JPS6349753A - Silver halide photographic sensitive material hardened with polymer hardener - Google Patents

Abstract

PURPOSE:To improve the solubility of a hardener in water, to prevent change of hardening action due to time lapse, and to selectively harden only a desired layer by using a polymer hardener composed of specified repeating units. CONSTITUTION:One or more of nonphotosensitive layers and silver halide emulsion layers are hardened with the polymer hardener having the repeating units each represented by the formula shown on the right in which A is a copolymerizable monomer unit; R1 is H or 1-6C alkyl or the like; J is -COO- or -CONR2-; R2 is H, 1-6C alkyl, or the like; L is a 3-15C divalent bonding group having one or more -CONR3-, or the like; R3 is 6-12C aryl; X is -CH=CH2 or -CH2CH2-Q; Q is a group substitutable by a nucleophilic group or the like; each of (a) and (b) is a molar percentage and (a)=0-99, (b)=1-100; and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material hardened with a polymer hardener.

(Background of the Invention Generally, silver halide photographic materials contain hydrophilic colloids such as gelatin as a binder component, and specifically include a silver halide emulsion layer, a protective layer, a filter layer, an intermediate layer, and an antihalation layer. It is used for layers, backing layers, film base undercoat layers, baryta layers, etc.

In particular, the protective layer is susceptible to environmental changes and contact with devices, etc., and is therefore required to be durable. A number of compounds are known for hardening gelatin to increase the water and scratch resistance of the protective layer. These are well known as "hardening agents" used in the production of photographic materials. For example, inorganic compounds such as chromium alum, formaldehyde,
Aldehyde compounds such as glutaraldehyde, active halogen-containing compounds described in U.S. Pat. No. 3,288,775, etc., reactive ethylenic compounds described in U.S. Pat. Compounds with saturated groups, aziridine compounds described in U.S. Patent No. 3,017,280, etc., U.S. Patent No. 3,091,5
Organic compounds such as epoxy compounds described in No. 31 and halogenocarboxaldehydes such as mucochloric acid are known as hardening agents.

However, such hardeners, when added to any emulsion layer, may have an adverse effect on the properties of the light-sensitive material (e.g., increase in fog, decrease in sensitivity, change in gradation, etc.), or cause "back hardening".
This may cause a long-term change in the curing effect called ``curing'', or may cause non-uniformity in the photosensitive material due to insufficient solubility in water during use, or may cause other commonly used photographic additives (such as color couplers for color photosensitive materials). ), the hardening agent itself is unstable and has poor storage stability, and it is difficult to synthesize the hardening agent itself, making it difficult to manufacture it to a large size. ing.

In addition, the low molecular weight hardening agents that have traditionally been used to harden gelatin migrate through the gelatin layer by diffusion, so in gelatin coated products in which many different layers are stacked, the degree of hardening of each gelatin layer can be controlled. It was not possible to freely adjust it according to the purpose. On the other hand, currently well-known polymeric diffusion-resistant gelatin hardeners such as dialdehyde starch or polyacrolein are difficult to use in light-sensitive materials because they adversely affect photographic properties such as increased fog and decreased sensitivity. could not be used satisfactorily. Also US Patent 4,761,407
The polymer hardener having a nyl sulfone group as an active group described in JP-A-56-142524 has a slow hardening reaction;
There was a problem in that the degree of swelling changed over time, which caused posterior dura mater. It also has low solubility in water,
It had to be dissolved using a large amount of organic solvent.

Therefore, it has been desired to develop a hardening agent that can harden a specific layer, does not adversely affect photographic properties, and has excellent solubility and does not cause post-hardening.

(Objectives of the Invention) Therefore, the first object of the present invention is to provide a film hardened with a polymeric hardener having diffusion resistance that does not adversely affect photographic properties such as an increase in fog or a decrease in sensitivity. The object of the present invention is to provide a silver halide photographic light-sensitive material.

Second, there is no post-hardening film whose degree of swelling changes over time, and the halogenated film is hardened with a polymeric hardening agent that has excellent solubility and can selectively harden only specific layers. Our objective is to provide silver photographic materials.

(Structure of the Invention) The above object of the present invention is to provide a silver halide photographic material having at least one non-photosensitive layer and at least one silver halide emulsion layer on a support. This was achieved using a silver halide photographic material in which at least one layer selected from the silver halide emulsion layers is hardened with a polymer hardener having a repeating unit represented by the following general formula [I].

General formula [I] R5 In the formula, A represents a copolymerizable monomer unit or -CON- (R2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

! L has at least one 10ON- bond and has 3 carbon atoms
~15 divalent bonding groups or a divalent bonding group having 1 to 12 carbon atoms (R3 is a carbon number of 6
~12ff! represents an aryl group. 2 is at least 1
Represents a group of atoms necessary to form a ring containing one nitrogen atom. ).

X represents -CH-CH2 or -CH2CH2-Q (Q represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HQ by a base).

a and b each represent a molar percentage, a is O~9
9, and b is 1-100.

n is 0 or 1.

(Specific structure of the invention) In the polymer hardener of the present invention, A of the general formula [I]
represents a monomer unit, and examples of monomers forming such a monomer unit include, for example, ethylenically unsaturated monomers. Examples of preferred ethylenically unsaturated monomers include ethylene, propylene, 1-butene, isobutyne, styrene, chloromethylstyrene, human O-oxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate,
N,N,N-trimethyl-N-vinylbenzylammonium chloride, N,N-dimethyl-N-benzyl-N
-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinyl and lysine, 2-
Vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone,
1-vinyl-2-methylimidazole, vinylsulfonic acid, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts, e.g. acrylic acid , methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate], maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids [e.g. lobutyl acrylate, n-hexyl acrylate, human O
xyethyl acrylate, cyanethyl acrylate,
N,N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, and droxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N.

N-diethylaminoethyl methacrylate, N.

N,N-triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimedyl itaconate, maleic monobenzyl ester, 3-sulfobyl acrylate, 2-ethylsulfomethacrylate]
, amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids [e.g. acrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N
-(N,N-dimethylaminopropylobyl)acrylamide, N,N,N-trimethyl-N-(N-acryloylpropyl)ammonium p-toluenesulfonate,
Sodium 2-acrylamide-2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N
, N-dimethyl-N'-acryloylpropanediamine probionate betaine, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine, and the like.

The monomer unit represented by A in the general formula [I] is a photosensitive material hardened with the polymer hardener of the present invention (for example, X
I! arbitrarily selected depending on the properties (e.g. solubility, glass transition point, ionicity, etc.) of the polymer hardener of the present invention and other additives used in the light-sensitive material for photosensitive material plates and color negative films, etc. be done. Further, in order to exhibit multiple functions as a polymer, the monomer represented by A may contain two or more types of monomer units.

As an example of selecting the monomer of A, for example, when the polymer of the present invention is to have R ability as an antistatic agent, A is preferably a cationic monomer or anionic monomer,
When providing a function as a mordant, A is preferably a cationic monomer.

Further, in order to further increase solubility in water, A is preferably an ionic monomer, acrylamide, N-vinylpyrrolidone, or vinyl acetate.

As the ionic monomer, anionic monomers are particularly preferred.

In addition, when the polymer of the present invention is used as a crosslinked latex, in addition to the above-mentioned ethylenically unsaturated monomers, at least two copolymerizable ethylenically unsaturated groups are used as A.
Monomers having more than 100% monomer (for example, divinylbenzene, methylene bisacrylamide, ethylene glycol diacrylate, tri-, methylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.) are used.

In general formula [I], carbon number 1 to 6 represented by R1
Examples of the alkyl group include a methyl group, ethyl group, and propyl group, and examples of the halogen atom include a chlorine atom and a fluorine atom.

In the general formula [I], J represents 1000- or.

In the general formula [I], a divalent bonding group represented by L is preferable, and specific examples include the following.

General formula [I] 1jT, X is -CH=CH2 or -C
H20H20, where Q represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HQ with a base.

Preferred examples of X include -CH=CI-h, -CH2CH2C2゜-CH2C
H28r, -CH2CH2035Ct-h.

-CH2CH20H, -CH2CH202CCH3-C
H2CH202CCF3.

-CH2CH202CCHCl2 and the like, among which -〇H-CH2゜-CH2CH2Br, -CH2Cf-hct.

aSb represents mole percentage, a is O~99, b is 1~
Takes a value of 100.

aSb is arbitrarily selected depending on the purpose of the present invention, and for example,
When used as a polymeric hardener that selectively hardens only a specific layer with increased diffusion resistance, a is 50 to 9.
9. b takes a value of 1 to 50, and when used as a polymer hardening agent that has no posterior dura, increases fog, and decreases sensitivity, a takes a value of 0 to 75, and b takes a value of 25 to 100. Among the hard IEl agents that can take a value, those in which It is obtained by polymerizing monomers.

In addition, when X is -CH-CH2, X is -CH2C
It can be easily obtained by treating a H2Q polymer with a base such as triethylamine or pyridine.

General formula [II] R2 CH,=C (L)n TS O, -X However, R1, J, L, X and n have the same meanings as those described in general formula [I].

Next, among the ethylenically unsaturated monomers represented by the general formula [11], the following are preferred.

The method for synthesizing the polymer hardener of the present invention is shown below.

Synthesis Example 1 Synthesis of 8M-layer 3,69 mL of N-piperazine ethanol is dissolved in 60 cc of tetrahydrofuran and kept at 0 to 5°C, and 2.7 g of chloroethanesulfonyl chloride dissolved in 20 cc of tetrahydrofuran is added dropwise thereto. After the dropwise addition was completed, stirring was continued for another hour, and then the precipitated crystals were filtered. These crystals are suspended in 50 cc of acetone, 1.8 g of acrylic acid chloride is added thereto while maintaining the temperature at 0 to 5°C, and 8 cc of an aqueous sodium bicarbonate solution (50%) is slowly added dropwise.

After the reaction is complete, the precipitated crystals are separated by filtration, and the filtrate is extracted with acetone,
Water was distilled off under reduced pressure to obtain 1 g of yellow crystals.

Synthesis Example 2 Synthesis of HP-layer In a reaction vessel of 200d, 3 g of the monomer of the synthesis example layer and 9.3 g of 3-sulfopropyl acrylate potassium salt (1,80
Add 50% ethanol aqueous solution of Dai, stir to dissolve, heat to 80°C while passing nitrogen gas, and add 0.6 g of 2
,2'-azobis(2,4-dimethylvaleronitrile)
30 minutes later, the same substance was added at the same time, and heating and stirring were continued for 8 hours. Then cool to 10℃,
．． A mixture of 59 triethylamine and 80 ml of ethanol was added, stirring was continued for 1 hour, the reaction sample was added to 21° acetone, the formed precipitate was taken, and vacuum dried to obtain the white polymer of 9.69. Obtained.

The intrinsic viscosity of this polymer is 0.221 centivoise and the vinyl sulfone content is 0.87 x 10' equivalents.
/g polymer. Other polymers can also be easily synthesized according to these synthesis methods.

Since the polymer hardener of the present invention has a highly reactive vinyl sulfone group, it not only acts as a hardener for the gelatin layer in the silver halide photographic light-sensitive material to which it is added, but also acts as a hardener for the gelatin layer. i) Polymer mordants with diffusion resistance, antistatic agents, neutralizing agents, thickeners, sensitizers, etc.
ii) Also acts as a polymer for immobilizing or diffusing other photographic additives used in combination.

The polymer hardener of the present invention is used in an amount corresponding to a range of 0.5 x 10-3 equivalents to 5 x 10-2 equivalents of vinyl sulfone groups per 100 g of dry gelatin. is preferable. Particularly preferably 5 x 10-3
range from 5 x 10-2 equivalents.

Further, the polymer hardener of the present invention may be used alone or in combination with other low molecular weight hardeners or polymer hardeners. Hardeners that can be used in combination include 2-hydroxy-4゜6-dichloro-1,3,5
- Compounds having a reactive halogen atom such as triazine, compounds having a reactive olefin such as divinyl sulfone, isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chromic bread, and aldehydes.

The polymer hardener of the present invention is a reactive polymer having pendant vinyl sulfone groups, and gelatin hardens quickly due to the high reactivity of the vinyl sulfone groups. With this agent, there are almost no defects in the posterior dura.

In addition, the polymer hardener of the present invention can have its solubility arbitrarily adjusted by copolymerization monomers, etc., and has diffusion resistance, so that it can be used in combination with a specific layer added, that is, a large number of gelatin layers. It has excellent properties such as the ability to independently adjust the degree of hardening of each gelatin layer in a laminated gelatin coating to suit the purpose. Furthermore, the polymer hardener of the present invention hardly has any adverse effects on the photographic performance of the photographic material used, such as increased fog or decreased sensitivity.

Silver halide, chemical sensitizer, silver halide solvent, spectral sensitizing dye, antifoggant, hydrophilic protective colloid such as gelatin, ultraviolet rays used in the silver halide emulsion layer or other layers of the photographic light-sensitive material of the present invention. Absorbers, polymer latexes, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc. are not particularly limited; for example, Research Disclosure t-(Research
[)isclosure] Vol. 176, pages 22-31 (December 1978) can be referred to.

Further, regarding the support of the photographic light-sensitive material, the development method, the constituent layers of the light-sensitive material, etc., the description in the above-mentioned Research Disclosure magazine can be referred to.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; m-derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Ph
ot, Japan.

No. 16.30Ef ((1966) 2) may be used, and gelatin hydrolysates and enzymatic decomposition products may also be used.

[Example] The present invention will be further explained with reference to Examples below, but the present invention is not limited thereto.

Example 1 When polymer hardeners HP-1 to HP-9 of the present invention and polymer hardener 1.2 for comparison below were dissolved in a water-methanol solvent, HP-1 of the present invention was dissolved. -1~HP-
In case 9, water/methanol was dissolved at a ratio of 10010 to 80/20 (volume ratio), but in comparison 1 it was 60/40 and in comparison 2 it was 7.
It did not dissolve unless it was 0/30. Therefore, it can be seen that the polymer hardener of the present invention has excellent solubility in water.

Example 2 The polymer hardener of the present invention and the comparative polymer hardener shown in Table 1 were added to a 7% by weight gelatin solution, and the dry film thickness was measured on a polyethylene terephthalate support with an undercoat. Samples 1 to 7 were prepared by applying the coating uniformly to a thickness of approximately 7 μm and drying.

While keeping these samples at a humidity of 25°C and 5o% RH, a portion of each sample was taken out on the 1st, 7th, and 14th day after coating, swollen in water at 30°C for 5 minutes, and swelled using the following formula. The degree of swelling (■) was measured.

The film thickness when dried was also determined by immersing the sample in water at 30°C for 5 minutes, and the radius was 0.3.
ml sapphire needle is pressed onto the sample surface, and the speed is 2 m per second.
0 to 200 while moving parallel on the film surface at the speed of 11 layers.
Needle load (scratch resistance) when damage occurs to the membrane surface of the sample by continuously changing the crimp load of the sapphire needle within the range of g.
I asked for The results are shown in Table-1.

Table 1 Below Table 1 shows that the gelatin layer containing the polymer hardener of the present invention can obtain a hardness suitable for a photographic light-sensitive material in a short period of time, and the phenomenon of post-hardening is a result of the swelling degree V. It is not recognized from

It also has sufficient scratch resistance. On the other hand, in sample 5, a sufficient degree of hardness could not be obtained in a short period of time, and posterior hardening continued. Also, sample 6 (comparison) still did not have sufficient hardness,
It can be seen that the scratch resistance is also insufficient.

Example 3 Additives in a silver halide photographic light-sensitive material are shown per 1f unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic material was prepared by sequentially forming a core layer having the composition shown below on a triacetylcellulose film support from the support side.

First layer; antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Gelatin 2.2<1/f 2nd B: Intermediate layer (1,L,) Gelatin layer comprising an emulsified dispersion of 2.5-di-octylhydroquinone.

Gelatin 1.2 (] /f 3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size (r) 0.30 μm, A (lI 6 mol%
Monodisperse emulsion (emulsion I) consisting of AgBr I containing: Silver coating amount 1.8111/f Sensitizing dye I... 6 x 10-5 mol sensitizing dye ■ per 1 mol silver・・・・・・ For 1 mole of silver 1. OX 10-5 molesian coupler (C-1)...0.06 per mole of silver
Molar colored cyan coupler (CCf1>...0.003 mol DIR compound per 1 mol of silver (D-1>...0.0045 mol DIR compound per 1 mol of silver (D-2)・・・・・・ 0.002 mol gelatin per 1 mol of silver 1.4 (1/l') 4th layer: Highly sensitive red-sensitive silver halide emulsion layer (RH-1) Average grain size (r ) 0 .5μm, Ag1 7.0
Monodispersed emulsion (emulsion ■) consisting of A (IBrl) containing mol %... Silver coating amount 1.3 g/i' Sensitizing dye I... 3X10-5 mole sensitization per mole of silver Dye ■... i, ox 10-5 mol cyan coupler (C-1>... 0.02 mol colored cyan coupler (CC- 1)... 0.0015 mol DIR compound per 1 mol of silver (D-2>... o, ooi mol gelatin 1.0 g/v2 per mol of silver 5th layer: Intermediate ( 1,L,) Same as the second layer, gelatin layer.

Gelatin 1.0g/i' 6th layer; Low sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion - ■... Coated silver 111.5g/f Sensitizing dye ■...・ 2.5X 10-5 mol sensitizing dye for 1 mol of silver ■・
...... 1.2X 10' mole magenta coupler (M-1) for 1 mole of silver...0.0 for 1 mole of silver
5 mol colored magenta coupler (CM-1)...0.009 mol DIR compound (D-1)... per 1 mol of silver
... 0.0010 mol to 1 mol of silver DIR compound (D-3) 0.0030 mol to 1 mol of silver Gelatin 2.0 g/v 7th layer; High sensitivity green sensitivity Silver halide emulsion layer (GH-1
> Emulsion - ■... 1.4 g of coated silver, /+' sensitizing dye ■... 1.5X 10-5 mol sensitizing dye ■... per 1 mole of silver
... 1 mole of silver. Ox 10-5 mole magenta coupler (M-1>...0.02 per mole of silver
0 mol colored magenta coupler (CM-1>...0.002 mol DIR compound (D-3) per 1 mol of silver...
... 0.0010 mol gelatin per mol silver 1.80/z 8th layer: Yellow filter layer (YC-1) Emulsified dispersion of yellow colloidal silver and 2.5-di-t-octylhydroquinone gelatin layer containing.

Gelatin 1. sg /f 9th layer: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Consisting of AG Sr I having an average grain size of 0.48 μ+n and containing 16 mol % of Ag.

Monodispersed emulsion (emulsion ■)... II coating amount 0.9 (1/f) Sensitizing dye V... 1.3X i Q-5 mol Yellow coupler (Y-1 >...0 per mole of silver.
29 mol gelatin 1.9<1/f 10th layer; high sensitivity blue sensitive emulsion m (BH-1) average grain size 0.8 μm, AgBr containing 15 mol% AQI
Monodispersed emulsion consisting of 1 (emulsion ■)... Silver type cloth ffi O,5 (1/f Sensitizing dye ■...... 1.OX 10" 5 mol yellow coupler (1/f) per 1 mol of silver Y-1)...008 per mole of silver
Mol DIR compound (D-2)... 0.0015 mol gelatin 1.6 (1/l') for 1 mol of silver 11th layer: 1st protective layer (Pro-1> Silver iodobromide (A(]I mol% average particle size 0.07 μm)
Silver coating amount o, 5g/f Ultraviolet absorber UV-1,
Gelatin layer containing UV-2.

Gelatin 1.2 g/f 12th layer; 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter 1.5 μm) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm ) Gelatin layer containing Ca I-+7SC)+ NCH2C○○Na2 Hs 101B,/f and formalin scavenger (H3-1) Gelatin 1.2 g/l' In addition to the above composition, each layer contains hardened gelatin. agent (H-1
), the polymer hardener of the present invention (shown in Table 2), and a surfactant.

The compounds contained in each layer are as follows.

Sensitizing dye: anhydro 5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye ■; anhydro 9-ethyl-3,3'-di (3-Sulfopropyl)-4゜5.4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye propyl)oxacarbocyanine hydroxide sensitizing dye ■; anhydro9-ethyl-3,3'-di(3-sulfopropyl)-5°6.5',6'-dibenzoxacarbocyanine hydroxide sensitizing dye V ; anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo-5'-methoxythiacyanine Ω-t゛C,H.

C-1 ■ l-1 Hs I Y-1 C7! V-1 V-2 H, C-C10 Each sample prepared in this manner was wedge-exposed with white light, and then subjected to the following development treatment, and the scratch resistance and degree of swelling were measured in the same manner as in Example 2. . The sensitivity is the reciprocal of the exposure flatness that gives a density of fog + 0.5, and the blank sensitivity is 100.
It is expressed as relative sensitivity.

The blank did not contain the polymeric hardener of the present invention.

The results are shown in Table-2.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying The composition of the processing solution used in each processing step is as follows. It is as follows.

[Color developer 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, sulfate 4.7SQ anhydrous sodium sulfite 4.25i; 1-hydroxylamine, 1-2 sulfate 2 .0g anhydrous potassium carbonate 37.3g sodium bromide
1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5Q Potassium hydroxide 1.0g Add water to make 1y.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 Ethylenediaminetetraacetic acid diammonium salt 10. OQ ammonium bromide 150.0g glacial acetic acid
Add 10.0% water to make 1y, and adjust to 1) H-6.0 using ammonia water.

[Fixer] Thiolii! ! Ammonium acid 175.
0 (1 anhydrous sodium sulfite 8.5g
Add 2.3 g of sodium metasulfite to bring the total volume to 12, and adjust pi-1 to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 Daikonidax (Konishiroku Photo Industry Co., Ltd. FJ) 7.51ρ
Add water to make 11.

Table 2 shows that the photosensitive materials to which the polymer hardener of the present invention was added showed no decrease in sensitivity and little fogging.
In addition, even under forced conditions, the increase in fog was small, and the expansion rA
The damage resistance is extremely small, and the scratch resistance has also been greatly improved.

On the other hand, in the comparative example, a decrease in sensitivity and an increase in fog were observed, the scratch resistance was not sufficiently obtained compared to the sample of the present invention, and the problem of posterior dura still remained.

Example 4 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain an X-ray photosensitive material sample.

Additives other than silver halide are shown in amounts per mole of silver halide unless otherwise specified.

1st layer Crossover layer Dye (I) below 3111G/1' gelatin 0.2g/f 2nd layer Emulsion layer Average grain size 1.2μ, Ag containing 1.5 mol% AgI
Amount of trowel for coating emulsion consisting of Br I...4 (1/v'4-hydroxy-6-methyl-1,3゜38.7-detrazaindene...1,2g Diethylene glycol... ...11.0g para-nitrophenyltriphenylphosphite chloride ...0.2g gelatin ...2.0 (1/i' polyethyl acrylate latex ...-1 .0g/l' 3rd layer Protective layer Sodium diethylhexyl succinate sulfonate
...0.015 (1/v2 glyoxal ...0.02g/f mucochloric acid
...0.015+1/v' Polymethyl methacrylate particles (average particle size 3-4μ) ...50 mg/l' Sodium polyoxyethylene dinonyl phenyl ether sulfate -... -・50mo/v' gelatin ・・・・−・1. OIJ/n' polyethyl acrylate latex...-0.5 (1/n' Ca F+7SO3K...311J/i
'Polymer hardener of the present invention (listed in Table 3) Each sample was exposed in the same manner as in Example 3, and then subjected to the following treatments, and the photographic properties and film strength were measured in the same manner as in Example 3. The results are shown in Table-3.

[Processing step 1 Development 30℃ 45
Second fixation 25℃ 3
Wash with water for 5 seconds 15℃ 3
Dry for 5 seconds at 45℃ 2
0 seconds [Developer] Phenidone 0.4g Metol 5g Hydroquinone
19 Anhydrous sodium sulfite
60g hydrated sodium carbonate
54g5-nitroimidazole 100m
g Potassium bromide 2.5g Add water to make 100, (1)H10.20.

[Fixer] (Bert A) Ammonium thiosulfate 1709 Sodium sulfite 15g Boric acid
6.5g glacial acetic acid
12d Sodium citrate (dihydrate)
2.5 (Add 1 water to make 275if.

(Bert B) Aluminum sulfate 15g 98% sulfuric acid 265g Add water for 40i
Finish to N.

When using Part A: 275+N, Part B: 40
Add water to tI2 to make 1 tl.

From Table 3, X with the polymer hardener of the present invention added to the protective layer
In line-sensitive materials, there is only a very slight decrease in sensitivity, and there is no occurrence of fog or an increase in fog under forced conditions. In terms of membrane strength, the degree of swelling is low, and the scratch resistance is extremely improved.

On the other hand, in the comparative example, there was a slight decrease in sensitivity and a slight increase in fog, and it cannot be said that the scratch resistance was sufficient.

Example 5 Layers having the compositions shown below were sequentially formed on both sides of an undercoated polyethylene terephthalate support from the support side to obtain a photosensitive material sample for plate making.

Additives other than silver halide are expressed per mole of silver halide unless otherwise specified.

1st meal Emulsion layer average grain size 0.2μ 8gS containing 24 mol% AgBr
r Amount of silver coated in emulsion consisting of C1...4.0 g/f 4-hydroxy-6-methyl-1,1゜3a,7-titrazaindene...0.6 g Polyoxyethylene nonylphenyl ether
...50IO/12 Borico (Styrene-
butyl acrylate) latex...
・1,5m (1/f gelatin...
...2.517/n2 2nd layer Protective layer gelatin ...1.0g/f Borico (styrene-butyl acrylate) latex
...0.8 (1/f polymethyl mecrite particles (average particle size 3 to 4 μ) ...501'8!It/
f Mucochloric acid...151(]/v
'Each sample of the polymer hardener of the present invention (listed in Table 4) was exposed to wedge light, subjected to the following treatments, and examined for sensitivity, fog, and film strength in the same manner as in Example 3. The results are shown in Table 4.

[Processing conditions: Development: 29°C, 30 seconds Fixation: 28°C, 20
Wash with water for 20℃ 2
Dry for 0 seconds at 45℃ 3
0 seconds [Developer (undiluted solution)] Potassium bromide 2.5g Disodium ethylenediaminetetraacetate 1g Potassium sulfite (
55% aqueous solution) 9 (hR potassium carbonate
2513 Hydroquinone
10g 5-methylbenzotriazole
100mg 5-nitrobenzotriazole 1
0.0mg 1-phenyl-5-mercaptotetrazole 30n+g 5-nitroimidazole 50mg 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 0. 5 (1 diethylene glycol 6 ag sodium hydroxide Adjust pH to 10.6 m Add water, s
o o,, Finish to 2. (p)-110.6)
When used, the above stock solution is diluted to 2 times with water.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 159 Boric acid
6.5g glacial acetic acid
121g Sodium citrate (dihydrate)
2. 5 (Add 1 water to make 275.12.

(Part B) Aluminum sulfate (18 hydrate) 15 g 98% sulfuric acid 2.50 Add water to make 401 g.

The method for preparing the liquid used is to add 600 n12 of Hondori to the above Part A 2751ff, then add Part B40, and then add water to make it to iooo1ρ.

Table 4 shows that in the photosensitive materials for plate making in which the polymer hardener of the present invention is added to the protective layer, the decrease in sensitivity is extremely small, and only a slight increase in the decrease in sensitivity under forced conditions is observed.

Furthermore, in terms of membrane strength, the degree of swelling is small and the scratch resistance is extremely improved. On the other hand, in the comparative example, a decrease in sensitivity and a slight increase in fog under forced conditions were observed, and the scratch resistance was also insufficient.

Patent applicant Roku Konishi Photo Industry Co., Ltd. Procedural publication IJE book (spontaneous) November 27, 1985 1. (Cow indication 1986 Patent FE! No. 194908 2. Name of invention Polymer hardening agent) Relation to the case of a person making a deposit on a silver halide photosensitive material that has not been hardened Patent applicant address Tokyo 111 Shinjuku-ku Nishi-Shinjuku 1-chome] 2G No. 2 Name (127) Roku Konishi Representative Director of Photo Industry Co., Ltd.
Benko Osamu 4, Agent Address: 102-1, 4-1-1, Marudankita, Chiyoda-ku, Tokyo, Kuchomata-
B1 Anti-bill telephone 2 G 3-95246, [3. Detailed description of the invention] in the statement of contents of the amendment is amended as follows.

(1) Details ffm24FTo-9 ('i'o [...
0.221-t='c...'' is written in η (also, if it is, Niro is written as ``...0.221g/df...''
``...'' is corrected).

(21!l]1lllil'Qk 41 page CC'1
No fM formula 3 The following corrections are made.

C-1 (3) Correct the following 911<<911> for the details entry ``51st Shinsen 11 (+)''.

that's all

Claims (1)

[Scope of Claims] At least one non-photosensitive layer and at least one
In a silver halide photographic light-sensitive material having a silver halide emulsion layer, at least one layer selected from the non-photosensitive layer and the silver halide emulsion layer is a polymer having a repeating unit represented by the following general formula [I]. A silver halide photographic material characterized by being hardened with a hardening agent. General formula [I] ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents a copolymerizable monomer unit. R
_1 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. J represents -COO- or ▲There are numerical formulas, chemical formulas, tables, etc.▼ (R_2 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). L is ▲There are mathematical formulas, chemical formulas, tables, etc.▼Divalent bonding groups with 3 to 15 carbon atoms having at least one bond, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. Represents a divalent bonding group (R_3 represents an aryl group having 6 to 12 carbon atoms. Z represents an atomic group necessary to form a ring containing at least one nitrogen atom). X is -CH=CH_2 or -CH_2CH_2-Q(Q
represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HQ by a base. ). a and b each represent a molar percentage, a is 0 to 9
9, and b is 1-100. n is 0 or 1. ]