JPS63135935A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having excellent strength, without giving no adverse effect to photographic characteristics by hardening the photographic constituting layers of the titled material provided a non-photosensitive layer and a silver halide emulsion layer on a supporting body, with a specific compd. CONSTITUTION:In the titled material provided at least one layer of the non- photosensitive layer and at least one layer of the photographic constituting layer on the supporting body, at least one layer of the photographic constituting layer is hardened with the compd. shown by formula I wherein R is 1-6C alkyl group, X is an anion necessary to neutralizing a positive charge. In case that R contains an acidic anion at the terminal of a molecule, X is unnecessary. The used amount of the hardener is usually 0.01-100wt.%, preferably 0.1-10wt.% on the dry weight basis of a binder. Thus, the titled material having a sufficient film strength, without injuring the photographic characteristics 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 silver halide photographic light-sensitive material in which the photographic grooves R&layer are hardened with a specific compound.

[Background of the invention]

In general, a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) includes, for example, a silver halide emulsion layer, an intermediate layer, a
Consisting of various photographic constituent layers such as NI, filter layer, subbing layer, antihalation layer, ultraviolet absorbing layer, antistatic layer, backing layer, etc., on a support such as glass, paper, or synthetic resin film. It is something.

Since these photographic constituent layers are coated with an aqueous coating solution consisting of a hydrophilic polymer and/or a water-dispersible polymer, the mechanical strength of the film is weak as it is.For example, a gelatin film has a low melting point and is It is water-swellable.

In addition, the latex film has very poor adhesion to the support.
It has drawbacks such as easy peeling.

For this reason, it is known to add a compound called a "hardening agent" to the photographic constituent layer to improve the mechanical strength of the film. For example, aldehyde compounds such as formaldehyde and grugulaldehyde, reactivity described in U.S. Pat. Compounds with adenoids, noacetyl, ketone compounds such as cyclobentanedione, bis(2-chloroethyl)urea, 2-hydroquine-4,6-dichloro-1°3.5-
) riazine, novinylsulfone 1,3-diacryloylhexahydro-1.3.5-tri7one, U.S. Pat.
No. 232,763, No. 3,635,718, compounds having reactive olefins described in British Patent No. 994,809, etc., N-hydroxymethyl 7-talimide, U.S. Pat. No. 2,732,316, British Patent No. 2,586 , No. 168, etc., U.S. Patent No. 3,103,43
Incyanates described in No. 7, etc., U.S. Patent No. 2,983
, 811, 3,107,280, etc., U.S. Pat. No. 2,725,294, 2,
Acid derivatives described in US Pat. No. 725,295, etc., U.S. Pat.
・Carboimide compounds described in US Pat. No. 100,704, etc., epoxy compounds described in US Pat. No. 3,091,537, etc., US Pat.
, organic hardeners such as inoxazole compounds described in , No. 292, halides/urboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydinoxane and dichloronooxane, chromium alum, and zirconium sulfate. , chromium trichloride, and other inorganic hardeners.

However, when these known hardening agents are used in light-sensitive materials, they may not have sufficient hardening action, or there may be a long-term change in hardening action called "post-hardening" that occurs due to the slow hardening reaction to gelatin. materials, materials that adversely affect the performance of the photosensitive material (in particular, increased fog, decreased sensitivity or maximum density, softened gradation, etc.), loss of hardening effect due to coexisting photographic additives, or Hardeners that reduce the effectiveness of additives (e.g. couplers in internal color emulsions) or cause contamination; Hardeners themselves are difficult to synthesize and cannot be synthesized in large quantities; Hardeners themselves are unstable and have a long shelf life. Many of them have some kind of drawback, such as those with poor adhesion to the support, and those with insufficient adhesion to the support that cause the film to peel off.

In recent years, there has been a demand for rapid processing of photosensitive materials, and in order to ensure rapid penetration of processing liquids, the photosensitive material layers have been made thinner, automatic processing machines,
High-temperature, short-time processing is attempted by combining powerful processing liquids. Therefore, there is a need to develop a hardening agent that does not impair photographic properties and provides sufficient film strength and adhesion to a support.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a photographic material in which a photographic constituent layer is hardened with sufficient strength using a hardening agent that does not adversely affect photographic properties such as an increase in fog or a decrease in sensitivity. It's about doing.

The second object is to provide a photographic material in which the photographic constituent layers are hardened with a hardening agent that does not have a post-hardening effect in which the degree of swelling changes over time.

The third object is to provide a photosensitive material in which the adhesion between the photographic constituent layers and the support is sufficiently strong.

[Structure of the invention]

The above object of the present invention is to form at least one photographic constituent layer of a light-sensitive material having at least one non-photosensitive layer and at least one silver halide emulsion layer on a support using the following general formula (
This was achieved by hardening with the compound represented by 1).

General Formula (1) In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and X represents an anion necessary to neutralize positive charges.

However, when R has an acid 7 anion at the end, X is unnecessary.

The present invention will be explained in detail below.

In the general formula (1), the furkyl group represented by R is an optionally substituted straight or branched furkyl group, specifically methyl, ethyl, i-propyl, butyl, sec-
Groups such as butyl, (-butyl, 3-hydroxypropyl, 3-chloropropyl, 3-sul7amoylpropyl, 2-carboxyethyl, 2-(2-carboxyethylsulfonyl)ethyl) can be mentioned.

The 7-ion represented by X is not limited as long as it neutralizes two positive charges; for example, 2C1-12NO,
-,28F,-,2CH,504-52CI+30SO
3-, SO4''-, etc.

Further, when R has an acid anion (COO-1SO, -, etc.) at the end, X is not necessary.

Next, the above-mentioned representative compound of the filter hardening agent represented by the general formula (1) used in the present invention (hereinafter referred to as the hardening agent of the present invention) is obtained by reacting bisimidazoles with a quaternizing reagent. For example, it can be easily synthesized by referring to the method described in JP-A-61-112065.

In the present invention, photographic constituent layers refer to all layers provided on the support, such as silver halide hole cuttings, medium ntt layer, protective layer, filter layer, subbing layer, () resin tan prevention layer,
It means an ultraviolet absorbing layer, an antistatic layer, a backing layer, etc.

The amount of the hardening agent used in the present invention varies depending on the type of photosensitive material to which it is applied and the hydrophilic binder 118, etc., but is generally 0.01 to 100% by weight, preferably 0.1 to 100% by weight of the dry weight of the binder. % by weight.

As the binder of the present invention, it is preferable to use a hydrophilic polymer, a water-dispersible polymer, or a combination thereof.

Hydrophilic polymers include gelatin, 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; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, Polyvinyl alcohol moiety 7 setal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl alcohol, polyvinylpyrazole, etc., single or copolymers, and various synthetic hydrophilic compounds such as water-soluble polyesters. Polymeric substances can be used.

Examples of water-dispersible polymers include hydrophobic polymers obtained from vinyl compounds such as styrene, butanoene, acrylic acid, methacrylic acid, itaconic acid, methyl acrylate, ethyl heptacrylate, hydroxyethyltu-taacrylate, butyl acrylate, etc. An aqueous dispersion of a copolymer or an aqueous dispersion of a polycondensation polymer such as polyester can be used.

Halogenated kites, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, hydrophilic protective colloids such as gelatin, ultraviolet absorption used in silver halide emulsion M or other layers of the light-sensitive material of the present invention agent, polymer latex,
There are no particular restrictions on whitening agents, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc.
isclo-sure) volume 176, pages 22-31 (19
(December 1978) can be referred to.

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

〔Example〕

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

Example 1 In the following examples, the amount added to the silver halide photographic light-sensitive material is per 112 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 tria-7tylcellulose film support from the support side.

Multilayer Color Photographic Element No. 17W; Antihalation Layer (HC) Gelatin layer containing black colloidal silver.

Gelatin 2.2y/z2 PtS2 layer; intermediate! <TL) Gelatin layer comprising an emulsified dispersion of 2.5-octylhydroquinone.

Gelatin 1.2y/z2 3rd M; low sensitivity red-sensitive silver halide emulsion layer (RL) average grain size (〒), 0.30μ! , Contains 6 mol% of gl
Monodisperse emulsion (emulsion I) consisting of HIlrl... Silver coating amount 1.8y/z2 Sensitizing dye I... 6 x 10-' mol sensitizing dye ■... per 1 mol of silver
... 1 mole of silver. OX 10-5 mol cyan coupler (c-i) 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 to 1 mol of silver DIR compound (D-2) ・・・・・・00OO2 mol to 1 mol of silver Gelatin 1.4y/z2 4th M; High sensitivity red sensitivity Silver halide emulsion layer (RH) Monodispersed emulsion (emulsion ■) consisting of 8 gBrl containing average grain size (r) 0.5μ11^g+ 7.0 mol%... Silver coating amount L3g/w" Sensitizing dye I...3 x 10'' mole sensitizing dye for 1 mole of silver...
... 1 mole of silver. OX 10-'Morsian coupler (C-1)...0.02 mol per mol of silver Colored cyan coupler (CC-1)...0.0015 mol per mol of silver DIR Compound (D-2): 0.001 mol gelatin per 1 mol silver. Og/z” 5th layer; Intermediate (IL) Same as 2nd layer, gelatin layer.

Gelatin 1.0IF/II2 6th/ii low sensitivity red-sensitive silver halide emulsion layer (GL)
Emulsion-1... Coated silver amount 1.5y/z2 sensitizing dye ■... 2.5X 10-S mol sensitizing dye ■ per 1 mole of silver
... 1.2X 10-S 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 (D-1)... per 1 mol of silver
... 0.0010 mol per mol of silver DIR compound (D-3) ... 0.0030 mol per mol of silver Gelatin 2.0 g / 2 7th layer; High-sensitivity green Sensitive silver halide emulsion layer (GH) Emulsion - ■... Coated sheet weight 1-4 g/z2 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 mole colored magenta coupler (CM-1)...! ! t1
o, ooz mole to mole DIR compound (D-3)
...0.0O10 mole gelatin 1.8g/z2 per mole of silver @II; Yellow filter single layer (YC) emulsified dispersion of yellow colloidal silver and 2,5-di-L-octylhydroquinone Contains a gelatin layer.

Gelatin 1.5g/z2 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL) average grain size (r) 0.48μ shoulder, 8gB containing 8g16 mol%
Monodisperse emulsion consisting of rI (emulsion ■)... Silver coating amount 0.9 g/x2 Sensitizing dye ■... 1.3X 10 moles yellow coupler (Y-1) per mole of silver・・・・・・1 mole of silver (2 large, 1 and 0.
29mol gelatin 1.9g/fake 2 tPJIOJ1! ; High-speed blue-sensitive emulsion layer (BH) average grain size (bottom) 0.8μ, 8g containing Δg + 15 mol%
Monodispersed emulsion consisting of BrI (emulsion ■)... Silver coating amount 0.51/x'' Sensitizing dye ■... 1.OX 10 moles yellow coupler (Y -1)...O, OS mol per 1 mol of silver DIR compound (D -2)... 0.0015 mol per 1111 mol Gelatin 1.6 g/z2 117I; First protective layer (Pro 1) Silver iodobromide (^
, I 1 mol%, average particle size (〒) 0.07 μl)...
Silver coating amount 0.51F/12 UV absorption cutting UV-1
, a gelatin layer containing uV-2.

Gelatin 1.2 g/m"127ff; 2nd Hokkaido, NN (Pro-2) Polymethyl methacrylate particles (average particle size 1.5 μl) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average Particle size 2.5μl) C,FlysOzNclI2cOONa Lon
g7m2C,l+.

and formalin scavenger Gelatin layer containing (HS-1).

Gelatin: 1.2 g/z' In addition to the above composition, a hardener of the present invention or a comparative hardener, and a surfactant were added to each layer as shown in Table 1.

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

Sensitizing dye I
3-sulfopenyl)-4,5,4',5'-nobenzothi7carpocy7ine hydroxide dye m: anhydro5,5'-nophenyl-9-ethyl-3,3'-di(3-sulfonate) propyl) oxacarbocyanine hydroxide sensitizing dye ■; anhydro 9-ethyl-3,3'-no (
3-sulfopropyl)-5,6,5',6'-nobenzoxalpocyanine hydroxide sensitizing dye V; anhydro 3,3'-no(3-sulfopropyl)-4,5-benzo-57-med Margin below xithiacyanine hydroxide CC-I D-I I Cl1゜M-1 ('1 I V-1 V-2 s-1 Each sample thus prepared was made into 7-recipe samples and incubated at room temperature for 7 days. Left unattended and at 50°C, 50%RH
A forced deterioration sample was prepared by leaving it for two 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. Sensitivity is Capri +0
．． It is expressed as the reciprocal of the amount of fog light that gives a density of 5, and is expressed as a relative sensitivity with the sensitivity of the blank as 100.

In addition, the sample kept under the above conditions for 7 days was immersed in 30°C water for 5 minutes, and a sapphire needle with a radius of 0.3 mm was pressed onto the sample surface and moved by hand over the membrane surface at a speed of 2xa per second. The crimp load of the sapphire needle was continuously changed in the range from 0 to 0 to 0 to 0, and the load of the needle (scratch resistance) at which damage occurred on the membrane surface of the sample was determined.

The results are also shown in Table-1.

The blank contained no hardener.

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

[Color developer 1 4-7mi/-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.751F anhydrous sodium sulfite 4.259 hydroxylamine 1/2 sulfate 2. 0g anhydrous potassium carbonate a7. sy Sodium senka 1.32 Nitrilotriacetic acid trisodium salt (monohydrate) 2.52 Potassium hydroxide Add 1.0 g of water to make 11.

[) White liquid 1 Ethylenedi7minetetraacetic acid iron ammonium salt 00g Ethylenediamine quadruple M2 ammonium salt 10, Oy Ammonium bromide 150.01F
Hydroacetic acid 10. Oy1
Add water to make 11, add ammonia water to -1 and pl+6
．． Set 'I4 to 0.

[Fixer] Thiosulfate 7mmonium 175. O.

Anhydrous sodium sulfite 8.5g Sodium metasulfite Z, 39 Add water to make 11, and adjust the pH to 6.01 with acetic acid.

[Stabilizing solution 1 Formalin (37% aqueous solution) 1.5 liters
(manufactured by Konishiroku Photo Industry Co., Ltd.) Add 7.5xl water to 11
shall be.

Below is the margin of this comparative hardening agent ^ This comparative hardening agent B CIl□= CHSO2CI+20CI1.5O2CH
= C112 As is clear from Table 1, the photosensitive materials using the hardener of the present invention do not suffer from deterioration of photographic properties such as a decrease in sensitivity or an increase in capri, and have sufficient film strength.

Example 2 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#1 photosensitive material sample.

Additives other than silver halide are expressed in amounts of 1 per mole of silver halide unless otherwise specified.

m1 layer: Crossover 1 layer below dye (1) 3 layers g/z' gelatin O, Z
g/w2: White second layer: emulsion layer average grain size 1.2 μl, ^, 8 gB containing 11.5 mol%
Amount of coated silver in emulsion consisting of rl: 4 g/z"4-hydroxy-6-methyl-1,3,3a, 7-chitrazaindene: 1.2 g ethylene glycol: ...11,0゜p-nitrophenyltriphenylphosphonium chloride ...0.2g gelatin ...2.Og/z2 polyethyl acrylate latex ...1.Og/x ” Pt113 layer: Protective layer sodium noethylhexyl succinate sulfonate ...0,015y/z
2 polymethyl methacrylate (average particle size 3-4 μl) 50jy/z
"Polyoxyethylene-nononylphenyl ether sodium sulfate...50zg/x2 Gelatin...1.0g/z2
Polynityl actyl acrylate latex... 0.5g/x" CsF l, SOJ...
3H/x2 dura abrasion (listed in Table 2) Dye (N) After a storage test for each sample in the same manner as in Example 1, exposure was applied and the following treatment was performed to obtain the same photographic properties and film strength as in Example 1. The results are shown in Table 2.

[Processing step 1 Development 30℃ 45 seconds fixation
Wash with water for 35 seconds at 25℃ 1
Dry for 35 seconds at 5℃ 45℃
20 seconds [Developer 1 7enidone 0.4 g Metol 5 g Hydroquinone 1 g Anhydrous sodium sulfite 60 g Sodium carbonate (l hydrate) 54 g 5-Ditroimiguzole 100 mg Potassium bromide 2.5 g Add water to make 1r, pH 10,201 : ;14'l t
Le.

[Fixer] (Par) A) Ammonium thiosulfate 170g Sodium sulfite isy boric acid
6.5g Ice Vinegar
1211 Sodium citrate (dihydrate) 2.5° Add water and make 2
Finished with 75z1.

(bar) B) Aluminum sulfate 15998
% sulfuric acid 2.52 Add water to make up to 40ml.

When using part A: 275 waterfall 11 bars) B: 40
Add water to xl to make 11.

In addition, while maintaining the sample at 25°C and a humidity of 50% old 1, a part of each sample was taken out 2 hours, 1 day, and 7 days after application, and was swollen in water at 30°C for 5 minutes and expressed by the following formula. The swelling degree V was measured and the change in curing effect over time (posterior hardness) was observed.
The results are also shown in Table 3.

As is clear from Margin Table 2 below, in the X-ray photosensitive material samples containing the hardening agent of the present invention and added to the J layer, there was almost no change in photographic properties such as a decrease in sensitivity or an increase in fog. , Moreover, application and drying f! After 2 hours or more, the degree of swelling was stable, and the post-hardening properties were significantly improved compared to the comparative sample.

Example 3 On both sides of an undercoated polyethylene terephthalate support, 11 samples each having the composition shown below were sequentially formed from the support side to obtain a photosensitive material sample for plate making.

Additives other than silver halide are not specified. 1 limit 9 ha
The amount is shown per mole of silver gunkide.

1st layer, 2 emulsion layers, average grain size: 0.2μ [8g containing 24 mol% lr]
Emulsion coating silver amount consisting of BrCZ 4.0g/x”4-
Hydroxy-6-methyl-1+3.3a,7-chitrazaindene...0.6g Polyoxyethylene/nylphenyl ether styrene-butyl acrylate copolymer latex...1.511F/layer 2
Gelatin 2,511/shoes 2 2nd layer: Protective layer Gelatin 1. Oy/i2
Styrene-butyl acrylate copolymer latex...0.8g/x2 polymethyl methacrylate (average particle size 3-4μl)...50ng/w'
Hardening agent (listed in Table 3) Each sample was stored in the same manner as in Example 2, exposed with a wedge, and subjected to the following treatments, and the sensitivity, fog, and film strength were examined in the same manner as in Example 2. The results are shown in Table-3.

[Processing conditions 1 Development 29℃ 30 seconds fixation
Wash with water for 20 seconds at 28℃ 2
0℃ 20 seconds dry 45℃
30 seconds Current FFI solution (undiluted solution) J Potassium bromide 2.59 Ethylenenoaminetetravinegar W12 Sodium 12 Potassium sulfite (55% water soluble 90m #Potassium carbonate 25g Hydroquine/N
10g5-methylbenzotriazole 100zg5-nitrobenzotriazole 100zg1-phenyl-5-mercaptotetrazole 30 translations 2 5-nidroimiguzole 501g1
-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone 0.5 g Diethylene glycol 60 g Add water to make 500 ml, and adjust to pH 10.6 using sodium hydroxide.

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

[Fixer 1 (Bert A) Ammonium thiosulfate 170° Sodium sulfite 15g Boric acid
6.5f glacial acetic acid
12ml Sodium citrate (dihydrate) Add 2.5y water and make 27
Finished to 5m1.

(Part B) Sulfur 11 fluminium (18 hydrate) 15g 98% sulfur
Add 2.5g water and make 40
Finish to zN.

The method for adjusting the liquid used is as described above. After adding Hondori 6001 to A 275z1, add Part 840ze, and then add water to finish it to 1000d.

Margin below \,.

As is clear from Table 3, the photosensitive material according to the present invention has improved post-hardening properties and film strength. ! Example 4 A polyethylene terephthalate film having a thickness of 175 .mu.R, which had been heat-set by two-sleeve stretching, was subjected to a corona group 1 electric treatment of 30111/2w1n. This is quoted below ° Resin 10
i+i', 1xl of a 2% aqueous solution of a surfactant with the following structure;
It was applied to a thickness of 0μ and dried at 100°C for 1 minute.

Next, add 1 g of gelatin and 0.2 ml of 10% saponin aqueous solution.
20μ of upper layer coating solution made with pure water to 100i+1
It was applied to a film thickness of m and dried at 100° C. for 1 minute.

Each layer having the composition shown below was sequentially coated from the support side onto the undercoated polyester film obtained by the above procedure to prepare an X-ray photosensitive material sample.

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

~1 layer: Crossover layer below dye (1) 3xg7x2 gelatin 0.2
g/x” to 2M: Emulsion layer average grain size 1.2μ11^g11.5 mol% containing
Amount of coated silver in emulsion consisting of rl...4g/z24-hydroxy-6-methyl-1,3,3at 7-chitrazaindene...1.2gdiethylene glycol...11.0yp - Nitrophenyltriphenylphosphonium chloride ・・・・・・0.23 Gelatin ・・・・・・2.0g/l” Polydityl acrylate latex ・・・1.0g7x2 Shadow 3 layer: Protective layer diethyl Sodium hexyl succinate sulfonate...0,015y/m
"Polymethylnotacrylate (average particle size 3-4 μl)...50zg/a'
Polyoxyethylene-no/nyl 7 enyl ether sodium sulfate 50zy/12 Gelatin 1. Og/++
2 Polyethyl 7 acrylate latex...0.5y/z2 CaF, tsOyK...
3eg/x2 Hardener (described in S-4) Dye (It) Each of the obtained samples was subjected to the following adhesion test. The results are shown in Table 4.

Adhesion test and dry film test〉 Make shallow scratches on the emulsion surface of the sample with a razor in the shape of the substrate,
After pressing a cellophane adhesive tape thereon, the tape was suddenly peeled off, and the residual rate of the emulsion film relative to the adhesive area of the cellophane tape was expressed as a percentage.

Sample with treated film> During processing, the emulsion surface of the sample was scratched in the shape of the substrate with a sharp conical point, and the surface was rubbed and the remaining rate of the emulsion film was expressed as a percentage.

In practice, there is no problem if this percentage is 80% or more.

Below □ Margin Book comparison hardener E Book comparison hardener F Bis7E/-Lglycinol ether Book comparison hardener G HOCII2CH2SO2CH2C1IC112SO□
CtlzCth011H Resin cited below Dry solid content obtained by polymerizing monomers with the following composition From Table 4, the light-sensitive material using the hardening agent of the present invention has a lower support than the comparative example using a comparative hardening agent. It can be seen that the adhesive strength between the emulsions M is greatly improved.

In particular, when the hardening agent of the present invention is used in the subbing layer, the treatment PI
! Film adhesion is noticeably improved.

Claims (1)

[Scope of Claims] At least one non-photosensitive layer and at least one
A silver halide photographic material having a silver halide emulsion layer, characterized in that at least one of the photographic constituent layers is hardened with a compound represented by the following general formula [I]. Photographic material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R represents an alkyl group having 1 to 6 carbon atoms, and X represents an anion necessary to neutralize positive charges. However, when R has an acid anion at the end, X is not necessary. ]