JPH04157452A - Silver halide photosensitive material for photograph - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material for photograph which achieves the sufficient film hardness and is film-hardened by a film hardening agent free from after film hardening action by film-hardening at least one layer of the hydrophilic colloid layers by the specific compounds. CONSTITUTION:A film is hardened by at least one layer of the hydrophilic colloid layers and at least one kind of the compound represented by the formula I. In the formula I, R1, R2 is an alkyl group, aryl groups, etc., which may be same or different, and these groups may be substituted, and further R1 and R2 may combine to form a penta or hexa nitrogen-containing heterocyclic ring R3 is a hydrogen atom or the substitution group, and A is a bivalent organic group including at least one connecting group selected from -O-, -NH-, -CO2-, etc., L represents -O- or single bond. Accordingly, a silver halide photosensitive material for photographs can be obtained which does not deteriorate photograph performance and efficiently develops film hardening action with a small quantity of the film hardening agent, and is free from after-film hardening action.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material whose photographic constituent layers are hardened with a specific compound.

[Background of the Invention] In general, a silver halide photographic material (hereinafter referred to as a "photosensitive material") includes, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, a subbing layer, a /S anti-reaction layer, and an ultraviolet light-sensitive material. It consists of various photographic constituent layers such as an absorption layer, an antistatic layer, and a backing layer placed 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. Further, the latex film has disadvantages 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. 2,732,303,
No. 3,288,775, British Patent No. 974.723,
1.167.207 etc., ketone compounds such as diacetyl and cyclobentanedione, bis(2-chloroethyl)urea, 2-hydroxy-4,6-dichloro-1, 3,5-)
riazine, divinylsulfone, 5-acetyl-1,3-
Diacryloyl hexahythro 1.3.5-1 riazine, U.S. Pat. No. 3,232.763, U.S. Pat. No. 3,635,71
No. 8, compounds having reactive olefins as described in British Patent No. 994.809, etc., U.S. Patent No. 3,539,644, U.S. Pat. No. 56-48860, JP-A No. 53-57257, No. 61-128240, No. 6
No. 2-4275, No. 63-53541, No. 63-26
Vinylsulfonyl compounds described in No. 4572 etc., N-hydroxymethylphthalimide, U.S. Pat. No. 2,732,3
No. 16, N-methylol compounds described in US Pat. No. 2,586,188, etc.; Isocyanates described in LO3,437 etc., aziridine compounds described in U.S. Patent Nos. 2.983,611 and 3,107,280, etc.
U.S. Patent No. 2,725,294, U.S. Patent No. 2,725,295
Acid derivatives described in US Pat. No. 3. LOo, 704
Carbodiimide compounds described in US Patent No. 3,0, etc.
91,537, etc., isoxazole compounds described in U.S. Pat. No. 3,321,313, U.S. Pat. These are organic hardeners such as dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate, and chromium trichloride.

However, when these known hardening agents are used in light-sensitive materials, they may not have sufficient hardening effect or may cause a long-term change in hardening effect called "post-hardening" which occurs due to the slow hardening reaction to gelatin. materials, those that adversely affect the performance of photosensitive materials (in particular, increased fog, decreased sensitivity or maximum density, softened gradation, etc.), those that lose their hardening effect due to coexisting photographic additives, or other All have had some drawbacks, such as those that reduce the effectiveness of photographic additives (such as couplers in internal color emulsions) or cause contamination.

As hardening agents that have a relatively fast hardening effect on gelatin and cause less post-hardening, there are compounds having a dihydroquinoline skeleton described in JP-A-50-38540, and JP-A-51-5.
No. 9625, No. 62-262854, No. 62-264
No. 044, N-carbamoylpyridinium salts described in Japanese Patent Publication No. 63-184741, acylimidazoles described in Japanese Patent Publication No. 55-38655, Japanese Patent Publication No. 53-22089
Compounds containing two or more N-acyloxyimino groups in the molecule as described in JP-A No. 52-93470, compounds having N-sulfonyloxyimide groups as described in JP-A No. 58-113929, Compounds having phosphorus-halogen bonds, JP-A-60-225148, JP-A-61-2
Chloroformamidinium compounds described in No. 40236 and No. 63-41580 are known.

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.

[Object of the Invention] Therefore, the object of the present invention is, firstly, 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.

The second object is to provide a photographic light-sensitive material hardened with a hardening agent that has a rapid hardening effect 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 efficiently hardens gelatin.

[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,
At least one of the hydrophilic colloid layers has the following formula [
This was achieved by hardening with at least one compound represented by I].

General formula [■] In the formula, R, and R2 represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different.

Alkyl groups include methyl group, ethyl group, propyl group,
Isopropyl group, butyl group, 5ee-butyl group, isobutyl group, tret-butyl group, etc., phenyl group, tolyl group, etc. are mentioned as the aryl group, benzyl group, phenethyl group, α-xylyl group, etc. as the aralkyl group. It will be done. These groups may be substituted. Substituents include fluorine atoms, halogen atoms such as chlorine atoms, methoxy groups,
Examples include alkoxy groups such as ethoxy groups, aryloxy groups such as phenoxy groups and naphthoxy groups, acyl groups such as acetyl groups, propionyl groups, and benzoyl groups, sulfo groups, sulfooxy groups, and sulfamino groups.

Furthermore, R1 and R2 may be combined with each other to form a 5- or 6-membered nitrogen-containing heterocycle. Examples of these nitrogen-containing heterocycles include pyrrolidine rings, piperidine rings, N-substituted piperazine rings, morpholine rings, thiomorpholine rings, and the like.

R1 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, benzyl groups, phenethyl groups, and α-xylyl groups. Examples include aralkyl groups, halogen atoms such as fluorine atoms and 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 lower alkyl group or a hydrogen atom.

A is 10-1-NH-1-CO□-1-CONH-1-
NHCONH-1-NHCO-1-〇-〇〇-1-SO
, -1-SO, NH-1-NH5O□-.

Examples of the divalent organic group include at least one linking group selected from the above linking groups, alkylene groups such as methylene group and ethylene group, arylene groups such as phenylene group and naphthylene group, and aralkylene groups such as xylylene group. Examples include divalent organic groups formed by combining groups. Preferably, it is a 2m organic group in which an alkylene group is bonded to a pyridine ring via the above linking group.

L represents 10-1-N- or a single bond, and R4 represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom. Alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 5ec-butyl group,
Examples of the aryl group include a phenyl group and tolyl group, and examples of the aralkyl group include a benzyl group, a phenethyl group, and an α-xylyl group.

R4 is preferably a hydrogen atom.

The compounds used in the present invention are listed below, but the present invention is not limited thereto. Margin: 22° to 23° or less The compound of the present invention can be easily synthesized by a known method, but
One of the methods is to react an amine compound represented by the following general formula [11] with phosgene or trichloromethyl chloroformate to N-chloroformylate, and then react with a pyridine compound represented by the general formula [ml]. A reaction method is mentioned, and the synthesis can be performed with good yield by this method.

General formula [11] % formula % [In the formula, R,, R, are each R in general formula [1]
1, has the same meaning as R. ] General formula [ml [In the formula, R, , ASL are respectively synonymous with R, ], ASL in general formula [I]. ] Next, the above exemplified compound (
The synthesis method will be specifically explained using 4) as an example.

Synthesis of Exemplary Compound 4 - (1) Synthesis of Morpholinyl Carbonyl Chloride A solution of 50 g of phosgene in 300 ml of toluene is prepared, and a solution of 87 g of morpholine in 20 Gml of toluene is added dropwise thereto at room temperature. After the dropwise addition was completed, heating was started and the mixture was stirred at 90°C for 1 hour. After cooling, the precipitate was filtered and the filtrate was concentrated under reduced pressure to obtain an oil. This product was distilled under reduced pressure to obtain 130 g of a colorless oil. (Boiling point: 86°C/3°Hg) (2) Synthesis of Exemplary Compound 4 N-(2-sulfoethyl)-isonicotinamide 67,
Og was suspended in 100 ml of dimethylformamide and 200 ml of methanol. Then triethylamine 35
．． Add 6g and dissolve completely. A solution of 40.4 g of morpholinylcarbonyl chloride in dimethylformamide was added dropwise to the resulting clear solution at room temperature. After completion of the dropwise addition, the mixture was left in the apparatus overnight, and the precipitated crystals were collected by filtration, washed with methanol, and dried to obtain Compound 4. (Yield: 80.4 g) 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.

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 10% of the dry weight of the binder.
0% by weight, more preferably 0.1-30% by weight.

In addition, the hydrophilic binder used when carrying out the present invention is
Any commonly used gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, etc. may be used.

Further, 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, etc. 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 light-sensitive materials in carrying out the present invention. There are no particular restrictions on hydrophilic protective colloids, ultraviolet absorbers, polymer latex, brighteners, color couplers, anti-fading agents, dyes, matting agents, surfactants, etc. (Disclosure)
176, pp. 22-31 (December 1978) can be used.

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

[Examples] 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 in the silver halide photographic light-sensitive material indicates the number of grams per one 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 each layer having the composition 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) 0.2 (] Colored cyan coupler (CC-1) 0.02 High boiling point solvent (OiΩ-1) 0. 20 High boiling point solvent (O1Jll-2) 0.20 Gelatin
1.6 Second layer; intermediate layer (I
L-1) Gelatin 1.3 Third layer - low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (Em-1)
0.4 silver iodobromide emulsion (E m -2)
0.3 Sensitizing dye (S-1) 3
．． 2x to-' sensitizing dye (S-2)
3.2X 10-' sensitizing dye (S-3)
0.2x 10-' cyan coupler (C-1)
[1,5111 Cyan coupler (C-2)
0.13 Colored cyan coupler (CC-1) 0.07
DIR compound (D-1>0.006D
IR compound (D-2) 0.01 High boiling point solvent Co11-1 0.55 Additive (S C-
1) 0.003 gelatin
1゜4th layer; high sensitivity red-sensitive emulsion layer (R
-H) Silver iodobromide emulsion (E m -3) 0.
9 Sensitizing dye (S-1) 1.7xlO-'
Sensitizing dye (S-2) L, 6xlO-' Sensitizing dye (S-3) 0.1xlO-' Cyan coupler (C~2) 0.23 Colored cyan coupler (CC-1) 0.03
DIR compound (D-2) 0.02 High boiling point solvent (OiI-1) 0.25 Additive (S
C-1) 0.003 gelatin
i.

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 (E m -2)
0.2 Sensitizing dye (S-4) 6
．． 7x 10-' sensitizing dye (S-5) 0
．． 8X10-' Magenta coupler (M-1)
0.17 Magenta coupler (M-2) 0.4
3-color magenta coupler (CM-1) 0.1
0DIR compound (D-3) 0.02
High boiling point solvent (OiN-2) 0.70 Additive (S C-1) 0.003 Gelatin 1.0 7th layer; High sensitivity green-sensitive emulsion layer (G-H) Silver iodobromide emulsion (Em-3 )
0.9 Sensitizing dye (S-6) 1.
1xlO-'sensitizing dye (S-7) 2.0
xlO' sensitizing dye (S-8) 0.3x
10-' Magenta coupler (M-1) 0.
03 magenta coupler (M-2) O, 13 colored magenta coupler ((1-cho-1)
0.04DIR compound (D
-3) 0.004 high boiling point solvent (O1g-
2) 0.35 additive (SC-1)
0.003 gelatin
1.0 8th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (I(S
-1) (1,07 additive (MS
-2) 0.07 additive (SC-2)
0.12 high boiling point solvent (O1fI-2
) 0.15 gelatin
1.0 9th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S
-9) 5.8x 10-' Yellow Coupler (Y-1) 0.60 Yellow Coupler (
Y-2) 0.32DIR compound (D-1
) 0.003DIR compound (D-2)
0.006 High boiling point solvent (Oif -2
) 0.18 additive (S C-1)
0.004 gelatin
1.3 10th layer; High sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (E m -4) 0.5 Sensitizing dye (S -10) 3.0xlO-' Sensitizing dye (S = 11) L, 2XIO-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) ' 0.10 High boiling point solvent (
O1II-2) 0.05 additive (S C-
1) 0.002 gelatin
10 11th layer; first protective layer (PRO-
1) Silver iodobromide emulsion (E m -5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV -2) 0.1 Additive (H5-
1) 0.2 additive (H5-2)
0.1 high boiling point solvent (OiN -1)
0.07 high boiling point solvent (OiR-3)
0.07 Gelatin 0.8
12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX-1) 0. 04 Charge control agent (SU-1) 0.004 Charge control agent (S
U-2) 0.02 gelatin
05 In addition to the above, samples NG and L to 8 were prepared by adding the hardening agent of the present invention or a comparative hardening agent as shown in Table 1 to each layer.

In addition, each layer contains a coating aid (SU-4) and a dispersion aid (
SU-3), stabilizer (ST-1), preservative (DI-
1), antifoggants (AF-1), (AF-2), and 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 grain size 0
．． 08 μm -I CI CI l C-I M-1 CI H M-1 H CJ, (t) M-2 □ 2H5 S-1 ! (2C-C=0 S-2 5U-1 NaOtS-CH-COOC[12(CFzCFz)J
CH2-COOCR2(CF2CF2)3HU-2 U-3 U-4 NiOtS-CH-COOCaH+7 CTo-COOC,H,.

C2H9(CH2)4SO3 C2H5C2H6 C3I% (CH2)4SO-+ CJsC-1 H COOC+Jzs(n) 5C-2 OfI Mixture of OH (2:
3) Oi, Q-1 2H5 ■ 2H5 0i9. -2 0i, 2-3 A(-1 I-2 T-1 OH (Component A) (Component B) (
Component C) (Component molar ratio Component A: Component B: Component C-5
0:4B:4) F-1 F-2 Each sample created with the following margins was considered a fresh sample, and this sample was left at room temperature for 7 days, and the sample was left at 50°C and 50% RH for 2 days and forced. Deteriorated samples were prepared for each.

These samples were wedge-exposed to white light, then subjected to the following processing, and sensitivity and fog were measured.

The sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog + 0.5, and is expressed as a relative sensitivity with the sensitivity of sample No. 1, which was left under the room for 7 days after coating, as 100.

In addition, the sample that had been left at the above room temperature for 7 days was immersed in 30°C water for 5 minutes, and a sapphire needle with a radius of 0.31 m was pressed against the sample surface and moved in parallel on the membrane surface at a speed of 21111 per second. The pressure load of the sapphire needle was continuously changed from 0 to 200 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℃ 3 minutes 15 seconds Bleaching
Wash at 38℃ for 6 minutes and 30 seconds.
Fixation at 38℃ for 3 minutes and 15 seconds 3
8℃ 6 minutes 30 seconds Wash with water 38℃
Stabilization for 3 minutes and 15 seconds at 25°C Drying for 1 minute and 30 seconds at 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 2.0g anhydrous Potassium carbonate 37゜5g Sodium bromide
1.3g nitrilotriacetic acid 3
Sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1g.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt ioog Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10°0 ml of water to make 1 g, and adjust the pH to -6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate L75.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water and 1
g and pa-e using acetic acid.

Adjust to.

(Stabilizing liquid) Formalin (37% aqueous solution) 1.5m
l Konidax (manufactured by Konica Corporation) 7, 5
Add ml water to make 1 g.

The following margins Comparative compound (1) (Compound described in JP-A-51-59625) Comparative compound (n) (Compound described in JP-A-61-9641) Comparative compound (m) CFIz: CH302CHzCONl'1CHzCHJ
) lcOcH2sOzcH=cHz (Unexamined Japanese Patent Publication No. 53-41
As is clear from the results in Table 1 above, Samples No. 1 to 5 using the hardening agent according to the present invention are all Comparative Samples No. 6 to 8. There is only a slight decrease in relative sensitivity compared to the above, and no deterioration in fogging is observed.

In addition, even when forced deterioration is performed, comparative samples Nα6~
Compared to Sample No. 8, Samples Nos. 1 to 5 of the present invention show 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.

In addition, from the results of scratch resistance, which indicates film strength, the present invention sample N
Since samples Nos. 1 to 5 all exhibit higher film strength compared to comparative samples No. 8 to 7, it can be concluded that the hardener of the present invention hardens the film more efficiently than the comparative compounds. Recognize.

Example 2 Each layer having the composition shown below was sequentially formed on both sides of a subbed polyethylene terephthalate support from the support side to obtain X-ray photosensitive material samples Nos. 9 to 14.

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

1st layer: Cross-over cut layer Dye (1) 3mg/Go mordant (I
I) 0.12g/gogelatin
0.2 g/rrr Second layer: Emulsion layer average grain size 0.57 μm AgBr containing 12 mol% SAg
Amount of silver coated in emulsion consisting of 4,5 g/rn' sensitizing dye (A) 4501I1 g sensitizing dye (B
) 205g4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene 3. Ogt-butyl-catechol 4001g polyvinylpyrrolidone (molecular weight to, 000) 1.0g styrene-maleic anhydride copolymer 2.5g trimethylolpropane 10g diethylene glycol
5gp-Nitrophenyl-triphenylphosphonium chloride 50mg1.3-dihydroxybenzene-4-ammonium sulfonate 4g 2-mercaptobenzimidazole-5-sulfonate sodium 15+agH 1,1-dimethylol-1-promo-1-nitromethane 10 mg gelatin
2g/rn" Third layer: Protective layer polymethyl methacrylate (average particle size 5μm) 7mg/rriI colloidal silica (average particle size 0.013μm) 70II1g/r+f
CLCOO(CL)scHz CHCOO(CHz)2C)I(CL)*
7 mg/Go5O3N! (Mixture of n-2 to 5) Gelatin 1g/rrr Hardener (listed in Table-2) Dye (I) Mordant (II) H1C2C2H5 1/2 So<2e x:y-25 near 5 (CH2)3SOJ ( CH2hδ03 (shi21b23N1 1e fcl(2Lso3Na (CLLSO.

Note that the preservative DI-1 was appropriately added to each sample.

I-1 Decrease A) (Component B) (Component C) (Component molar ratio Component A: Component B: Component C-50
:4B+4) 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 was expressed as relative sensitivity, where the sensitivity of sample No. 9 7 days after application was taken as 10 (l).

The results are shown in Table-2.

(Processing process) Insert 1.2 seconds development + transition
35℃ 14.6 seconds fixing + crossing 33℃
8. 2 seconds water wash + crossing 25℃ 7.
Squeeze for 2 seconds, dry at 40℃ for 5.7 seconds
45℃ 8.1 seconds (Developer) Hydroquinone 25.0g Phenidone 1.2g Potassium sulfite 55.0g Boric acid
10.0g sodium hydroxide
21.0g triethylene glycol 17.
5g5-Nitroimidazole 0.10g5-
Nitropenzimidazole 0. lOg glutaraldehyde bisulfite L5.0g glacial acetic acid
16゜0g potassium bromide
4. Og triethylenetetraminehexaacetic acid 2.
Add 5g of water to make 1ft.

(Fixer) Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid
7.0g acetic acid (90vt%)
5.5g Sodium acetate (trihydrate)
25.8g aluminum sulfate (18 hydrate)
14.6g sulfuric acid (50vt%)
Add 6.77g of water to make 1g.

In addition, the samples were kept at 25°C and 50% RH, and 2 hours, 1 day, and 7 days after application, a portion of each sample was taken out and allowed to swell in water at 30°C for 5 minutes. The film thickness was measured, the degree of swelling V expressed by the following formula was calculated, and the change in curing effect with red time (posterior hardness) was observed.

The results are shown in Table 2 below.

Comparative Compound (IV) HCHO (V) CHO HO As is clear from the results in Table 2, X-ray photosensitive material samples Nos. 9 to 11 in which the hardening agent of the present invention was added to the protective layer had a lower sensitivity. There is almost no change in photographic properties such as deterioration or increase in fog, and the change in swelling degree is small and stable after one day or more after application and drying. has been significantly improved. In addition, when compared with sample 12, it can be seen that the dura mater was removed efficiently.

[Effects of the Invention] According to the present invention, a silver halide containing a novel hardening agent that efficiently hardens with a small amount of hardening agent without impairing photographic performance and has no post-hardening effect. A photographic material can be provided.

Applicant Co., Ltd.

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, at least one of the hydrophilic colloid layers is a compound represented by the following general formula [I]. A silver halide photographic material characterized by being hardened with at least one of the following. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 and R_2 represent an alkyl group, an aryl group, or an aralkyl group, which may be the same or different from each other. These groups may be substituted, and R_1,
R_2 may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. R_3 represents a hydrogen atom or a substituent. A is -O-, -NH-, -CO_2-, -CONH-,
-NHCONH-, -NHCO-, -O-CO-, -S
Represents a divalent organic group containing at least one linking group selected from O_2-, -SO_2NH-, and -NHSO_2-. L represents -O-, -N- or a single bond. R^4 represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom. ]