JPS61251849A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce color stain by incorporating a specified color stain inhibitor. CONSTITUTION:At least one kind of color stain inhibitor represented by formula 1 (where X is hydroxyl or sulfonamido, Y is sulfonamido, acylamino, cyano or the like, and Z is H, alkyl, a heterocyclic group or the like) is incorporated. A compound represented by formula 1-1 may be used as the color stain inhibitor. When the color stain inhibitor having high efficiency is used, color stain can be reduced without causing color mixing, and a silver halide photographic sensitive material having superior raw stock preservability can be obtd. in the form of a thin film.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photograph containing a novel color stain inhibitor capable of preventing color stains that are disadvantageous in photography. It relates to photosensitive materials.

[Prior Art and Problems] As is well known, in subtractive color photography, oxidation products of a color developing agent are produced when an aromatic primary amine color developing agent reduces exposed silver halide grains. Dye images are formed by oxidative coupling of yellow, cyan, and magenta dye-forming couplers in a silver halide emulsion. At this time, it is known that the oxidation product of the color developing agent that has migrated to the adjacent image forming layer by diffusion reacts with the coupler in the adjacent layer to form a dye that is undesirable photographically, which is the so-called color staining phenomenon.

When such color contamination occurs between layers of the same light-sensitive silver halide emulsion, it causes variations in sensitometry or deterioration of graininess and sharpness. Furthermore, if the above color contamination occurs between silver halide emulsion layers with different photosensitivity,
In addition to these, the use of different types of couplers to develop colors has negative effects such as a decrease in color reproducibility.

On the other hand, fog in silver halide emulsions and fog caused by air oxidation are also known as color stains, and color stain preventive agents are required in zero-color stain preventive agents, which are essential technologies for improving photographic performance. The basic properties are (a
) It has a fast reaction rate and has the ability to efficiently remove the oxidized form of the color developing agent, (b) It remains substantially colorless even after reacting with the oxidized form of the color developing agent, and (C) It is stably exposed to light. (d) It can be contained in the material and does not affect the emulsion, and (d) it does not adversely affect the storage stability of the dye image.

So, let's look at conventional color stain inhibitors.

The following techniques are known.

(a) Alkylhydroquinones; For example, the use of monolinear alkylhydroquinone is described in US Pat. Patent No. 3,700.453, West German Patent Publication No. 2,149,789, Japanese Patent Application Publication No. 156438/1983
No. 49-106329, etc.

On the other hand, regarding dilinear alkylhydroquinone, US Pat.
British Patent No. 752,148, British Patent No. 1,088,208,
"Chemical □Abstract J Magazine Vol. 58, 838
7h, etc., and for di-branched alkylhydroquinones, see U.S. Pat.
No. 300, British Patent No. 1,088,208, the above-mentioned "Chemical Abstracts" magazine, JP-A-50-158438, JP-A-50-21249, JP-B No. 56-40818, etc.

In addition, regarding the use of alkylhydroquinone as a color stain prevention agent, see British Patent No. 558.258, British Patent No. 557,750, British Patent No. 557,802, British Patent No. 73 f.
, No. 301, U.S. Patent No. 2,3313.327, No. 2
, No. 403,721, No. 3.582.333, West German Patent Publication No. 2,505,018, Special Publication No. 1983-40816
There is a description in the issue etc.

These alkylhydroquinones have a slow reaction rate and must be used in large quantities, which poses a major constraint in the design of silver halide photographic materials. Furthermore, the compound itself is unstable and has the disadvantage that it tends to form a quinone form over time.

(b) Gallic acids: For example, JP-A No. 59-9657, JP-A No. 59-133544, JP-A No. 5B-156932, JP-A No. 5
It is described in No. 8-152235, etc.

Although these gallic acids have a faster reaction rate than the alkylhydroquinones mentioned above, they have the disadvantage of having an adverse effect on biophotonic materials (photosensitive materials before exposure).

(C) Sulfonamide phenol, sulfonamide naphthol: For example, JP-A-59-5247, JP-A-59-1
No. 92246, No. 59-192247, No. 59-19
No. 5238, No. 59-195239, No. 59-202
No. 465, No. 59-204039, No. 59-2040
There is a description in No. 40 etc.

Although these sulfonamide phenols and sulfonamide naphthols have a faster reaction rate and better storage stability than the above (a) and (b), they are still not sufficient and may cause color development in highly active developers. Because it has more color due to oxidation, it may actually increase color staining.

Therefore, the object of the present invention is, firstly, to provide a silver halide photographic material with reduced color staining by containing a novel color stain preventive agent that can efficiently remove the undesirable oxidized form of a color developing agent. Second, the present invention provides a silver halide photographic light-sensitive material with excellent storage stability as an ecological photosensitive material (photosensitive material before exposure) by containing a novel color stain inhibitor with excellent storage stability. Thirdly, by using a color stain preventive agent that remains substantially colorless even after development processing, it is possible to provide a silver halide photographic material that eliminates color mixing caused by the color stain preventive agent. Fourthly, it is an object of the present invention to provide a silver halide photographic light-sensitive material which is made into a thin film by using a highly efficient color stain inhibitor.

[Means for Solving the Problems] The silver halide photographic light-sensitive material of the present invention which achieves the above object has a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support. In the silver photographic light-sensitive material, at least one of the photographic constituent layers contains at least one color stain preventive agent represented by the following general formula (1).
It is characterized by containing seeds.

General formula (1) In the formula, X represents a hydroxyl group or a sulfonamide group, and Y represents a sulfonamide group, an acylamino group, an anilino group, a sulfamoyl group, a carbamoyl group, a ureido group, a carboxy group, a hydroxyl group, an ester group, an alkyl group. Z represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or a heterocyclic group.

Here, the photographic constituent layers refer to all the wood-philic colloid layers involved in image formation.
These include a subbing layer, an intermediate layer (a mere intermediate layer, a single filter layer, an ultraviolet absorbing layer, an anti-halation layer, etc.), a protective layer, and the like.

Note that Japanese Patent Publication No. 56-44422 describes a 2-equivalent magenta coupler of 4-sulfonamido-5-pyrazolone, but this invention is completely different from the present invention in which one of its basic features is that it does not develop color. It is.

The present invention will be explained in detail below.

First, the color stain preventive agent represented by general formula (1) (hereinafter referred to as the color stain preventive agent of the present invention) will be explained.

In general formula (1), the sulfonamide group represented by X is:
For example, methylsulfonamide group, ethylsulfonamide group, propylsulfonamide group, 1so-propylsulfonamide group, butylsulfonamide group, 1so-
butylsulfonamide group, 5ec-butylsulfonamide group, tert-butylsulfonamide group, pentylsulfonamide group, 1so-pentylsulfonamide group, 5ec-pentylsulfonamide group, tert-pentylsulfonamide group, hexylsulfonamide group,
Heptylsulfonamide group, octylsulfonamide group, tert-octylsulfonamide group, dodecylsulfonamide group.

Examples include a tetradecylsulfonamide group, a phenylsulfonamide group, a naphthylsulfonamide group, a benzoxacylylsulfonamide group, a benzimidazolylsulfonamide group, a thiacyasilysulfonamide group, a pyridylsulfonamide group, and each of the above groups is substituted. Examples of preferable substituents that can be introduced into each of the above groups include the following.

That is, halogen atoms (e.g. fluorine, chlorine, bromine, etc.),
Hydroxy group, nitro group, cyano group, alkyl group (e.g. methyl group, ethyl group, propyl group, 1so-propyl group, butyl group, 1so-butyl group, 5ec-butyl group, tert-butyl group, pentyl group).

1so-pentyl group, 5eC-pentyl group, tart-
pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, 1so-dodecyl group,
cetyl group, etc.), cyanoalkyl group (e.g. cyanomethyl group, etc.), fluorinated alkyl group (e.g. trifluoromethyl group, octafluorobutyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, propyloxy group, 1so-propyloxy group, butoxy group, 1so-butoxy group,
5ec-butoxy group, tert-butoxy group, pentyloxy group, 1so-pentyloxy group, tert-pentyloxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group, tolyloxy group, etc.), carboxyl group, alkyloxy carbonyl group (e.g. ethoxycarbonyl group, dodecyloxycarbonyl group, etc.),
Aryloxy group (e.g., phenoxycarbonyl group, etc.), alkylacyloxy & (e.g., acetyloxy group, cyclohexylcarbonyloxy group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.)
, an alkylamine group (e.g. ethylamino group, dimethylamino group, jetanolamino group, dodecylamino group,
hexadecylamino group, etc.), arylamino group (e.g., anilino group, naphthylamino group, etc.), alkylcarbamoyl group (e.g., ethylcarbamoyl group, carboxyethylcarbamoyl group, dodecylcarbamoyl group, etc.), arylcarbamoyl group (e.g., phenylcarbamoyl group, etc.) ), acylamino group (e.g. methanamide group, dodecanamide group, hexadecaneamide group, penzamide group, etc.)
, acyl groups (e.g. benzoyl group, pentafluorobenzoyl group, ethylcarbonyl group, propylcarbonyl group, etc.), alkylthio groups (e.g. methylthio group, propylthio group, octylthio group, dodecylthio group, etc.), alkylsulfonyl groups (e.g. methylsulfonyl group, ethyl sulfonyl group, octylsulfonyl group, decylsulfonyl group, dodecylsulfonyl group, etc.), alkylsulfamoyl group (for example, ethylsulfamoyl group, pentylsulfamoyl group, dodecylsulfamoyl group).

tomethylsulfamoyl group, N,N-dimethylsulfamoyl group, etc.), alkylsulfonamide groups (e.g., methylsulfonamide group, ethylsulfonamide group, dodecylsulfonamide group, p-dodecylphenylsulfonamide group, etc.), Examples include arylsulfonyl groups (eg, phenylsulfonyl groups, etc.).

In the general formula (1), the sulfonamide group represented by Y can be the same as the above-mentioned examples of Examples of the sulfamoyl group include a methylsulfamoyl group, a benzamide group, and a benzamide group.
Ethylsulfamoyl group, butylsulfamoyl group, hexylsulfamoyl group, dodecylsulfamoyl group,
Examples of the carbamoyl group include a methylcarbamoyl group, an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, an octylcarbamoyl phenylcarbamoyl group, and an example of the ureido group. Examples of ester groups include methylureido group, ethylureido group, phenylureido group, naphthylureido group, benzoxacylylureido group, etc., and examples of ester groups include ethoxycarbonyl group, butoxycarbonyl group, dodecyloxycarbonyl group, phenoxycarbonyl group, etc. Examples of the sulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a dodecylsulfonyl group, a phenylsulfonyl group, and an argyl group. , such as methyl, ethyl, propyl.

4so-propyl L butyl group, iso-butyl group,
sec-butyl group, tert-butyl group, pentyl group,
iso-pentyl group, 3eC-pentyl group, tert-
pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, iso-dodecyl group,
Examples of the cycloalkyl group include a cetyl group, and examples of the cycloalkyl group include a cyclohexyl group and a cyclopentyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, butoxy group, iso-butoxy group, sec
-butoxy group, tert-butoxy group, pentyloxy group, iso-pentyloxy group, tert-pentyloxy group, dodecyloxy group and the like.

In general formula (1), the alkyl group represented by Z is the above-mentioned Y
The same groups as in the case where is an alkyl group can be mentioned, and as a cycloalkyl group.

The same groups as in the case where Y is a cycloalkyl group can be mentioned, and examples of the acyl group include an acetyl group,
Examples of the aryl group include a phenyl group, a naphthyl group, and the like; examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a furyl group,
Examples include 5-negative or 6-membered heterocycles such as a benzoxacylyl group and a benzthiazolyl group, or fused rings having these as a basic skeleton.

Each group represented by Y and Z above may have a substituent,
Preferred examples of substitution include the same substituents as described for X above.

Among the groups represented by X in the above general formula (1), hydroxyl groups and sulfonamide groups are preferred, and hydroxyl groups and phenylsulfonamide groups are particularly preferred.

In the above general formula (1), among the groups represented by Y, sulfonamide groups, acylamino groups, anilino groups and alkyl groups are preferable, and among these, sulfonamide groups and acylamino groups are preferable, particularly sulfonamide groups are preferable, and phenylsulfone groups are preferable. Most preferred is an amide group.

Among the groups represented by Z in General Formula (1), an alkyl group and an aryl group are preferable, an aryl group is preferable, and a phenyl group is most preferable.

Specific examples of the color stain preventive agent of the present invention are listed below, but the color stain preventive agent of the present invention is not limited thereto.

Margin below (3)
(G02II5 N02 O2 (E) O2 Ct (Found) OC2■I5 C2rI5 (C) F3 (To) "05I■II C2■I5 C11 (0113)2 (To) ctt (an,)2? CF3 (To) 2II5 θυ (Foundation) C8H,□ (Foundation) 2fI5 4n9 θQ cocr;”3 (Foundation) @
6k00. ll9 0, ll9 The color stain preventive agent of the present invention can be easily synthesized by a known method.

For the synthesis of a compound excluding X in general formula (1).

The method described in the patent publication or the synthesis method in the specification of the pyrazolone type magenta coupler F can be used.

When X is a hydroxy group, the corresponding pyrazolo-4,5-dione compound is prepared by a conventional method (for example, catalytic hydrogenation using a metal catalyst such as palladium-carbon, zinc-acetic acid or borohydride). It can be obtained in good yield by reduction using a method using sodium or the like.

Furthermore, the pyrazolo-4,5-dione compounds are described, for example, in U.S. Pat. No. 3,311,478.
A method in which pyrazolone is converted to the corresponding azomethine dye and then hydrolyzed with sulfuric acid, or US Pat. No. 3,419,
As described in No. 391, 5-pyrazolone can be converted into 4-
It can be easily obtained by converting it into amino-5-pyrazolone and then fermenting the amino group.

On the other hand, when X is a sulfonamide group, the corresponding 4
After nitrosation or nitration at the position, reduction is performed in the same manner as in the reduction method described above to obtain 4-amino-5-pyrazolone,
By reacting this amino acid with sulfonyl chloride in the presence of a base, 4-sulfonamide-5-
Pyrazolone can be easily obtained.

A specific synthesis example of one representative example will be given and explained in detail below.

Synthesis Example 1 (Synthesis of Exemplified Compound (22)) 30g of 3-
(4-dodecyloxyphenyl)sulfonamide-1-
Dissolve phenyl-4,5-dioxopyrazoline in a mixed solvent of 300ml of ethyl acetate and 200tjL of methanol, add 5g of 5% palladium-carbon catalyst (Pd/C), and perform atmospheric hydrogenation. After hydrogen absorption, Pd/C is filtered under reduced pressure, and the solvent is concentrated under reduced pressure. The obtained residue was recrystallized from a mixed solvent of 7cetonitrile and methanol to obtain 25 g of target crystals.

mp, 157-171”C1FD-Mass: M
” ~515 confirmed that it was the target object.

Synthesis Example 2 (Synthesis of Exemplified Compound (13)) [Reaction Scheme] Reaction (a): 50 g of 3-(4-dodecyloxyphenyl)sulfonamide F-t-phenyl-5-hirazolone was dissolved in 5005 M acetic acid. A solution of 8 g of sodium nitrite dissolved in 50 tal of water is added dropwise at room temperature. After stirring at room temperature for 1 hour, the mixture was poured into ice water, extracted with ethyl acetate, washed with water, dried, and evaporated under reduced pressure to obtain 45 g of residual liquid.

Reaction (b): The above residue was dissolved in 800 mM ethanol, and a solution of 50 g of hydrosaluite dissolved in 120 ml of water was added dropwise at an internal temperature of 50 to 60°C. After 0 dropwise addition, the mixture was stirred for 1 hour to precipitate crystals. was filtered under reduced pressure to obtain 41 g of crystals.

Reaction (C): The crystals obtained in reaction (b) were dissolved in 200 layers of pyridine, and 29 g of p-dodecyloxyphenylsulfonyl chloride dissolved in 100 ml of pyridine was added dropwise under a nitrogen stream. After stirring at room temperature for 5 hours, the mixture was poured into diluted salt solution, extracted with ethyl acetate, and dried.

After distilling off the solvent under reduced pressure, it was recrystallized from acetonitrile to obtain 53 g of target crystals.
It was confirmed from O1FD-Mass; M”=838 that it was the target product.

The color stain preventive agent of the present invention may be contained in at least one of the photographic constituent layers, and the color stain preventive agent may be used alone or in combination of two or more types.

The color stain preventive agent of the present invention may be used in combination with various color stain preventive agents other than the present invention, such as hydroquinone derivatives, aminephenol derivatives, gallic acid derivatives, ascorbic acid derivatives, and the like.

A specific example is US Patent 2. ．． No. 380, 290, 2.
33 [(, No. 327, No. 2,403,721, No. 2,
No. 418,813, No. 2.875,314, No. 2.7
No. 01,197, No. 2,704,713, No. 2.72
8.8511, 2,732,300, 2,73
No. 5,385, JP-A-50-92988, JP-A No. 50-9
No. 2989, No. 50-93928, No. 50-1103
No. 37, No. 52-146235, Special Publication No. 50-238
No. 13, and other patent publications cited in the explanation of the prior art.

The amount of the color stain inhibitor of the present invention to be used is not limited, but when it is contained in a photosensitive silver halide emulsion layer, it is preferably from 0.01 mol to 1 mol per mol of coupler. When included in the photographic constituent layer, it is 1M! j
``!1 each 0.001 mmol ~ 1 mmol/m''
is preferred.

Furthermore, it can be added to both the photosensitive silver halide emulsion layer and other photographic constituent layers to prevent color turbidity and color fogging.

The method for incorporating the color stain preventive agent 5 of the present invention into the photographic constituent layer will be described in detail.1f: When the color stain preventive agent of the present invention is alkali-soluble, it may be added as an alkaline solution; If it is soluble, for example, US Pat. No. 2,322,027, US Pat.
, No. 801,171, No. 2,272,191 and No. 2,304,940, the color stain inhibitor of the present invention is added to a high boiling point solvent and, if necessary, a low boiling point solvent is added. It is preferable to dissolve them in combination, disperse them in the form of fine particles, and add them to silver halide emulsions and other coating solutions for photographic constituent layers. A wide variety of gelatin derivatives, gelatin graft polymers, various cellulose derivatives, polyvinyl alcohol partial oxides, sodium alginate, poly-N-vinylpyrrolidone, etc. can be used. At this time, if necessary, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination.

In addition to the above methods, methods using other polymers such as latex dispersion are known.

Further, in detailing the method of adding the color stain preventive agent of the present invention to a silver halide emulsion, which is preferred in the present invention, one or more types of the color stain preventive agent of the present invention may be added to the silver halide emulsion as necessary. Couplers, hydroquinone derivatives, anti-fading agents, ultraviolet absorbers, etc., as well as organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, trichloride resin, etc. Phosphate, triphenyl phosphate, di-
isooctyl azelate, di-n-butyl sebacate,
Tri-n-hexyl phosphate, N.

triethyl-caprylamidobutyl, N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-n-octyl phthalate, di-1so-dotesyl phthalate, di-n-nonyl phthalate.

2.4-di-tert-pentylphenol, n-nonylphenol, 3-pentadecyl phenylethyl ether, 2,5-di9eC-amylphenylbutyl ether, monophenyl-di-lowchlorophenyl phosphate or fluoroparaffin, etc. high boiling point solvents, and/
or methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate.

Dissolved in low boiling point solvents such as cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, and anioleic acids such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids. Surfactants and/or nonionic surfactants such as sorbitanseth-t-oleate and sorbitan monolauryl ester;
Alternatively, it is mixed with an aqueous solution containing a cationic surfactant and a wood-philic binder such as gelatin, emulsified and dispersed using a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc., and then added to a silver halide emulsion.

In addition, the above-mentioned latex dispersion method and its effects are disclosed in JP-A-49-74538, JP-A-51-59943, and JP-A-54.
-32552 Publications and Research Disclosure August 1978, No. 1485Q.

It is described on pages 77-78.

Suitable latexes include styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-7 Cetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, to(2-(2-methyl-4 -ogisopentyl)] acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.

As a method for processing the photographic material of the present invention, for example, a color developing bath containing a color developing agent can be used. In addition to bath processing, various other methods such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid, etc. Processing schemes can be used.

There are no particular limitations on the method of processing the photographic material of the present invention, and any processing method can be applied.

For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are carried out separately after color development, followed by further washing with water if necessary. and/or a method of stabilizing; or prehardening, neutralization, one-color development, stop-fixing,
Washing with water, bleaching, fixing, washing with water, post-hardening, washing with water in that order, color development, washing with water, supplementary color development, stopping, bleaching, fixing.

Washing with water and stabilization in that order Method 1: After halogenation bleaching of the developed silver produced by color development, color development is performed again to increase the amount of dye produced. good.

The color developing solution that may be used for processing the light-sensitive material of the present invention contains a color developing agent and preferably has a pH of 8 or more;
More preferably, it is an alkaline aqueous solution having a pH of 8 to 12. The aromatic primary amine developing agent used as the color developing agent is a compound having a primary amino group on an aromatic ring and has the ability to develop silver halide exposed to light. Precursors that form such compounds may also be added.

The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples.

4-Amino-N, N-diethylaniline, 3-methyl-
4-amino-N, N-diethylaniline, 4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methoxy-4-amino-
N-ethyl-N-β-methoxyethylaniline, 3-7
Cetamido 4-amino-N,N-dimethylaniline,
Toethyl N-β-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, toethyl β-(β-methoxyethoxy)ethyl-3-
Methyl-4-aminoaniline and salts thereof such as sulfate, hydrochloride, sulfite, p-)luenesulfonate and the like.

Furthermore, for example, JP-A-48-64932, JP-A-50-1
No. 31526, No. 51-95849, and Bent et al.'s Journal Fist of the American Chemical Society, Vol. 73, pp. 3100-3125 (1951)
The ones described above are also listed as representative ones.

The amount of these aromatic primary amine compounds to be used depends on where the activity of the developer is set, but in order to increase the activity, it is preferable to increase the amount used, and the amount used is 0. It is used in a range from 0,002 mol/liter to 0.7 mol/liter. In addition, two or more compounds may be used in appropriate combination depending on the purpose. For example, 3-methyl-4-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methane. Sulfonamidoethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamide ethylaniline and 3-methyl-4-amino-N-ethylroot β-hydroxyethylaniline, etc. The color developing agent can be used in any combination depending on the purpose.The color developing agent is a precursor. In that case, it can be incorporated into the photosensitive material of the present invention.

The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, chilkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates,
Alkaline earth halides, benzyl alcohol, water softeners, thickening agents, development accelerators, and the like may optionally be included.

Examples of additives other than the above added to the color developing solution include bromides such as potassium bromide and ammonium bromide;
Alkali iodide, nitrobenzimidazole, mercap′
Compounds for quick processing solutions such as tobenzimidazole, 5-methyl-benzotriazole, l-phenyl-5-mercaptotetrazole, anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. There is.

As the polishing agent used in the bleach solution or bleach-fix solution in the bleaching process, those in which metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid, oxalic acid, citric acid, etc. are generally known. ing. Representative examples of the above aminopolycarboxylic acids include the following.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl ether diaminetetraacetic acidethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium saltBleaching solution contains various additives along with the above bleaching agents. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fix solution may further contain a halogen compound such as potassium bromide, and as in the case of the bleach solution described above, various other additives such as pHM buffers, optical brighteners, # Foaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. may be added or contained.

The silver halide fixing agent is, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned.

Color development of the silver halide color photographic light-sensitive material of the present invention,
The processing temperature of bleach-fixing (or bleaching, fixing), and various processing steps such as washing with water, stabilization, and drying, which are carried out as necessary, is preferably carried out at 30° C. or higher from the viewpoint of rapid processing.

The silver halide photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58-14
No. 834, No. 58-105145, No. 58-1346
No. 34 and No. 58-18631 and patent application No. 58-2
A stabilization treatment as an alternative to water washing as shown in Japanese Patent Application No. 709 and No. 59-89288 may also be performed.

The photographic constituent layers of the silver halide photographic light-sensitive material of the present invention include:
A dye (AI dye) that is water-soluble or decolorable with a color development processing solution can be added, and the AI dye includes oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include Fukoku Patent No. 584
．． No. 609, No. 1,277.429, Japanese Unexamined Patent Publication No. 1989-8
No. 5130, No. 49-99620, No. 49-1144
No. 20, No. 49-129537, No. 52-10811
No. 5, No. 59-25845, No. 59-111640, No. 59-111641, U.S. Patent No. 2.274.78
No. 2, No. 2,533,472, No. 2,958,879
No. 3,125,448, No. 3,148,187, No. 3,177.078, No. 3,247,127,
No. 3,280,801, No. 3,540,887, No. 3,575,704, No. 3,853,905, No. 3
, No. 718,472, No. 4,071,312, No. 4,
Examples include those described in No. 070.352.

These AI dyes are generally used at a concentration of 2 per mole silver in the emulsion layer.
It is preferable to use XIQ-3 to sx1 g-*mol,
More preferably, IXIQ-2 to 1X10-1 mol is used.

The amount of silver (silver deposition amount) in the silver halide emulsion layer in the silver halide photographic light-sensitive material of the present invention is not limited, but it is 0.3 to Ig/m'' in the entire photosensitive silver halide emulsion layer. In other words, in order to obtain excellent image quality, the silver amount is preferably less than Ig/m'', while in order to obtain high maximum density and high sensitivity, the silver amount is preferably 0. ．．
It is preferable that it is 3 g/m'' or more.

Silver halide compositions preferably used in the present invention include silver bromide, silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, in order to realize fast developability, it is preferable that the halogen composition of the silver halide contains a chlorine atom, and at least one
Particular preference is given to silver chlorobromide or silver chloroiodobromide containing % silver chloride.

Further, the crystals of these silver halide grains may be normal crystals, twin crystals, or other crystals, and have [1,0,01 planes and [1,1
, 1] Any ratio can be used for the plane. Furthermore, even if the crystal structure of these silver halide grains is uniform from the inside to the outside, it has a layered structure (
Furthermore, these silver halides may be of the type that forms a latent image mainly on the surface or of the type that forms it inside one grain. Silver oxide particles (Japanese Patent Application Laid-open No. 58-11393
No. 4, Japanese Patent Application No. 170070/1983) may also be used.

Silver halide grains particularly preferably used in the present invention are:
It is substantially monodisperse, and may be obtained by any preparation method such as an acidic method, a neutral method, or an ammonia method.

For example, when growing silver halide grains, p) 1. It is preferable to control PAg and the like, and to sequentially and simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains as described in, for example, JP-A No. 54-48521.

Preferably, the silver halide grains used in the present invention are prepared as described above. A composition containing the silver halide grains is herein referred to as a silver halide emulsion.

These silver halide emulsions contain activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; Noble metal sensitizers such as gold sensitizers, Jt such as potassium aurithiocyanate, potassium chloroaurate, 2-orothio-3-methylbenzothiazolium chloride, etc., or such as ruthenium, palladium, platinum, rhodium, iridium Sensitizers of water-soluble salts such as ammonium chloroparadate, potassium chlorooleate, and sodium chloroparadate (these types can be used as sensitizers or fog suppressants depending on the amount) ) may be chemically sensitized either alone or in appropriate combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). .

The silver halide emulsion used in the present invention is chemically ripened by adding a sulfur-containing compound, and before and during this chemical ripening,
Alternatively, after aging, at least one hydroxytetrazaindene and at least one nitrogen-containing heterocyclic compound having a mercapto group may be added.

The silver halide used in the present invention is mixed with a suitable sensitizing dye at a concentration of 5 x 10-8 to 3
Optical sensitization may be achieved by adding 3 moles.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more types. Examples of the sensitizing dyes that can be advantageously used in the present invention include the following: I can list kimono.

That is, one example of the sensitizing dye used in the blue-sensitive silver halide emulsion layer is West German Patent No. 929,080.

U.S. Patent Nos. 2,231,858 and 2,493,748
No. 2.503.778, No. 2.5111,001
No. 2,912,329, 3.85fl, 959
No. 3, 872, 897, No. 3,894, 21
? No. 4.025,349, No. 4,048,572
No., British Patent No. 1.242,588, Special Publication No. 1977-14
Examples include those described in No. 030, No. 52-24844, and the like. In addition, as a sensitizing dye used in a green-sensitive silver halide emulsion, for example, US Pat.
．． No. 201, No. 2,072,908, No. 2,739,
No. 149, No. 2.945.763, British Patent No. 505.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 97θ. Furthermore, sensitizing dyes used in red-sensitive silver halide emulsions include 1, for example, U.S. Pat.
, No. 442,710, No. 2,454,829, No. 2.
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 7713,280. Furthermore, cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in U.S. Pat. No. 2,213,995, U.S. Pat. It can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

A typical particularly preferred spectral sensitization method is, for example, Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 48-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 58-153926, No. 59-116646
No. 59-116647 and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-11
No. 114, No. 47-25379, No. 48-38406
No. 48-38407, No. 54-34535, No. 55-1569, JP-A-50-33220, No. 50
-38526, 51-107127, 51-1
No. 15820, No. 51-135528, No. 52-10
No. 4916, No. 52-104917, and the like.

Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 46
-11627, Japanese Unexamined Patent Publication No. 1483/1983, and Japanese Patent Publication No. 38408/1983 regarding merocyanine.
No. 48-41204, No. 50-40662, JP-A No. 56-25728, No. 58-10753, No. 5
No. 8-91445, No. 59-116645, No. 50-
No. 33828 etc. are mentioned.

Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications Nos. 43-4932, 43-4933, 45-26470, and 46
-18107, No. 47-8741, JP-A-59-1
No. 14533, etc., and the method described in Japanese Patent Publication No. 49-6207, which uses zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye, can be advantageously used.

In order to add these sensitizing dyes to a silver halide emulsion, a dye solution containing, for example, methyl alcohol, ethyl alcohol, acetone, dimethyl formamide, or a fluorinated alcohol as described in Japanese Patent Publication No. 40659/1980 is prepared in advance. It is used by dissolving it in an organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

When the silver halide photographic material of the present invention is constructed as a full color material, red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layers are provided. The coupler contained in the emulsion layer may be a so-called 2-equivalent coupler or a 4-equivalent coupler.

The yellow couplers to be contained in the blue-sensitive silver halide emulsion layer include open chain ketomethylene compounds, active point -〇-aryl substituted couplers called so-called 2-equivalent type couplers, active point -〇-acyl substituted couplers, and active point hydantoins. Compound substituted couplers, active point urazole compound substituted couplers, active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -〇-sulfonyl substituted couplers, etc. are used as effective yellow couplers. be able to. Specific examples of yellow couplers that can be used include US Pat. No. 2,875,057.

No. 3,285,506, No. 3,408,194, No. 3,551,155, No. 3,582,322, No. 3
, No. 725,072, No. 3,891.445, West German Patent No. 1,547,888, West German Application Publication No. 2.219.9
No. 17, No. 2,281,361, No. 2,414,00
No. 6.

British Patent No. 1,425,020, Special Publication No. 1978-1078
No. 3, JP-A-47-26133, JP-A No. 48-73147
No. 51-102636, No. 50-6341, No. 50-123342, No. 50-130442, No. 5
No. 1-21827, No. 50-87650, No. 52-8
No. 2424, No. 52-115219, No. 58-953
Examples include those described in No. 46 and the like.

Examples of the magenta coupler used in the green-sensitive silver halide emulsion layer include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indasilone-based compounds. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of magenta couplers are described in U.S. Pat. No. 2,800,788.
No. 2,1383.808, No. 3,082,853
No. 3,127.263, No. 3,311,478, No. 3,419,391, No. 3.519,429,
No. 3,558,319, No. 3,582,322, No. 3,815,506, No. 3,834,908, No. 3
, No. 891,445, West German Patent No. 1,810,484,
West German Patent Application (OLS) No. 2,408,885,
No. 2,417,845, No. 2,418.958, No. 2,424,487, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1982, No. 52-58922, No. 49
-129538, 49-74027, 50-1
No. 59336, No. 52-42121, No. 49-740
Examples include those described in No. 28, No. 50-60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Further, cyan couplers that can be used in the blue-sensitive emulsion layer include, for example, phenol couplers and naphthol couplers. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers.
A specific example of the cyan coupler is US Pat. No. 2,369.
, No. 929, No. 2,434,272, No. 2,474.
No. 21113, No. 2,521.908, No. 2,895
, No. 828, No. 3,034,892, No. 3.311,
No. 478, No. 3,458,315, No. 3,478,5
No. 83.

3,583. IJ71, 3,591,383,
No. 3,787,411, No. 3,772,002, No. 3. 1333,494, 4,004.929, West German patent application (OL S) 2,414,830, 2.454.329, JP 48-59838, JP 51-26034, OL S No. 48-5055, No. 51-1
No. 46827, No. 52-69624, No. 52-909
No. 32, No. 58-95346, Special Publication No. 49-1157
Examples include those described in No. 2 and the like.

In the silver halide emulsion layer and other photographic constituent layers of the present invention, a non-diffusible DIR compound may be used in combination with a coupler such as a non-diffusible DIR compound, a colored magenta or cyan coupler, a polymer coupler, or a diffusible DIR compound. , colored magenta or cyan couplers are described in Japanese Patent Application No. 59-193611 by the present applicant, and polymer couplers are described in Japanese Patent Application No. 59-17 by the present applicant.
The descriptions in No. 2151 can be referred to.

” As a bipedally diffusible DIR compound, U.S. Patent No. 4.234
．． No. 878, No. 3,227,554, No. 3.6i1?
, 2!31, 3,958,993, 4,149
, No. 886, No. 3,933,500, JP-A-57-5
No. 6837, Special Publication No. 51-13239, British Patent No. 2,
Examples include those described in No. 072,383, No. 2,070,266, Research Disclosure No. 21228, December 1981, and the like.

The method of adding the coupler to the photographic constituent layer of the present invention can refer to the method of adding the color stain inhibitor of the present invention described above, and the amount added is not limited to IX per mole of silver.
IQ-3 to 5 mol is preferable, more preferably I
10-2 to 5 X 10-mol.

The silver halide photographic material of the present invention may contain various other photographic additives, such as an anti-capri agent, a stabilizer, and an ultraviolet absorber described in Research Disclosure No. 17843. Color stain preventive agents, optical brighteners, color image fading preventive agents, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, etc. that are not in the invention can be used.

In the silver halide photographic light-sensitive material of the present invention, the woody colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, and hydroxyl colloids. Examples include cellulose derivatives such as ethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide.

The support for the silver halide photographic material of the present invention includes:
For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflector, such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, or polyethylene terephthalate, polyamide films, polycarbonate. Films, polystyrene films, etc. may be used, and ordinary transparent supports may also be used, and these supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, U.S. Patent No. 2,781
, No. 791 and No. 2,941,898 can also be used to simultaneously coat two or more layers.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily6.For example, in the case of a full-color photosensitive material for photographic paper, the blue-sensitive silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the green-sensitive silver halide emulsion layer are sequentially applied from the support side. It is preferable to arrange a silver emulsion layer and a red-sensitive silver halide emulsion layer, and each of these light-sensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

The color stain preventing agent of the present invention can be used in these constituent layers.

Furthermore, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and various photographic additives that can be contained in the emulsion layer as described above can also be used in the layer. It is possible to contain an agent.

[Effects of the Invention] According to the present invention, a highly efficient color stain inhibitor that can efficiently remove the undesirable oxidized form of a color developing agent, has excellent storage stability, remains substantially colorless even after development processing, and is highly efficient. By using this, color staining can be reduced, the storage stability of small light-sensitive materials is excellent, color mixing due to color stain preventing agents can be eliminated, and a silver halide photographic light-sensitive material formed into an R1 film can be provided.

[Example] A specific example will be described below, but the embodiment of the present invention is not limited to these.

Example 1 A blue-sensitive silver iodobromide (silver iodide 6 mol%, lR bromide 94 mol%) emulsion layer containing a yellow coupler (y-i) was prepared as a first layer on a triacetyl cellulose support by 5 l. Coated to a thickness of (Coupler coating amount 0.9X 1O-3 mol/m
'', coated silver amount 1 g/rn') L, on which a gelatin layer containing the exemplary compound (5) of the present invention was coated as a second layer to a thickness of 1 μm (color stain prevention agent coating; 2× carbon dioxide 0″4 mol/rrf), and a magenta coupler (
A gelatin layer containing M-1) was coated to a thickness of 5 gm, coupler coating amount l x 10 = mol/rn') Sample No.
1 was created.

Moreover, in place of the exemplified compound (5) in the second layer, exemplified compound (
7), (13), (24) and the comparative color stain preventive agent A in the same moles were used as silver halide photographic light-sensitive material samples No. 2 and 2, respectively. No, 3, No, 4 and No
, 5 was tested. In addition, as a comparison sample for color staining, a sample was prepared in which a gelatin protective film (gelatin layer containing no color staining preventive agent at all) was coated on the first layer of sample No. 1 above, and a blank sample No. 1 of the color stain preventing agent was prepared. , E
It was set as l.

After each of these samples was wedge exposed using a conventional method, the samples were processed using the following processing steps and the processing liquid composition shown below.

Processing process (38℃) Color development 3 minutes 15 seconds Bleach fixing 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes! Stable bath for 5 seconds 1 minute 30 seconds [Color developing solution composition] 4-amino-3-ethyl-N-ethyl root (β-hydroxyethyl)-aniline sulfate 4.75 g Anhydrous sulfite average 4.25 g Hydroxylamine 1 /2 sulfate 2.0g anhydrous potassium carbonate
3.75g sodium bromide
1.3g nitrilotriacetic acid trisodium salt (l hydrate) 2.5g potassium hydroxide 1.0g Add water to ti
and adjust the pH to 10.0 using saponified potassium water.

[Bleach solution composition] Ethylenediaminetetraacetic acid ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 15Q, 0g Glacial acetic acid
Add 10.0 ml water to make one sentence, and adjust the pH to 6.0 using aqueous ammonia.

[Fixer Composition] Ammonium periosulfate 175.0 g Anhydrous sodium sulfite 8.68 Sodium metasulfite 2.3 g Water was added to make tU, and the pH was adjusted to 8.0 using acetic acid.

[Stabilizing liquid composition] Formalin (37% aqueous solution) 1.5++
+ Kokonidatsukus (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5 ozumizu was added to make lfJ.

The magenta dye image obtained above was measured using a densitometer (FD-
7R, manufactured by Konishiroku Photo Industry Co., Ltd.), sensitometry was performed using blue light and green light.

When the yellow density was 1.5, the magenta density was compared and the value divided by the magenta density of the blank was defined as the degree of color contamination. The results are shown in Table 1.

Margin Table 1 Below: In Table 1 above, the smaller the numerical value, the lower the degree of color contamination. In other words, Samples No., 1-No., and 4 containing the color stain preventive agent of the present invention had smaller color stains than Comparative Compound A, so it is clear that they have a higher ability to remove the oxidized product of the color developing agent, and therefore are suitable for use. It can be seen that by reducing the amount, it is possible to make the film thinner.

[Y-]] [M-1] t [Comparative Compound A] O Summer I Example 2 Magenta coupler (M-2) 2X+o-2 mol and exemplified compounds of the present invention (10, (22), (48), (52) and Comparative Compounds B and C (3 x 1 G-3 moles each) were heated and dissolved in a mixture of the same weight of tricresyl phosphate and 3 times the amount of ethyl acetate to prepare 6 types of mixed solutions of magenta coupler and color stain inhibitor. A blank solution containing only the magenta coupler was prepared, and Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont) was prepared.

The mixture was mixed with 30 OsJl of a 5% gelatin aqueous solution containing 1.5 g, and emulsified and dispersed using a colloid mill. This coupler dispersion was mixed with I kg of a photographic emulsion containing 0.2 mol of green-sensitive silver iodobromide (6 mol % silver iodide, 94 mol % silver bromide) with an average grain size Q of 8 ILs and 40 g gelatin. 2% solution of 1,2-bis(vinylsulfonyl)ethane as hardener2
The mixture was coated on a cellulose triacetate film base and dried. Samples No. 7 to No. 13 of silver halide photographic materials with a gelatin protective layer coated on top of this layer.
It was created. The amount of silver coated on each sample at this time was 2g/r.
It was r1'. These samples were subjected to the same treatment as in Example 1.

The magenta dye image obtained above was measured using a densitometer (FD-
7R1 (manufactured by Konishiroku Photo Industry Co., Ltd.) using green light to determine fog (Fog), maximum density (Dm), and color development sensitivity (relative values are displayed when the sensitivity of sample No. 13 is set to 100). Ta. The results are shown in Table 2.

Table 2 As is clear from the results in Table 2 above, Samples Nos. 7 to 10 using the color stain preventive agent of the present invention have low fog, indicating that they have excellent color stain prevention effects in fogged areas. . Furthermore, the maximum density and relative sensitivity decreased less than in comparison, and it was found to be an excellent color stain preventive agent with less adverse effects.

Example 3 The sample prepared in Example 2 was kept unexposed at a relative humidity of 40%.
After storage at a temperature of 55° C. for 4 days, the same treatment as in Example 2 was performed to determine sensitometry. Changes in fog and maximum density are compared with those processed without a preservability test. sample) was obtained. The results are shown in Table 3.

Margin Table 3 Below: As is clear from the results of Table 3 above, Samples No. 7 to No. 10 using the color stain inhibitor of the present invention were compared to Sample No. 13, which did not contain the color stain inhibitor. Also F.

The fluctuations in both g and D-zen aX are small. On the other hand, samples No. 11 and No. 1 using comparative compounds B and C
2 increases the fluctuations regarding D shoes aX, and what is disassembled during storage reacts to D shoes a! It can be inferred that this had an adverse effect of causing a decline in

(M-2) t [Comparative Compound B] (Described in JP-A-59-195239) (Described in JP-A-59-5247) Example 4 The following layers were supported on a paper support laminated on both sides with polyethylene. The silver halide color photographic light-sensitive material sample No. 14 was prepared by coating sequentially from the body side.

Layer l...1.2g/rr1' gelatin, 0.32
blue-sensitive silver chlorobromide emulsion (silver bromide content 80 mol%) of g/rn' (in terms of silver, the same hereinafter), l), 0.80 g/ln'' of yellow dissolved in 50 g/rrf of dioctyl phthalate. Coupler (Y-2) and lXl04a mol/
A layer containing exemplified compound (3) of “rn”.

Layer 2 ・e l), 70 g/m'' gelatin, 12 m
g/rn' anti-irradiation dye (AI-1),
(A I-2) and 5XIQ-5 at 81 g/m'
An intermediate layer containing the exemplary compound (3) of -TI-ru/rrf.

Layer 3 @ -# 1.25g/m' gelatin, 0
．． 25 g/rn' green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 0.82 g/rn' magenta camera (M-3) dissolved in 0.30 g/rn' dioctyl phthalate. A layer containing.

R4φ: Intermediate layer made of gelatin of 1.20 g/rn'.

Layer 5---1.20 g/rr11 gelatin, 0.
30 g/rn' red-sensitive silver chlorobromide emulsion (silver bromide content 7
0.45 g/rn' cyan coupler (0.45 g/rn' dissolved in 0.20 g/ni' dioctyl phthalate),
A layer containing C-1).

Layer 6 e * * Layer containing 0.30 g/m'' ultraviolet absorber (UV-1) dissolved in 1.00 g/IT+'' gelatin and 0.20 g/m dioctyl phthalate.

Layer 7: Layer containing 0.50 g/m'' of gelatin.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S-) riazine sodium was added in layers 2.4 and 7.
Gelatin each! 0 per g. (Added to make 117g.

The following margin (Y-'2) (M-3) t t (Person 1-1) N a O3S CH2NH00H (AI-2) (UV-1) 05H□ (1) Also, the layer l in the sample No. 14 and Exemplified Compound (3) of Layer 2, 4 mol of Exemplified Compound (31), (3)
2) and 1: Sample N above except that the comparative compound R was replaced.
Samples No. 15 to No. 17 were prepared in the same manner as No. 14.

Each of the photosensitive material samples No. 14 to No. 17 was exposed through an optical wedge and then processed in the first step.

Processing steps (38°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows.

[Color developer] Pure water 80% benzyl alcohol 15m Standing sulfur sulfur resistant roxyamine 2.0g Potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine 2.
0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-7 minoaniline sulfate 4,581-hydroxyethylidene-1,1'-diphosphonic acid (60% aqueous solution)
1.5m41 potassium carbonate
32g Whitex BB (50% aqueous solution)
2tjl (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 20% potassium hydroxide or 10%
Adjust pi (= 10.2) with dilute sulfuric acid.

[Bleach-fix solution] Pure water 550 ■ Iron cross-ethylenediaminetetraacetate (m) Ammonium 85 g Ammonium thiosulfate 85 g Sodium hydrogen sulfite 10 g Sodium metabisulfite
2g Ethylenediaminetetraacetic acid-disodium 20g Sodium bromide 10g Add pure water to make one sentence, and adjust PH= with aqueous ammonia or dilute sulfuric acid.
Adjust to 7.0.

Sensitometry was performed using blue light for each sample after the above treatment, and the capri (Fog) and maximum density (Dm) were determined. The results are shown in Table 4.

Margin Table 4 Below: As is clear from Table 4 above, Sample No. 14 of the present invention
-No. 1I3 was found to be an excellent silver halide color photographic light-sensitive material with less fog and a higher maximum density than comparative sample No. 17.

Claims (1)

[Scope of Claims] In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support, at least one of the photographic constituent layers has the following general formula: A silver halide photographic material containing at least one color stain inhibitor represented by (1). General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, X represents a hydroxyl group or a sulfonamide group, and Y represents a sulfonamide group, acylamino group, anilino group, sulfamoyl group, carbamoyl group, ureido group, Represents a group selected from a carboxyl group, a hydroxyl group, an ester group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, a sulfonyl group, and a cyano group, and Z is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, and an aryl group. represents a group or a heterocyclic group.