JPH07119944B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a quick-acting hardener and having little fog and excellent storage stability.

(Prior Art) In recent years, silver halide color photographic light-sensitive materials have been made large in size of silver halide grains and highly activated in couplers for high sensitivity, and various high-quality images have been obtained for high image quality. Functional couplers are used.

For example, the developer deactivating DIR coupler disclosed in JP-A-57-151944 and JP-A-58-217932, U.S. Pat.
Timing type DIR couplers disclosed in JP-A Nos. 4,248,962 and JP-A-57-154234, and reaction-type DIR couplers disclosed in JP-A-60-184248 and JP-A-60-185950, etc. It is used for the purpose of improving sharpness.

These functional couplers are designed for the purpose of causing a rapid chemical reaction at a target time (for example, during development processing) and causing a predetermined effect (for example, development inhibiting effect).
Therefore, it has a structural portion with high chemical reactivity inevitably in the molecule, which makes it particularly susceptible to hydrolysis and the like due to moisture and the like.

In general, since silver halide color photographic materials use gelatin, which easily absorbs moisture, as a binder, if the silver halide color photographic materials containing the above-mentioned functional couplers are stored in a high humidity atmosphere, the functional couplers will be hydrolyzed. Probably due to decomposition, not only the prescribed image quality improving effect was not exhibited, but it could even have a fatal adverse effect on the silver halide color photographic material such as a decrease in maximum density or a decrease in sensitivity. Therefore, in order to maintain high image quality, it is necessary to store the silver halide color photographic light-sensitive material in a low humidity atmosphere.

On the other hand, in general, a layered gelatin is often used as a binder of a photographic light-sensitive material, and various compounds called hardeners are used to enhance the durability and mechanical strength of the gelatin layer. It is well known. Examples of hardeners include aldehyde compounds such as formaldehyde, compounds having a reactive halogen described in U.S. Pat.No. 3,288,775, and Japanese Patent Publication Nos. 56-48860 and 49-13563. Compounds having a reactive ethylenically unsaturated bond, aziridine compounds described in US Pat. No. 3,017,280, epoxy compounds described in US Pat. No. 3,091,537, and mucochloric acid Well-known are halogen carboxylaldehydes, dihydroxydioxane, dioxane such as dichlorodioxane, and the like. However, in all of these hardeners, the hardening action is slow in a low humidity atmosphere, and a change in photographic property due to long-term aging called "post-hardening" in the art is unavoidable.

Extremely interesting hardeners are Japanese Patent Publications Nos. 44-29622 and 47-242.
59 and 47-25373. Among the compounds disclosed in these publications, the compound containing an ether bond showed a relatively high hardening rate even in a low humidity atmosphere.

(Problems to be Solved by the Invention) However, a high-sensitivity and high-image-quality silver halide color photographic light-sensitive material to which these hardeners are applied has a minimum image density when stored for a long time under low humidity conditions. That is, there was a serious problem that the fog increased. It is often observed that the fog of a silver halide light-sensitive material increases during storage due to the presence of a reducing substance, a basic substance or the like or various chemical substances. Fog caused by these chemical substances is generally considered to be accelerated in a high-humidity atmosphere, and physical factors may be considered as the cause of the above-mentioned phenomenon of increase in fog in a low-humidity atmosphere, but details are still unknown. Not clear.

In general, a method of adding an antifoggant to a silver halide color photographic light-sensitive material is well known in the art as one means for solving the fog problem.

That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles, heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptos. Many compounds known as antifoggants or stabilizers such as tetrazoles, mercaptopyrimidines, thioketo compounds such as oxazoline thiones, azaindene compounds such as tetraazaindenes can be added.

For more detailed specific examples of these and methods for using them, see, for example, U.S. Patent Nos. 3,954,474 and 3,982,947.
No. 4,021,248 each specification, or Japanese Patent Publication No. 52-28660
The description in the publication can be referred to.

However, even if the antifoggant is applied to a silver halide color photographic light-sensitive material, various side effects are involved, so that the addition amount of the antifoggant is limited and it is difficult to sufficiently exhibit the antifoggant action.

(Object of the Invention) That is, a first object of the present invention is to provide a silver halide color photographic light-sensitive material which has less fog, excellent storability and high sensitivity and high image quality.

The second object of the present invention is to have stable performance over time,
An object of the present invention is to provide a high-sensitivity and high-quality silver halide color photographic light-sensitive material with little change in photographic performance due to post-hardening.

(Means for Achieving the Object of the Invention) As a result of various researches conducted by the present inventors, the above-described object of the present invention was to provide a silver halide color photograph having a photosensitive silver halide emulsion layer on a support. A halogen containing a light-sensitive material containing at least one mercapto compound represented by the following general formula (1) and being hardened with at least one vinyl sulfone compound represented by the general formula (2). It has been found to be achieved by a silver halide color photographic light-sensitive material.

Formula (1) Q-SH wherein Q is _{-SO 3 H, -CO 2 H,} OH, Represents a heterocyclic group having, directly or indirectly, at least one group selected from the group or a salt thereof, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, or Represents an aralkyl group.

Formula _{(2) CH 2 = CHSO 2} (CH 2) m O- (LO) p - (CH 2) n SO 2 CH = CH ₂ where, L represents a divalent organic group. m and n represent a positive integer, and p represents 0 or 1.

The mercapto compound represented by the general formula (1) in the present invention will be described in more detail.

Q in the general formula (1) represents a heterocyclic group in which at least one selected from a sulfo group, a carboxyl group, a hydroxyl group and an amino group is directly or indirectly bonded, and examples thereof include an oxazole ring, a thiazole ring and an imidazole ring,
Selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, pentazole ring, pyrimidine ring, thiazine ring, triazine ring, thiodiazine ring, etc. and rings in which these heterocycles are condensed with other carbon rings or heterocycles. Examples thereof include a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthoxazole ring, a triazaindolizine ring, a diazaindolizine ring, and a tetraazaindolizine ring.

More preferably, the mercapto compound represented by the general formula (1) can be represented by the following general formula (3).

General formula (3) In the formula, X represents COOM or SO ₃ M (M represents a hydrogen atom, an alkali metal or ammonium), n is 1 or 2, R represents a group capable of substituting for a phenyl group, and m represents 0 to 0. It is an integer of 2.

In the general formula (3), specific examples of the alkali metal include sodium, potassium, lithium and the like. Examples of ammonium include NH ₄ , N (CH ₃ ) ₄ and N (C ₂ H ₅ ) ₄ .

Further, as X, COOM is particularly preferable.

Specific examples of R in the general formula (3) include the following. That is, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, hydroxyethyl group, benzyl group, β-dimethylaminoethyl group, etc.), aryl group (eg, phenyl group, etc.) ), An alkoxy group (eg, methoxy group, ethoxy group, etc.), an aryloxy group (eg, phenyloxy group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.), an acylamino group (eg, acetylamino group, methoxymethylcarbonylamino group, etc.) ), Carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group etc.), dialkylcarbamoyl group (eg dimethylcarbamoyl group etc.), arylcarbamoyl group (eg phenylcarbamoyl group etc.), Group (eg, methylsulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group), alkylsulfonamide group (eg, methanesulfonamide group), arylsulfonamide group (eg, phenylsulfonamide group), sulfamoyl group An alkylsulfamoyl group (eg, an ethylsulfamoyl group),
A dialkylsulfamoyl group (eg, dimethylsulfamoyl group), an alkylthio group (eg, methylthio group), an arylthio group (eg, phenylthio group), a cyano group, a nitro group, a hydroxy group, an amino group and the like. When m is 2, these two substituents R may be the same or different.

Among them, R is preferably an alkyl group having 3 or less carbon atoms, a substituted alkyl group, an alkoxy group or a substituted alkoxy group.

Further, m is particularly preferably 0.

The following compounds can be illustrated as specific examples of the mercapto compound represented by the general formula (1). However, it is not limited to these compounds.

These mercapto compounds are disclosed in JP-B-40-28496 and JP-A-50
It can be synthesized by the method described in JP-A-89034.

The addition amount of the mercapto compound represented by the general formula (1) or the general formula (3) is preferably 10 ⁻⁵ mol to 10 ⁻¹ mol, and more preferably 10 ⁻⁴ mol to 5 × 10 ⁴ mol per 1 mol of silver. ^-2 mol. Further, two or more kinds of these mercapto compounds may be used in combination.

The mercapto compound used in the present invention is contained in at least one of a protective layer, a silver halide emulsion layer, an intermediate layer, a filter layer, an undercoat layer, an antihalation layer and other auxiliary layers of a silver halide color photographic light-sensitive material. Can be used.

In order to add the mercapto compound used in the present invention to these layers, the mercapto compound as it is in the coating solution, or water,
It can be added after being dissolved in a solvent such as alcohol.

Next, the hardener of the general formula (2) used in the present invention will be described in more detail. The divalent group represented by L of the general formula (2) is preferably an alkylene group having 1 to 10 carbon atoms (for example, Ethylene, trimethylene, etc.), an arylene group having 6 to 10 carbon atoms (for example, 1,4-phenylene, 1,3-phenylene, etc.), -0-, -S-, -SO-, -SO _2- , A divalent group represented by or a divalent group formed by combining a plurality of these divalent groups (for example, Etc.) are preferred. Further, it is preferable that both ends of the divalent group represented by L (portions that bond with oxygen atoms) are carbon atoms. L may be substituted. n and m are preferably integers of 1 to 6, and particularly preferably 1.

Examples of the hardener represented by the general formula (2) used in the present invention are given below, but the present invention is not limited thereto.

(H-1) CH ₂ = CHSO ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ (H-2) CH ₂ = CHSO ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ (H-3) CH ₂ = CHSO ₂ CH ₂ OCH ₂ CH ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ (H-4) CH ₂ = CHSO ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ OCH ₂ SO ₂ CH = CH ₂ These hardeners are available in Japanese Examined Patent Publication Nos. 44-29622, 47-24259, and
It is a part of the group of compounds described in publications such as 47-25373, and the synthetic method is also described in the publication.

The amount of the hardener used in the present invention can be arbitrarily selected according to the purpose. Usually 0.01 for dry gelatin
Can be used in proportions ranging from up to 20% by weight.
Particularly preferably, it is used in a proportion ranging from 0.05 to 15 weight percent.

The photographic layer using the hardener of the present invention is not particularly limited, and any gelatin-containing photographic material such as a silver halide emulsion layer and a non-photosensitive layer such as an undercoat layer, a back layer, a filter layer, an intermediate layer and an overcoat layer can be used. It can also be used for layers.

The hardener of the present invention may be used alone, or two or more hardeners of the present invention may be mixed and used. It may be used in combination with other hardeners known so far. Known hardeners include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde,
Ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-
4,6-Dichloro-1,3,5-triazine, other U.S. Pat.Nos. 3,288,775 and 2,732,303, British Patent 974,723
Nos. 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others U.S. Pat.No. 3,635,718 , Same 3,232,763
Compounds having reactive olefins described in U.S. Pat. No. 994,869, N-hydroxymethylphthalimide, and other U.S. Pat. Nos. 2,732,316 and 2,586,1
N-methylol compounds described in 68, etc., isocyanates described in U.S. Pat.No. 3,103,437, etc., aziridine compounds described in U.S. Pat.Nos. 3,017,280, 2,983,611, U.S. Pat. 2,725,294
Nos. 2,725,295 and the like, acid derivatives described in U.S. Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. Alternatively, as a hardening agent of an inorganic compound, there are chromium alum, zirconium sulfate and the like. Also, instead of the above compound, a precursor is used, for example, an alkali metal bisulfite aldehyde adduct, a methylol derivative of hydantoin, a primary aliphatic nitroalcohol, a mesyloxyethylsulfonyl compound, chloroethylsulfonyl. You may use together with a system compound. When the hardener of the present invention is used in combination with other hardeners, the use ratio of the hardener of the present invention can be selected arbitrarily depending on the purpose and effect, but the hardener of the present invention Is preferably 50 mol% or more.

A compound that accelerates hardening of gelatin may be used in combination with the hardener of the present invention. For example, the hardener of the present invention may be used in combination with a polymer having a sulfinic acid group described in JP-A-56-4141 as a hardener.

Gelatin to which the hardener of the present invention is applied, in the manufacturing process thereof, is a so-called alkali-treated (lime-treated) gelatin that is immersed in an alkali bath, a so-called alkali-treated gelatin that is immersed in an acid bath, and both treatments before extraction of gelatin. Any of double-dipped gelatin and enzyme-treated gelatin which have been subjected to Further, the hardener of the present invention can be applied to low molecular weight gelatin obtained by heating these gelatins in a water bath or causing them to act on a protease to partially hydrolyze them.

The silver halide color photographic light-sensitive material according to the present invention is preferably stored under conditions of relative humidity of 60% or less at 25 ° C., and particularly preferably of 30 to 55% relative humidity at 25 ° C.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is about 2 mol% to about 25 mol%
It is a silver iodobromide containing up to silver iodide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chemic et Phisique Photogr
aphique Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VLZelikman et al. Making and Coating Photog.
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,434.
It can be easily prepared by the method described in 226, 4,414,310, 4,433,048, 4,439,520 and British Patent 2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the above Research Disclosure (RD) No. 17643, VII-C to G.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Examined Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
No. 9, No. 4,351,897, European Patent No. 73,636, US Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (June 1984
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and U.S. Pat.
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,4.
46,622, 4,333,999, 4,451,559, 4,
Those described in 427,767, EP 161,626A and the like are preferable.

Research Disclosure No. 17643, VII-G, is a colored coupler for correcting unwanted absorption of coloring dyes.
Section, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, and British Patent 1,14.
Those described in 6,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII to F patents, JP-A-57-151944 and JP-A-57-154234.
Nos. 60-184248 and US Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
5950, couplers releasing DIR redox compounds or DIR couplers such as JP-A-62-24252 or redox compounds releasing DIR redox compounds or DIR couplers, releasing dyes that recolor after release as described in EP 173,302A Coupler, RD No. 11449, 24241, JP-A-6
Examples thereof include bleaching accelerator releasing couplers described in 1-201247 and the like, and ligand releasing couplers described in US Pat. No. 4,553,477 and the like.

Specific examples of the color coupler that can be used in the present invention are shown below, but the invention is not limited thereto.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester Kinds (trifel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexyl phenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone, etc., alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
D.No.17643, page 28, and Mo.18716, page 647, right column, 6
See page 48, left column.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD.
The development processing can be carried out by a usual method described on pages 28 to 29 of 643 and 651 left column to right column of No. 18716.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. Agent, auxiliary developing agent such as 1-phenyl-3-pyrazolidone, viscosity imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, Ethylenedia Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine- Representative examples are N, N, N ', N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, black and white development is usually performed before color development. In this black-and-white developer, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Alternatively, they can be used in combination.

The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers is
Although it depends on the color photographic light-sensitive material to be processed, it is generally 3 l or less per 1 m 2 of the light-sensitive material and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenisher. When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.
Examples of bleaching agents include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; iron (II
I) or cobalt (III) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Aminopolycarboxylic acids such as diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid or complex salts such as citric acid, tartaric acid and malic acid; persulfates; bromates; permanganates; nitrobenzenes and the like can be used. it can. Of these, aminopolycarboxylic acid iron (II) including ethylenediaminetetraacetic acid iron (III) complex salts
I) Complex salts and persulfates are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching solutions and bleach-fixing solutions. The pH of a bleaching solution or a bleach-fixing solution using these amonipolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but a lower pH can be used for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath. Specific examples of useful bleach accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988.
No. 53 / 32,736, 53-57,831, 53-37,418
No. 53, No. 53-72,623, No. 53-95,630, No. 53-95,631,
53-10,4232, 53-124,424, 53-141,623,
53-28,426, Research Disclosure No.17,129
Compounds having a mercapto group or a disulfide group described in JP-A No. 1978, July 1978; thiazolidine derivatives described in JP-A-50-140,129; JP-B-45-8,506, JP-A-52-2.
0,832, 53-32,735, thiourea derivatives described in US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-5
Iodide salts described in 8-16,235; West German Patent No. 966,410,
Polyoxyethylene compounds described in No. 2,748,430;
Polyamine compounds described in JP-B-45-8836; Other JP-A-49-42,434, 49-59,644, 53-94,927, 54-
Compounds described in Nos. 35,727 and 55-26,506 and 58-163,940; bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West Patent No. 1,290,812 and JP-A-53-95,630 are particularly preferable. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, but thiosulfates are generally used, and ammonium thiosulfate is the most widely used. Can be used for As a preservative for the bleach-fix solution, sulfite, bisulfite or carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and Televisio
n Engineers, Volume 64, P.248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In processing the color light-sensitive material of the present invention, as a solution to such a problem,
The method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Technologies" edited by the Society of Hygiene Technology and "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society for Antibacterial and Antifungal Agents can also be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9.
And preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics and use of the light-sensitive material, but in general, the range is 20 seconds to 10 minutes at 15-45 ° C, and preferably 30 seconds to 5 minutes at 25-40 ° C. To be selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No.
All known methods described in Nos. 8,543, 58-14,834 and 60-220,345 can be used.

Further, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. . Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indaniline compounds described in U.S. Pat. Salt complex, JP-A-5
The urethane compound described in 3-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention contains various 1-phenyl-containing compounds, if necessary, for the purpose of promoting color development.
You may incorporate 3-pyrazolidones. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-11.
No. 5,438 is listed.

The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is described in US Pat.
0,626, JP-A-60-133449, 59-218443, 61-23
It can also be applied to the photothermographic materials described in 8056 and European Patent 210,660A2.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

EXAMPLE On a subbed cellulose triacetate film support,
A sample 1, which is a multilayer color light-sensitive material having the following compositions, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by.

1st layer (antihalation layer) Black colloidal silver ・ ・ ・ 0.2 Gelatin ・ ・ ・ 1.3 ExM-9 ・ ・ ・ 0.06 UV-1 ・ ・ ・ 0.03 UV-2 ・ ・ ・ 0.06 UV-3 ・ ・ ・ 0.06 Solv- 1 ・ ・ ・ 0.15 Solv-2 ・ ・ ・ 0.15 Solv-3 ・ ・ ・ 0.05 Second layer (intermediate layer) Gelatin ・ ・ ・ 1.0 UV-1 ・ ・ ・ 0.03 ExC-4 ・ ・ ・ 0.02 ExF-1 ・ ・・ 0.004 Solv-1 ・ ・ ・ 0.1 Solv-2 ・ ・ ・ 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter 0.5 μm, equivalent sphere) Coefficient of diameter variation 20%, tabular grains, diameter / thickness ratio 3.0) Coating amount Silver: 1.2 Silver iodobromide emulsion (Agl 3 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, sphere equivalent diameter variation) Coefficient 15%, spherical particles, diameter / thickness ratio 1.0) Coating silver amount ・ ・ ・ 0.6 Gelatin ・ ・ ・ 1.0 ExS-1 ・ ・ ・ 4 × 10 ^-4 ExS-2 ・ ・ ・ 5 × 10 ^-5 ExC-1・ ・ ・ 0.05 ExC-2 ・ ・ ・ 0.50 ExC-3 ・ ・ ・ 0.03 ExC-4 ・ ・ ・ 0.12 ExC-5 ・ ・ ・ 0.01 4th layer (high sensitivity red Emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core shell ratio 1: 1, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 5.0) Coating silver amount ・ ・ ・ 0.7 Gelatin ・ ・ ・ 1.0 ExS-1 ・ ・ ・ 3 × 10 ^-4 ExS-2 ・ ・ ・ 2.3 × 10 ^-5 ExC-6 ・ ・ ・ 0.11 ExC-7 ・ ・ ・ 0.05 ExC-4 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.05 Solv-3 ・ ・ ・ 0.05 5th layer (intermediate layer) Gelatin ・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.1 Solv-1 ・ ・ ・ 0.05 6th layer (Low-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface high AgI type with core shell ratio 1: 1, equivalent sphere diameter 0.5 μm, variation coefficient of equivalent sphere diameter 15%, plate-like grains , Diameter / thickness ratio 4.0) Coating silver amount ・ ・ ・ 0.35 Silver iodobromide emulsion (Agl 3 mol%, uniform AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 25%, spherical particles, diameter / thickness Ratio 1.0) Coating silver amount ・ ・ ・ 0.20 Gelatin ・ ・ ・ 1.0 ExS-3 ・ ・ ・ 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 Ex S-5 ・ ・ ・ 1 × 10 ^-4 ExM-8 ・ ・ ・ 0.4 ExM-9 ・ ・ ・ 0.07 ExM-10 ・ ・ ・ 0.02 ExY-11 ・ ・ ・ 0.03 Solv-1 ・ ・ ・ 0.3 Solv-4 ・..0.05 7th layer (high-sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core shell ratio 1: 3, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter) 20%, plate-like particles, diameter / thickness ratio 5.0) Coating silver amount ・ ・ ・ 0.8 Gelatin ・ ・ ・ 0.5 ExS-3 ・ ・ ・ 5 × 10 ^-4 ExS-4 ・ ・ ・ 3 × 10 ^-4 ExS-5・ ・ ・ 1 × 10 ^-4 ExM-8 ・ ・ ・ 0.1 ExM-9 ・ ・ ・ 0.02 ExY-11 ・ ・ ・ 0.03 ExC-2 ・ ・ ・ 0.03 ExM-14 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.2 Solv-4 ・ ・ ・ 0.01 Eighth layer (intermediate layer) Gelatin ・ ・ ・ 0.5 Cpd-1 ・ ・ ・ 0.05 Solv-1 ・ ・ ・ 0.02 Ninth layer (donor layer having a multilayer effect on the red-sensitive layer) Iodobromide Silver emulsion (AgI 2 mol%, internal high AgI type with core shell ratio 2: 1, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 15%, plate-shaped particles, diameter / thickness ratio 6.0) Silver coating amount ・・ ・ 0. 35 Silver iodobromide emulsion (AgI 2 mol%, core high AgI type with core shell ratio 1: 1, sphere equivalent diameter 0.4 μm, variation coefficient of sphere equivalent diameter 20%, plate-like grain, diameter / thickness ratio 6.0) Coating silver amount ・ ・ ・ 0.20 Gelatin ・ ・ ・ 0.5 ExS-3 ・ ・ ・ 8 × 10 ^-4 ExY-13 ・ ・ ・ 0.11 ExM-12 ・ ・ ・ 0.03 ExM-14 ・ ・ ・ 0.10 Solv-1 ・ ・ ・0.20 10th layer (yellow filter layer) Yellow colloidal silver ・ ・ ・ 0.05 Gelatin ・ ・ ・ 0.5 Cpd-2 ・ ・ ・ 0.13 Solv-1 ・ ・ ・ 0.13 Cpd-1 ・ ・ ・ 0.15 11th layer (low sensitivity blue feeling) Emulsion layer) Silver iodobromide emulsion (Agl 4.5 mol%, uniform AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating amount of silver: 0.3 Silver iodobromide emulsion (Agl 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped grains, diameter / thickness ratio 7.0) Coating silver amount ・ ・ ・ 0.15 gelatin ・ ・· 1.6 ExS-6 ··· 2 × 10 -4 ExC-16 ··· 0.05 ExC-2 ·・ 0.10 ExC-3 ・ ・ ・ 0.02 ExY-13 ・ ・ ・ 0.07 ExY-15 ・ ・ ・ 1.0 Solv-1 ・ ・ ・ 0.20 12th layer (high sensitivity blue emulsion layer) Silver iodobromide emulsion (Agl 10 mol %, Internal high AgI type, sphere equivalent diameter 1.0 μm, variation coefficient of sphere equivalent diameter 25%, multiple twinned plate-like grains, diameter / thickness ratio 2.0) Coating silver amount ・ ・ ・ 0.5 Gelatin ・ ・ ・ 0.5 ExS-6・ ・ ・ 1 × 10 ^-4 ExY-15 ・ ・ ・ 0.20 ExY-13 ・ ・ ・ 0.01 Solv-1 ・ ・ ・ 0.10 13th layer (first protective layer) Gelatin ・ ・ ・ 0.8 UV-4 ・ ・ ・ 0.1 UV-5 ・ ・ ・ 0.15 Solv-1 ・ ・ ・ 0.01 Solv-2 ・ ・ ・ 0.01 14th layer (2nd protective layer) Fine grain silver iodobromide emulsion (Agl 2 mol%, uniform AgI type, equivalent spherical diameter 0.07) μm) ・ ・ ・ 0.5 Gelatin ・ ・ ・ 0.45 Polymethylmethacrylate particles (diameter 1.5 μm) ・ ・ ・ 0.2 H-1 (invention) ・ ・ ・ 0.3 Cpd-5 ・ ・ ・ 0.3 Cpd-6 ・ ・ ・ 0.3 Each layer In addition to the above ingredients, the emulsion stabilizer Cpd-3 (0.04 g
/ m ² ) and the surfactant Cpd-4 (0.02 g / m ² ) were added as coating aids.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Next, samples 2 to 7 were prepared as described below.

(Sample 2) ... Inventive Example 1 In the fourth layer, the seventh layer, and the twelfth layer of Compound 1, the compound F of the present invention was used.
-1 methanol solution at 2.5 x 10 ^-4 g / m ² , 1.8
Sample 2 was prepared in the same manner as Sample 1, except that the coating amount was × 10 ⁻⁴ g / m ² and 1.0 × 10 ⁻⁴ g / m ² .

(Sample 3) ... Inventive Sample 3 was prepared in the same manner as in Sample 2, except that F-1 added to the fourth layer, the seventh layer, and the twelfth layer of Sample 2 was replaced with the compound F-2 of the present invention. did.

(Sample 4) ... Inventive Sample 4 was prepared in the same manner as in Sample 2 except that F-1 added to the fourth layer, the seventh layer, and the twelfth layer of Sample 2 was replaced with the compound F-4 of the present invention. did.

(Sample 5) Instead of the hardener H-1 of Sample 1, the following hardener Cpd-7 was added to 0.4
Sample 5 was prepared in the same manner as Sample 1 except that the coating amount was changed to g / m ² .

The _{Cpd-7 CH 2 = CHSO 2} CH 2 CONHCH 2 CH 2 NHCOCH 2 SO 2 CH = CH 2 ( Sample 6) comparative hardener Cpd-7 instead of hardener H-1 Sample 2
0.4 g / m of except that replaced so that the coating amount ² Sample 2
Sample 6 was prepared in the same manner as in.

(Sample 7) 5.0 × 10 each of the methanol solution of the antifoggant Cpd-8 having the following chemical structure was added to the 4th layer, 7th layer and 12th layer of Sample 1 respectively.
Sample 7 was prepared in the same manner as Sample 1 except that the coating amounts were ⁻⁶ g / m ² , 3.6 × 10 ⁻⁶ g / m ² , and 2.0 × 10 ⁻⁶ g / m ² .

(Test of change in hardness over time) The prepared sample was stored in an atmosphere of 25 ° C and 40% RH, and after application, the sample was taken out at 7 days and 30 days and placed in water at 25 ° C for 3 minutes. The swollen film thickness upon immersion was measured. The swelling degree of the measured results was calculated according to the following formula, and the results are shown in Table 1.

From the results shown in Table 1, it was observed that Samples 1 to 4 and Sample 7 had an elapsed time of
The change in swelling degree was extremely small between the sample on the day and the sample on the 30th day after the elapse of time, whereas in Samples 5 and 6, the dura mater reaction was slow and the post-dural was large.

(Fog and storability test) Samples 1 to 7 were tested in an atmosphere of 25 ° C and 40% RH for 10
Sensitometry was performed by exposing the sample stored for a day and the sample further stored for 10 days in an atmosphere of 60 ° C. and 30% RH, for exposure for sensitometry, and performing the development processing described below. The results are summarized in Table 2.

(Developing method) Engineering more processing time processing temperature color developing 3 min 15 sec 38 ° C. Bleaching 6 min 30 sec 38 ° C. Washing 2 min 10 sec 24 ° C. Fixing 4 min 20 sec 38 ° C. Washing (1) 1 minute 05 seconds 24 ℃ Washing with water (2) 2 minutes 10 seconds 24 ℃ Stability 1 minute 05 seconds 38 ℃ Dry 4 minutes 20 seconds 55 ℃ Next, the composition of the treatment liquid is described.

(Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-3.0 1,1-Diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- (N- Ethyl-N-β-4.5 hydroxyethylamino) -2-methylaniline sulphate Add water 1.0l pH 10.05 (bleaching solution) (unit g) Ethylenediaminetetraacetic acid ferric iron 100.0 Sodium trihydrate ethylenediaminetetraacetic acid dinatto 10.0 Lithium salt Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5ml Add water 1.0l pH 6.0 (fixer) (Unit g) Ethylenediaminetetraacetic acid 0.5 Disodium salt sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution 170.0 ml (70%) Add water 1.0 l pH 6.7 (Stabilizer) ( Position g) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (average polymerization degree: 10) was added ethylenediamine tetraacetate 0.05 disodium salt water 1.0 l pH 5.0 to 8.0 From the results in Table 2, the sample 1 not using the antifoggant according to the present invention, the sample 5 not using the hardener and antifoggant according to the present invention and the antifoggant of the general formula (1) were used. However, in Sample 6 in which the hardener according to the present invention is not used, the fog is greatly increased by aging for 10 days at 60 ° C., 30% RH which is a severe condition for the silver halide photosensitive material. On the other hand, Samples 2, 3, and 4 using both the hardener and the antifoggant according to the present invention
Then, it can be seen that the increase in fog is small. Further, in Sample 7, a significant decrease in sensitivity was observed.

As is clear from the results shown in Tables 1 and 2, Sample 2, which is a silver halide color photographic light-sensitive material according to the present invention,
In Nos. 3 and 4, no post-dural matter was observed and it was possible to suppress an increase in fog of the photographic material stored with time.

Further, the samples 2, 3, and 4 of the present invention were processed into a 35 mm film shape, mounted on a cartridge, and stored in a cylindrical plastic cartridge case at 25 ° C. and 50% RH for 6 months. There was no deterioration in photographic performance.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photosensitive silver halide emulsion layer on a support, containing at least one mercapto compound represented by the following general formula (1), A silver halide color photographic light-sensitive material characterized by being hardened with at least one of the vinyl sulfone compounds represented by 2). Formula (1) Q-SH wherein Q is _{-SO 3 H, -CO 2 H,} OH, Represents a heterocyclic group having, directly or indirectly, at least one group selected from the group or a salt thereof, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group, or Represents an aralkyl group. Formula _{(2) CH 2 = CHSO 2} (CH 2) m O- (LO) p - (CH 2) n SO 2 CH = CH ₂ where, L represents a divalent organic group. m and n represent a positive integer, and p represents 0 or 1.