JPH04306645A - 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 formula I. In the formula I, A is a halogen atom, alcoxy group, aryl oxy group, etc., and L is a group selected from the group represented by the formula II or III. In the formula II, R2 is a hydrogen atom-substitution group, and J is a bivalent organic group- single bond, and Q is an -O- single bond, -N(R4)- single bond, etc., and R4 is analkyl group, aryl group, aralkyl group, etc., and M+ is an alkali metal ion, or ammonium ion. In the foumula III, each of R5, R6 is an alkyl group, aryl group, acyl group or a substituted sulfonyl group.

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 a particular 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] The object of the present invention is to provide a silver halide photographic 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]. A silver halide photographic material, characterized in that it is hardened with at least one compound represented by: General formula [I]

0012

embedded image [In the formula, A represents a group selected from a halogen atom, an alkoxy group, an aryloxy group, or a group represented by the general formula [II]. General formula [II]

[0013]

embedded image (In the above general formula [II], R1 and R2 represent an alkyl group, an aryl group, an acyl group, or a substituted sulfonyl group, which may be the same or different from each other. These groups may be further substituted. Also, R1, R
2 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. ) Also, L is the general formula [
III] or a group selected from the group represented by the general formula [IV]. General formula [III]

[0014]

[Chemical formula 7] (In the above general formula [III], R3 represents a hydrogen atom or a substituent. J represents a divalent organic group or a single bond. Q represents -O-, -N(R4)- or a single bond. Represents a bond. R4 represents an alkyl group, aryl group, aralkyl group, or hydrogen atom. M+ represents an alkali metal ion or ammonium ion.) General formula [IV]

00
15]

embedded image (In the above general formula [IV], R5 and R6 represent an alkyl group, an aryl group, an acyl group, or a substituted sulfonyl group, which may be the same or different from each other. These groups may be further substituted. Also, R5, R
6 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. )] The present invention will be further explained in detail.

Examples of the halogen atom represented by A include a chlorine atom and a bromine atom. Preferably it is a chlorine atom.

Examples of the alkoxy group include methoxy group, ethoxy group, 1-propyloxy group, 2-propyloxy group, and butyloxy group. Further, examples of the aryloxy group include phenyloxy group, tolyloxy group, xylyl group, mesityl group, and naphthoxy group. These alkoxy groups and aryloxy groups may be further substituted, and examples of substituents include halogen atoms (e.g., chlorine atom, fluorine atom, bromine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), and acyl groups. (
For example, acetyl group, propionyl group, etc.), nitro group,
Examples include carbamoyl group, sulfamoyl group, and sulfo group.

R1 and R2 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.), aryl group having 6 to 20 carbon atoms (e.g. phenyl group, tolyl group, naphthyl group, etc.), acyl group having 2 to 10 carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, etc.), substituted sulfonyl groups having 1 to 10 carbon atoms (for example, methanesulfonyl group, benzenesulfonyl group, para-toluenesulfonyl group, etc.), and may be the same or different. It's okay. Furthermore, it may have a substituent. As a substituent, an alkyl group (e.g. methyl group, ethyl group, propyl group, etc.)
, alkenyl group (e.g. vinyl group, allyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), halogen atom (e.g. chlorine atom, fluorine atom, etc.), alkoxy group (e.g. methoxy group, ethoxy group, etc.), aryl Oxy group (e.g. phenoxy group, naphthoxy group, etc.)
, an acyl group (for example, an acetyl group, a propionyl group, a benzoyl group, etc.), a sulfo group, a sulfooxy group, a sulfamino group, and the like. Preferred examples of R1 and R2 bonding to each other to form a 5- or 6-membered nitrogen-containing heterocycle include a pyrrolidine ring, a piperidine ring, an N'-substituted piperazine ring, a morpholine ring, a thiomorpholine ring, and a pyrrolidinone ring. ring, piperidinone ring, succinimide ring, maleic imide ring, phthalic imide ring, and the like.

R3 represents a hydrogen atom or a substituent. Examples of substituents include alkyl groups such as methyl, ethyl, and propyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and naphthyl groups, aralkyl groups such as benzyl and phenethyl groups, and fluorine. Examples include halogen atoms such as chlorine atoms, alkoxy groups such as methoxy groups and ethoxy groups, aryloxy groups such as phenoxy groups and naphthoxy groups, and acyl groups such as acetyl groups, propionyl groups, and benzoyl groups. R3 is preferably a hydrogen atom.

J represents a divalent organic group or a single bond. Examples of divalent organic groups include alkylene groups having 1 to 10 carbon atoms (e.g., methylene group, ethylene group, propylene group, etc.)
, an arylene group having 6 to 12 carbon atoms (e.g. 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-naphthalenediyl group, etc.), or -
O-, -NH-, -CO2-, -CONH-, -OCO
-, -NHCO-, -SO2-, -SO2NH-, -N
Examples include divalent organic groups formed by combining a linking group such as HSO2- with two or more groups selected from the above alkylene groups and arylene groups. Preferably carbon number 1-4
are an alkylene group and a single bond.

Q represents -O-, -N(R4)- or a single bond, and R4 represents an alkyl group (such as a methyl group, an ethyl group, a propyl group, a butyl group, etc.), an aryl group (such as a phenyl group, a tolyl group, etc.) ), an aralkyl group (e.g. benzyl group, phenethyl group, etc.), or a hydrogen atom. R4 is preferably a hydrogen atom.

M+ is an alkali metal ion (eg, sodium ion, potassium ion, lithium ion, etc.),
Or it represents an ammonium ion (for example, trimethylammonium ion, triethylammonium ion, tetramethylammonium ion, etc.). Preferred are sodium ions or potassium ions.

R5 or R6 is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, 2-ethylhexyl group, dodecyl group, etc.), or an alkyl group having 6 to 20 carbon atoms. 20 aryl groups (e.g. phenyl group, tolyl group, naphthyl group, etc.), acyl groups having 2 to 20 carbon atoms (e.g. acetyl group, propionyl group, benzoyl group, etc.) or substituted sulfonyl groups (e.g. methanesulfonyl group, benzenesulfonyl group) , paratoluenesulfonyl group, etc.), and may be the same or different. Moreover, it may further have a substituent. Examples of substituents include alkyl groups (for example, methyl group, ethyl group, propyl group, etc.),
Alkenyl groups (e.g. vinyl groups, allyl groups, etc.), aryl groups (e.g. phenyl groups, naphthyl groups, etc.), aralkyl groups (e.g. benzyl groups, phenethyl groups, etc.), halogen atoms (e.g. chlorine atoms, fluorine atoms, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, etc.)
, an acyl group (for example, an acetyl group, a propionyl group, a benzoyl group, etc.), a sulfo group, a sulfooxy group, a sulfamino group, and the like. Preferred substituents are an alkoxy group or a sulfo group.

It is also preferred that R5 and R6 combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. Examples of such heterocycles are shown below, but the present invention is not limited thereto.

[0025]

[Chemical formula 9]

In the formula, R7 represents a substituent. Examples of substituents include the same substituents as R5 and R6. m represents 0, 1 or 2.

Examples of compounds represented by the general formula [I] are listed below, but the present invention is not limited thereto.

[0028]

[Chemical formula 10]

[0029]

[Chemical formula 11]

[0030]

[Chemical formula 12]

[0031]

[Chemical formula 13]

The compounds of the present invention can be easily synthesized by known methods. For example, it can be easily synthesized by reacting a compound represented by the following general formula [V] with a compound represented by general formula [VI] or general formula [VII].

[0033]

[Chemical formula 14] General formula [V]

[0034]

[Chemical formula 15] General formula [VI]

[0035]

General Formula [VII] [In the above general formula [V], A represents the same thing as A in the general formula [I]. Further, R represents a lower alkyl group, and X represents a halogen atom. In general formula [VI], R
3, J, Q and M+ represent the same as R3, J, Q and M+ in general formula [III]. In general formula [VII], R5 and R6 represent the same as R5 and R6 in general formula [IV]. ] Next, the synthesis method will be specifically explained using Exemplified Compounds 2 and 4 as examples. Synthesis of Exemplified Compound 2 61 g of 4-dimethylaminopyridine 80 g of methylene chloride
75 g of methyl phosphate dichloride cooled to 0°C.
was added dropwise to a solution of 80 ml of methylene chloride over 10 minutes under cooling. After completion of the dropwise addition, the temperature was raised to room temperature, and then stirred at room temperature for 2 hours. The precipitated crystals were filtered, washed with methylene chloride, and dried under reduced pressure to obtain 110 g of crude crystals. This was recrystallized from acetonitrile to obtain 100 g of white crystals. The structure of this product was confirmed by NMR and IR.

Synthesis of Exemplified Compound 4 Sodium 2-(4-pyridyl)-ethanesulfonate 2
A mixed solution of 0.9 g of dimethylformamide (500 ml) and methanol (500 ml) was cooled to 0° C., 14.5 g of dimethyl chloride phosphate was added, and the mixture was stirred until uniform. The resulting solution was allowed to stand overnight, and then 1 liter of ether was added to precipitate crystals. The precipitated crystals were filtered, washed with ether, and dried under reduced pressure to obtain 30 g of crude crystals. This was recrystallized with methanol-acetonitrile, and white crystals 2
6g was obtained. The structure of this product was confirmed by NMR and IR.

Other compounds of the present invention can also be synthesized in good yields by similar methods.

[0038] The amount of hardening agent used when carrying out the present invention is as follows:
Although it varies depending on the type of photosensitive material to be applied and the type of hydrophilic binder, it is preferable that the dry weight of the binder is 0.
．． It ranges from 0.01 to 100% by weight, more preferably from 0.1 to 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.

As the water-dispersible polymer contained in the photographic constituent layer, hydrophobic polymers obtained from vinyl compounds, aqueous dispersions of copolymers, and aqueous dispersions of polycondensation polymers such as polyesters 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. 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.

[0042]

[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 light-sensitive 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 triacetylcellulose 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

[0045] In addition to the above, samples 1 to 8 were prepared by adding the hardener of the present invention or a comparative hardener as shown in Table 1 to each layer. In addition, 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

[0048]

[Chemical formula 17]

[0049]

[Chemical formula 18]

[0050]

[Chemical formula 19]

[0051]

[C20]

[0052]

[C21]

[0053]

[C22]

[0054]

[C23]

[0055]

[C24]

[0056]

[C25]

[0057]

[C26]

[0058] 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. These samples were wedge-exposed to white light, then subjected to the following processing, and sensitivity and fog were measured. Sensitivity is expressed as the reciprocal of the exposure that gives a density of fog + 0.5,
Relative sensitivity is shown, with the sensitivity of Sample 1, which was left at room temperature for 7 days after coating, taken as 100. In addition, the sample left at the above room temperature for 7 days was immersed in water at 30°C for 5 minutes, and the radius was 0.3 m.
A sapphire needle of m is pressed against the sample surface, and the speed is 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 on the membrane surface at a speed of 2.5 g, 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.

[0064]

[C27]

[0065]

[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. In addition, even when forced deterioration was performed, inventive samples 1 to 8 compared to comparative samples 6 to 8.
No. 5 shows a slight decrease in sensitivity and only a slight increase in fog. Therefore, it can be seen that the hardener according to the present invention hardly inhibits photographic properties.

[0067] 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 On both sides of a subbed polyethylene terephthalate support, layers having the compositions shown below were successively formed from the support side to obtain X-ray photosensitive material samples 9 to 14. Additives other than silver halide are silver halide 1 unless otherwise specified.
Amounts per mole are shown. 1st layer: Crossover cut layer Dye (I)

3mg/m2 Mordant (II)

0.12g/m2 gelatin

0.2g/m2 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 3rd 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.

[0069]

[C28]

[0070]

[C29]

[0071]

[C30]

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. The sensitivity was expressed as a relative sensitivity, with the sensitivity of Sample 9 7 days after application being taken as 100. 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 and 1
Make it to liters.

[0076] Also, while maintaining the sample at 25°C and 50% RH, 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.

[0077]

[Math 1] comparative compound

[0078]

[Chemical formula 31]

[0079]

[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.

[0081]

[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, A represents a group selected from a halogen atom, an alkoxy group, an aryloxy group, or a group represented by the general formula [II]. General formula [II] [Formula 2] (In the above general formula [II], R1 and R2 represent an alkyl group, an aryl group, an acyl group, or a substituted sulfonyl group, which may be the same or different from each other. The group may be further substituted.Also, R1, R
2 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. ) Also, L is the general formula [
III] or a group selected from the group represented by the general formula [IV]. General formula [III] [Formula 3] (In the above general formula [III], R3 represents a hydrogen atom or a substituent. J represents a divalent organic group or a single bond. Q represents -O-, -N( R4)- or a single bond.R4 represents an alkyl group, aryl group, aralkyl group, or hydrogen atom.M+ represents an alkali metal ion or ammonium ion.) General formula [IV] [Chemical formula 4]
] (In the above general formula [IV], R5 and R6 represent an alkyl group, an aryl group, an acyl group, or a substituted sulfonyl group, which may be the same or different from each other. These groups are further substituted and Also, R5, R
6 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. )〕