JPH06266075A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance preservability and to prevent discoloration of a color image for a long period by incorporating a kind of yellow coupler and a specified compound in one layer of the silver halide color photographic sensitive material. CONSTITUTION:The silver halide color photographic sensitive material contains, in one layer, one of the yellow coupler and one of the compounds represented by formula I in which each of Ra1, Ra2, Ra3, and Ra4 is, independently, an aliphatic or aryl group or each of (Ra1 and Ra2) and (Ra3 and Ra4) may combine with each other to form a 5-, 6-, 7-membered ring through alkylene groups, but each of (Ra2 and Ra3) and (Ra1 and Ra4) do not combine with each other to form a ring, and the total C number of Ra1-Ra4 is >=10. This compound prevents discoloration of a dye image formed from the yellow coupler and it is a colorless compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer which is sensitive to the three primary colors of red, green and blue, and three kinds of color forming agents (couplers) in each emulsion layer are provided in respective layers. A color image is formed by a so-called subtractive method in which a color is developed in a relationship between the perceived color and the complementary color. The color image obtained by photographic processing of this silver halide color photographic light-sensitive material is composed of an azomethine dye or an indoaniline dye formed by the reaction of an oxide of an aromatic primary amine color developing agent with a coupler. Is common.

However, it is insufficient to meet the demand of customers who demand high quality. Among them, the color-forming dye obtained from the yellow dye-forming coupler has some problems to be overcome. First, the extinction coefficient of the coloring dye is smaller than that of the dye obtained from the magenta dye-forming coupler or the cyan dye-forming coupler. Therefore, in order to obtain the same density as that of magenta or cyan, many yellow dye-forming couplers are used. That's what you have to do. Second
In addition, the hue is not always satisfactory in order to faithfully reproduce the color of the subject. Thirdly, the coloring dyes and uncolored couplers are not stable against light and heat, and if they are exposed to sunlight for a long time or stored under high temperature and high humidity,
This causes the fading or discoloration of the dye image and the coloring of the white background, resulting in deterioration of the image quality.

In order to solve these problems of color density and color hue, improvements have been attempted by adding couplers and coexisting substances such as specific phenol compounds and sulfonamide compounds. Was enough. In recent years, yellow dye-forming couplers which have improved these problems have been developed. For example, a yellow dye-forming coupler characterized by an acyl group is disclosed in European Patent No. 48255.
No. 2A, No. 447920A, No. 447969, etc. However, although these yellow dye-forming couplers are improved in color density and hue, the fastness of dye image is rather deteriorated.

On the other hand, as a method for removing the defect of the fastness of the dye image, an ultraviolet absorber is used to develop a coupler having high fastness of the obtained dye, to use an anti-fading agent or to prevent image deterioration by ultraviolet rays. Have been proposed. Among them, the effect of preventing image deterioration by the anti-fading agent is large, for example, hydroquinones, hydrazines,
Hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines, chromanoles, indans and phenolic hydroxyl groups of these compounds are silylated and acylated. It is known to add modified or alkylated ethers or esters, as well as metal complexes and the like. For example, as an example of using hydrazines as an anti-fading agent, Japanese Patent Application Laid-Open No. 2-1
No. 81145, No. 5-2248.

However, although these compounds have been recognized as effective agents for preventing fading and discoloration of dye images, they are not sufficient to meet the demands of customers who have come to demand high image quality. It was Moreover, these compounds cause large coloring on the white background, color development in the unexposed area (hereinafter referred to as fog), color inhibition of the coupler, and reaction with the oxidized product of the developing agent during color development, resulting in dye formation. It is not sufficient because some of them may cause color turbidity and adversely affect so-called photographic characteristics. Further, since these compounds cause poor dispersion or produce fine crystals after coating the emulsion, they have not been able to exert overall excellent effects for color photography.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a light-sensitive material which does not discolor a yellow image for a long time and has a high storability. A second object of the present invention is that the yellow image does not discolor for a long period of time and has a high degree of storage stability,
Another object is to provide a light-sensitive material having excellent color reproducibility.
A third object of the present invention is to contain a photographic additive that does not cause a change in hue or fog, and does not cause a decrease in color density, and that has a sufficient effect of preventing fading or discoloration of a color image. To provide a light-sensitive material that

A fourth object of the present invention is to contain a photographic additive which is excellent in solubility in a high boiling point organic solvent or the like and which does not adversely affect the color developability of the coupler or other photographic additives. To provide a light-sensitive material. A fifth object of the present invention is to provide a photographic additive which does not cause a dye image formed by color development of a yellow dye-forming coupler to fade even after a long period of time and does not cause white background coloration (yellow stain). Another object of the present invention is to provide a light-sensitive material containing a high storability.

[0009]

As a result of various investigations, the present inventors have found that at least one of yellow couplers and at least one of compounds represented by the following general formula (A) are used in silver halide color photographic light-sensitive materials. It has been found that the purpose of the present invention can be achieved by incorporating it in one layer.

[0010]

[Chemical 3]

In the formula, R _a1 , R _a2 , R _a3 and R _a4 may be the same or different and each represents an aliphatic group or an aryl group. Incidentally, R _a1 and R _{a2 and} R _a3 and R _a4 may be bonded to each other by an alkylene chain to form a 5- to 7-membered ring, but R _a2 and R _{a3 and} R _a1 and R _a4 are bonded to each other. It does not form a ring. The total number of carbon atoms of R _a1 , R _a2 , R _a3 and R _a4 is 10 or more.

The present invention will be described in detail below. The compound of the present invention is a compound which prevents fading of a dye image formed from a yellow coupler and is a non-color forming compound. The non-color-forming compound is a compound that gives substantially no dye when processed with a color developing solution.

Unless otherwise specified, when a group in the present specification contains an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic and saturated or unsaturated. May represent, for example, alkyl, alkenyl, cycloalkyl, or cycloalkenyl, which may be unsubstituted or may have a substituent. When the aryl moiety is included, the aryl moiety may be a monocycle or a condensed ring, and may be unsubstituted or may have a substituent. When it contains a heterocyclic moiety,
The heterocyclic moiety has a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and may be a saturated ring or an unsaturated ring, or a single ring. It may be a condensed ring, may be unsubstituted or may have a substituent.

The substituent described in this specification may be a substitutable group, for example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group. Group, heterocyclic oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group,
Heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, arylsulfonamide group, amino group, aliphatic amino group , An arylamino group,
Aliphatic oxycarbonylamino group, aryloxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, mercapto group, hydroxy group, cyano group, nitro group, sulfo group,
Hydroxyamino group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfamoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl, diaryloxy Examples include phosphinyl and the like.

The yellow couplers in the present invention include ring-opening active methylene type couplers. Among them, the α-acylacetamide type couplers are generally so-called pivaloylacetanilide type yellow couplers and benzoylacetanilide type yellow couplers. However, in addition thereto, the above-mentioned acyl group is a 1-substituted-cycloalkylacyl group or a 1-substituted-heterocyclic acyl group. Further, it may be a malondiamide type coupler, and one of the amide groups may be substituted or may form a ring. Examples of the yellow coupler of the present invention include US Pat. Nos. 3,227,554 and 3,408,1.
No. 94, No. 3,894,875, No. 3,933,
501, 3,973,968, 4,02
No. 2,620, No. 4,057,432, No. 4,1
No. 15,121, No. 4,203,768, No. 4,
No. 248,961, No. 4,266,019, No. 4,314,023, No. 4,327,175, No. 4,401,752, No. 4,404,274,
No. 4,420,556, No. 4,711,837
No. 4,729,944, European Patent No. 30,74
No. 7A, No. 284,081A, No. 296,793
No. A, No. 313, 308A, No. 447, 969A
No. 482,552A, West German Patent No. 3,107,1
73C, JP-A-58-42044, and JP-A-59-174.
No. 839, No. 62-276547, No. 63-1230.
No. 47 etc. In the present invention, a yellow coupler represented by the following general formula (Y) is preferable.

[0016]

[Chemical 4]

In the formula, R ₁ is an alkyl group, an aryl group,
Represents a substituted amino group or a heterocyclic group, R ₂ represents a halogen atom, an alkoxy group or an aryloxy group, R ₃ represents a group capable of substituting for a benzene ring, and X represents a hydrogen atom or an aromatic first group. It represents a group capable of leaving by a coupling reaction with an oxidized product of a primary amine developing agent (hereinafter referred to as a leaving group). k
Represents an integer of 0 or 1 to 4. However, when k is 2 or more, a plurality of R ₃ may be the same or different. The general formula (Y) will be described in detail. In the formula, R ₁ is an alkyl group (preferably having a carbon number of 1 to 30 and having a substituent, for example, t-butyl, 1-ethyl-cyclopropyl, 1-methyl-cyclopentyl, 1-benzyl-
Cyclopropyl, adamantyl), aryl group (preferably having 6 to 36 carbon atoms and having a substituent, for example, phenyl, 4-methoxyphenyl), substituted amino group (preferably having 1 to 30 carbon atoms) An alkylamino group which may have a substituent or an anilino group, for example,
Dimethylamino, dipropylamino, anilino, N-methylanilino) or a heterocyclic group (preferably having 3 to 3 carbon atoms).
A 5- to 7-membered monocyclic or condensed ring group which may have a substituent, such as piperidyl, indolinyl, 2-tetrahydropyranyl, 1,4,4-trimethyl-3, It is 5-dioxacyclohexyl. More preferably, it is a heterocyclic group which may be condensed with a 5- or 6-membered benzene ring linked by a nitrogen atom. R ₂ represents a halogen atom (eg, fluorine, bromine, chlorine) or an alkoxy group (preferably having a carbon number of 1 to 30) and may have a substituent, for example, methoxy, octadecyloxy, cyclohexyloxy, benzyl. Oxy) or an aryloxy group (preferably having 6 to 36 carbon atoms and optionally having a substituent, for example, phenoxy, 4-methoxyphenoxy), R ₃ represents a group capable of being substituted on the benzene ring, X _y is
It represents a group capable of splitting off by a coupling reaction with a hydrogen atom or an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as splitting group). k represents an integer of 0 or 1 to 4. However,
When k is 2 or more, plural R ₃ may be the same or different.

In the general formula (Y), R ₃ includes the groups described in the section of the description of the above-mentioned substituents. Preferred examples of the substituents include, for example, a halogen atom and the following all have a substituent. Which may be carried out, an aliphatic group having 1 to 30 carbon atoms, an aryl group having 6 to 36 carbon atoms, an aliphatic oxy group having 1 to 30 carbon atoms, an aliphatic oxycarbonyl group having 2 to 32 carbon atoms, and carbon number 7-37 aryloxycarbonyl group, C2-32 acylamino group, C1-C30
Sulfonamide group, C1-30 carbamoyl group, C0-30 sulfamoyl group, C1-3
An aliphatic sulfonyl group having 0, an arylsulfonyl group having 6 to 36 carbon atoms, a carbamoylamino group having 1 to 30 carbon atoms,
Sulfamoylamino group having 1 to 30 carbon atoms, 2 to 2 carbon atoms
32 alkoxycarbonylamino groups, 1 to 30 carbon atoms
Heterocyclic group, C2-C2 acyl group, C1-C3
Examples thereof include an aliphatic sulfonyloxy group having 0 and an arylsulfonyloxy group having 6 to 36 carbon atoms. Here, the aliphatic is preferably alkyl. Also, preferred k
Is 1 or 2, and the substitution position of R ₃ is preferably para to R ₂ .

In the general formula (Y), X _y is preferably a heterocyclic group to which a nitrogen atom is bonded at the coupling active position of the coupler, or an aryloxy group. When X _y represents a heterocyclic group, preferable X _y has 1 to 30 carbon atoms.
A 5- to 7-membered monocyclic or condensed heterocyclic ring which may have a substituent, such as succinimide, pyrrole, 1,2,4-triazole, imidazolidine-2,
4-dione, oxazolidine-2,4-dione and the like can be mentioned. When X _y represents an aryloxy group, preferable X
_y is an aryloxy group which may have a substituent having 6 to 36 carbon atoms, and is, for example, 4-cyanophenoxy, 4-benzenesulfonylphenoxy, 4-propyloxycarbonylphenoxy, 2-trifluoromethyl. Examples include phenoxy. In terms of the effect of the present invention, R
₁ is more preferably represented by the following general formulas (Y _a ) and (Y _b ).

[0020]

[Chemical 5]

Here, R _y represents an alkyl group, and Q represents C
Together with a non-metallic atomic group necessary for forming a 3- to 5-membered hydrocarbon ring or a 3- to 6-membered heterocycle having at least one heteroatom selected from N, S, O and P in the ring. Represent X ₃ represents a non-metal atomic group necessary for forming a 5- to 8-membered nitrogen-containing heterocyclic group with N.

From the viewpoint of the effect of the present invention, R _y is preferably a methyl group, an ethyl group or a benzyl group (which may have a substituent), and an ethyl group or a benzyl group (having a substituent). Is more preferable), and Q preferably forms a 3-membered hydrocarbon ring with C.
From the viewpoint of the effect of the present invention, X ₃ preferably forms a 5-membered nitrogen-containing heterocyclic group together with N, and more preferably 1-indolinyl group (which may have a substituent). . From the viewpoint of the effect of the present invention, R ₂ is preferably a chlorine atom or an alkoxy group, and when R ₁ is the general formula (Y _a ), it is particularly preferably a chlorine atom, and R ₁ is generally In the case of the formula (Y _b ), an alkoxy group is particularly preferable.

In view of the effects of the present invention, R ₃ is a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group, a sulfamoyl group, an acylsulfamoyl group, a carbamoylsulfamoyl group, a sulfamoyl group. It is preferably a rucarbamoyl group, more preferably a chlorine atom, an acylamino group, a sulfonamide group, a sulfamoyl group, an acylsulfamoyl group, a sulfamoylcarbamoyl group, or a carbamoylsulfamoyl group, and a dialkoxyphosphini group. Most preferred is an acylamino group substituted with a phenyl group or a diaryloxyphosphinyl group. From the viewpoint of the effect of the present invention, it is most preferable that R ₁ is the general formula (Y _a ).

The coupler represented by the general formula (Y) is R
_{In 1} , R ₂ , R ₃ or X _y , a dimer bonded through a divalent or divalent or higher valent group, or a multimer or more thereof, a homopolymer or a copolymer containing a non-color-forming polymerized unit. May be From the viewpoint of the effect of the present invention, when R ₁ is the general formula (Y _a ) or (Y _b ), X _y is preferably a nitrogen-containing heterocyclic group, and at that time, a 5-membered nitrogen-containing heterocyclic group. Is more preferable.

Next, specific examples of the yellow coupler represented by the general formula (Y) are shown below, but the couplers used in the present invention are not limited thereto. Further, a yellow coupler represented by the general formula of EP 482,552A (specific examples (1) to (61)) and a yellow coupler represented by the general formula of EP 447,969A (specific example Y). -1-Y-78) are also preferable yellow couplers for use in the present invention.

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

Examples of compounds other than the above-mentioned yellow couplers used in the present invention and / or methods for synthesizing these yellow couplers are described in the aforementioned patents. The yellow coupler of the present invention is generally used in an amount of 0.001 to 1 mol per mol of photosensitive silver halide.
01 to 0.5 mol is preferable.

Next, the general formula (A) will be described in more detail. In the formula, R _a1 , R _a2 , R _a3 and R _a4 may be the same or different and each is an aliphatic group (preferably an alkyl group having 1 to 40 carbon atoms which may have a substituent). A group such as methyl, ethyl, i-propyl,
Cyclohexyl, t-butyl, benzyl, dodecyl, 2
-(2,4-di-t-pentylphenoxy) ethyl, 2
-(Butoxycarbonyl) ethyl) or aryl group (preferably having a substituent having 6 to 36 carbon atoms, for example, phenyl, 4-methylphenyl, 2,4-di-t-butylphenyl) , 4-myristoylaminophenyl, 3-dodecyloxyphenyl). R _a1 and R _a2
And R _a3 and R _a4 are bound to each other by an alkylene chain
A 7-membered ring (which may have a substituent, for example, a piperidine ring or a pyrrolidine ring) may be formed, but R _a2 and R _{a3 and} R _a1 and R _a4 are bonded to each other to form a ring. There is no. The total number of carbon atoms of R _a1 , R _a2 , R _a3 and R _a4 is 10 or more.

From the viewpoint of the effect of the present invention, it is preferable that R _a1 , R _a2 , R _a3 and R _a4 are all aliphatic groups, and it is further preferable that all are alkyl groups. From the viewpoint of the effect of the present invention, the total carbon number of R _a1 , R _a2 , R _a3 and R _a4 is preferably 10 or more and 80 or less, more preferably 15 or more and 80 or less, and more preferably 20 or more 60 Most preferred is when

From the viewpoint of the effect of the present invention, it is preferred that at least one of the alkyl groups of R _a1 , R _a2 , R _a3 and R _{a4 is} an alkyl group represented by the following general formula (A _a ).

[0044]

[Chemical 20]

In the general formula (A _a ), R _a5 represents a substituent and n represents an integer of 0 or 1 to 3. X _a represents an oxygen atom or a single bond, and Y _a represents an alkylene group which may have _a substituent. In terms of the effect of the present invention, n is 1 to
It is preferably an integer of 3, and R _a5 is an alkyl group (preferably having a carbon number of 1 to 20 and optionally having a substituent,
For example, methyl, ethyl, i-propyl, t-butyl, t
-Pentyl, t-octyl, 2-ethylhexyl, dodecyl, t-dodecyl) is preferable, and a branched chain alkyl group is more preferable.

From the viewpoint of the effect of the present invention, X _a is preferably an oxygen atom. In view of the effect of the present invention, Ya is an alkylene group (preferably a methylene group, an ethylene group, a trimethylene group, a tetramethylene group) which may have _a substituent (preferably an alkyl group having 1 to 14 carbon atoms). The case is preferable, and an ethylene group, a trimethylene group and a tetramethylene group which may have a substituent are more preferable. Next, specific compound examples of these compounds are shown below,
This does not limit the compounds used in the present invention.

[0047]

[Chemical 21]

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

[0050]

[Chemical formula 24]

[0051]

[Chemical 25]

[0052]

[Chemical formula 26]

The compound represented by the general formula (A) of the present invention is described in Shin Jikken Kagaku Koza, Vol. 14-3, page 1573 (197).
8 years) or a method similar thereto. The synthesis examples of typical compounds are shown below.

Synthesis Example 1 (Synthesis of Exemplified Compound (A-2)) Under nitrogen stream, dimethylacetamide 50 ml acetonitrile 100 ml and triethylamine 22.4 ml were added to 1,2-dimethylhydrazine 5 g, and the mixture was stirred at 10 to 15 ° C. 26.3 g of 4- (2,4-di-t-amylphenoxy) butyric chloride was added dropwise over 30 minutes, and 3
After the temperature was raised to 0 to 35 ° C, the mixture was further stirred for 1 hour. The reaction solution was poured into 200 ml of cold water, and 250 ml of ethyl acetate was added.
It was extracted with. Acetic acid ethyl ester layer is saturated brine 250
After washing twice with ml and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain a viscous colorless liquid (intermediate).
Yield 23.7 g Yield 93.5%

15-20 ml of tetrahydrofuran 15-20
Lithium aluminum hydride 2.2 with stirring at ℃
g was added slowly. To this, 16 ml of a tetrahydrofuran solution containing 16 g of the intermediate was added dropwise over 30 minutes. The reaction solution is slowly raised to 40 ° C, and further 30
Stir for minutes. The reaction solution was kept at 20 to 25 ° C., 100 ml of ethyl acetate was added dropwise over 30 minutes, and water 1
00 ml was slowly added dropwise. After liquid separation, the ethyl acetate layer was washed twice with 150 ml of saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography to obtain a viscous colorless liquid. The obtained compound was confirmed to be Exemplified Compound (A-2) by mass spectrum, NMR spectrum and infrared absorption spectrum. Yield 12.8g Yield 83.5%

Synthesis Example 2 (Synthesis of Exemplified Compound (A-10)) In the method of synthesizing Exemplified Compound (A-2), 4- (2,4)
-Di-t-amylphenoxy) butyric chloride 2
Exemplified compound (A-1) was synthesized in the same manner as Exemplified compound (A-2) except that 6.3 g was changed to 2,4--di-t-amylphenoxy) acetyl chloride 24.2 g.
An oily substance of 0) was obtained. This oily substance was crystallized with methanol to obtain white crystals. Yield 75.6%, melting point 69-71
℃

The compound represented by the general formula (A) of the present invention varies depending on the kind of the coupler, but is used in an amount of 0.5 to 300 mol% based on the coupler (preferably the coupler used in the same layer). It is suitable to use in the range, preferably in the range of 1 to 200 mol%.

The yellow dye-forming coupler represented by the general formula (Y) and the compound represented by the general formula (A) of the present invention are monomers of acrylic acid amide and methacrylic acid amide in view of the effects of the present invention. It is preferable to use it after co-emulsifying it with the polymer. The compound represented by formula (A) of the present invention may be used in combination with a known anti-fading agent, in which case the anti-fading effect is further enhanced. Similarly, two or more compounds represented by formula (A) may be used in combination.

From the viewpoint of the effect of the present invention, the compound represented by the general formula (A) of the present invention is used together with the yellow dye-forming coupler represented by the general formula (Y) in the light-sensitive silver halide emulsion layer. It is preferable to use by emulsifying, and at this time, it is particularly preferable to use the compound represented by the following general formula (B) by co-emulsifying.

[0060]

[Chemical 27]

In the formula, R _b1 is an aliphatic group (preferably an alkyl group having 1 to 30 carbon atoms and optionally having a substituent, such as methyl, i-propyl, benzyl, hexadecyl and cyclohexyl. , 2-phenoxyethyl, 2
-Methanesulfonamidoethyl) or a heterocyclic group (preferably a saturated heterocyclic group having 3 to 30 carbon atoms, for example, 2-tetrahydropyranyl). R _b2 , R _b3 ,
R _b4 , R _b5 and R _b6 may be the same or different and each is a hydrogen atom or an aliphatic group (preferably an alkyl group having 1 to 30 carbon atoms and optionally having a substituent). For example, methyl, t-octyl, benzyl, cyclohexyl, n-dodecyl, s-butyl, 1,1-dimethyl-4-methoxycarbonylbutyl), an acyl group (preferably having 2 to 36 carbon atoms and having a substituent). May have, for example, acetyl, pivaloyl, dodecanoyl, benzoyl, 3-hexadecyloxybenzoyl), an acylamino group (preferably having a carbon number of 2 to 36 and a substituent, for example, acetamino, pivaloylamino, Two
-Ethylhexanoylamino, 2- (2,4-di-t-
Amylphenoxy) octanoylamino, dodecanoylamino, 3-butoxybenzoylamino), an aliphatic oxycarbonyl group (preferably an alkoxycarbonyl group which may have a substituent having 2 to 36 carbon atoms,
For example, methoxycarbonyl, dodecyloxycarbonyl, 2-hexyloxyethoxycarbonyl), ali-
Ruoxycarbonyl group (preferably having 7 to 42 carbon atoms and having a substituent, for example, 2,4-di-t-amylphenoxycarbonyl, 4-methoxyphenoxycarbonyl), a halogen atom (for example, fluorine, Chlorine, bromine), a sulfonyl group (preferably having a carbon number of 1 to 30 and having a substituent, for example, methanesulfonyl, octanesulfonyl, 4- (4-t-octylphenoxy) butanesulfonyl, 4-dodecyl). Oxybenzenesulfonyl), carbamoyl group (preferably having 2 to 2 carbon atoms)
36 may have a substituent, for example, methylcarbamoyl, diethylcarbamoyl, N-methyl-N-phenylcarbamoyl), sulfamoyl group (preferably,
It may be substituted with 1 to 30 carbon atoms, represented for example methylsulfamoyl, dibutylsulfamoyl, phenyl sulfamoyl) or -X b _{'-R b1'. Xb} and _{Xb '} represent -O-, -S- or -N ( _Rb7 )-.
Bonded substituents in the ortho position to each other among the _{-X b -R b1, R b2 ~R} b6, 5~8 -membered ring (e.g. a substituent a good coumaran ring optionally having, chroman ring, indane ring , A quinoline ring and the like, which may further form a spiro ring or a bicyclo ring). R
_b1 and R _b7 or R _{b1 ′} and R _b7 may combine with each other to form a 5- to 7-membered ring (for example, a piperazine ring which may have a substituent or a morpholine ring). R _{b1 ′} and R _b7 are R
Synonymous with _b1 . Provided that at least one of R _b2 to R _b6 is a -X _{b '-R b1'.}

In view of the effect of the present invention, R _b1 , R _{b1 '} and R _b7
Is preferably an alkyl group. From the viewpoint of the effect of the present invention, it is preferable that R _{b2 to} R _b6 are a hydrogen atom, an alkyl group, an acylamino group, or —X _{b ′} —R _{b1 ′} . From the viewpoint of the effect of the present invention, the compounds represented by the following general formulas (BI) to (BX) are more preferable.

[0063]

[Chemical 28]

[0064]

[Chemical 29]

[0065]

[Chemical 30]

[0066]

[Chemical 31]

In the general formulas (BI) to (BX),
R _{b1 to} R _b7 and R _{b1 ′} are the same as those defined in the general formula (B). R _{51 to} R ₇₂ may be the same or different and each is a hydrogen atom or an alkyl group (preferably having 1 to 20 carbon atoms).
May have a substituent, for example, methyl, ethyl,
i-propyl, odecyl, benzyl) or an aryl group (preferably a phenyl group having 6 to 26 carbon atoms which may have a substituent, for example, phenyl, 4-methylphenyl). R ₅₄ and R ₅₅ , R ₅₅ and R ₅₆ may combine with each other to form a 5- to 7-membered hydrocarbon ring. B
And D are single bonds, -C ( _R80 ) ( _R81 )-or -O-.
And E represents a single bond or -C ( _R80 ) ( _R81 )-. R ₈₀ and R ₈₁ may be the same or different and each may be a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 20 and having a substituent, such as methyl, ethyl, i-propyl, dodecyl, Benzyl) or aryl group (preferably a phenyl group having 6 to 26 carbon atoms and optionally having a substituent, for example, phenyl, 4-methylphenyl).

Among the compounds represented by the general formulas (BI) to (BX) of the present invention, the general formula (B
-I), (B-III), (B-IV), (BV), (B
-VI), (B-VII) and (B-VIII) are preferable, and the compounds represented by the general formulas (B-IV), (B-VI) and (B-VI) are preferable.
Compounds represented by I) and (B-VIII) are more preferable,
The compounds represented by formulas (B-IV) and (B-VI) are most preferred. Specific examples of the compound represented by formula (B) are shown below, but the compound used in the present invention is not limited thereby.

[0069]

[Chemical 32]

[0070]

[Chemical 33]

[0071]

[Chemical 34]

[0072]

[Chemical 35]

[0073]

[Chemical 36]

[0074]

[Chemical 37]

[0075]

[Chemical 38]

[0076]

[Chemical Formula 39]

[0077]

[Chemical 40]

[0078]

[Chemical 41]

These compounds are disclosed in Japanese Examined Patent Publication No. 45-1403.
No. 4, No. 56-24257, No. 59-52421,
JP-A-55-89835, JP-A-56-159644,
62-244045, 62-244246, 62-273531, 63-95439, 63.
-95448, 63-95450, European Patent No. 2
39,972, JP-A-4-330440, JP-A-5
It can be synthesized by the method described in 8-105147 or the like or a method analogous thereto.

In the present invention, the amount of the compound represented by the general formula (B) used varies depending on the kind and amount of the yellow dye-forming coupler used, but it is 0.5 to 300 mol per 1 mol of the coupler used. %, Preferably 1-20
It is in the range of 0 mol%, most preferably 2 to 100 mol%.

The light-sensitive material of the present invention has the advantages of the present invention.
It is preferably used in combination with an azo dye-forming coupler. When used in combination with an azo coupler, the formula (B) described in JP-A-3-233448 and the formula (III) described in JP-A-3-48241 are further used.
At least one selected from the compounds represented by
When it is used in the form of a co-emulsified dye-forming coupler, the effect of preventing discoloration becomes large, which is particularly preferable. The addition amount of these compounds used in combination is preferably within the range of the addition amount described in each specification.

The compounds and couplers represented by the general formulas (A) and / or (B) of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and can be used in high-boiling organic solvents (and low-boiling organic solvents as necessary). Is used in combination), and is emulsified and dispersed in a gelatin aqueous solution and added to a silver halide emulsion. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , The same 2,541,23
No. 0, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 0.
No. 29104, PCT International Publication No. WO.
88/00723.

As the high-boiling-point organic solvent that can be used in the above-mentioned oil-in-water dispersion method, phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2 , 4-di-ter
t-amylphenyl) isophthalate, bis (1,1-
Diethylpropyl) phthalate), phosphoric acid or phosphonic acid esters (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, 2
-Ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-dichloro) Benzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg N, N
-Diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic esters (e.g., dibutoxyethyl succinate, Di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate,
Diethyl azelate, isostearyl lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (chlorine content 10% to 80)
% Paraffins) trimesic acid esters (eg,
(Tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg 2,4-
Di-tert-amylphenol, 4-dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (for example, 2- (2,4-di-tert-amyl) Phenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, di-2
(Ethylhexyl) phosphoric acid, diphenylphosphoric acid) and the like. The auxiliary solvent has a melting point of 30 ° C or higher and about 1
An organic solvent having a temperature of 60 ° C. or lower (for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The high boiling point organic solvent can be used in an amount of 0 to 10.0 times, preferably 0 to 5.0 times, and more preferably 0 to 1.0 times the weight ratio of the coupler. In the practice of the present invention, it can be used in combination with a magenta dye-forming coupler and a cyan dye-forming coupler capable of forming magenta and cyan, respectively, by coupling with an oxidized product of an aromatic primary amine color developing agent. preferable.

The couplers used in combination with these may be 4 equivalents or 2 equivalents with respect to silver ion, and may be in the form of polymer or oligomer. Further, the couplers used in combination may be a single type or a mixture of two or more types.

The couplers preferably used in the present invention will be described. Examples of cyan couplers include phenol-type and naphthol-type couplers. US Pat. Nos. 4,052,212 and 4,146,396.
No. 4,228,233, 4,296,20
No. 0, No. 2,369,929, No. 2,801,1
No. 71, No. 2,772, 162, No. 2,895.
No. 826, No. 3,772,002, No. 3,75
No. 8,308, No. 4,334,011, No. 4,3
27,173, West German Patent Publication No. 3,329,729
No., European Patent Nos. 121,365A and 249,45
3A, 333, 185A2, and U.S. Pat.
No. 46,622, No. 4,333, 999, No. 4,
775,616, 4,451,559, 4,427,767, 4,690,889, 4,254,212, 4,296,199,
Those described in JP-A-61-42658 and the like are preferable.
Furthermore, JP-A 64-553, 64-554, 64-555, 64-556, and European Patent Publication No. 4
88,248, 491,197, 484,
909 and 456226, azole couplers, U.S. Pat. No. 4,818,672, and JP-A-2-
The imidazole couplers described in JP-A-33144 or the cyclic active methylene type cyan couplers described in JP-A-64-32260 can also be used.

Particularly preferred cyan couplers are couplers represented by the general formulas (CI) and (C-II) described in JP-A-2-139544, page 17, lower left column to page 20, lower left column,
European Patent Publication Nos. 488,248 and 491,197
No. 484, 909, and No. 456226.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619, 4,351,897 and European Patent 73,6 are preferred.
36, U.S. Pat. Nos. 3,061,432 and 3,725,067, Research Disclosure No. 24220 (6 June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61
-72238, 60-35730, 55-118034, 60-18595
Those described in US Pat. No. 4,500,630, US Pat. No. 4,540,654, US Pat. No. 4,556,630, and International Publication WO88 / 04795 are more preferable. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-139544. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) from page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers.

Couplers that release a photographically useful residue upon coupling can also be used in the present invention. The DIR coupler releasing the development inhibitor is described in RD magazine No. 176 mentioned above.
Patents described in paragraphs 43 and VII to F, JP-A-57-151944
Issue 57-154234, Issue 60-184248, Issue 63-37346,
Those described in US Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, there is described in British Patent 2,097,140.
No. 2,131,188, JP-A-59-157638, 59-17084.
Those described in No. 0 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4
Competitive couplers described in US Pat. No. 4,283,472
Nos. 4,338,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox couplers described in JP-A-60-185950 and 62-24252. Compounds or DIR redox releasing redox compounds, couplers releasing a dye that recolors after withdrawal described in European Patent 173,302A, RD No. 11449, No. 24241,
Bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No.4,553,477, couplers releasing leuco dyes described in JP-A-63-75747, U.S. Pat. Examples thereof include couplers that release the fluorescent dye described in 4,774,181. Next, examples of typical couplers used in the present invention are shown.

[0091]

[Chemical 42]

[0092]

[Chemical 43]

[0093]

[Chemical 44]

[0094]

[Chemical formula 45]

[0095]

[Chemical formula 46]

[0096]

[Chemical 47]

The standard amount of these color couplers which can be used in combination in the invention is in the range of 0.001 to 1 mol per 1 mol of the light-sensitive silver halide in the same layer, preferably yellow. For couplers, 0.01-
0.5 mol, with magenta couplers 0.003-0.
3 moles, for cyan couplers, it is 0.002-0.3 moles.

Various anti-fading agents can be used in combination with the light-sensitive material of the present invention. As an organic anti-fading agent for cyan, magenta and / or yellow images, hindered phenols centering on hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols , Gallic acid derivatives, methylenedioxybenzenes,
Typical examples include aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Further, a metal complex represented by a (bissalicylaldoximato) nickel complex and a (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent include US Pat. Nos. 2,360,290 and 2,418,613,
2,700,453, 2,701,197, 2,728,659, 2,732,300, 2,735,765, 3,982,944, 4 , 430,425, British Patent No. 1,363,921
No. 2,710,801 and 2,816, US Pat.
No. 028, etc .; hydroquinones; US Pat. No. 3,
Nos. 432,300, 3,573,050, 3,5
74,627, 3,698,909, 3,76
4,337, 6-hydroxychromans, 5-hydroxychromans, spirochromans described in JP-A-52-152225; U.S. Pat. No. 4,360,589.
Spiroindans described in US Pat. No. 2,735,735.
765, British Patent 2,066,975, JP-A-5
9-10539, p-alkoxyphenols described in JP-B-57-19765, etc .; US Pat. No. 3,70.
0,455, 4,228,235, JP-A-52-1
No. 72224, Japanese Patent Publication No. 52-6623 and the like; gallic acid derivatives described in US Pat. No. 3,457,079; US Pat. No. 4,332,88.
Methylenedioxybenzenes described in No. 6; Japanese Patent Publication No. 56
Aminophenols described in JP-A-21144; U.S. Pat. Nos. 3,336,135, 4,268,593, British Patents 1,326,889, 1,354,313.
No. 1,410,846, Japanese Patent Publication No. 51-1420
JP-A-58-114036 and 59-53846.
Nos. 59-78344 and the like; hindered amines described in U.S. Pat. Nos. 4,050,938 and 4,241.
155, British Patent No. 2,027,731 (A) and the like, and the metal complexes and the like. These compounds are usually used in an amount of 5 to 10 with respect to the corresponding color coupler.
The object can be achieved by co-emulsifying 0% by weight of the coupler and adding it to the photosensitive layer.

When the compound represented by the general formula (A) of the present invention is used in the same layer as the yellow dye-forming coupler, even if an amide polymer having acrylic acid amide or methacrylic acid amide as a monomer is used in combination, the color fading occurs. The prevention effect is improved, which is preferable.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative,
It may contain a gallic acid derivative, an ascorbic acid derivative or the like. Further, in order to prevent deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent thereto. Further, it may be a layer farthest from the support, a layer containing a yellow coupler, or an intermediate layer.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (see, for example, US Pat.
533,794), 4-thiazolidone compounds (for example, those described in US Pat. Nos. 3,314,794 and 3,352,681), and benzophenone compounds (for example, JP-A-46-2784).
No. 1, those described in European Patent Publication No. 521823), cinnamic acid ester compounds (for example, US Pat.
707,395), butadiene compounds (described in U.S. Pat. No. 4,045,229), triazine compounds (such as those described in JP-A-46-3335 and European Patent Publication 520938) or benzoxazole compounds ( (For example, those described in US Pat. Nos. 3,406,070 and 4,271,307)
Can be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorbers may be mordanted in a specific layer. Among them, benzotriazole compounds and triazine compounds substituted with the above aryl group are preferable.

Further, in the light-sensitive material according to the present invention, a coupler is used together with European Patent Publication No. 0,277,589A2.
It is preferred to use color image-storing improving compounds as described in US Pat. In particular, it is preferably used in combination with a pyrazoloazole-based magenta coupler. That is, the compound described in European Patent Publication No. 0,277,589A2 which forms a chemically inactive and substantially colorless compound by chemically bonding with an aromatic amine developing agent remaining after color development processing ( A) and / or European Patent Publication No. 0,27 which chemically bonds with the oxidation product of the aromatic amine type color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound.
The use of the compound (B) described in 7,589A2, simultaneously or independently, may cause stains or other side effects due to the formation of a coloring dye by the reaction of the residual color developing agent in the film or its oxidant with the coupler during storage after processing. It is preferable for prevention. The light-sensitive material according to the present invention includes
In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a mildewproofing agent as described in JP-A-63-271247.

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide and the like can be used, but especially for the purpose of rapid processing. It is preferable to use a silver chlorobromide or pure silver chloride emulsion having a silver chloride content substantially free of silver iodide of 90 mol% or more, further 95% or more, and particularly 98% or more. Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the European Patent Publication No. 0,337,4 for the purpose of improving image sharpness and the like.
90A2, pp. 27-76, dyes that can be decolorized by processing (among others, oxonol dyes) are added so that the optical reflection density at 680 nm of the light-sensitive material is 0.70 or more, and the dyes are supported. It is preferable that the water-resistant resin layer of the body contains 12% by weight or more (more preferably 14% by weight or more) of a titanium oxide surface-treated with a divalent to tetravalent alcohol (for example, trimethylolethane (and the like).

As the support used in the light-sensitive material of the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 0.8. The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Also, upon exposure, U.S. Pat. No. 4,880,72
It is preferable to use the band and stop filter described in No. 6. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The present invention is preferably applied to a light-sensitive material in which a developing agent (paraphenylenediamine derivative) is not present in the light-sensitive material before development processing. For example, a color paper, a color reversal paper, a direct positive color light-sensitive material, It can be applied to color negative films, color positive films, color reversal films and the like. Among them, color light-sensitive materials having a reflective support (for example, color paper, color reversal paper)
It is preferably applied to a color light-sensitive material that forms a positive image (eg, a direct positive color light-sensitive material, a color positive film, a color reversal film), and particularly preferably a color light-sensitive material having a reflective support.

The light-sensitive material according to the present invention has the above-mentioned RD N.
O.17643, pages 28-29, and No. 18716, 615, left-right columns, the development can be carried out by a usual method. For example, a color development processing step, a desilvering processing step, and a water washing processing step are performed. In the desilvering step, instead of the bleaching step using a bleaching solution and the fixing step using a fixing solution, a bleach-fixing processing step using a bleach-fixing solution can be performed, a bleaching processing step, a fixing processing step, The bleach-fixing steps may be combined in any order. The stabilizing step may be performed instead of the washing step, or the stabilizing step may be performed after the washing step. It is also possible to perform a monobath processing step using a one-bath development bleach-fix processing solution in which color development, bleaching and fixing are carried out in one bath. In combination with these treatment steps, the pre-dural treatment step, its neutralization step,
You may perform a stop fixing process process, a post-hardening process process, an adjustment process, an intensification process, etc. An intermediate water washing step may be optionally provided between the above steps. In these processings, a so-called activator processing step may be performed instead of the color development processing step.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and processing methods and processing additions applied to process the light-sensitive material. As the agent, JP-A-4-35924
No. 9 and the following patent publications, especially European Patent Publication No. 0,35.
Those described in No. 5,660A2 are preferably used.

[0109]

[Table 1]

[0110]

[Table 2]

[0111]

[Table 3]

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Example 1

16.1 g of the yellow coupler (Y-1)
16.1 g of a high-boiling point organic solvent dibutyl phthalate was added to and dissolved in 24 ml of ethyl acetate, and this solution was emulsified and dispersed in 200 g of a 10 wt% gelatin aqueous solution containing 1.5 g of sodium dodecylbenzenesulfonate.

The total amount of this emulsified dispersion was added to a high silver chloride emulsion 24.
7 g (silver 70.0 g / Kg emulsion, silver bromide content 0.5 mol%) on a triacetate film base on which an undercoat layer was applied so that the coated silver amount was 1.73 g / m ^2. Then, a gelatin layer was provided as a protective layer on the coated layer so as to have a dry film thickness of 1.0 μm to prepare a trial sample 101. As a gelatin hardener, 1-oxy-3,
5-Dichloro-s-triazine sodium salt was used.

When the above emulsified dispersion was prepared in the same manner as in Sample 101, as shown in Table A, yellow coupler (added equimolar to Y-1) and color image stabilizer A (general formula (A)) were used.
And a color image stabilizer B (the compound represented by the general formula (B): the addition amount is described in Table B) are co-emulsified with a combination of Samples were prepared by using the same method, and otherwise emulsified and applied in the same manner as in Sample 101 to prepare Samples 102 to 138.

The above light-sensitive material was exposed through an optical wedge and then processed in the next step. Treatment process Temperature Time Color development 35 ° C 45 seconds Bleach fixing 35 ° C 45 seconds Rinse (1) 35 ° C 30 seconds Rinse (2) 35 ° C 30 seconds Rinse (3) 35 ° C 30 seconds Dry 80 ° C 60 seconds (rinse is ( A 3 tank counter-current system from 3) to (1) was adopted.)

The composition of each processing liquid is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid salt 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 2.5 g Odor Potassium bromide 0.01 g Potassium carbonate 27.0 g Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 5.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g Water was added to 1000 ml pH (25 ° C / hydroxylation (With potassium and sulfuric acid) 10.05

[Bleach-fixing solution] Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Ammonium bromide 40 g Nitric acid (67%) 30 g Water was added. 1000 ml pH (25 ° C / acetic acid and aqueous ammonia) 5.8

[Rinse Solution] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

101 to form a dye image in this way
In each sample of 147, the yellow density was measured, and the maximum color density (Dmax) of the dye-stabilizer-free sample (10
1, 112, 128, 142) was calculated. In each sample, 400
A UV absorption filter manufactured by Fuji Photo Film Co., Ltd., which cuts light of nm or less, was attached, and exposure was performed for 10 days using a xenon tester (illuminance: 200,000 lux). The evaluation was carried out by the residual ratio of the dye concentration at the initial concentration of 2.0 of each sample.

The measurement was carried out with a Fuji Denshi Densitometer. The results obtained are shown in Table A.

[0124]

[Table 6]

[0125]

[Table 7]

[0126]

[Chemical 48]

From Table A, it was found that the compound represented by the general formula (A) of the present invention did not deteriorate the color developability of the yellow coupler and was effective in preventing the photobleaching of a color image. Further, it is found that the magnitude of the effect of improving the fastness is unexpected from the known phenolic compounds. Further, it can be seen that the effect is further enhanced by adding the compound represented by the general formula (B), and each of them is superior to the other alone and cannot be expected.

Example 2 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form A multilayer color photographic paper (Sample 001) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 158.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate and dissolved in 10 cc of this solution.
1000 g of 10% gelatin aqueous solution containing 60 cc of sodium dodecylbenzene sulfonate and 10 g of citric acid
Was emulsified and dispersed to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, large size emulsion A having an average grain size of 0.88 μm and small size emulsion A having a grain size of 0.70 μm: 3:
7 mixture (silver mole ratio) The grain size distribution variation coefficient was 0.08 and 0.10, respectively, and for each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface). It was In this emulsion, blue-sensitive sensitizing dyes A and B shown below were respectively added to large size emulsion A per mol of silver in an amount of 2.0.
X10 mol- ⁴ mol, and to the small-sized emulsion A, 2.5 x ^10-4 mol was added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. Incidentally, the emulsion coating amount indicates the coating amount converted to the silver amount.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50 mg / m ² , respectively.
^It was added to be ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue sensitive emulsion layer]

[0131]

[Chemical 49]

(Each mole of silver halide is 2.0 × 10 ^-4 mole for large size emulsion and 2.5 × 10 ^-4 mole for small size emulsion) [Green-sensitive emulsion] layer〕

[0133]

[Chemical 50]

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion and 5.6 × 10 ^-4 mol for small-sized emulsion)

[0135]

[Chemical 51]

(1 mol of silver halide: 7.0 × 10 ^-5 mol for large size emulsion and 1.0 × 10 ^-4 mol for small size emulsion) [Red-sensitive emulsion layer]

[0137]

[Chemical 52]

(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Further, red-sensitive emulsion layer Has
The following compound F was added in an amount of 2.6 × 10 1 per mol of silver halide.
^-3 mol was added.

[0139]

[Chemical 53]

1- (5-methylureidophenyl) is added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer.
-5-mercaptotetrazole was added to each of 8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 and 2.
5 × 10 ⁻⁴ mol was added. Also, 4-hydroxy-6-methyl-1,1, for blue-sensitive emulsion layer and green-sensitive emulsion layer
3a, 7-tetrazaindene was added to silver halide 1
1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol were added per mol.
Further, in order to prevent irradiation, the following dyes (in parentheses represent coating amount) were added to the emulsion layer.

[0141]

[Chemical 54]

(Layer Structure) The composition of each layer is shown below. Numbers represent coating weight (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet). ]

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A 0.27 Gelatin 1.36 Yellow Coupler (ExY) 0.79 Color Image Stabilizer (Cpd-1) 0.08 Color Image Stabilization Agent (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13 Second layer (color mixing prevention layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-7) 0.03 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag mol) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of the grain surface in each size emulsion.) 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 Color image stabilizer (Cpd-5) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-) 7) 0.01 color image stabilizer (Cpd-8) 0.08 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15 fourth layer (color mixture prevention Layer) Gelatin 0.70 Color mixing inhibitor 0.04 Solvent Solv-7) 0.02 solvent (Solv-2) 0.18 solvent (Solv-3) 0.18

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol) The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface.) 0.20 Gelatin 0.85 Cyan Coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.30 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) ) 0.01 color image stabilizer (Cpd-11) 0.01 solvent (Solv-6) 0.22 color image stabilizer (Cpd-8) 0.01 color image stabilizer (Cpd-6) 0.01 solvent (Solv-1) 0.01 Sixth layer (UV absorbing layer) Gelatin 0.55 Ultraviolet absorber (UV-1) 0.38 Color image stabilizer (Cpd-12) 0.15 Color image stabilizer (Cpd-5) 0.02 Seventh layer (protective layer) Gelatin 1.13 Acrylic modified copolymer of polyvinyl alcohol (modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0146]

[Chemical 55]

[0147]

[Chemical 56]

[0148]

[Chemical 57]

[0149]

[Chemical 58]

[0150]

[Chemical 59]

[0151]

[Chemical 60]

[0152]

[Chemical formula 61]

[0153]

[Chemical formula 62]

[0154]

[Chemical formula 63]

Next, for sample 001, the yellow coupler ExY of the first layer and the color image stabilizers A and B (color image stabilizer C) were used.
pd-1, 3) was added and co-emulsified by combining as shown in Table B.
02-010 was produced. The amount of coupler added is ExY
The color image stabilizers A and B were added in an amount of 20 mol% with respect to the yellow coupler. In addition,
The comparative compound is the same as in Example 1.

First, a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd., color temperature of light source: 3200 ° K) manufactured by Fuji Photo Film Co., Ltd. was used for sample 001, and a gray exposure was performed so that about 30% of the coated silver amount was developed. Gave. The exposed sample was subjected to continuous processing using a paper processor using a solution having the following processing step and processing solution composition to prepare a developing processing state in a running equilibrium state.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ° C. 45 seconds 161 ml 17 liter Bleach fixing 30-35 ° C. 45 seconds 215 ml 17 liters Rinse 30 ° C. 90 seconds 350 ml 10 liter Dry 70-80 ° C. 60 seconds * Replenishment amount The composition of each processing solution per 1 m ² of the light-sensitive material is as follows.

[0158] (Color developer) Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine ^{-N, N, N ', N} ' - tetramethylene phosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g - triethanolamine - triethanolamine 8. 0 g 12.0 g sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N-di (sulfoethyl) hydroxylamine / 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1. 0 g 2.0 g Add water 1000 ml 1000 ml pH (25 ° C) 10.05 10.45

(Bleach-fixing solution) The tank solution and the replenisher are the same water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0 (rinse solution) Tank solution and replenisher solution are the same Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

Next, samples 001 to 010 were subjected to imagewise exposure using an optical wedge for three-color separation, and were processed using the above-mentioned processing liquid. A color fading test was performed on each sample on which a dye image was formed in this manner. To evaluate the effect of preventing discoloration, the yellow dye density residual rate at an initial density of 2.0 after 10 days of exposure with a Xenon tester (illuminance: 200,000 lux) was obtained. The results obtained are shown in Table B.

[0161]

[Table 8]

From the results shown in Table B, it is understood that the compound of the present invention exhibits an excellent anti-fading effect even in a light-sensitive material having a multilayer structure.

Example 3 In the sample 401 of Example 4 described in JP-A-4-359249, the couplers of the 15th, 16th and 17th layers were replaced with the coupler (Y-16) or (Y of the present invention. -23)
, And 25 for each layer coupler
Mol% of the compound (A-2), (A-4), (A
-8), (A-10) or (A-12) was co-emulsified and added to each layer, and a sample was prepared in the same manner as sample 401. When these samples were exposed and developed in the same manner as in Process 12 of Example 6 described in JP-A-4-359249 and subjected to a fading test, all of the samples of the present invention showed excellent fastness and photographic characteristics. Was also good. It has been found that the compound of the present invention exhibits excellent effects even in this light-sensitive material.

Example 4 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, the couplers of the 11th and 12th layers were replaced by the coupler (Y-16) or (Y-23) of the present invention. ), And instead of Cpd-9 in each layer, the compounds (A-2), (A-10) and (A-1) of the present invention.
A sample was prepared in the same manner as in the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, except that 1), (A-14) or (A-16) was replaced with Cpd-9 in an equimolar amount. Prepared. These samples were exposed and developed in the same manner as in Example 2 described in JP-A-1-158431, and the color fading test and photographic characteristics were examined. All of the samples of the present invention showed excellent fastness, The photographic characteristics were also good. It has been found that the compound of the present invention exhibits excellent effects even in this light-sensitive material system.

[0165]

By carrying out the present invention, it is possible to form a color image which is excellent in color developability and fastness.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masakazu Morigaki 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Photo Film Co., Ltd.

Claims (2)

[Claims] 1. At least one yellow dye-forming coupler and at least one of the following general formula (A) on at least one layer on a support.
A silver halide color photographic light-sensitive material containing at least one compound represented by: [Chemical 1] (In the formula, R _a1 , R _a2 , R _a3 and R _{a4, which} may be the same or different, each represents an aliphatic group or an aryl group. In addition, R _a1 , R _{a2 and} R _a3 R _a4 may be bonded to each other by an alkylene chain to form a 5- to 7-membered ring.
_a2 and R _{a3 and} R _a1 and R _a4 do not bond to each other to form a ring. The total number of carbon atoms of R _a1 , R _a2 , R _a3 and R _a4 is 10 or more. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one layer further contains at least one compound represented by the following general formula (B). [Chemical 2] (In the formula, R _b1 represents an aliphatic group or a heterocyclic group. R _b2 ,
R _b3 , R _b4 , R _b5 and R _b6 may be the same or different and each is a hydrogen atom, an aliphatic group, an acyl group, an acylamino group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, halogen atom, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or -X _{b '-R b1'.} X _b represents —O—, —S— or —N (R _b7 ) —. Of —X _b —R _b1 and R _{b2 to} R _b6 , the substituents in the ortho positions may be bonded to each other to form a 5- to 8-membered ring.
R _b1 and R _b7 or R _{b1 ′} and R _b7 are bonded to each other to form 5 to 7
A member ring may be formed. _{Xb '} has the same meaning as _Xb and R
_{b1 ′} and R _b7 have the same _meaning as R _b1 . However, R _{b2 to} R _b6
At least one of is a -X _{b '-R b1'.} )