JPH02254441A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sensitive material contg. a malondianilide coupler having high heat resistance and high coupling activity by incorporating the coupler represented by a specified general formula into a constituent layer of a silver halide color photographic sensitive material. CONSTITUTION:When at least one silver halide emulsion layer is formed on a support to obtain a sensitive material, at least one kind of coupler represented by general formula I is incorporated into the constituent layer. In the formula I, each of R1 and R2 is 1-24C alkyl, alkylthio, etc., 2-24C alkoxy, alkoxycarbonyl, etc., 6-24C aryl, aryloxy, etc., or 7-24C aryloxycarbonyl, each of R3 and R4 is a group substitutable on a benzene ring, T is a group cleaving an arom. prim. amine developing agent, Het is a heterocyclic group contg. N, O, etc., and each of m and n is an integer of 0-4.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a silver halide color photographic photosensitive material containing a novel malondianilide coupler, which has excellent image storage stability and quality, and in particular has improved heat fastness. It's about materials.

(Prior Art) Silver halide color photographic light-sensitive materials are produced by exposing the material to light and then performing color development, whereby an oxidized aromatic primary amine developer reacts with a dye-forming coupler (hereinafter referred to as coupler). A color image is formed by this.

Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed, respectively. Acylacetamide coupler and malondianilide coupler are used as a yellow dye-forming coupler (hereinafter referred to as yellow coupler) to form a yellow image, and 5 is a magenta coupler to form a magenta image.
- Pyrazolone couplers, pyrazolotriazole couplers, etc. are generally used as cyan couplers, and phenol couplers and naphthol couplers, respectively, are commonly used to form cyan images.

The yellow, magenta, and cyan dyes obtained from these couplers are produced in silver halide emulsion layers or adjacent layers sensitive to radiation that is complementary to the radiation absorbed by the dyes. It is common to be formed.

Incidentally, yellow couplers, particularly acylacetamide couplers typified by benzoylacetanilide couplers and pivaloylacetanilide couplers, are commonly used for image formation. The former generally has a high coupling activity with the oxidized aromatic primary amine developer during development, and the produced yellow dye has a large extinction coefficient, so it is used in color photographic materials that require high sensitivity, especially color negatives. The latter is mainly used for color papers and color reversal films because of its excellent spectral absorption characteristics and fastness of yellow dye. On the other hand, French Patent No. 1,558,452, U.S. Patent No. 4,095.984, U.S. Patent No. 4,149,
No. 886, No. 4.4'7'1.563, No. 4.5
The malondianilide couplers described in No. 00,634 and JP-A-52-154631 are characterized by high coupling activity, and in particular, the leaving group that leaves during the coupling reaction enters the coupling active position at the nitrogen atom. This type of coupler has particularly high coupling activity and is therefore used as a development inhibitor-releasing coupler (so-called DIR coupler). As is already known, the use of DIR couplers improves graininess by making dye mottles finer (fine grains of color images), improves image sharpness due to edge effects, and suppresses development between layers. Effects such as improved color reproducibility and gradation control can be obtained.The four US patents mentioned above all relate to DIR couplers.

The compound that is separated by the coupling reaction and produced is a mercapto-substituted heterocycle or its precursor is released into the developer depending on the structure, and has the above-mentioned development inhibiting effect as well as the fogging effect. Bleaching promotion, bleaching inhibition,
Various functions such as development promotion and fog prevention can be imparted. Examples of couplers that release bleach accelerators are described in European Patent No. 0193389A2, and examples of couplers that release capacitive agents are described in US Pat. No. 4,628,024.

(Problems to be Solved by the Invention) JP-A-52-154631 discloses a malondianilide coupler that releases a mercapto compound having a development inhibiting effect, and claims high coupling reactivity.

By the way, the yellow dye obtained from malondianilide coupler has a relatively large molecular extinction coefficient, so it has a yellow density not only when used for image formation, but also when used as an additive for image formation couplers such as DIR couplers. The color image needs to be sufficiently robust. However, color images obtained from malondianilide couplers are generally sensitive to heat, and have had major problems in storage stability when stored in the dark.

A first object of the present invention is to provide a silver halide color photographic light-sensitive material containing a malondianilide coupler which has improved color image fastness, particularly heat fastness.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material containing a malondianilide coupler having high coupling activity.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material containing a malondianilide coupler capable of releasing a photographically useful group (compound) through a coupling reaction.

(Means for Solving the Problems) These objects of the present invention are as follows (1), (2) or (3).
) is achieved using a silver halide color photographic light-sensitive material.

(1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the following general formula (I
) A silver halide color photographic material containing a coupler represented by:

General formula [I] Het (wherein R1 and R2 each independently have 1 to 1 carbon atoms)
24, alkyl group, alkylthio group, alkylsulfonyl group or alkoxysulfonyl group, number of carbon atoms 2
~24 alkoxy group or alkoxycarbonyl group, an aryl group, aryloxy group, arylthio group, or arylsulfonyl group having 6 to 24 carbon atoms, or an aryloxycarbonyl group having 7 to 24 carbon atoms, R8 and R4 each independently represents a group that can be substituted on the benzene ring, and T represents a bond with -CH- that is cleaved by a coupling reaction with an oxidized product of an aromatic primary amine developer. &S indicates a group that is cleaved or a simple bond, and Het is a group in which at least one heteroatom selected from nitrogen, oxygen, sulfur, phosphorus, selenium, or tellurium atoms is inserted into the ring. 3 to 8 included in
represents a membered monocyclic or condensed ring heterocyclic group, m and n each independently represent an integer of 0 to 4, provided that m or n
When there is a plurality of R1s or R4s, the plurality of R1s or R4s may be the same or different. ) (2) The halogenated compound according to item (1), wherein at least one of m or n in general formula [1] is not O, and at least one of R1 or R4 is an electron-withdrawing substituent. Silver color photographic material.

(3) Silver halide color photographic photosensitive material according to item (1), wherein in the general formula [11, both m and n are not O, and at least one R1 or R4 is an electron-withdrawing substituent. material.

The ortho-position substituent of the anilide moiety of conventionally known malondianilide couplers is generally a chlorine atom or a methoxy group, but other than these, there are compounds described in French Patent No. 1,558,452. 16, i.e., the octyloxy group of α-(4-methoxyphenoxy)-2,2''-dioctyloxymalondianilide. However, the purpose of this patent was to achieve high coupling activity and prevent staining during storage, and the color image There is no disclosure regarding the fastness of this compound.Also, the leaving group 4methoxyphenoxy group of this compound is not a photographically useful group, and no photographically useful action can be expected from this compound.Therefore, compound 16 of the patent has a different purpose from that of the present invention.

The coupler represented by the general formula [I] used in the present invention will be described in detail below.

In the general formula [I], R1 and R3 are each independently an alkyl group, an alkylthio group, an alkylsulfonyl group or an alkoxysulfonyl group having 1 to 24 carbon atoms;
represents an ano-koxy group or alkoxycarbonyl group having 2 to 24 carbon atoms, an aryl group, arylthio group, or arylsulfonyl group having 6 to 24 carbon atoms, or an aryloxycarbonyl group having 7 to 24 carbon atoms; The alkyl group or aryl group part of the group is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkoxy group, aryloxy group, alkylthio group, arylthio group, aryl group, alkoxycarbonyl group, carbamoyl group, carboxyl group. It may be substituted with an amide group, a sulfonamide group, a sulfamoyl group, a hydroxyl group, an acyl group, an acyloxy group, an imide group, an alkylsulfonyl group, an arylsulfonyl group, or the like. Furthermore, the alkyl group portion may be branched or cyclic,
aR where the aryl moiety may be substituted with an alkyl group
Specific examples of + and R2 include alkyl groups (e.g. methyl,
n-butyl, n-hexyl, n-octyl, n-decyl, 2-decyl, phenethyl), aryl groups (e.g. phenyl, 1-naphthyl, 4-butoxyphenyl), alkoxy groups (e.g. ethoxy, n-butoxy, n -hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-dodecyloxy, 2-decylthioethoxy, 2-hexyldecyloxy, 3-dodecyloxyprobyl), aryloxy groups (e.g. phenoxy, 4-t-butylphenoxy, 4-octyloxyphenoxy), alkylthio groups (e.g. n-octylthio, 2-ethylhexylthio, n-decylthio, n-
dodecylthio, n-hexadecyldio), arylthio groups (e.g. phenylthio, 4-dodecylphenylthio)
, an alkylsulfonyl group (e.g. methylsulfonyl, n
-octylsulfonyl, 2-ethylhexylsulfonyl, phenethylsulfonyl, n-decylsulfonyl, n-
dodecylsulfonyl, 3-dodecyloxyprobylsulfonyl), arylsulfonyl groups (e.g. p-tolylsulfonyl, 4-methoxyphenylsulfonyl, 4-dodecylphenylsulfonyl), alkoxycarbonyl groups (
For example, methoxycarbonyl, n-butoxycarbonyl,
n-hexyloxycarbonyl, n-octyloxycarbonyl, 2-ethylhexyloxycarbonyl, 1-
(octyloxycarbonyl)ethoxycarbonyl, n
-decyloxycarbonyl, n-dodecyloxycarbonyl, n-hexadecyloxycarbonyl), alkoxysulfonyl groups (eg, n-octyloxysulfonyl, n-decyloxysulfonyl), aryloxycarbonyl groups (eg, phenoxycarbonyl), and the like.

The number of carbon atoms in R or R2 is preferably 4 to 20, and 6
-16 is more preferable. Furthermore, R or R2 is preferably an alkoxy group, an alkylthio group, an alkylsulfonyl group, or an alkoxycarbonyl group, and more preferably an alkylsulfonyl group or an alkoxycarbonyl group.

In the general formula [I], R1 and R1 represent a group that can be substituted on the benzene ring, and specifically, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (such as methyl, trifluoromethyl, trichloromethyl,
ethyl, isopropyl, t-butyl, cyclopentyl,
cyclohexyl, t-pentyl, 1,1.33-tetramethylbutyl, n-decyl), aryl groups (e.g. phenyl, p-tolyl, 2-chlorophenyl), alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, benzyloxy) , butoxy, n-octyloxy), aryloxy groups (e.g. phenoxy, 4-methoxyphenoxy), alkylthio groups (e.g. methylthio, ethylthio, hexylthio, benzylthio), arylthio groups (e.g. phenylthio, 4-chlorophenylthio),
Alkylsulfonyl groups (e.g. methylsulfonyl, edylsulfonyl, trifluoromethylsulfonyl), arylsulfonyl groups (e.g. phenylsulfonyl, p-1
-lylsulfonyl), acyl groups (e.g. formyl, acetyl, benzoyl), acyloxy groups (e.g. acetoxy, benzoyloxy), carbonamide groups (e.g. acetamide, trifluoroacetamide, benzamide, octanamide), sulfonamide groups (e.g. methanesulfonamide), , trifluoromethanesulfonamide, toluenesulfonamide), hydroxyl group, carboxyl group, sulfo group, cyano group, alkoxycarbonyl group (e.g. methoxycarbonyl, ethoxycarbonyl)
, aryloxycarbonyl (e.g. phenoxycarbonyl, 4-methoxyphenoxycarbonyl), amino group (e.g. amino group, N-methylamino, N,N-dimethylamino, pyrrolidino, piperidino, morpholino), heterocyclic group (e.g. 2-furyl) , 2-thienyl, 4-pyridyl), imide groups (e.g. succinimide, phthalimide), carbamoyl groups (e.g. N-methylcarbamoyl), sulfamoyl groups (e.g. N,N-dimethylsulfamoyl), etc. Certain 0m and n are integers of 0 to 4, but 0 to 2 are more preferable.

(R3) or (R4). The total number of carbon atoms is O~24
It is.

In the general formula (Il, T is a group or a simple bond that cleaves the bond with -C1-1- and then cleaves the bond with X by the coupling reaction with the oxidized product of the aromatic primary amine developer. represents.

The former involves adjusting the coupling activity of the coupler, stabilizing the coupler, and combining the oxidized product of the aromatic primary amine developer with the general formula [
1] by a coupling reaction with a compound represented by
-IJIJ of X after X leaves.

This group has functions such as adjusting the release timing.

Although it is generally preferable for T to be a bond, the former group may be selected depending on the purpose. Examples of the former group include the following known linking groups.

(1) A group that utilizes the hemi-secure cleavage reaction, such as U.S. Pat. No. 4,146,396 and JP-A-60-2491.
48 and No. 60-249149, and is a group represented by the following general formula. Here, the * mark represents the general formula [I
I represents the position where it is bonded to -CH-, and the mark ** represents the position where it is bonded to X in the general formula [Il.

General formula (T-1) In the formula, W represents an oxygen atom, a sulfur atom or a -N-at group, Ras and Rss represent a hydrogen atom or a substituent, Rat represents a substituent, and t is 1 or 2
represents. When t is 2, there are two. Rsa and R1
When 16 represents a substituent and R-t representative examples include each '2 Rg9 group, R6, CO- group, RsoSOt- group, RaeN CO- group or R7゜ aliphatic group, aromatic group or heterocyclic group. RTO represents an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom.

Rea, R66 and R117 each represent a divalent group, and cases in which they are linked to form a cyclic structure are also included. Specific examples of the group represented by general formula (T-1) include the following groups.

*-0CH2 -** *-OCH-** HzCfb (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction, such as the timing group described in U.S. Patent No. 4,248,962. It will be done. It can be expressed by the following general formula.

General formula (T-2) *-Nu-Link-E-** In the formula, the * mark represents the bonding position to -CH- in the general formula [11], and the ** mark represents the bonding position to -CH- in the general formula [I]. It represents the bonding position, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, and E represents an electrophilic group, which undergoes nucleophilic attack from Nu and forms a bond with the mark **. Link, which is a cleavable group, represents a linking group that sterically relates Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by general formula (T-2) are as follows.

■ C.I.

* − * − (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system.

For example, US Patent No. 4409323, US Patent No. 442184
No. 5, JP-A-57-188035, JP-A No. 58-9872
No. 8, No. 58-209736, No. 58-209737
No. 58-209738, etc., and is a group represented by the following general formula (T-3).

General formula (T-3) *-O * - * - In the formula, * mark, ** mark, W, R6! , R6B and t are (
It has the same meaning as explained for T-1). However, R8B and Ras may be combined to form a constituent element of a benzene ring or a heterocycle. Specifically, the following groups may be mentioned.

(4) A group that utilizes a cleavage reaction due to ester hydrolysis.

Examples of the linking groups described in West German Published Patent Application No. 2,626.315 include the following groups.

In the formula, * and ** have the same meaning as explained for general formula (T-1).

Specific examples of groups represented by maximum (T-4) - maximum (T-5) include the following groups.

*-0-C~** (5) A group that utilizes the iminoke cool cleavage reaction.

For example, it is a linking group described in US Pat. No. 4,546,073, and is a group represented by the following general formula.

General formula (T-6) Ra- 〆*-W-C \ * * In the formula, * mark, ** mark and W have the same meaning as explained in general formula (T-1), and Raa is R6 ? Expressing the same meaning as, - maximum (T-6) (6) (1) ~
A group that combines any of the mechanisms in (5).

For example, JP-A-57-56837, JP-A No. 6021864.
No. 5, No. 60-229030, No. 61-156127
No. 63-3734.6, etc., and specific examples include the following groups.

CJ, -+ In the general formula [1], Het is a 3- to 8-membered ring containing at least one heteroatom selected from a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a selenium atom, or a tellurium atom. represents a monocyclic or condensed ring heterocyclic group, examples include l, 3.4-oxadiazol-2-ylthio group, 1,3.4thiadiazol-2-ylthio group, 2-benzimidazolylthio group, 2 -penzoxazolyldio group, 2-benzothiazolylthio group, 2-pyrimidylthio group, 2-pyridylthio group, 3-pyridylthio group, 4-pyridylthio group, 4-pyrimidylthio group, 2-quinolylthio group, 4- quinolylthio group, 2-imidazolylthio group,
1,2.4-triazol-5-ylthio group, 1,2,
Examples include 3,4-tetrazol-5-ylthio group, and these groups may have a substituent.

Preferred groups as Het are l, 2,3.4-tetrazol-5-ylthio group, 1.34-year-old xadiazole-2
-ylthio group, l, 3.4-thiadiazol-2-ylthio group, 1-benzotriazolyl group, 2-benzothiazolylthio group and 2-pyrimidylthio group, more preferably the following maximum [11] to [■ ] It is expressed as .

- Maximum (I[) R+4 Maximum (1) General formula (IV) General formula (V) General formula [■] In the above formula, R8 is an alkyl group having 1 to 16 carbon atoms [
For example, ethyl, hexyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-carboxyethyl,
1-(methoxycarbonyl)ethyl or an aryl group having 6 to 24 carbon atoms (e.g. phenyl, 4-hydroxyphenyl, 3-hydroxyphenyl, 3-sulfamoylphenyl, 3-succinimidophenyl, 4-methylphenyl, 4 RI8 represents a hydrogen atom, a halogen atom, an amino group, an alkyl group having 1 to 16 carbon atoms; (e.g. methyl, hydroxyethyl, methoxyethyl, butyl), 6 carbon atoms
~24 aryl groups (e.g. phenyl, 4-methoxyphenyl, 4-chlorophenyl), carbonamide groups having 1 to 24 carbon atoms (e.g. acetamide, benzamide), alkylthio groups having 1 to 16 carbon atoms (e.g. methylthio, ethylthio). , benzylthio, octylthio, methoxycarbonylmethylthio), arylthio groups having 6 to 24 carbon atoms (e.g. 4-acetamidophenylthio, 4-methanesulfonamidophenylthio), or sulfonamide groups having 1 to 24 carbon atoms (e.g. metalsulfone). amide, toluenesulfonamide, octanesulfonamide), and R16 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 16 carbon atoms (e.g. methyl, butyl), an alkoxy group having 1 to 16 carbon atoms ( For example, methoxy, butoxy, methoxyethoxy, benzyloxy), tetranido groups, cyano groups, amine groups, carbonamide groups having 1 to 24 carbon atoms (e.g. acetamide, benzamide), sulfonamide groups having 1 to 24 carbon atoms ( (e.g. methanesulfonamide, benzenesulfone, amide), alkoxycarbonyl groups having 2 to 16 carbon atoms (e.g. methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl groups having 6 to 16 carbon atoms (e.g. phenoxycarbonyl, 4-methylphenoxy R1? and R+a represents a hydrogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 8 carbon atoms (for example, methyl, butyl), or an alkoxy group having 1 to B carbon atoms (for example, methoxy, butoxy, methoxyethoxy).

-M Among the groups represented by the formulas [113 to [VI], the groups represented by the general formulas (n) to [IV] are preferred, and the groups represented by the general formula [■] are more preferred.

R3 or R4 of the compound represented by general formula [I]
A compound in which at least one of the substituents is an electron-withdrawing substituent has a high coupling activity (preferably) with an oxidized product of an aromatic primary amine developer. is 0 or more, preferably 0.
Two or more substituents, specific examples include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), trichloromethyl group, trifluoromethyl group, cyano group, acyl group, nitro group, carboxyl group, carbamoyl group , sulfamoyl group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, aryloxycarbonyl group, alkoxysulfonyl group, aryloxysulfonyl group, heterocyclic group (e.g. tetrazolyl, pyrrolyl, benzotriazolyl, benzoxacylyl), imide group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, trifluoromethoxy group,
Examples include thiocyanate group, alkylsulfinyl group, and arylsulfinyl group. In addition, ) lammet's Op
Values are C, Hansch et at, J, MedCh
em, 16, 1207 (1973) and 20
304 (1977) etc. Among these electron-withdrawing groups, halogen atoms, cyan groups, nitro groups, trifluoromethyl groups, alkoxycarbonyl groups, alkylsulfonyl groups and arylsulfonyl groups are preferred in the present invention.

Below is the general formula [I] An example of a substructure in and General formula [I] A specific example of a compound represented by vinegar.

Example of 0 Party 2H5 5-Het - These couplers represented by formula 6 [13]
It can be synthesized by the method described in No. 2-154631, Japanese Patent Application No. 62-316973, etc. A synthesis example is shown below.

Coupler I-2 to A 1 2-tetradecyloxyaniline 80. Og and 13.6 g of malonic acid were mixed with acetonitrile 200g and ethyl acetate 3
56.8 g of dicyclohexylcarbodiimide dissolved in a mixed solvent of 0.00 g and 200 g of acetonitrile was added dropwise over about 20 minutes. After the reaction, the mixture was separated, the filtrate was concentrated, and 500 ml of acetonitrile was added for crystallization. The resulting crystals were filtered and dried to obtain 62.5 g of malonic acid di-2tetradecyloxyanilide.

(Yield: 35.1%, 7.12 g of 5-mercapto-1-phenyltetrazole)
was dissolved in 100 ml of methylene chloride, and 3.4 ml of sulfuryl chloride was added dropwise while cooling with water. After stirring for 30 minutes, the pressure was reduced to 1 level using an aspirator. Add 50ml of methylene chloride to the residue, dissolve it, and add 20.4g of malonic acid di-2-tetradecyloxyanilide to a solution of 100ml of methylene chloride at room temperature for 30ml.
It was dripped in minutes. After further stirring for 5 hours, the reaction solution was washed with water and concentrated. The residue was dissolved in a methanol-ethyl acetate mixed solvent and crystallized to obtain 20.3 g of the desired exemplary coupler I-2. The melting point of this compound is 78-7
The temperature was 9°C, and the structure was confirmed by mass spectrum, 'HNMR spectrum, and elemental analysis.

A2, A of coupler 1-4 83.5 g of O-nitrobenzoic acid, dimedylpolamide [1] and 1 ood of thionyl chloride were heated under reflux for 3 hours.

The mixture was concentrated under reduced pressure using an aspirator to obtain 0-nitrobenzoyl chloride as a yellow oil. n-dodecanol88.
4 g and 41 ml of pyridine were dissolved in 300 ml of acetonitrile, and 0-nitrobenzoyl chloride was added dropwise over 30 minutes while stirring at room temperature. After stirring for 1 hour, 600 d of Egul acetate was added, and the mixture was washed with 500 ml of water three times and extracted.

The ethyl acetate solution was concentrated with sodium sulfate to give 143 g of dodecyl 0-nitrobenzoate as a pale yellow oil.

3g of ammonium chloride, 60ml of water! and isopropanol 300 was heated to reflux under a nitrogen stream to remove dodecyl 0.
-67 g of nitrobenzoate were added dropwise over 15 minutes. 30
After heating under reflux for several minutes, the reaction solution was filtered under reduced pressure, and the filtrate was concentrated under reduced pressure. Add 300ml of acetic acid to the concentrate and add 200ml
The mixture was washed twice with water, dried over sodium sulfate, and then concentrated to obtain 58.6 g of dodecyl O-aminobenzoate as a pale yellow oil.

22.9 g of malonic acid and 139.5 g of dodecyl 0-aminobenzoate were dissolved in 240 g of dimethylformamide, and 94.2 g of dicyclohexylcarbodiimide dissolved in 40 ml of dimethylformamide was added dropwise over 30 minutes while stirring at room temperature.

After the addition, the mixture was heated and stirred on a steam bath at 80° C. for 5 hours, and the reaction solution was cooled. The reaction solution was filtered under reduced pressure, and the filtrate was filtered for 600 m
1 of ethyl acetate was added thereto for extraction. The ethyl acetate solution was dried over sodium sulfate, concentrated under reduced pressure, and ethanol was added to cause crystallization. By filtering and drying the resulting crystals, malonic acid di-2-dodecyloxycarbonylanilide is
33. ]g (yield 89.1%) was obtained. Melting point 65-67℃
2.6 g of 1-ethyl-5-mercaptotetrazole was dissolved in 50 d of methylene chloride, and sulfuryl chloride 1.
After stirring for 630 minutes, the mixture was concentrated under reduced pressure using an aspirator. The residue was dissolved in 30 g of methylene chloride, and added dropwise to a solution of 10.2 g of malonic acid di-2-dodecyloxycarbonylanilide in 50 d of methylene chloride at room temperature for 30 minutes. After further stirring for 3 hours, the reaction solution was washed with water.
Concentrated. The target example coupler I-4 was obtained by dissolving the residue in a mixed solvent of acetonyl-I and ethyl acetate and crystallizing it to obtain a compound with a melting point of 8.8 g'4.
~56°C, and the structure was confirmed by mass spectra, 'NMR spectra, and elemental analysis.

A 3 Scrubler 1-8 of 4 5.0.9 g of 4-methylthiophenol, 125 g of potassium carbonate, and 300 g of N,N-dimethylformamide were heated and stirred on a steam bath under a nitrogen stream, and 1-
90.5 g of bromododecane was added dropwise over 1 hour. After the dropwise addition, the mixture was stirred for 3 hours, extracted with ethyl acetate, and washed with water. The ethyl acetate solution was concentrated, and methanol was added to the residue for precipitation to obtain 100 g of white crystals of dodecyl 4-methylthiophenyl ether.

95.4 g of dodecyl 4-methylthiophenyl ether was dissolved in 400 g of acetic acid, and 0.0 g of sodium tungstate was dissolved in 400 g of acetic acid.
5 g of diluted sodium hydroxide hot solution was added, heated and stirred at 80° C., and 66.3 g of 35% hydrogen peroxide solution was added dropwise therein over 30 minutes. After all, the mixture was heated and stirred for 2 hours, water was added for cooling, and the precipitated crude crystals were filtered. The crude crystals were recrystallized from methanol to obtain 101.5 g of dodecyl 4-methylsulfonylphenyl ether crystals.

Dodecyl 4-methylsulfonylphenyl ether29.
Dissolve 4 g in 100 mfl of acetic anhydride and add 10 ml under ice-cooling.
of sulfuric acid was added dropwise, and then 6.4 g of 94% nitric acid was added dropwise. After dropping, the mixture was stirred for 1 hour, then poured into ice water and stirred. The precipitated crystals were filtered and recrystallized from methanol to obtain 27.7 g of flaky pale yellow crystals of dodecyl 4-methylsulfonyl-2-nitrophenyl ether.

25.2 g of iron powder, 1 g of ammonium chloride, 25 d of water and 250 g of isopropanol were heated and stirred under a nitrogen stream, and 23.1 g of dodecyl 4-methylsulfonyl-2-nitrophenyl ether was added thereto. After stirring for 1 hour, the reaction solution was filtered through a Nutsche filter lined with Celai. The reaction solution was concentrated and crystallized by adding methanol to obtain 17.5 g of crystals of dodecyl 2-amino-4-methylsulfonylphenyl ether.

A reaction operation was carried out in the same manner as in Synthesis Example 1 using 17.5 g of dodecyl 2-amino-4-methylsulfonylphenyl ether and 2.44 g of malonic acid, and by crystallization from methanol, malonic acid di(2-dodecyloxy-5 8 g of crystals of -methylsulfonylanilide) were obtained. The melting point of this compound was 92-94°C.

5-mercapto-1-phenyltetrazole 5.35g
and 7.8 g of malonic acid di(2-dodecyloxy-5-methylsulfonylanilide) in the same manner as in Synthesis Example 1, and the product was crystallized from acetonitrile to obtain the desired exemplary coupler I-8. 8.4g of was obtained. The melting point of this compound was 133-135°C, and the structure was confirmed by mass spectra, NMR spectra, and elemental analysis.

The compound of general formula [11] of the present invention is applied to a multilayer multicolor photographic material having at least three different spectral sensitivities on a support.
It can be applied mainly to improve sharpness, sensitivity, and color reproducibility. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these calendars is up to you and chosen according to your needs. The compounds of the present invention can be used in emulsion layers or t
Used for the layer adjacent to the mast. Moreover, the compound of the present invention is
It can be used in any layer such as a high-sensitivity layer, a low-sensitivity layer, or a medium-sensitivity layer.

The amount of addition of the compound of general large CI] varies depending on the structure of the compound, but is preferably 1xto-' to 0.5 mol per mol of silver present in the same layer or an adjacent layer, particularly preferably lXl0-' to 1xlO - moles.

The light-sensitive material of the present invention has a small number of silver halide emulsion layers (one layer is sufficient for each of the blue-sensitive layer, green-sensitive layer, and red-sensitive layer) on the support; There is no particular restriction on the number and order of the silver emulsion layer and the non-light-sensitive layer.A typical example is a support having a plurality of halogenated layers having substantially the same color sensitivity but different light sensitivities. A silver halide photographic light-sensitive material having one or fewer photosensitive layers consisting of a silver emulsion layer, and the photosensitive layer is a unit photosensitive material sensitive to blue light, green light, or red light. In multilayer silver halide color photographic light-sensitive materials, the unit photosensitive layers are generally arranged in the following order from the support side: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the above-mentioned installation order may be reversed, or the installation order may be such that a different number of color-sensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity edge sensitive layer (GH) / low sensitivity green sensitive layer (GL) /high-sensitivity red-sensitive layer (RH)/low-sensitivity red-sensitive layer (RL) order, or BH/BL/GL/GH/RH/RL order,
Alternatively, they can be installed in the order of BH/B L/G H/G L/RL/RH.

Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of RH/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive rays can be arranged in the order of /GL/RL/GH/RH from the side farthest from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with a lower sensitivity, and the lower layer is a silver halide emulsion layer that is more sensitive than the middle layer. An example is an arrangement consisting of three layers having different photosensitivity, in which a silver halide emulsion layer with a low density is arranged, and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side away from the support, and in addition, high-sensitivity emulsion layer/low-sensitivity emulsion layer/medium-sensitivity emulsion layer They may be arranged in the order of emulsion layer or low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc. Also, when there are four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent 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 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), No. 1764.
3 (December 1978), pp. 22-23, “Engineering, Emulsion Preparation
and types)” and same No. 1871
6 (November 1979), 648 pages, graphic “
"Physics and Chemistry of Photography", published by Paul Montell (p.

Glafkides, Chemie et Ph1s
ique PhotographiquePaul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffi)
n.

P, Photographic Emulsion Ch
emistry (Focal Press.

1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
Manet al, Making and Coat
ing Photographic Emulsion,
Focal Press, 1964).

U.S. Patent No. 3,574,628, U.S. Patent No. 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 by Gutoff, Photographic Science and Engineering.
nce and Engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, No. 434.226, No. 4,414,310, No. 433.048, No. 4,439,520, and British Patent No. 2,112,157. I can do it.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be 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 rhodan 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 sensitization. The additives used in such a process are described in the aforementioned Research Disclosure No. 17643 and Research Disclosure 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.

l Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Anti-fogging agents and stabilizers 6 Light absorbers, filter dyes UV absorbers 7 Anti-stinting agents dye image stabilizers hardening agents Film binder plasticizer, lubricant coating aid, surface active agent 13 Static inhibitor RD 17643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 right column 25 pages 26 pages 26 pages 27 pages 26 - Page 27 Page 27 RD 18716 Page 648 Right column Same as above Page 648 Right column - Page 649 Right column Page 649 Right column - Page 649 Right column - Page 650 Left column Page 650 Left - Right column Page 651 Left column Same as above Page 650 Right column Same as above Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, compounds that can be immobilized by reacting with formaldehyde as described in U.S. Pat. It is preferable to add it to a photosensitive material.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure.
(RD) No. 1 7643, V■-C to G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401.752, No. 4,
248.961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425°020, British Patent No. 1,476.760, U.S. Patent No. 3,973,968, Japanese Patent No. 4,314.
No. 023, No. 4,511,649, European Patent No. 24
9.473A, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0,619, European Patent No. 4.351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure No. 24220 (1984) June), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-436
No. 59, No. 61-72238, No. 60-35730, No. 55-118034, No. 60-185951,
U.S. Patent Nos. 4,500,630 and 4,540,6
No. 54, No. 4.556 630, International Publication W088
Particularly preferred are those described in No. 104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat. No. 4,052.21.
No. 2, No. 4,146,396, No. 4,228,2
No. 33, No. 4,296,200, No. 2,369.
No. 929, No. 2,801.171, No. 2,772
, No. 162, No. 2.895,826, No. 3,77
No. 2,002, No. 3,758,308, No. 4.3
No. 34.011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121.36
No. 5A, No. 249,453A, U.S. Patent No. 3,44
No. 6,622, No. 4.333.999, No. 4,7
No. 75,616, No. 4.451.559, No. 4,
No. 427,767, No. 4,690.889, No. 4
．． Preferred are those described in No. 254.212, No. 4,296.199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No. 17643.
-G section, U.S. Patent No. 4,163.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, No. 4,138゜258, British Patent No. 1,146,
No. 368 is preferred, and also US Pat.
, 774.181, it is also preferred to use a coupler that compensates for unwanted absorption of the chromogenic dye by the fluorescent dye released during coupling as described herein.

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.
No. 4,576.910, British Patent No. 2,102
, No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. In addition to those represented by the general formula (I) of the present invention, DIR couplers that release a development inhibitor include the above-mentioned RD17643, ■-F
Preferred are the patents described in Section 1, JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and US Pat. No. 4,248,962.

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. Pat. No. 4,130,427, U.S. Pat. , long equivalent couplers described in JP-A No. 4,310,618, I) IR redox compound releasing couplers or DrR couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc. coupler-releasing couplers, DIR coupler-releasing redox compounds or DIR redox compound-releasing redox compounds, couplers releasing reciprocating colored dyes as described in European Patent No. 173,302A, R;
D, No. l 1449, 24241, JP-A-1986-
Bleach accelerator-releasing couplers described in US Pat. ,774.181
Examples include couplers that emit fluorescent dyes as described in this issue.

The coupler used in the present invention can be introduced into the light-sensitive material 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-t-amylphenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,l-diethylbrobyl) phthalate, etc.), phosphoric acid or Phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2
-ethylhexyldiphenyl 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 (stearyl alcohol, 2.4
-di-t-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-t-octylaniline, etc.), and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.). It will be done. Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and Patent Application No. 1983-
Benzisothiazolone, n-butyl p-hydroxybenzoate, phenol, 2-(
It is preferable to add various preservatives or antifungal agents such as 4-thiazolyl)benzimidazole.

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 vapor.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, and same No. 187
16, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is 28 μm or less, more preferably 23 μm or less, and even more preferably 20 ILm or less.
Further, the membrane swelling rate T1/2 is preferably 30 seconds or less, and 2
The film thickness is more preferably 0 seconds or less at 25°C relative humidity 55
% refers to the film thickness measured under humidity control (2 days), and the film swelling rate TI/□ can be measured according to a method known in the art. For example, Ni Green (A,
Photographic Science and Engineering (Photogr. Green) et al.

Set Eng, ), Volume 19, No. 2, 124~
It can be measured by using a swellometer (swelling membrane) of the type described on page 129, and T1/2 can be measured by
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at 0° C. for 3 minutes and 15 seconds, and is defined as the time required to reach the film thickness of T1/2.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. In addition, the swelling rate is preferably 150 to 400%. The swelling rate is defined as the saturated film thickness, which is 90% of the maximum swollen film thickness under the conditions described above, and the time required to reach the film thickness of T1/2. Define as time.

The membrane swelling rate T,/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
o, 17643, pages 28-2, and same No. 187
16, No. 651, 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-phenylenediamine compounds are preferably used, representative examples of which include 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, hydrochlorides, p-+-luenesulfonates, and the like. Among these, 3-methyl-4-amino-N-
Ethyl-N-β-hydroxyethylaniline sulfate is preferred. 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, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, as necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, diethylene glycol, etc. organic solvents such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-virazolidone, tackifying agents. , various chelating agents such as aminopolycarboxylic acid, aminopolyphosponic acid, alkylphosphonic acid, and phosphonocarboxylic acid, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxy Ethyliminodiacetic acid, 1-hydroxyethylidene-1,l-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid,
Typical examples include ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally less than 3β per square meter of light-sensitive material, and by reducing the bromide ions in the replenisher by 1 degree, it can be increased to 500+ tons.
It can also be less than t. When reducing the amount of replenishment, it is preferable to reduce the contact area with the air in the processing tank to prevent evaporation of the solution and air oxidation.The contact area between the photographic processing solution and the air in the processing tank is It can be expressed by the aperture ratio defined below.In other words, the above aperture ratio is
It is preferably 0.1 or less, more preferably 0.1 or less.
001 to 0.05.

As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, methods using a movable lid as described in Japanese Patent Application No. 62-241342, Examples include the slit development method described in Japanese Patent No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development steps, but also in all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but it is possible to shorten the processing time by using high temperature, high pH, and a high concentration of color developing agent. can.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing.6
Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as amino acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (III) complex salts, including ethylenediaminetetraacetic acid iron (In) complex salt and 1,3-diaminopropane tetraacetic acid iron (In) complex salt, are preferable from the viewpoint of rapid processing and environmental pollution prevention. . Furthermore, iron(III) aminopolycarboxylate
Complex salts are particularly useful in both bleach and bleach-fix solutions. These iron(III) aminopolycarboxylic acids
The pH of the bleach or bleach-fix solution using 58 salt is usually 4.
0 to 8, but lower p for faster processing.
It can also be treated with H.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893.858, West German Pat.
, No. 290,812, No. 2.059.988, JP-A-53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (July 1978), etc.;
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61; West German Patent No. 1,127
, 715, and the iodide salts described in JP-A-58-16235; West German Patent Nos. 966.410 and 2.748.43.
Polyoxyethylene compounds described in No. 0; Japanese Patent Publication No. 1973
-Polyamine compound described in No. 8836; Other JP-A No. 4
No. 9-42434, No. 49-596'44, No. 53-
No. 94927, No. 54-35727, No. 55-265
Compounds described in No. 06 and No. 58-163940; 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, such as U.S. Pat.
The compounds described in No. 1 are preferred.

Further preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pk, a) of 2.
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a thiosulfate in combination with a thiocyanate, a thioether compound, thiourea, or the like. As a preservative for fixer and bleach-fixer,
Preferred are sulfites, bisulfites, carbonyl bisulfite adducts, and sulfinic acid compounds described in EP 294,769A.

Further, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25℃ ~
The temperature is 50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, No. 62-183461, the emulsion surface of a photosensitive material is also collided with a jet of a treatment liquid, and JP-A No. 62-18346.
No. 183461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. and a method of increasing the circulation flow rate of the entire treatment liquid.

Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing +gi machine used for processing the photosensitive material of the present invention preferably has means for feeding the photosensitive material described in JP-A-60-191257, JP-A-191258, and JP-A-191259. The above-mentioned Japanese Patent Application Laid-Open No. 60-191257
As stated in the issue, this type of conveyance means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing performance deterioration of the processing liquid.This effect reduces the processing time in each process. This is particularly effective in shortening the processing time and reducing the amount of processing liquid replenishment.

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

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used, such as couplers), the application, the temperature of the washing water, and the RI of the washing tank. It can be set over a wide range depending on i (number of stages), replenishment method such as counterflow, forward flow, and various other conditions. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the 5ociety.
of MotionPicture and Te1e
Vision Engineers Volume 64, 9.24
8-253 (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 the water in the tank, bacteria will multiply and the generated suspended matter will adhere 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 reducing calcium ions and magnesium ions described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, isothiazolone compounds and thiabengzoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, are included in ``Chemistry of Antibacterial and Antifungal Agents'' by Hiroshi Horiguchi, ``Sterilization of Microorganisms, Disinfection, and Antifungal Technology'' edited by the Sanitation Technology Society, and ``Encyclopedia of Antibacterial and Antifungal Agents'' edited by the Japan Society of Antibacterial and Mildew Prevention. The fungicides mentioned can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 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 to 45°C, preferably 25 to 45°C.
A range of 30 seconds to 5 minutes at ~40°C is selected. moreover,
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 Nos. 57-8543 and 58-1483
No. 4, No. 60-220345, all of the known methods can be used.Furthermore, subsequent to the water washing treatment, a further stabilization treatment may be performed. Mention may be made of stabilizing baths which are used as baths and which contain dye stabilizers and surfactants. Examples of the dye stabilizer include formalin, glutaraldehydrol compounds, hexamethylenetetramine, aldehyde bisulfite adducts, etc., and nonionic surfactants are preferred, particularly alkylphenyl ether and silicon compounds. is preferred.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or stabilizing liquid replenishment can be reused in other processes such as the desilvering process. When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

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 the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 1 4850
No. 1 and Schiff base-type compounds described in No. 15159, No. 1
Aldol compounds described in No. 3924, U.S. Pat. Nos. 3 and 7
Metal salt complex described in No. 19,492, JP-A-53-135
Examples include urethane compounds described in No. 628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

The various processing solutions used in the present invention are used at temperatures of 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, for saving silver in photosensitive materials, West German Patent No. 2,226,770 or U.S. Patent No. 3
A treatment using cobalt intensification or hydrogen peroxide intensification as described in , 674, 499 may be performed.

Further, the silver halide photosensitive material f4 of the present invention is disclosed in U.S. Pat.
, 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-61-238056, and European Patent No. 210,660A2.

(Effects of the Invention) The silver halide color photographic light-sensitive material H of the present invention has excellent color image fastness (prevention of photofading and dark fading) and exhibits a high multilayer effect. Therefore, it not only has excellent storage stability (color reproducibility and other qualities).

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) Coating amounts are expressed in g/rrr units of silver for silver halides and colloidal silver, and in g/ni small units for couplers, additives and gelatin. For sensitive dyes, silver halide 1 in the same layer
Expressed in moles per mole.

1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・O Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜Ex
M-9・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0UV-1・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜UV
-2・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・06UV-3・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
゜5olv-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・0Solv−2・・・・・・・・・
・・・・・・・・・・・・・・・・・・0゜5olv-
3・・・・・・・・・・・・・・・・・・・・・・・・
・・・0゜Second layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜UV-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0ExC-4・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜ExF-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
0゜5oLv-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜5olv−2・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0゜Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform-AgI type, spherical Equivalent diameter 0.5 μ, coefficient of variation of legal equivalent diameter 20%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount: 1° Silver iodobromide emulsion (AgI 3 mol%, uniform-AgI type) , equivalent sphere diameter 0.3
μ, coefficient of variation of equivalent sphere diameter 15%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...O.

Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1゜ExS-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
4×ExS-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・5×ExC-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
゜ExC-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・06ExC-3・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・ 0゜ExC-4・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜ExC-5・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0° 4th M (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core shell ratio 1:
1 internal height Agr type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount...Oo10-' Gelatin...・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・1゜ExS-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
3×ExS-2・・・・・・・・・・・・・・・・・・
・・・・・・2.3×ExC-6・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜ExC
-7・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜ExC-4・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0Solv-
1・・・・・・・・・・・・・・・・・・・・・・・・
・・・0゜5olv-3・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0゜5th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0Cpd-1・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0
゜5olv-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・0 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core-shell ratio l:
1 surface height AgI type, equivalent sphere diameter 0.5μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount: 0° Silver iodobromide emulsion (AgI) 3 mol%, average-AgI type 1 sphere equivalent diameter 0.3
μ, normal phase 10-' Coefficient of variation of equivalent diameter 25%, spherical particles, diameter/thickness ratio 1.0) Coated silver amount...0 Gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・IExS-3・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・5XE x S
-4・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・3×ExS-5・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・1×E x
M-8・・・・・・・・・・・・・・・・・・
・・・・・・・・・OE x M −9・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・OE
xM-10・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜ExY-41・・・・・・・・・・
・・・・・・・・・・・・・・・・・・0゜5olv-1
・・・・・・・・・・・・・・・・・・・・・・・・
・・0Solv-4・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0゜7th layer (high sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, core shell ratio 1
:3 internal height AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount...08 gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・0,5ExS-3・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・5X101
．． 0-'ExS-4・・・・・・・・・・・・・・・・・・
・・・・・・・・・3XIO-'ExS-5txto
-' E x M -8・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.1ExM-9・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.02ExY-11・・・・・・・・・・・・・・・
・・・・・・・・・・・・003ExC-2・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・0.03ExM-14・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.01Solv-1・・
・・・・・・・・・・・・・・・・・・・・・・・・
0.2Solv-4・・・・・・・・・・・・・・・
・・・・・・・・・・・・0.01 8th layer (middle layer) Gelatin ・・・・・・・・・・・・・・・・・・・・・
・・・・・・ 0.5Cpd-1・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0,05S
olv-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・002 9th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 2 mol%, internal high density gI type with core-shell ratio 2:1, equivalent sphere diameter 1.0 μm) , coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 6.0) Coated silver amount...0.35 Silver iodobromide emulsion (AgI 2 mol%, core shell ratio l:1 internal height Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 6.0) Coated silver amount...0 Gelatin...
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・04ExS-3・・・・・・・・・・・・
・・・・・・・・・・・・・・・8XExY-1
3・・・・・・・・・・・・・・・・・・・・・・・・
・・・0゜ExM-12・・・・・・・・・・・・・・・
・・・・・・・・・・・・OlExM-14・・・・
・・・・・・・・・・・・・・・・・・・・・・・・0S
olv-1・・・・・・・・・・・・・・・・・・
・・・・・・・・・010th layer (yellow filter layer) Yellow colloidal silver ・・・・・・・・・・・・・・・・・・
・・・・・・・・・0, Gelatin ・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・ 0゜℃
pa-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜5olv−1・・・・・・・・・
・・・・・・・・・・・・・・・・・・00Cpd-
1・・・・・・・・・・・・・・・・・・・・・・・・
...0゜11th layer (low sensitivity blue emulsion M) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 15%, plate-like 1 O" grains, diameter/thickness ratio 70) Coated silver amount...0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.311, equivalent sphere) Coefficient of variation in diameter 25%, plate-like particles, diameter/thickness ratio 7.0) Coated silver amount...0°gelatin ・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・1゜ExS-6・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・2×ExC-
16-”・・・・・・・・・・・・・・・・・・
・・0゜ExC-2・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・00ExC-3・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・O comparison coupler■ ・・・・・・・・・・・・・・・
・・・・・・・・・0ExY-15・・・・・・・・・
・・・・・・・・・・・・・・・・・・1゜5olv-1
・・・・・・・・・・・・・・・・・・・・・・・・
...0° 12th layer (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 10 mol%, internal high AgI type,
Equivalent ball diameter 1. OIL, coefficient of variation of equivalent sphere diameter 2S%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver 1...0.5 Gelatin...・・・・・・
・・・・・・・・・・・・0゜ExS２６ ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・1×ExY-15・・・・・・・・・・・・・・・
・・・・・・・・・・・・0ExY-13・・・・・・・
・・・・・・・・・・・・・・・・・・・・・0゜5ol
v-1・・・・・・・・・・・・・・・・・・・・・
...013th layer (first protective layer) Gelatin ...................................................................
・・・・・・・・・・・・08UV-4・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・0゜UV-5・・・・・・・・・・・・・・・・
......River...0゜5olv-1...
・・・・・・・・・・・・・・・・・・・・・・・・0
3olv-2・・・・・・・・・・・・・・・・・・
・・・・・・・・・0゜14th layer (second protective layer) Fine grain silver bromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μ) ・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・0゜gelatin ・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・
・・・・・・0゜Polymethyl methacrylate particle diameter 1.5μ ・・・・・・・・・・・・・・・・・・
・・・・・・09H-1・・・・・・・・・・・・・・・
・・・・・・・・・・・・・・・・・・・・・・・・01C
pd-5・・・・・・・・・・・・・・・・・・
・・・・・・・・・0, cpci-6... river...
・・・・・・Old・・・・・・・・・・・・0.5 In addition to the above sensitivity, each store also has emulsion stabilizer Cpd-3 (0.04
g/rr+”), interfacial staining agent ICpd-4 (0,0
2 g/i) was added as a coating aid.

aU UV-μ 5olv-gUV, -r pd-1 06H! 3 5olv-/tricresyl phosphate 5olv-dibutyl cophthalate cpd-,! 01v-J Cpd, -J Cpd-μ Cpd-YoCpd-x ExC-/ (n)C4Hg ExC-gExC-I CH2 ExC-J ExC-3 Q City2 (-1”12 Siri2LM3xc-A CH2 C (CH3) 3 ExC-7 Lll 4Mg1JtJcNH UCH2CH2SCH2COOH ExM-r ExM riExM ExY-// α H3 ExM-/J ExY-/J α ExM-/≠ ExY-/r BxS-, z BxS-J ExS- α ExC-7G ExS-/ BxS-j BxS-6 H-/ CH2=CH-802-CH2-CONH-CH2CH
2=CH-3o2-CH2-CONH-CH2ExF-
/ (Creation of Samples 102 to 110) Sample 101 except that the same mole of the coupler shown in Table 1 was added in place of the comparative coupler ■ in the 11th layer in Sample 101.
Created in the same way. (Comparative coupler) in Table 1 refers to the following formula.

Comparison coupler ■ Coupler described in French Patent No. 1,558,452 Comparison coupler ■ Coupler described in JP-A No. 52-154631 Comparison coupler ■ Coupler described in JP-A-KOKAI No. 52-154631 Comparative coupler ■ Special Coupler sample 1 described in Kaishotsutsu No. 52-154631
After wedge exposure of samples 01 to 110, the following treatments were performed.

In order to examine the color image preservation of the obtained processed sample, 75
One sample was stored in the dark at 70% RH for 14 days, and the other sample was irradiated with a xenon light source (200,000 ux) for 20 hours. Dark fading and photobleaching were evaluated for each sample.

The results are shown in Table 1.

The multilayer effect was evaluated as follows.

First, each sample was exposed to uniform green light, the exposure amount was adjusted so that the G density was 1.5, and the exposed sample was then imagewise (wedge) exposed to red light. Thereafter, the following development treatment was carried out to obtain a characteristic curve (1) of a yellow color image and a density curve (2) of a magenta color image as shown in FIG. When the blue-sensitive emulsion layer is developed from the unexposed area (point A) to the exposed area (point B), the density curve of the green-sensitive emulsion layer that has been uniformly exposed is from the blue-sensitive layer to the green-sensitive layer. It is meant to indicate the degree of suppression (ΔD,) experienced by the green-sensitive emulsion layer in response to the development of the blue-sensitive emulsion layer. That is, in the first round, curve 1 represents the characteristic curve of the yellow color image of the blue-sensitive emulsion layer, and curve 2 represents the characteristic curve of the yellow color image of the blue-sensitive emulsion layer.
is magenta in a green-sensitive emulsion layer due to uniform exposure to green light.
Represents color image density. Point A represents the minimum 181 degree portion of the yellow color image, and point B represents the exposed M portion that provides a yellow density of 2.0.

The density difference (ΔDa) between the magenta density (D, = 1.5) at point A in the unexposed area and the magenta density (D,
=D, -D11), and this ΔDo was evaluated as a measure of the multilayer effect.

The above method was used for samples 101 to 110. The results are shown in Table 1.

Processing method Process Processing time Color development 3 minutes 15 seconds Bleach White 1 minute OO seconds Bleach fixing 3 minutes 15 seconds Washing with water (1) 40 seconds Washing with water (2) 1 minute 00 seconds Stability 40 seconds Drying 1 minute 15 seconds Next, the composition of the treatment liquid will be described.

(Color developer) Diethylenetriaminepentaacetic acid l-Hydroxyethylidene-1゜1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxyamine sulfate 4-(N-ethyl-N-β-H treatment temperature 38°C 38 ℃ 38℃ 35℃ 35℃ 38℃ 55℃ (Unit: g) 1, O Droxyethylamine)-2- Add methylaniline sulfate and pH (Bleach solution) Ethylenediaminetetraacetic acid ferric ammonia water dihydrate Ethylenediaminetetraacetic acid Disodium acetate Salt Ammonium bromide Ammonium nitrate 4.5 1,02 10.05 (Unit g) 120.0 10.0 100.0 10.0 Ammonia water (27%) 15.0mj2 Add water and heat to 1.0℃ pH 6,3 (Bleach-fix solution) (Unit g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50.0 Ethylenediaminetetraacetic acid dinatrilam salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0mj2 Ammonia Water (27%) 6.0 Add water to pH 1.0 pH 7.2 (Washing liquid) Tap water was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin. Water was passed through a mixed bed column packed with Amberlite I R-400 to treat calcium and magnesium zeo 2181 degrees to 3 mg/I2 or less, followed by 20 mg/l of sodium isocyanurate dichloride and sodium sulfate. 150 mg/j2 was added.

The pH of this solution is in the range 6.5-7.5.

(Stabilizing solution) (Unit: g) Formalin (37%) 2. oPolyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0. o5 Add water 1.0j2 pH5,0-8,
0 As is clear from Table 1, the comparative couplers ■, ■, ■
Samples 101 to 103 using the above-mentioned samples showed a certain degree of single-layer effect, but were extremely poor in darkness and photobleaching. In addition, in sample 104 using comparative coupler (2), although darkness and photobleaching were improved, almost no interlayer effect was observed.

On the other hand, samples 105 to 110 of the present invention have good image storage properties and
Excellent multilayer effect.

(Table 1) Shows the density after storage in the dark at 75° C. for this yellow with a strength of 1.0.

The concentration is shown after 20 hours of irradiation with Canon light (200,011 JX) at 70% RH for 4 days at 21 Ik with a degree of soaking of 1.0.

Example 2 Samples 101 to 110 prepared by the method described in Example 1 were cut to a width of 35111 oI, and a typical subject was photographed using a color negative processor FP manufactured by Fuji Photo Film ■.
A running test of 500 m was conducted using the -350 according to the method described below.

After the running, samples toi to ito were wedge-exposed with white light, and the following treatments were performed, and dark fading and photofading were evaluated in the same manner as in Example 2.

As a result, as in Example 1, in Example 2 as well, results were obtained that the sample to which the coupler having the structure of the present invention was added had excellent dark fading and photobleaching, and had a large multilayer effect.

Processing method Color development 3 minutes 15 seconds 38℃ 45 prints 1o flood drift
White 1 minute OO seconds 38℃ 20rrl 4g
Bleach fixing 3 minutes 15 seconds 38℃ 30m1! iog
Washing with water (2) 1 minute 00 seconds 35℃ 30mg 442
Stable 40 seconds 38℃ 20℃m
4Q.

Drying 1 minute 15 seconds 55°C The amount of replenishment is per 35 mm width and 1 m length. In the above process, the amount of bleach-fix solution brought into the washing process is 2 slides per 1 m length of photosensitive material with a width of 35 m/m. Ta.

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution (g) Replenisher (gl Diethylenetriaminepentaacetic acid 1.0 1,11-hydroxyaminedene-11-diphosphonic acid 3° Sodium sulfite 4 Potassium carbonate 30° Potassium bromide 1° Potassium iodide 1° Hydroxyamine sulfate 2゜4-(N-Ethyl-N-β-hydroxyethylamino)-2- Add methylaniline sulfate and pH (Bleach solution) Common to mother solution and replenisher Ethylenediaminetetraacetic acid ferric ammonium dihydrate Salt Ethylenediaminetetraacetic acid disodium salt 1.0 ℃ 4.5 to, 05 0 3゜0 4゜0 37゜5mji4 2゜5.5 1.0 β (unit g) 120゜10.0 Ammonium bromide Ammonium nitrate Bleach accelerator Aqueous ammonia (27%) Add water to pH (Bleach-fix solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite Ammonium thiosulfate aqueous solution (70%) Ammonia water (27%) Add water to pH 100.0 io.

O,005 moles t5. ont 1, OC (unit: g) 5.0 12.0 240.0 + 1986, Ontsu 1, 0j2 7.2 (Washing liquid) Mother liquor, replenisher Common tap water was mixed with H-type strongly acidic cation exchange resin (ROHM AND Water was passed through a mixed bed column packed with Haas Amberlite IR-120B) and an OH type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 3 mg/β or less. , followed by sodium incyanurate dichloride 20 B/! 1 and 150 mg/β of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 2.0 ml! Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
], 0ρp8
5.0-8.0 Example 3 The same test as in Example 2 was conducted except that only the treatment process in Example 2 was changed to the treatment process shown below, and dark fading and photofading were evaluated.

As a result, as in Example 1, in Example 3, dark fading and
The results showed that the photobleaching was excellent and the interlayer effect was large.

Processing method Color development 2 minutes 30 seconds 40℃ 10 prints 8C bleach fixing 3 minutes 00 seconds 40℃ 20 prints 8ρ water washing (212
0 seconds 35℃ 10m1 Stable 20 seconds 35℃ 10 slide drying
Drying 50 seconds 65℃ Replenishment amount is Q 2f per 35mm width and 1m length! .

Next, the composition of the treatment liquid will be described.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1-hydroxyedyritin-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 5.5 Potassium carbonate
30.045.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxyamine sulfate 2.4 3.04-[N-
Add ethyl-N-(β-hydroxyethyl)amino]-2-methylaniline sulfate to pH 1,0ε 7.5 0β 10.20 2°10.05 2° (Bleach-fix solution) Mother solution and replenisher common Ferric ammonium ethylenediaminetetraacetate Disodium salt of ethylenediaminetetraacetate Sodium sulfite ammonium thiosulfate aqueous solution (70%) Acetic acid (98%) Bleach accelerator (unit g) 5, 0 12, 0 260.0 nt s, 0 nJ 0 101 mol water In addition 1.01pH6,
0ff (Washing solution) Mother liquor and replenisher Common tap water was filled with H-type strongly acidic cation exchange resin (Amberlite TR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3 mg/A or less, and then 20 mg/β of sodium incyanurate dichloride and 1.5 g/β of sodium sulfate were added.

The pH of this solution is in the range 6.5-7.5.

(Stable solution) Mother solution and replenisher common (Unit: g) Forma+) :/ (37%) 2.0T11i
l! Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0! pH5.0-8.0

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between the characteristic curve of a yellow image and the density curve of a magenta color image with the multilayer effect. Procedural amendment (March 9, 1990, Commissioner of the Japan Patent Office Yoshi 1) Moon Tsuyoshi 1, Indication of the case 1999 Patent Application No. 77888 2, Name of the invention Silver halide color photographic light-sensitive material 3, Amendment Relationship with the case of a person who does
) Fuji Photo Film Co., Ltd. Representative: Sho Ohnishi 4, Agent address: 7th floor, Midoriya 2nd Building, 3-7-3 Shinbashi, Minato-ku, Tokyo Telephone: Tokyo 03 (591) 7387 ≦ Name (764)
3) Patent attorney Mei 1) Satoshi Sanra-5, assistant engineer IQB+t
- Weight 6, Target of amendment 7, Contents of amendment (1) "3-dodecyloxypropyl" in lines 15-16 of page 12 of the specification will be corrected to [3-dodecyloxypropoxy]. (2) On page 29, line 5 of the same book, next to “representation,” r
I'm adding "Het-S-'s". (3) From line 20 on page 30 of the same book to line 1 on page 30, “
1-Benzotriazolyl group" is deleted. (4) Same book, page 30 - Correct the chemical formula of maximum (V) as follows. [ ” (5) Compounds (66) and (67) on page 40 of the same book
Correct the chemical formula of as follows. “ ” (6) “1st” in the 2nd line of page 111 of the same book is replaced with “1st
Correct it to "Figure". (7) Delete this ΔDaJ by expressing it as ``in lines 1O to 11 on page 116 of the same book.'' (8) Delete ΔDaJ in lines 4 to 1 from the bottom on page 116 of the same book.
Ikuro concentration: The concentration after 20 hours is shown. ” has been corrected to the following description. [11 75°C, 70% R at a concentration of 2.0
After storage in the dark for 4 days, the concentration D8° was measured, and DQ'/2
．． 0 was calculated and used as a measure of dark fading. ■Xenon light at a yellow density of 2.0 (200,001
ux) Measure the concentration DI' 20 hours after irradiation, D,'/
2.0 was calculated and used as a measure of photobleaching. "(that's all)

Claims (3)

[Claims] (1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the following general formulas is included in the constituent layers of the light-sensitive material.
A silver halide color photographic material containing a coupler represented by I]. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 and R_2 are each independently an alkyl group, alkylthio group, an alkylsulfonyl group, or an alkoxysulfonyl group having 1 to 24 carbon atoms, a carbon atom R_3 represents an alkoxy group or alkoxycarbonyl group having 2 to 24 carbon atoms, an aryl group, aryloxy group, arylthio group, or arylsulfonyl group having 6 to 24 carbon atoms, or an aryloxycarbonyl group having 7 to 24 carbon atoms; and R_4 each independently represent a group that can be substituted on the benzene ring, and T represents a group that can be substituted with S after the bond with -CH- is cleaved by the coupling reaction with the oxidized product of the aromatic primary amine developer. A group in which a bond is cleaved or a simple bond; Het is a group containing at least one heteroatom selected from nitrogen, oxygen, sulfur, phosphorus, selenium, or tellurium atoms in the ring; Represents an 8-membered monocyclic or condensed ring heterocyclic group, and m and n each independently represent an integer of 0 to 4.However, when m or n is multiple, multiple R_3 or R_4 may be the same or different. ) (2) The halogenated compound according to claim (1), wherein in the general formula [I], at least one of m or n is not 0, and at least one of R_3 or R_4 is an electron-withdrawing substituent. Silver color photographic material. (3) The silver halide color according to claim (1), wherein in the general formula [I], both m and n are not 0, and at least one R_3 or R_4 is an electron-withdrawing substituent. Photographic material.