JPH01178961A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material hardly causing fogging and having superior preservability by incorporating at least one kind of specified mercapto compd. and carrying out hardening with at least one kind of specified vinylsulfone compd. CONSTITUTION:At least one kind of mercapto compd. represented by formula I is incorporated and hardening is carried out with at least one kind of vinylsulfone compd. represented by formula II. In the formula I, Q is a heterocyclic group having directly or indirectly bonded at least one group selected among -SO3H, -CO2H, -OH and -N-R<1>(-R<2>) or a salt thereof and each of R<1> and R<2> is H, alkyl or aralkyl and may be different from each other. In the formula II, L is a bivalent org. group, each of (m) and (n) is a positive integer and (p) is 0 or 1. A sensitive material hardly causing fogging and having superior raw stock preservability can be obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material which contains a rapid-acting hardening agent, has little fog and has excellent storage stability.

(Prior art) In recent years, silver halide color photographic light-sensitive materials have been made with larger silver halide grains and more active couplers in order to achieve higher sensitivity. Functional couplers are used.

For example, JP-A-57-151944 and JP-A-58-2
Developer deactivation type DIR disclosed in publications such as No. 17932
Timing type DIR couplers disclosed in publications such as U.S. Pat. Reactive DIR couplers and the like are used for purposes such as sharpening images.

These functional couplers are designed to quickly cause a chemical reaction at a desired time (for example, during development) and to bring about a predetermined effect (for example, development inhibition effect).

For this reason, it necessarily has a highly chemically reactive structural part in its molecule, which makes it susceptible to hydrolysis, etc., particularly due to moisture.

Generally, gelatin, which easily absorbs moisture, is used as a binder in silver halide color photographic materials, so if a silver halide color photographic material containing the above-mentioned functional couplers is stored in a high humidity atmosphere, the functional couplers may Perhaps because it undergoes hydrolysis, it not only does not exhibit the desired image quality improvement effect, but also causes fatal sensitization effects on silver halide color photographic materials, such as a decrease in maximum density or a decrease in sensitivity. Therefore, in order to maintain high image quality, silver halide color photographic materials must be stored in a low humidity atmosphere.

On the other hand, layered gelatin is generally used as a binder for photographic materials, and various compounds called hardeners are used to increase the water resistance and mechanical strength of the gelatin layer. This is well known. Examples of hardening agents include aldehyde compounds such as formaldehyde, compounds containing reactive halogens as described in U.S. Pat.
Compounds having reactive ethylenically unsaturated bonds as described in No. 63 and others, aziridine compounds described in U.S. Pat. No. 3,017.280, etc., U.S. Pat. No. 3,091,537, etc. Epoxy compounds described in , halogencarboxylic aldehydes such as mucochloric acid, dioxanes such as dihydroxydioxane and dichlorodioxane, and the like are well known. However, all of these hardeners have a slow hardening effect in a low-humidity atmosphere, and unavoidable changes in photographic properties due to long-term aging, which is called "post-hardening" in the art.

A very interesting hardening agent is Japanese Patent Publication No. 44-29622,
It is described in No. 47-24259 and No. 47-25373. Among the compounds disclosed in these publications, compounds containing an ether bond showed a relatively high hardening rate even in a low humidity atmosphere.

(Problems to be Solved by the Invention) However, when silver halide color photographic materials with high sensitivity and high image quality to which these hardening agents are applied, when stored for a long period of time under low humidity conditions, the minimum density of the image decreases. In other words, a serious problem occurred in that fog increased. It is often observed that fog increases in silver halide photosensitive materials during storage due to the presence of reducing substances, basic substances, etc., or due to various chemical substances. Normally, fog caused by these chemicals is thought to be more accelerated in a high-humidity atmosphere, and physical factors may also be responsible for the phenomenon of increased fog in a low-humidity atmosphere, but the details are still unclear. It's not clear.

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

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

For more detailed information on these and how to use them, see, for example, the specifications of U.S. Pat. No. 3,954.474, U.S. Pat. The description in Publication No. 28660 can be referred to.

However, even when the above-mentioned anti-fogging agent is applied to a silver halide color photographic light-sensitive material, various side effects occur, and the amount of the anti-fogging agent added is limited, making it difficult to fully exhibit its anti-fogging effect.

(Objective of the Invention) A first object of the present invention is to provide a silver halide color photographic light-sensitive material with low fog, excellent storage stability, 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 silver halide color photographic light-sensitive material with high sensitivity and high image quality with little change in photographic performance due to post-hardening.

(Means for Achieving the Object of the Invention) As a result of various studies, the present inventors have found that the above-mentioned object of the present invention is to provide a silver halide color photograph having a light-sensitive silver halide emulsion layer on a support. In photosensitive materials, the following general formula (
A silver halide color photographic light-sensitive material containing at least one mercapto compound represented by formula (1) and further hardened with at least one vinyl sulfone compound represented by general formula (2). It was found that this can be achieved by

RISR2 represents a heterocyclic group having directly or indirectly at least one group selected from general formula (1) or a salt thereof, and RISR2 may be the same or different, and may be a hydrogen atom, an alkyl group, or an aralkyl group. Hail to the foundation.

General formula (2) % formula % In the formula, L represents a divalent organic group. m and n represent positive integers, and p represents 0 or l.

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

Q in the general formula (1) represents a ring group directly or indirectly bonded to at least one selected from a sulfo group, a carboxyl group, a hydroxyl group, and an amino group, such as an oxazole ring, a thiazole ring, and an imidazole ring. ,
Selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, bentazole ring, pyrimidine ring, thiazine ring, triazine ring, thiodiazine ring, etc., and rings in which these heterocycles are further fused with other carbocycles or heterocycles, such as Examples 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 of general formula (1) can be represented by the following general formula (3).

General formula [3] In the formula, X represents C [lOM or SD, M represents a hydrogen atom, an alkali metal or ammonium),
n is 1 or 2, R is a group capable of substituting a phenyl group, and m is an integer of 0 to 2.

In the above general formula (3), specific examples of the alkali metal include sodium, potassium, and lithium. As ammonium, NH<, N(C)13)
4, N(C2H5)4, and the like.

Further, as X, C00M is particularly preferable.

In general formula (3), R can specifically include the following. That is, halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, hydroxyethyl group, benzyl group, β-dimethylaminoethyl group, etc.), aryl groups (e.g. phenyl group, etc.) ), alkoxy groups (e.g., methoxy group, ethoxy group, etc.), aryloxy groups (e.g., phenyloxy group, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl group, etc.), acylamino groups (e.g., acetylamino group, methoxymethylcarbonylamino group, etc.) ), carbamoyl group, alkylcarbamoyl group (e.g. methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (e.g. dimethylcarbamoyl group etc.), arylcarbamoyl group (e.g. phenylcarbamoyl group etc.), alkylsulfonyl group (e.g. methylsulfonyl group) ), arylsulfonyl group (e.g. tlf phenylsulfonyl group, etc.), alkylsulfonamide group (e.g. methanesulfonamide group etc.), arylsulfonamide group (e.g. phenylsulfonamide group etc.), sulfamoyl group, alkylsulfamoyl group ( For example, ethylsulfamoyl group)
, dialkylsulfamoyl group (eg, dimethylsulfamoyl group), alkylthio group (eg, methylthio group), arylthio group (eg, phenylthio group, etc.), cyan group, nitro group, hydroxy group, amino group, etc. When m is 2, these two substituents R may be the same or different.

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

Furthermore, m is particularly preferably 0.

Specific examples of the mercapto compound represented by general formula (1) include the following compounds. However, it is not limited to these compounds.

F-I F-2 F-3F-4 F -5F -6 -7F-8 F-9F-10 and UUNH4 F -11F -12 iuu F-18 F-19 O3H These mercapto compounds are issue,
It can be synthesized by the method described in JP-A-50-89034.

The amount of the mercapto compound represented by general formula (1) or general formula (3) added is 10-' mol-1 per mol of silver.
The amount is preferably 0-1 mol, more preferably 10-4 mol-5X10-'' mol. Two or more of these mercapto compounds may also be used in combination.

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

The mercapto compound used in the present invention can be added to these layers either directly in the coating solution or in water,
It can be added after being dissolved in a solvent such as alcohol.

Next, to explain in more detail about the hardening agent of general formula (2) used in the present invention, the divalent group represented by
For example, ethylene, trimethylene, etc.), carbon number 6-1
0 arylene groups (e.g., 1,4-phenylene, 1.
3-phenylene, etc.), -0-1-S-, -5O-1
-SO2-, divalent C)I2- represented by -C- is preferred. Further, both ends (portions bonding to oxygen atoms) of the divalent group represented by are preferably carbon atoms.

L may be substituted. n1m is preferably an integer of 1 to 6, and particularly preferably 1.

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

(H-1) C)1. =CH5O2CH20CH,SO,CH=CH
2(H-2) CHa=CH302C)1-QC)lacH20C)1
2SO2CH=CH2()I-3) CH,=CH502CH20CH2CHICH20CI
(2SO21JI=CH2(H-4) C11,=CH302CH20CH2C)120C11
,CH,0CH2SO□C)I=CII.

These hardening agents are disclosed in Japanese Patent Publication No. 44-29622 and No. 47-
It is part of a group of compounds described in publications such as No. 24259 and No. 47-25373, and the synthesis method is also described in the above publications.

The amount of hardening agent used in the present invention can be arbitrarily selected depending on the purpose. Usually 0 for dry gelatin
．． It can be used in proportions ranging from 10% to 20% by weight. Particular preference is given to using proportions ranging from 0.05 to 15 percent by weight.

There is no particular limitation on the photographic layer using the hardener of the present invention, and any gelatin-containing photographic layer, such as a silver halide emulsion layer, as well as a non-light-sensitive layer, such as an undercoat layer, a back layer, a filter layer, an intermediate layer, an overcoat layer, etc. It can also be used for layers.

The hardener of the present invention may be used alone, or two or more kinds of hardeners of the present invention may be used in combination. It may also be used in combination with other hardening agents known so far. Known hardeners include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetinopecyclopentanedione, bis(2-chloroethyl urea), and 2-hydroxy-4
, 6-dichloro-1,3,5-) riazine, and other U.S. Pat.
No., British Patent No. 974,723, 1. 167,
Compounds containing reactive ologens, divinylsulfone, 5-acetyl-1, etc., as described in No. 207, etc.
3-diacryloylhexahydro-1,3,5-triazine, etc. U.S. Pat. No. 3.635.718, No. 3
, 232,763, British Patent No. 994°869, etc., compounds having reactive olefins,
N-hydroxymethylphthalimide, other N-methylol compounds described in U.S. Pat. Nos. 2,732,316 and 2,586,168, U.S. Pat.
103,437 etc.)
, U.S. Pat. No. 3,017,280, 2. 983.
Aziridine compounds described in No. 611, etc., U.S. Pat. No. 2,725,294, U.S. Pat.
Acid derivatives described in US Pat. No. 3.09, etc.
Epoxy compounds described in No. 1,537, etc.
Examples include halogencarboxaldehydes such as mucochloric acid.

Alternatively, inorganic compound hardeners include chrome light pan, zirconium sulfate, and the like. In addition, compounds in the form of precursors instead of the above compounds, such as alkali metal bisulfite aldehyde adducts, methylol derivatives of hydantoin, primary aliphatic ditroalcohols, mesyloxyethylsulfonyl compounds, chloroethyl It may also be used in combination with sulfonyl compounds. When using the hardener of the present invention in combination with other hardeners, the ratio of the hardener of the present invention to be used can be selected as desired depending on the purpose and effect. is preferably 50 mol% or more.

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

The gelatin to which the hardening agent of the present invention is applied is subjected to so-called alkali-treated (lime-treated) gelatin immersed in an alkaline bath, acid-treated gelatin immersed in an acid bath, or both treatments before gelatin extraction. Either double-soaked gelatin or enzyme-treated gelatin may be used. Furthermore, this hardening agent can also be applied to low molecular weight gelatin which has been partially hydrolyzed by heating the gelatin in a water bath or by treating it with a proteolytic enzyme.

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

(Left below) The preferred silver halide contained in the photographic opalescent layer of the photographic photonic material used in the invention is silver iodobromide, silver iodochloride, or silver iodochloride, which contains about 30 mol% or less of silver iodide. This is chlorbromide. Particularly preferred is about 2 mol % to about 25 mol %.
Silver iodobromide containing up to mol% silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or may be a composite form thereof.

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

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD),
(December 1978), pp. 22-23, 2■, Emulsion preparation and
18716 (November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, Glafkides).

Chewic at Ph1Sique Photog
raphique paul montel.

1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Duffin, Photog)
rapicEmulsion Che+m1stry
(Focal Press+ 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelikman at al,
Making and Coating Photogr
aphic Emulgion+ Focal Pre
ss.

(1964) and others.

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4,
434゜226, 4,414,310, 4,4
33.048, British Patent No. 4,439.520 and British Patent No. 2,112.157.

The crystal structure may be --like, or it may have a layered structure in which the inside and outside have different halogen compositions, or it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver oxide or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement. Additives used in such processes are Research Disclosure N11
17643 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 descriptions are shown in the table below.

Additive type RD17643 RD18716
1 Chemical sensitizers Page 23 Page 648 2 Sensitivity increasing agents
Same as above 4 Brightening agent page 24 8 Dye image stabilizer page 25 9 Hardening agent page 26 Page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27, page 650, right (funds) prevention.In the present invention, various color couplers can be used.
RD) No. 17643, described in the patent described in ■-cc.

As a yellow coupler, for example, U.S. Patent Box 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1,425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, No. 4.351°897, European Poetry No. 73,636, U.S. Patent Box No. 3.061.432, No. 3,725.067, Research Disclosure? h 24220 (June 1984), Japanese Patent Application Publication No. 1986-
No. 33552, Research Disclosure 242
30 (June 1984), JP-A No. 60-43659,
U.S. Patent Box 4,500,630, U.S. Patent No. 4,540.6
Particularly preferred are those described in No. 54 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 4°-052,21.
No. 2, No. 4.146.396, No. 4,228,2
No. 33, same No. 4. No. 296.200, No. 2,369
．． No. 929, No. 2,801.171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
No. 72.002, No. 3,758,308, No. 4,
No. 334.011, No. 4.327,173, West German Patent Publication No. 3.329,729, European Patent No. 121.3
No. 65A, U.S. Patent Box 3,446,622, U.S. Patent No. 4.
No. 333,999, No. 4,451.559, No. 4
, 427.767, European Patent No. 161.62'6A, etc. are preferred.

Colored couplers to correct unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent Box 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent Box 4,004,929, U.S. Patent Box 4,138,258, British Patent Box 1,146.36
The one described in No. 8 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96.570 and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820, U.S. Pat.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Patent No. 4,130,427, U.S. Pat. , the multi-light coupler described in JP-A-60-185950, etc.
Couplers or D that release DIR redox compounds or DIR couplers described in JP-A No. 62-24252, etc.
IR redox compounds or redox compounds releasing DIR couplers, couplers releasing color after separation as described in European Patent No. 173°302A, R,D
, Nα11449, Nα24241, JP-A-61-20
Examples include bleach accelerator-releasing couplers such as those described in US Pat.

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

C-(21 C-f3) C-(4) C-+5+ I C-(61 Cβ Molecular weight approximately 40.000 C-(71 C-(81 C-αυ II H CJ+t(t) H H H (i) CJq(IUUNH C-0I CHi C-0η ■ 5CI1.C112COJ C-(To) H C-Shout H bUkoNa C-(24) C-(25) C-(26) II C-(27) C- (28) 0■ C-(29) H C-(30) C-(31) C-(32) H 0CHzGHzCON)ICHzCHzOCHsc -
(33) N -"l'1 C-(34) H H C-(35) C-(36) OH C-(3B) C+oHz+ C-(39) I C-(40) H-I C-( 41) OH C-(44) C-(45) C! c-(46) HC-(47) I C-(48) HC-(49) C-(50) C-(51) C= (53) Il C-(54) c-(55) C-(56) C-(57) Cσ C-(58) Cσ 13 C-(59) r σ C-(60) Used in the present invention Couplers can be introduced into light-sensitive materials by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2.322.027 and the like.

Specific examples of high-boiling organic solvents with 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(2,4-di(-amylphenyl)phthalate, bis(2,4-di-t-amylphenyl)isophthalate, bis(l,1-diethylpropyl)phthalate, etc.), phosphoric acid or Phosphonic acid esters (trifel phosphate, tricresyl phosphate, 2
-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
di-2-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N,N-diethyldodecanamide, N,N-diethyllaurylamide, N-tetra decylpyrrolidone, 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.). In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C.
Any organic solvent having a temperature above about 160° C. or below can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like. .

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. etc. are listed.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643, and 6 of 18716
It is described from the right column on page 47 to the left column on page 648.

The color photographic light-sensitive material according to the present invention is described in the above-mentioned RD, 17643, pages 28-29, and 6th page of the same point 18716.
51. Development processing can be carried out by the usual methods described in the left column to right column.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phinidine diamine compounds are preferably used, and a typical example is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-N-ethyl-N
-β-゛Hydroxyethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-)luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl t-mycarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabicyclo[2゜2.2]octane), various preservatives such as ethylene glycol, organic solvents such as diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, foggers such as sodium poron hydride. agents, auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various calcinates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, e.g. , ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1
, 1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N.

N'', N''-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid).

and their salts are representative examples.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer may be a known black and white developer, such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. is common. The amount of replenishment of these developing solutions depends on the color photographic material to be processed, but it is generally less than 31 d per square meter of photosensitive material, and can be reduced to less than 500 d by reducing the bromide ion concentration in the replenishing solution. You can also do that. When reducing the amount of replenishment, it is preferable to prevent evaporation of the solution and air oxidation by reducing the contact area with the air in the processing tank, and by using means to suppress the accumulation of bromide ions in the developer. It is also possible to reduce the amount of replenishment.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As a bleaching agent, for example, iron(]III, Kobal)
Compounds of polyvalent metals such as (I [[), chromium (■), copper (It)), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methylimino vinegar fl, 1. Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfates; bromates; permanganates; nitrobenzenes, etc. may be used. Can be done. Among these, aminopolycarboxylic acid iron (III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (I ) Complex salts are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach or bleach-fix solution using these aminopolycarboxylic acid iron (nr) FF salts is usually 5.5 to 8, but in order to speed up the processing, the pH may be lower. can.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, US Pat.
．． No. 290,812, No. 2,059°988, JP-A No. 53-32.736, No. 53-57.831, No. 5
No. 3-37.418, No. 53-72,623, No. 53
-95.630, 53-95,631, 53-
No. 10.4232, No. 53-124,424, No. 53
-141.623, 53-28.426, Research Disclosure! No. 17,129 (1978
Compounds having a mercapto group or disulfide group as described in J.K. Publication No. 50-1'40.129; Japanese Patent Publication No. 45-8,506; No. 20,832, No. 53-32,735
Thiourea derivatives described in U.S. Pat. No. 3,706,561;
- Iodide salt described in No. 16゜235; West German special product lol 966
Polyoxyethylene compounds described in Japanese Patent Publication No. 410, No. 2,748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836; Others No. 49-42.434;
No. 49-59,644, No. 53-94,927, No. 54-35.727, No. 55-26.506 No. 58
Compounds described in No.-163.940; bromide ions, etc. can be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred in the US.
Sakusaku Sho 3.893.858, Nishi Tokusaku Sho 1.290.81
No. 2, JP-A No. 53-95,630 is preferred, and compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization process after the a-silver treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, the materials used, such as couplers).

It can be set over a wide range depending on the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as counterflow or forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the
5ociety of Motion Picture
and Televisjon Engineers Vol. 64, P, 248-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8.542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, "Microbial It is also possible to use disinfectants described in "Sterilization, Disinfection, and Anti-Mildew Techniques" and "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japan Antibacterial and Antifungal Society.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Laid-Open Nos. 57-8,543 and 58-14.8
All known methods described in No. 34 and No. 60-220.345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. US special lol 3,342.59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159, aldol compounds described in No. 13.924, US Special Works 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35.628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Typical compounds that may contain pyrazolidones are disclosed in JP-A-56-64,339 and JP-A-7-144,547.
No. 58-115.438, etc.

The various processing solutions used in the present invention are used at a temperature of 10°C to 50°C. Normally, the temperature is 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time, or vice versa. It is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Tokusaku No. 2, 226.770 or American Tokusaku No. 3.674.499 is carried out. Good too.

Furthermore, the silver halide photosensitive material of the present invention is a US special product.
No. 500.626, JP-A No. 60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.660A2, and the like.

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

EXAMPLE On a subbed cellulose triacetate film support,
Sample 1, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/m'' of silver for silver halide and colloidal silver, and the amount expressed in g/m'' for couplers, additives and gelatin.
Regarding the sensitizing dye, the number of moles is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver...0,2 gelatin
...1.3ExM-9...0.
06 UV-1...0.03 UV-2...0.06 UV-3...0.06 Solv, -1...0. 15 SO1v-2・・・0.15 Solv-3・・・・Ol 05 2nd layer (middle layer) Gelatin...1.0UV-1・
...0.03 ExC-4...0.02 ExF-1...0.004 Solv-1...0. l 501v-2...0.1 3rd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform Agl type, equivalent sphere diameter 0.5 μm 1 sphere equivalent diameter coefficient of variation 2
0%, plate-like grains, diameter/thickness ratio 3.0) Coating amount silver...1.2 Silver iodobromide emulsion (AgI 3 mol%, uniform Agl type, equivalent sphere diameter 0.3 μm, variation in 1 sphere equivalent diameter) coefficient 1
5%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0.6 Gelatin...1.0ExS-1
...4x10-4 ExS-2...5X10-" ExC-1...0.05 ExC-2...l), 50 ExC-3...0.03 ExC-4...0. 12 ExC-5=・0101 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 mol%, internal cloth AgI type with core-shell ratio 1:1, equivalent sphere diameter 0.7 μm, variation in 1 sphere equivalent diameter) Coefficient 15%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount...0.7 Gelatin...1.0ExS-1
...3X10-'ExS-2...2.3XIO-' ExC-6...0. 11 ExC-7...0.05 ExC-4=・0.05 SO1v-1・・・0.05 Solv-3・・l), 05 5th layer (middle layer) Gelatin...0.5Cpd -1
, -0O,1 S01v-1...0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface cloth Agl type with core-shell ratio 1:1, equivalent sphere diameter 0 Coefficient of variation of .5 μm 1 sphere equivalent diameter 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount...0.35 Silver iodobromide emulsion (AgI 3 mol%, uniform-Agl type, sphere equivalent diameter Coefficient of variation of 0.3 μm 1 sphere equivalent diameter 2
5%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0.20 Gelatin...1.0ExS-3
...5X10-'ExS-4...axto-' ExS-5... 1x10-4 ExM-8... 0.4 ExM-9... 0.07 ExM-10... 0. 02 ExY-11・・・0. 03 Solv-1・・11. 3 Solv-4・・・0.05 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type with core-shell ratio 1:3, equivalent sphere diameter 0.7 μm, equivalent to 1 sphere) Coefficient of variation of diameter 20%, plate-like particles, diameter/thickness ratio 5.0) Coated silver amount...0.8 Gelatin...0.5ExS-3
...5 X 10-'ExS-4...axto-' EXS-5...1x104 ExM-8...0. I ExM-9...0. 02 ExY-11...0. 03 ExC-2・ ・ ・0.03 ExM-14・ ・・0.01 SO1v-1・ ・・0.2 Solv-4・ ・・0. 01 8th layer (middle layer) Gelatin...0.5Cpd-1
...0.05 SO1v-1 ...0.02 9th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, core shell ratio 2:1 internal height A)
gI type, equivalent sphere diameter 1.0 μm, coefficient of variation of 1 sphere equivalent diameter 15
%, plate-like grains, diameter/thickness ratio 6.0) Coated silver amount...0.35 Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type with core-shell ratio 1:1, equivalent sphere diameter 0.4 μm1) Coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 6.0) Coated silver amount...0.20 Gelatin...0. 5ExS-
3...8xlO-' ExY-13...0.11 ExM-12...0.03 ExM-14. . . . 0. 10 Solv-1・・・0.20 1st O layer (yellow filter layer) Yellow colloidal silver...0.05 Gelatin...0.5Cpd-2...
0.13 SO1v-1...0.13 Cpd-1...0.10 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4.5 mol%, uniform-Agl type,
Equivalent sphere diameter: 0.7 μm Coefficient of variation of equivalent sphere diameter: 15%, plate-like grains, diameter/thickness ratio: 7.0) Coated silver amount: 0.3 Silver iodobromide emulsion (Ag: 13 mol%, uniformly Agl type) , equivalent sphere diameter 0.3 μm 1 coefficient of variation of equivalent sphere diameter 2
5%, plate-shaped particles, diameter/thickness ratio 7.0) Coated silver amount...0.15 Gelatin...1.6ExS-6
...2 X 10-'ExC-16-'・""0. 05 ExC-2-...0. 10 ExC-3...0.02 ExY-13...0.07 ExY-15=1. 0 SOIv-1...0.20 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm, coefficient of variation of one sphere equivalent diameter 25 %, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver amount...0.5 Gelatin...0.5ExS-6
...lX1O-4 ExY-15...0.20 ExY-13...0.01 5O1v-1...0.10 13th layer (first protective layer) Gelatin...0.8UV- 4.
・・0. l UV-5...0.15 SO1v-1...0.01 S01v-2...0.01 14th layer (second protective layer) Fine grain silver iodobromide emulsion (Ag 12 mol%, uniform AgI type,
Equivalent sphere diameter: 0.07 μm)...0.5 Gelatin...0.45 Polymethyl methacrylate particles (diameter: 1.5 μm)...0.2H-1(
present invention)...0.3Cpd-5...
0.3 Cpd-6...0.3 In addition to the above components, each layer contains emulsion stabilizer cpa-3 (
0,04 g/m'), surfactant Cpd-4 (0,0
2 g/m'') was added as a coating aid.

v-5 SOIV-1 tricresyl phosphate 5olv-2 dibutyl phthalate 0IV-3 3o1. v-4 Cpd' C6H13Cpd-2 Cpd, -3 Cpd-4 Cpd-5 Cpd-5 CH3 1(H xC-1 xC-2 H (+)C4HsOCNl(I xC-3 H XC-4 H mouth CH2 H, C-C-CH3 CH3 c (CH3)s ExC-7 DH (i)C,H,0OCN)l 0CHzCH2
SCH2CDDHxM-8 C1molowt, FIXυ, υUυExM 9
0CH3I XM-10 l xY-11 IOs xY-13 XM-14 ExY-15 ExC-16 H xS-I xS-2 xS-3 (CI'12) 5s03Na ~7 were created as follows.

(Sample 2) ... 2.5XIP'g/methanol solution of the compound F-1 of the present invention was added to the 4th layer, 7th layer, and 12th layer of the present sample 1, respectively.
rn', 1.8 Xl0-'g/m', 1. OXl0-
Sample 1 except that it was added to give a coating amount of 'g/m'.
Sample 2 was prepared in the same manner as above.

(Sample 3) Sample 3 was prepared in the same manner as Sample 2 except that F-1 added to the 4th layer, 7th layer, and 12th layer of Sample 2 of the present invention was replaced with Compound F-2 of the present invention. It was created.

(Sample 4) Sample 4 was prepared in the same manner as Sample 2 except that F-1 added to the 4th layer, 7th layer, and 12th layer of Sample 2 of the present invention was replaced with compound F-4 of the present invention. It was created.

(Sample 5) The following hardener (: pcl
Sample 5 was prepared in the same manner as Sample 1 except that -7 was replaced with a coating amount of 0.4 g/rn'.

pd-7 CTo=CH3口2CH2CONHCH2CH, NHC
OCH2SO2CH=C)l.

(Sample 6) Comparative hardener Cpd- instead of hardener H-1 of sample 2
Sample 6 was prepared in the same manner as Sample 2 except that Sample 7 was changed to have a coating amount of 0.4 g/m'.

(Sample 7) A methanol solution of Cpd-8, an antifoggant having the following chemical structure, was added to the 4th layer, 7th layer, and 12th layer of Sample 1 at 5.0 x 10-'g/m'' and 3.6 x 10-g/m, respectively. -' g
Sample 7 was prepared in the same manner as Sample 1 except that it was added in a coating amount of 2.0XIO'g/m'.

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

Table 1 From the results in Table 1, samples 1 to 4 and sample 7 showed
The change in wIfJ degree is extremely small between the 300-day sample and the 300-day sample, whereas in Samples 5 and 6, the dura reaction is slow (and the posterior dura is large).

(Fog, preservation test) Samples 1 to 4 and sample 7 where the posterior dura was hardly seen
A sample stored for 10 days in an atmosphere of 25°C and 40% RH and a sample further stored for 10 days in an atmosphere of 60°C and 30% RH were exposed to light for sensitometry, and developed as shown below. I went there and did sensitometry. The results are summarized in Table 2.

(Development processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38℃ Bleaching 6 minutes 30 seconds 38℃ water washing
2 minutes 10 seconds 24℃ fixation 4 minutes 20
Seconds Wash with water at 38℃ (1) 1 minute 05 seconds Wash with water at 24℃ (2) 2 minutes 10 seconds 24℃ Stable 1 minute 05 seconds Dry at 38℃
4 minutes 20 seconds 55°C Next, the composition of the treatment liquid will be described.

(Color developer) (Unit g) Diethylenetriaminepentaacetic acid 1.01-hydroxyethylidene-3,0 1,1-diphosphonic acid sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide
1.4 potassium iodide
Add 1.5 mg hydroxylamine sulfate 2.4 4-(N-ethyl-N-β-4,5 hydroxyethylamino)-2-methylaniline sulfate water and 1.01 pi
to, 05 (bleaching solution) (unit: g) Ferric ethylenediaminetetraacetate 100.0 Sodium trihydrate Ethylenediaminetetraacetic acid disodium 10.0 Lium Ammonium chlorobromide 140.0 Ammonium nitrate 30.0 Aqueous ammonia (
27% > Add 6.5ml water
1.0RpH6.0 (Fixer) (Unit g) Ethylenediaminetetraacetic acid 0.5 Disodium salt Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate aqueous solution 170. Omf (70%) Add water 1. Ol1pH
6,7 (Stabilizing liquid) (Unit: g) Formalin (37%) 2. Ord
Polyoxyethylene-p-0,3 Monononyl phenyl ether (average degree of polymerization 10) Ethylenediaminetetraacetic acid 0.05 Add disodium salt water 1.0R pH5
, 0 to 8.0 (blank below) Table 2 From the results in Table 2, for sample 1, 60°C, 30% RH11
It can be seen that while the fog greatly increases after 0 days of aging, the increase in fog is small in Sample 2.3.4 of the present invention. Further, in sample 7, a significant decrease in sensitivity was observed.

As is clear from the results in Tables 1 and 2, Sample 2.
In No. 3.4, no posterior dura mater was observed, and it was possible to suppress the increase in fog on the raw material over time.

Furthermore, even if sample 2.3.4 of the present invention was processed into a 35 mm film, attached to a cartridge, and stored in a cylindrical plastic cartridge case for 6 months in an atmosphere of 25°C and 50% RH, no There was no deterioration in photographic performance.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having a light-sensitive silver halide emulsion layer on a support, containing at least one mercapto compound represented by the following general formula (1), and further comprising a mercapto compound represented by the general formula (1). A silver halide color photographic light-sensitive material, characterized in that it is hardened with at least one vinyl sulfone compound represented by (2). General formula (1) Q-SH In the formula, Q directly or indirectly represents at least one group selected from the group of -SO_3H, -CO_2H, -OH, ▲a mathematical formula, a chemical formula, a table, etc., or a salt thereof. R^1 and R^2 may be the same or different, and represent a hydrogen atom, an alkyl group, or an aralkyl group. General formula (2) CH_2=CHSO_2(CH_2)_mO-(L-O
)_p-(CH_2)_nSO_2CH=CH_2 In the formula, L represents a divalent organic group. m and n represent positive integers, and p represents 0 or 1.