JPS63254453A - Silver halide color photographic sensitive material and method for processing same - Google Patents

Abstract

PURPOSE:To improve the sharpness and the graininess of a color image, and to prevent the pollution of a color developer by incorporating a specified DIR coupler in the titled material. CONSTITUTION:The DIR coupler shown by formula I is incorporated in the titled material. In the formula, A is a component capable of releasing a residual group shown by formula II by a reaction with the oxidant of an aromatic primary amine developing agent, TIME is a timing group capable of releasing a residual group shown by formula III after releasing from the group A by a reaction, Z is a nonmetallic atom group necessary for forming a heterocyclic ring together with C and N atoms, L is a divalent bonding group or a single bonding group, R is 1-6C alkyl group, (m) is 0 or 1. The concrete example of the coupler shown by the formula is a compd. shown by formula IV, etc. The titled material is preferably processed with the color developer which has 8-10<-2>mol./l a sulfite ion concn., at pH of 9.5-10.5.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material.
Inhibitor Releasing Co.
The present invention relates to a silver halide color photographic light-sensitive material which has better color image sharpness and graininess than K and which is free from contamination of a color developing solution.

(Prior art) When a silver chloride color photographic material is subjected to seven-color development, an oxidized aromatic-amine color developing agent and a coupler react with each other to produce indophenol, indoanyl,
It is known that dyes such as i/damine, azomethine, phenoxazine, phenazine and similar dyes are produced and color images are formed. In this method, a subtractive color method is usually used for color reproduction, with a silver halide emulsion selectively sensitive to evening, green, and red, and yellow, which has a relationship with the remaining colors, respectively.
Maze/red and cyan color VFI imagers are used. To form a yellow color image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta color image, pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetophenone or the like are mainly used. For example, indacylon couplers are used, and phenolic couplers such as phenols and naphthols are mainly used to form cyan images.

Normally, color photographic materials are roughly divided into two types: an external method in which couplers are placed in a developing solution, and an internal method in which couplers are incorporated in each photosensitive layer of the material so as to maintain their independent functions. Ru. In the latter, the dye-forming coupler is added to the Helog/Silver Fide emulsion. The coupler added to the emulsion must be non-diffuse (diffusion resistant) in the emulsion binder matrix.

Conventionally, it has been known to include a compound t1 in a photographic light-sensitive material, which releases a development inhibitor in accordance with the density of an image during development. This compound generally reacts with the oxidation product of the color developing agent to release a development inhibitor, and typically it is placed in the active position of the coupler, and when released from the active position, it releases a development inhibitor. So-called DIR couplers into which a group having an inhibitory effect is introduced are known. DIR,
The coupler couples with the oxidation product of the color developing agent to form a dye while releasing a development inhibitor.

As a DIR coupler, U.S. Patent No. 3.227°111
No. 7, J, 70/, No. 713, No. 3. t/, t, 1
Compounds described in No. 04, J, t/7, 2ri No. 1, etc.
Moreover, as further improved versions of these compounds, compounds described in US Pat.

As is well known from the above-mentioned specification υ, DIR couplers are used for purposes such as improving the sharpness of color images due to the edge effect and improving color reproducibility due to the multilayer effect.

Although known DIR couplers have a certain degree of performance, it has been desired to further improve the performance. In particular, known DIR couplers have a drawback in that when the development inhibitor released during color development diffuses from the light-sensitive material into the processing solution, it accumulates in the processing solution, resulting in the processing solution exhibiting a development inhibiting effect.

In the method of continuously processing a large amount of sensitive material, that is, the processing method that is common commercially, it is difficult to always obtain a constant gradation, and the processing solution using the development inhibitor released by DI Kagura is difficult to obtain. Pollution was a serious problem.

In the past, expedient measures have been taken to solve this problem, but they have some drawbacks, and no fundamental solution is known. For example, the usage amount t″ of D L coupler
There are two methods: a method in which the color development processing solution is repeatedly replaced with a new one, and a method in which a new fine grain emulsion layer is provided on the photosensitive material to capture the development inhibitor washed away from the photosensitive layer. These methods have drawbacks such as reducing the photographic quality improvement effect of the DI coupler or greatly increasing costs.

On the other hand, U.S. Patent No. 1≠77JtJ and Japanese Patent Application Laid-Open No. 77-2OJO propose a method to fundamentally solve this problem, in which a development inhibitor released by the DIR coupler is introduced into the developer solution (e.g. DI lucazoles have been proposed that are designed to lose development inhibitors by the action of hydroxide ions, hydroxylamine, etc.). However, it has been found that among the development inhibitors released by DIR Kagura described in this patent, mercapto-substituted heterocycles are not deactivated at an appropriate speed in a developing solution.

In other words, if it is too early, it may not exhibit sufficient development inhibiting properties to express the function of the DIR coupler, or if it is too late, it may accumulate in the developer and deteriorate the performance of the developer, or it may react with components in the developer. 5) The resulting product accumulates in the developing solution, causing stains such as coloring. 5) L) IR couplers have disadvantages such as poor manufacturing suitability and high cost.

(Problems to be Solved by the Invention) The first object of the present invention is to provide excellent image sharpness and graininess;
Another object of the present invention is to provide a silver halide color photographic light-sensitive material and a processing method thereof, which are free from contamination of a developing solution.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing an IR compound, which is excellent in manufacturing suitability and is inexpensive, and a processing method thereof.

An object of the present invention is to provide a silver nine halide color photographic material having excellent storage stability.

(Means for Solving the Problems) The objects of the present invention have been achieved by the following (1) and (2).

(1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer 1 on a support, which contains at least one halogen compound represented by the following general formula [I]. Silver chemical color photographic material.

General formula (1) In general formula (1), the coupler component that releases a residue by the coupling reaction or redox reaction with the oxidized product of the AFi aromatic primary amine developer is represented by the reducing agent component. , TIMEFi and after bonding to S (ion atom) or N (nitrogen atom) and leaving from A in a coupling reaction or redox reaction, q is represented, and Z forms a heterocycle with a carbon atom and a nitrogen atom. Represents an essential nonmetallic atomic group, L represents an aliphatic or aromatic covalent linking group that may contain an ether bond or a thioether linkage, or a simple linkage group, and R represents a carbon atom number of 1 to 2. It represents a straight chain or branched chain alkyl, m represents θ and fc represents an integer of /.

(2) The silver halide color photographic light-sensitive material of item (1) above is prepared with p)t of 2.3 or more and 10. ! 1. A method for processing a silver halide color photographic light-sensitive material, characterized in that it is processed with a color developer having a sulfite ion concentration of rxto moll/13 or less.

The compound represented by the general formula [I] will be explained in detail below.

In the general formula (1), A represents an aromatic 7th class amine fJ
Coupling reaction 17'c with an oxidant of a drug represents a coupler component or a reducing agent component that releases less than TIME by a redox reaction, and A is an example of a yellow image-forming coupler (yellow coupler). ) residue, magenta image-forming coupler (abbreviated as mi/ta coupler) residue, cyan image-forming coupler (abbreviated as cyan coupler) residue, and coupling product have substantially no absorption in the visible light range. Examples include coupler (so-called colorless coupler) residues, and when A is the latter, examples include hydroquinone residues, naphthohydroquinone residues, catechol residues, p-aminophenol residues, and O-aminephenol residues. Can be mentioned.

The yellow image forming coupler residue represented by A includes piparoylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type,
Coupler residues of malone ester monoamide type, benzothiazolylacetate type, benzimidazolylacetamide type, benzolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, US Patent J, 1
141/, coupler residues derived from heterocycle IIL-converted acetamides or heterocycle-compatible acetates contained in No. 110 or U.S. Pat. p, /7/, West German patent (t)LrS)
2. j03. Ofri issue, Japanese published patent 3O-13P,
No. 731 or Research Disclosure/173
Examples include coupler residues derived from acylacetamides described in No. 7, and heterocyclic Kagler residues described in US Pat.

As the maze/color image-forming coupler residue represented by A! -oxocopyrazoline nucleus, pyraya- [i, z
Coupler residues having an all benzimidazole nucleus, a pyrazoloimidazole nucleus, a virazolotriazole nucleus, a pyrazolotetrazole nucleus or a cyanoacetophenone type coupler residue are preferred.

The cyan image-forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Further, even if the coupler does not substantially form the dye after coupling with the oxidized form of the developing agent and releasing all the development inhibitor, the effect as 1) I) L coupler is the same. As the colorless coupler residue represented by A, US Patent a, o
rco, λlJ issue, same group.

orr, ariwo issue, 4(,/71.5'AJ-1, 44.1113, 712, same J, t, 32.34A!
q, same 3. Risr, yri No. 3 or same 3. Ribu/, W! j
Examples include the coupler residues described in No.

The reducing agent component represented by A is a hydroquinone residue (bonded with S at the 2nd position of the hydroxyl group), a naphthohydroquinone residue (bonded with S at the 1st position of the hydroxyl group), and a catechol residue (bonded with S at the 1st position of the hydroxyl group). S in position or μ position
), p-aminophenol residue (amino group is an aliphatic group, aromatic group, acyl group, carbamoyl group, aliphatic oxycarbonyl group, sulfonyl group, sulfamoi JLM
May be replaced with %. bonded to 8 at the co-position or 3-position of the hydroxyl group) or O-aminophenol residue (amino group is an aliphatic group, aromatic group, acyl group, carbamoyl group, aliphatic oxycarbonyl group, sulfonyl group, sulfamoyl group, etc.) 1 may be substituted or may be bonded to 8 at any n position on the benzene ring.
1j J, No. 72 and the specification of No. 40-1070λ, etc. The hydroxyl groups of these reducing agent components can be cleaved in the developer to improve stability. &(
For example, it may be substituted with a trifluoroacetyl group, a chloroacetyl group, a cyanethyl group, a methylsulfonyl group, etc.). The reducing agent component represented by A is preferably a hydroquinone residue or a naphthohydroquino/lA group.

Among the coupler residues or reducing agent components represented by A, acryl acetanilide type yellow coupler residues and cyan coupler residues having a phenol nucleus or naphthol nucleus are particularly preferable, and among them, the following general formulas (n), (l
Particularly preferred are coupler residues represented by it) and [■].

General formula (n) General formula (fil) General formula (IV) In general formula (II), □ is a tertiary alkyl group having 4I-2μ carbon atoms (for example, butyl group, /, /-dimethylpropyl group, or ethyl group) -7-meterzoa-pyr group, -1-chloro7.l-dimethylethyl group, -1-phenoxy/,
/-dimethylethyl group, λ-phenylthio7. l-dimethylether f A/i, adamantyl group, bisic Q (J
.
μm methylphenyl group, cometerphenyl group, dermethoxy-3-(-2-(λ, darsey is pentylphenoxy)butanamide] phenyl group, etc. 1, where R2 is a hydrogen atom and the following is a fatty acid with the number of carbon atoms /-/If Group groups (e.g. methyl group, ethyl group, benzyl group, methoΦdiethyl group, etc.)
t@Washi, 几, is an aromatic group having 4 to 4 CF carbon atoms, such as phenyl group, -1methoxyphenyl group, no-chlorophenyl group, x-p Rorhoda.

! -dimethoxyphenyl group, cochroro! -hexadecylsulfamoylphenyl group, -one Roro J-two Φ-cyclocarbonylphenylene group, -one Roro! -Octyloxycarzenylphenylphenyl group, -monochloroj-dodecyloxycarbonylphenyl group, λ-hexadecyloxyj-methylsulfamoylphenyl group, λ-chloro3-phenylsulfamoylphenyl group, Coke o o
-j-(codedecyloxycarbonylethoxycarbonyl)phenyl group, nochloro-Z-[a-(co, darsey, pentylphenoxy)phthanamide]phenyl group, corkmilo-! -[No(2,44-di-pentylphenol)butanamide] represents a phenyl group 1.

In the general formula (ul), R4 is a carbo/amide group with carbon number/~ar ['For example, an acetamide group, a benzamide group, a -1 (co, darsey and pentylphenoxy) butanamide group, -1 (, co, and a 4 and a di) pentylphenoxy)
hexaneamide group, co-(J, methylphenoxy)octanamide group, -(nochloro-μ)
m is a pentylphenoxy)octanamide group, no(3
-Ntadecylphenoxy)butanamide group, λ-(terptylsulfonamidophenoxy)tetradecanamide group, co(-monocyanophenoxy)tetradecanamide group, tetradecaneamide group, cohexyldecadiamide group, piparoylamino group, R5 represents a carbon amide group having 7 to 360 carbon atoms [e.g., benzamide group, -monochloropenzamide group, co-, l-dichloride group, etc.]; Lopenzamide group! -Methylsulfonamide benzamide group, a- is 1 methylbenzamide group, ) to -fluorobenzamide group, trifluoroacetamide group, heptafluorobutanoamide group, co, co, J,! , j1. da T'S
j-octafluoro eI hantanamido group, hivaloylamino group, co (co, group, 3-cyanophenylureido group, 3-methylsulfonamide phenylureido group, Hiro-cyanonaphthalene 7-/-ylureido group, 3, μm dichlorophenylureido group, tert-trifluoromethylphenylureido group, France-methylsulfonylphenylureido group , ≠-propylsulfonylphenylureido group, p-butylsulfonylphenylureido group, J-/ellow-niethylsulfonylphenylureido group-dimethylsulfamoylphenylureido group, methoxycarmenylphenylureido group, reference- chloro-3-cyanophenylureido group, J-chloro-3-cyanophenylureido group, fluorophenylureido group, co, u, trichlorophenylclade group, phenylureido group, etc.).

In the general formula (fV), R6 and R7 may be the same or different and may be a hydrogen atom or an aliphatic group having -47 carbon atoms [e.g. methyl group, ethyl group, allyl group, be/zyl group, methoxyethyl group, cyclohexyl group] group, λ-ethylhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, 3-(coethylhexyloxy)propyl group, 3-decyloxypropyl group, 3-dodecyloxytucubiru group%'-(22 μm di- (pentylphenoxy)frobyl group, a(co,darzyt-pentylphenoxy)butyl group, etc.) or an aromatic group having a carbon number tN≠r (e.g. phenyl group, -monoethoxyphenyl group,
Co-propoxyphenyl group, co-chlorophenyl group, cochtradecyloxyphenyl group, fudiphenyl group in μm tetradecyl co-chloro! -dodecyloxycarbonylphenyl group, etc.).

In the general formula (1), TIME represents a timing group that releases all of S or N after being separated from A by a coupling reaction with an oxidized product of an aromatic primary amine developer,
It usually binds to the coupling active site of coupler component A.

m represents O or an integer of /, and when m is O, A is directly bonded to [lS or N without a timing group. The timing group is used to control the reactivity of the compound represented by the general formula [I] with the oxidized product of the aromatic 7th class amine developer, to improve the stability of the core compound, and to control the Adjust the timing until releasing S and below as appropriate, and
It is used for various purposes such as adjusting the diffusivity of the compound after it has been separated from the compound, and preferably the following general formula [■] or (
Vl). However, general formula ['V] and [■]
A that dies is the same as A in general formula (1), and Y
represents S or Ny in general formula (1).

General formula (V) General formula (Vl) A -N u -L 2- E Y In the general formula (V), Q represents an oxygen atom, a sulfur atom represents a substituted imino group, and Ll represents a substituted or unsubstituted group. represents an ethylenyl/group, n represents an integer from O to C, and 几 and 几 may be the same or different and represent a hydrogen atom, an aliphatic group, or an aromatic group group. When Q represents a substituted imino group, the substituent is bonded to L and both the nitrogen atom and L□! to 7-membered nitrogen-containing heterocycle (#, which may be substituted or a 1jXa@- ring) is preferably constituted.

In the general formula (Vl), Nu represents an electron-rich oxygen atom, a sulfur atom or a nucleophilic group containing a nitrogen atom,
E represents an electron-deficient carmenyl group, thiocarbonyl group, or phosphinyl group. M9 represents an electrophilic group containing a thiophosphinyl group, and L2 is sterically related to Nu and E, and Nu is released from humans. Represents a linking group that makes it possible to release Y and below through an intramolecular nucleophilic substitution reaction between Nu and E via a 3- to 7-membered ring intermediate metal.

Among the timing groups represented by the general formula (V), more preferable ones are the following general formulas [■], [■), (iK), (X) or (
XI).

General formula [■] 1'11 General formula [■] General formula [■] General formula (X) General formula (XI) General formula (Vil) ~ (XI) K Oite V and H V2
With f1 bonding atomic group! Or a non-gold striped atomic group necessary to form a 7-membered t-nitrogen heterocycle (which may be f-substituted or a fused ring)? ! - Expression, v3 together with the bonding atomic group! to 7-membered polychord ring (which may be substituted or fused ring) Takatake aromatic #a (1i
t, may be substituted or may be a fused ring)? 2 and Z2 may be the same or different. An unsubstituted or substituted methine group represents =N-', and 1 and 1 (+1□ may be the same or They may be different hydrogen atoms, aliphatic groups or aromatic groups, and R represents a hydrogen atom or a monovalent group.

It may be combined with R□2Fiv to form a ring.

R□.

and R1□ is preferably a hydrogen atom, alkyl 7iIj having 7 to 3 carbon atoms (e.g., methyl group, ethyl group, benzyl group, dodecyl group, cyclohenyl group, allyl group, etc.) and 9 is carbon number 6 to 3t aryl group (e.g. evaphenyl group, μ
mm methofodiphenyl group, terchlorophenyl group, nitrophenyl group, j-7thyl group, etc.), but % is preferably a hydrogen atom.

Among the timing groups represented by the general formula (Vl), a more preferable one is represented by the following general formula [Kari] together with A and Y in the general formula (Vl).

General formula [Kari] In the general formula [Kari], Nu is -〇-1)V
几/O Each independently represents a hydrogen atom, an alkyl group having 20 carbon atoms, preferably an alkyl group having 7 μm carbon atoms. ), and ■4 is with the bonding atomic group! or lOj
Aromatic θ ring consisting of solid ring atoms 1 fc id fi
A non-metallic hydrogen atom that is necessary to form a metal ring (which may be substituted with one of these rings or a metal ring),
It represents an alkyl group having a carbon number of /~Jo, preferably an alkyl group having a carbon number of 1-μ. ) seven, and p is due to the reaction between the nucleophilic center in Nu and the electrophilic center in E! 0 to 4 such that it is possible to form a 7-membered ring intermediate! represents an integer.

Among the timing groups represented by general formulas [■] to [Kari], particularly preferable timing groups are represented by the following general formulas (XI[l) and general formula 0GV) together with A and Y in general formula (V) or (Vl). It will be done.

General formula (Xlll) "11 General formula (XfV) Rou, 0 In the general formula (X[l), R□. and R□ are 几 in the above general formulas [■] to (XI). and R□□ They have the same meaning, H
3t aryl group (e.g. phenyl group, French-tetradecyl, oxyphenyl group, methoxyphenyl group, Hiroshi-
Chlorophenyl group, λ, S, -cyclophenyl group, co, hirot') 'J dichlorohenyl group, co, b-dichloro-meth, diphenyl group, dermethylphenyl group, μ-nitrophenyl group, -carboxyphenyl group, dicarbonylphenyl group, etc.) wo light, R
Y is a hydrogen atom, an alkyl group having 7 to 3 carbon atoms (e.g., methyl group, ethyl group, Kundecyl group, etc.), and t to 3 carbon atoms.
t aryl group (e.g., phenyl group, Hiro-methoxyphenyl group, etc.), alkoxy group having 7 to 3 carbon atoms (e.g., meth: ?7 group, ethoxy group, dodecyloxy 7 group, etc.), cyano group, carbon number O ~3 amino groups (e.g. amino group, dimethylamino group, piperidino group, dimethylamino group, anilino group, etc.), carmenamide group having 7 to 3 carbon atoms (e.g. acetamide group, be/zamide group, tetradecaneamide group, etc.) ), a sulfonamide group having from 1 to 36 carbon atoms (e.g., methylsulfonamide group, phenylsulfonamide group, etc.), a carboxy group, a dicarbonyl group in alcohol having 2 to 2u carbon atoms (e.g., methoxycarbonyl group, dodechloride f-7 carbonyl group) etc.) or a carbamoyl group having 7 to 3 carbon atoms (fil, t-carpamoyl group, dimethylcarbamoyl group, pyrrolidinocarbonyl group, etc.).

In the general formula (XfV), Q□ is -0-1(J,
(represents Jl or -NHC-, f(+15 is 7 to 0 carbon atoms)
Alkyl group (e.g. methyl group, ethyl group, inopropyl group, be/zyl group, etc.) is represented by gold, q is an integer of 0 or l, X is a hydrogen atom, nitro group, cyano group, halogen atom (chlorine atom, Bromine atom, fluorine atom, iodine atom), alkyl group having 7 to -0 carbon atoms ('@e, methyl group,
butyl group, benzyl group, trifluoromethyl group, etc.),
Alcokyne groups with a carbon number of 1N2O (e.g. methoxy group, dobucloxy fS4), aryloxy groups with a carbon number of t to 0 (e.g. 1noxy group, μm chlorophenoxy group, etc.), alkoxycarbonyl groups with a carbon number of λ to 20 (e.g. methoxycarbonyl group, dobucuroxycarbonyl Zhao, etc.), carbamoyl group having 7 to 0 carbon atoms (e.g. dimethylcarbamoyl group, phenylcarbamoyl group, tetradecylcarbamoyl group, etc.), carbonamide group having lN2O carbon atoms (e.g. acetamide group, benzamide group, etc.), a sulfonamide group with a carbon number of 1-λO (e.g., methylsulfonamide group, p-)lylsulfonamide group, hexadecylsulfonamide group, etc.), a sulfamoyl group with a carbon number of 0-20 (e.g., dimethylsulfonamide group), moyl group, dimethylcarbamoyl group, dodecylsulfamoyl group, etc.) or a sulfonyl group having 7 to 20 carbon atoms (for example, methylsulfonyl group, p-)lylsulfonyl group, μm and diphenylsulfonyl group, etc.).

-e Formula (1) For details, see the following general formulas (XV) and (XM)
It is represented by

General formula (XV) General formula (XVI) General formula [X■] and [x■] Nioite, Z3 and Hi Z4~
Represents a group of non-metal paulownia atoms necessary to form a 7-membered heterocycle, which may be substituted or fused. -C=N-
Examples of heterocycles formed by and Z3 include pyrrole,
Pyrazole, imidazole, l, co, 3-triazole, 'l co, μ-triazole, tetrazole, oxazole, thiazole, /, 3.41-) lyazole, isoxazole, inthiazole, benzimidazole,
Indazole, tetrazaindene, /,! , μm thiadiazole, /, J, μm thiadiazole, pyridine,
There are pyrimidine, pyrazine, pyridazine, indole, naka-nori/, quinazoline, purine, triashif, etc. Among these, triazole, tetrazole, 'l'1 μm
Thiadiazole and l, 31 μm Φ oxadiazole.

As imidazoline/-corchion, oxazoline-corchion, thiazoline-corchion, / , , 2゜3-
Triazolin-dartheon, /, 2. ! -triazoline-3-thione, tetrazoline-3-thione, /, 3.
≠-thiadiazoline-λ-thione, /, j, II-oxadiazolin-corchion, pyrazoline-3-thione,
There are cortiviride/, thiopyridone, dihydropyrimidine-φ-thione, dihydropyridazin-3-one, etc. Among these, 1. 4A-triazine-λ-
Thione, tetrazoline! -thione, 'l'#μm thiacyasili/-λ-thione and l, 3. μm oxadiazoline-corchion is preferred.

Examples of substituents on these heterocycles < rtt-substituted @ combination) include hydroxy groups, amino groups, and X of the general formula 0GV).
The substituents mentioned above can be mentioned.

Therefore, examples of heterocycles particularly preferably used in the present invention among the heterocycles formed are those of the general formula (XV).
) is shown below together with L.

1L 几I S S S
Here, R' is a hydrogen atom, an aliphatic group having /-/, 2 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, i-
Propyl group, methoxyethyl group, and diethyl group,
Allyl group, benzyl group, etc.) Next, aromatic groups having t to l carbon atoms (e.g. phenyl group, p-)lyl group, m-)lyl group, p-hydroxyphenyl group, p-methoxyphenyl group, (naphthyl group, etc.). (9) The heterocycles listed here may be substituted with the substituents listed for the substituent X above. Among the compounds represented by the general formula (XV) and [Punishment], the compound represented by the general formula (XV) is more preferred.

In general formula (1), L is preferably a substituted or unsubstituted methylene group, an ethylene group, a J-propylene group, a substituted or unsubstituted oxymethylene group or an oxyethylene group (ZK bonded through an oxygen atom), or a substituted Alternatively, the unsubstituted thiomethylene group represents a thioethylene group (bonded to Z through 9 atoms), or a substituted or unsubstituted phenylene group.

L is a substituted methylene group, ethylene group or Fit.

3-propylene group, substituted oxyethylene group or oxyethylene group, or substituted thioethylene group or thioethylene group, examples of the substituent include carbon number/-
20 alkyl groups (e.g. methyl group, ethyl group, dobucle group, benzyl group, etc.), alkoxycarpamoyl group having 2 to -0 carbon atoms (e.g. ethoxycarbonyl group, ethoxycarbonyl group, dodecyloxycarbonyl group, etc.), carbon number A carbamoyl group with l to coQ (e.g., dimethylcarbamoyl group, methoxydiethylcarbamoyl group, tetradecylcar/lmoyl group, etc.) or an aryl group with carbon number of co0 (e.g., phenyl group, l-methoxyphenyl group, etc.), etc. can be mentioned. When L is 7 phenyle groups, it may be any of O-phenylene 7 groups, m-phenylene groups, and p-phenylene groups, and examples of the substituents include hydroxy groups as well as those listed in X of the general formula (XiV) above. Examples of substituents include: However, when L is a substituted or unsubstituted oxymethylene group, an oxyethylene group, a substituted or unsubstituted thiomethylene group, or a thioethylene group, L is bonded to the carbon atom on 2.

When L is a substituted or unsubstituted methylene group, it is preferably bonded to the nitrogen atom on Z. Particularly preferred as L are unsubstituted methylene group, unsubstituted ethylene group, unsubstituted oxymethylene group, unsubstituted oxyethylene group, unsubstituted thiomethylene group, unsubstituted thioethylene group, unsubstituted m-phenylene group and unsubstituted p - 7 phenylene groups.

In the general formula (1), R represents an unsubstituted linear or branched alkyl group having 1 to 2 carbon atoms, examples include methyl group, ethyl group, n-gummy group, isobutyl group, n-butyl group, and isobutyl group. group, 5aC-butyl group, n-pentyl group, isopentyl group, co-dimethylbutyl group, co-etherbutyl group, n-hemoyl group, cyclopropyl group, cyclobutyl group, cyclobaethyl group, cyclohexyl group, etc. There is. Preferred examples include alkyl groups having 7 carbon atoms, with methyl and ethyl groups being more preferred.

Next, specific examples of those preferably used as a side dish in the present invention in the general formula (1) of the present invention are shown below, but the invention is not limited to these.

ouch3 eUUcl food.

C)120H2CL)QC,H,(c112)3co□
H3801櫨p)12C(J(JC)i3 Specific examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited thereto.

He=he iML;1t2L;LJLIL;2M5C5H1l-house C no CUUC2H.

CUUC3H,-n Oη 　　　　　0 U(J(JC2)1゜ C(J(JCB)

euue, n.

0 α 0 α CI-t20LIUC2) 1゜ Naυ NkiCUCl, H3□-n Coacit.

C (J (Je2) to 1°) H uucu3 (b) ... H 1N2 H O0GH3 BCH2C) i2U (JuClis oH C, Hl, -1 Ren H2 雛These compounds of the present invention are used, for example, in the United States!ff (US ) No. μ No. μ43F1, No. μ-3R Ribuko No. 4444
2/11441, same number $4!77j6J, JP-A-Shoj
O-j j J J No. 2, 47-/1103j, same! I-9! No. 1721, same! ! -2031JO issue,
Same j1-. No. 10973, No. 1 x.

? No. 737, No. JR-2097Jt, No. ZR-Co11
) 5F7, No. 0, tO-1070λ, etc.

Synthesis Example 1 Synthesis of Exemplified Compound (1) p-aminobenzoic acid ether 15ty, triethylamine 7no, /f, carbon disulfide ivy? Add 20 go to 241. Stir for hours. The reaction solution was cooled to fJOc, and after stirring for 1 hour, the precipitated crystals were filtered, washed with ethyl acetate, and dried. Next, this crystal/7. The gold was dispersed in ethyl acetate Osl, and ethyl chlorocarbonate was added dropwise over about 73 minutes while stirring at room temperature. After stirring for 30 minutes, the mixture was washed with water three times, dried over sodium sulfate, and concentrated using an evaporator. Concentrate f J j ri
Sodium azide J dissolved in l acetonitrile,
+Lf.

Water/2. Jr, acetonitrile 2! Add it dropwise for 3 minutes to the mixed solution under heating at reflux. After cooling with water, 10 d of water and dilute hydrochloric acid were added to neutralize, and 70-d of ethyl acetate was added for extraction. The extract was washed once with 70-mL water, dried over sodium sulfate, and concentrated. Methanol JO to concentrate
By adding 4ef, dissolving and crystallizing on ice, /-(@
-Ethoxycarbonisylphenyl-! - White crystals of mercaptotetrasol 1j (r, J f, yield -1
4j%, melting point 130~/J/"C/-(&-ethoxycartnylphenyl)-3-mercactodetrazole J, jf and triethylamine co, O
f was dissolved in methylene chloride-〇tttl, and α-promo α-(41-methoxybenzoyl)cochloro! - Powder of dicarbonylacetanilide in dodecyl chloride! , Pf
Added f. After stirring for 1 hour, the reaction solution was 2 iN diluted hydrochloric acid! It was then washed twice with water/10g. By adding all of methanol JOyxl to the concentrate and crystallizing, white crystals t7.21 of the target exemplary compound (1) were obtained. Yield firmness, melting point //? ~t2o, j6c The structure of Exemplary Compound (1) was confirmed by NμR spectrum, μASS spectral and elemental analysis.

Synthesis Example 2 Exemplary compound? Synthesis of 1(7) Synthesis was carried out from methyl p-aminobenzoate in the same manner as in Synthesis Example 1/-(IA-methoxycari-nylphenyl)
-4-Merkabutotetetol 51-l was obtained. Total yield 7
0.3%, melting point 137~NoJriCi-<a-meth*cycarzenylphenyl)-! -Mercagutotetrazole 2.4Iff Dissolved in 20ml of methylene chloride, and added sulfuryl chloride/≠2 under water cooling. After stirring for 1 hour, a solution of 44.71f of methylene chloride (cochtradecyloxyphenyllupamoyl)-/-f7toll was added dropwise over about 30 minutes. After 70 hours of stirring! Washed three times with 0 ml of water, dried over sodium sulfate, and concentrated. By adding methanol JOsJf to the concentrate and crystallizing, the desired exemplary compound (7) 1
r: 4, / was obtained. Yield rtden, melting point 10~1
The structure of 07°C Exemplary Compound (7) was confirmed by NμR spectrum, μASS spectrum, and elemental analysis.

Synthesis Example 3 Synthesis of exemplified ft product (8) λ,! -dimercapto-7,31 μm thiadiazole/
j, Off and triethylamine 10. /2 ethyl bromoacetate dissolved in 200ml of methylene and cooled with water /J
, 7? 'FF dripping just in case. After stirring for 30 minutes, 6 tons of continuous water is added by water flow. Then, the methylene chloride layer was separated and concentrated. By dissolving the concentrate in toluene jOd and crystallizing it by adding n-hexane, l-mercapto-! −
Ethoxycarbonylmethylthio-/, J, μm pale yellow crystals of thiadiazole 'i/jF,/y were obtained. Yield 1/%
, melting point t7~70''C 7-mercapto-!-ethoxycarbonylmethylthio-
1,3,≠-thiadiazole, jiff dissolved in methylene chloride-Od, under water cooling sulfuryl chloride/, <Aff
dripped. After stirring for 7 hours, -1(J-(1-cyanophenyl)ureido)-j-(a-(z, s-C-<
Phenol powder A
, Otkai was added. After stirring at room temperature for 2 μ hours, the mixture was washed with JOrd water three times and concentrated. Methanol J for concentrated Jtl
The desired exemplary compound (8) kA was obtained by adding Oml f and crystallizing it.

I got it. Yield: 47-%, melting point: /lr~/21@C The structure of exemplified compound (8) was confirmed by flNμR spectrum, μA88 spectrum, and elemental analysis.

The compound of the present invention has excellent manufacturing suitability, particularly in the synthesis of its leaving group, and can be provided at low cost. For example, synthesis example /of/-(terethoxycarbonylphenyl)-j
-Mercaptotetrazole and Preparation Example λ's 7-(μm methoxycarbonylphenyl)-1-mercaptotetrazole are cheap and easily available p-aminobenzoic acid ether and p-aminobenzoic acid methyl, respectively. Can be synthesized beautifully. On the other hand, JP-A-Shoj7-/! /rit
The leaving group /-(
4C-(J-chloroethoxylphenyl)-
! -Leaving group of mercagutotetrazole and exemplified compound 4/
-(4-phenoxylphenol)-! -Mercaptotetrazole is not only more expensive than methanol, ethanol, etc. as a starting material alcohol, but also easily hydrolyzed, so it is impossible to apply the synthesis method listed in Synthesis Example 1''! All synthetic routes as below are required.

CO<JC2H.

From the above, it can be seen that the chemical compound of the present invention has excellent manufacturing suitability.

The sensitive material containing the compound of the present invention has a pH value of j to 10.
! It is preferable to develop with a color developer between 1 and 2, but at a pH higher than this, deterioration of sharpness is seen, and at a pH lower than this,
) is not preferred because color development progresses slowly.

It is preferable that the sensitive material containing the compound 1 of the present invention be processed with a color developing solution having a sulfite ion fiK of 1xio mol/l or less, more preferably j
X/0 ~A
A treatment of 1/1 sulfurous acid ion/one time is preferred.

If the sulfite ion daughterness is high, the sharpness deteriorates, and if it is low, it is unfavorable from the viewpoint of the stability of the developer.

The preferred silver halide contained in the photographic emulsion of the photographic light-sensitive material used in the present invention is about 30 moles or less of silver iodide, silver iodobromide, silver chloride, or silver iodochloride. be. Particularly preferred is about 2 mol% to about 4j
Silver iodobromide contains up to mol% of 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 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 io 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), Mu/74443 (
/December 7I], pp.-2-23, “1. Emulsion production (
Emulsion preparation an
d types )”, and ('MpF, / r
7/j (/F7F July/Month), tar page, “Physics and Chemistry of Photography” by Grafkide, published by Beaumontel (P,
Glafkides, Chemic et Physi
que Photographique Paul
Montel, /f A7), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F
, Duffin.

Pbotographic Emulsion C
hemistry(Focal Press, /
96 A)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L, Zelikm
an et at.

Making and coating photo
graphicEmulsion, Focal
Press, if Au) and others.

U.S. Pat. No. 3,37μ, 422, J, tJ! , 35
P≠ issue and British patent @l, <t/J, 7μr issue etc. (
Monodisperse emulsions as described in (a) are also preferred; tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic
Science and x7 Geneering (Gutoff
, Photo-graphic 5science
and Engineering), Volume 1, Cog R-2. t7 negative (IP70 years); U.S. Patent No. μ, 413
44.2 Kobu issue, the same μ, Gu/Pi.

No. 310, 44. ll-33,0441, same <7,
4tJ Re, No. 320 and British Patent No. 2,1i-2,i
It can be easily prepared by the method described in No. s7.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. In addition, Herog/silver oxide having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Mixtures of particles of various crystalline forms may also be used.

Halogenated bride emulsions are usually 8! Those that have been aged, chemically ripened, and spectrally sensitized are used. Additives used in such processes are available from Research Disclosure Shop/
744tJ and the same is described in 1r71t,
All relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the above Lambda Adhesive Search Disclosure, and the relevant descriptions are shown in the table below.

Additive type RD/74413 RD/171
tl Chemical sensitizer KO Jg 4441 Tei right column 2 G degree increase agent Same as above 3 Spectral sensitizer, -3 to -μ page Buhiro page right column ~ Super sensitizer 41 page right column 4
Brightening agent λ≠Te5 Antifogging agent 2μ～-2da page t4A'p page right column and stabilizer 6 Light absorber, fu 2! ~Page t4L Page right column ~ Ilter dye 410 Self left column Ultraviolet absorber 7 Stain inhibitor 2J Page right column Page 120 Left ~
Right Column 8 Dye Image Stabilizer Coj Direction 9 Hardener Page 2 Page A37 Left Column 1
0 Pie/Goo, page 2 Same as above 11
Lubricant for plasticizer λ7 Sada 120 Wataru right catch 12
Coating aid, Table C, page 27 Same as above Surface activator 13 Static prevention Core page Same as above
In the present invention, Kashira's color couplers can be used.
, D) Rin/-7bu4AJ, ■-CNG and described in the following patents.

As a yellow cutler, for example, U.S. Patent No. J, P3
No. 3,101, No. 41,022,620, No. G,
3 pieces 4. <7J-No. 4t, 410/.

7tJ, Tokuko Sho 1 to 107J British nationality license No. 1. Gu J, Oko No. 0, same No. 7. ≠ Those described in 7B, 7jO, etc. are preferable.

As magenta couplers, j-pyrazolone and virazoloazole compounds are preferred, and are disclosed in U.S. Pat. No. 44,3
10.61P issue, 44.3! /.

7, European Patent No. 73,434, US Patent #g,
J, 04/, 4AJ- No. 3.72! , No. 047,
Research Disclosure & Coco Coco O (/rir
JP-A-4O-33112, Research Disclosure A-μm30 (lyra-year is month), JP-A-4O-uJtjP, U.S. Patent No. 44,100,4
No. 30, same issue.

Those described in luo, ≦j≠, etc. are particularly preferred.

Cyan couplers include phenolic and naphthol couplers, as described in US patent ig≠.

Oj J, 2 t', 2 q', same fJ41t,
/4AA, No. 391a, No. ≠, λ Cor, No. 233, No. μ, No. λ, Koo No., Ha, 3by, No. yxy, j
p, 2, 10/.

No. 171, No. λ, No. 77, No. 1, No. 2, @-9ryz
, ratst, No. 3,772,002, No. 3,
7! I, No. 301, No. ≠, JJe, No. 07, No. μ
, 327. /73, West German Patent Application No. 3,322,7λ
European Patent No. 1J/.

J 4 j A, U.S. Patent No. 3,4L Hiroj, No. 6-2, U.S. Patent No. μ, 333. Tatata No. μ, μJ/, jjri No. 27,747, European Patent No. 14/, ≦
- Those described in No. A etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure A/74≠3, Section ■-G, Yoneo Patent No.≠, No./63,470, and Tokko Sho J.
No. 7-324413, US license number p, 004c, W Kota issue, same temperature IA, /31. Co., Ltd., British Patent No. 1. /4
1Δ, 3Δ! Preferably, those described in No.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. μ# J t J *-z J 7 and British Patent Nos. Co, l Co! , No. 170, European Patent No. 24,770
No. 3, West German Patent (Publication) No. 3. λIII,! Those described in No. JJ are preferred.

Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. Hiroshi, rko O issue, same No. 3, otrO, co l/
No. 4', Jr7. Jr, No. 2, British Patent No. 1
It is described in 0co, /73, etc.

Couplers that upon coupling release onto photographically useful residues can also be preferably used in the present invention. The DIR coupler that releases all of the development inhibitor has the above-mentioned RD/74≠3.
The patents listed in paragraphs 4-2 are published by JP-A-Sho! 7-/! /944
Da issue, same! 7-/! uλJ41, 0-/r≠Kopir, U.S. Pat.

Companions described in Coat, No. 1λ are preferred.

Couplers that release all of the nucleating agent or development accelerator image-wise during development include British Patent Nos. 7.1440 and 2. /J/, No. 111, -% Kaisho 3 Ter 1174
No. 31, and those described in JP-1701rlAO are preferred.

Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 41. /30. Competitive couplers such as those described in U.S. Pat.

Cors, ≠7- No. DA, JJr, Jri No. 3, Same No. U
, 3io, ttr, etc.; DIkL redox compound-releasing couplers described in JP-A No. 173,30λA; Examples include couplers that emit light.

The couplers used in the present invention can be incorporated into the WI4 optical material by a variety of known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat.

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

No. 343, West German Patent Application (UL8) No. 2. jμ7゜27
No. U and No. λ, 10/230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/74!3's Jr page, and wholesaler 1rytt's 4
It is written from the right column to the left column on page 447.

The color photographic material according to the present invention includes the above-mentioned R, D,
I6/7tu3f) it N2? Page, and the same grave/17
/l tzi is described in the left column to right column and can be developed by a conventional method.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a water washing and/or stabilization step after desilvering treatment such as fixing or bleach-fixing.

The amount of water washed during the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the same speed, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. can be set over a wide range. Among these, the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Telecommunications Engineering/Genius.
urnalof the 5ociety of
Motion Picture and Te1evi
sion Engineers) Volume t4L, P, 2
≠λ! You can obtain it by the method described in J (/ri! J month issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of washing water t can be greatly reduced, but due to the increase in water residence time in the tank, bacteria propagate and the generated suspended matter adheres to the photosensitive material. Problems such as In the processing of the color photosensitive material of the present invention, as a solution to such problems, %
The method for total reduction of calcium and magnesium described in No. 1 J1432 can be used very effectively. Chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, and chlorinated sodium isocyanurate described in JP-A-77-RJT4C, and other chlorine-based disinfectants such as benzotriazole, etc. Chemistry”,
Disinfectant 2 described in Hygiene Technology Gold Wire ``Sterilization of Microorganisms, Disinfection, and Antifungal Technology'' and Japan Antibacterial and Antifungal Science Gold Wire ``Encyclopedia of Antibacterial and Antifungal Agents.''
It can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is dark and preferably! -l. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but in general, the washing time is 10 minutes, preferably 30 seconds at μo'c. A range of 3 minutes is selected.

Furthermore, the photosensitive 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 Application Laid-open No. 17-1183,! tr-/a
r3a, ttar1ru3u3, 40-220344
! No. 60-23113, reference to Bu0-λ3ri7,
Bu0-ko3ri74A2, t/-4AO! No. 44, t/
All known methods described in Japanese Patent No.-1117449 and the like can be used. In particular, l-hydroxyethylidene-
/, /-diphosphonic acid,! A stabilizing bath containing -chlorocomethylruder inteazolin-3-one, a bismuth compound, an ammonium compound, etc. is preferably 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. .

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1 Sample 10/ was prepared by coating an emulsion layer as shown below on a triacetyl cellulose film support provided with an undercoat layer.

(Sample lO/) (1) Antihalation layer black colloidal silver ...... Silver 0.3f/
m2 gelatin town... /, 017m2
(2) Intermediate layer gelatin ・・・・・・・・・／ , O
f / m 2 (3) Emulsion layer negative silver iodobromide (average grain size 0.7 μm Grain size modification coefficient / 7% monodispersed emulsion, silver iodide 7 mol) ・・・・・・・・・・・1.21/m
2EX-/ko ・−・−−−−−0, 3O1
7m 2EX-/J ----------・-o
, 3ot/m”HB8-/・・・・・・
-0, J O17m” gelatin...
... Ko, at/m" (4) Protective layer) 1- / ・Old-・-0, / O17
m ”Gelatin ・・・・・・・・・λ,
of/m" (Samples io ~ 1ot) A comparative compound and a compound of the present invention were added to the emulsion layer of Sample 10/ in a coating amount of 10-' mol/m2, respectively, and Samples 102-1O1 were added. Create a friend.

These samples were exposed under conditions of 10% co'o'C relative humidity through λr day (A condition) and uo@c relative humidity 1 medium exposure and MTF value measurement patterns, and color development processing described below was performed. The nine results obtained are shown in Table 7.

M'rpo measurement is based on The Theory of
thePhotographbic Process
J rd ed.

(McQuillan Publishing, written by Mies).

Color development processing is done in JR'C according to the processing steps below.
A was given.

Color tax source 3 minutes/J seconds Xu Bai minutes 30 seconds Water wash 2 minutes 10 seconds Fixed arrival time: 3 minutes to 0 seconds Water washing 1 minute/j seconds Stability 1 minute OJ seconds The composition of the subsequent treatment liquid used in each step was as follows.

Color developer diethylenetriamine 5 sections # / , Of /
-Hydroxyethylidene-7゜l-diphosphonic acid -1Of sodium sulfite, Of potassium carbonate
JO6Of Potassium Bromide
/, 4'r chalicum iodide
7.3 ■ Hydroxylamine sulfate
J,! ? ! -(N-Ether-N-β-hydroxyethyl ε)]-1-methylaniline fi, acid acid ≠, j Add water /, Olp H/ 0
, 0 bleaching solution ethylenediaminetetraacetic acid ferric a/monicum salt 100. Of ethylenediaminetetraacetic acid disodium salt /. ,ot ammonium bromide/J0. Of ammonium nitrate
io, add water
/, Olp Ht, 0 Fixer ethylenediaminetetraacetic acid disodium salt /, Off sodium sulfite, da, oy ammonium thiosulfate 9m aqueous solution (70 arc) /7! , 0tt1 Sodium bisulfite 蓼, 11 Calorie water /, 09p) 1
4,4 Stable liquid formalism 7 (410%) Co, O polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.39 Add water /, O4 From Table 7, the chemical composition of the present invention It is clear that the sample containing all of the compounds shows almost no change in performance or deterioration even under forced deterioration conditions such as B condition, compared to samples containing the chemical component *W outside the present invention.

Example 2 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material, sample KO/, was prepared by coating each layer with the composition shown below.

(Photosensitive layer composition) The numbers corresponding to each component are expressed in units of 27 m 2 and indicate the fc coating amount, and for silver halide, the number indicates the coating amount in terms of silver. However, for sensitizing dyes, Herog/
The coating amount is expressed in units of t moles per mole of silveride.

(Sample λ0/) 7th layer; antihalation layer black colloidal silver・・・・・・・・・・・・・・・・・・
・・・・・・・・・go, tr gelachi/・・・・・・・・・
・・・・・・・・・・・・・・・◆・・・・・・・・・・・・
...oog.

First layer 8 Middle layer 2, J-G: Tadecylhydroquinone・・・・・・・・・・・・・・・・・・
・・・・・・・・・0. /rEX-/・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0.07EX-J・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・0.02 [J-/・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...o, arU-ko......
・・・・・・・・・・・・・・・・・・・・・・・・
・・o,or)1B8-／・・・・・・・・・・・・・・・
・・・・・・・・・9・・・・・・・・・o, i.

HBS-ko・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・O0O Cogelatin・
――・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・1. O Hirodai J Iil (1st
Red Sensitive Emulsion Layer) Silver iodobromide emulsion (silver iodide 1 mole 1 average grain size 0.70μ)... Silver 0. j1 sensitizing dye I・・・・・・・・・・・・・・・・・・・・・
・・・Otsu, Ri×10-5 sensitizing dye・・・・・・・・・・・・
・・・・・・・・・・・・・・・／ ,! rx/0-
5 Sensitizing dye■・・・・・・・・・・・・・・・・・・
・・・・・・J, /×10-'sensitizing dye■・・・・・・
・・・・・・・・・・・・・・・・・・44 ,0X/
0-5EX-ko・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0. J! 0)I
BS-／・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・o、00! ......Tatami-tatami-
・Italy・・・・・・・・・e−■・1・・0,0/2 Gelatin・・・・・・・・・・・・・・・・・・・・・・・・
・1・1・・1. CoO 2nd layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 1 mole 1 average grain size 0.71μ)...@1. Ko0 sensitizing dye■・・・・・・・・・・・・・・・・・・・・・
・・・J, /X10-”sensitizing dye■・・・・・・・・・・
・・・・・・・・・φ−・Φ・・・t, axio 'sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・
・・・2.1×10-'sensitizing dye■・・・・・・・・・
・・・・・・・・・・・・・・・3. θX1O-5EX
-2・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・◆・・・・・・・0. JOOEX-J...
···················three·····
...Conflict...o, oj.

EX-to・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・o, ooaHB8-, z・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.0!0 gelati/・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...1.30th J layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide lμ mol%, average grain size/, 00μ)...Silver/, 40 sensitized color combination ■...・・・・・・・・・・・・・・・・・・・・・
・j,μ×1osensitizing dye■・・・・・・・・・・・・
・・・・・・・・・・・・・i, uy, io-'sensitizing dye ■・・・・・・・・・・・・・・・・・・・・・・
・K, u×io-' sensitizing dye ■・・・・・・・・・・・・
・・・・・・・・・・・・・・・1. /XIO"EX-J・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0. OJ! EX-u......
・・・・・・・・・・・・・・・・・・・・・・・・・・・
・o,ot.

EX-ti・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Q, 001HB8-/・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・O@3 Cogelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・／、jJ th # (middle class) ) (BS-ko・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・O0θl gelatin・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・／、06EX-／G...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.0λ 7th layer (7th green-sensitive emulsion 1 m
) Silver iodobromide emulsion (6 moles of silver iodide, average grain size 0.tjμ)...Silver o, p.

Sensitizing dye V・・・・・・・・・・・・・・・・・・・・・
...j, O x 10-' sensitizing dye ■...
・・・・・・・・・・・・・・・・・・／ , 0×10−
'Sensitizing dye■・・・・・・・・・・・・・・・・・・
...J,! ×10-'R-μ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・θ, 0/7EX-t・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.2tOEX-／・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・θ, Oko/
EX-7・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0.030EX-r・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0.02! HB S -/...
・・・・・・・・・・・・・・・・・・・・・・・・
... o, io.

)IBS-3・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o, ot.

gelatin·····················
・・・・・・・・・・・・・・・0,7! 1st layer (2nd layer
Green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide mol%, average grain size 0.70μ)...Silver o, t.

Sensitized color: IgV・・・・・・・・・・・・・・・
......λ, /x10-'sensitized color code■...
・・・・・・・・・・・・・・・・・・7.0X10-
5 sensitized color accumulation ■・・・・・・・・・・・・・・・・・・
...2. tXlo 'R-μ・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・o,oiri EX-4・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0. /10EX-r・・・・・・・・・・・・・・・
・・・・・・・・・・・・Old・・・・・・0.010E
X-／・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・o、oorEX-7・・
・・・・・・・・・・・・・・・・・・・・・ Old・
・・Old・・0,0/2) IBS −／・・・・・・・・・
・・・・・・－・・・・・・・・・・・・・・・0 old・
・θ, 4θHBS-μ・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.030 Gelatin・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・/, 10th P/1! (@J green-sensitive emulsion layer) Silver iodobromide emulsion (iodide@nocomole, average grain size/, θμ)...Silver/,
Sensitizing dye■・・・・・・・・・・・・・・・・・・
...J,! ×/0-5 sensitizing dye ■・・・
・・・・・・・・・・・・・・・・・・・・・I, O×
/ 0-' Sensitized color accumulation■・・・・・・・・・・・・・・・
......J, 0X10-'EX-j...
···············salary·········
・・・・・・・・・0.043EX-／・・・・・・・・・
...Old...Old...0.
021) IBS-2・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0,! r
! gelatin····················
・・・・・・・・・・・・・・・・・・・・・・74L 10th layer (yellow filter single layer) Yellow colloidal silver・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・Silver 0.0! EX-/a・・・・・・
・・・・・・・・・・・・・・・ Old・・・・・・・・・
...00OU)1B8-/...old...
・・・・・・・・・・・・・・・・・・・・・0. O
J! gelatin···················
・・・・・・・・・・・・・・・・・・・・・ 0.2J 1st/layer (7th positive emulsion Jd) Silver iodobromide emulsion (silver iodide t mole, average grain Diameter O04μ)・・・・・・・・・Silver 0.2
μ sensitizing dye■・・・・・・・・・・・・・・・・・・
・・・・・・J、jXlo-'EX-F・・・・・・・・・
...... Old... Old... Old...
0. r! EX-r・・・・・・・・・・・・・・・・・・
・・・・・・・・・・kawa・・old・・o, 1sEX-
//・・・・・・・・・・・・・・・・・・・・・ Old・・・・・・・・・0.03DHBS-／・・・・・・・・・
·················Mountain·······
・・・o, λt gelatin・・・・・・・・・・・・・・・
・－・・・・・・・・・・・・・・・・・・・・・・・・1
．． 1st column (2nd green-sensitive emulsion layer) Iodized silver emulsion (silver iodide 10 molar size, average grain size o, (oμ) --- Silver 0.4A! Sensitizing dye ■...・・・・・・・・・・・・・・・・・・
...K, lNl0-'EX-P......
・・・・・・・・・・・・・・・Reason...0.20EX-
to・・・・・・・・・・・・・・・・・・・・・
......0.0/j) IB8-/...
・・・・・・・・・・・・・・・1・・・・・・・・・・・・・
・・・・・・0.03 Gelatin・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. Hiro 6 13th layer (3rd W emulsion layer) Silver iodobromide emulsion (10 moles of iodide, average grain size 1.λμ)... Silver 0.77 sensitizing dye ■...・・・・・・・・・・・・・・・・・・
...λ,,2×io-'EX-?・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
...0. λ0HBf9-/・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.07 Gelatin・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・O0
≦2 First layer (first protective layer) Silver iodobromide emulsion (silver iodide 1 mole, average grain size 0.07μ)... Silver 0.07U
-／・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0.1/U-
one························
・・・・・・・・・・・・・・・・・・0. /7HB8
-ノ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・Oori Q Gelatin・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・／, 00 1st layer (second protective layer) Polymethyl acrylate particles (diameter approx./,!μm)・・・・・・・・・・・・・・・
...0.2μs-/......--
・・・・・・・・・・・・・Water・・・－・－・・・0.
0! rS-ko・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・o,
or gelatin・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・ 0.72 In addition to the above ingredients, gelatin hardening agent H-co and surfactant were added to each 1.9.

(Sample 20λ~CoOX) Added to the 7th layer and rN4 of sample 20/, and added 2 times the mole to the comparative compound R-s and 3 moles to the compound (1) of the present invention. Samples 202 to 0 were prepared in the same manner except that (7) was replaced with 0.41 times the mole.

These samples were left for 1 day under tOS conditions with relative humidity changes (C conditions), and for 7≠ days (D conditions) under μz 'C relative humidity conditions of 10 times (D conditions). Super HR-10o with exposure for measurement
- 300 microphotographs (one out of three was processed with a detonated one and subjected to color development using the balanced processing solution described below).The results are shown in Table 2.

Color development processing Color development 3 minutes/J seconds bleaching 7 minutes bleach fixing 3 minutes/j seconds water washing ■ 30 seconds water washing ■ 1 minute stable μO seconds drying (, t O”C) / minute it seconds above In the treatment process, water washing (1) and (2) were performed using a countercurrent water washing method from (1) to (2).Next, the composition of each treatment liquid is described.

The replenishment amount of each processing solution was 7 m for color photosensitive material, 1 for color development and 100 ytl for everything else, including washing with water. Also, the amount of pre-bath brought into the washing process is color photosensitive material/m.
Hit! Atatsu next in Odl.

(Color developer) Mother solution Replenisher diethylenetriaminepentaacetic acid No, Of /, /fl-
Hydroxyethylidene-7,/- diphosphonic acid Co, Ot Co, 2f Sodium sulfite μ, Ota, Da, Potassium carbonate! 0.0f J2. Of Potassium bromide A /, at O, 7f Potassium iodide /, J'9 - Zylamine sulfate in human a λ, Pif 2.11 μm (
N-Ethyl-N-β-hydroxyethyl a1)) -λ-Methylaniline sulfate 4c,! ? ! ,Of water added t,oll t,olp
Hlo, 0 10.0. (Bleach solution) Common to mother liquor and replenisher ethylenediamine 4-section cR ferric ammonium salt / 0, ot ethylenediamine 4-section ferric ammonium salt io, ot ammonium nitrate 10.Of ammonium bromide 100.Of bleaching accelerator
! Add ×10-”mol ammonia water and pH
B, 3rd water meeting plus ノ, oB
(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium salt common to mother solution and replenisher! IO, Of ethylene diamine acetic acid disodium salt! , Of sodium sulfite/λ, ot ammonium thiosulfate aqueous solution (70 whispers) Add 24 AOd aqueous ammonia, pH 7.7 Add aqueous solution
/l (washing water) Calcium ion jJ~/l, Magnesium ion 7-
Tap water containing JIL9/l was passed through a column packed with H-swelled acidic cation exchange resin and OH type strong basic anion exchange resin, and calcium ions/--211Ig/J% were collected.
In water treated with magnesium ions O0μ■/llIc,
Sodium incyanurate dichloride coomg per kill
It was added and used.

(Stable solution) Mother solution/replenisher common formalism 7 (37$W/V), 2.0d
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.39 ethylenediaminetetraacetic acid disodium salt 0, ozt Total water added /l pH, 1 (drying) Drying temperature was set to @c.

Also, instead of super HR-/DO, sample
The results obtained with each equilibrium treatment solution treated with p are also summarized in Table 2.

From Table 2, the sensitivity of the sample of the present invention under conditions C and D,
It is clear that there is little variation in the MTF value and that there is significantly less contamination of the processing solution during equilibrium processing.

Example 3 The color developing solution used in Example I was p;
1 and the tiger is N a OH%H28U 4 > and N
By changing the amount of a2803 added, the following color developer tw4 was used.
I arranged it.

(a) pH 10, o Sulfite ion concentration J, /
7XIOmol/71 (b) p) lr, O sulfite ion concentration 3, ty×to mol/1 (c) pH//, 0 sulfite ion concentration s, t
yxto mo(1/1 (d) pH 10,0 sulfite ion concentration t, ztxt
o mol/(1 (e) pH1o, o sulfite ion concentration j,
/7X10-'mol/l Sample 20 J exposed for sensitometry and for MTF value measurement! ', and treated with these developers instead of the color developing solution of Example 1. The results obtained are shown in Table 3.

Table 3 From Table 3, color developer (b)% (Φ has low sensitivity and poor sharpness expressed by MTF value, (C) has high sensitivity but poor sharpness, while (a) ) and (e) are both clearly preferable.
Samples b) and (d) showed almost the same performance even after 3 days of post-treatment, whereas samples (C) and (e) showed a significant decrease in color density.

Example/Structure of the compound used in λ, 3 EX-10 (JC)12 EX-t/ EX-t coEX-/J (t)CIsHlI EX-/ daHB8-/ ) licresyl phosphate HBS-co dibutyl phthalate) lBR-, y bis(- (monoethylhexyl) phthalate) IBS-≠ H-/ -J 8-/i:l-λ Sensitizing dye ■ (C)i,)3SO3Na (C town) 4803Na Comparative compound R-7 (JP-A-Shoj7-/ j151$4 No. 1) R-λ (compound included in U.S. Patent No. J Coco m reference) kL-3 (lW!
13(2)) Lou ≠ (% Kaisho 37-/!≠Ko 3 Hiro No.,
Compound cut included in JR-/42F-Taka, etc.) υ1 R-1 (Compound of Unexamined Japanese Patent Publication No. Sho J!-201/!0) Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendments Commissioner of the Patent Office 1. +.

1.Indication of the incident 1937 Shogan No. 4Ia4
A No. 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment The description in the "Detailed Explanation" section has been amended as follows.

1) @ on the 7th line of the page ``Fall'' "both" and correct it.

2) Number of pages to rows "to be washed away" "leak" and correct it.

3) Insert "cyclopentanone residue, cyclohexanone residue, indanone residue, benzophenone residue" after "as an example" on page 1, line 70.

4) Correct "(4A-butylsulfonamidophenoxy)" in the first line from directly below it to [(France-butanesulfonamidophenoxy)].

5) 3rd row from the bottom of the first row [3-methylsulfonamide] "3-Methanesulfo/amide" and correct it.

6) Line 6 of page 6 "≠-tetradecyl, oxyphenyl group," Correct as "≠-tetradecyloxyphenyl extraction."

7) 30th Sadada row "Methylsulfonamide group," "Methanesulfonamide group," and correct it.

8) The 30th Sada≠~! row "Phenylsulfonamide group" “Benzenesulfone amyl’fiJ and correct it.

9) Page 31, lines 13-1II- "Methylsulfonamide group" [Methanesulfonamide group] and correct it.

10) Page 37/Hiroyukime "p-tolylsulfonamide" "p-Toluenesulfonamide" and correct it.

11) Page 37, line is "Hexadecylsulfonamide group" "Hexadecane sulfonamide group" and correct it.

12) Page 3, line 3' "dihydropyridazin-3-one" "Dihydropyridazine-3-thione" and correct it.

13) 3rd ≠ 2nd line of page "Hydroxy group," "Hydroxyl group" and correct it.

14) Page 32, line 2 K after "ethylene group," "l, l-ethylene 41.z, -propylene group," Insert.

15) On the third page, line 70 "5OC-butyl group," "5ec-butyl group," and correct it.

16) No. ≠ O page Hiroki " "of and correct it.

17) The structural formula of the chemical compound r(t)J on page 7. and correct it.

1g) The structural formula of the compound “c3riJ” on page to is “ ” and correct it.

19) Page t3, line 3 After “Lit ni” "Acetonitrile" Insert.

2o) Gap page/≠th line [NμRJ NMRJ and correct it.

21) 1st column ≠ row “μASSJ “MAssJ and correct it.

22) At page/3rd line “NμRJ NMRJ and correct it.

23) Page jj, line 13 “μASSJ MASSJ and correct it.

24) Page 4, 3rd line from the bottom “NμRJ NMRJ and correct it.

25) Page t6, lines ir-l “μASSJ MASSJ and correct it.

Claims (2)

[Claims] (1) A silver halide color photographic material having at least one silver halide emulsion layer on a support, which is characterized by containing at least one compound represented by the following general formula [I]. Photographic material. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the general formula [I], A is ▲ mathematical formulas, chemical formulas, tables, etc. etc. ▼ Represents a coupler component or a reducing agent component that releases a residue, and TIME is bonded to A and S (sulfur atom) or N (nitrogen atom) and is released from A by the coupling reaction or redox reaction. Back ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ Represents a timing group for leaving a residue, Z represents a group of nonmetallic atoms necessary to form a heterocycle with a carbon atom and a nitrogen atom, and L represents an ether bond or thioether bond. represents an aliphatic or aromatic divalent linking group that may contain a bond or a simple bond, R represents an unsubstituted linear or branched alkyl having 1 to 6 carbon atoms, and m represents 0 or 1. Represents an integer. (2) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing at least one compound represented by the following general formula [I] has a pH of 9.5 or more and 10 A method for processing a silver halide color photographic light-sensitive material, comprising processing with a color developer having a sulfite ion concentration of 8×10^-^2 mol/l or less. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the general formula [I], A is ▲ mathematical formulas, chemical formulas, tables, etc. etc. ▼ Represents a coupler component or a reducing agent component that releases a residue, and TIME is bonded to A and S (sulfur atom) or N (nitrogen atom) and is released from A by the coupling reaction or redox reaction. After ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Represents a timing group for leaving a residue, Z represents a group of nonmetallic atoms necessary to form a heterocycle with carbon atoms and nitrogen atoms, and L represents an ether bond or thioether bond. represents an aliphatic or aromatic divalent linking group that may contain a bond or a simple bond, R represents an unsubstituted linear or branched alkyl having 1 to 6 carbon atoms, and m represents 0 or 1. Represents an integer.