JPH03161742A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material small in sweating property and low in fog by incorporating a water-soluble ultraviolet absorbing polymer prepared by combining a ultraviolet absorber with a polymer. CONSTITUTION:The ultraviolet absorber is combined with the water-soluble polymer to form the water-soluble ultraviolet absorbing polymer and it is added to the photographic sensitive material. Whatever water-soluble polymer can be used so long as it does not impairs the characteristics of the ultraviolet absorber, but it is preferred to use gelatin and polyvinyl alcohol especially superior in film forming ability. Whatever generally used ultraviolet absorber may be used so long as it has a functional group capable of combining with the water-soluble polymer, and such ultraviolet absorbers as benzotriazole, 4-thiazolidone, benzophenone, cinnamic ester, butadiene, and benzoxazole compounds or derivative each having the functional group, can be used, and ultraviolet absorbing couplers and ultraviolet absorbing polymers may be used, thus permitting sweating property to be suppressed and fog to be reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material with low perspiration and low capri.

[Background of the invention]

Silver halide photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) usually contain an ultraviolet absorber. The purpose is wide-ranging, such as improving color reproducibility and preventing static electricity caused by static electricity during the production and/or processing of photosensitive materials. In other words, UV absorbers can serve various purposes simultaneously and easily, so they can be said to be indispensable additives for photosensitive materials.

Ultraviolet absorbers are usually lipophilic, so they are dissolved in a high-boiling organic solvent and dispersed in an aqueous gelatin solution. It is often used for the layer near it, or the layer closest to the light source or the layer near it.
These layers will also contain significant amounts of high boiling point organic solvents.

Containing a large amount of high boiling point organic solvent in a layer near the top often has a negative effect on photographic performance. For example, during storage, especially when stored under high humidity, so-called sweating is likely to occur.
Therefore, especially in the case of a transparent support, there are problems such as devitrification after development, poor color development, or increased fog, which causes desensitization.

By applying the polymerized ultraviolet absorber disclosed in JP-A-63-65140, etc., the sweating phenomenon can be somewhat reduced, but fogging has not been improved at all.

[Purpose of the invention]

Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which perspiration is suppressed and fog is reduced.

[Structure of invention]

The above objects of the present invention have been achieved by a silver halide photographic material containing a water-soluble polymer ultraviolet absorber formed by combining a water-soluble polymer and an ultraviolet absorber.

The present invention will be described in more detail below.

The water-soluble polymer used in the present invention may be any polymer as long as it does not impair the properties of the ultraviolet absorber, such as gelatin, casein, sericin, soluble collagen, zein, serum albumin, lactalpmin, ovalbumin, poly-L-lysine, Examples include isopoly L-lysine, vectin, dextran, polyethyleneimine, polyvinylene glycol, polyethylene glycol, and derivatives thereof, which can be used alone or in combination. especially,
Gelatin and polyvinyl alcohol, which have good film-forming properties, are preferred.

Further, the ultraviolet absorber to be bonded to the water-soluble polymer used in the present invention may be any commonly used ultraviolet absorber as long as it has a functional group capable of bonding to the water-soluble polymer used. For example, a penzotriazole compound, a 4-thiazolidone compound, a benzo7enone compound, a cinnamic acid ester compound, a putadiene compound, or a penzoxazole compound having a reactive group can be used. An ultraviolet absorbing coupler or an ultraviolet absorbing polymer may also be used.

Among the ultraviolet absorbers bonded to water-soluble polymers, preferred ones are represented by the following general formulas (1) to (mV).

General formula (1) General formula (II) General formula (III) In the above general formula, at least one of R l"" R s, R. at least one of ~Rs, Rho~Rl4
at least one of Rl3 to R1. At least one of them is a group that binds to a water-soluble polymer, preferably {-J
．． ) ttl+J is a group represented by 1 boundary Rat.

Here, RlF represents a carpoxyl group, an ano←koxycarbonyl group, an aryloxylponyl group, a chloroformyl group, a chlorosulfonyl group, an incyanate group, an inthiocyanate group, a chlorocanolebonyloxy group, an amino group, a bidroxyl group. represents, J, is -0-, -NH-,
-CONH-. -NHCO--sOx-, -
SO,NH-, -N}ISO,-, -COO-
-OCOO- -NHCONH-, -NCOO-,
-OCON-, J8 represents a divalent linking group, such as a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group, and n1 and n are 0 or represents l.

In the above general formulas (1) to (IV), R, to R. may be the same or different, and R. 〇1 or R. , So. - represents R. ~R, may be the same or different, and represent a hydrogen atom, a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, a carponamide group, a sulfonamide group, a sulfo group, a carboxyl group, or a R. 0- represents %Rl11 and Rll may be the same or different,
Hydrogen atom, aliphatic group, halogen atom or R. Represents 0- and Rl! , Rll and R. may be the same or different and represent a hydrogen atom, an aliphatic group, or an aromatic group (however, R
ll and R,. cannot be a hydrogen atom at the same time. ),
R. and R. may be the same or different; cyano group, carbamoyl group, sulfamoyl group, formyl group, -
coRta, SOR r a, -SO,R. ,,-
SOzOR+i or -COOR. represents l. Here, the aliphatic group refers to a substituted or unsubstituted linear, branched, or cyclic alkyl group, and the aromatic group refers to a substituted or unsubstituted group consisting of a monocyclic or condensed bezene ring. shows.

Substituents R1 to R. used in the compounds represented by general formulas CI) to [■]. An example is shown below.

That is, halogen atoms (fluorine, chlorine, bromine atoms, etc.),
Aliphatic groups (methyl, ethyl, probyl, i-propyl,
SeQ-butyl, t-butyl, E-amyl, t-hexyl, octyl, 2-ethylhexyl, t-octyl, dodecyl, hexadecyl, trinoloroacetyl, benzyl group, etc.), aromatic groups (phenyl, tolyl, 4- methoxy7enyl, na7tyl group, etc.), acyloxy group (acetyloxy, benzoyloxy, p-chloropenzoinoleoxy group, etc.), canoleponamide group (acetamide, penzamide, tri7fluoroacetamide group, etc.), sulfonamide group (methanesulfonamide, benzenesulfonamide, toluenesulfonamide groups, etc.), carbamoyl groups (carbamoyl, dimethylcarbamoyl, dodecylcarbamoyl groups, etc.), sulfamoyl groups (sulfamoyl,
(dimethylsulf-7-amoyl, 7-engineered dilsulfamoyl group, etc.).

Examples of compounds represented by general formulas (1) to [■] are UV-
1 UV-2 UV- 3 UV 4 UV-5 UV-a UV-7 UV-8 UV- 9 U・V-10 UV-11 11 V-12 U V-13 U V-14 U V-15 U V - 16 UV - 17 UV - 18 0 UV - 19 UV - 20 UV-21 The method for producing the compound of the present invention, that is, the method for bonding a water-soluble polymer and an ultraviolet absorber, depends on the characteristics of the ultraviolet absorber. Any method that does not cause damage is fine.

For specific binding methods, see "Chemical Modification of Collagen and Gelatin," Harukazu Toyoda and Yasumasa Chonan: Leather Chemistry. 30(
1). 3 (1984), representative methods are listed below.

l) Amino group possessed by the main chain or side chain of the water-soluble polymer (when the water-soluble polymer represents gelatin, the a-amino group of the amino terminal amino acid of the polypeptide V chain of gelatin or the side of the lysine or hydroxylysine residue) (representing the ε-amino group of the chain), the carpoxyl group, alkoxylponyl group, aryloxylponyl group, chloroformyl group, chlorosulfonyl group, isocyanate group, inthiocyanate group, chlorocanoleponyloxy group that the ultraviolet absorber has By reacting groups, amide bonds, sulfonamide bonds,
A method for forming ureido bonds, thiourido bonds, and urethane bonds.

2) Carpoxyl group possessed by the main chain or side chain of the water-soluble polymer (when the water-soluble polymer represents gelatin, the σ-carpoxyl group of the carboxyl-terminal amino acid of the polypeptide chain of gelatin, the carpoxyl group of the aspartic acid residue side chain) After activating the carpoxyl group by acting water-soluble carbodiimide on the β-carboxyl group (representing the β-carboxyl group or the γ-carboxyl group of the side chain of the glutamic acid residue), the amino group or hydroxyl group of the ultraviolet absorber is reacted. , a method to form amide bonds and ester bonds.

3) A method of activating and reacting a carpoxyl group of an ultraviolet absorber with a hydroxyl group of the main chain or side chain of a water-soluble polymer to form an ester bond.

4) The amino group, carpoxyl group, or hydroxyl group that the main chain or side chain of the water-soluble polymer has and the amino group, carpoxyl group, or hydroxyl group that the ultraviolet absorber has are combined with X. A method of linking using a compound having two reactive groups represented by -L-X.

Here, X and x2 are each a carpoxyl group, an alkoxycarponyl group, an aryloxycarbonyl group, a chloroformyl group, a chlorosulfonyl group, an isocyanato group,
Represents an inthiocyanate group, chloroluponyloxy group, arylcarbonyloxy group, hydroxyl group, amino group, fluorine atom, chlorine atom, bromine atom, iodine atom, alkylsulfonyloxy group and arylsulfonyloxy group, and L is a divalent linkage. represents a group such as a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted heterocyclic group.

As a method for activating carboxyl groups, N,N'
-dicyclohexyllupodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carpodiimide (EDC), l-cyclohexyl-3-(2-morpholinyl-4-ethyl)carpodiimide meth-p-}
J leens nolephonate (CMC), l-benzenolephonate (CMC)
3-(3-dimethylaminoprobyl)carpodiimide (
BDC) and other water-soluble lupodiimides and N-ethyl-5-
Method using a condensing reagent such as 7-enyl isozazolium-3'-sulfonate (Woodward reagent K), pentachloro 7-enyl chloroacetate (TCA-OPCP)
, p-nitrophenyl trifluoroacetate (TFA
- OPNP), an active ester method using p-bitrophenyl chloroformate, etc., and an acid chloride method using thionyl chloride, etc.

Example 1 PCP ester synthesis of ultraviolet absorber UV-3 36.7 g (0.1 mol) of ultraviolet absorber (UV 3) dissolved in 370 mQ of dimethyl sulfoxide, 25.3 g (0.25 mol) of triethylamine and 39.0 g (0.25 mol) of pencchloro7enyltrichloroacetate was added, and the mixture was stirred at 0°C for 6 hours. After the reaction, the solvent was removed under reduced pressure to obtain 61.6 g (0.1 mol) of PCP ester of ultraviolet absorber (UV-3).

Combined ratio of gelatin conjugate of ultraviolet absorber UV-3
55.4 mg (0.09 mmol) of the pcp ester synthesized above was added to 20 g of gelatin solution (pH - 10.0). N-dimethylformamide 20+off
The mixture was added to the solution and reacted overnight. After the reaction, the pH was adjusted to 7, and water and N,N-dimethylformamide were distilled off. The residue was dissolved in warm water, dialyzed, concentrated by ultrafiltration, and then lyophilized to obtain 2.0 g of gelatin-bound ultraviolet absorber. The introduction rate of ultraviolet absorber is l. It was 5vt%.

Synthesis Example 2 Synthesis of PNP ester of UV absorber UV-12 UV absorber (UV-12) 18.7g (0.
1 mol) Dissolved in 90ml of dimethyl sulfoxide (1 mol) and dicyclohexylinolepodiimide (DCC)
20.6 g (0.1 monole) was added and stirred for 1 hour. followed by p-nitrophenol (PNP) 13.9
g (0.1 mol) and stirred at 0°C for 1 hour, then at room temperature for 2 hours, and then left at 4°C overnight. Ice water was added to precipitate crystals, which were filtered off, washed with water, and dried to obtain 22.0 g (0.0715 mol) of PNP ester.

Synthesis of gelatin conjugate of ultraviolet absorber UV-12 Next, 10 g of 1O% gelatin solution was added to the PN obtained above.
After adding 27.7 mg (0.09 mmol) of P ester, 9.1 mg (0.09 mmol) of triethylamine was added, and the mixture was stirred at room temperature for 24 hours. After the reaction, the solvent was distilled off, the residue was redissolved in water, and after dialysis, ultrafiltration and concentration,
Freeze-drying yielded 2.0 g of gelatin-bound ultraviolet absorber. The introduction rate of the ultraviolet absorber was 0-75vt%.

Synthesis Example 3 5% gelatin solution of gelatin conjugate of ultraviolet absorber UV-18 (0.1M phosphate buffer pH 7.0)
To 120 g, 682 g (3.55
mmol) and stirred for 1 hour. Furthermore, 20all of a dimethyl sulfoxide solution containing 1241g (0.413 mmol) of ultraviolet absorber (UV-18) was added,
The reaction was allowed to proceed for 2 hours.

After the reaction, the mixture was subjected to dialysis, ultrafiltration, concentration, and freeze-drying to obtain 5.5 g of gelatin-bound ultraviolet absorber. The ultraviolet absorber introduction rate is 2. It was Ovt%.

Although the amount of the compound of the present invention to be added varies depending on the photosensitive material and the type of compound, the water-soluble polymer conjugate of the compound represented by the general formulas (1 to (IV)) is equivalent to 1 mole of silver halide. It is preferably used in the range of lQ+ag-100g per coating, more preferably 100mg to 50g.The amount added to the hydrophilic colloid layer is 1kg per 11 coats.
It is preferable to use it in the range of ~lag.

The photosensitive material used in the present invention can be applied to the following various types of photosensitive materials.

For example, for general black and white, for X-ray recording, for plate making, for color positive, for color negative, for color paper, for reverse color,
U.S. Pat. No. 2,996.382, U.S. Pat. Although it can be used in photosensitive materials prepared by the method described in No. 282, it is particularly advantageous to apply it to color photosensitive materials having a multilayer structure.

The silver halide emulsion used in the present invention is any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. can be used.

Silver halide grains used in silver halide emulsions may have a uniform silver halide composition or distribution within the grain, or core/shell grains with different silver halide compositions in the interior and surface layer of the grain. You can.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more silver halide emulsions formed separately.

The emulsion can be chemically sensitized by conventional methods, or optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer, a water-insoluble or poorly soluble polymer, or a dispersion (latex) of a polymer.

Couplers are used in the emulsion layer of color light-sensitive materials.

Furthermore, by coupling with a competing coupler having a color correction effect and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent,
Compounds that release photographically useful fragments such as fogging agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye coupler, known acylacetanilide couplers can be preferably used.

Among these, penzoylacetanilide and bivaloylacetanilide compounds are advantageous.

As the magenta dye type or coupler, 5-pyrazolone couplers, pyrazoloazole couplers, pyrazolobenzimidazole couplers, acylacetonitrile couplers, indazolone couplers, etc. can be used.

Phenol or naphthol couplers are generally used as cyan dye couplers.

The photosensitive material can be provided with auxiliary layers such as a 7-ilter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layers may contain dyes that are leached from the light-sensitive material or bleached during the development process.

A matting agent, a lubricant, an image stabilizer, a formalin scavenger, a commonly used ultraviolet absorber, an optical brightener, a surfactant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene tele 7 talate 7 ilm, baryta paper, cellulose triacetate, etc. can be used.

A known method can be used to develop the photosensitive material used in the present invention. The processing temperature used is between 18°C and 50°C, and depending on the purpose, any of black and white photographic processing, lithographic development processing, or color photographic processing in which a dye image is formed can be applied. In addition, in photosensitive materials for heat development, 10
Processed at temperatures above 0°C.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

In all the examples below, the amount added in the silver halide photographic light-sensitive material is expressed in Durham number per 11 unless otherwise specified. Furthermore, silver halogenide and colloidal silver are shown in terms of silver.

Example 1 A multilayer color photographic material sample was prepared by sequentially forming each layer of the following composition on a triacetylcellulose film support from the support side.

Sample-101 (Comparison) 1st layer: Antihalation layer (HC-1) Black colloidal silver 042 UV absorber (UV-a
) 0.2 high boiling point solvent (Oi(l l
) 0.2 gelatin
l・5 2nd layer: Intermediate layer (IL-1) UV absorber (UV-a) 0
．． 04 High boiling point solvent (Oiα-1) 0.04 Gelatin l・2 3rd layer:
Low-sensitivity red-sensitive emulsion layer (R L) Silver iodobromide emulsion (E amount -1
) 0.6 silver iodobromide emulsion (Em-2)
0.2 sensitizing dye (SD-1
) 2.2X 1G"" (mol/silver 1 mol) Sensitizing dye (SD-2) 2.2X 10-
'(mol/silver mol) Sensitizing dye (SD-3') 0.44X 1
G-' (mol/silver mol) Cyan coupler (C-1) 0.65 Colored cyan coupler (CC-1) 0.12 DIR compound (D-1) 0.004 DIR compound (D
-2) 0.013 high boiling point solvent (O
iI2-1) 0.6 gelatin
1.5 4th layer: High sensitivity red-sensitive emulsion layer (R H) Silver iodobromide emulsion (Em-3)
0.8 sensitizing dye (SD-1) l. 2XlO-'(
mol/silver mol) Sensitizing dye (SD-2) l. 2X 10-
'(mol/silver mol) Sensitizing dye (SD-3) 0. lX 10-'(
mole/l mole of silver) Cyan coupler (C-2) 0.16 Cyan coupler (C-3) 0.02 Colored cyan coupler (CG-1) 0.03 DIR compound (
D-2) 0.016 High boiling point solvent (OiQ-1) 0.2 Gelatin
1.3 Fifth layer: Intermediate layer (IL-2
) Gelatin 0.7 6th layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) Sensitizing dye (SD-4) 3. OX 1G-
'(mol/silver l Sensitizing dye (SD-5') 5.OX 10
-' (mol/silver l 0.8 mol) mol) Magenta coupler (M-1) 0.2 Magenta coupler (M-2) 0.2' Colored magenta coupler (CM-1) 0.1 DIR compound ( D-3) 0.02DI
R compound (D.-4') 0.00
4 High boiling point solvent (0412-2) 0.4
Gelatin 1.0 7th layer:
High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Es-3) 0.9 Sensitizing dye (s D-4) l. 5x 10-'(
mol/silver mol) Sensitizing dye (SD-5) 2.5X 10-
'(mol/silver 1 mol) Sensitizing dye (SD-6) 0.55X 10
-' (mol/silver mol) Magenta coupler (M-2) 0.09 Colored magenta coupler (CM-2) 0.04 DIR compound (D-3) 0.
006 High boiling point solvent (Oil2-2) Gelatin 8th layer: Yellow filter layer (YC) Yellow colloid silver stain inhibitor (SC-1) High boiling point solvent (OiQ-3) Gelatin 9th layer: Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (
Em-1) Silver iodobromide emulsion (Em-2) Sensitizing dye (SD-10) 0.6X 10-
” (mol/silver liter) Yellow coupler (Y-1) Yellow coupler (Y-2) DIR compound (D-2) High-boiling point solvent (Oil2-3) Gelatin 1O layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver bromide emulsion (
Em-3) Silver iodobromide emulsion (Era'-1) 0.3 1.0 0.1 0.1 0.1 0.8 0.35 0. 10 mol) 0.6 0.1 0.01 0.3 1.0 0.4 0.1 Sensitizing dye (SD-7) IXIO-' (mol/silver 1 mol) Sensitizing dye (SD-8 ') 0.3X 10
-” (mol/silver 1 mol) Yellow coupler (Y-1) 0.20 Yellow coupler (Y-2) 0.03 High boiling point solvent (Oil2 -3) 0.07 Gelatin 1.1 11th layer: 1st
#: Protective layer (PRO-1) fine grain silver iodobromide emulsion (average grain size 0.08μ + *Agl 2 mol%) 0.2UV
Absorbent (UV-a) 0.1
0UV absorber (UV-b)
0.05 High boiling point solvent CO+Q-1) 0.
1 High boiling point solvent COiQ-4) 0.1 Formalin scavenger (MS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 12th layer: 2nd protective layer (PRO-2) Surface activity Agent (S u-1) 0
．． 005 Alkali-soluble matting agent (average particle size 2 μm + m) 0.05 Polymethyl methacrylate (average particle size 3 μm) 0.05 Slip agent (WAX-1) 0.04 Gelatin 0.5 In addition to the above composition, apply Auxiliary agent Su-2, dispersion agent Su-3 and Su-
4. Hardener H-1, H-2, Stabilizer ST-1 Anti-capri agent AF- 11mw: 10.000 and 17:
1,100.000 of two types of AF-2 were added.

The emulsion used in the above sample is as follows.

E-11 core with average grain size 0.45 μm, average silver iodide content 6.0 mol%, monodisperse (width of distribution 18%) outer phase silver iodide content 2 mol%/ Shell type silver iodobromide emulsion Em-2 Average grain size 0.25 μm, average silver iodide content 6.0 mol%, monodisperse (width of distribution 18%) silver iodide content in the outer phase 0.5 mol% core/shell type silver iodobromide emulsion Em-3, average grain size 0.80μ, average silver iodide content 7.0 mol%, monodispersity (width of distribution 16%). A core/shell type silver iodobromide emulsion with a silver iodide content of 1.0% in the outer phase.The compounds used in the above samples were as follows: 5 D-1 SD-2 SD-3 SD-4 SD - 5 SD-8 SD- 7 SD-8 C-1 C 2 M-1 M 2 Y-1 CI2 CC- 1 0H CM- 1 D-1 D-3 OH 0 ■ D-4 IJV-a UV- b HS- 1 0H MS-2 H-1 H-2 S l Su-2 Su-3 Su-4 SC- 1 0H 0H WAX-1 0 l a 1 O 1 a - 3 O 1 C 4 AF- 1 01Q-2 0H ST- 1 0H AF-2 Sample 1. Add the UV absorbers in layers 1.2 and 11 and the gelatin in the layers instead of the compound of the present invention as shown in Table 1, and prepare the sample in the same way. 102 to 104 were created.

The upper row of each column in Table 1 shows the UV absorbers to be added in a dispersed manner.
The lower row shows Uv added as the water-soluble polymer compound of the present invention.
Represents an absorbent.

Also, the amount added represents the amount as a UV absorber. In sample 102, a polymerized solid polymer containing UV-18 as a monomer (referred to as UV-18') was used.

Each of the samples thus prepared, indicated by g/1, was exposed to a wedge using white light, and then subjected to the following development treatment.

Processing process 1i (38@O) White development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing with water 3 minutes 15 seconds fixing
Wash with water for 6 minutes and 30 seconds
Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

Color developer> 4-Amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make Iff and adjust the pH to -10.1.

<Bleach solution> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100 g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid
Add 10 mQ water and
and adjust the pH to 6.0 using ammonium water.

<Fixer> Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water to make IQ, and adjust to pH = 6.0 using acetic acid.

Stabilizer> Formalin (37% aqueous solution) 1.5m
4 Konidax (manufactured by Konica Corporation) 7.5a
Add +α water to make 11f.

Also, E N 101-104t- Heat 11. After being stored at 55° C. and 20% RH for 3 hours, the same development was performed.

The density of each color of blue, green, and red of these treated samples was measured, and the fog was determined and shown in Table 2.

Note that the fog due to heat treatment is shown as a value relative to the fog of each untreated sample.

As is clear from Table 2, for the samples according to the present invention,
Even when stored at 55° C. and 20% RH for 3 days, no devitrification occurs and there is little change in fog.

Claims (1)

[Claims] A silver halide photographic material characterized by containing a water-soluble polymer ultraviolet absorber formed by combining a water-soluble polymer and an ultraviolet absorber.