 1
0 μm, more preferably 0.3 to 5.0 μm, and particularly preferably 0.5 to 4.0 μm. In general, tabular silver halide grains are tabular having two parallel main planes. Therefore, the "thickness" in the present invention is defined as the distance between two parallel main planes constituting the tabular silver halide grains. expressed. The advantages of such tabular grains are: improved spectral sensitization efficiency;
As improvements in image graininess and sharpness are obtained,
For example, UK Patent 2,112,157, US Patent 4,
439,520, 4,433,048, 4,4
14,310, 4,434,226, JP-A-58
-113927, 58-127921, 63-
No. 138342, No. 63-284272, No. 63-3
The emulsions can be prepared by the methods described in these publications. In particular, Japanese Patent Application No. 6-138568 (pages 1 to 3) and JP-A-59-177.
No. 535 (pages 2 to 5) and JP-A-62-42146 (1.
4 to 15) are preferably used. U.S. Pat. Nos. 4,063,951 and 4,386,156
No. 5,275,930 and 5,314,798, tabular grains having a (100) major plane are also preferably used.

Further preferred silver halide emulsions for use in the present invention are silver iodobromide, silver iodochlorobromide, silver bromide, silver chlorobromide and silver chloride of less than 3 mol% of silver iodide. Preferred is silver iodobromide or silver iodochloride having a silver iodide content of less than 1.0 mol%. The emulsion described above may be either a surface latent image type for forming a latent image on the grain surface, an internal latent image type for forming a latent image inside the grain, or a type for forming a surface and an internal latent image. These emulsions may contain a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt, a rhodium salt, an iron salt or a complex salt thereof at the stage of physical ripening, that is, grain formation. The emulsion may be subjected to a water washing method such as a noodle washing method, flocculation sedimentation method, and ultrafiltration method in order to remove soluble salts (desalting). As a preferred water washing method, for example, a method using a sulfo group-containing aromatic hydrocarbon aldehyde resin described in JP-B No. 35-16086, or G3, G8 exemplified by coagulated polymer agents described in JP-A-63-158644 Is a particularly preferred desalting method. The method of chemical ripening of the emulsion used in the light-sensitive material of the present invention is preferably sensitization with a chalcogen compound such as gold sensitization, reduction sensitization, and selenium sensitization including sulfur sensitization, or a combination thereof. .

The silver halide emulsion according to the present invention is preferably monodisperse, and has a variation coefficient of grain size of 30.
%, Especially those within 20% are preferably used. In addition, the cube as described above, 14
You may mix and use a planar particle and a tabular particle.

The silver halide emulsion of the present invention can be spectrally sensitized. Examples of the spectral sensitizing dye used include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl dye, and hemioxonol dye.

For example, oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolooxacarbocyanine and the like as described in JP-A-5-13619 are mentioned. Japanese Patent Application Laid-Open No. 6-332102
Dyes having a sensitizing effect in the blue light region described in the above publication are also preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye can be added as a solution dissolved in an organic solvent such as methanol. Further, a dispersion in the form of solid fine particles can be prepared and added. The amount of the spectral sensitizing dye to be added is not uniform depending on the type of the dye and the emulsion conditions, but is preferably from 10 to 900 mg, more preferably from 60 to 400 mg, per mol of silver halide. The spectral sensitizing dye is preferably added before the completion of the chemical ripening step, and may be added in several portions before the completion of the chemical ripening. More preferably, after the completion of the silver halide grain forming step and before the completion of the chemical ripening step, particularly preferably before the start of the chemical ripening.

In the present invention, in order to stop the chemical sensitization (chemical ripening), it is preferable to use a chemical ripening terminator in consideration of the stability of the emulsion. Examples of the chemical ripening inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene) and the like. These may be used alone or in combination of a plurality of compounds.

In the emulsion of the light-sensitive material used in the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Examples thereof include a hydrazine compound and a tetrazolium salt.

Examples of the support which can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided. Emulsion layers may be present on both sides of the support, or only one side may be used. In the case of both sides, both sides may have the same performance or may have different performances.

[0116]

The present invention is not limited to the following examples. << Preparation of photosensitive material >> First, seed emulsion-1 was prepared as follows.
Was prepared. A1 ossein gelatin 24.2 g water 9657 ml S-3 (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 841 g water 2825 ml D1 1.75 N Potassium bromide aqueous solution The following silver potential control amount

At 42 ° C, JP-B-58-58288, 5
Solution A using a mixing stirrer described in JP-A-8-58289.
464.3 ml of each of the solution B1 and the solution C1 were added to the sample No. 1 by a simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm, (Circle diameter conversion)
Was confirmed to be 0.595 μm by an electron microscope. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%. The average volume particle size of this seed emulsion was 0.26 μm.

<Preparation of Em-1> A tabular silver halide emulsion Em-1 was prepared using Seed Emulsion-1 and the following four kinds of solutions.
Was prepared. A2 Ossein gelatin 34.03 g S-3 (10% aqueous ethanol solution) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3150 ml with water. B2 1734 g potassium bromide Make up to 3644 ml with water. C2 Silver nitrate 2478g Make up to 4165ml with water. D2 Fine grain emulsion composed of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05 μm) Equivalent to 0.080 mol * 5.0% by weight of gelatin containing 0.06 mol of potassium iodide To 6.64 liters of the aqueous solution, 2 liters each of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

In the reaction vessel, the solution A2 was vigorously stirred while being kept at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Thereafter, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a portion of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. Was added with the remaining amounts of the solution B2 and the solution C2. During this time, the pH was kept at 5.8 and the pAg was kept at 8.8 throughout. Here, the addition rate of the solution B2 and the solution C2 was changed like a function with respect to the time corresponding to the critical growth rate.

Further, the solution D2 was added in an amount corresponding to 0.15 mol% based on the total silver amount to perform halogen substitution.

After the addition was completed, the emulsion was cooled to 40 ° C.
1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregated polymer, and the mixture was stirred for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid was added to adjust the pH of the emulsion to 4.
After stirring for 3 minutes, the mixture was allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then 4
9.0 L of distilled water at 0 ° C. was added, the supernatant was drained after stirring and standing, and 11.25 L of distilled water was further added. After stirring and standing, the supernatant was drained. Subsequently, an aqueous gelatin solution and a 10% (by weight) aqueous sodium carbonate solution were added, and the pH was adjusted.
Was adjusted to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, the pH was adjusted to 5.8 at 40 ° C, p
Ag was adjusted to 8.06.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.13 μm and the average thickness was 0.2.
Tabular silver halide grains having a size of 5 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained.

After the above emulsion was heated to 60 ° C., a predetermined amount of the spectral sensitizing dye was added as a dispersion in the form of solid fine particles. Ten minutes afterward, adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added. And a dispersion of triphenylphosphine selenide were added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The above additives and their amounts (AgX1
(Per mole) is shown below. 5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 400 mg 5,5'-di- (butoxycarbonyl) -1,1'-diethyl -3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride 4.0 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0 0.2 mg silver iodide fine particles 280 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg

A dispersion of the solid fine particles of the spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the above-mentioned spectral sensitizing dye was added to water whose temperature had been previously adjusted to 27 ° C., and high-speed stirring (dissolver) was performed for 3,5
Obtained by stirring at 00 rpm for 30-120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above Examples.

<Preparation of Emulsion Layer Coating Solution> The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² 1,1-dimethylol-1-bromo-1 -Nitromethane 70 mg t-butyl-catechol 130 mg / m ² Polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / ^{m 2} nitrophenyl - triphenyl - phosphonium chloride 20 mg ^/ m 2 1,3-dihydroxybenzene-4-sulfonic acid ammonium 500 mg ^{/ m} 2 2-mercaptobenzimidazole-5-sulfonic acid sodium 5mg / ² Compound _{^{(H) 0.5mg / m 2 n}} -C 4 H 9 OCH 2 CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (M) 5mg / ^{m 2} Compound (N) 5 mg / m ² colloidal silica (Ludox AM: particle size 0.013 μm manufactured by DuPont) 0.5 g / m ² active methylene latex described in Tables 2 and 3 Iodine ion releasing agent described in Tables 4 and 5 Oxazoline-based polymer described in Tables 2 and 5 Description Developing agent Described in Tables 2 to 5 Gelatin 1.25 g / m ^{2 The} amount of emulsion was adjusted so that the amount of silver applied was 1.5 g / m ² on one side when the coating solution was applied to the support. .

The sample No. in Table 3 was used. Sample Nos. 37 and 39 and Table 5 in Table 5 77 and 79 are obtained by dissolving a developing agent in 18 ml / m ² of water, adding an oxazoline polymer to the solution, heating the mixture to 40 ° C., and stirring for 30 minutes.
Added to above emulsion.

(Preparation of Coating Solution for Protective Layer) Matting agent consisting of gelatin 0.8 g / m ² polymethyl methacrylate (area average particle size 7.0 μm) 50 mg / m ² hardening agent (CH ₂ = CHSO ₂ CH ₂ ) ₂ O The addition amount is adjusted so that the swelling ratio is 200% or less in an alkaline solution at 35 ° C. 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² polyacrylamide (average Molecular weight 10,000) 0.2 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² compound (F-1) 3 mg / m ² Compound (F-2) 2 mg / m ² Compound (F-3) 1 mg / m ² Active methylene latex Described in Tables 2 and 3 Iodine ion releasing agent Described in Tables 4 and 5 Oxazoline-based polymer Described in Tables 2 and 5 Developing agent according to Table 2-5 it should be noted that the amount with the material is a single-sided 1 m ² per.

The sample No. in Table 3 was used. Sample Nos. 38, 40 and Table 5 in Table 5. 78 and 80 are 12.4 ml / m ^{2 of} water
Then, the oxazoline polymer was added thereto, and the mixture was stirred for 30 minutes while heating to 40 ° C. to prepare a coating solution.

(Preparation of Filter Layer) Glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%,
A copolymer having a copolymer dispersion composed of three kinds of monomers, i.e., butyl methacrylate 40 wt% and diluted to 10 wt%, was coated as a subbing liquid with a thickness of 17 applied.
On both sides of 5μm blue colored polyethylene terephthalate support to prepare a support sample coating amount per surface 1 m ² was coated with a filter layer so that the following composition.

Solid fine particle dispersion dye (AH) 50 mg Gelatin 0.1 g Sodium dodecylbenzenesulfonate 5 mg Compound (I) 5 mg 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg Colloidal silica ( Average particle size 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

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[0137]

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(Coating) Using these coating solutions, two slide hopper type coaters were used at a speed of 120 M / min using two slide hopper coaters so that the coating amount was 1.5 g / m ² per side. On the body sample, both sides were simultaneously coated with the following layer constitution, and dried for 2 minutes and 20 seconds to prepare a coated sample. Layer position Layer type Upper layer Protective layer Intermediate layer Emulsion layer Lower layer Filter layer

<Preparation of Solid Developer> [Granulation A] Glutaraldehyde sodium bisulfite 25
0 g, potassium carbonate 5150 g, lithium hydroxide monohydrate (adjusting the amount so that the pH after dissolving the tablet becomes 13.0), 1-phenyl-5-mercaptotetrazole 5
g, 3 (5 mercaptotetrazol 1-yl) benzenesulfonic acid 15 g, DTPA 100 g, mannitol 10
00 g and 300 g of D-Sorbit were placed in a commercially available stirring granulator, and mixed by stirring at room temperature for 3 minutes, and 60 ml of water was added while stirring and mixing to granulate.

The stirring was stopped two minutes after the start of water addition. Thereafter, 1.0% of the total weight of sodium 1-octanesulfonate was added to the granulated product in the stirring granulator, and the mixture was further stirred and mixed for 1 minute.

[Compression tableting] The mixed granules were taken out from a stirring granulator, and were tough press collect 152 manufactured by Kikusui Seisakusho Co., Ltd.
Compressed tableting was performed using a rotary tableting machine modified from 7HU to prepare a developed tablet (A). The filling amount per tablet was 12.5 g. An aqueous solution obtained by dissolving 11 tablets (A) in water to make up to 1 liter is the prescribed amount per liter of the alkali developing solution of the present invention. 55 tablets (A) were placed in a moisture-proof aluminum-evaporated pillow bag as a 5-liter kit.

<Preparation of Solid Fixing Agent> [Granulation B] 5250 g of ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio) and 65 g of 5-mercaptotetrazole are each pulverized in a commercially available bandam mill to an average of 50 μm. To these fine powders, 36 g of sodium sulfite, 400 g of sodium metabisulfite, and 320 g of binder pine flow were added, mixed in a commercially available stirring granulator for 1 minute, and granulated by adding 20 ml of water while stirring and mixing.

The stirring was stopped two minutes after the start of the water addition. Then, β-alanine 5 was added to the granulated material in the stirring granulator.
40 g, 1150 g of sodium acetate, and 1.5% of the total weight of sodium 1-octanesulfonate were added, and the mixture was further stirred and mixed for 1 minute.

[Granulation C] 2000 g of succinic acid, 52 tartaric acid
5 g, 435 g of mannitol, and 200 g of D-sorbit were stirred and mixed in a commercially available stirring granulator for 1 minute, and 24 ml of water was added while stirring and mixing to granulate.

The stirring was stopped two minutes after the start of water addition. Thereafter, 2020 g of aluminum sulfate octahydrate, 750 g of polyethylene glycol (molecular weight 4000), 1750 g of sodium acetate were added to the granulated product in the stirring granulator.
Sodium 1-octanesulfonate was added at 1.0% of the total weight.
%, Respectively, and the mixture was further stirred and mixed for 1 minute.

[Compression tableting] The mixed granules of granulation B and granulation C were taken out from an agitation granulator, and compression tableting was performed using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Fixing tablets (B) and (C) were prepared.
The filling amount per tablet is (B) 10.9 g, (C) 9.
3 g. An aqueous solution obtained by dissolving 17 tablets (B) and 4 tablets (C) in water to make up to 1 liter is the prescribed amount per liter of the fixing solution of the present invention. As a 5-liter kit, 85 tablets (B) and 20 tablets (C) were placed in a moisture-proof aluminum-evaporated pillow bag.

Development starter formulation (addition amount per liter of developer) Acetic acid (90% solution) 6.5 g KBr 5.5 g Finished with pure water 20 ml

A large automatic developing machine SRX-701 (manufactured by Konica) was modified to incorporate a chemical mixer for tablet dissolution. At the start, 13.7 liters of the developing solution in which the developing tablet (A) is dissolved is added as the alkali developing solution in the developing tank.
The processing was started by adding the above-mentioned development starter and filling the developing tank as a starting liquid. The development starter addition amount is 20
An amount corresponding to a developing tank capacity of 13.7 liters was added at a rate of 1 ml / ml. The fixer 13.5 was prepared in the same manner.
One liter was placed in the fixing processing tank of SRX-701 to be used as a starting liquid.

In each of the developing and fixing steps, each of the packaging bags was opened by hand at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer.
(0 ° C) and dissolving with stirring for 17 minutes.
Adjust to 0 liters. This was used as a developing and fixing replenisher.

The pH when the starter was added to the aqueous solution in which the alkali developing tablet was dissolved was 12.8. The dissolution pH of the fixing solution was 4.80.

The built-in chemical mixer is divided into a solution dissolving tank and a spare tank tank.
The reserve tank capacity is also 5.0 liters, so that even if the replenisher created in the solution dissolving tank runs out during the running process of the film, it does not become replenished during the stirring dissolution time (about 25 minutes). A spare tank was provided to supply the replenisher. The automatic developing machine is a modified machine of the SRX-701 (manufactured by Konica), and has a developing temperature of 36 ° C. (the replenishing amount is 7 ml).
/ 4 cut), fixing temperature 35 ° C. (replenishment amount is 10 ml / 4 cut), water 18 ° C. (5 liter / min), drying temperature 55
The evaluation was performed at a processing time Dry to Dry of 30 seconds at ℃.

<Evaluation of Processing Property> Each of the prepared films was exposed so that the density after processing became 1.2, and each of the processing described in Tables 2 to 4 was cut into four pieces for a total of 2,000 pieces of running processing. And the following items were evaluated. Table 2 shows the results.

[Evaluation of Drying Unevenness] The prepared sample (quarter size) was uniformly exposed so that the transmission density after development was 2.5, and then developed using the automatic developing machine. . Unevenness observed when the obtained developed sample was reflected by light and observed was classified into the following five stages to evaluate drying unevenness. 5: No drying unevenness is observed at all. 4: Slight drying unevenness is observed at the edge of the film. 3: Dry unevenness is observed around the film (frame shape). 2: Mottled from about half to the center of the film. Dry unevenness is observed 1: Large dry unevenness is observed on the entire surface of the film. Level 3 or higher is a practically acceptable level, but is preferably level 4 or higher.

[Evaluation of Drying Level] The film coming out from the drying outlet (outlet) of the automatic developing machine was evaluated for the drying level according to the following rank by touch. ：: Dry △: The film surface is slightly moist ×: The film surface is not moist and dry The practical allowable levels are Δ level and ○ level,
It is preferably at the O level.

<Evaluation of Sensitometric Photographic Performance> The obtained coated sample was sandwiched between two fluorescent intensifying screens XG-S (manufactured by Konica Corporation) under the conditions of a tube voltage of 90 KVp, a current of 100 mA and a time of 0.05 second. Irradiates with X-ray to create sensitometric curve by distance method, sensitivity fog, maximum density Dma
x was determined. The sensitivity value was determined as the reciprocal of the X-ray dose required to obtain Fog + 1.0.

The results are shown in Tables 2, 3, 4 and 5. In addition, the sensitivity is the sample No. The relative sensitivities are shown by setting the sensitivity of 1 to 100.

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[Table 2]

[0159]

[Table 3]

[0160]

[Table 4]

[0161]

[Table 5]

[0162]

According to the present invention, it is possible to provide a photosensitive material which is suitable for ultra-rapid processing and low replenishment processing and achieves low pollution and a processing method therefor. In particular, the maximum density (Dmax) can be sufficiently obtained. In addition, it is possible to provide a photosensitive material with less drying unevenness failure and a processing method therefor.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 5/38 G03C 5/38

Claims (8)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer is provided. Comprises a developing agent and a latex derived from an ethylenically unsaturated monomer having an active methylene group. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer is provided. Contains a developing agent and a compound having an electron-withdrawing group and releasing iodine ions in an alkaline atmosphere. 3. A silver halide photographic material having at least one silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the silver halide emulsion layer and / or the hydrophilic colloid is used. A silver halide photographic material, wherein the layer contains a developing agent and an oxazoline-based polymer. 4. The silver halide photographic material according to claim 1, wherein the silver halide emulsion layer and / or the hydrophilic colloid layer contains an oxazoline-based polymer. 5. An aqueous resin dispersion of an oxazoline-based polymer containing a developing agent, comprising: a silver halide emulsion coating solution;
Or a silver halide photographic light-sensitive material characterized by being coated after being added to a hydrophilic colloid coating solution. 6. The silver halide photographic light-sensitive material according to claim 1, which is treated with a processing solution having a pH of 8.0 or more, which does not contain a developing agent and a sulfite and contains an alkali agent. And processing with a fixing solution containing no borate. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the processing solution containing an alkali agent is prepared by dissolving a solid processing agent formed into tablets by compression molding. A method for processing a silver halide photographic light-sensitive material. 8. According to the processing of a silver halide photographic light-sensitive material,
7. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the processing solution is replenished, and the replenishment amount is 10 ml or less per four pieces of the silver halide photographic light-sensitive material.