JPH01179041A - 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 R<1> and R<2> is an electron withdrawing group, R<1> and R<2> may be different from each other, each of R<3> and R<4> is H, halogen, optionally substd. alkyl, carboxyl, etc., R<3> and R<4> may be different from each other, X is O or S, R<5> is optionally substd. alkyl, alkenyl or aryl and (n) is an integer of 1-3]. 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] Generally, in silver halide photographic materials (hereinafter referred to as "photosensitive materials"), for the purpose of adjusting the sensitivity of light absorption filters, antihalation, antiirradiation dyes, or photosensitive emulsions, It is well known that dyes are included in the constituent layers of photosensitive materials in order to absorb light of a specific wavelength, and therefore, it has been conventionally practiced to color hydrophilic colloid layers with the above dyes. .

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.

[Objective of the Invention] Therefore, the first object of the present invention is to provide a dye that has excellent decolorization and dissolution properties during photographic processing, does not recolor during subsequent storage over time, and has excellent facilitation through 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 [1F [wherein, R1 and R2 represent electron-withdrawing groups, R1 and R2
may be the same or different. Also ns.

R4 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, ureido group, carbamoyl group, sulfamoyl group, nitro group, cyano group, hydroxy group , at least one of the optionally substituted amino groups representing an alkoxy group or a mercapto group is substituted at the meta position of the benzene nucleus. R
3 and R4 may be the same or different. X represents an oxygen atom or a sulfur atom, and R5 represents an optionally substituted alkyl group, alkenyl group or aryl group.

n represents an integer of 1 to 3. ] The present invention will be explained in more detail below.

In general formula [1], 11. The electron-withdrawing group represented by R2 is σ, which is shown in "Structure-Activity Relationship of Drugs - Guidelines for Drug Design and Mechanism Research" Structure-Activity Relationship Conference (Chemistry Special Edition No. 122, Nankodo) P95, It means something whose value is positive. More specifically, al, R
2 may be the same or different and represent a cyano group, an acyl group, a carbamoyl group, an alkoxycarbonyl group, an ary-oxycarbonyl group, a sulfonyl group, a sulfinyl group, and an alphamoyl group.

Examples of the acyl group represented by RI and R2 include an acetyl group, a propionyl group, a cyclohexylcarbonyl group,
benzoyl group, 4-nitrobenzoyl group, 4-cyanobenzoyl group, 4-aminobenzoyl group, 2-nitrobenzoyl group, 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 -Propanesulfonylaminobenzoyl group, 3-methanesulfonylaminobenzoyl group, 3-propanesulfonylaminobenzoyl group, 4-pentanesulfonylaminobenzoyl group, 4
-Octanesulfonylaminobenzoyl group, 4-dodecanesulfonylaminobenzoyl group, 4-methanesulfinylaminobenzoyl group, 4-propanesulfinylaminobenzoyl group, 2-methanesulfonylaminobenzoyl group, dimethylaminosulfonylaminobenzoyl group, 4-methoxy carbonylaminobenzoyl group, 4
-Ethoxycarbonylaminobenzoyl group, 4-propyloxycarbonylaminobenzoyl group, 4-octyloxycarbonylaminobenzoyl group, 3-methoxycarbonylaminobenzoyl group, and the like.

Examples of the carbamoyl group represented by R1 and R2 include a methylcarbamoyl group, an ethylcarbamoyl group, a propylcarbamoyl group, a phenylcarbamoyl group, a 4-nitrophenylcarbazoyl group, a 4-cyanophenylcarbamoyl group, and a 4-methoxyphenylcarbamoyl group. , 2-
Nitrophenylcarbamoyl group, 4-aminocarbamoyl group, 2-methoxyphenylcarbamoyl group, 4-methanesulfonylaminophenylcarbamoyl group, 4-propanesulfonylaminophenylcarbamoyl group, 3-methanesulfonylaminophenylcarbamoyl group, 4-methoxycarbonylphenyl group Carbamoyl group, 4-propyloxycarbonylphenylcarbamoyl group, 4-isopropyloxycarbonylphenylcarbamoyl group, 4
-methylphenylcarbamoyl group and the like.

Examples of the alkoxycarbonyl group represented by nl and R2 include methoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl group, t-butyloxycarbonyl group, octyloxycarbonyl group, pentadecylcarbonyl group, benzyloxycarbonyl group, cyclohexyloxy Carbonyl group, chloroethoxycarbonyl group, 2.2.2-trifluoroethoxycarbonyl group, cyanoethoxycarbonyl group, methoxyethyloxycarbonyl group, acetylethyloxycarbonyl group, acetylaminoethyloxycarbonyl group, methylaminoethyloxycarbonyl group , dimethylaminoethyloxycarbonyl group, carboxyethyloxycarbonyl group, methoxycarbonylmethyloxycarbonyl group,
Examples include methylsulfonylpropyloxycarbonyl group, methanesulfonylaminoethyloxycarbonyl group, and phenylethoxycarbonyl group.

Examples of the aryloxycarbonyl group represented by R1 and R2 include phenoxycarbonyl group, 4-nitrophenyloxygalbonyl group, 2-cyanophenyloxycarbonyl group, 4-hydroxyphenyloxycarbonyl group, and 4-methoxycarbonylphenyl group. Examples include oxycarbonyl group, 4-carboxylphenyloxycarbonyl group, 4-aminophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, and 4-methanesulfonylaminophenyloxycarbonyl group.

Examples of the sulfonyl group represented by ttl and R2 include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, t-butylsulfonyl group, octylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, etc. can.

Examples of the sulfinyl group represented by ul and R2 include methylsulfinyl group, ethylsulfinyl group, propylsulfenyl group, isopropylsulfinyl group, t-butylsulfinyl group, octylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc. can.

Examples of the sulfamoyl group represented by R1 and R2 include methylsulfamoyl group, ethylsulfamoyl group,
Examples include propylsulfamoyl group, isopropylsulfamoyl group, t-butylsulfamoyl group, octylsulfamoyl group, dodecylsulfamoyl group, phenylsulfamoyl group, and amoyl group.

R3 and 14 in the general formula [II may be the same or different, hydrogen atom, halogen atom, carboxyl group,
Alkoxycarbonyl group, aryloxycarbonyl group, optionally substituted alkyl group, optionally substituted amino group, ureido group, carbamoyl group, alphamoyl group, nitro group, cyano group, hydroxy group, alkoxy group, mercapto represents a 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 R1 and R4 include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, t-butoxy group, octyloxy group, dodecyloxy group, 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 ureido group substituted at the ortho and/or meta positions of the benzene nucleus represented by R3 and R4 include a methylureido group, an ethylureido group, a propylureido group,
Examples include isopropylureido group, 1-butylfreido group, phenylureido group, and benzylureido group.

The alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, and sulfamoyl group represented by R3 and R4 are each 11. Same as R2.

The optionally substituted amino group substituted at the meta-position of the benzene nucleus represented by R3 and R4 is represented by the general formula [II
].

General formula [II] In the formula, R@ and R'l may be the same or different and represent a hydrogen atom, an optionally substituted alkyl group, an alkenyl group, an aryl group, and a sulfonyl group, and R6 and R7 may be combined to form a 5- to 6-membered ring.

311, R? Examples of the optionally substituted alkyl group represented by include methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, dodecyl group, pentadecyl group, eicosyl group, cyclopropyl group,
Cyclohexyl group, chloroethyl group, bromoethyl group,
Fluorinated ethyl group, 2.2-dichloroethyl group, hydroxyethyl group, hydroxybutyl group, cyanoethyl group, cyanopropyl group, methoxyethyl group, ethoxymethyl group, butoxyethyl group, isopropyloxyethyl group, acetylmethyl group, acetyl group Ethyl group, benzoylmethyl group, acetyloxymethyl group, acetyloxyethyl group, butyryloxyethyl group, t-butyryloxymethyl group, benzoyloxyethyl group, carboxylmethyl group, carboxylethyl group, carboxyl octyl group, acetylamino Ethyl group, propionylaminoethyl group,
Methylcarbamoylethyl group, methylaminoethyl group,
Ethylaminomethyl group, dimethylaminoethyl group, octylaminomethyl group, dimethylaminobutyl group, dimethylaminooctyl group, dibutylaminobutyl group, hydroxymethyl group, hydroxyethyl group, hydroxyhexyl group, hydroxydodecyl group, methoxyethyl group, Ethoxymethyl group, prooxymethyl group, butoxymethyl group, methoxycarbonylmethyl group, ethoxycarbonylethyl group, butoxycarbonylethyl group, octyloxymethyl group, bis(methoxycarbonyl)methyl group,
Bis(ethoxycarbonyl)methyl group, 2,2.2-”
trifluoroethoxycarbonylmethyl group, methylsulfonylmethoxycarbonylmethyl group, 2-methylsulfonylethoxycarbonylmethyl group, 2-cyanoethoxycarbonylethyl group, ethoxycarbonylpropyl group,
Octyloxycarbonylbutyl group, phenoxycarbonylmethyl group, methylsulfonylmethyl group, methylsulfonylethyl group, methanesulfonylaminoethyl group, methanesulfonylaminobutyl group, methylsulfamoylethyl group, methylaminocarbonylaminoethyl group, phenylpropyl group etc.

Examples of the optionally substituted alkenyl group represented by R6 and R7 include a vinyl group and an allyl group.

R6, R? Examples of the optionally substituted amino group represented by include amino group, dimethylamino group, N-ethyl-N-propyloxycarbonylmethylamino group, bis(dimethyloxycarbonylmethyl)amino group, bis(dibutyloxycarbonyl) ethyl) amino group, bis(
hydroxyethyl)amino group, N-(2,2,2-trifluoroethyloxycarbonylmethyl)-N-methylamino group, N-methyl-N-cyanoethylamino group,
N-methoxyethyl-N-methylamino group, N-methylsulfonylethyl-N-dithylamino group, N-(2-chloroethyl)-N-methyloxycarbonylmethylamino group, bis(isopropyloxycarbonylmethyl)amino group, Includes N-dodecyloxycarbonylmethyl-N-methylamino group and the like.

R6, R? Examples of the optionally substituted aryl group represented by include phenyl group, 3-chlorophenyl group,
z, 5-dichlorophenyl group, 4-cyanophenyl group,
4-aminophenyl group, 2-methoxyphenyl group, 4-
Examples include methoxyphenyl group and 4-acetylphenyl group.

Examples of the sulfonyl group represented by R6 and R7 include a methylsulfonyl group, an ethylsulfonyl group, a brobylsulfonyl group, an octylsulfonyl group, a dodecylsulfonyl group, a phenylsulfonyl group, a 4-dodecyloxyphenylsulfonyl group, and a 4-cyanosulfonyl group. Examples include phenylsulfonyl group and 4-acetylphenylsulfonyl group.

Examples of the 5- to 6-membered ring formed by combining R6 and R7 include heterocycles such as pyrrolidine; piperidine, morpholine, and piperazine.

R11 in general formula [11] represents an optionally substituted alkyl group, alkenyl group, or aryl group.

Examples of the optionally substituted alkyl group represented by R5 include methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, octyl group, dodecyl group, cyclohexyl group, methoxyethyl group, aminoethyl group, Dimethylaminoethyl group, acetylaminoethyl group, dimethylaminocarbonylethyl group, hydroxyethyl group,
Carboxyethyl group, ethoxycarbonylethyl group, di(methoxycarbonylmethyl)aminomethyl group, acetylethyl group, dichloroethyl group, phenylethyl group, 4
-dimethoxyethyl group, 2-methoxyethyl group, etc.

Examples of the optionally substituted alkenyl group represented by R8 include a vinyl group and an allyl group.

Examples of the optionally substituted aryl group represented by R' include phenyl group, naphthyl group, 4-nitrophenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 4-dimethylaminophenyl group, 4- Examples include a cyanophenyl group and a 2,3-di-t-amylphenyl group.

When using the dye represented by the general formula [1] as a filter dye or 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 800 mg per 1++'' area on the photosensitive material.It may be added at any step before coating.

The dye according to the invention can be dispersed in the emulsion layer and other wood-philic 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. 3,756,8
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 No. 30, and then dissolving or dispersing it in an emulsion layer or a hydrophilic colloid layer.

(2) A method in which a liquid dissolved in a substantially water-insoluble high-boiling solvent as described in U.S. Pat. No. 2,322,027 is added to and dispersed in a wood-philic colloid solution.

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 5B-19043, JP 56
-19047, 56-126830, 58-1
No. 49038, US Pat. No. 4,420,555, etc.

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

(Left below) N \ CH2C00CJs (t) \ CthCONHCJs H21; H2UH 42,
CF+3/ The compound represented by the general formula [I] shown in the above example 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 Example-1 (Synthesis of Exemplified Compound 5) 3.8 g of 4-methanesulfonylaminobenzoylacetonitrile 2' synthesized from methanesulfonyl chloride and 4-aminobenzoylacetonitrile according to the method described in U.S. Patent No. 4,420,555. (0.1 mole)
and 2.4.6-trimethoxybenzaldehyde 19.6
g (0.1 mol) was dissolved in 300 ml of acetonitrile to which 10 drops of piperidine was added as a catalyst, and the mixture was heated under reflux with stirring for about 3 hours.

When allowed to cool, crystals precipitated and were collected by filtration, washed with ether, and dried. The desired product was obtained by recrystallizing this with acetonitrile.

Yield: 26.3g Yield: 63.2% The structure of the compound was confirmed by NMR, IR, and FD-MS.

Synthesis Example 2 (Synthesis of Compound Example 19) 20.2 g (0.1 mol) of 4-acetylaminobenzoylacetonitrile synthesized from acetyl chloride and 4-aminobenzoylacetonitrile according to the method described in U.S. Pat. No. 4,420,555. ) and 19.6 g (0.1 mol) of 2.4.6-trimethoxybenzaldehyde were added to 10 drops of piperidine as a catalyst in 30 hj of acetonitrile, and the mixture was heated under reflux with stirring for about 3 hours.

When allowed to cool, crystals precipitated and were collected by filtration, washed with ether, and dried.

This was recrystallized from acetonitrile to obtain the desired product.

Yield: 23.8g Yield: 62.6% The structure of the compound was confirmed by NMR, 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 that are washed out or bleached from the light-sensitive material 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 the examples below, the amount added in the silver halide photographic light-sensitive material is per 112 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

[Example 1] On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to prepare a multilayer color photographic element sample (2).

Sample-1 (comparison) First layer; antihalation layer () Ic-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') 0.40 μ■, Agl 6 mol%
A monodisperse emulsion (emulsion...silver coating amount: 1.9 g/■2 sensitizing dyes) consisting of AgBrI containing
- 5 x 1 G-' moles of sensitizing dye II per mole of silver
--- o, a x to-' mol cyan coupler (C-1) per mol of silver Colored cyan coupler (CC-1) --- silver 1 o, oos mole per mole DIR compound (D-1) -... 0.0015 mole per 1 mole of silver D, IR compound (D-2) -... 0.002 per mole of silver Mol 4th layer; high sensitivity red-sensitive silver halide emulsion layer (RH-1)
Monodisperse emulsion (emulsion II) consisting of 8 gBrl containing average grain size (F) 0.81 Jm and Agl 8.0 mol%... Silver coating amount 1.4 g/m' Sensitizing dye I... Silver 1 2.5 X 10-' moles per mole sensitizing dye 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 0.027 mol per mole Colored cyan coupler (C (nee 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 2nd layer, gelatin layer.

6th layer; low sensitivity green-sensitive silver halide emulsion layer (GL-1)
Emulsion I... Silver coating amount 1.6 g/m'' Sensitizing dye ■... 2.OX 10-' mol sensitizing dye ■ per 1 mole of silver
... 1.0 x 10-mol magenta coupler (M-1) per mol of silver... 0.090 mol per mol of silver Colored magenta coupler (CM-1)... per mol of silver 0.004 mol DIR compound (D-1)... 0.0010 mol to 1 mol of silver DIR compound (D-3)... 0.0030 mol to 1 mol of silver 7th layer; High sensitivity Green-sensitive silver halide emulsion layer (G) l-1
) Emulsion ■...Amount of coated silver 1.4 g/m2 Sensitizing dye III... 1.2 Xl0-' mol per mol of silver Sensitizing dye ■...
... o, a x to-' moles per mole of silver Magenta coupler (M-1)... 0.015 moles per mole of silver Colored magenta coupler (CM-1)...-1 mole 0.002 mol per mol of DIR compound (D-3)... 0.0010 mol per mol of silver 8th layer; Yellow filter layer (YC-1) Yellow colloidal silver and 2.5-di-t - gelatin layer containing an emulsified dispersion of octylhydroquinone, silver coating amount 0.1 g/m' 9th layer; low sensitivity blue-sensitive silver halide emulsion layer (BL-1)
Average particle size 0.48μm, 8gB containing 6mol% AgI
Monodispersed emulsion (emulsion III) consisting of rl...Silver coverage: 0.9 g/m'' Sensitizing dye V...1.3 Xl0-' mol per 1 mol of silver Yellow coupler (Y-1). ... 0.29 mol per silver 10th layer; high sensitivity blue-sensitive emulsion layer (BH-1) average grain size 0
．． 8. Monodisperse emulsion (emulsion ■) consisting of AgBrI containing u+n%AgI 7 mol%...silver coating amount 0.5g/m' sensitizing dye V.
... 1.0 Xl0-' mol per mol of silver Yellow coupler (V-t)... 0.08 mol per mol of silver DIR compound (D-2)... per mol of silver 0.0030 mol Eleventh layer; First protective layer (Pro-1) Silver iodobromide (AgI 1 mol % average particle diameter 0.07 μm) Silver coating amount 0.5 g/m' Ultraviolet absorber tlV-1, Gelatin layer containing UV-2.

12th layer; Second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (diameter 1.5 μm) In addition to the above composition, each layer contains a gelatin hardening agent () l-
1) and ()l-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,S,4',S'-dibenzothiacarbocyanine hydroxide dye m: Anhydro5.5'-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 sensitizing dye V; anhydro-3,3'-di(3-sulfopropyl)-4,,5-benzo-5'-methoxythiacyanine hydroxide (hereinafter blank) C- 3 -I M-1 V-2 ph: Phenyl group Next, instead of yellow colloidal silver in the 8th layer, Exemplary Compound 1
was dissolved in tricresyl phosphate and ethyl acetate,
Sample I except that the emulsified dispersion with gelatin was applied.
A multilayer photosensitive material was prepared in the same manner as described above, and this was designated as Sample II. However, 20 ml of tricresyl phosphate was used for 10 g of Exemplified Compound 1, so that the coating amount of Exemplified Compound 1 was 0.18 g/m''.

Also, in place of Exemplified Compound 1 in the eighth layer of Sample II, Exemplified Compound 5. 6.8.10.24.31.38, 37.3
Samples prepared in the same manner as sample II except that 9 and comparative compounds A, B, and C were used were m, IT, V, and V, respectively.
l.

Vll, Vll, IX, X, X I, Xl
1, X1ll and XIV.

Further, a sample similar to Sample I was prepared except that yellow colloidal silver was not added to the 8th layer, and this sample was designated as sample ℃.

υ After sample I-X was exposed to wedge light, it was subjected to the development treatment described below, and the sensitivity and fog of the green-sensitive emulsion layer in each test 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 (ΔDBmin) between each yellow density of samples I-X and the yellow density of sample °C was measured.

The results are shown in Table 1.

Processing process (38℃) Color development 3 minutes 15 minutes 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 4.75g anhydrous sodium sulfite 4.25g hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5 g Sodium bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.5g potassium hydroxide 1.0g Add water to prepare IA.

(Bleach solution) Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide tso,o g Glacial acetic acid 10. Add Omj water to 1 ft and adjust pH to 6.0 using aqueous ammonia.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 f
t, and adjust pl = a, o using acetic acid.

(Stabilizer) Formalin (37% aqueous solution) 1.5 m
J Konidax (manufactured by Konica)? , St.J.
! Add water and make 1 cup.

(Left below) The results in Table 1 show that the samples containing the dye compound of the present invention have a higher relative sensitivity of the green-sensitive emulsion layer than the comparative yellow colloidal silver and the sample containing the comparative dye compound, and have less fog. It can be seen that the degree 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 2 according to the present invention, )-Liclesyl phosphate 20a+1. Dissolve in ethyl acetate. Next, this was mixed with 500 g of 10% gelatin solution containing a surfactant, and after emulsifying and dispersing it, a gelatin hardening agent was added, and it was coated on an acetyl cellulose film support and dried to obtain Sample XX. Exemplified Compounds 4, 7, 9.12°14, 15.19.
Samples were prepared in the same manner using No. 20, 22, 23, 25.2B, 32, 311.41 and the comparative compounds A, B, and C, and the temperature was set at x°C to xxx■, respectively.

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 (1 water place) ao, o g Potassium bromide 2.0 g Add water to make ill .

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.

Decolorization rate = gtNie → 1Oo (%) (El is the absorbance before immersion in the developer, and E2 is the absorbance after immersion in the developer.) (Left below in the margin) Table 2 As is clear from the results in Table 2. Furthermore, it was found that the dye compound of the present invention exhibits better decolorizing properties than the comparative compounds.

[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, R^1 and R^2 represent electron-withdrawing groups, and R^1
and R^2 may be the same or different. Also R
^3 and R^4 are hydrogen atoms, halogen atoms, optionally substituted alkyl groups, carboxyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, amino groups,
Represents a ureido group, carbamoyl group, alphamole group, nitro group, cyano group, hydroxy group, alkoxy group or mercapto group. At least one of the above optionally substituted amino groups is substituted at the meta position of the benzene nucleus. R^3 and R^4 may be the same or different. X represents an oxygen atom or a sulfur atom, and R^5 represents an optionally substituted alkyl group, alkenyl group, or aryl group. n represents an integer of 1 to 3. ]