JPS63118738A - Silver halide photographic sensitive material hardened with high molecular hardening agent - Google Patents

Abstract

PURPOSE:To prevent increase of fog and reduction of sensitivity of a silver halide photographic sensitive material by hardening either one layer of a nonsensitive layer or a silver halide emulsion layer with a high molecular hardening agent having a specified structure in the principal chain. CONSTITUTION:A layer of a nonsensitive layer or a silver halide emulsion layer is hardened with a high molecular hardening agent having a structure expressed by the formula I in the principal chain. The high molecular hardening agent is obtd. by allowing a compd. having three vinyl sulfone groups in a molecule to react with a compd. having one group which reacts with two vinyl sulfone groups, or a compd. having two groups which react with one vinyl sulfone group in the molecular structure. By this method, a specified layer can be hardened and a hardening agent causing no adverse effect on the photographic characteristics nor causing no after-hardening, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material in which a specific layer is hardened with a polymer hardener.

[Background of the invention]

In general, many photographic materials contain hydrophilic colloids such as gelatin as binder components, and these binder components include silver halide emulsion layers, protective layers, filter layers, intermediate layers, anti-halation layers, and backing layers. , film base undercoat layer, baryta layer, etc. For example, photosensitive materials containing gelatin are processed with various aqueous solutions with different pHs or temperatures, but a layer containing gelatin that has not been treated with a hardening agent has poor water resistance and swells excessively in the aqueous solution. In extreme cases, the gelatin layer may even dissolve or flow out, especially in high-temperature processing solutions of 30°C or higher.

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 resistance and scratch resistance of the protective layer. These are well known as ``hardeners'' used in the production of photographic materials6 such as chrome alum! M-organic compounds, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds having active halogens as described in U.S. Pat. No. 3,288,775, etc., U.S. Pat. [Compounds with reactive ethylenically unsaturated groups described in U.S. Pat. No. 35,718, etc., aziridine compounds described in U.S. Pat.
Organic compounds such as epoxy compounds and halodefcarboxaldehydes such as mucochloric acid, which are described in No. 1, are known as hardening agents.

However, when such hardeners are added to any emulsion layer, they may affect the properties of the light-sensitive material (e.g., increase in capri, decrease in sensitivity, change in gradation, etc.), or cause "post-dural" effects. '' may cause long-term changes in the curing effect, 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 (e.g. color for color photosensitive materials). All of them have some drawbacks, such as the hardening period being lost due to the hardening agent (coupler), the hardening agent itself being unstable and having poor storage stability, and the hardening agent itself being difficult to synthesize and producing in large quantities. ing.

In addition, the light and low molecular weight curing agents that are conventionally used to harden gelatin move 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 is could not be adjusted freely according to the purpose. On the other hand, currently well-known polymeric diffusion-resistant gelatin hardeners such as noaldehyde starch or poly-7-chlorein have adverse effects on photographic properties such as an increase in capri and a decrease in sensitivity. could not be used satisfactorily. Also, U.S. Patent No. 4,161,407,
The polymer hardener described in JP-A-56-142524 having a vinylsulfonyl group as an active group has the problem that the hardening reaction is slow and the degree of swelling changes over time, which is the occurrence of post-hardening.

Therefore, it has been desired to develop a hardening agent that can harden specific layers without adversely affecting photographic properties and that does not cause post-hardening.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a photographic light-sensitive material hardened with a polymeric hardener having diffusion resistance that does not adversely affect photographic properties such as an increase in capri or a decrease in sensitivity. It is about providing.

VI2 does not have a post-hardening film in which the degree of swelling changes over time. The purpose is to provide 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, the non-photosensitive layer and the silver halide emulsion layer. At least 1 of! This was achieved using a silver halide photographic light-sensitive material hardened with a polymer hardener having a structure represented by the following general formula (1) in the bird molecule main chain.

General formula (1) %formula% In the formula, J represents N or S.

The present invention will be explained in more detail below.

The polymer hardener used in the present invention is a compound having at least three vinylsulfonyl groups in its molecular structure, and a compound having one group that reacts with two vinylsulfonyl groups in its molecular structure or one vinylsulfonyl group. It can be obtained by reacting the compound with a compound having two reactive groups.

When a compound having at least three vinylsulfonyl groups in its molecular structure is reacted with a compound having one group that reacts with two vinylsulfonyl groups in its molecular structure,
In order to improve the solubility of the resulting polymer hardener, the compound having one group that reacts with two vinylsulfonyl groups preferably further has a hydrophilic group.

The polymer hardener obtained in this way has the following general formula (
Those having a repeating unit represented by n) are preferred.

General formula (II) L ■ In general formula (n), A represents a group having at least one vinylsulfonyl group, L represents a divalent linking group, and B represents a hydrophilic group.

A polymer hardening agent obtained by reacting a compound having at least three vinylsulfonyl groups in its molecular structure with a compound having two groups that react with one vinylsulfonyl group in its molecular structure has the following general formula ( Those having a repeating unit represented by III) are preferred.

General formula (I[[) %Formula% In general formula (III), A has the same meaning as A in general formula (II), and Jl is -S- or -N-2J2 is -8- or -N- represents.

R3 and R2 each represent a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different; R1 and R2 may combine with each other to form a ring; Dl and D2 each represent a hydrophilic group; A group having a functional group or a simple bonding group (R1
and R2 form a ring), each n represents O or 1, but when the key is 0, n is 1.

The following compounds can be mentioned as typical examples of compounds having at least three vinylsulfonyl groups in their molecular structure.

C.I.

CHsC(CHJCHzSO2CI= CH2)3C(
CH20CH2SO2C1l= CH2)4N(CHz
CHzOCIlzSOzCH= CL)iSO. CH=
CH.

C2HsC(CHzSO□CH=CH.)3■-10 CsH+tC(C)H2SO,CH=CH2)*■-
11 CB. =CHSO□CH2CllSO, CI=CH2S
OzCll=Clh ■−12 (CH=CH2(hcHz)*CCHJr■ −13 (CH. = CHSO□C)12) ICICB(CH
ISO. CII = CHz)z■-14 (CH2 = CHSO, CH.), CCH20CH2
C(CH2SO□CH=CHri3■ -15 C(CH2SO2CH=CH2)4 V-16 ■-17 (CH2=CHSO□CHt)*CCHtSO□CHz
CIl□C1■-18 COCH, CH25O□Cl1=CII.

The group that reacts with two vinylsulfonyl groups is -NH
Two groups are preferable, and the following compounds can be mentioned as typical examples of compounds having one group that reacts with two vinylsulfonyl groups in the molecular structure.

HzNCOONa)1. NSO,K HffiNCH2CH,OH HJCHiCH2SOsH 11JcH2cHzsO,Na 82NCR2COOH HJCH2COONa 11iNCI'1zCHzOSOJ H2NCI2CH20S03 has a group that reacts with one vinylsulfonyl group. 15 liters
I group and >>■ group are preferable, and the following compounds can be mentioned as typical examples of compounds having two groups that react with one vinylsulfonyl group in the molecular structure.

HSCH2CHCHCH2SH HOH HSCH2CHCH,SH OOH +1scH,CH,CHS)1 (CH,),C0OH Leave a blank space below. Although the present invention is not limited thereto, the present invention is not limited thereto.

(Compound example) P-1 1P-2 CH20CI(,SO□CH=　CH.

P-3 CHzSOzCH=CH2 CHiSOtCH=CHz Mn=4600
P-4 Js P-6 πn=4000 πn=5600 8n=3400 P-11 CH20CH2SO2CI=CHz -ゝ、Is this the undercolor? 11' P-12 CIl, SO□CH=C11°Mn = 2400 Examples of the synthesis of the polymer hardener of the present invention are shown below.

Synthesis Example 1 (Synthesis of Exemplary Compound IP-1) 1.3.5-
) Lisvinylsulfonylbenzene (Exemplary Compound V-1)
Add 140z1 of an aqueous solution containing 3.51g (0,018mol) of sodium p-amino/benzenesulfonate (exemplified compound A-4) to a solution of 6.96y (0.02 mol) dissolved in 100t1 of 77 tons. , heat and reflux for 2 hours.

The solvent of the reaction solution was distilled off under reduced pressure, and 80 zl of water was added to the residue, stirred thoroughly and filtered. The filtrate was poured into 500 ml of ethanol, and the precipitate was collected and dried to obtain 4.6 g of white powder. The number average molecule j1 (in) measured by vapor pressure method is 280
It was 0. In addition, the vinyl sulfonyl group content is 1.9X
10-'mol/g.

Synthesis Example 2 (Synthesis of Exemplified Compound HP-7) Tetrakis(vinylsulfonyl)methane (Exemplified Compound V-15) 8.8
To a solution of 4g (0.02 mol) dissolved in 77 tons of 100z&, 50xffi of an aqueous solution containing 2.401F (0.016 mol) of sodium 2-7 minoethanesulfonate (exemplified compound A-7) was added. One reaction solution heated to 0.degree. C. and reacted for 3 hours was treated in the same manner as in Synthesis Example 1 to obtain 1.8 g of white powder.

Mn=3700 Vinylsulfonyl group content 3,2X1
0-comole/g Synthesis Example 3 (Synthesis of Exemplified Compound 11P-11) Tetrakis(vinylsulfonylmethoxymethyl)methane (Exemplified Compound V-5) 11,042 (0.02 mol) was dissolved in 77 tons of 100z1, and dithio Erythritol (Exemplary Compound A-12) 2.78 g < 0.018 mol) + 7) Add water-soluble filoozN and react at room temperature for 24 hours.
The reaction solution was distilled off as the solvent in the same manner as in Synthesis Example 1, dissolved in water, and evaporated with ethyl alcohol.
The precipitate was precipitated and dried in a vacuum tube to obtain 2.2 g of white powder.

Mn = 3200 Vinylsulfonyl Fund j12.7
X 10-' mol/g Synthesis Example 4 (Synthesis of Exemplified Compound HP-14) Tetrakis (
vinylsulfonylmethyl)ethane 8.64y(0,02
1.55 g (0,018 mol) of pivefudin (Exemplified Compound A-20) was dissolved in 150 aj! The reaction solution was treated in the same manner as in Synthesis Example 1 to obtain 3.7 g of white powder. Mn=2400 Vinylsulfonyl group content 4. OX
10” mol/g These polymeric hardeners have -N) 1. group, >N) I group,
Since almost no -SH groups are observed, at least 3
It is thought to have two vinylsulfonyl groups. Further, from a comparison of the molecular weight and the number of vinyl groups and other protons determined by NMR measurement, it is presumed that some intramolecular crosslinking occurs.

The polymer hardener of the present invention also contains compounds in the so-called oligomer region of relatively low molecular weight, and these can also sufficiently exhibit the effects of the present invention.

The amount of the polymer hardener of the present invention used is 0.5×1o-a vinylsulfonyl group per 1009 dry gelatin.
Preferably, an amount corresponding to ~5X 10-'' equivalents is used, with * preferably in the range from 1X10-'' to 1X10-'' equivalents.

Furthermore, the polymer hardener of the present invention may be used alone or in combination with other low-molecular hardeners or polymer hardeners. As an agent, 2-hydroxy-4,6-dichloro-1,3,5
- Compounds with a reactive ologen atom such as trianone, compounds with a reactive olefin such as divinyl sulfone, incyanates, aziridine compounds, evoquine compounds, mucochloric acid, chrome light pan, and aldehydes. .

The polymeric hardener of the present invention is a reactive polymer having a vinylsulfonyl group in the llI chain. Because gelatin hardens rapidly due to the high reactivity of its vinyl sulfonyl groups, the polymer hardener of the present invention hardly exhibits any defects in post-hardening. It has almost no adverse effect on the photographic performance of the photographic material used, such as an increase in capri or a decrease in sensitivity.

Silver halide, chemical sensitizer, silver halide solvent, spectral sensitizing dye, antifoggant, hydrophilic protective colloid such as gelatin, ultraviolet rays used in the halogenated emulsion layer or other layers of the photographic light-sensitive material of the present invention. There are no particular restrictions on absorbents, polymer latexes, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc.
176, pages 22-31 (December 1978).

Further, regarding the support of the photographic light-sensitive material, the development processing 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 human axyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, etc., sugars such as sodium alginate, starch derivatives, etc. Derivatives; Synthesis of various types such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol moiety 7-setal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylic 7mide, polyvinylimidazole, polyvinyl bizole, etc. Hydrophilic polymeric substances can be used.

Examples of polymer latex include alkyl (meth)
Acrylate, flukydialkyl (meth)acrylate, glycicle (methacrylate, (meth)acrylic 7mide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic Polymers whose monomer components are combinations of acids, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acids, etc. can be used.

〔Example〕

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

Example 1 A polymeric hardener of the present invention and a comparative hardener were added to a m% gelatin solution for 7 days and coated on a subbed polyethylene terephthalate support so that the dry film thickness was approximately 7 μm. Samples 1 to 6 were prepared by uniformly coating and drying. Sample 7 was coated with a gelatin solution without the addition of a hardening agent.
(blank), these samples were heated at 25°C, 50% R
A portion of each sample was taken out on the 1st, 7th, and 14th day after application while maintaining the humidity at 30°C, and was swollen in water at 30°C for 5 minutes to give the following formula: I! l Moisture Moisture level was determined.

In addition, the sample kept under the above conditions for 7 days was placed in water at 30°C for 5 days.
After soaking for a minute, a sapphire needle with a radius of 0.3 mm is crimped onto the sample surface, and the crimping load of the sapphire needle is continuously changed in the range of 0 to 200 g while moving in parallel on the membrane surface at a speed of 2 mm per second. The load on the needle (scratch resistance) at which damage occurred on the membrane surface of the sample was determined.

Comparison-1 (compound described in U.S. Pat. No. 4,161,407): rI3 x:y=2:1 Comparison-2 (compound described in JP-A-56-142524): CH,x:y=3: 1 From Table 1, it can be seen that in the gelatin layer to which the polymer hardener of the present invention is added, a hardness suitable for a photographic light-sensitive material can be obtained in a short period of time, and the phenomenon of post-hardening is not observed from the results of the swelling degree V. .

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

Example 2 In the following examples, the amount added in the silver halide photographic light-sensitive material is per 1 m'' unless otherwise specified.
In addition, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

multilayer color photo elements 1st layer: Halic acid prevention layer (HC) Gelatin layer containing black colloidal silver.

2.2 g of gelatin/2 shoes Second layer; Intermediate Jl (IL) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

Gelatin 1.2y/m" 3rd M4; Low-sensitivity red-sensitive silver halide emulsion layer (RL) average grain size (r), monodispersed emulsion (emulsion ■)... Silver coating fil, 8 g/z2 Sensitizing dye ■... 6 x 10-' mole sensitizing dye for 1 mole of silver ■... T, ox for ff11 mole to-'Morsian coupler (C-1) 0.06 mol per mol of silver Colored cyan coupler (CC-1)...0.003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2) 0.002 mol per mol of silver Gelatin 1,49/Shoulder 2 4th layer; High Sensitivity Red-sensitive silver halide emulsion layer (RH) Monodispersed emulsion (emulsion ■) consisting of 8 gBrl containing average grain size (r) 0.5 μl, 8 gl 7.0 mol%... Silver coating f11.3 g/ x” Sensitizing dye l... 3 x 10-5 mol per mol of silver Sensitizing dye ■... 1. OX 10-'Morsian coupler (C-1)...0.02 mol per 1 mol of silver Colored cyan coupler (CC-1)...I [0.0015 mol per 1 mol DIR compound (D-2)...1!0.001 mol for 11 mol of gelatin 1. OH/Taki 2 5th layer; Intermediate (IL) Same as 2N, gelatin layer.

Gelatin 1.0y/z” 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL)
Emulsion-I: Coated silver amount: 1.5y/z" sensitizing dye ■: 2.5X 10-' mol sensitizing dye per 1 mole of silver.
... 1.2X 10-5 mole magenta coupler (M-1) for 1 mole of silver...0.05 for 1 mole of silver
Mol colored magenta coupler (CM-1)...0.009 mol DIR compound CD-1) per 1 mol silver
... 0.0010 mol per mol of silver DIR compound (D-3) 0.0030 mol per mol of silver Gelatin 2.0 g/Maro 2 7th layer; High sensitivity green Sensitive silver halide emulsion layer (GH) Emulsion - ■... Coated silver fi 1.4y/m" Sensitizing dye ■... 1,5X 10-' mole increase per mole of silver Sensitive pigment ■・
... 1 mole of silver. OX 10-' 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 fi
...0.0010 mol gelatin per mol silver 1,817x2 IjS8N; Yellow filter layer (yc) Gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone .

Gelatin 1.5g/i+' m9 layer; low sensitivity blue-sensitive silver halide emulsion layer (BL) average grain size (r)o, 4sμl, 8g containing ^gl 6 mol%
Monodispersed emulsion (emulsion ■) consisting of Brl... Silver coating amount 0.9y/z' Sensitizing dye V... 1,3X 10-' mole yellow coupler (Y- 1) 0.29 per mole of silver
Morgelatin 1.9g/2 layers 10th layer; high sensitivity blue sensitive emulsion layer (BH) average particle size (F)
Monodispersed emulsion (emulsion ■) consisting of AgBr1 containing 0.8μ11^gl 15 mol%... Silver coating amount 0.5y/z' Sensitizing dye V... 1.5% by mole of silver. OX 10-' mol Yellow coupler (Y-1)...0.0 per 1 mol of silver
8 mol DIR compound (D-2>...0.0015 mol gelatin per 1 mol silver 1.6y/z" Iji11 layer; 1st protective layer (Pro-1) silver iodobromide (8 mol) g11 mol%, average particle size (〒) 0.07 μl)...
Silver coating amount 0.51F/12 UV absorber UV-1,
Gelatin layer containing UV-2.

Gelatin 1.2y/z” 1M12M: Second protective layer (Pro 2) Polymethyl methacrylate particles (average particle size 1.5 μl) Ethyl methacrylate: Methyl/tafrylate: methacrylic acid copolymer particles (average particle size 2.5 μl) ) CsFuSO2NC1liCOONa 101g
/x” Gelatin layer containing C18% and formalin scavenger (HS-1).

Gelatin 1, 2, 7 rin 2 In addition to the above composition, each layer contains a gelatin hardening agent (H-
1), the polymer dura shell of the present invention (shown in Table 2), and a surfactant.

The compounds contained in each layer of the photographic element are as follows.

316 colors 11; anhydro 5,5'-nochloro 9-
Ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye■; anhydro9-ethyl-3,3'-no(
Anhydro 5,5'-diphenyl-9-ethyl-3,3'-cy(3-sulfopropyl)-4,5,4',5'-nopenzothi7carpocyanine hydroxide sensitizing dye ) Oxacarbocyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-no (
3-sulfopropyl)-5,6,5',6'-nobenzoxalpocyanine hydroxide sensitized color IV; Methoxythia-I C-I M-1 l I tlV-1 L: Js (I tlV-1 A forced deterioration sample was prepared by leaving it at 50% RH for 2 days.

Thereafter, the film was exposed to a wedge of white light, and then subjected to the following development process, and the sensitivity and capri were measured. In addition, the dominance resistance and Ml moisture content were measured in the same manner as in Example 1. The sensitivity is expressed as the reciprocal of the exposure amount that gives a density of Capri +0.5, and is expressed as a relative sensitivity with the blank sensitivity as 100.

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

The results are shown in Table-2.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of treatment 81 used in each treatment step is as follows.

[Color developer] 4-7mi/-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g anhydrous sodium sulfite 4,25y Hydroquinamine φ1/2 sulfate 2. 09 Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid 3
Lamb salt (monohydrate) 2.52 Potassium hydroxide Add 1.0 g of water to make 11.

White ticket 8! ] Ethylenecyaminetetraacetic acid iron ammonium salt 10G.

Ethylenedi7minetetraacetic acid W127ammonium salt 10,Of ammonium bromide 150.0°glacial acetic acid 10. Add Oif water to make it 11, and use ammonia water to make DH6.0 to 1.
Make 1 adjustment.

[Fixer 1 Ammonium thiosulfate 175. O.

Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.32 Add water to make 11, and adjust to pile with acetic acid.

[Stabilizing liquid] Formalin (37% aqueous solution) 1.5
t1 Konigutsukusu (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5
Add zZ water to make 11.

As shown in Table 2 below, in the photosensitive materials to which the polymer hardener of the present invention was added, no decrease in sensitivity was observed, and the occurrence of capri was small.
In addition, even under forced aging conditions, the increase in capri is small.

Furthermore, the degree of swelling is almost the same as that of comparative polymer hardeners, and the scratch resistance is greatly improved.

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

Example 3 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: Ri-a-super layer The following dye (T) 331g/I" Gelatin 0.
2g/z" 2nd layer: emulsion layer average grain size 1.2μL, 8g containing 1.5mol%
Amount of coated silver in emulsion consisting of irl... 4g/z"4-hydroxy-6-methyl-1,3,3m, 7-titrazaindene... 1.22 diethylene glycol... 11.0゜p-nitrophenyl) +
7 Phenylphosphonium chloride...0.
2゜gelatin...Z, 0g7
m2 polyethyl acrylate latex...1.0g/x" 3rd layer: retention i1/1 Sodium diethylhexyl succinate sulfonate...0.015g/z
"Glyoxal...0.02g/z
"Mucochroic acid...0.015g
/i+”polymethyl methacrylate (average particle size 3-4 μl) 5011F/I
2 Polyoxyethylene-nononylphenyl ether sodium sulfate... 5ony/z" Gelatin... 1.Oy/z"
Polyethyl acrylate latex --- 0.5g/*2 CJ+ySOJ --1-311F
/x2 Polymer hardener of the present invention (listed in Table 3) Dye (1
) Each sample was subjected to a storage test in the same manner as in Example 2, and then exposed to light and subjected to the following treatments, and the photographic properties and film strength were measured in the same manner as in Example 2. The results are shown in Table-3.

[Processing process] Development 30℃ 45 seconds fixation
Wash with water for 35 seconds at 25℃ 1
Dry for 35 seconds at 5℃ 45℃
20 seconds [Developer] Phenidone 0.4g Metol 5g Hydroquinone 1g Anhydrous Sodium Sulfite 60I? Sodium carbonate (monohydrate) 54g 5-nitroimidazole 100iy Potassium bromide 2.5g Add water to make 11, and adjust pH to 20.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid
6.5g glacial acetic acid
Add 12ml 1' sodium citrate (dihydrate) and 2.5y water
Finished to 75m1.

(Par) B) Fluminium sulfate
15I? 98% sulfuric acid 2
．． Add 5g of water to make 40R1.

When used: Bart A: 275x1, par) B: 40m
1 and water <J-.

From Table 3, X with the polymer hardener of the present invention added to the protective layer
Light-sensitive material for #l, very slight decrease in sensitivity of photographic performance was observed, no generation of capri, no increase in capri under forced deterioration conditions, and the degree of swelling was higher than that of comparative polymer hardeners even at strength 11. Although there is no big difference, the scratch resistance is significantly improved.

In the comparative example, a slight decrease in sensitivity and an increase in capri were observed,
Moreover, it cannot be said that the scratch resistance is sufficient.

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 a photosensitive material sample for plate making.

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

1st layer: Emulsion layer average grain size 0.2 μa 8 g containing 24 mol% AgBr
Emulsion coating silver amount consisting of BrC1...4.0g/x24-
Hydroquine-6-methyl-1,3,3a,7-chitrazaindene...0.6g Polyoxyethylene nonyl 7enyl ether...50xg/l styrene-butyl acrylate copolymer latex... ...1.5B/m"Gelatin ...2.5g/i+"Second layer: Protective layer gelatin ...1.0g7m"
Styrene-butyl 7-acrylate copolymer latex...0.8g/z2 polymethyl methacrylate (average particle size 3-4μm)...501g/ll
+” Mucochloric acid ・・・・・・ 15xg/
m"Polymer hardener of the present invention (listed in Table 4) Each sample was stored in the same manner as in Example 2, exposed with a wedge, and subjected to the following treatment, and the sensitivity, capri, The film strength was examined.The results are shown in Table 4.

[Processing conditions] Development 29℃ 30 seconds fixation
Wash with water for 20 seconds at 28℃ 2
0℃ 20 seconds dry 45℃
30 seconds [Developer solution (undiluted solution)] Potassium bromide 2.5g ethylenediaminetetravinegar l! ! 2 Sodium 1g Potassium sulfite (55% water soluble ig,) 90zl Potassium carbonate 259 Octahydroquinone 10゜5-Methylbenzotriazole 1001g 5-Nitrobenzotri7zole 100IIF1-phenyl-5
-Mercaptotetrazole 0mg 5-nitroimidazole 50zg1
-phenyl-4-methyl-4-human axymethyl-3-
Pyrazolidone 0.5g Diethylene glycol 60° Add water to make 500x1, and use sodium hydroxide to adjust to puto and e.

When used, the above stock solution is diluted to twice the volume with water.

[Fixing II (Par) A) Ammonium thiosulfate 170° Sodium sulfite 15g Boric acid
6.5g glacial acetic acid
1211 Sodium citrate (dihydrate) 2.5° Add water to 275
Finish it as i+f.

(Par) B) Add 15 g of aluminum sulfate (18 hydrate) and 2.5 g of 98% sulfuric acid to make 4011.

*For the preparation method of the liquid, see above.) A Add 600z1 of Honsuri to 75ml of liquid, then add 840ml of Bart, and then add water to make 100011.

1ゝ, More than 100 below.

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, there is very little decrease in the sensitivity of photographic performance, and very little decrease in sensitivity or increase in fog is observed under forced aging conditions. .

The film strength and swelling degree are almost the same as those of comparative hardeners, and the scratch resistance is extremely improved.

On the other hand, in the comparative example, a decrease in sensitivity and a slight increase in capri under forced deterioration conditions were observed, and the scratch resistance was insufficient.

Claims (1)

[Scope of Claims] At least one non-photosensitive layer and at least one
In a silver halide photographic material having a silver halide emulsion layer, at least one of the non-photosensitive layer and the silver halide emulsion layer has the following general formula [I
] A silver halide photographic light-sensitive material characterized by being hardened with a polymer hardener having a structure represented by the following. General formula [I] -SO_2CH_2CH_2-J- [In the formula, J represents ■ or S. ]