JPH04113351A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material hardened without adversely affecting its photographic characteristics by hardening at least one layer of hydrophilic colloidal layers by phosphate compds. having a specific structure. CONSTITUTION:This silver halide photographic sensitive material is constituted by hardening at least one layer of the hydrophilic colloidal layers by at least one kind of the compds. expressed by formula. An aryl group is exemplified by a phenyl group, tolyl group, xylyl group, mesityl group, p-methoxyphenyl group, p-chlorophenyl group. An alkyl group is preferably a methyl group and ethyl group. The substituent of the alkyl group and aryl group is exemplified by an alkyl group, aryl group, halogen atom, alkoxy group, acyl group, alkoxycarbonyl group, etc. The silver halide photographic sensitive material which acts to harden the film with the small amt. of hardening agent without impairing the photographic performance and has no post-hardening effect is obtd. in this way.

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 photosensitive 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, an undercoat layer, an antihalation layer, and an ultraviolet absorbing layer. It is composed of various photographic constituent layers such as a photosensitive layer, an antistatic layer, a backing layer, etc., 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 low 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. 2,732,303,
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. 3,232.7H, U.S. Pat. No. 3,885,718
Compounds having reactive olefins as described in British Patent No. 994.809, U.S. Patent No. 3,539,844,
JP 3,1342.486, JP 49-13583, JP 51-47271, JP 56-48860, JP 53-57257, JP 81-128240, JP 6
No. L-4275, No. 63-58541, No. 63-28
Vinylsulfonyl compounds described in No. 4572 etc., N-hydroxymethylphthalimide, U.S. Pat. No. 2,732,3
N-methylol compounds described in U.S. Pat. No. 16, No. 2,586,168, etc., isocyanates described in U.S. Pat. No. 3,103.437, etc., U.S. Pat. aziridine compounds described in et al.
Acid derivatives described in U.S. Patent No. 2725.294, U.S. Patent No. 2,725.295, etc., carbodiimide compounds described in U.S. Patent No. 3,100,704, etc., U.S. Patent No. 3,09
Epoxy compounds described in No. 1,537, etc., U.S. Patent L
Organic hardeners such as isoxazole compounds described in No. 321,313 and No. 3543.292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and chromium alum. , zirconium sulfate, chromium trichloride, and other inorganic hardeners.

However, when these known hardening agents are used in light-sensitive materials, they do not have sufficient hardening action, or there is a long-term change in hardening action called "post-hardening" 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, and other photographic additives. All had some drawbacks, such as those that reduced the effectiveness of additives (such as couplers in internal color emulsions) or caused 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. 9825, No. 82-282854, No. 82-284
N-carbamoylpyrinidinium salts described in No. 044 and No. 63-184741, compounds containing two or more N-acyloxyimino groups in the molecule as described in Japanese Patent Publication No. 53-22089, and compounds containing two or more N-acyloxyimino groups in the molecule as described in Japanese Patent Publication No. 5193470. N-
Compounds having sulfonyloxyimide groups, JP-A-58
Compounds having a phosphorus-halogen bond described in JP-A-11.3929, JP-A-60-225148 and JP-A-61-24
Chloroformamidinium compounds described in No. 0236 and No. 133-41580 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 is prepared by the following ritual [
This was achieved by hardening with at least one compound represented by I].

General Formula [I] In the formula, R represents a substituted or unsubstituted alkyl group or aryl group.

Examples of the alkyl group include methyl group, ethyl group,
Examples include propyl group, isopropyl group, butyl group, chloroethyl group, methoxyethyl group, acetylmethyl group, and methoxycarbonylmethyl group.

Further, examples of the aryl group include phenyl group, tolyl group, xylyl group, mesityl group, p-methoxyphenyl group, and p-chlorophenyl group.

As the alkyl group, a lower alkyl group is preferable, and a methyl group and an ethyl group are particularly preferable.

In addition, as substituents for alkyl groups and aryl groups,
Examples include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyl group, an alkoxycarbonyl group, and the like.

A represents an n-valent organic group or a single bond bonded to a carbonyl group through a carbon atom or a nitrogen atom.

The n-valent organic group is not particularly limited and may be saturated or unsaturated, and may be linear, branched, or cyclic. When a ring is formed, the ring may be a hydrocarbon ring or a heterocyclic ring.

Examples of n-valent organic groups include alkylene group, alkenylene group, alkynylene group, phenylene group, aralkylene group, CH2-CH*CH2-1CHxCHCH2-1 Silkworm CH
x +s, -(cH*)4, CH3 (CH2 masu 6, -(CH2 masu a, CH*C0CHq-
1CfbOCH*-1CH2NCII*-Hi R2R3 CH2 OJa Each represents a lower alkyl group. ) can be mentioned as a group formed by combining one or more groups selected from However, the present invention is not limited to this.5 These groups may be further substituted, and examples of the substituent include an alkyl group, a norogen atom, an alkoxy group,
Examples include sulfo group.

Examples of n-valent organic groups are listed below, but the present invention is not limited thereto.

CH3 CHzCONHCH2CHJHCOCHz-1C1(2
SO2CH2-C)lJsOzcH*cH2sOJcH
z-1-Cll-CH-1-C=CCH, Cl13C2H5ΦM represents an alkali metal cation or ammonium ion.

As alkali metal cations, sodium cations,
Examples include potassium cations and lithium cations. Preferred are sodium cations or potassium cations.

The ammonium ion may be primary, secondary, tertiary, or quaternary, but is preferably a quaternary ammonium ion.

Examples of ammonium ions include trimethylammonium and tetramethylammonium.

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

Exemplary compound II II II 111, CH+
-0-P-0-C-CH2-C-0-P-0-C) b5
゜II II Ill IICHi-0-P
-0-C-C-C-C-OP 0-CH3Na” 0゜0°Na■ 1]II ] 4 1!11 Na@0e-t'0 O-CHl 12゜II II II II II
CH3-0-P-0-C-CHz-SO*(:H2-C
-0-P-0-CT.

Φ0°08Φ The compound of the present invention can be easily synthesized by a known method. Specifically, Journal of Organic Chemistry Vol. 55, p. 2864 (1990)
[J, Org, Chem, 55.2884 (1990
) It can be synthesized according to the synthesis method described in .

The synthesis method will be specifically explained below using Exemplified Compound 5 as an example.

Synthesis of Exemplary Compound 5 Synthesis of fumaroyl bis(dimethyl phosphate)> Sodium dimethyl phosphate 14.8 g (0.1 mol)
and 7.7 g (0.05 mol) of fumaroyl dichloride were added to 130 ml of dry tetrahydrofuran and suspended for 2 days under a nitrogen atmosphere. After filtering off insoluble matter, the solvent was distilled off under reduced pressure to obtain crude crystals. This was recrystallized from benzene ether to obtain 10.8 g (yield: 65%) of white crystals of fumaroyl bis(dimethyl phosphate).

Synthesis of Exemplified Compound 5> Fumaroyl bis(dimethyl phosphate) L8. Bg
(0.05 mol) dissolved in 50 ml of dry acetone,
A solution of 15.0 g (0.1 mol) of sodium iodide in 50 ml of dry acetone was added dropwise into the mixture. When the mixture was left in a nitrogen atmosphere for 12 hours, crystals of Exemplified Compound 5 were precipitated. Handle the crystals by filtration, wash with dry acetone,
After drying under reduced pressure, pale yellow crystals were obtained. This was recrystallized with ethanol-isopropanol to produce white crystals.
4 g (yield 90%) was obtained.

The structure of this product was confirmed by NMR, IR, and elemental analysis.

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

The amount of hardening agent used in 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 1% of the dry weight of the hardener.
00% by weight, more preferably in the range of 01 to 30% by weight.

The hardeners of the present invention may be used alone or in combination of two or more. It may also be used in combination with other known hardeners.

Known hardening agents include aldehyde compounds such as formaldehyde and glutaraldehyde, and US Pat.
No. 2,303, No. 3,288.775, British Patent No. 97
Compounds containing reactive halogens such as those described in No. 4.723 and No. 167.207, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl)urea, 2-hydroxy-46-dichloro -1
,3,5-h riazine, divinylsulfone, 5-acetyl-], ]3-diacrylohexahydro-1,3,5
-1 riazine, a compound having a reactive olefin described in US Pat. No. 3,232,783, US Pat. No. 3,642,488, Japanese Patent Publication No. 49-13563, No. 53-47271, No. 5B-48860, Japanese Patent Publication No. 5B-48860
No. 3-57257, No. 61-128240, No. 62-
No. 4275, No. 6L-58541, No. 6L-58541, [ii 2B4
Vinylsulfonyl compound described in No. 572 etc., N-hydroxymethylphthalimide, U.S. Patent No. 2,732,31
6, N-methylol compounds described in US Pat. No. 2,586,168, etc., isocyanates described in US Pat. No. 3,103,437, etc., US Pat. No. 2,983,811, US Pat.
, 107,280, etc., acid derivatives described in U.S. Pat. No. 2,725,294, U.S. Pat. system compound, U.S. Patent No. 3,09
Epoxy compounds described in No. 1,537, etc., U.S. Patent No. 3
, 321,313 and 3,543,292, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and JP-A-50-H540 Compounds having a dihydroquinoline skeleton described in JP-A-51-59625, SL-2 [
No. f2854, No. 62-264044, No. 63-11
N-carbamoylpyrinidinium salts described in No. 14741, compounds containing two or more N-acyloxyimino groups in the molecule as described in Japanese Patent Publication No. 5L-22089, N-sulfonyl described in JP-A No. 5L-93470 Compounds having an oximide group, compounds having a phosphorus-halogen bond described in JP-A-58-113929, JP-A-60-
No. 225148, No. 61-240236, No. 63-4
Organic hardeners such as chloroformamidinium compounds described in No. 1580, chromium alum, zirconium sulfate,
Examples include inorganic hardeners such as chromium trichloride.

Preferred hardeners to be used in combination with the hardener of the present invention include the following compounds.

HI CHz=CH3OzCH*CH25O2CH
=CHzH-2 (CH2=CH5O2C)1214C IO 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.

I\Silver halide used in the silver halide emulsion layer or other layers of the photosensitive material when carrying out the present invention,
Chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, hydrophilic protective colloids such as gelatin, ultraviolet absorbers, polymer latex, brighteners, color couplers, anti-fading agents, dyes, matting agents, There are no particular restrictions on surfactants, etc., and 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.

[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 indicates the number of grams per one silver halide 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) 0.20 Colored cyan coupler (CC-1) 0
．． 02 High boiling point solvent (Oiρ-1) 0.20
High boiling point solvent (OiU -2) 0.20 Gelatin 1.8 2nd layer; Intermediate layer (IL-1) Gelatin 1.3 3rd layer; Low sensitivity red-sensitive emulsion layer (R-L) Silver iodobromide emulsion (E m −
1) 0.4 silver iodobromide emulsion (Em-2)
0.3 sensitizing dye (S-1) 8.
2x 10-' sensitizing dye (S-2) 8
．． 2xlO-' sensitizing dye (S-3>0
．． 2X 10-' cyan coupler (C-1)
0.50 cyan coupler (C-2)
0.13 Colored cyan coupler (CC-1) DIR compound (, D-1) DIR compound (D-2) High boiling point solvent (Oifl-1) Additive (SC-1) 0.07 o, ooe Olol 0. 55 o, ooa Gelatin 4th layer, high sensitivity red-sensitive emulsion layer (R Silver iodobromide emulsion (Em-3) Sensitizing dye (S-1) Sensitizing dye (S-2) Sensitizing dye (S-3 ) Cyan coupler (C-2) Colored cyan coupler (CC-1) DIR compound (D-2) High boiling point solvent (OiΩ-1) Additive (SC-1) Gelatin 5th layer, intermediate layer, (IL-2 ) Gelatin 6th layer; low sensitivity green-sensitive emulsion layer (G Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (S-4) Sensitizing dye (S-5) 1.0 H) 0.9 L, 7X 10-' 1.6x 10-4 0, lx 10-' 0.23 L) 0.02 0.25 1.0 0.8 0.6 7X 10-'8X10-' Magenta coupler (M-1) Magenta coupler (M-2) Colored magenta coupler (CM-1) DIR compound (D-3) High boiling point solvent (Oiρ-2) Additive (S C-1) Gelatin No. 7 layers; high-sensitivity green-sensitive pore layer (G) Silver iodobromide emulsion (Em-3) Sensitizing dye (S-6) Sensitizing dye (S-7) Sensitizing dye (S-8) Magenta coupler ( M-1) Magenta coupler (M-2) Colored magenta coupler (CM-1) DIR compound (D-3) High boiling point solvent (Oi, Q-2) Additive (S C-1) 0.17 0゜10 0.70 0.003 1゜0 H) 1.1X10' 2, OX 10-'0.3XiO-' 0.04 Gelatin 8th layer: Yellow filter layer Yellow colloidal silver additive (H3-1) Additive ( H8-2) Additive (SC-2) High boiling point solvent (Oif!-2) Gelatin 9th layer, low sensitivity blue-sensitive emulsion layer (B Silver iodobromide emulsion (Em-1) Silver iodobromide emulsion (Em -2) Sensitizing dye (S-9) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (I)-1) DIR compound (D-2) High boiling point solvent (OiF -2) Additive (SC-1) Gelatin 10th layer, high sensitivity blue-sensitive emulsion layer (B (YC) 1.0 0.07 0.07 0.12 0.15 L) 0.25 0.25 5.8X 10-' 0.32 0.003 0.00B 0.18 1.3 H) Silver iodobromide emulsion (Em-4) Sensitizing dye (S-10) Sensitizing dye (S-11) Yellow coupler (Y-1) Yellow coupler (Y-2) High boiling point solvent (OifI-2) Additive (SC-1) Gelatin 11th layer; 1st protective layer (P RO-: 1. ) Silver iodobromide emulsion (Em-5) Ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Additive (Is-1) Additive (H3-2) High boiling point solvent (O19-1) High Boiling point solvent (Oiβ-3) Gelatin 12th layer: 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.5 3, OXl, O-' L, 2X10' 0. 10 0.002 1.0 0.07 0.1 0.2 0.1 0.07 0.8 Two polymethyl methacrylate (average particle size 3 μm) 0.02 Slip agent (WAX-1) 0.04 Charge Regulator (SU-1) 0.004 Charge regulator (SU-2) 0.02 Gelatin
0.5 In addition to the above, a hardening agent of the present invention or a comparative hardening agent as shown in Table 1 was added to each layer to prepare samples Nos. 1 to 8.

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 Em Em Em 2: Average silver iodide content 2.5 mol% Average grain size 036 μm Grain shape 3: Average silver iodide content 8.0 mol% Average grain size 0.84 μm Grains Shape Octahedron 4: Average silver iodide content 8.5 mol% Average grain size 1.02 μm Grain shape Octahedron 5: Average silver iodide content 2.0 mol% Average grain size 0.08 μm Below margin M'- 2 4H9 J ShiI CM ] Shi1 V M V-2 2H5 S H2CC=0 υ SI( M Of( 36゛U Na0zS-CH-COOCHz (CF2CF2)JC
H2-COOCH2 (CF2CF2)3HU U U Na0zS-CH-COOCaH+□ CH, -COOC8H,7 2H5 (CH2)4SO3 (CH2)3SO3H (CH2)3S03 C-1 H 2H5 J5 C mixture (2: 3) 1fi- 1 2H5 2H5 0iffi-2 01 sentence-3 Al-1 WAX-1 I-2 F-1 F-2 T-1 HI-1 Each sample prepared is a fresh sample, and this sample is kept at room temperature for 7 days. A sample that was left to stand and a sample that was forced to deteriorate by being left at 50° C. and 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.

The sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog +05, and is expressed as a relative sensitivity with the sensitivity of Sample No. I, which was left under the chamber 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 0.3 mm was brought into pressure contact with the sample surface, and the sample was moved over 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 without parallel movement, 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 seconds Bleaching 38°C 6 minutes 30 seconds Water washing 38°C 3 minutes 15 seconds
Wash at 38°C for 6 minutes and 30 seconds.
Stabilization at 38°C for 3 minutes and 15 seconds 25°C] Minutes and 30 seconds Drying 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-hydroquinethyl) aniline sulfate 475g anhydrous sodium sulfite 4.25g hydroxylamine 1. / Disulfate 20g Anhydrous potassium carbonate 37.5g Sourium chloride 1.3g Nitrilotriacetic acid tristrium salt (monohydrate) 25g Potassium hydroxide 1.0g Add water to adjust to 1Ω.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide, 150.0g Glacial acetic acid LO, 0ml Add water to make 1g, and use ammonia water to adjust pH to 6.
．． Adjust to 0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 g, and adjust to pH -6.0 using acetic acid.

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

The following margins are Comparative Compound (I) (Compound described in JP-A No. 51-59825) Comparative Compound (II) (Compound described in JP-A-53-118486) Comparative Compound (m) CH2=CH302CH, C0NHCH2CH2NHC
OCH, 5O2CH = Compound described in CH241221 Publication) As is clear from the results of Table 1 above, samples No. 1 to 5 using the hardening agent according to the present invention are all comparative sample No. , 6 to 8, there was only a slight decrease in relative sensitivity, and no deterioration in fog was observed.

In addition, even when forced deterioration was performed, comparative sample No.
Compared to samples Nos. 6 to 8, samples Nos. 1 to 5 of the present invention showed a slight decrease in sensitivity and only a slight increase in fog.

Therefore, it can be seen that the hardening agent 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 No. 0 and L-5 all showed higher film strength compared to Comparative Samples No. 6 and 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 for silver halide I are shown in amounts per mole of silver halide unless otherwise specified.

1st layer: Crossover cut layer Dye (I) 3mg/Mordant resistant agent (II
) O, 12g/rrr gelatin
02g/a 2nd layer: Emulsion layer average grain size 0.57μm AgBr containing 12 mol% SAg
Coating amount of emulsion consisting of (2) 4.5 g/sensitizing dye (A) 450 mg sensitizing dye (B) 20 mg 4-hydroxy-6
-Methylco 3,3a,7-chitrazaindene 3. Ogt-butyl-catechol 40 (l mg polyvinylpyrrolidone (molecular weight 1.0.000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane diethylene glycol p-nitrophenyl-triphenylphosphonium chloride 13-dihydroquine Hensen 4-ammonium sulfonate 2-mercaptobenzimidazole-5-sodium sulfonate 1.0 g g 0 mg g 5 mg H 1,1-dimethylol-] Mo 1-nitromethane gelatin 3rd layer: Protective layer polymethyl methacrylate ( Average particle size: 5μm) Pro0mg 2g/Go7mg/r+f Colloidal silica (average particle size [), 013μm) 7[]mg/r# Dye (1) Mordant (n) CH2COO(CH2)9CH3 CHCOO(CH2)2CH( CH3) 27mg/rr
? 0Ja HSC2" C2H5 1/2 SO4"' After the test, exposure was applied to perform the following processing, and photographic properties were measured in the same manner as in Example 1.

The sensitivity was expressed as a relative sensitivity based on the sensitivity of sample No. 39 7 days after application as 100.

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℃ 7.2
Second squeeze 40℃ 5.7 seconds drying
45℃ 8.1 seconds (Developer) Hydroquinone 25.0g Phenidone Potassium sulfite Borate Sodium hydroxide Triethylene glycol 5-Nitroimidazole 5-nitropenzimidazole Glutaraldehyde Bisulfite Glacial acetic acid Potassium bromide Triethylene Tetramine Hexaacetic acid Add water to make tU.

(Fixer) ammonium thiosulfate anhydrous sodium sulfite Boric acid Acetic acid (90wt%) Sodium acetate (trihydrate) Aluminum sulfate (18 hydrate) Sulfuric acid (50wt%) 1.2g 55.0g 10.0g 21.0g 17.5g O, 10g 0.10g 15.0g te,og 4.Og 2.5g 130.9g 7.3g 7.0g 5.5g 25.8g 14.6° 6.77g Add water to make 1g.

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 allowed to swell in water at 30°C for 5 minutes. The thickness was measured, the swelling degree V expressed by the following formula was calculated, and the change over time in the curing effect (post-curability) was observed.

The results are shown in Table 2 below.

Comparative Compound (IV) HCHO (V) CHO RO As is clear from the results in Margin Table 2 below, X-ray photosensitive material samples Nos. 9 to 11 in which the hardening agent of the present invention was added to the protective layer were as follows: 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, compared to comparative samples No. 13 and 14. Durality has significantly improved. Moreover, when compared with Sample 12, it can be seen that the dura mater was made efficiently.

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

Applicant Co., Ltd. Agent Yoshio Iwa

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 represents a substituted or unsubstituted alkyl group or aryl group. A represents an n-valent organic group or a single bond bonded to a carbonyl group through a carbon atom or a nitrogen atom. M^■ represents an alkali metal cation or ammonium ion. n represents an integer of 2 or more.