JPH01179042A - Silver halide photographic sensitive material containing yellow dye - Google Patents

Abstract

PURPOSE:To improve decolorability and leachability during development and to prevent recoloring during storage and lowering of sensitivity by incorporating a specified yellow dye. CONSTITUTION:This silver halide photographic sensitive material contains a compd. represented by formula I (where each of X and Y is an electron attracting group, X and Y may be different from each other, each of R<1> and R<2> is H, optionally substd. alkyl, alkenyl, etc., and each of R<3> and R<4> is H, halogen, optionally substd. alkyl, carboxyl, etc., and R<1>, R<2> and R<3>, R<4> may be different from each other). The compd. has superior decolorability and leachability in a photographic processing stage, is not recolored during storage and exerts no influence on the photographic characteristics of the photosensitive silver halide emulsion, that is, causes no fogging or desensitization.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a multilayer silver halide photographic material having a novel yellow dye-containing layer, and more specifically, to a multilayer silver halide photographic light-sensitive material having improved decolorization properties and washout properties during development processing. The present invention relates to a silver halide photographic material containing a novel diffusion-resistant dye that does not restore color during storage over time and does not cause a decrease in sensitivity.

[Background of the Invention] - In silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials), speci?c It is well known that a dye is contained in the constituent layers of a photosensitive material in order to absorb light with a wavelength of ing.

Dyes used for such purposes must, of course, have good absorption spectrum characteristics depending on the purpose of use; for example, they must be completely decolorized during development, easily eluted from the photosensitive material during development, and After processing, there is no residual color staining caused by the dye, there is no other negative effect on the photosensitive emulsion such as fogging or desensitization, and there is no diffusion from the colored layer to other layers. Furthermore, it must satisfy various conditions, such as excellent stability over time in a photosensitive material or an aqueous solution, and no discoloration or fading.

To date, many studies have been conducted with the aim of developing dyes that satisfy the above conditions, and methods using diffusion-resistant dyes are described, for example, in U.S. Pat. No. 4,420,
No. 555, JP-A No. 61-204630, JP-A No. 61-20
There is a method using a benzylidene dye described in No. 5934, etc., but it is insufficient in terms of decolorization in the processing step, insufficient in terms of diffusion resistance, and has an adverse effect on sensitivity and fog.

Therefore, the reality is that a dye that satisfies the above conditions has not yet been found, and the development of such a dye is desired.゛ [Object of the Invention] Therefore, the first object of the present invention is to provide a dye that has excellent decolorization and dissolution properties during the photographic processing process, does not restore color during subsequent storage over time, and has excellent suitability for photographic processing. An object of the present invention is to provide a silver halide photographic material containing the following.

A second object of the present invention is to provide a silver halide photographic material containing a diffusion-resistant dye in a light-sensitive silver halide emulsion layer or a light-insensitive colloid layer.

A third object of the present invention is to provide a silver halide photographic material containing a dye that does not adversely affect photographic properties such as fog or desensitization of a light-sensitive silver halide emulsion.

[Structure of the Invention] The above objects of the present invention have been achieved by a silver halide photographic material containing a compound represented by the following general formula [I].

General formula [I1%Formula% [In the formula, X and Y represent electron-withdrawing groups, and X and Y may be the same or different.

al and R2 represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, aryl group, acyl group, or sulfonyl group, and these R1 and R2 may be the same or different. . Also, R' and R2 combine to form 5-6
It may form a member ring.

R3 and R4 are hydrogen atoms, halogen atoms, optionally substituted alkyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups, nitro groups, cyano groups, hydroxy groups, alkoxy groups, or It represents a mercapto group, and R3 and R4 may be the same or different. ] Hereinafter, the present invention will be explained in more detail.

What is the electron-withdrawing group represented by X and Y in the general formula [I1? "Structure-activity relationship of drugs - Guidelines for drug design and mechanism of action research" Structure-Activity Relationship Discussion Lifeline (Chemistry Special Edition No. 122, Nankodo) σ denoted by P95 means a positive value. More specifically, X and Y may be the same or different, and these include a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, and an aryl group.
Oxycarbonyl group, sulfonyl group, sulfinyl group,
Represents a sulfamoyl group.

As the acyl group represented by , 4-methanesulfonylaminobenzoyl group, 4-
Methylsulfonylbenzoyl group, 4-trifluoroacetylaminobenzoyl group, 4-trichloroacetylbenzoyl group, 4-acetylbenzoyl group, 4-methoxybenzoyl group, 2-methoxybenzoyl group, 4-ethanesulfonylaminobenzoyl group, 4-propane Sulfonylaminobenzoyl group, 3-methanesulfonylaminobenzoyl group, 3-propanesulfonylaminobenzoyl group, 4-pentanesulfonylaminobenzoyl group, 4-octanesulfonylaminobenzoyl group, 4-dodecanesulfonylaminobenzoyl group, 4-methanesulfonylaminobenzoyl group benzoyl group, 4-propanesulfinylaminobenzoyl group, 2-methanesulfinylaminobenzoyl group, dimethylaminosulfonylaminobenzoyl group,
Examples include 4-methoxycarbonylaminobenzoyl group, 4-ethoxycarbonylaminobenzoyl group, 4-propyloxycarbonylaminobenzoyl group, 4-octyloxycarbonylaminobenzoyl group, and 3-methoxycarbonylaminobenzoyl group.

Examples of the carbamoyl group represented by -Nitrophenylcarbamoyl group, 4-aminocarbamoyl group, 2-methoxyphenylcarbamoyl group, 4-methanesulfonylaminophenylcarbamoyl group, 4-propanesulfonylaminophenylcarbamoyl group, 3-methanesulfonylaminophenylcarbamoyl group, 4-methoxycarbonyl group Examples include phenylcarbamoyl group, 4-propyloxycarbonylphenylcarbamoyl group, 4-isopropyloxycarbonylphenylcarbamoyl group, and 4-methylphenylcarbamoyl group.

Examples of the alkoxycarbonyl group represented by xyloxycarbonyl group, chloroethoxycarbonyl group, 2.2.2-trifluoroethoxycarbonyl group, cyanoethoxycarbonyl group, methoxyethyloxycarbonyl group, acetylethyloxycarbonyl group, acetylaminoethyloxycarbonyl group, methylaminoethyloxy Examples include carbonyl group, dimethylaminoethyloxycarbonyl group, carboxyethyloxycarbonyl group, methoxycarbonylmethyloxycarbonyl group, methylsulfonylpropyloxycarbonyl group, methanesulfonylaminoethyloxycarbonyl group, phenylethoxycarbonyl group, and the like.

Examples of the aryloxycarbonyl group represented by X and Y include phenoxycarbonyl group, 4-nitrophenyloxycarbonyl group, 2-cyanophenyloxycarbonyl group, 4-hydroxyphenyloxycarbonyl group,
4-methoxycarbonylphenyloxycarbonyl group,
Examples include 4-carboxylphenyloxycarbonyl group, 4-aminophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, and 4-methanesulfonylaminophenyloxycarbonyl group.

Examples of the sulfonyl group represented by X and Y include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, t-butylsulfonyl group, octylsulfonyl group, dodecylsulfonyl group,
Examples include phenylsulfonyl group.

As the sulfinyl group represented by can.

Examples of the sulfamoyl group represented by X and Y include methylsulfamoyl group, ethylsulfamoyl group, propylsulfamoyl group, isopropylsulfamoyl group, t-butylsulfamoyl group, octylsulfamoyl group, Examples include dodecylsulfamoyl group and phenylsulfamoyl group.

B1. Examples of the optionally substituted alkyl group represented by B2 include methyl group, ethyl group, propyl group,
Isopropyl group, t-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, 2-phenylethyl group, chloroethyl group, bromoethyl group, chloropropyl group, trifluoroethyl group, hydroxyethyl group, methoxy Ethyl group, isopro and hydroxyethyl group,
Cyanopropyl group, acetylmethyl group, acetylethyl group, benzoyloxymethyl group, acetyloxyethyl group, propionyloxyethyl group, acetylaminoethyl group, propionylaminoethyl group, methylcarbamoylethyl group, methylaminoethyl group, ethylaminoethyl group group, dimethylaminoethyl group, dimethylaminopropyl group, carboxymethyl group, carboxyethyl group, carboxypropyl group, carboxyoctyl group, methoxycarbonylethyl group, ethoxycarbonylethyl group, isopropyloxycarbonylethyl group, butyloxycarbonylmethyl group, Bis(butyloxycarbonyl)methyl group, bis(octyloxycarbonyl)methyl group, bis(methoxycarbonyl)ethyl group, 2.2.2-
trifluoroethoxycarbonylmethyl group, 2-cyanoethoxycarbonylmethyl group, ethoxycarbonylprobyl group, phenoxycarbonylmethyl group, methylsulfonylethyl group, p-toluenesulfonylethyl group, methanesulfonylaminoethyl group, propanesulfonylaminomethyl group, Examples include a butanesulfonylaminomethyl group, a methanesulfonylaminopropyl group, a methylsulfamoylethyl group, a methylaminocarbonylamino group, a phenylethyl group, a cyclohexyl group, a cyclopentyl group, and the like.

Examples of the optionally substituted alkenyl group represented by R1 and R2 include a vinyl group and an allyl group.

Examples of the optionally substituted aryl group represented by R1 and R2 include phenyl group, 4-chlorophenyl group,
4-aminophenyl group, 2-methoxyphenyl group, 4-
Examples include methoxyphenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group, and 4-acetylphenyl group.

Examples of the acyl group represented by R1 and R2 include an acetyl group, a propionyl group, and a benzoyl group.

Examples of the sulfonyl group represented by nl and R2 include methylsulfonyl group, ethylsulfonyl group, hexylsulfonyl group, octylsulfonyl group, phenylsulfonyl group, 4-chlorosulfonyl group, 4-cyanophenylsulfonyl group, etc. .

Examples of the 5- to 6-membered ring formed by combining R1 and R2 include pyrrolidine, piperazine, morpholine, piperidine, and the like.

B3. of general formula CI]. R4 may be the same or different; hydrogen atom, halogen atom, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, optionally substituted alkyl group, carbamoyl group, alphamoyl group, nitro group , a cyano group, a hydroxy group, an alkoxy group, or a mercapto group, and these groups may further have a substituent.

Examples of the halogen atom represented by R3 and R4 include a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and the like.

Examples of the optionally substituted alkyl group represented by R3 and R4 include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, octyl group, t-octyl group, dodecyl group, cyclohexyl group, Examples include -ethylhexyl group, cyclopropyl group, benzyl group, allyl group, vinyl group, trifluoromethyl group, 4-nitrophenylmethyl group, and 4-dimethylaminophenylmethyl group.

Examples of the optionally substituted alkoxy group represented by R3 and R4 include methoxy group, ethoxy group, propyloxy group, isopro-ruoxy group, t-butoxy group, octyloxy group, dodecyloxy group, and cyclohexyloxy group. , methoxyethoxy group, aminoethoxy group, dimethylaminoethoxy group, acetylaminoethoxy group, cyanoethoxy group, methanesulfonylaminoethoxy group,
Acetyloxyethoxy group, dimethylaminocarbonylethoxy group, hydroxyethoxy group, carboxyethoxy group, ethoxycarbonylmethoxy group, di(methoxycarbonylmethyl)aminomethoxy group, acetylethoxy group, dichloroethoxy group, phenylethoxy group, benzyloxy group, 4-dimethylaminobenzyloxy group, phenoxy group, 2.5-di-t-amylphenoxy group, 4
-dimethylaminophenoxy group and the like.

Examples of the optionally substituted mercapto group represented by R3 and R4 include methylmercapto group, ethylmercapto group, propylmercapto group, isopropylmercapto group, t-butylmercapto group, octylmercapto group, dodecylmercapto group, methoxymethyl Examples include mercapto group, aminoethylmercapto group, dimethylaminoethylmercapto group, phenylethylmercapto group, cyanoethylmercapto group, hydroxyethylmercapto group, phenylmercapto group, and aminoethylmercapto group.

Examples of the carbamoyl group represented by the substituent BS and R4 of R3R4 include methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, phenylcarbamoyl group, 4-nitrophenylcarbamoyl group, 4-cyanophenylcarbamoyl group, and 4-methoxyphenyl group. Carbamoyl group, 2
-Nitrophenylcarbamoyl group, 4-aminocarbamoyl group, 2-methoxyphenylcarbamoyl group, 4-methanesulfonylaminophenylcarbamoyl group, 4-propanesulfonylaminophenylcarbamoyl group, 3-
methanesulfonylaminophenylcarbamoyl group, 4-
methoxycarbonylphenylcarbamoyl group, 4-propyloxycarbonylphenylcarbamoyl group, 4-isopropyloxycarbonylphenylcarbamoyl group,
Examples include 4-methylphenylcarbamoyl group.

Examples of the alkoxycarbonyl group represented by R3 and R4 include methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, t-butyloxycarbonyl group, octyloxycarbonyl group, pentadecylcarbonyl group, benzyloxycarbonyl group, and cyclocarbonyl group. xyloxycarbonyl group, chloroethoxycarbonyl group, 2.2.2-trifluoroethoxycarbonyl group, cyanoethoxycarbonyl group, methoxyethyloxycarbonyl group, acetylethyloxycarbonyl group, acetylaminoethyloxycarbonyl group, methylaminoethyloxy carbonyl group, dimethylaminoethyloxycarbonyl group, carboxyethyloxycarbonyl group, methoxycarbonylmethyloxycarbonyl group,
Examples include methylsulfonylpropyloxycarbonyl group, methanesulfonylaminoethyloxycarbonyl group, and phenylethoxycarbonyl group.

Examples of the aryloxycarbonyl group represented by R3 and R4 include phenoxycarbonyl group, 4-nitrophenyloxycarbonyl group, 2-cyanophenyloxycarbonyl group, 4-hydroxyphenyloxycarbonyl group, and 4-methoxycarbonylphenyloxycarbonyl group. , 4-carboxylphenyloxycarbonyl group, 4
Examples include -aminophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, and 4-methanesulfonylaminophenyloxycarbonyl group.

Examples of the sulfamoyl group represented by R3 and R4 include methylsulfamoyl group, ethylsulfamoyl group,
Examples include propylsulfamoyl group, isopropylsulfamoyl group, t-butylsulfamoyl group, octylsulfamoyl group, dodecylsulfamoyl group, and phenylsulfamoyl group.

When the dye represented by the general formula [I] is used as a filter dye or an antihalation dye, any effective amount can be used, but the optical density is 0.05 to 3.
．． Generally, it is applied in an amount of 1 to 8 QQmg per area 1+a2 on the photosensitive material. The addition time may be any step before coating.

The dye according to the invention can be dispersed in the emulsion layer and other hydrophilic colloid layers (interlayer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

■ For example, methanol, ethanol, methylcellosolve, propyl alcohol, acetone, water, and lysine, JP-A-48-9715, U.S. Patent No. 3.756.830
A method of dissolving or dispersing the dye of the present invention in an aqueous solvent such as a halogenated alcohol or a mixed solvent thereof described in the above-mentioned No. 1, and then dissolving or dispersing it in an emulsion layer or a wood-philic colloid layer.

(2) A method of adding and dispersing a solution dissolved in a substantially water-insoluble high-boiling solvent to a hydrophilic colloid solution, as described in US Pat. No. '1fi2,322,027.

Further, at this time, a low boiling point solvent having a boiling point of 30°C to 150°C can also be used.

(2) A method of adding the dye of the present invention to a polymer latex composition filled with a photographic emulsion layer or other hydrophilic colloid layer. These polymer latexes are
, JP 51-59943, JP 53-137131, JP 54-32552, JP 54-107941, JP 55-133465, JP 56-19043, JP 58
-19047, 56-126830, 58-1
No. 49038, US Pat. No. 4.420.555, and the like.

Next, specific examples of compounds used in the present invention will be given, but the present invention is not limited thereto.

I, (: (hcHzc C)12cOOcHsH3
H2(
:H2CG32CH2CN H3CCOH2CH2 CH2CH20COCH
3CH302CH2CCH2C00CH3H1G402
CH2(: C1(2COOC4)19HOH2C
H2CCH2CH20)1 CH3C0N)l HOH2CH2CG)12G
HzOHNCH2CH2CCH2CH2(:N 11BL; 2 Li1i2tiUL; 3tltH
yCs(hC)12CCH2C00C3H7H9C40
2CH2CCH2C00C4)+9HOHzCHzCC
N to H2CH2 and i3 tlsL; 2 L; t12 and P3H17C
602CH2CCHzCOOCaH+yH? C300C
H2CG) I2COOC3Ht General formula [I
] The compound represented by can be easily synthesized according to the method described in US Pat. No. 4,420,555. Typical synthesis examples are listed below, but other compounds can be synthesized in the same way.

Synthesis of Exemplary Compound 5 23.8 g (0.1 mol) of 4-methanesulfonylaminobenzoylacetonitrile synthesized from methylsulfonyl chloride and 4-aminobenzoylacetonitrile according to the method described in U.S. Pat. No. 4,420,555 and 2
34.9 g (0.1 mol) of -formyl-N,N-bis(butyloxycarbonylmethyl)aniline was added to 9210 drops of piperi as a catalyst in 300 mj of acetonitrile, and the mixture was heated under reflux with stirring for about 3 hours. When the mixture was allowed to cool, crystals precipitated, and the yellow crystals were collected by filtration, washed with ether, and then dried. This was recrystallized from acetonitrile to obtain Exemplary Compound 5. Yield 35.8g (62.8%) NMR structure of compound.

Confirmed by IR and FD-MS.

Synthesis of Exemplary Compound 7 28.6 g (0.1 mol) of 4-propanesulfonylaminobenzoylacetonitrile synthesized from propylsulfonyl chloride and 4-aminobenzoylacetonitrile according to the method described in U.S. Pat. No. 4,420.555.
and 2-formyl-N-ethyl-N-(2,2,2-trifluoroethoxycarbonylmethyl)aniline 28.9
g (0.1 mol) was added to 300 mj' of acetonitrile with 10 drops of piperidine as a catalyst, and the mixture was heated under reflux with stirring for about 3 hours. When the mixture was allowed to cool, crystals precipitated, and the yellow crystals were collected by filtration, washed with ether, and then dried. This was recrystallized from acetonitrile to obtain Exemplary Compound 7.

Yield 36.1g (67.1%) The structure of the compound was determined by NMR,
Confirmed by IR and FD-MS.

(Hereinafter, blank spaces) Silver halide emulsions used in the light-sensitive material of the present invention include:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods, and can be 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 dispersion (latex) of a water-insoluble or silver-soluble synthetic polymer.

When the compound of the present invention is used in a color photographic light-sensitive material, a coupler is used in the emulsion layer.

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

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

A formalin scavenger-1 fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, 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 terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain an image using the light-sensitive material of the present invention, commonly known black-and-white photographic processing or color photographic processing can be performed after exposure.

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

In all of the following Examples, the amount added in the silver halide photographic light-sensitive material is shown per 1 m2 unless otherwise specified. Silver halide and colloidal silver are shown in terms of silver.

[Example 1] Sample I of a multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) First layer; antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Coating amount of silver: 0.2 g/m2 Second layer; Intermediate layer (1, L,) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1)
Average particle size (r) 0.4G, um%Ag! 6 mol%
Monodisperse emulsion (emulsion I) consisting of AgBrI containing... silver coating amount 1.9 g/m'' sensitizing dye I.
...5 X 10-' moles of sensitizing dye per mole of silver! !・
... 0.8 x 1G-' mol cyan coupler (C-1) per 1 mol of silver... 0.085 mol colored cyan coupler (cc-1... per 1 mol of silver) 0.005 mol DIR compound (D-1)... 0.0015 mol DIR compound (D-2)... 0.002 mol based on 1 mol silver Fourth layer; High sensitivity red-sensitive silver halide emulsion layer (RH-1)
Average particle size (r) 0.8Gm, AgI 6.0
Monodispersed emulsion (emulsion II) consisting of AgBrI containing mol % - Silver coating amount 1.4 g/m" Sensitizing dye I... 2.5 X to' moles of sensitizing dye per 1 mole of silver I
I... 0.8 x 10-' mol cyan coupler (C-2) for 1 mole of silver... 0.007 mol cyan coupler (C-3) for 1 mol of silver... Silver 1 Colored cyan coupler (cc-1): 0.0015 mol per mol of silver DIR compound (D-2): 0.001 mol per mol of silver 5th layer; Middle layer (1, L,) Same as the second layer, gelatin layer.

6th layer; low sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion I: Silver coating amount: 1.6 g/m2 Sensitizing dye III: 2.0 g/m2 per mole of silver. OXl0-'molar sensitizing dye■...
- 1.0% per mole of silver. OXl0-'mol magenta coupler (M-1)... 0.090 mol per mol of silver Colored magenta coupler (CM()... 0.004 mol DIR compound (D-1) per mol of silver )... 0.0010 mol per mol of silver DIR compound (D-3)... 0.003 Q mol per mol of silver 7th layer; Highly sensitive green-sensitive silver halide emulsion layer (GH- 1)
emulsion! ! ... Coated silver amount 1, 4 g/m2 Sensitizing dye II
I... 1.2 x 10-' mol sensitizing dye ■ per 1 mol silver
...0.8 x 10-' mole magenta coupler (M-1) per mole of silver...0.015 mole colored magenta coupler (CM-1) per mole of silver...silver 1 0.002 mol to mol DIR compound (D-3)... o, ooto mol to 1 mol of silver 8th layer; Yellow filter layer (YC-1) Yellow colloidal silver and 2.5-di- A gelatin layer comprising an emulsified dispersion of t-octylhydroquinone. Silver coating amount: 0.1 g/m” 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Ag containing 6 mol% AgI with an average particle size of 0.48 μm
Silver coating amount for monodisperse emulsion (emulsion 1) consisting of BrI: 0.9 g/m" Sensitizing dye V.
... 1.3 x 10-' moles per mole of silver Yellow coupler (Y-1) ... 0.29 moles per mole of silver 10th layer; Highly sensitive blue-sensitive emulsion layer (B) I -1) Monodisperse emulsion (emulsion ■) consisting of AgBr1 with an average grain size of 0.8 μm and containing 7 mol% of AgI...Silver coating amount: 0.5 g/m2 Sensitizing dye V.
... 1 mole of silver. OX 10-3 mol Yellow coupler (Y-1)... O, Oa mol per mol of silver DIR compound (D-2)... 0.0030 mol per mol of silver 11th layer; 1 protective layer (Pro-1) Silver iodobromide (^gl 1 mol% average grain size 0.07 μn+)
Silver coating amount: 0.5 g/m" Gelatin layer containing ultraviolet absorbers UV-1 and UV-2.

12th layer; second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5μ■) In addition to the above composition, each layer also contains a gelatin hardening agent (H-1
) and (H-2) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide sensitizing dye II, anhydro-9-ethyl-3,3' −
Di(3-sulfopropyl)-4,5,4', 5'-
Dibenzothiacarbocyanine hydroxide sensitizing dye■! ! ;Anhydro-5,5'-diphenyl-
9-Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■; Anhydro 9-ethyl-3,3'-di(3-sulfopropyl)-5,6,5' , 6'-dibenzoxacarbocyanine hydroxide ms color iv; anhydro-3,3'-di(3-sulfopropyl)-4,S-benzo-5'-methoxythiacyanine hydroxide (blank below) ph: phenyl Group M-I CM-1 V-2 Next, in place of yellow colloidal silver in the 8th layer, Exemplary Compound 5
was dissolved in tricresyl phosphate and ethyl acetate,
Samples except that the dispersion emulsified with gelatin was applied
A multilayer photosensitive material was prepared in the same manner as described above, and this was designated as Sample 11. However, 20 mR of tricresyl phosphate was used for 10 g of Exemplified Compound 5, so that the coating amount of Exemplified Compound 1 was 0.18 g/m2.

Also, instead of Exemplified Compound 5 in the 8th layer of Sample II, Exemplified Compound 7.1G, 11.17.35 and Comparative Compound A,
Samples prepared in the same manner as Sample II except that B and C were used were each subjected to 111. IV, V, ■, ■, ■, ■.

I set it as X.

In addition, a sample similar to sample (2) was prepared except that yellow colloidal silver was not added to the eighth layer, and this was used as a sample blade.

L113:) UiNtl Comparative Compound C υ After sample 1-X was exposed to wedge light, the development treatment described below was performed, and the sensitivity and fog of the green-sensitive emulsion layer of each sample were measured.

In addition, in order to evaluate the decolorizing property of the dye, 4-amino-3-methyl-N-ethyl-N-
After processing in the same manner except that (β-hydroxyethyl)-aniline sulfate was removed, the difference (ΔD'a+in) between each of the yellow densities of Samples 1 to X and the yellow density of the sample ℃ was measured.

The results are shown in Table 1.

Processing process (38℃) Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
6 minutes 30 seconds washing with water 3 minutes 15 minutes
Second stabilization, 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-hydroxyethyl)-aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2. 0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid
Trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 11.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 mA Add water to bring the temperature to 1°C, and use ammonia water. Adjust pH = 6.0.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 f
t and adjusted to pi (= 6.0) using acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 m
p! Konidax (manufactured by Konica) 7.5m
Add A+water to make 1ft.

(Margin below) From the results in Table 1 below, the relative sensitivity of the green-sensitive emulsion layer of the sample containing the dye compound of the present invention is higher than that of the comparative yellow colloidal silver and the sample containing the comparative dye compound. It can be seen that the degree of fogging is low. In addition, the samples containing comparative dye compounds were not sufficient in terms of decolorizing properties.

Example 2 10 g of Exemplified Compound 6 according to the present invention, 20 ml of tricresyl phosphate, and 100 mJ of ethyl acetate are dissolved. Next, this was mixed with 500 g of a 10% gelatin solution containing a surfactant, and after emulsifying and dispersing it, a gelatin hardening agent was added, and the mixture was coated on an acetyl cellulose film support and dried to obtain Sample XX. Exemplified Compound 8.9.11.14°1B instead of Exemplified Compound 2. 22.23.27
．． Samples were prepared in the same manner using 37.40 and the comparative compound A1B%C, and each sample was XX[~XXX
It was set as I.

Each of these samples was immersed in a developer having the composition shown below at 25° C. for 1 minute, washed with water for 20 seconds, and then dried.

(Composition of developer) Metol 3.0 g Sodium sulfite (anhydrous) 45.0 g Hydroquinone 12.0 g Sodium carbonate (monohydrate) ao, o g Potassium bromide 2.0 g Add water and i
Let it be j2.

The visible spectrum of each sample was measured before and after immersion in the developer, and the decolorization rate was determined from the difference in absorbance at the maximum absorption wavelength. The results are shown in Table 2 below.

(El is the absorbance before being immersed in the developer, and El is the absorbance after being immersed in the developer.) (The following is a blank space) Table 2 As is clear from the results in Table 2, the dye compound of the present invention is superior to the comparative compound. It was found that it exhibited better decolorizing properties compared to

[Effects of the Invention] As in the present invention, the silver halide photographic material containing the compound represented by the general formula [I] has excellent decolorization and dissolution properties during the photographic processing step, and also The color does not recover even after storage over time. Furthermore, it has excellent effects on photosensitive silver halide emulsions, such as not affecting photographic properties such as fog and desensitization.

Claims (1)

[Claims] A silver halide photographic material containing a compound represented by the general formula [I]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, X and Y represent electron-withdrawing groups, and these X, Y
may be the same or different. R^1 and R^2 represent a hydrogen atom, an optionally substituted alkyl group, alkenyl group, aryl group, acyl group, or sulfonyl group, and these R^1 and R^2 may be the same. May be different. Moreover, R^1 and R^2 may be combined to form a 5- to 6-membered ring. R^3 and R^4 are hydrogen atoms, halogen atoms, optionally substituted alkyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups, nitro groups, cyano groups, hydroxy groups , represents an alkoxy group or a mercapto group, and these R^3 and R^4 may be the same or different. ]