JPH04306644A - Silver halide photosensitive material for photograph - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material for photograph on which the film is hardened by a film hardening agent for efficiently hardening gelatine and with which the sufficient film hardness can be achieved without deteriorating the photograph performance by forming a hard film of a specific compound on a hydrophilic colloid layer and the posterior film hardening is prevented because of the speedy hardening action. CONSTITUTION:A hydrophilic colloid layer on a supporting body is covered by a hard film of the compound represented by the furmula I. In the formula I, R1-R12 is an alkyl group, alkenyl group, aralkyl group, or an aryl group. These groups may be same or different, or may be substituted. Further, in R1-R6 or R7-R12, two arbitrary groups may join to form a ring. Y is an anion for offsetting the electric charge in a molecule. This compound can be synthesized easily by the well-known method. Accordingly, the film hardening action can be achieved efficiently by a small quantity of film hardening agent without deteriorating the photograph quality, and a film hardening agent free from the posterior film hardening action can be obtained.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material whose photographic constituent layers are hardened with a specific compound.

0002

BACKGROUND OF THE INVENTION In general, silver halide photographic materials (hereinafter referred to as "photosensitive materials") include, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, a subbing layer, an antihalation layer, and an ultraviolet absorbing layer. , an antistatic layer, a backing layer, and other various photographic constituent layers are formed on a support such as glass, paper, or synthetic resin film.

Since these photographic constituent layers are coated with an aqueous coating solution comprising a hydrophilic polymer and/or a water-dispersible polymer, their mechanical strength is weak as is. For example, gelatin films have low melting points and are excessively water-swellable. In addition, latex films have drawbacks such as extremely poor adhesion to the support and easy peeling.

For this reason, it is known to add a compound called a "hardening agent" to a photographic constituent layer to improve its mechanical strength. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732
, No. 303, No. 3,288,775, British Patent No. 974
, 723, 1,167,207, etc., ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl)urea, 2-hydroxy-4,6- dichloro-1
, 3,5-triazine, divinylsulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5
- Triazine, U.S. Pat. No. 3,232,763,
No. 635,718, compounds having reactive olefins described in British Patent No. 994,809, etc., U.S. Patent No. 3,53
No. 9,644, No. 3,642,486, Special Publication No. 1977-
No. 13563, No. 53-47271, No. 56-488
No. 60, JP-A-53-57257, JP-A No. 61-1282
No. 40, No. 62-4275, No. 63-53541,
Vinylsulfonyl compound described in 63-264572 etc., N-hydroxymethylphthalimide, U.S. Patent 2
, 732,316, 2,586,168, etc., and U.S. Pat. No. 3,103,437.
Isocyanates described in US Pat. No. 2,983, etc.
Aziridine compounds described in U.S. Pat. No. 611, U.S. Pat. No. 3,107,280, etc.;
Acid derivatives described in US Pat. No. 25,295, etc., U.S. Patent No. 3,1
Carbodiimide compounds described in US Pat. No. 00,704, etc., epoxy compounds described in US Pat. No. 3,091,537, etc., US Pat.
Organic hardeners such as isoxazole compounds described in No. 92, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate, and chromium trichloride. It is a hardening agent.

However, when these known hardening agents are used in photosensitive materials, they do not have sufficient hardening action.
There is a long-term change in the hardening effect called "post-hardening" caused by the slow hardening reaction to gelatin, which has a negative effect on the performance of light-sensitive materials (especially increased fog, decreased sensitivity or maximum density, and soft gradation). (e.g.), may lose its hardening effect due to coexisting photographic additives, or may be affected by other photographic additives (e.g., couplers in internal color emulsions).
All of them had some kind of drawback, such as those that reduced the effectiveness or caused contamination.

[0006] The hardening effect on gelatin is relatively fast;
As a hardening agent with less posterior dura mater, JP-A-50-3854
Compounds having a dihydroquinoline skeleton described in No. 0, N-carbamoylpyridinium salts described in JP-A Nos. 51-59625, 62-262854, 62-264044, and 63-184741; 3
Acylimidazoles described in No. 8655, Japanese Patent Publication No. 1983
Compounds containing two or more N-acyloxyimino groups in the molecule as described in No.-22089, JP-A-52-9347
Compounds having an N-sulfonyloxyimide group as described in No. 0, compounds having a phosphorus-halogen bond as described in JP-A-58-113929, JP-A-60-225148, JP-A-61-240236, JP-A-63- Chloroformamidinium compounds described in No. 41580 are known.

[0007] These hardeners have a fast curing action and are therefore characterized by less post-hardening. However, many of these hardeners affect the photographic properties, and the curing reaction of gelatin is fast, as well as the side reaction of decomposition by water. This technique has the disadvantage that the effective use efficiency of the hardening agent is extremely low, and that a large amount of hardening agent must be used in order to obtain a gelatin film with sufficient hardness.

[0008]

OBJECTS OF THE INVENTION Therefore, the first object of the present invention is to provide a photographic light-sensitive material hardened with a novel hardening agent that achieves sufficient hardness without any adverse effect on photographic properties. There is one thing.

A second object of the present invention is to provide a photographic light-sensitive material hardened with a hardening agent that has rapid curing action and does not require a post-hardening film.

A third object of the present invention is to provide a photographic material hardened with a hardening agent that reacts with high selectivity to reactive residues in gelatin and hardens gelatin efficiently.

[0011]

[Structure of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, in which at least one of the hydrophilic colloid layers has the following general formula [I]. This was achieved by hardening with at least one compound represented by: General formula [I]

0012

embedded image [In the formula, R1 to R12 represent an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. These may be the same, different, or substituted.

Furthermore, any two of R1 to R6 or R7 to R12 may be combined to form a ring.

Y- represents an anion for canceling charges within the molecule. ] The present invention will be further explained in detail.

R1 to R12 are preferably alkyl groups having 1 to 20 carbon atoms (for example, methyl group, ethyl group,
propyl group, butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, etc.), aralkyl group with 6 to 20 carbon atoms (e.g. benzyl group, phenethyl group, etc.), 5 carbon atoms
~20 aryl groups (e.g. phenyl, naphthyl,
tolyl group, etc.), and may be the same as each other,
They may be different or may be further substituted.

Examples of substituents include halogen atoms (for example, chlorine atoms, fluorine atoms, bromine atoms, etc.), alkoxy groups (
For example, methoxy group, ethoxy group, 1-propyloxy group, 2-propyloxy group, etc.), aryloxy group (for example, phenoxy group, tolyloxy group, naphthoxy group, etc.), acyl group (for example, acetyl group, propionyl group, benzoyl group, etc.) ), carbamoyl group, sulfamoyl group, sulfo group, sulfooxy group, sulfamino group, etc. The number and substitution positions of these substituents can be arbitrarily selected.

[0017] R1 to R6 or R7 to R12
In this case, it is also preferable that any two of them be bonded to form a ring.

For example, R1 and R2, R3 and R4,
R5 and R6, R7 and R8, R9 and R10, R
Examples include cases in which 11 and R12 are each combined with a nitrogen atom to form a pyrrolidine ring, piperazine ring, 4-alkylpiperidine ring, morpholine ring, thiomorpholine ring, 4,4-dioxothiomorpholine ring, pyrrole ring, etc. .

Y- represents an anion for canceling charges within the molecule. Examples include halide ions (e.g. chloride, bromide, etc.), sulfonate ions (e.g. methanesulfonate, p-toluenesulfonate, etc.), sulfate ions, phosphonate ions (e.g. methylphosphonate, ethylphosphonate, phenyl phosphonate ions, etc.)
, phosphate ion, BF4-, ClO4-, PF6-, etc., but preferably Cl-, BF4-, C
lO4-, PF6- and sulfonate ions. A sulfonate ion may bind to R1 to R12 to form an inner salt.

Examples of compounds used in the present invention are listed below, but the present invention is not limited thereto.

[0021]

[Chemical formula 3]

[0022]

[C4]

[0023]

[C5]

[0024]

[C6]

The compounds of the present invention can be easily synthesized by known methods. For example, the Journal of the
American Chemical Society Volume 91 (196
9) can be synthesized by the method described on pages 5669-5671.

Next, the synthesis method will be specifically explained using the above Exemplified Compounds 1 and 2 as examples. Synthesis of Exemplary Compound 1 Para-toluenesulfonic anhydride was added to a solution of 17.9 g (0.1 mol) of N,N,N',N',N'',N''-hexamethylphosphoric acid triamide in 30 ml of 1,2-dichloroethane. After adding 16.3 g (0.05 mol) and stirring overnight at room temperature under a nitrogen atmosphere, 1,2,dichloroethane was distilled off under reduced pressure. The residue was poured into 200 ml of dry ether to precipitate, then filtered and dried under reduced pressure to obtain Exemplary Compound 1. (Yield: 27.4 g) The structure of this product was confirmed by NMR and elemental analysis. Synthesis of Exemplified Compound 2 Exemplified Compound 1 (34.2 g) was dissolved in NH4 BF4 (10
．． A solution of 5 g) was added to 50 ml of water under cooling, and the mixture was stirred for 5 minutes. The precipitated crystals were collected by filtration, washed with cold water, and then dried. Recrystallize from acetone (120 ml) to obtain Exemplified Compound 2.
I got it. (Yield: 7.7 g) The structure of this product was confirmed by NMR and elemental analysis.

Other compounds of the present invention can be synthesized by similar methods. The amount of hardening agent used when carrying out the present invention varies depending on the type of photosensitive material to be applied, the type of hydrophilic binder, etc., but is preferably 0.01 to 100% by weight of the dry weight of the binder, more preferably is 0.1
-30% by weight.

The hydrophilic binder used in carrying out the present invention may be any commonly used gelatin, gelatin derivatives, or graft polymers of gelatin and other polymers.

Furthermore, as the water-dispersible polymer contained in the photographic constituent layer, a hydrophobic polymer obtained from a vinyl compound, an aqueous dispersion of a copolymer, an aqueous dispersion of a polycondensation polymer such as polyester can be used. .

Silver halide, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, gelatin, etc. used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention There are no particular restrictions on hydrophilic protective colloids, ultraviolet absorbers, polymer latexes, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc., for example, Research Disclosure.
176, pp. 22-31 (December 1978) can be used.

[0031] In addition, supports for photosensitive materials, development processing methods,
Regarding the constituent layers of the photosensitive material, the description in the above-mentioned Research Disclosure magazine can be referred to.

[0032]

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

Example 1 In the following examples, the amount added in the silver halide photographic material is expressed in grams per m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

A multilayer color photographic material was prepared by sequentially forming layers having the compositions shown below on a triacetyl cellulose film support from the support side. 1st layer;
Antihalation layer (HC) Black colloidal silver
0.15
Ultraviolet absorber (UV-1)
0.20 Colored cyan coupler (CC-1)
0.02 High boiling point solvent (O-1)
0
．． 20 High boiling point solvent (O-2)
0.20
gelatin
1.6
2nd layer; intermediate layer (IL-1) gelatin
1.
3 Third layer; low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (Em-1)
0.4 Silver iodobromide emulsion (Em
-2)
0.3 Sensitizing dye (S-1)
3.2×10
-4 Sensitizing dye (S-2)
3.2×10-4
Sensitizing dye (S-3)
0.2×10-4
Cyan coupler (C-1)
0.50 Cyan coupler (C-2)
0.13 Colored cyan coupler (
CC-1) 0.07
DIR compound (D-1)
0.006 D.I.
R compound (D-2)
0.01 High boiling point solvent (O
-1)
0.55 Additive (SC-1)

0.003 gelatin

1.0 4th layer; high sensitivity red-sensitive emulsion layer (R-
H) Silver iodobromide emulsion (Em-3)
0.9 Sensitizing dye (S-1)
1.7×10-4 Sensitizing dye (S-2)
1.6×10-4 Sensitizing dye (S-
3)
0.1×10-4 Cyan coupler (C-
2)
0.23 Colored cyan coupler (CC-1
) 0.03 DI
R compound (D-2)
0.02 High boiling point solvent (O
-1)
0.25 Additive (SC-1)

0.003 gelatin

1.0 5th layer; intermediate layer (IL-2) gelatin
0.
8 6th layer; low-sensitivity green-sensitive emulsion layer (GL) silver iodobromide emulsion (Em-1)
0.6 Silver iodobromide emulsion (Em
-2)
0.2 Sensitizing dye (S-4)
6.7×10
-4 Sensitizing dye (S-5)
0.8×10-4
Magenta coupler (M-1)
0.17 Magenta coupler (M-2)
0.43 Colored magenta coupler (CM-1) 0.10
DIR compound (D-3)
0.02 High boiling point solvent (O-2)
0.70 Additive (SC-
1)
0.003 gelatin

1.0 7th layer; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3)
0.9
Sensitizing dye (S-6)
1.1×10-4
Sensitizing dye (S-7)
2.0×10-4 Sensitizing dye (S-8)
0.3×10-4 Magenta coupler (M-1)
0.03 Magenta coupler (M-2)
0.1
3 Colored magenta coupler (CM-1)
0.04 DIR compound (
D-3)
0.004 High boiling point solvent (O-2)

0.35 Additive (SC-1)
0
．． 003 Gelatin

1.0 8th layer; yellow filter layer (YC)
yellow colloidal silver
0.1
Additive (HS-1)
0.07 Additive (HS-2)
0.07 Additive (SC
-2)
0.12 High boiling point solvent (O-2
)
0.15 gelatin

1.0 9th layer; low-speed blue-sensitive emulsion layer (B-
L) Silver iodobromide emulsion (Em-1)
0.25
Silver iodobromide emulsion (Em-2)
0.25 Sensitizing dye (S
-9)
5.8×10-4 yellow coupler (
Y-1)
0.60 Yellow coupler (Y-2)
0.32
DIR compound (D-1)
0.003 D.I.
R compound (D-2)
0.006 High boiling point solvent (
O-2)
0.18 Additive (SC-1)

0.004 gelatin

1.3 10th layer; Highly sensitive blue-sensitive emulsion layer (
B-H) Silver iodobromide emulsion (Em-4)
0.5
Sensitizing dye (S-10)
3.0×10-4 Sensitizing dye (S-11)
1.2×10-4 Yellow coupler (Y-1)
0.18 Yellow coupler (Y-2)
0.10
High boiling point solvent (O-2)
0.05
Additive (SC-1)
0.002 gelatin
1.0 11th layer;
First protective layer (PRO-1) Silver iodobromide emulsion (Em-5)
0.3 Ultraviolet absorber (UV-1)
0.07 Ultraviolet absorber (UV
-2)
0.1 Additive (HS-1)
0.
2 Additive (HS-2)
0.1
High boiling point solvent (O-1)
0.07 High boiling point solvent (O-3)
0.07 Gelatin

0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2μ
m) 0.13 Polymethyl methacrylate (
Average particle size 3μm) 0.02 Slip agent (WAX-1)
0.04 Charge control agent (SU
-1)
0.004 Charge control agent (SU-2)

0.02 gelatin

0.5

Samples 1 to 8 were prepared by adding to each layer, in addition to the above, the hardener of the present invention or a comparative hardener as shown in Table 1.

[0036] Each layer contains a coating aid (SU-4),
Dispersion aid (SU-3), stabilizer (ST-1), preservative (
DI-1), antifoggant (AF-1), (AF-2)
, dyes (AI-1) and (AI-2) were added as appropriate.

The emulsions used in the above samples are as follows. Both are monodisperse emulsions with high internal iodine content.

Em-1: Average silver iodide content 7.5 mol%
Average grain size: 0.55 μm Grain shape: Octahedral Em-2: Average silver iodide content 2.5 mol% Average grain size: 0.36 μm Grain shape: Octahedral Em-3: Average silver iodide content: 8.0 mol% Average grain size 0.84 μm Grain shape octahedral Em-4: Average silver iodide content 8.5 mol% Average grain size 1.02 μm Grain shape octahedral Em-5: Average silver iodide content 2.0 mol% Average particle size 0.08μm

[0039]

[C7]

[0040]

[Chemical formula 8]

[0041]

[Chemical formula 9]

[0042]

[Chemical formula 10]

[0043]

[Chemical formula 11]

[0044]

[Chemical formula 12]

[0045]

[Chemical formula 13]

[0046]

[Chemical formula 14]

[0047]

[Chemical formula 15]

[0048]

[Chemical formula 16]

[0049] Each sample prepared is taken as a fresh sample,
A sample in which this sample was left at room temperature for 7 days, and a sample at 50°C.
Samples that were forced to deteriorate by being left at 50% RH for 2 days were prepared.

[0050] After these samples were wedge-exposed with white light, they were subjected to the following processing and the sensitivity and fog were measured.

Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5. Sample 1 was left at room temperature for 7 days after coating.
The relative sensitivity is shown with the sensitivity of 100 as 100.

[0052] The sample left at room temperature for 7 days was immersed in water at 30°C for 5 minutes, and a sapphire needle with a radius of 0.3 mm was brought into pressure contact with the sample surface, and a sapphire needle with a radius of 0.3 mm was pressed onto the membrane surface at a speed of 2 mm per second. The pressure load of the sapphire needle was continuously changed in the range of 0 to 200 g while the sample was moved in parallel, and the load at which damage occurred on the membrane surface of the sample was determined as the scratch resistance strength.

The results are also shown in Table 1 below.

Processing process Color development 38°C 3 minutes 15
Second bleaching 38℃ 6
Wash with water for 30 seconds at 38℃
Fixed for 3 minutes and 15 seconds at 38℃
Wash with water for 6 minutes and 30 seconds 3
Stabilized at 8℃ for 3 minutes and 15 seconds
Dry at 25℃ for 1 minute and 30 seconds.
45°C The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) 4-amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) Aniline Sulfate

4.75g anhydrous sodium sulfite

4.25g Hydroxylamine 1/2 sulfate 2.0
g Anhydrous potassium carbonate
37.5g
sodium bromide
1.3
g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide

Add 1.0g water to make 1 liter.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt
100g ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide

150.0g glacial acetic acid

Add 10.0 ml of water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate
175.0g
anhydrous sodium sulfite
8.5g
sodium metasulfite
Add 2.3 g of water to make 1 liter, and adjust the pH to 6.0 using acetic acid.

(Stabilizing liquid) Formalin (37% aqueous solution)
1.5ml
Konidax (manufactured by Konica Corporation)
Add 7.5 ml water to make 1 liter.

[0059]

[Chemical formula 17]

[0060]

[Table 1]

As is clear from the results in Table 1 above, Samples 1 to 5 using the hardening agent according to the present invention showed only a slight decrease in relative sensitivity compared to Comparative Samples 6 to 8. ,
No deterioration of fog was observed.

Further, even when forced deterioration is performed, samples 1 to 5 of the present invention show a slight decrease in sensitivity and only a slight increase in fog compared to comparative samples 6 to 8.

Therefore, it can be seen that the hardening agent according to the present invention hardly inhibits photographic properties.

[0064] Also, from the results of scratch resistance, which indicates film strength,
Samples 1 to 5 of the present invention all exhibit higher film strength than Comparative Samples 6 to 7, which indicates that the hardener of the present invention hardens the film more efficiently than the comparative compounds. .

Example 2 Each layer having the composition shown below was sequentially formed on both sides of an undercoated polyethylene terephthalate support, starting from the support side.
I got 14.

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

1st layer: Crossover cut layer
Dye (I)
3
mg/m2 Mordant (II)

0.12g/m2 gelatin

0.2g/m2

[0068] Second
Layer: Emulsion layer Emulsion consisting of AgBrI with an average grain size of 0.57 μm and containing 2 mol% of AgI
Coated silver amount
4.5mg/m2 Sensitizing dye (A)
450mg
Sensitizing dye (B)

20mg 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene


3.0g t-butyl-catechol

400mg polyvinylpyrrolidone (molecular weight 1
0,000) 1.0g
Styrene-maleic anhydride copolymer
2.5g trimethylolpropane
10g diethylene glycol
5g
p-Nitrophenyl-triphenylphosphonium chloride 50mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4g
Sodium 2-mercaptobenzimidazole-5-sulfonate 15mg Additive A

70mg Additive B

1g 1,1-dimethylol-1-bromo-
1-nitromethane 10mg gelatin
2g/
m2

Third layer: protective layer polymethyl methacrylate (average particle size 5 μm)
7mg/m2 Colloidal silica (average particle size 0.013μm)
70mg/m2 Additive C

10mg/m2 Additive D
2m
g/m2 Additive E

7mg/m2 Additive F

15mg/m2
gelatin

1 g/m2 Hardener (listed in Table 2) Preservative DI-1 was added to each sample.

[0070]

[Chemical formula 18]

[0071]

[Chemical formula 19]

[0072]

[C20]

Each sample was subjected to a storage test in the same manner as in Example 1, and then exposed to light and subjected to the following treatments, and photographic properties were measured in the same manner as in Example 1.

Sensitivity is the sensitivity of sample 9 7 days after application.
It is expressed as relative sensitivity.

The results are shown in Table 2.

(Processing process) Insertion
1.2 seconds development + transfer
35℃ 14.6 seconds fixing + transition
33℃ 8.2 seconds washing + crossing 25℃ 7.2 seconds squeeze 40℃
Dry for 5.7 seconds 4
5℃ 8.1 seconds

(Developer) Hydroquinone
25.0g Phenidone
1.2g potassium sulfite
55.0g boric acid

10.0g Sodium hydroxide
21.0
g triethylene glycol
17.5g 5-nitroimidazole
0.10g 5-nitrobenzimidazole
0.10g glutaraldehyde bisulfite
15.0g glacial acetic acid
16
．． 0g potassium bromide
4.0g
triethylenetetraminehexaacetic acid
Add 2.5g water to make 1 liter.

(Fixer) Ammonium thiosulfate
130.9g Anhydrous sodium sulfite
7.3g boric acid

7.0g acetic acid (90wt%)
5.5g
Sodium acetate (trihydrate)
25.8g Aluminum sulfate (18 hydrate) 14.6g
Sulfuric acid (50wt%)
Add 6.77g water to make 1 liter.

[0079] In addition, while maintaining the sample at 25°C and 50% RH humidity, a portion of each sample was taken out 2 hours, 1 day, and 7 days after coating, and swollen in water at 30°C for 5 minutes. Measure the film thickness of the sample, calculate the swelling degree V expressed by the following formula,
The change in hardening effect over time (postdurality) was observed.

The results are shown in Table 2 below.

[0081]

[Math 1] comparative compound

[0082]

[C21]

[0083]

[Table 2]

As is clear from the results in Table 2, X-ray photosensitive material samples 9 to 11 in which the hardening agent of the present invention was added to the protective layer
, there was almost no change in photographic properties such as a decrease in sensitivity or an increase in fog, and furthermore, the change in swelling degree was small and stable after one day or more after coating and drying. Film properties are significantly improved. Moreover, when compared with Sample 12, it can be seen that the dura mater was made efficiently.

[0085]

[Effects of the Invention] According to the present invention, the hardening effect can be efficiently achieved even with a small amount of hardening agent without impairing photographic performance.
It is possible to provide a silver halide photographic light-sensitive material containing a novel hardening agent that does not have a post-hardening effect.

Claims (1)

[Claims] Claim 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, comprising:
At least one of the hydrophilic colloid layers has the following general formula [
A silver halide photographic light-sensitive material, characterized in that it is hardened with at least one compound represented by [I]. General formula [I] [Formula, R1 to R12 represent an alkyl group, an alkenyl group, an aralkyl group, or an aryl group. These may be the same, different, or substituted. Furthermore, R1 to R6 or R7 to R12
In, any two may be combined to form a ring. Y- represents an anion for canceling charges within the molecule. ]