JPH07333797A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To enable a silver halide color photographic material to form a color image that does not discolor over a long period and to have high preservability by containing a specific compound in a layer on a carrier. CONSTITUTION:This silver halide color photographic material contains, in at least one layer on a carrier, at least one kind of compound represented by the formula. In the formula, Ra1 represents hydrogen atom, an aliphatic group, an acyl group, or an arylsulfonyl group; Ra2 represents hydrogen atom or a substituent; Ra3, Ra4 each represent hydrogen atom, an aliphatic group, or an aryl group; Ra5 represents an aliphatic group, an aryl group, an acyl group, an aryloxycarbonyl group, a carbamoyl group, an arylsulfonyl group, or a sulfamoyl group; Xa represents oxygen atom or sulfur atom; and (m) represents an integer from 1 to 4. That is, the compound represented by the formula is a compound for preventing the discoloring of a pigment image formed from a coupler and is not colored, so it does not substantially provide pigment when processed with a color developer.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A silver halide color light-sensitive material generally has a silver halide emulsion layer which is sensitive to three primary colors of red, green and blue, and three kinds of color formers (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 subjecting this silver halide color light-sensitive material to photographic processing is the aromatic first
It is generally composed of an azomethine dye or an indoaniline dye formed by the reaction of an oxide of a primary amine color developing agent and a coupler.

The color image thus obtained is not always stable to light and moist heat, and when it is exposed to light for a long period of time or is stored under high temperature and high humidity, the dye image is discolored or discolored. Cause deterioration of the image. Such image fading or discoloration is a fatal defect for recording materials. As a method of removing these defects, it has been proposed to develop a coupler having high fastness of the obtained dye, to use an anti-fading agent, and to use an ultraviolet absorber in order to prevent image deterioration due to ultraviolet rays. ing.

Among them, the anti-fading agent has a great effect of preventing image deterioration. For example, hydroquinones, hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines, chromanol. Kind,
It is known to add ethers or esters in which phenolic hydroxyl groups of indans and their respective compounds are silylated, acylated or alkylated, and metal complexes.

Although these compounds have been confirmed to be effective as inhibitors for fading and discoloration of dye images, they were insufficient to meet the demands of customers who have come to demand high image quality. In addition, these compounds have a large white background coloration, cause color development in unexposed areas (hereinafter referred to as fog), cause color inhibition of the coupler, and react with the developing agent oxidant during color development to give a dye. However, there are some cases in which the so-called photographic characteristics are adversely affected by the generation of turbidity, which is not sufficient. further,
Some of these compounds may cause poor dispersion, or may cause fine crystals after coating with an emulsion, and thus have not yet been able to exert overall excellent effects for color photography. Further, a compound having a chroman structure, a coumaran structure or a structure similar thereto, or a compound having a bisphenol structure is also known as an image deterioration preventing agent. Although all of these compounds exhibit the effect of preventing discoloration, they are not sufficient for the strong requirement for image fastness, and the white background is colored yellow (yellow stain) with the passage of time, or the developing agent is oxidized during development. It is not an excellent one because it may react with the body to form a pigment and cause color turbidity.

[0006]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a light-sensitive material which does not discolor a color image for a long period of time and has a high storability. A second object of the present invention is not to cause a change in hue or fog, and to not generate a dye by reacting with an oxidized product of a developing agent at the time of development, or to not cause a decrease in color density. Another object of the present invention is to provide a light-sensitive material containing a photographic additive and a dispersant, which has a sufficient effect of preventing fading and discoloration of A third object of the present invention is to provide a light-sensitive material containing a photographic additive which has excellent solubility in a high-boiling organic solvent and does not adversely affect the color forming property of a dye-forming coupler and other photographic additives. To provide. The fourth object of the present invention is to provide a dye-forming coupler.
A highly storable photographic material containing a photographic additive and a dispersant, in which the dye image generated by the color development of the above does not fade over a long period of time and does not cause white background coloring (yellow stain). To provide.

[0007]

As a result of various studies, the inventors of the present invention have incorporated at least one compound represented by the following general formula (A) into a silver halide color photographic light-sensitive material. It has been found that the objects of the invention are achieved.

[0008]

[Chemical 6]

(In the formula, R _a1 represents a hydrogen atom, an aliphatic group, an acyl group, or an aliphatic or arylsulfonyl group. R _a2 represents a hydrogen atom or a substituent. R _a3 and R _a4
May be the same or different and each represents a hydrogen atom, an aliphatic group or an aryl group, and R _a5 represents an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group, It represents a carbamoyl group, an aliphatic or arylsulfonyl group or a sulfamoyl group. X _a
Represents an oxygen atom or a sulfur atom. m represents an integer of 1 to 4, and when m is 2 or more, R _{a2 s} may be the same or different, and m is 2 or more and R _a2
May be bound to each other when they are ortho to each other. However, R _a1 and R _a5 do not bond to each other. )

The compound represented by the general formula (A) is preferably a compound represented by the following general formula (AI) or the general formula (A-II),

[0011]

[Chemical 7]

(Wherein R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and X _a are the same as those defined in the general formula (A), and R _a11 , R _a21 , R _a31 and R a _a41 , R _a51 and X
_a1 is R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and X, respectively.
is the same as those defined in _a. Z _a represents an oxygen atom, a sulfur atom or —C (R _a6 ) (R _a7 ) —, and p and q each represent an integer of 1 to 3. R _a6 and R _a7 may be the same or different and each represents a hydrogen atom, an aliphatic group or an aryl group. When p or q is 2 or more, a plurality of R _a2 or R _a21 may be the same or different. When p or q is 2 or more and a plurality of R _a2 or R _a21 are in the ortho positions, they may be bonded to each other. However, R _a1 and R _a5 and R _a11 and R _a51
Do not bind to each other. )

[0013]

[Chemical 8]

[0014] (wherein, R _a32, R _a52, respectively, .R _a22 to R _a23 have the same meanings as R _a3, R _a5 in the general formula (A) may be the same or different, respectively,
It has the same _meaning as R _a2 in formula (A). )

It has been found that it is particularly preferable that the compound represented by the general formula (A) is a compound represented by the following general formula (A-III).

[0016]

[Chemical 9]

(In the formula, R _a11 has the same _{meaning as} R _a1 defined in the general formula (A). R _a32 and R _a33 may be the same or different and each is represented by the general formula (A). R
Synonymous with _a3 . R _a52 and R _a53 may be the same or different and each has the same _{meaning as} R _a5 in formula (A). R _a22 and R _a24 may be the same or different and each has the same _{meaning as} R _a2 in formula (A). R _a6 and R _a7 may be the same or different,
Each represents a hydrogen atom, an aliphatic group or an aryl group. However, R _a11 and R _a53 do not bond to each other. )

The present invention will be described in detail below. The compound of the present invention is a compound which prevents fading of the dye image formed from the 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 is 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, hydroxy group, cyano group, nitro group, sulfo group, hydroxyamino group, aliphatic oxyamino group Group, aryloxyamino group, carbamoylamino group, sulfamoylamino group,
Examples thereof include a halogen atom, a sulfamoylcarbamoyl group, a carbamoylsulfamoyl group, a dialiphatic oxyphosphinyl, and a diaryloxyphosphinyl.

In the formula, R _a1 and R _a11 are each a hydrogen atom or an aliphatic group which may have a substituent (preferably an alkyl group which may have a substituent and has 1 to 40 carbon atoms). There
For example, methyl, ethyl, i-propyl, cyclohexyl, benzyl, dodecyl, 2- (2,4-di-t-pentylphenoxy) ethyl, 2- (butoxycarbonyl)
Ethyl), an acyl group which may have a substituent (preferably an alkylcarbonyl group having a carbon number of 2 to 42 which may have a substituent, a carbon atom which may have a substituent of 3)
To 42 alkenyl carbonyl groups or C 7 to C 47 arylcarbonyl groups which may have a substituent, such as acetyl, pivaloyl, myristoyl,
Benzoyl, 4-t-butyribenzoyl, acryloyl, methacryloyl), an aliphatic or arylsulfonyl group which may have a substituent (preferably an alkanesulfonyl group having 1 to 40 carbon atoms which may have a substituent). Alternatively, it represents an arylsulfonyl group having 6 to 46 carbon atoms which may have a substituent and represents, for example, butanesulfonyl, hexyloxyethanesulfonyl, benzenesulfonyl, 4-dodecyloxybenzenesulfonyl).

R _a2 , R _a21 , R _a22 , R _a23 , R
_a24 is a hydrogen atom or a substituent (as a preferable substituent, an aliphatic group, a heterocyclic group, an acylamino group, a sulfonamide group, a carbamoylamino group, an aliphatic group or an aryl group;
A hydroxy group, an aliphatic or aryloxycarbonylamino group, an aliphatic or aryloxy group, an aliphatic or arylthio group, an aliphatic or arylsulfonyl group, a halogen atom, which are possible In that case, it may further have a substituent).

R _a3 , R _a31 , R _a32 , R _a33 , R _a4 , R
_a41 may be the same or different, and is a hydrogen atom, an aliphatic group which may have a substituent (preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent). Such as methyl, ethyl, i-propyl, dodecyl,
And cyclohexyl, benzyl) or an aryl group which may have a substituent (preferably phenyl and 4-methoxyphenyl having 6 to 30 carbon atoms and which may have a substituent).

R _a5 , R _a51 , R _a52 and R _a53 are each an aliphatic group which may have a substituent (preferably an alkyl group having 1 to 40 carbon atoms which may have a substituent or a substituent). An alkenyl group having 2 to 42 carbon atoms which may have a group, such as methyl, ethyl, i-propyl, cyclohexyl, t-butyl, benzyl, dodecyl, methoxymethyl, butylthiomethyl, phenethyl, allyl, Vinyl), an aryl group which may have a substituent (preferably having a carbon number of 6 to 36 and having a substituent, for example, phenyl, 4-methylphenyl, 2,4-di-t -Butylphenyl, 4-myristoylaminophenyl, 3-dodecyloxyphenyl), an acyl group which may have a substituent (preferably a carbon number 2 which may have a substituent)
To an alkylcarbonyl group having 42 to 42 or an alkenylcarbonyl group having 3 to 42 carbon atoms which may have a substituent or an arylcarbonyl group having 7 to 47 carbon atoms which may have a substituent, and examples thereof include acetyl. , Pivaloyl, myristoyl, acryloyl, methacryloyl, benzoyl), an aliphatic or aryloxycarbonyl group which may have a substituent (preferably an alkoxycarbonyl having 2 to 42 carbon atoms which may have a substituent). A group or a C7-C47 aryloxycarbonyl group which may have a substituent, for example, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, phenoxycarbonyl, 2,4-di-t-butyl. Phenoxycarbonyl), a carbamoyl group which may have a substituent (preferably Is an alkylcarbamoyl group having 2 to 42 carbon atoms which may have a substituent or an arylcarbamoyl group having 7 to 47 carbon atoms which may have a substituent, and examples thereof include diethylcarbamoyl and N-methyl. -N-phenylcarbamoyl), an aliphatic or arylsulfonyl group which may have a substituent (preferably an alkanesulfonyl group having 1 to 40 carbon atoms which may have a substituent or a substituent). An optionally substituted arylsulfonyl group having 6 to 46 carbon atoms, such as a butanesulfonyl group, a cyclohexylsulfonyl group, a benzenesulfonyl group, 4-dodecyloxybenzenesulfonyl), or a substituent Good sulfamoyl group (preferably having 1 to 4 carbon atoms which may have a substituent)
An alkylsulfamoyl group of 0 or an arylsulfamoyl group having 6 to 46 carbon atoms which may have a substituent, and examples thereof include dibutylsulfamoyl, dodecylsulfamoyl, phenylsulfamoyl and N-octyl. -N-phenylsulfamoyl).

X _a represents an oxygen atom or a sulfur atom. m represents 1 to 4, and when m is 2 or more, a plurality of R _a2 may be the same or different. When m is 2 or more and a plurality of R _{a2 s} are in the ortho positions, they may be bonded to each other. However, R _a1 and R _a5 , R _a11 and R _a51 ,
R _a11 and R _a53 do not bind to each other.

The preferred groups in the present invention will be described. In the general formula (A), in terms of the effect of the present invention, R _a1
Is preferably a hydrogen atom or an aliphatic group, and more preferably a hydrogen atom. R _a2 is a hydrogen atom,
It is preferably an aliphatic group or an acylamino group, more preferably an aliphatic group, and most preferably an alkyl group. R _a3 and R _a4 are preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a case where at least one of R _a3 and R _a4 is a hydrogen atom. R
_a5 is preferably an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group and a carbamoyl group, more preferably an aliphatic group, an aryl group and an acyl group, particularly preferably an alkyl group, an alkenyl group and an alkenylcarbonyl group. , Alkyl groups and alkenyl groups are most preferred. X _a is preferably an oxygen atom. R
_a2 is preferably substituted at least in the ortho group or para position of -OR _a1 , and more preferably in the ortho position and para position.

In the general formula (A), R _a1 is a hydrogen atom, R _a2 is an alkyl group, and m is 1 or 2 (in the case where m is 1), R ₁ is a hydrogen atom. _a2 is ortho or para position of at least -OR _a1, when m is 2, the R _a2 may be the same or different, -OR _a1
This is the case where the para position and the ortho position are replaced. ), R
_a3 is a hydrogen atom or an alkyl group, R _a4 is a hydrogen atom, R _a5
Is preferably an alkyl group, an alkenyl group or an alkenylcarbonyl group, X _a is a compound in which O _a is an oxygen atom, R _a1 is a hydrogen atom, R _a2 is an alkyl group,
m is 2 (in this case, R _a2 may be the same or different and is a para position or an ortho position of —OR _a1 ), R _a3 is a hydrogen atom or an alkyl group, R _a4 is a hydrogen atom, It is more preferable that R _a5 is an alkyl group or an alkenyl group and X _a is an oxygen atom.

In the general formula (AI), R _a1 and R _a11 are preferably a hydrogen atom, an aliphatic group or an acyl group from the viewpoint of the effect of the present invention, and a hydrogen atom, an alkyl group, an alkenyl group, An alkylcarbonyl group or an alkenylcarbonyl group is more preferred. R _a2
And R _a21 are preferably aliphatic groups, and more preferably alkyl groups. R _a3 , R _a31 , R _a4
And R _a41 is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and at least one of R _a3 and R _a4 and R _a4
Most preferably, at least one of _a31 and R _a41 is a hydrogen atom. R _a5 and R _a51 are _preferably a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group or a carbamoyl group, and more preferably an aliphatic group, an aryl group or an acyl group. , An alkyl group, an alkenyl group or an alkenylcarbonyl group is particularly preferable, and an alkyl group or an alkenyl group is most preferable. X _a and X _a1 are preferably oxygen atoms. It is preferable that R _a2 is substituted at -OR _a1 and R _a21 is substituted at the ortho position or para position of -OR _a11 . In that case, it is more preferable that p and q are 1. Z
_a is preferably -C (R _a6 ) (R _a7 )-,
More preferred is -CH (R _a7 )-. R _a6 and R _a7 are preferably a hydrogen atom or an alkyl group.

In the general formula (AI), R _a1 is a hydrogen atom, R _a11 is a hydrogen atom, from the viewpoint of the effect of the present invention.
An alkyl group, an alkenyl group, an alkylcarbonyl group or an alkenylcarbonyl group, wherein R _a2 and R _a21 are alkyl groups (p and q are 1, R _a2 is an ortho position or a para position of —OR _a1 , and a ₂₁ is —OR _a11; In the ortho or para position of R _a3 and R _a31 are hydrogen atoms or alkyl groups, R _a4 and R _a41 are hydrogen atoms, R _a5 and R _a51 are alkyl groups, alkenyl groups or alkenylcarbonyl groups, X _a and X _a1 represents an oxygen atom, Z _a is -C
A compound having a combination of H (R _a7 ) — (R _a7 is a hydrogen atom or an alkyl group, and particularly preferably an alkyl group) is preferable. In these cases, it is more preferable that R _a5 and R _a51 are an alkyl group or an alkenyl group.

In the general formula (A-II), R _a22 is preferably an aliphatic group, and more preferably an alkyl group, from the viewpoint of the effect of the present invention. R _a23 is preferably a hydrogen atom or an aliphatic group, and more preferably an alkyl group. Ra ₃₂ is preferably a hydrogen atom or an aliphatic group, and more preferably a hydrogen atom or an alkyl group. R _a52 is _preferably a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group or a carbamoyl group, more preferably an aliphatic group, an aryl group or an acyl group, and an alkyl group. , An alkenyl group or an alkenylcarbonyl group is particularly preferable, and an alkyl group or an alkenyl group is most preferable.

[0031] Among the general formula (A-II) is also the viewpoint of the effect of the present invention, R _a22 is an alkyl group, with R _a23 is a hydrogen atom or an alkyl group, R _a32 is a hydrogen atom or an alkyl group, R _a52 Is preferably a compound having a combination of an alkyl group, an alkenyl group or an alkenylcarbonyl group, among which a compound in which R _a23 is an alkyl group is particularly preferable, and among them, a case in which R _a52 is an alkyl group or an alkenyl group is most preferable. .

The preferred groups in formula (A-III) will be described. In the general formula (A-III), R _a11 is preferably a hydrogen atom, an aliphatic group or an acyl group from the viewpoint of the effect of the present invention, and a hydrogen atom, an alkyl group, an alkenyl group, an alkylcarbonyl group or an alkenylcarbonyl group. More preferably, it is a group. R _a22 and R _a24 are preferably a hydrogen atom or an aliphatic group,
More preferably, it is an alkyl group. R _a32 and R
_a33 is preferably a hydrogen atom or an aliphatic group, and more preferably an alkyl group. R _a52 and R _a53 are _preferably a hydrogen atom, an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group or a carbamoyl group, and more preferably an aliphatic group, an aryl group or an acyl group. , An alkyl group, an alkenyl group or an alkenylcarbonyl group is particularly preferable, and an alkyl group or an alkenyl group is most preferable. R _a6 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. R _a7 is preferably a hydrogen atom or an alkyl group, and more preferably an alkyl group.

In the general formula (A-III), R _a11 is a hydrogen atom, an alkyl group, an alkenyl group, an alkylcarbonyl group or an alkenylcarbonyl group, and R _a22 and R _a24 are alkyl groups from the viewpoint of the effect of the present invention. in combination R _a32 and R _a33 are a hydrogen atom or an alkyl group, R _a52 and R _a53 is an alkyl group, an alkenyl group or alkenylcarbonyl group, R _a6 is hydrogen atom, R _a7 is a hydrogen atom or an alkyl group Compounds of are preferred. Among these, those in which R _a32 and R _a33 are alkyl groups are particularly preferable, and among these, it is most preferable that R _a52 and R _a53 are alkyl groups or alkenyl groups and R _a7 is an alkyl group.

Next, specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

The compound represented by the general formula (A) of the present invention can be synthesized by the method described in JP-A-63-275620, US Pat. No. 485,772 or the like or a method analogous thereto. The synthesis examples of typical compounds are shown below.

Synthesis Example 1 (Exemplified Compound (A-43,44)
Synthesis of Exemplified Compounds A-43 and 44 were synthesized by the following routes.

[0044]

[Chemical 17]

Synthesis of intermediate (1) 70 g of para-cresol was dissolved in 150 ml of benzene,
Under heating under reflux, 70 g of isobutyryl chloride was added dropwise over 30 minutes, and the mixture was further heated under reflux for 4 hours. After distilling off benzene under reduced pressure, 90 g of aluminum chloride was added over 30 minutes while maintaining the internal temperature at 80 to 95 ° C. After heating and stirring at 90 ° C. for another hour, the reaction solution was poured into 300 ml of cold water and extracted with 250 ml of ethyl acetate. The ethyl acetate layer was washed twice with 250 ml of saturated saline, and then the solvent was distilled off under reduced pressure. The residue was purified by alumina column chromatography to obtain a colorless liquid intermediate (1). Yield 1
02g Yield 88.4%

Synthesis of Intermediate (3) 30 g of Intermediate (1) was dissolved in 60 ml of tetrahydrofuran and 30 ml of isopropyl alcohol, and 6.3 g of sodium borohydride was added over 30 minutes with stirring at 20 to 25 ° C. After that, the temperature was raised to 30 to 40 ° C. and the mixture was stirred for 2 hours, and then the reaction solution was cooled to 200 ml of cold water containing 10 ml of acetic acid.
And extracted with 200 ml of ethyl acetate. The ethyl acetate layer was washed twice with 250 ml of saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain an intermediate (2).

Paracresol 50 g acetic acid 20 ml
Add and dissolve, and add concentrated sulfuric acid 0.9 under stirring at 20-25 ° C.
ml was added dropwise. The internal temperature was raised to 40 ° C. with dropping.
After stirring at 40 ° C. for 30 minutes, 200 ml of ethyl acetate was added and dissolved. The ethyl acetate layer was washed 3 times with 250 ml of saturated saline and the solvent was distilled off under reduced pressure to obtain an amorphous solid. This was crystallized with 100 ml of n-hexane and recrystallized with 100 ml of n-hexane to obtain an intermediate (3). Melting point 163-165 ° C
Yield 32g Yield 70.3%

Synthesis of A-44 22 g of intermediate (3) and 8.2 g of potassium hydroxide were added to 3 parts of water.
It was dissolved in 0 ml and 30 ml of methanol and stirred at 50 to 60 ° C. To this, add 170 ml of 37% formalin water to 30
The mixture was added dropwise over minutes, and the mixture was further stirred for 6 hours at 50 to 60 ° C.
The reaction solution was cooled, 10 ml of acetic acid was added, and the mixture was extracted with 300 ml of ethyl acetate. The ethyl acetate layer was washed 3 times with 300 ml of saturated saline and the solvent was distilled off under reduced pressure.
An amorphous solid was obtained. This is acetonitrile 5
The crystals were crystallized with 0 ml and recrystallized with 50 ml of acetonitrile to obtain an intermediate (4). Melting point 190-192 ° C. Yield 18.5 g Yield 70.6%

Synthesis of A-43 15 g of the intermediate (4) was dissolved in 100 ml of methanol and stirred at 40 to 45 ° C. Add 5 ml of concentrated sulfuric acid to this.
The mixture was added dropwise over 1 minute and the mixture was stirred for 5 hours. The reaction solution is cold water 2
It was poured into 50 ml and extracted with 250 ml of ethyl acetate. The ethyl acetate layer was washed twice with 250 ml of saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain an amorphous solid. The obtained oily substance was crystallized with 30 ml of methanol to obtain white crystals.
Melting point 109-111 ° C. Yield 13.0 g Yield 79.9
% Other compounds can be similarly synthesized.

In the light-sensitive material of the present invention, at least one layer on the support contains at least one compound represented by the general formula (A) of the present invention. Among the hydrophilic colloid layers, a silver halide emulsion layer containing a coupler is preferable as the layer to be contained.

The compound represented by formula (A) of the present invention is preferably used in an amount of 0.0002 to 5 g, more preferably 0.001 to 3 g, per 1 m ² of the light-sensitive material. Is different depending on the type of coupler, but is 0.5 to 3 with respect to the coupler used (preferably the coupler used in the same layer).
It is suitable to use it in a range of 00 mol%, and preferably in a range of 1 to 200 mol%.

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 preferably used together with the compound represented by the following general formula (B) in the same layer. Is more preferable.

[0054]

[Chemical 18]

(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. , Aliphatic groups,
Aliphatic or aryl acyl group, an aliphatic or aryl acyl amino group, an aliphatic or an aryloxycarbonyl group, a halogen atom, an aliphatic or ants - Rusuruhoniru group, a carbamoyl group, a sulfamoyl group or -X b _{'-R b1'} Represent X _b and X _{b ′} each represent —O—, —S— or —N (R _b7 ) —. −
X _b -R _b1 , R _b2 , R _b3 , R _b4 , R _b5 and R _b6 may be bonded to each other at the ortho positions to form a 5- to 8-membered ring, and R _b1 and R _b7 Alternatively, R _{b1 ′} and R _b7 may combine with each other to form a 5- to 7-membered ring. R _{b1 ′} and R _b7 have the same _meaning as R _b1 . Provided that at least one of R _b2 to R _b6 is a -X _{b '-R b1'.} )

The general formula (B) will be described in detail. R
_b1 is an aliphatic group which may have a substituent (preferably an alkyl group which may have a substituent having 1 to 30 carbon atoms, and examples thereof include methyl, i-propyl, benzyl and hexadecyl. , Cyclohexyl, 2-phenoxyethyl, 2-methanesulfonamidoethyl) or a heterocyclic group which may have a substituent (preferably a carbon atom having 3 to 30 carbon atoms which may have a substituent). And a saturated heterocyclic group represented by, 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 which may have a substituent (preferably a substituent). An alkyl group having 1 to 30 carbon atoms which may have a group, for example, methyl, t-octyl, benzyl, cyclohexyl, n-dodecyl, s-butyl, 1,1-dimethyl-4-methoxycarbonylbutyl. ), An optionally substituted aliphatic or arylacyl group (preferably an optionally substituted alkylacyl group having 2 to 36 carbon atoms or an arylacyl group having 7 to 43 carbon atoms) And, for example, acetyl, pivaloyl, dodecanoyl, benzoyl, 3-hexadecyloxybenzoyl), an optionally substituted aliphatic or arylacylamino group (preferably Is an alkylacylamino group having 2 to 36 carbon atoms which may have a substituent or an arylacylamino group having 7 to 43 carbon atoms which may have a substituent, and examples thereof include acetamino, pivaloylamino, 2-ethylhexanoylamino, 2- (2,
4-di-t-amylphenoxy) octanoylamino,
Dodecanoylamino, 3-butoxybenzoylamino), an optionally substituted aliphatic or aryloxycarbonyl group (preferably an optionally substituted alkoxycarbonyl group having 2 to 36 carbon atoms, or An aryloxycarbonyl group having 7 to 42 carbon atoms which may have a substituent, for example, methoxycarbonyl, dodecyloxycarbonyl, 2-hexyloxyethoxycarbonyl, 2,4-di-t-amylphenoxycarbonyl. , 4-methoxyphenoxycarbonyl), a halogen atom (eg, fluorine, chlorine, bromine), an optionally substituted aliphatic or arylsulfonyl group (preferably a optionally substituted carbon). 6 to 4 carbon atoms which may have an alkanesulfonyl group of 1 to 30 or a substituent An arylsulfonyl group of, for example, methanesulfonyl, octanesulfonyl, 4- (4-t-octylphenoxy) butanesulfonyl, 4-dodecyloxybenzenesulfonyl), a carbamoyl group which may have a substituent (preferably , May have a substituent having 2 to 36 carbon atoms, for example, methylcarbamoyl, diethylcarbamoyl, N-methyl-
N-phenylcarbamoyl), an optionally substituted sulfamoyl group (preferably having a carbon number of 1 to 30 and optionally having a substituent, for example, methylsulfamoyl, dibutylsulfamoyl, phenylsulfyl). It represents a Famoiru) 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 have the same _meaning as R _b1 .
Provided that at least one of R _b2 to R _b6 is, -X _{b '-R b1'}
Is.

In view of the effects of the present invention, R _b1 , R _{b1 '} and R _b1
b7 is preferably an alkyl group, R _{b2 to} R
_b6 is a hydrogen atom, an alkyl group, an acylamino group, -Xb _'
The case where it is -R _{b1 '} is preferable.

From the viewpoint of the effect of the present invention, the following general formula (B-
The compounds represented by I) to (BX) are more preferable.

[0061]

[Chemical 19]

[0062]

[Chemical 20]

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 which may have a substituent (preferably having a carbon number of 1 to 20 and having a substituent, for example, methyl, ethyl , I-propyl, octadecyl, benzyl) or optionally substituted aryl-
Group (preferably having from 6 to 6 carbon atoms which may have a substituent)
And a phenyl group of 26, 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 represent a single bond, -C ( _R80 ) ( _R81 )-or -O-, and E is a single bond or -C ( _R80 ) (R.
₈₁ ) -represents. Here, R ₈₀ and R ₈₁ may be the same or different and each represents a hydrogen atom or an alkyl group (preferably having 1 carbon atom).
To 20 may have a substituent, for example, methyl, ethyl, i-propyl, dodecyl, benzyl) or an aryl group (preferably having 6 carbon atoms which may have a substituent).
~ 26 phenyl groups, 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-IV), (B-VI), (B-VII), (B-
VIII) and (B-IX) are preferable, and the compounds represented by the general formulas (B-IV), (B-VI), (B-VII), and (B-VIII) are preferable.
The compound represented by formula (B-I)
The compounds represented by V) and (B-VI) are most preferable.

Specific examples of the compound represented by formula (B) are shown below, but the compounds used in the present invention are not limited thereto.

[0066]

[Chemical 21]

[0067]

[Chemical formula 22]

[0068]

[Chemical formula 23]

[0069]

[Chemical formula 24]

[0070]

[Chemical 25]

[0071]

[Chemical formula 26]

These compounds are disclosed in Japanese Examined Patent Publication No. 14034/45,
56-24257, 59-52421, JP-A-55-89835, 56-1
59644, 62-244045, 62-244246, 62-273
531, 63-95439, 63-95448, 63-95450,
European Patent No. 239,972, JP-A-4-330440, JP-A-58-1
The compound can be synthesized by the method described in 05147 or the like or a method analogous thereto.

In the present invention, the amount of the compound represented by the general formula (B) to be used varies depending on the kind and amount of the coupler used, but is 0.5 to 1 mol of the coupler used.
The range is 300 mol%, preferably 1 to 200 mol%, and most preferably 2 to 100 mol%.

The compounds represented by the general formulas (A) and (B) of the present invention are compounds which prevent fading of the dye image formed from the coupler and are non-color forming compounds.
The non-color-forming compound is a compound that gives substantially no dye when treated with a color developing solution.

The compound represented by the general formula (A), the compound represented by the general formula (B) and the coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, and a high boiling point organic solvent (if necessary) can be used. Dissolved in a low boiling point organic solvent)
The oil-in-water dispersion method of emulsifying and dispersing in a gelatin aqueous solution and adding to a silver halide emulsion is preferable. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, the steps of the latex dispersion method as one of the polymer dispersion methods, the effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. -Four
1091 and European Patent Publication No. 029,104 and the like, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

As the high-boiling organic solvent that can be used in the oil-in-water dispersion method described above, phthalic acid esters (for example, 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
-Diethyl dodecane amide), alcohols (isostearyl alcohol, oleyl alcohol, etc.), aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate). , Aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%) trimesic acid esters (for example, tributyl trimesic acid tributyl ester) ), Dodecylbenzene, diisopropylnaphthalene, phenols (eg, 2,4-di-tert-amylphenol, 4-
Dodecyloxyphenol, 4-dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol), carboxylic acids (eg, 2-
(2,4-di-tert-amylphenoxybutyric acid, 2-
Examples include ethoxyoctanedecanoic acid), alkylphosphoric acids (eg, di-2 (ethylhexyl) phosphoric acid, diphenylphosphoric acid, dihexylphenylphosphate). The melting point of the auxiliary solvent is 30 ° C or higher and about 160 ° C.
The following organic solvents (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. To carry out the present invention, a yellow dye-forming coupler, a magenta dye-forming coupler, and a cyan dye-forming coupler, which form yellow, magenta, and cyan, respectively, by coupling with an oxidized product of an aromatic primary amine type color developing agent, are formed. It is preferably used in combination with a coupler.

The couplers used in combination may have 4 equivalents or 2 equivalents with respect to silver ion, and may have a polymer or oligomer form. 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 dye-forming couplers include phenol-type and naphthol-type couplers, and U.S. Pat. Nos. 4,052,212, 4,146,396, and
4,228,233, 4,296,200, 2,369,929,
No. 2,801,171, No. 2,772,162, No. 2,895,826
No. 3, No. 3,772,002, No. 3,758,308, No. 4,334,
011, 4,327,173, West German Patent Publication 3,329,729
No., European Patent Nos. 121,365A, 249,453A, 333,
185A2, U.S. Pat.Nos. 3,446,622 and 4,333,999
No., No. 4,775,616, No. 4,451,559, No. 4,427,
No. 767, No. 4,690,889, No. 4,254,212, No. 4,
Those described in 296,199, JP-A-61-42653 and the like are preferable. Furthermore, JP-A-64-553, JP-A-64-554, and JP-A-64-555
No. 64-556, European Patent Publication No. 488,248, No. 491,
No. 197, No. 484,909, No. 456,226, and azole couplers, U.S. Pat.
Imidazole couplers described in 33144 or JP-A-64
The cyclic active methylene type cyan coupler described in -32260 can also be used.

From the viewpoint of the effect of the present invention, the compound represented by the general formula (A) is preferably used by coemulsifying with a cyan dye-forming coupler, and in that case, a preferable general formula of the cyan dye-forming coupler. Is shown below.

[0081]

[Chemical 27]

In the formula, R _C1 represents an aliphatic group, and R _C2 represents
Represents an alkyl group or an aryl group, and X _C1 represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as a leaving group).

Particularly preferable cyan dye-forming 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, 491,197, 484,
909 and 456,226 are examples.

As the magenta dye-forming coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Pat.
067, Research Disclosure No. 24220 (19
June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659.
No. 61, No. 72238, No. 60-35730, No. 55-118034, No.
60-185951, U.S. Pat.Nos. 4,500,630 and 4,540,65
Those described in No. 4, No. 4,556,630, International Publication No. WO88 / 04795 and the like are more preferable. Particularly preferred magenta dye-forming couplers are the pyrazoloazole-based magenta dye-forming couplers of the general formula (I) described in JP-A-2-139544, page 3, lower right column to page 10, lower right column, and JP-A-2-139544. No. 139544, page 17, lower left column to page 21, upper left column, general formula (M-1) 5
-Pyrazolone magenta dye-forming couplers.
Most preferred are the pyrazoloazole-based magenta dye-forming couplers described above.

Examples of yellow dye-forming couplers include, for example, US Pat. Nos. 3,933,501, 4,022,620, and
326,024, 4,401,752, 4,248,961, 5,118,599, 3,973,968, 4,314,023
No. 4,511,649, No. 5,118,599, European Patent No.
249,473A, JP 63-23145, JP 63-123047, JP 1-250944, JP 1-213648, JP 58-10739, UK Patents 1,425,020, 1,476,760, etc. As long as what is described does not impair the present invention, they can be used in combination.

From the viewpoint of the effect of the present invention, the compound represented by formula (A) is also preferably used when coemulsified with a yellow-dye forming coupler, and in that case, a preferable yellow-dye forming coupler is used. The general formula is shown below.

[0087]

[Chemical 28]

In the formula, R _y1 represents an alkyl group, a substituted amino group or a heterocyclic group, R _y2 represents a halogen atom, an alkoxy group or an aryloxy group, and R _y3 can be a benzene ring. Represents a group, and X _y1 represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized product of an aromatic primary amine developing agent (hereinafter referred to as a leaving group). k
Represents an integer of 0, 1 to 4. However, when k is 2 or more,
A plurality of R _y3 may be the same or different. A particularly preferred yellow dye-forming coupler is represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column.
A yellow-dye-forming coupler represented by JP-A-5-2248,
An acylacetamide type yellow-dye forming coupler characterized by an acyl group described in EP-A-0447969 and a yellow dye of the general formula (Cp-2) described in JP-A-5-27389 and EP-A-0446863A2. Forming couplers. When the compound represented by the general formula (A) is used by being co-emulsified with a yellow dye-forming coupler, from the viewpoint of the effect of the present invention, it is used together with a polymer having acrylic acid amide or methacrylic acid amide as a monomer. It is also preferable to use it after coemulsification.

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. 1764 mentioned above.
3, patents described in paragraphs VII to F, JP-A-57-151944
Issue 57-154234, Issue 60-184248, Issue 63-37346,
Those described in U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferable.

As a coupler which releases an image-forming nucleating agent or a development accelerator during development, there is described in British Patent No. 2,097,140.
No. 2,131,188, JP-A-59-157638, and 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. 4,130,42.
Competitive couplers described in US Pat. No. 4,283,472
Nos. 4,338,393, 4,310,618, etc., multiequivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox, DIR redox compound releasing couplers described in JP-A-60-185950 and 62-24252. Compounds or DIR redox releasing redox compounds, couplers releasing a dye that recovers color after withdrawal described in European Patent 173,302A, RD No. 11449, No. 24241, JP-A-61-201247, etc. A bleach accelerator releasing coupler as described,
Examples thereof include ligand releasing couplers described in US Pat. No. 4,553,477, couplers releasing leuco dyes described in JP-A-63-75747, couplers releasing fluorescent dyes described in US Pat. No. 4,774,181, and the like. Next, examples of typical couplers used in the present invention are shown.

[0091]

[Chemical 29]

[0092]

[Chemical 30]

[0093]

[Chemical 31]

[0094]

[Chemical 32]

[0095]

[Chemical 33]

[0096]

[Chemical 34]

[0097]

[Chemical 35]

[0098]

[Chemical 36]

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 dye-forming couplers, 0.
01-0.5 mole, for magenta dye-forming couplers,
0.003 to 0.3 mol, for cyan dye forming couplers 0.002 to 0.3 mol.

Various known 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 Representative examples thereof include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl groups of these compounds. Also (bissalicylaldoximato)
A metal complex represented by a nickel complex and a (bis-N, N-dialkyldithiocarbamate) nickel complex can also be used.

Specific examples of the organic anti-fading agent include US Pat. Nos. 2,360,290, 2,418,613 and 2,700,453,
2,701,197, 2,728,659, 2,732,300, and
2,735,765, 3,982,944, 4,430,425, British Patent 1,363,921, U.S. Patents 2,710,801, 2,81
Hydroquinones described in US Pat. No. 6,028; US Pat. No. 3,43
2,300, 3,573,050, 3,574,627, 3,698,
909, 3,764,337, 6-hydroxychromans described in JP-A-52-152225, 5-hydroxychromans, spirochromans; spiroindanes described in US Pat. No. 4,360,589; US Pat. No. 2,735,765, British Patent No. 2,066,975, JP-A-59-10539, JP-B-57-19765
P-alkoxyphenols described in U.S. Pat.
3,700,455, 4,228,235, JP-A-52-72224, JP-B-52-6623 and the like; hindered phenols; gallic acid derivatives described in US Pat. No. 3,457,079; described in US Pat. No. 4,332,886 Methylenedioxybenzenes; aminophenols described in Japanese Patent Publication No. 56-21144; U.S. Pat. Nos. 3,336,135, 4,268,593, British Patent 1,32
6,889, 1,354,313, 1,410,846, Japanese Patent Sho 51
-1420, JP-A-58-114036, 59-53846, 59-7
Hindered amines described in 8344 and the like; US Pat. No. 4,05
Examples thereof include metal complexes described in 0,938, 4,241,155 and British Patent No. 2,027,731A. These compounds are
Usually 5 to 1 for each corresponding color coupler
The object can be achieved by co-emulsifying 00% by weight of the coupler and adding it to the photosensitive layer.

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, it is preferable to use a color image storability-improving compound as described in European Patent Publication No. 0,277,589A2 together with a coupler.
In particular, it is preferably used in combination with an azole type magenta dye forming coupler or a cyan dye forming coupler. That is, the compound (A) described in European Patent Publication No. 0,277,589A2, which chemically bonds with an aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and substantially colorless compound, and And / or the compound described in European Patent Publication No. 0,277,589A2, which chemically bonds with the oxidation product of the aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound. It is preferable to use (B) at the same time or alone in order to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or its oxidant with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably.

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. Is substantially free of silver iodide and has a silver chloride content of 90 mol% or more and 100 mol% or less, more preferably 95% or more and 100 mol% or less, and particularly 98% or more and 100 mol% or less, or pure chlorination. The use of silver emulsions is preferred. Further, in the light-sensitive material according to the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is provided with a dye which can be decolorized by a treatment (described in EP No. 0,337,490A2, pages 27 to 76). Among them, oxonol-based dyes) are used in the light-sensitive material at 680 nm.
Is added so that the optical reflection density is 0.70 or more, and a titanium oxide surface-treated with a dihydric or tetrahydric alcohol (for example, trimethylolethane (, etc.) is added to the water resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more).

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. Further, upon exposure, it is preferable to use the band and stop filter described in US Pat. No. 4,880,726. 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 column to right column, 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 processing steps, a pre-hardening step, a neutralizing step thereof, a stop-fixing step, a post-hardening step, an adjusting step, an intensifying step and the like may be performed. 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.

Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied in the present invention, and processing methods and processing additions applied for processing the light-sensitive material. As the agent, those described in JP-A-4-359249 and the following patent publications, particularly European Patent Publication No. 0,355,660A2 are preferably used.

[0110]

[Table 1]

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

[Table 4]

[0114]

[Table 5]

[0115]

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

Yellow-Dye-forming coupler (Y-1) 1
High boiling point organic solvent dibutyl phthalate 16.
1 g was added, and 24 ml of ethyl acetate was further added to dissolve the solution, 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.

In the same manner as in Sample 101, in making the above emulsified dispersion, as shown in Table A, a yellow-dye forming coupler (added equimolar to Y-1), a color image stabilizer A (general formula: The compound represented by (A): the addition amount is described in Table A) was co-emulsified to prepare a sample, and otherwise, sample 10 was used.
Samples 102 to 142 were prepared by emulsifying and coating in the same manner as in 1.

The above light-sensitive material was exposed through an optical wedge and then processed in the next step. Treatment process Temperature Time Color development 38.5 ° 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 , (3) to (1) in a three-tank countercurrent system.)

The composition of each processing liquid is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Bromide Potassium 0.03 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 Sodium triisopropyl naphthalene (β) sulfonate 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g water 1000 ml pH (prepared at 25 ° C./potassium hydroxide and sulfuric acid) 10.00

[Bleaching Fixing Solution] Water 600 ml Ammonium thiosulfate (750 g / liter) 93 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Nitric acid (67%) 30 g Water was added. 1,000 ml pH (prepared with 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

For each sample thus formed with a dye image, the spectral absorption spectrum was measured and then 400 nm
A UV absorption filter manufactured by Fuji Photo Film Co., Ltd. that cuts the following light is attached, and a xenon tester (illuminance 20
Exposure for 10 days. The evaluation was based on the ratio of cyan color density = (650nm density / 45
The density of λ Max around 0 nm) × 100, and the effect of preventing discoloration was determined by the residual ratio of the dye concentration at the yellow initial density of 2.0 of each sample.

The measurement was carried out with a Shimadzu spectrophotometer and Fuji's own densitometer. The results obtained are shown in Table A.

[0125]

[Table 6]

[0126]

[Table 7]

[0127]

[Chemical 37]

[0128]

[Chemical 38]

From Table A, it was found that the compound represented by the general formula (A) of the present invention had little color turbidity and was effective in preventing photobleaching of a color image. Further, it is understood that the magnitudes of the color turbidity improving effect and the fastness improving effect are unexpected from known techniques. In addition, the effect is further enhanced by adding the compound represented by the general formula (B),
It turns out that each one is unexpectedly superior.

Example 2 Yellow dye-forming coupler Y-1, 16.1 of Example 1.
g to magenta dye-forming coupler M-1, 11.5 g,
11.1 g of high boiling organic solvent dibutyl phthalate
Sample 20 was prepared in the same manner as in Example 1 except that 5 g was used.
Made one. In the same manner as in Sample 201, when the above-mentioned emulsified dispersion was prepared, as shown in Table B, co-emulsification was performed with a combination of couplers and color image stabilizers A and B (addition amounts are shown in Table B). Samples were prepared by applying the same method as Sample 201, and Samples 202 to 223 were prepared. Each sample thus obtained was subjected to the same exposure, development treatment, and color fading test (however, xenon exposure time was 12 days) as in Example 1. The evaluation was performed by the residual ratio of the dye concentration at the initial concentrations of 0.5 and 1.0 of the sample. The results obtained are shown in Table B. The comparative compound is the same as in Example 1.

[0131]

[Table 8]

From these results, the compound of the present invention is effective for preventing photobleaching of magenta color image, particularly for preventing photobleaching in a low density region, and the result shows a fading preventing effect which is not expected from known compounds. It was

Example 3 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, followed by providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constituent layers to prepare A multilayer color photographic paper (Sample 001) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-3)
16.0 g, solvent (Solv-1) 25 g, solvent (S
Olv-2) was dissolved in 25 g of ethyl acetate and 180 cc of ethyl acetate, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, a 3: 7 mixture of 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 (silver molar ratio) 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the surface of grains based on silver chloride for each size emulsion). In this emulsion, blue-sensitive sensitizing dyes A and B shown below were added in an amount of 2.0 × 10 moles per mole of silver for large-sized emulsion A.
^-4 mol, and for small size emulsion A, 2.
5 × 10 ⁻⁴ mol is 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 following composition. The emulsion coating amount indicates the coating amount in terms of silver.

The 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 Cp are added to each layer.
the total amount d-15 respectively is 25.0 mg / m ² and 50 mg / m ²
Was added. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue sensitive emulsion layer]

[0136]

[Chemical Formula 39]

(2.0 × 10 ⁻⁴ mol for large size emulsion and 2.5 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) [Green-sensitive emulsion] layer〕

[0138]

[Chemical 40]

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

[0140]

[Chemical 41]

(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]

[0142]

[Chemical 42]

(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 In the above, the following compound F was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0144]

[Chemical 43]

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.

[0146]

[Chemical 44]

(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 of 0.39 μm (Ag mol The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride 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 4th layer (color mixing 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: 4 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 was 0.09 and 0.11, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride in each size emulsion). 20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image Stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-6) 0.22 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-) 10) 0.01 Solvent (Solv-1) 0.01 Sixth (Ultraviolet absorbing layer) Gelatin 0.55 Ultraviolet absorbing agent (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 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Color image stabilizer (Cpd-13) 0.01

[0151]

[Chemical formula 45]

[0152]

[Chemical formula 46]

[0153]

[Chemical 47]

[0154]

[Chemical 48]

[0155]

[Chemical 49]

[0156]

[Chemical 50]

[0157]

[Chemical 51]

Next, the first yellow dye-forming coupler ExY and color image stabilizers A and B (additional to color image stabilizers Cpd-1 and 3) were combined with Sample 001 as shown in Table C and combined. Other samples 002 to 010 were produced in the same manner as the sample 001 except that it was emulsified. The amount of coupler added is
The color image stabilizers A and B were replaced with ExY in an equimolar amount, and 20 mol% each was added to the yellow coupler.
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.

Processing Step Temperature Time Replenishment ^* Color Development 38.5 ° C. 45 seconds 73 ml Bleaching Fixing 35 ° C. 45 seconds 60 ml ^** Rinse (1) 35 ° C. 30 seconds-Rinse (2) 35 ° C. 30 seconds-Rinse (3) 35 ° C 30 seconds 360 ml Dry 80 ° C 60 seconds ^* Replenishment amount per 1 m ^{2 of} light-sensitive material ^{** In} addition to the above 60 ml, 120 ml per 1 m ^{2 of} tourist material was poured from the rinse (1). (Rinse was a three-tank countercurrent system from (3) to (1)) The composition of each processing liquid is as follows.

(Color Developer) Tank Solution Replenisher Water 800 ml 800 ml Ethylenediamine-tetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethano -Luamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3. 0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N -Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate. Monohydrate 5.0 g 11.5 g Water was added to 1000 ml 1000 ml pH (25 ° C / prepared with potassium hydroxide and sulfuric acid) 10.00 11.00

(Bleaching Fixing Solution) Tank Solution Replenishing Solution Water 600 ml 150 ml Ammonium thiosulfate (750 g / l) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water was added 1000 ml 1000 ml pH (prepared at 25 ° C./acetic acid and ammonia water) 5.8 5.6 (rinse solution) (tank solution and replenisher are the same) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Next, samples 001 to 010 were subjected to imagewise exposure using an optical wedge of three-color separation, and 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 C.

[0164]

[Table 9]

From the results shown in Table C, 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 4 In the sample 401 of Example 4 described in JP-A-4-359249, the couplers of the 15th, 16th and 17th layers were used as couplers (Y-3) or (Y-7). Replaced with
In addition, 25 mol% of the compound (A-2), (A-18), (A-24) of the present invention relative to the coupler of each layer,
(A-41) or (A-43) was co-emulsified and added to each layer, and otherwise the 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 5 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-3) or (Y-7) of the present invention. ), Or instead of Cpd-9 in each layer, the compounds (A-3), (A-16), (A-22) 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 (A-27) or (A-48) was replaced with Cpd-9 in an equimolar amount. 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.

[0168]

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

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 3, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction content]

In the formula, R _a1 and R _a11 are each a hydrogen atom or an aliphatic group which may have a substituent (preferably an alkyl group which may have a substituent and has 1 to 40 carbon atoms). There
For example, methyl, ethyl, i-propyl, cyclohexyl, benzyl, dodecyl, 2- (2,4-di-t-pentylphenoxy) ethyl, 2- (butoxycarbonyl)
Ethyl), an acyl group which may have a substituent (preferably an alkylcarbonyl group having a carbon number of 2 to 42 which may have a substituent, a carbon atom which may have a substituent of 3)
To 42 alkenyl carbonyl groups or C 7 to C 47 arylcarbonyl groups which may have a substituent, such as acetyl, pivaloyl, myristoyl,
Benzoyl, 4-t-butylbenzoyl, acryloyl, methacryloyl), an aliphatic or arylsulfonyl group which may have a substituent (preferably an alkanesulfonyl group having 1 to 40 carbon atoms which may have a substituent). Alternatively, it represents an arylsulfonyl group having 6 to 46 carbon atoms which may have a substituent and represents, for example, butanesulfonyl, hexyloxyethanesulfonyl, benzenesulfonyl, 4-dodecyloxybenzenesulfonyl).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

The preferred groups in the present invention will be described. In the general formula (A), in terms of the effect of the present invention, R _a1
Is preferably a hydrogen atom or an aliphatic group, and more preferably a hydrogen atom. R _a2 is a hydrogen atom,
It is preferably an aliphatic group or an acylamino group, more preferably an aliphatic group, and most preferably an alkyl group. R _a3 and R _a4 are preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, and particularly preferably a case where at least one of R _a3 and R _a4 is a hydrogen atom. R
_a5 is preferably an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group and a carbamoyl group, more preferably an aliphatic group, an aryl group and an acyl group, particularly preferably an alkyl group, an alkenyl group and an alkenylcarbonyl group. , Alkyl groups and alkenyl groups are most preferred. X _a is preferably an oxygen atom. R
_a2 is preferably substituted at least in the ortho or para position of -OR _a1 , and more preferably in the ortho and para positions.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

Synthesis of Intermediate (3) 30 g of Intermediate (1) was dissolved in 60 ml of tetrahydrofuran and 30 ml of isopropyl alcohol, and 6.3 g of sodium borohydride was added over 30 minutes with stirring at 20 to 25 ° C. After that, the temperature was raised to 30 to 40 ° C., and the mixture was stirred for 2 hours.
And extracted with 200 ml of ethyl acetate. The ethyl acetate layer was washed twice with 250 ml of saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure to obtain an intermediate (2).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction content]

Paracresol 50 g acetic acid 20 ml
Was added and dissolved, and concentrated sulfuric acid 0.9 with stirring at 20 to 25 ° C.
ml was added dropwise. The internal temperature was raised to 40 ° C. with dropping.
After stirring at 40 ° C. for 30 minutes, 200 ml of ethyl acetate was added and dissolved. The ethyl acetate layer was washed 3 times with 250 ml of saturated saline and the solvent was distilled off under reduced pressure to obtain an amorphous solid. This was crystallized with 100 ml of n-hexane and recrystallized with 100 ml of n-hexane to obtain an intermediate (3). Melting point 163-165 ° C
Yield 32g Yield 70.3%

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0049

[Correction method] Change

[Correction content]

Synthesis of A-43 15 g of intermediate (4) was dissolved in 100 ml of methanol and stirred at 40 to 45 ° C. Add 5 ml of concentrated sulfuric acid to this.
The solution was added dropwise over 1 minute and the mixture was further stirred for 5 hours. The reaction solution is cold water 2
It was poured into 50 ml and extracted with 250 ml of ethyl acetate. The ethyl acetate layer was washed twice with 250 ml of saturated saline and dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain an amorphous solid. The obtained oily substance was crystallized with 30 ml of methanol to obtain white crystals.
Melting point 109-111 ° C. Yield 13.0 g Yield 79.9
% Other compounds can be similarly synthesized.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction content]

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. Is substantially free of silver iodide and has a silver chloride content of 90 mol% or more and 100 mol% or less, more preferably 95% or more and 100 mol% or less, and particularly 98% or more and 100 mol% or less, or pure chlorination. The use of silver emulsions is preferred. Further, in the light-sensitive material according to the present invention, for the purpose of improving the sharpness of an image, a hydrophilic colloid layer is provided with a dye which can be decolorized by a treatment (described in EP No. 0,337,490A2, pages 27 to 76). Among them, oxonol-based dyes) are used in the light-sensitive material at 680 nm.
In order to have an optical reflection density of 0.70 or more, or titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane) in the water resistant resin layer of the support. It is preferable to contain 12% by weight or more (more preferably 14% by weight or more).

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0127

[Correction method] Change

[Correction content]

[0127]

[Chemical 37]

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains at least one compound represented by the following general formula (A). [Chemical 1] (In the formula, R _a1 represents a hydrogen atom, an aliphatic group, an acyl group, or an aliphatic or arylsulfonyl group. R _a2 represents a hydrogen atom or a substituent. R _a3 and R _a4 are the same. And R _a5 represents an aliphatic group, an aryl group, an acyl group, an aliphatic or aryloxycarbonyl group, a carbamoyl group, an aliphatic group or an aliphatic group or an aliphatic group or an aliphatic group or an aryl group. Represents an arylsulfonyl group or a sulfamoyl group, X _a represents an oxygen atom or a sulfur atom, m represents an integer of 1 to 4, and when m is 2 or more, a plurality of R _a2 are the same. May be different from each other, and when m is 2 or more and a plurality of R _a2 are in the ortho positions, R _a2 may be bonded to each other, provided that R _a1
And R _a5 do not bind to each other. ) 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (AI). [Chemical 2] (In the formula, R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and X _a are
The same as defined in the general formula (A), R _a11 , R
_a21 , R _a31 , R _a41 , R _a51 and X _a1 are the same as defined for R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and X _a , respectively. Z _a is an oxygen atom, a sulfur atom or −
C (R _a6 ) (R _a7 )-, p and q each represent an integer of 1 to 3. R _a6 and R _a7 may be the same or different and each represents a hydrogen atom, an aliphatic group or an aryl group. When p or q is 2 or more, a plurality of R _a2 or R _a21 may be the same or different. a plurality of R _a2 or R _{a21 in} which p or q is 2 or more
May be bound to each other when they are ortho to each other. However, R _a1 and R _a5 and R _a11 and R _a51 do not bond to each other. ) 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (A-II). [Chemical 3] (Wherein, R _a32, R _a52, respectively, .R _a22 to R _a23 have the same meanings as R _a3, R _a5 in the general formula (A) may be the same or different, respectively, the general formula ( A)
_{Has the} same meaning as R _{a2 in} . ) 4. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (A) is a compound represented by the following general formula (A-III). [Chemical 4] (In the formula, R _a11 has the same _{meaning as} R _a1 defined in the general formula (A). R _a32 and R _a33 may be the same or different, and are respectively R _a3 and R _a3 in the general formula (A). R _a52 and R _a53 may be the same or different and each has the same _{meaning as} R _a5 in formula (A).
R _a22 and R _a24 may be the same or different and each has the same _{meaning as} R _a2 in formula (A). R _a6
And R _a7 may be the same or different, and
Represents a hydrogen atom, an aliphatic group or an aryl group. However, R
_a11 and R _a53 do not bind to each other. ) 5. A compound represented by the following general formula (B) is further used in the same layer.
Alternatively, the silver halide color photographic light-sensitive material described in 4 above. [Chemical 5] (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 aliphatic or arylacyl group, an aliphatic or arylacylamino group, an aliphatic or aryl group. An oxycarbonyl group,
A halogen atom, an aliphatic or arylsulfonyl group,
A carbamoyl group, a sulfamoyl group or -X _b '-R
represents _{b1 '} . _Xb and _{Xb '} are -O- and-, respectively.
Represents S- or -N (R _b7 )-. -X _b -R _b1, R
_b2 , _Rb3 , _Rb4 , _Rb5 and _Rb6 may be bonded to each other at the ortho positions to form a 5- to 8-membered ring.
_b1 and R _b7 or R _{b1 ′} and R _b7 are bonded to each other,
A 7-membered ring may be formed. R _{b1 ′} and R _b7 have the same _meaning as R _b1 . However, at least one of R _{b2 to} R _{b6 is-}
A X _{b '-R b1'.} )