JPS61114238A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain sufficient color development density at the time of development without causing desensitization, fog, stains, etc., during storage by incorporating a specified compd. in at least one of photographic constituent layers. CONSTITUTION:A silver halide color photographic sensitive material has photographic constituent layers including at least one photosensitive silver halide emulsion layer on a support, and at least one of said constituent layer contains, preferably, in an amt of 0.01-5mol per mol of total silver halide in the photosensitive material, at least one of precursors of a color developing agent represented by the formula shown on the right in which R1, R2 are each 1-4C optionally substd. alkyl; each of R3-R6 is H, halogen, OH, 1-2C optionally substd. alkyl or alkoxy; and Ar is aryl having at least one sulfonic acid or its salt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a precursor of a photographic chemical, and more particularly to a silver halide color photographic light-sensitive material containing a precursor of a color developing agent.

[Prior Art] Photographic chemicals are generally used by being added to a light-sensitive material or contained in a photographic processing solution, depending on the purpose. Recently, for the purpose of simplifying the processing steps and speeding up the processing, attempts have often been made to add or blend specific photographic processing agents, such as developing agents, into photosensitive materials.

As described above, the method of adding and blending a photographic processing agent into the photosensitive material 11 has the advantage of simplifying the processing because the components contained in the processing solution are reduced, and also has the advantage of being insensitive to alkalinity, for example. Some ingredients are too stable to be stored as developer components, some are difficult to use because they are reactive with other chemicals in the developer, or some are difficult to dissolve in the developer at the required concentration. As a means of making the components usable, it is a very effective method to add these components to the photosensitive material in advance.

However, in order for each chemical added to the photosensitive material to exhibit its effect in a timely manner, it is necessary to consider in advance which layer of the photosensitive material it should be added to. It is desirable that each chemical added be non-diffusible within the layer and chemically stable. This is particularly required when the chemical added to the photosensitive material is a precursor of an aromatic primary amine developing agent.

Among the above-mentioned problems, the present invention particularly relates to the stabilization of chemicals added to constituent layers of light-sensitive materials, and more specifically, to the stabilization of precursors of color developing agents. In particular, among the chemicals used for photography, compounds containing nitrogen-containing organic bases and quaternary nitrogen atoms are an important type of photographic chemicals, partly because so many compounds have been put into practical use. For example, paraphenol compounds are black and white developing agents, aromatic primary amine compounds are color developing agents, and nitrogen-containing heterocyclic compounds, especially azole compounds, are photographic stabilizers.
Fog suppressants or toning agents, hydroxylamine compounds are used as preservatives, hydrazine compounds are used as fogging agents for direct positive photosensitive materials, etc. In addition, N, N
, N,N-tetraalkyl-p-phenylenediamines and alkylamine compounds are known as development accelerators.

However, many of the above-mentioned nitrogen-containing organic bases and compounds containing quaternary nitrogen atoms, especially aromatic primary amine developing agents or their precursors, are chemically active and easily oxidized in the atmosphere, and sometimes The compound may easily react with silver halide to cause desensitization or contamination, or it may have properties that make it difficult to use as is, or its molecules may not be large enough to provide diffusion resistance. It has the disadvantage that it cannot be easily used because it has various problems such as diffusion to other layers. To this end, attempts have been made to select compounds with practically excellent performance or to research improved addition methods. As a result, several methods for stably incorporating nitrogen-containing organic bases, particularly color developing agents, into light-sensitive materials have become known. That is, (1) the reaction product of a color developing agent and a metal salt is disclosed in U.S. Patent No. 3.719,
492, etc., salts of two color developing agents and acids are disclosed in U.S. Patent No. 3,784.328 and JP-A-5
No. 6-6235, No. 56-16133, No. 56-54
No. 430, No. 56-67842, IW! 56-592
No. 32, No. 56-81837, No. 56-83734, No. 56-83735, No. 56-83736, No. 5
No. 6-89735, No. 58-200233, etc., and ``''! is described in U.S. Patent No. 2, U.S. Pat.
50? , No. 114, No. 3,342,599, Japanese Unexamined Patent Publication No. 1973
No. 4-9924, No. 56-106241, No. 56-1
No. 07236, No. 58-192031, No. 59-13
It is described in No. 239 etc. 1. U.S. Patent No. 80 for amide and imide types of 4+ color developing agents
No. 3.783, British Patent No. 1.08JOθ1, Research Disclosure
1,20 of West German Patent No. 1,159,758.
No. 0,879, Research Disclosure (Res.
searchDisclosure) No. 13, 8
24, U.S. Pat. No. 2,6115.234, etc., and the urethane type I is described in U.S. Pat. No. 57-179842, No. 58
-1139, 58-1140, 58-9534
4, etc.; ■ Indoaniline type is described in U.S. Patent No. 3,342.5137, etc.; No. 59-81643, etc.

[Problems to be Solved by the Invention] The reaction product of the color developing agent and the metal salt described in (1) above is poorly soluble and difficult to add to a light-sensitive material, and sufficient color development cannot be obtained during development. Salt formed products of color developing agents and acids produce good color, but they have problems such as desensitization and staining during raw storage.Furthermore, the Schiff base type described in (2) above tends to cause desensitization of the emulsion, and even after processing, the Schiff base does not change. The color tends to remain,
Furthermore, the above-mentioned urethane type is highly hydrophobic and has low solubility in water, so it tends to remain in the photosensitive material. Therefore, there are drawbacks such as easy contamination and failure to obtain sufficient color density. At the very least, there may be problems such as not being able to obtain sufficient color density during development, or substantially remaining of the aromatic primary amine developing agent precursor in the silver halide color photographic light-sensitive material after development. There is one problem.

The present invention has been developed in view of the above, and contains a stable aromatic primary amine developing agent precursor that does not cause desensitization, fogging, staining, etc. during storage, and provides sufficient color density during development. To provide a silver halide color photographic light-sensitive material containing an aromatic primary amine developing agent precursor, and in which the aromatic primary amine developing agent precursor does not substantially remain in the photographic light-sensitive material after completion of development. is a technical issue.

[Means for Solving the Problems] The silver halide color photographic light-sensitive material of the present invention which solves the above-mentioned technical problems comprises a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support. In at least one of the photographic constituent layers, a silver halide color photographic light-sensitive material containing a compound represented by the following general formula [I] (
It is characterized in that it contains at least one of the following: (hereinafter referred to as a precursor of the color developing agent of the present invention or a precursor compound of the present invention).

The following is a blank general formula [I] In the formula, R1 and R2 represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and may be linked to each other to form a 5- to 7-membered heterocycle. R3, R4, R5, and R6 are each a hydrogen atom, a halogen atom, a hydroxy group, or a carbon number of 1 to
2 represents a substituted or unsubstituted alkyl group or alkoxy group. Ar represents an aryl group having at least one sulfonic acid or sulfonate.

The present invention will be described in further detail below.

Groups represented by R1 and R2 in general formula [I] include methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, hydroxypropyl group, methoxyethyl group,
Examples include ethoxyethyl group, methylsulfonamide ethyl group, hydroxy group, methoxy group, ethoxy group, methylsulfonamide group, and the like.

Examples of the aryl group having at least one sulfonic acid or sulfonate represented by "A" include a phenyl group, a naphthyl group, etc., and preferably a phenyl group having a sulfonic acid or sulfonate.Sulfonic acid Examples of the salt include inorganic salts such as sodium, potassium, calcium, magnesium, and ammonium, and organic salts such as pyridine, pyrimidine, triethylamine, and triethanolamine.

When the aryl group has other substituents, examples of the substituents include halogen atoms (e.g. fluorine, chlorine, bromine, etc.), hydroxy groups, nitro groups, cyano groups, alkyl groups (e.g. methyl groups, trifluoromethyl groups, butyl group, cyanomethyl group, etc.), carboxyl group, alkyloxy group (e.g. methoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, etc.), alkyloxycarbonyl group (e.g. ethoxycarbonyl group, etc.), aryloxycarbonyl group groups (e.g. fetugidicarbonyl, W, etc.), alkylsulfonyl groups (e.g. methylsulfonyl group, ethylsulfokol group, propylsulfonyl group, etc.), arylsulfonyl! (e.g., phenylsulfonyl group, etc.), fulkylacyloxy group (e.g., acetyloxy group, cyclohexyl group, etc.), arylacyloxy group (e.g., benzoyloxy group, etc.),
Alkylamine groups (e.g. ethylamino, dimethylamino, jetanolamino, etc.), arylamino groups (e.g. anilino), alkylcarbamoyl groups (e.g. ethylcarbamoyl), arylcarbamoyl groups (e.g. phenylcarbamoyl) , alkylacylamino groups (e.g., acetamido groups, etc.), aryl acylamino groups (e.g., benzamide groups, etc.), alkylsulfonamide groups (e.g., methylsulfonamide groups, ethylsulfonamide groups, etc.), arylsulfonamide groups (e.g., benzenesulfonamide groups, etc.). groups), alkylsulfamoyl groups (e.g. N-methylsulfamoyl groups, N, N
-dimethylsulfamoyl group, etc.), arylsulfamoyl group (eg, phenylsulfamoyl group, etc.), carboxyl group, carboxylate salt, etc.

As an example when R+ and R2 form a heterocycle,
Examples include a morpholino group and a piperazine group.

R3, R4, R5, R6 are alkyl groups having 1 to 2 carbon atoms,
Examples of alkoxy groups include methyl, ethyl, methoxy, and ethoxy groups.

The precursor of the color developing agent of the present invention represented by the general formula [I] is illustrated below.

Margin below [Exemplary compounds] OH3 0F■3 0H3803H OH30000H.

SO2)I CH35O3H 00H3 OH3 OHB S O3N a CH35O3K OH3 Synthesis method The precursor of the color developing agent of the present invention represented by the above general formula [I] can be synthesized by the following method. For example, sulfonic acid or a pure salt of sulfonic acid can be easily obtained by adding a base to free sulfonic acid in an organic solvent or in water.

Synthesis Example 1 (Synthesis of Exemplified Compound (3)) 13mM trichloromethyl chloroformate was dissolved in 200mJL of ethyl acetate, and while keeping the internal temperature below O'C, 20g of 4-hydroxybenzenesulfonic acid and 20g of pyridine were dissolved in 200mJL of ethyl acetate.
Drop a solution of M dissolved in ethyl acetate. After 0 drops, react at the same temperature for 1 hour. N-[2-(4-amino-N-ethyl-m-toluidino)ethylcomethanesulfonamide 30
A solution of g dissolved in 200mM pyridine is added dropwise again at below 0°C. After the 0 drop, the reaction is at room temperature, then purified by column chromatography, and hydrogenated using Pd-C as a catalyst.
The obtained compound is dissolved in an aqueous solution containing an equimolar amount of sodium hydrogen carbonate, and after dehydration, the desired compound is obtained. Yield 30g
, FD-Mass; M = 493, and it was confirmed that it was the target product.

Synthesis Example 2 (Synthesis of Exemplified Compound (5)) 20 g of 3-nobyroxybenzenesulfonic acid and 108 triethylamine were dissolved in 200 mJlj of ethyl acetate and heated at 0°C under stirring.
10 g of phosgene gas is added dropwise to 100 ml of toluene in which 100 ml of toluene is dissolved. A solution of the layered protein dissolved in pyridine is added dropwise and purified by column chromatography to obtain the desired product.

Yield: 31g, FD-Mass: M = 471te, confirming that it was the desired product.

The amount of the precursor of the color developing agent of the present invention added is preferably 0.01 to 5 times, more preferably 0.1 to 2 times, by mole relative to the total amount of silver in the light-sensitive material per unit area.

When the precursor of the color developing agent of the present invention is synthesized in a woody colloid solution, the precursor compound is maintained in a dispersed state in the woody colloid solution, so it can be used as is. However, when these compounds are in an isolated state, they are dissolved in a wood-philic organic solvent such as methyl alcohol, ethyl alcohol, or acetone, and added to and dispersed in a wood-philic colloid solution. Other dispersion methods include latex dispersion, a method using other polymers, and a method using a coupler solvent such as trilocresyl phosphate and dibutyl phthalate, which are used in oil-protected photosensitive materials, to form the color of the present invention. A method such as dispersing a precursor compound of a developing agent in a wood-philic colloid solution can be used. When dispersing these oil phases in the ice phase, generally known anionic, nonionic, cationic, etc. surfactants may be used. - a gelatin derivative known as
Gelatin graft polymers, various cellulose derivatives,
Polyvinyl alcohol partial oxide, sodium alginate,
Poly-N-vinylpyrrolidone and the like can be widely used. Various photographic antioxidants or stabilizers can also be added to these emulsions.

The method of incorporating the precursor of the color developing agent of the present invention into the silver halide emulsion or other photographic constituent layer coating solution according to the present invention will now be described in more detail.

When the precursor of the color developing agent of the present invention is alkali-soluble, it may be added as an alkaline solution, and when it is oil-soluble, it may be added as described in, for example, U.S. Pat.
No. 27, No. 2,801,170, No. 2,801.
No. 171, No. 2,272,191 and No. 2, 3
According to the method described in each specification of No. 04,840, the precursor of the color developing agent of the present invention is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and dispersed in fine particles to form silver halide. It is preferable to add it to the emulsion. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-fading agents, etc. may be used in combination, if necessary. It is also possible to use a mixture of two or more precursors of the color developing agent of the present invention. Further, in detailing the method of adding a precursor of the color developing agent of the present invention to a silver halide emulsion, which is preferred in the present invention, one or more kinds of precursors of the color developing agent of the present invention may be added to the silver halide emulsion. Depending on the situation, organic acid amides, caloctamates, esters, ketones,
Urea derivatives, ethers, hydrocarbons, etc., especially di-n-
Butyl phthalate, triresyl phosphate, triphenyl phosphate, di-isooctyl azelate,
Di-n-butyl sebacate, tri-n-hexyl phosphate, N,N-di-ethyl-caprylamidobutyl,
N,N-diethyl laurylamide, n-pentadecyl phenyl ether, di-octyl phthalate, n-nonylphenol, 3-hentadecyl phenylethyl ether, 2.5-di-5ec-amylphenyl butyl ether, monophenyl-di-0-chlorophenyl High boiling point solvents such as phosphates or fluorinated paraffins,
Or low boiling point materials such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Dissolved in a solvent, anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or nonionic surfactants such as sorbitan sesquioleate and nrubitan monolaurate, and/or hydrophilic surfactants such as gelatin. It is mixed with an aqueous solution containing a binder, emulsified and dispersed using a high-speed rotating 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 Specification Publication and Research φ Disclosure August 2018-6, No. 14850, pages 77-78.

Suitable latexes include, for example, styrene, acrylate,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N-(2-(2-methyl-4 -oxopentyl)]acrylamide, 2-acrylamide-2-
Homopolymers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like.

The precursor of the color developing agent of the present invention can be used in at least one of the constituent layers provided on the support of the silver halide photographic light-sensitive material, such as a silver halide emulsion layer, an intermediate layer, a protective layer, and a subbing layer. It is contained in the layer. Although it depends on the type of the precursor compound, it is generally preferable to include it in the silver halide emulsion layer or a layer adjacent thereto.

These precursor compounds of the present invention incorporated into the light-sensitive material according to the present invention are chemically stable unless they come into contact with an alkali activator, and are compatible with silver halide and other various additives in the light-sensitive material. Since it has extremely low reactivity with other agents, it can be useful for improving the storage stability and photographic properties of light-sensitive materials, especially desensitization, fogging, and staining.

Furthermore, when a developing agent precursor is contained in a photosensitive material according to the present invention, development can be carried out using a processing solution with a simple composition mainly consisting of an alkaline agent called an alkali activator, which simplifies processing. This is a very effective method not only for reducing pollution, but also for preventing pollution. −
For example, by incorporating the precursor compound of the present invention and a hydrazine compound as a fogging agent into a direct positive silver halide color photographic light-sensitive material according to the present invention, a reversal color image can be directly formed only by treatment with an alkali activator. be able to.

Alkaline activator liquid is basically a commonly used color developer with the developing agent removed.
Preferred p)I ranges from about 7 to 14, particularly preferred pH ranges from 8 to 13.

Also, the treatment temperature with alkaline activator liquid is 20℃.
-70°C is preferred, most preferred temperature is 30°C - 60°C
It is ℃. As a buffer for the alkaline activator solution, known compounds such as sodium hydroxide and sodium carbonate can be used alone or in combination.

In addition, other additives such as antifoggants, development accelerators,
Water softeners, organic solvents, etc. can also be added to the alkaline activator liquid.

In addition, as a method for processing the photographic light-sensitive material of the present invention, it is also possible to use a color developing bath containing a color developing agent. In addition, various other methods including bath processing, 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.

In addition to the above, there are no particular restrictions on the processing method for the photographic material of the present invention, and any processing method can be applied. For example, representative methods include alkaline activator treatment or bleach-fixing treatment after color development. A method in which bleaching and fixing are carried out separately after treatment with an alkali activator or color development, and further washing with water and/or stabilization treatment is carried out as necessary; or Prehardening, neutralization, alkaline activator treatment or color development, stop fixing, water washing,
A method in which bleaching, fixing, washing with water, post-hardening, washing with water is performed in the order, alkaline activator treatment or color development, washing with water, supplementary color development, stopping, bleaching, fixing, washing with water, stabilization in the order, alkaline activator treatment Or after bleaching the developed M produced by color development,
Any method may be used for processing, such as a developing method in which the amount of produced dye is increased by alkali activator treatment or color development again.

The color developing solution that may be used for processing the light-sensitive material of the present invention is an alkaline aqueous solution containing a color developing agent and preferably having a pH of 8 or more, more preferably 9 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 precursor compound of the present invention may be used as the precursor.

The alkaline activator processing solution or 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, alkali metal sulfites, alkali metal bisulfites, Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, development accelerators, and the like can also be optionally included.

Examples of additives other than those mentioned above that are added to the alkaline activator processing solution or color developing solution include bromides such as potassium bromide and ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptohenzimidazole, and 5-benzimidazole. Methyl-benzotriazole, 1-phenyl-
In addition to compounds for rapid processing solutions such as 5-mercaptotetrazole, there are anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like.

Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. The following are representative examples of the above-mentioned 7-minoboricarboxylic acid.

Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylenediaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacid resistant ethylenediaminetetrapropionic acidethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acidpentasodium saltnitrilotriacetic acid sodium saltThe bleaching solution is various in combination with the bleaching agent mentioned below. It may also contain additives. Also, when using a bleach-fix solution in the bleaching process,
A solution containing a silver halide fixing agent in addition to the bleaching agent is applied. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. As with the bleach solution mentioned above, various other additives such as pH buffers, optical brighteners, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added. addition,
It may be included.

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 water washing, stabilization, and drying, which are carried out as necessary, is preferably 30° C. or higher from the viewpoint of rapid processing.

The silver halide color photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58
-14834, 58-105145, 58-1
No. 34634 and No. 58-18631 and patent application 1973
A stabilizing treatment as an alternative to washing may be performed as shown in Japanese Patent No. 8-2709 and Japanese Patent No. 59-89288.

A dye (AI dye) that is water-soluble or decolorized with an alkali activator treatment solution or a color development treatment solution can be added to the photographic constituent layer of the silver halide color military photosensitive material 4 of the present invention, and the AI dye These include oxonol dyes, hemioquinol dyes, merocyanine dyes and azo dyes. Among them, oxonol dyes, hemioquinol dyes, merocyanine dyes, etc. are useful. Examples of AI dyes that can be used include Fukoku Patent No. 584.1 (0
No. 9, No. 1,277.429, Japanese Unexamined Patent Publication No. 48-8513
No. 0, No. 49-99620, No. 49-114420, No. 49-129537, No. 52-108115,
No. 59-25845, No. 59-111640, No. 5
No. 9-111641, U.S. Patent No. 2.274,782,
No. 2,533,472, No. 2,958,878, No. 3,125,448, No. 3,148,187, No. 3
, No. 177.078, No. 3,247,127, No. 3,
280,601, 3.540.887, 3.5
No. 75,704, No. 3,653,905, No. 3,71
No. 8,472, No. 4,071,312, No. 4.070
, No. 352 can be mentioned.

It is generally preferable to use these AI dyes in an amount of 2XIQ-3 to 5X10-' mol, more preferably in an amount of IXIQ-2 to 1XIQ-1 mol per mol of silver in the emulsion layer.

Silver in the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention! (Amount of silver material) is not limited, but
0.3 to Ig/r for the entire photosensitive silver halide emulsion layer
It is preferable to set it to n'. That is, in order to obtain excellent image quality, it is preferable that the silver amount is Ig/rn' or less, while in order to obtain high maximum density and high sensitivity, the silver amount is preferably 0.3 g/m'. It is preferable that it is above.

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 [+, 0.0] planes and [+,
1. I] Any ratio of the plane can be used. Furthermore,
The crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure (core-shell type) in which the inside and outside are different. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain.
No. 934 and 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.

Alternatively, for example, seed grains may be produced using an acidic method, and then grown to a predetermined size using an ammonia method, which has a fast growth rate.When growing silver halide grains, the PH, pAg, etc. in the reaction vessel may be adjusted. It is preferable to simultaneously implant and mix silver ions and halide ions in amounts commensurate with the growth rate of silver halide grains under controlled conditions, for example, as described in JP-A-54-48521.

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein 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, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzothiazolium chloride or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chlorooleate and sodium chlorovaladate (these These substances act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in an amount of 5 X IQ-'' to 3
Optical sensitization may be achieved by adding 0 to 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, examples of the sensitizing dye used in the blue-sensitive silver halide emulsion layer include West German Patent No. 929,080, US Patent No. 2,231,858, US Patent No. 2,493,748, and US Patent No. 2,503,778. No. 2,519,001, No. 2
, No. 912,329, No. 3.856,959, No. 3,
No. 672,897, No. 3,894.217, No. 4.0
No. 25,349, No. 4.048.572, British Patent 1
, No. 242,588, Special Publication No. 44-14030, No. 5
Examples include those described in No. 2-24844. In addition, examples of sensitizing dyes used in green-sensitive silver halide emulsions include US Pat. No. 1.939,201;
Typical examples include cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in Patent No. 2,072,908, No. 2,739,149, No. 2,945,783, British Patent No. 505,978, etc. It can be mentioned as such. Further, as a sensitizing dye used in a red-sensitive silver halide emulsion, for example, US Pat.
, No. 234, No. 2,270,378, No. 2.442,
No. 710, No. 2,454,829, No. 2,776.2
Typical examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 80 and the like. Furthermore, U.S. Patent 2,213
, No. 995, No. 2,493,748, No. 2,519,
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 001 and West German Patent No. 929,080 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.

Regarding the combination of carbocyanine with a benzimidazole nucleus with other nocyanines or merocyanines, 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 the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, or acetone is prepared in advance.

Dimethylformamide or Special Publication No. 50-40659
It is used by dissolving it in a wood-loving organic solvent such as fluorinated alcohol described in No.

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.

Each of the silver halide emulsion layers according to the invention can contain a coupler, that is, a compound capable of reacting with an oxidized product of a single color developing agent to form a dye.

As the couplers that can be used in the present invention, yellow couplers, magenta couplers and cyan couplers can be used without any particular limitations. These couplers may be so-called 2-equivalent type couplers or 4-equivalent type couplers, and in combination with these couplers, it is also possible to use diffusible dye-releasing type couplers.

The yellow coupler includes an open-chain ketomethylene compound and a so-called two-equivalent type coupler.
〇-7 aryl substituted coupler, active point -〇-acyl substituted coupler, active point hydantoin compound substituted coupler, active point urazole compound substituted coupler and active point co/\phosphoric acid imide compound substituted coupler, active point fluorine substituted coupler, active point Chlorine or bromine substituted couplers, active point -0-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
．． No. 551,155, No. 3,582,322, No. 3,
No. 725,072.

No. 3,891,445, West German Patent No. 1,547,888
No., West German Application No. 2,219,1317, No. 2,28
No. 1,381, No. 2,414.006, British Patent No. 1,
425,020, JP 51-10783, JP 47-26133, JP 48-73147, JP 51-
No. 102636, No. 50-6341, No. 50-123
No. 342, No. 50-130442, No. 51-2182
No. 7, No. 50-87650, No. 52-82424,
Examples include those described in No. 52-115219 and No. 58-95346.

Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indacylon compounds.

These magenta couplers are similar to the yellow couplers 4
A specific example of a magenta coupler that may be not only an equivalent coupler but also a two-equivalent coupler is U.S. Pat.
, No. 600,788, No. 2,983,608, No. 3,
No. 082,653, No. 3,127,269, No. 3,3
No. 11.476, No. 3,419,391, No. 3.51
No. 11,429, No. 3.558,318, No. 3,58
No. 2,322, No. 3,815,506, No. 3,834
．． ! No. 308, No. 3,891,445, West German Patent 1,
No. 810.464, West German Patent Application (OLS) 2,4
No. 08,885, No. 2,417,845, No. 2,41
8. I] 5fl1 No. 2,424.467, Japanese Patent Publication No. 40-6031, Japanese Patent Publication No. 20826-1977, No. 52
-58922, 49-129538, 49-7
No. 4027, No. 50-159336, No. 52-421
Examples include those described in No. 21, No. 49-74028, No. 50-60233, No. 51-26541, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Further, useful cyan couplers used in the present invention include, for example, phenol couplers, naphthol couplers, and the like. These cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of cyan couplers include US Pat. No. 2,3811.8213;
No. 2,434,272, No. 2,474.283, No. 2,521,808, No. 2,885,828, No. 3
, No. 034,882, No. 3,311.478, No. 3,
458.315, 3,476.583, 3,5
No. 83,971, No. 3.581,383, No. 3,78
No. 7,411, No. 4,004,11211, West German Patent Application (OLS) No. 2,414,830, No. 2,45
4.329, JP-A No. 48-59838, JP-A No. 51-2
No. 6034, No. 48-5055, No. 51-14682
No. 7, No. 52-69624, No. 52-90932,
Examples include those described in No. 58-95346.

In the silver halide emulsion layer of the present invention and other photographic constituent layers, couplers such as non-diffusible DIR compounds, colored magenta or cyan couplers, polymer couplers, and diffusible DIR compounds may be used in combination. Compounds, 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. 59-198 by the present applicant.
72151 can be referred to.

For the method of adding the above-mentioned coupler that can be used in the present invention into the photographic constituent layer of the present invention, reference can be made to the method of adding the precursor of the color developing agent of the present invention, and the amount added is not limited, but Preferably IXIQ-3 to 5 moles per mole of silver, more preferably IX+o-2 to 5XlQ-1
It is.

The silver halide color photographic light-sensitive material of the present invention may contain various other photographic additives, such as antifoggants, stabilizers, ultraviolet absorbers, etc. described in Research Disclosure No. 17643, A color stain inhibitor, a fluorescent whitening agent, a color image fading inhibitor, an antistatic agent, a hardening agent, a surfactant, a plasticizer, a wetting agent, etc. can be used.

In the silver halide color 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, Any of cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, single or copolymer synthetic wood-philic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included.

Examples of the support for the silver halide color photographic light-sensitive material of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, such as a glass plate, and cellulose acetate. , polyester films such as cellulose nitrate or polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, etc. Furthermore, ordinary transparent supports may also be used, and these supports are appropriately selected depending on the intended use of the photosensitive material. Ru.

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. 2,761
, No. 781 and No. 2,11141.898 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 arbitrarily.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.

In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be similarly used as a binder, and can also be contained in the emulsion layer as described above. Various photographic additives can be included.

[Effects of the Invention] The silver halide color photographic light-sensitive material of the present invention is characterized in that at least one of the photographic constituent layers contains a precursor of the color developing agent of the present invention. The developing agent precursor of the present invention is incorporated which is stable and does not cause desensitization, fogging, staining, etc. upon storage, and sufficient color density can be obtained during development. It exhibits effects such as not remaining in silver halide color photographic materials.

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

Example 1 Silver halide color photographic light-sensitive material sample No. 1 was prepared by sequentially coating the following layers from the support side onto a paper support laminated on both sides with polyethylene.

Layer 1---1.2g/rrI'nogelatin, 0.32
A blue-sensitive silver chlorobromide emulsion (silver bromide content: 480 mol%) of g/rn' (in terms of silver, the same applies hereinafter), a yellow coupler of 0.80 g/rn' dissolved in 0.50 g/rn' of dioctyl phthalate ( A layer containing Y-1).

Layer 2 ee* 0.70g/e gelatin, 12mg
/m' anti-irradiation dye (AI-1), 6
Intermediate layer consisting of (AI-2) in mg/m''.

Layer 3 @ 1.25g/m' gelatin, 0.25g
/m' green-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%
), 0.62 g/rn' (7) F zenta coupler (M
-1) A layer containing.

Layer 4: Intermediate layer consisting of 1.20 g/rn'' gelatin.

Layer 5/8: 1.20g/rn' of gelatin, 0.3
Red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%) of 0 g/rn', cyan coupler (C-1
).

R6e""l-00g/rrl' of gelatin,
I
0,308 dissolved in g/m' dioctyl phthalate
/rn' layer containing an ultraviolet absorber (UV-1).

Layer 7 - 2.0g/rrl' of gelatin and 2X
A layer containing IQ-' moles of Exemplary Compound (3).

The following margins (Y-1) L (M-1) tz (AI-1) (AI-2) (UV-1) H In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-S- sodium triazine in layers 2.4 and 7;
Each was added in an amount of 0.017 g per Ig of gelatin.

In addition, example compound (3) of layer 6 and layer 7 in sample No. 1 was replaced with example compound (5), (9), (
10), (13) and the following comparative compounds (A), (B
), (C), (D) except for the above sample No.
Samples No. 2 to No. 9 were prepared in the same manner as Sample No. 1.

Each of the photosensitive material samples Nos. 1 to 9 was exposed through an optical wedge and then processed in the following steps.

Processing steps (38°C) Activator 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.

[Activator developer] Pure water 800+s benzyl alcohol 15m hydroxyamine sulfate 2.0g potassium bromide
1.5g sodium chloride
1.0g potassium sulfite
2.0g triethanolamine 2
．． 0g1-Hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 1.5-hydropotassium carbonate 328White
x BB (50% aqueous solution) 2mM (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 14Q 20% potassium hydroxide or 10
Adjust the pH to 11.0 with % dilute sulfuric acid.

[Bleach-fix solution] Pure water 550mM ethylenediaminetetraacetic acid M (III) ammonium
65g ammonium thiosulfate
85g Sodium Bisulfite Jog Sodium Metabisulfite 2g Ethylenediaminetetraacetic acid-disodium 20g Sodium Bromide
Add 10g of pure water to make 11, and adjust the pH to 7.0 with aqueous ammonia or dilute sulfuric acid.

The results obtained are shown in Table 1.

^ As is clear from the results in Table 1, samples No. B to 9 used for comparison all had high fog, and both sensitivity and maximum density were low. , Trial number 4 No. 1 based on the present invention
It can be seen that Samples No. 5 to 5 are excellent color light-sensitive materials incorporating the precursor compound of the present invention, which have low fog, high sensitivity, and high maximum density.

Example 2 The color photosensitive material obtained in Example 1 was heated at 50°C and 80% R.
The sample was exposed to light after being left for one week in H.H., and then subjected to the development treatment shown in Example 1 (thermo treatment), coated, dried, and then immediately exposed and developed to determine the stability of sensitivity. The results are shown in Table 2.

Immediately after application, sensitivity below margin 58 Hehe Table 2 As is clear from the results in Table 2, samples No. 8 to 8 used for comparison all had large desensitization.
Samples Nos. 1 to 5 based on the present invention had desensitization widths that were not a problem in practical use, and were found to be color light-sensitive materials that were excellent in raw storage.

Example 3 The unexposed sample obtained in Example 1 was passed through the treatment solution shown in Example 1, and then heated at 60°C and 80% RH for 2 hours.
After leaving it for a week, the blue light concentration was measured and the degree of contamination (%) was calculated. The results are shown in Table 3.

Concentration after thermo-treatment Contamination level (%) = X + OO Concentration after thermo-treatment of sample without precursor Blank Table 3 As is clear from Table 3 above, sample No. 3 containing the precursor compound of the present invention, Samples Nos. 1 to 5 have almost no residue after treatment and have little contamination, while comparative samples No. 4 and Nos. 6 to 9
It can be seen that a large amount of the precursor compound remains and the contamination is large and becomes a practical problem.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having a photographic constituent layer including at least one light-sensitive silver halide emulsion layer on a support, in which at least one of the photographic constituent layers contains:
A silver halide color photographic material containing a compound represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ In the formula, R_1 and R_2 represent substituted or unsubstituted alkyl groups having 1 to 4 carbon atoms, and are linked together to form a 5- to 7-membered heterocycle. may be formed. R_3, R_4, R_5, R
_6 each represents a hydrogen atom, a halogen atom, a hydroxy group, a substituted or unsubstituted alkyl group having 1 to 2 carbon atoms, or an alkoxy group. Ar represents an aryl group having at least one sulfonic acid or sulfonate.