JP2673059B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material in which a dye image obtained by development processing is prevented from fading or discoloration. It is about materials.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material generally has silver halide emulsion layers sensitive to three primary colors of red, green and blue, and three types of color forming agents (couplers) in each emulsion layer are used for each layer. The color image is reproduced by a method of developing a color in a relationship between the color and the complementary color, which is felt by the so-called color reduction method. The color image obtained by photographic processing of the silver halide color photographic light-sensitive material is composed of an azomethine dye or an indoaniline dye formed by a reaction between an oxide of an aromatic primary amine color developing agent and a coupler. General.

However, the color photographic light-sensitive material having such an excellent system has become insufficient to meet the customer's demand for high quality. Among them, the color-forming dye obtained from the yellow dye-forming coupler still 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 magenta or cyan, many yellow couplers are used. Second, it is not necessarily a satisfactory hue to faithfully reproduce the color of the subject. Third, the coloring dyes and uncolored couplers are stable against light and heat and humidity. However, if it is exposed to sunlight for a long period of time or stored under high temperature and high humidity, it may cause fading or discoloration of the dye image and coloring of the white background, resulting in deterioration of image quality.

In order to solve these problems, attempts have been made to improve color development by improving couplers or adding coexisting substances such as specific phenol compounds and sulfonamide compounds, but these have been insufficient.

On the other hand, it is known to use an anti-fading agent or an ultraviolet absorber as a method for improving the fastness of an image. Of these, examples of anti-fading agents include hydroquinones, hindered phenols, catechols, gallic acid esters, aminophenols, hindered amines, chromanols, indanes, and silylated phenolic hydroxyl groups of each of these compounds. It is known to add etherified or alkylated ethers or esters, and metal complexes.

However, these compounds have little effect on increasing the extinction coefficient of the resulting yellow dye. Moreover, even though it has an effect on the magenta dye, it is not enough on the yellow dye, and changes the hue, causes fog, causes poor dispersion, or produces fine crystals after emulsion coating. There are also things.

For example, JP-A-2-262654 and 2-
No. 181145, Japanese Patent Application No. 2-35681, Japanese Unexamined Patent Publication No.
150841, 2-181753 and JP-A-2
No. -148034 describes applying an amine derivative or a hydrazine derivative to fasten a dye image obtained from a yellow dye-forming coupler. Also,
JP-A-62-239149 proposes to use an amine derivative having a specific structure in combination with another compound having a specific structure.

The combination of these compounds with the conventionally known yellow dye-forming coupler is insufficient in photographic properties, image fastness and the like as described above.

In this sense, the coupler has improved color-developing characteristics and photographic characteristics and has no adverse effect on them.
A technology for suppressing fading and discoloration of images has been desired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which does not discolor a color image for a long period of time and has a high storability.

Another object of the present invention is to have a sufficient effect for preventing fading or discoloration of a yellow image without changing the hue, inhibiting coupler color development, and causing fog, and microcrystals after coating. Contains an anti-fading agent that does not cause
It is to provide a novel silver halide color photographic light-sensitive material.

Another object of the present invention is that it has excellent solubility in high-boiling point organic solvents, does not produce fine crystals before and after coating, and does not adversely affect other photographic additives. An object is to provide a silver halide color photographic light-sensitive material containing an anti-fading agent.

Another object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color developability and photographic characteristics, has a strong yellow color image, and has little coloring in unexposed areas.

[0014]

As a result of various studies by the present inventors, at least one acylacetamide type yellow dye-forming coupler having an acyl group represented by the following general formula (I): General formulas (a-I), (a-II), (a-III), and (a-I) shown in Chemical formulas 8 to 12
It was found that the object of the present invention can be achieved by containing at least one selected from the compounds represented by V) and (aV).

[0015]

Embedded image In the formula, R ¹ represents a monovalent group, and Q is 3 to 5 together with C.
Represents a non-metal atomic group necessary for forming a 3-membered 5-membered heterocyclic ring having at least one hetero atom selected from N, S, O and P in the ring. However, R ¹ is not a hydrogen atom and does not bond with Q to form a ring.

[0016]

Embedded image In the formula, _Ra1 is -C (O) _-Ra21 , -S (O) _n3- R.
_a21 , -C (O) OR _a21 , -P (O) (R _a22 ) (R
_a23 ), -C (O) N ( _Ra21 ) ( _Ra24 ) and -S.
(O) _n4 N (R _a21 ) (R _a24 ) is represented. Z _a1 and Z _{a2, which} may be the same or different, each represents a divalent linking group bonding to the nitrogen atom and the carbon atom,
X _a1 is -O -, - S (O) n5 -, - N (R a25) - and _{-C (R a26) (R a27} ) - represent.

R _a21 represents an aliphatic group, an aromatic group or a heterocyclic group, R _a22 and R _a23 may be the same or different, and each of them may be an aliphatic group, an aromatic group or an aliphatic oxy group. , An aromatic oxy group, and R _a24 represents a hydrogen atom, an aliphatic group, or an aromatic group. R _a25 has the same _{meaning as an} aliphatic group and R _a1 , and R _a26 and R _a27 may be the same or different and each _represents a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aromatic oxy group, or a fat. Represents a group acyloxy group or an aromatic acyloxy group. n3
And n4 represents 1 or 2, and n5 represents 0, 1 or 2. R _a22 and R _a23 , R _a21 and R _a24 and R
_a26 and _Ra27 may combine with each other to form a 5- to 8-membered ring.

However, the nitrogen-containing heterocycle represented by Z _a1 , Z _a2 , X _a1 and a nitrogen atom is a 5- to 8-membered ring, and when a piperidine ring is formed, the carbon atom bonded to the nitrogen atom Is -C (O) _-or -CH (R _a28 )-. Here, R _a28 represents an aliphatic group or an aromatic group.
R _a1 may form a dimer or higher multimer.

[0019]

Embedded image In the formula, X _a2 and X _a3 may be the same or different, and are —N (R _a36 ) (R _a32 ), —C (O).
N (R _a31 ) (R _a32 ), —S (O) _n6 N (R _a31 ).
(R _a32 ) or -P (O) (R _a33 ) N (R _a31 ).
_Represents (R _a32 ). Z _a3 represents a mere bond or a divalent aliphatic group having 7 or less atoms contributing to the bond distance between X _a2 and X _a3 . n6 represents 1 or 2.

R _a36 is --C (O) R _a34 , --S (O) _n7.
Represent R _a34 and _{-P (O) (R a34)} (R a35).

R _a31 is --C (O) R _a34 , --S (O) _{n7.
R a34, -P (O) (} R a34) (R a35), represents an aromatic group and an aliphatic group. Here, R _a34 represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group or an aromatic amino group, and R _a35 represents an aliphatic group,
Represents an aromatic group, an aliphatic oxy group and an aromatic oxy group. n7 represents 1 or 2.

R _a32 is a hydrogen atom, a heterocyclic group or R _a31
Represents a group defined by.

R _a33 represents an aliphatic group, an aromatic group, an aliphatic oxy group or an aromatic oxy group. When Z _a3 is a single bond, R _a31 or R _a32 may form a dimer or higher multimer. The total number of carbon atoms of X _a2 and X _a3 is 6 or more.

R _a36 and R _a32 , and R _a31 and R _a32 may be bonded to each other to form a 5- to 8-membered ring.
It does not form a 6,6-tetramethylpiperidine ring.

Further, X _a2 and X _a3 are simultaneously -C (O).
When N (R _a31 ) (R _a32 ), Z _a3 cannot be methylene or monosubstituted methylene.

[0026]

Embedded image In the formula, R _a2 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —C (O) R _a41 , —S (O) _n8 R _a41 or —P.
(O) (R _a41 ) (R _a42 ) and R _a3 is -C.
(O) R _a41 , -S (O) _n8 R _a41 and -P (O)
(R _a41) represent (R _a42). R _a4 represents a hydrogen atom, an aliphatic group, an aromatic group, -C (O) R _a43 and -S (O) _{n9
Represents} R _a43 . Z _a4 represents -O- or -S-.

R _a41 represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group or an aromatic amino group, and R _a42 represents an aliphatic group, an aromatic group or an aliphatic oxy group. Represents a group and an aromatic oxy group. n8 represents 1 or 2.

R _a43 represents an aliphatic group, an aromatic group, an aliphatic amino group or an aromatic amino group, and n9 is 1 or 2
Represents

The total number of carbon atoms of R _a2 , R _a3 and R _a4 is 8
As described above, R _a2 , R _a3 or R _a4 may form a dimer or higher multimer.

R _a2 and R _a3 may combine with each other to form a 5- to 8-membered ring, but they do not form a 2,2,6,6-tetramethylpiperidine ring. )

[0031]

Embedded image In the formula, R _a5 is —C (O) R _a51 , —S (O) _n10.
R _a51 , —P (O) (R _a51 ) (R _a52 ), and R _a6 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a group defined by R _a5 . R _a7 represents a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a nitro group, a cyano group, -C _{(O) R a53} and -S _{(O) n11} R
represents _a53 . n1 represents an integer of 1 to 3, n2 represents an integer of 0 and 1 to 4, and n1 + n2 is an integer of 6 or less. When n1 and n2 are 2 or more, a plurality of -N
(R _a5 ) (R _a6 ), and R _a7 may be the same or different.
You may stay .

R _a51 and R _a53 represent an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group and an aromatic amino group, and R _a52 represents an aliphatic group, an aromatic group, Represents an aliphatic oxy group and an aromatic oxy group. n10 and n11 represent 1 or 2.

R _a5 and R _a6 may be bonded to each other to form a 5- to 8-membered ring. When n2 is 2 or more, R _a7 may be bonded to each other to form a 5- to 8-membered ring. , R _a5 or R _a7 may form a dimer or higher multimer.

[0034]

Embedded image In the formula, R _a8 and R _a9 are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —C (O) R _a61 , —S (O) _n12 R
_a61, represents _{-P (O) (R a61)} (R a62), Z a5
Represents a group of non-metal atoms necessary to form a 5- to 8-membered heterocycle with two nitrogen atoms. However, the total number of carbon atoms of R _a8 and R _a9 is 6 or more.

R _a61 represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group or an aromatic amino group, and R _a62 represents an aliphatic group, an aromatic group or an aliphatic oxy group. Represents a group and an aromatic oxy group.

R _a8 or R _a9 may form a dimer or higher multimer. n12 represents 1 or 2.

The aliphatic mentioned in the present invention may be linear, branched or cyclic and may be saturated or unsaturated, for example, alkyl, alkenyl, alkynyl, cycloalkyl,
Or cycloalkenyl, which may further have a substituent. The aromatic described in the present invention represents aryl, which may further have a substituent, and the heterocyclic ring has a hetero atom in the ring, and includes those which are aromatic. It may have a substituent.

The present invention will be described in more detail below.

The acylacetamide type yellow coupler of the present invention is preferably represented by the general formula (Y
It is represented by Y).

[0040]

Embedded image In the formula (YY), R ₁ is a monovalent substituent except hydrogen,
Q is a 3- to 5-membered hydrocarbon ring together with C or at least 1
Number of N, S, O, a non-metallic atomic group necessary to form a 3-5 membered heterocyclic ring containing a heteroatom selected from P in the ring, R ₂ is a hydrogen atom, a halogen atom (F , Cl, Br,
I. The same applies to the description of the formula (YY) below. ), An alkoxy group, an aryloxy group, an alkyl group or an amino group,
R ₃ represents a substitutable group on the benzene ring, X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidation product of an aromatic primary amine developing agent (hereinafter referred to as leaving group), k
Represents an integer of 0 to 4, respectively. However, when k is plural, plural R ₃ may be the same or different.

Here, as examples of R ₃ , a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, Alkylsulfonyl group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halogen. There is a child.

When the substituent in formula (YY) is or contains an alkyl group, the alkyl group may be linear, branched or cyclic, unless otherwise specified. An alkyl group which may contain a saturated bond (for example, methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, dodecyl, hexadecyl, allyl). , 3-cyclohexenyl,
Oleyl, benzyl, trifluoromethyl, hydroxymethyl , methoxyethyl, ethoxycarbonylmethyl,
Phenoxyethyl).

When the substituent in formula (YY) is or contains an aryl group, the aryl group may be a monocyclic or condensed ring aryl group which may be substituted (eg, phenyl, unless otherwise specified). 1-naphthyl, p-
Tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl, pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4- Di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,4-dichlorophenyl).

Whether the substituent in the formula (YY) is a heterocyclic group,
Or, when containing a heterocyclic ring, unless otherwise specified, the heterocyclic group is a 3 to 8-membered substituted group containing at least one heteroatom selected from O, N, S, P, Se and Te in the ring. Optionally a monocyclic or condensed-ring heterocyclic group (for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1
-Imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide, 1
-Benzyl-2,4-imidazolidindione-3-yl).

The substituents preferably used in formula (YY) will be described below.

In the formula (YY), R ₁ is preferably a halogen atom, a cyano group, or a monovalent group (for example, alkyl group) having a total carbon number (hereinafter abbreviated as C number) 1 to 30 which may be substituted. Alkoxy) or C number 6 to 30
A monovalent group (eg, aryl, aryloxy) whose substituents include, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, a carbonamido group, a sulfonamide group, and an acyl group.

In the formula (YY), Q is preferably a C number of 3 to 5 which may be substituted with C in any of 3 to 5 members.
30 hydrocarbon rings or at least one N, S, O, P
Represents a group of non-metal atoms necessary to form a heterocycle having a C number of 2 to 30 containing a heteroatom selected from Further, the ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, oxetane ring, oxolane ring, 1,3-dioxolane ring, thietane ring, thiolane ring, pyrrolidine There is a ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group,
There are aryl groups, acyl groups, alkoxy groups, aryloxy groups, cyano groups, alkoxycarbonyl groups, alkylthio groups, and arylthio groups.

In the formula (YY), R ₂ is preferably a halogen atom, which may be substituted, and has a C number of 1 to 3.
An alkoxy group of 0, an aryloxy group having a C number of 6 to 30,
It represents an alkyl group having 1 to 30 carbon atoms or an amino group having 0 to 30 carbon atoms, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula (YY), R ₃ is preferably a halogen atom, any of which may be substituted, and has a C number of 1 to 30.
Alkyl group, C6-30 aryl group, C1-3
0 alkoxy group, C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C
A carbonamido group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, and 0 to C atoms
30 sulfamoyl group, C1-30 alkylsulfonyl group, C6-30 arylsulfonyl group, C1-30 ureido group, C0-30 sulfamoylamino group, C2-2 30 alkoxycarbonylamino group, C1-30 heterocyclic group, C1-30 acyl group, C1-30 alkylsulfonyloxy group, C6-30 arylsulfonyloxy group, Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group and an arylsulfonyl group. , An acyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonylamino group, Sulfamoyl group, a ureido group, a cyano group, a nitro group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the formula (YY), k preferably represents an integer of 1 or 2, and the substitution position of R ₃ is represented by the following formula 14
Groups shown in

[0051]

Embedded image The meta position or the para position with respect to is preferred.

In the formula (YY), X preferably represents a heterocyclic group bonded to the coupling active position with a nitrogen atom or an aryloxy group.

When X represents a heterocyclic group, X is preferably a 5- to 7-membered monocyclic or condensed-ring heterocyclic group which may be substituted, and examples thereof include succinimide, maleimide, Phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4
-Triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4
-Dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidine, 2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one , 2-pyrrolin-5-one, 2-imidazoline-5-
On, indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-
3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4
-Thiazolidine-4-one, and these heterocycles may be substituted. Examples of the substituent of these heterocycles include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a sulfo group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, amino group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl There is an amino group. When X represents an aryloxy group, X preferably has 6 carbon atoms.
It represents an aryloxy group of 30 to 30 and may be substituted with a group selected from the substituent group mentioned when X is a heterocycle. As the substituent of the aryloxy group, a halogen atom, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group,
A sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a cyano group is preferable.

Substituents particularly preferably used in formula (YY) will be described below.

R ₁ is particularly preferably a halogen atom,
It is an alkyl group and most preferably a methyl group. Q
Is particularly preferably a group of non-metal atoms forming a ring with 3 to 5 members of a ring formed with C, for example,-[CR
_{2] 2 -, - [CR} 2] 3 -, - [CR 2] 4 - are. Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of R and CR ₂ may be the same or different.

[0056] Q is most preferably with C to bind to form a 3-membered ring - [CR _{2] 2} - is.

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having 1 to 6 C atoms (eg, methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), an alkoxy group having 1 to 8 C atoms. (Eg methoxy, ethoxy, methoxyethoxy, butoxy), or C number 6
To 24 aryloxy groups (eg, phenoxy, p-tolyloxy, p-methoxyphenoxy), most preferably chlorine atom, methoxy group or trifluoromethyl group.

R ₃ is particularly preferably a halogen atom,
It is an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, most preferably an alkoxy group, an alkoxycarbonyl group, a carbonamido group or a sulfonamide group.

X is particularly preferably a group represented by the formula (YY1), (YY2) or (YY3) shown in Chemical formulas 15 to 17 below.

[0060]

Embedded image Z is -O-CR ₄ in formula _{(YY1) (R 5) -} , -
S-CR ₄ (R ₅ )-, -NR ₆ -CR ₄ (R ₅ )-,
_{-NR 6 -NR 7 -, - NR} 6 -C (O) -, - CR 4
_{(R 5) -CR 8 (R} 9) - or -CR ₁₀ = CR ₁₁ -
Represents

Here, R ₄ , R ₅ , R ₈ and R ₉ are hydrogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group or amino group. the stands, R ₆ and R ₇ are a hydrogen atom, an alkyl group,
Represents an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁ represent a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R
₄ and R ₈ may combine with each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula (YY1), particularly preferable ones are those in which Z is —O— in the formula (YY1).
_{CR 4 (R 5) -,} - NR 6 -CR 4 (R 5) - or -NR ₆ -NR ₇ - is a heterocyclic group which is. Expression (YY
The C number of the heterocyclic group represented by 1) is 2 to 30, preferably 4 to 20, and more preferably 5 to 16.

[0063]

Embedded image In formula (YY2), at least one of R ₁₂ and R ₁₃
One is a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an alkoxycarbonyl group,
A group selected from a carbonamido group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group or an acyl group,
The other may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ represents a group having the same meaning as R ₁₂ or R _13, and m represents an integer of 0 to 2. The C number of the aryloxy group represented by the formula (YY2) is 6 to 30, preferably 6 to 24, and more preferably 6 to 15.

[0064]

Embedded image In formula (YY3), W represents a non-metal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. Here, the ring represented by formula (YY3) may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group,
An aryl group, an amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula (YY3) is 2 to 30, preferably 2 to 24,
More preferably, it is 2-16.

X is most preferably a group represented by the formula (YY1).

The coupler represented by the formula (YY) includes a substituent R ₁ , Q, X or a group represented by the following chemical formula 18.

[0067]

Embedded image In, a dimer or a multimer having more than two valences may be bonded to each other to form a multimer. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

Specific examples of each substituent in the formula (YY) are shown below. (I) Examples of the group represented by the following chemical formula 19 formed by R ₁ and Q together with C are shown in the following chemical formulas 20 to 21.

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image (Ii) An example of R ₂ is shown in Chemical Formula 22 below.

[0072]

Embedded image (iii) Examples of R ₃ are shown below in Chemical formulas 23 to 24.

[0073]

Embedded image

[0074]

Embedded image (Iv) Examples of X are shown in Chemical formulas 25 to 29 below.

[0075]

Embedded image

[0076]

Embedded image

[0077]

Embedded image

[0078]

Embedded image

[0079]

Embedded image Specific examples of the yellow coupler represented by the formula (YY) are shown below.

[0080]

Embedded image

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image The yellow coupler of the present invention represented by the formula (YY) can be synthesized by the synthetic route shown in the following Chemical Formula 43.

[0093]

Embedded image Here, the compound a is, for example, J.I. Chem. Soc.
(C), 1968, 2548, J. Am. Chem. S
oc. , 1934, 56, 2710, Synthesi
s, 1971, 258, J. Org. Chem. , 19
78, 43, 1729, CA, 1960, 66, 185
33y.

Compound b is synthesized using thionyl chloride, oxalyl chloride or the like without solvent or in a solvent such as methylene chloride, chloroform, carbon tetrachloride, dichloroethane, toluene, N, N-dimethylformamide, N, N-dimethylacetamide. It is carried out by reacting in. The reaction temperature is usually -20C to 150C, preferably -10C to 80C.

The compound c is synthesized by converting ethyl acetoacetate into an anion using magnesium methoxide or the like and adding the compound b therein. The reaction uses no solvent or tetrahydrofuran, ethyl ether, etc.,
The reaction temperature is generally -20 ° C to 60 ° C, preferably -10 ° C.
-30 ° C. The compound d is synthesized by reacting the compound c with the base, for example, ammonia water, an aqueous NaHCO ₃ solution or an aqueous sodium hydroxide solution without solvent or in a solvent such as methanol, ethanol or acetonitrile. The reaction temperature is generally -20 ° C to 50 ° C, preferably -10 ° C to 30 ° C.

Compound e is synthesized by reacting compounds d and g in the absence of solvent. The reaction temperature is usually 100
To 150 ° C, preferably 100 to 120 ° C.
When X is not H, the leaving group X after chlorination or bromination;
Is introduced to synthesize compound f. Compound e is chloro-substituted with sulfuryl chloride, N-chlorosuccinimide or the like, or bromo-substituted with bromine or N-bromosuccinimide in a solvent such as dichloroethane, carbon tetrachloride, chloroform, methylene chloride or tetrahydrofuran. At this time, the reaction temperature is -20C to 70C, preferably -10C to 50C.

Next, the chloro-substituted product or the bromo-substituted product and the proton adduct of the leaving group, H-X, are combined with methylene chloride, chloroform, tetrahydrofuran, acetone, acetonitrile, dioxane, N-methylpyrrolidone, N, N'-dimethylimidazolidine. Reaction temperature in a solvent such as 2-one, N, N-dimethylformamide, N, N-dimethylacetamide, -20 ° C to 150 ° C, preferably -10 ° C
By reacting at 〜100 ° C., the coupler f of the present invention can be obtained. At this time, triethylamine, N
Bases such as -ethylmorpholine, tetramethylguanidine, potassium carbonate, sodium hydroxide, sodium hydrogen carbonate and the like may be used.

The synthesis examples of the coupler of the present invention are shown below. Synthesis Example 1 Synthesis of Exemplified Compound YY-25 Gotkis, D. et al. et al, J.A. Am. Chem.
Soc. 1-methylcyclopropanecarboxylic acid 25 synthesized by the method described in No. 1, 1934, 56, 2710.
g, 100 ml of methylene chloride and 1 ml of N, N-dimethylformamide, 38.1 g of oxalyl chloride was added dropwise at room temperature over 30 minutes. 2 at room temperature after dropping
After reacting for a period of time, methylene chloride and excess oxalyl chloride were removed under reduced pressure of an aspirator to obtain an oily substance of 1-methylcyclopropanecarbonyl chloride.

100 ml of methanol was added dropwise to a mixture of 6 g of magnesium and 2 ml of carbon tetrachloride at room temperature over 30 minutes and then heated under reflux for 2 hours, and then 32.6 g of ethyl 3-oxobutanoate was added over 30 minutes under reflux under heating. To do. After the dropwise addition, the mixture is heated under reflux for another 2 hours, and methanol is completely distilled off under reduced pressure of an aspirator. Tetrahydrofuran 1
00 ml was added to the reaction product to disperse, and 1-
Methylcyclopropane carbonyl chloride is added dropwise. After reacting for 30 minutes, the reaction solution was extracted with 300 ml of ethyl acetate and diluted sulfuric acid water, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 2- (1-methylcyclopropanecarbonyl) -3-oxobutane. Ethyl acid oil 5
5.3 g were obtained.

Ethyl 2- (1-methylcyclopropanecarbonyl) -3-oxobutanoate 55 g, ethanol 1
The 60 ml solution is stirred at room temperature and 60 ml of 30% aqueous ammonia is added dropwise thereto over a period of 10 minutes. After stirring for 1 hour, the mixture was extracted with 300 ml of ethyl acetate, diluted hydrochloric acid, neutralized, washed with water, the organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off to give an oily product of (1-methylcyclopropanecarbonyl) ethyl acetate. 43 g were obtained.

(1-methylcyclopropanecarbonyl)
34 g of ethyl acetate and N- (3-amino-4-chlorophenyl) -2- (2,4-di-t-pentylphenoxy)
44.5 g of butanamide is heated and refluxed at an internal temperature of 100 to 120 ° C. under reduced pressure of an aspirator. After reacting for 4 hours, the reaction solution was purified by column chromatography with a mixed solvent of n-hexane and ethyl acetate to obtain 49 g of Exemplified Compound YY-25 as a viscous oil. The structure of the compound is MS spectrum, NMR
Confirmed by spectrum and elemental analysis. Synthesis Example 2
Synthesis of Exemplified Compound YY-1 Exemplified Compound YY-25 2
2.8 g was dissolved in 300 ml of methylene chloride, and 5.4 g of sulfuryl chloride was added dropwise over 10 minutes under ice cooling. After reacting for 30 minutes, the reaction solution was washed well with water, dried over anhydrous sodium sulfate, and concentrated to obtain a chloride of Exemplified Compound YY-25. 1-
Exemplified Compound YY-2 previously synthesized in a solution of 18.7 g of benzyl-5-ethoxyhydantoin, 11.2 ml of triethylamine and 50 ml of N, N-dimethylformamide.
Chloride of 5 was added with 50 ml of N, N-dimethylformaldehyde.
What was melt | dissolved in is dripped at room temperature over 30 minutes.

After reaction at 40 ° C. for 4 hours, the reaction solution is extracted with ethyl acetate (300 ml), washed with water, washed with 2% triethylamine aqueous solution (300 ml), and then neutralized with diluted hydrochloric acid. After the organic layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the resulting oil was crystallized from a mixed solvent of n-hexane and ethyl acetate. The precipitated crystals were filtered, washed with a mixed solvent of n-hexane and ethyl acetate, and dried to give crystals of Exemplified Compound YY-1 (22.8 g).

The structure of the compound was confirmed by MS spectrum, NMR spectrum and elemental analysis. The melting point is 132
It was ~ 133 ° C.

The standard amount of the yellow dye-forming coupler represented by formula (I) used in the present invention is 0.001 to 1 mol per mol of silver halide in the same layer. It is preferably 0.01 to 0.5 mol.

The yellow dye-forming coupler represented by formula (I) used in the present invention may be used in combination with a conventionally known coupler.

Next, the compound represented by formula (a-I) will be described.

The divalent linking group represented by Z _a1 and Z _a2 represents, for example, methylene, ethylene, propylene or carbonyl. Examples of the aliphatic group include methyl, ethyl, propyl, t-butyl, i-butyl, 2-ethylhexyl,
It represents dodecyl, hexadecyl, dodecyloxyethyl, benzyl, cyclohexyl, allyl, cyclohexenyl, and is preferably substituted or unsubstituted, straight-chain or branched-chain alkyl. The aromatic group represents, for example, phenyl, naphthyl or 4-methoxyphenyl, preferably phenyl or substituted phenyl. The heterocyclic group represents, for example, 2-pyridyl or 4-pyridyl. The aliphatic oxy group represents, for example, methoxy, t-butoxy or dodecyloxy, preferably substituted or unsubstituted, straight chain or branched chain alkoxy. The aromatic oxy group represents, for example, phenoxy or p-chlorophenoxy, preferably phenoxy or substituted phenoxy. The aliphatic acyloxy group represents, for example, acetoxy, myristoyloxy or isobutyryloxy, and preferably represents a substituted or unsubstituted, linear or branched alkylacyloxy group. The aromatic acyloxy group represents, for example, benzoyloxy, p-chlorobenzoyloxy or naphthoyloxy, preferably benzoyloxy or substituted benzoyloxy.

R _a22 and R _a23 , R _a21 and R _a24 and R
_a26 and R _a27 may be bonded to each other to form a 5- to 8-membered ring (eg piperazine, morpholine, pyrrolidine). The nitrogen-containing heterocycle represented by Z _a1 , Z _a2 , X _a1 and a nitrogen atom represents, for example, piperazine, morpholine, thiomorpholine, pyrrolidine or homopiperazine, and preferably, in addition to the nitrogen atom, a ring-forming atom is present. Further, it is a compound containing one or more heteroatoms.

In view of the effect of the present invention, R _a1 is —C (O) R.
_{a21, -SO 2 R a21, -C} (O) N (R a21) (R
_a24) and _{-SO 2 N (R a21) (} R a24) are preferred.

The compound represented by the general formula (aI) of the present invention is preferably the compound represented by the general formula (a-
I ').

[0111]

Embedded image In the formula, R _a1 has the same meaning as defined in formula ( _aI ), and n21 represents an integer of 1 to 3.

Among the compounds represented by the general formula (aI ′) of the present invention, R _a1 is —C (O) from the viewpoint of the effect of the present invention.
R _a21 , -SO ₂ R _a21 , -C (O) N (R _a21 ) (R
_a24 ) and —SO ₂ N (R _a21 ) (R _a24 ), preferably —C (O) R _a21 and —SO ₂ R _a21.
Is most preferred. At this time, it is preferable that n21 is 2, and it is more preferable that R _{a21 be} a linear or branched chain, a substituted or unsubstituted alkyl group and a phenyl group or a substituted phenyl group, and the larger the number of carbon atoms of R _a21 , the more preferable. The carbon number of 10 or more is more preferable.

The compound represented by formula (a-I) used in the present invention is described in, for example, JP-A-61-73152,
61-72246, 61-189539, 6
No. 2-24255, No. 62-278550, No. 62-
297847, 62-297848, 63-4
It can be easily synthesized by synthesizing amines by the method described in each publication of 3146 and then acylating or sulfonylating them.

The general formula (a-II) will be described.

The divalent aliphatic group having 7 or less atoms contributing to the bond distance between X _a2 and X _a3 of Z _a3 is, for example, ethylene, pentamethylene, propenylene or propylene, preferably an alkylene group. Represent.

[0116] R _a31, and the R _a33, aliphatic groups referred to R _a34 and R _a35, for example methyl, ethyl, i- propyl, t- butyl, cyclohexyl, benzyl, dodecyl, cyclohexene, allyl, vinyl, dodecyloxycarbonyl Represents ethyl and butoxycarbonylethyl, preferably linear or branched, substituted or unsubstituted alkyl.

The aromatic group is, for example, phenyl, naphthyl, 4-acetaminophenyl or 4-dodecyloxyphenyl, preferably phenyl or substituted phenyl.

Examples of the aliphatic oxy group include methoxy, butoxy, 2-ethylhexyloxy, benzyloxy,
Represents hexadecyloxy and cyclohexyloxy,
Preferred is a straight chain or branched chain, substituted or unsubstituted alkoxy.

The aromatic oxy group is, for example, phenoxy,
It represents naphthoxy, 4-methoxyphenoxy or 4-chlorophenoxy, preferably phenoxy or substituted phenoxy.

The heterocyclic group is, for example, 2-pyridyl, 2-
Represents piperidyl and 4-pyridyl.

The aliphatic amino group represents, for example, dimethylamino, butylamino, dodecylamino or 2-ethylhexylamino, preferably linear or branched, substituted or unsubstituted alkylamino.

The aromatic amino group means, for example, N-phenylamino, N-phenyl-N-methylamino, N-phenyl-N-dodecylamino, N-4-chlorophenylamino, preferably substituted or unsubstituted. Is phenylamino.

R _a31 and R _a32 may be bonded to each other to form a 5- to 8-membered ring (for example, piperidine, piperazine, pyrimidine), but they must form a 2,2,6,6-tetramethylpiperidine ring. There is no.

X _a2 and X _a3 are simultaneously -C (O) N
In the case of (R _a31 ) (R _a32 ), when Z _a3 is methylene or a mono-substituted methylene, it causes color inhibition of the coexisting yellow dye-forming coupler. Therefore, X _a2 and X _a3 are not simultaneously —C (O) N (R _a31 ) (R _a32 ), and Z _a3 is not methylene or monosubstituted methylene.

Among the compounds represented by the general formula (a-II) of the present invention, the compounds of the general formulas (a-II ′) and (a-II ″) represented by the following chemical formulas 45 to 46 are shown in terms of the effect of the present invention. ) Is preferred.

[0126]

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[0127]

Embedded image In the formula, R _a31 , R _a32 and R _a36 are each represented by the general formula (a-II).
It is synonymous with the one defined in.

Among the compounds represented by formula (a-II ′) of the present invention, R _a36 is —C in view of the effects of the present invention.
More preferably, it is (O) R _a34 or —SO ₂ R _a34 , and R _a32 is a hydrogen atom, an aliphatic group, an aromatic group or —C (O) R _a34 .

Of the compounds represented by the general formula (a-II ″) of the present invention, R _a31 is an aliphatic group, an aromatic group, —C (O) R _a34 or —SO from the viewpoint of the effect of the present invention. ₂ R _a34
It is more preferable that R _a32 is a hydrogen atom, an aliphatic group or an aromatic group.

The compound represented by formula (a-II) used in the present invention is described in, for example, Shin Jikken Kagaku Koza 14-II, pp. 1134 to 1189 (1977), amidation by Maruzen, JP-A-2- 181145, J. Am. Che
m. Soc. 72, 2762 (1950), Org.
Synth. , II, 395 (1943), New Experimental Chemistry Course 14-3, 1573 (1978), JP-A-62-27.
0954, 63-43145, European Patent No. 25
It can be synthesized according to the method described in No. 5,722.

The general formula (a-III) will be described.

Examples of the aliphatic group include methyl, ethyl,
It represents i-propyl, t-butyl, dodecyl, benzyl, cyclohexyl, cyclohexenyl, allyl, vinyl, ethoxycarbonylethyl, methanesulfonylethyl, preferably linear or branched, substituted or unsubstituted alkyl.

The aromatic group is, for example, phenyl, 4-chlorophenyl, 4-methoxyphenyl or naphthyl, preferably phenyl or substituted phenyl.

The aliphatic oxy group is, for example, methoxy, butoxy, 2-ethylhexyloxy, benzyloxy,
Represents hexadecyloxy and cyclohexyloxy,
Preferred is a straight chain or branched chain, substituted or unsubstituted alkoxy.

The aromatic oxy group is, for example, phenoxy,
It represents naphthoxy, 4-methoxyphenoxy or 4-chlorophenoxy, preferably phenoxy or substituted phenoxy.

The aliphatic amino group represents, for example, dimethylamino, butylamino, dodecylamino or 2-ethylhexylamino, and is preferably linear or branched, substituted or unsubstituted alkylamino.

The aromatic amino group means, for example, N-phenylamino, N-phenyl-N-methylamino, N-phenyl-N-dodecylamino, N-4-chlorophenylamino, preferably substituted or unsubstituted. Is phenylamino.

R _a2 and R _a3 may be bonded to each other to form a 5- to 8-membered ring (eg piperidine, piperazine, pyrimidine), but a 2,2,6,6-tetramethylpiperidine ring is formed. There is nothing to do.

Among the compounds represented by formula (a-III) of the present invention, Z _a4 is preferably —O— from the viewpoint of the effects of the present invention.

The compound represented by the formula (a-III) of the present invention
Among the compounds, R in terms of the effects of the present invention _a2Is an alkyl group,
C (O) R_a41Or -SO_TwoR_a41And R_a3Is -C
(O)_a41Or -SO_TwoR_a41Preferred if
R_a2Is an alkyl group, -C (O) R_a41In case of
Preferred.

Among the compounds represented by formula (a-III) of the present invention, R _a4 is an alkyl group,
C (O) R _a43 or -SO ₂ R _a43 are preferred.

The compound represented by formula (a-III) used in the present invention is described in, for example, JP-A-63-85548,
New Experimental Chemistry Course Vol. 14, pp. 1585 to 1594 (19
(1977) can be synthesized by the method described in Maruzen or a method analogous thereto.

The general formula (a-IV) will be described.

The aliphatic group is, for example, methyl, ethyl, i
-Propyl, t-butyl, dodecyl, benzyl, cyclohexyl, cyclohexenyl, allyl, vinyl, ethoxycarbonylethyl, methanesulfonylethyl, preferably linear or branched, substituted or unsubstituted alkyl.

The aromatic group is, for example, phenyl, 4-chlorophenyl, 4-methoxyphenyl or naphthyl, preferably phenyl or substituted phenyl.

The aliphatic oxy group is, for example, methoxy, butoxy, 2-ethylhexyloxy, benzyloxy,
Represents hexadecyloxy and cyclohexyloxy,
Preferred is a straight chain or branched chain, substituted or unsubstituted alkoxy.

The aromatic oxy group is, for example, phenoxy,
It represents naphthoxy, 4-methoxyphenoxy or 4-chlorophenoxy, preferably phenoxy or substituted phenoxy.

The aliphatic amino group represents, for example, dimethylamino, butylamino, dodecylamino or 2-ethylhexylamino, and is preferably linear or branched, substituted or unsubstituted alkylamino.

The aromatic amino group is, for example, N-phenylamino, N-phenyl-N-methylamino, N-phenyl-N-dodecylamino or N-4-chlorophenylamino, preferably substituted or unsubstituted. Is phenylamino.

The heterocyclic group is, for example, 2-pyridyl, 2-
Represents piperidyl and 4-pyridyl. Examples of the 5- to 8-membered ring formed by combining R _a5 and R _a6 with each other include pyrrolidin-2-one and piperidin-2-one.

Of the compounds represented by formula (a-IV) of the present invention, it is preferable that n1 is 2 or 3 from the viewpoint of the effect of the present invention.

Among the compounds represented by formula (a-IV) of the present invention, R _a5 is —C (O) R in terms of the effects of the present invention.
It is preferably _a51 , and more preferably R _a6 is a hydrogen atom, an alkyl group or —C (O) R _a5 .

The compound represented by the general formula (a-IV) used in the present invention is described in, for example, JP-A-63-95444,
63-115866, Helv. Chem. Act
a. , Vol. 36, p. 75 (1953), New Experimental Chemistry Lecture Vol. 14, p. 1220 (1977) Maruzen or a method analogous thereto.

The general formula (aV) will be described.

The aliphatic group is, for example, methyl, ethyl, i
-Propyl, t-butyl, dodecyl, benzyl, cyclohexyl, cyclohexenyl, allyl, vinyl, ethoxycarbonylethyl, methanesulfonylethyl, preferably linear or branched, substituted or unsubstituted alkyl.

The aromatic group is, for example, phenyl, 4-chlorophenyl, 4-methoxyphenyl or naphthyl, preferably phenyl or substituted phenyl.

Examples of the aliphatic oxy group include methoxy, butoxy, 2-ethylhexyloxy, benzyloxy,
Represents hexadecyloxy and cyclohexyloxy,
Preferred is a straight chain or branched chain, substituted or unsubstituted alkoxy.

The aromatic oxy group is, for example, phenoxy,
It represents naphthoxy, 4-methoxyphenoxy or 4-chlorophenoxy, preferably phenoxy or substituted phenoxy.

The aliphatic amino group represents, for example, dimethylamino, butylamino, dodecylamino or 2-ethylhexylamino, and is preferably linear or branched, substituted or unsubstituted alkylamino.

The aromatic amino group is, for example, N-phenylamino, N-phenyl-N-methylamino, N-phenyl-N-dodecylamino or N-4-chlorophenylamino, preferably substituted or unsubstituted. Is phenylamino.

The heterocyclic group is, for example, 2-pyridyl, 2-
Represents piperidyl and 4-pyridyl.

5 formed with Z _a5 and the two nitrogen atoms
Examples of the 8-membered heterocycle include pyrazolidine and pyrazoline.

Of the compounds represented by the general formula (aV) of the present invention, from the viewpoint of the effect of the present invention, at least one of the nitrogen atoms is bonded to a group selected from —CO— and —SO ₂ —. Are preferred compounds.

Among the compounds represented by the general formula (aV) of the present invention, from the viewpoint of the effects of the present invention, the following chemical formulas 47 to 48 are shown.
Compounds represented by the general formulas (a-V ') and (a-V ") shown in are preferred.

[0165]

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[0166]

Embedded image In the formula, R _a8 has the same meaning as defined in formula ( _aV ), R _a63 represents —CO (R _a61 ), a straight chain or a branched chain,
It represents a substituted or unsubstituted alkyl group and a substituted or unsubstituted phenyl group, and R _a64 represents a substituted or unsubstituted phenyl group. n13 represents an integer of 0, 1 to 4, and n14 represents 0 or 1, 2. R _a61 has the same _{meaning as} defined in formula (a-V).

Among the compounds represented by the general formulas (aV ′) and ( _{aV ″} ), R _a8 is an alkyl group, —C (O) R _a61 or —SO _{2 from} the viewpoint of the effect of the present invention. R _a61 is preferable, an alkyl group or —C (O) R _a61 is more preferable, and an alkyl group is most preferable.

Of the compounds represented by the general formula (aV ′), n13 is preferably an integer of 0, 1 to 3 from the viewpoint of the effect of the present invention.

The compound represented by the general formula (aV) used in the present invention is, for example, New Experimental Chemistry Course No. 14-II.
Volume, 1134-1220 (Maruzen), Journal of Organic Chemistry (J. Org. Che
m. ), Vol. 21, p. 667 (1956), or according to the synthetic method of representative compounds shown below.

From the viewpoint of the effect of the present invention, the compounds used in combination with the yellow dye-forming coupler represented by the general formula (I) of the present invention are represented by the general formulas (a-I) and (a-I).
I), (a-IV) and (a-V) are preferable, and general formulas (a-I ′), (a-II ′), (a-II ″) and (a
-V ') is more preferable, and (a-I'), (a
-II ') and (a-V') are most preferred.

General formulas (a-I), (a-II) of the present invention,
The compounds represented by (a-III), (a-IV) and (a-V) may be used in combination with a known anti-fading agent,
In that case, the effect of preventing fading is further enhanced. Similarly, general formulas (a-I), (a-II), (a-III) and (a-IV)
Two or more compounds represented by and (aV) may be used in combination.

General formulas (a-I), (a-II) of the present invention,
The compounds of (a-III), (a-IV) and (a-V) are different depending on the kind of the coupler, but are 0. to the yellow dye-forming coupler represented by the general formula (I) of the present invention. It is suitable to use in the range of 5 to 300 mol%, preferably 1 to 200 mol%.

The compounds represented by the general formulas (aI) to (aV) of the present invention are preferably added to the layer containing the yellow dye-forming coupler represented by the general formula (I) of the present invention. . More preferably, it is represented by the general formula (I)
It is preferable to co-emulsify with a yellow dye-forming coupler and add it.
Good.

Next, the general formulas (a-I) and (a-
II), (a-III), (a-IV) and specific examples of the compounds represented by (a-V) are shown in the following Chemical Formulas 49 to 88.
The compounds used in the present invention are not limited by these.

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[0185]

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[0186]

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[0202]

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[0213]

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[0214]

Embedded image The compound and / or color coupler of the present invention can be introduced into the light-sensitive material by various known dispersion methods. Usually, it can be added by an oil-in-water dispersion method known as an oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or a gelatin aqueous solution may be added to the solution of the compound of the present invention and / or the color coupler containing a surfactant to form an oil-in-water dispersion with phase inversion. Further, the alkali-soluble compound and / or color coupler of the present invention can be dispersed by a so-called Fisher dispersion method. The low boiling point organic solvent may be removed from the compound of the present invention and / or the color coupler dispersion by a method such as distillation, washing with noodles or ultrafiltration, and then mixed with a photographic emulsion. As the dispersion medium of the compound and color coupler of the present invention, a high boiling point organic solvent having a dielectric constant (25 ° C.) of 2 to 20 and a refractive index (25 ° C.) of 1.5 to 1.7 and / or a water-insoluble polymer compound is used. Preferably. The compound of the present invention is preferably used by being coemulsified with a color coupler.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in, for example, US Pat. No. 2,322,027. Further, the steps of the latex dispersion method as one of the polymer dispersion methods, effects, and specific examples of the latex for impregnation are, for example, US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. No. and ibid. 2,54
No. 1,230, PCT International Publication No. WO
88/00723.

Examples of the high-boiling point organic solvent that can be used in the oil-in-water dispersion method described above include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) isophthalate, bis (1,1)
-Diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg diphenyl phosphate,
Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexylphenyl phosphonate), benzoates (for example, 2-
Ethylhexyl benzoate, 2,4-dichlorobenzoate, dodecyl benzoate, 2-ethylhexyl-
p-hydroxybenzoate), amides (for example,
N, N-diethyldodecaneamide, N, N-diethyllaurylamide), alcohols or phenols (eg isostearyl alcohol, 2,4-di-tert)
-Amylphenol), aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate, isostearyl lactate, trioctyl citrate). , Aniline derivatives (for example, N, N-dibutyl-2-butoxy-5-tert-
Octylaniline), chlorinated paraffins (paraffins having a chlorine content of 10% to 80%), trimesic acid esters (eg, tributyl trimesate), dodecylbenzene, and diisopropylnaphthalene. As an auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and about 160 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

The color light-sensitive material of the present invention may contain, for example, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative or an ascorbic acid derivative as an antifoggant.

Various anti-fading agents can be used in combination with the light-sensitive material of the present invention. Hindered phenols centering on hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols and bisphenols as organic anti-fading agents for cyan, magenta and / or yellow images , Gallic acid derivatives, methylenedioxybenzenes,
Representative examples include aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. Further, for example, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent include, for example, US Pat. Nos. 2,360,290 and 2,418,61.
No. 3, No. 2,700,453, No. 2,701,197
No. 2,728,659, 2,732,300
No. 2, ibid. 2,735,765, ibid. 3,982,944
No. 4,430,425; British Patent No. 1,363.
921, U.S. Pat. Nos. 2,710,801 and 2,8.
Hydroquinones described in US Pat. Nos. 3,432,300, 3,573,050, 3,574,627, 3,698,909, and 3,764; No. 337, 6-hydroxychromans, 5-hydroxychromans, spirochromans described in JP-A No. 52-152225; US Pat. No. 4,360,
589, Spiroindanes; US Pat. No. 2,7
35,765, British Patent 2,066,975, JP-A-59-10539, JP-B-57-19765, and the like; p-alkoxyphenols; US Pat.
700,455, 4,228,235, JP-A-5
2-72224, Japanese Patent Publication No. 52-6623 and the like; U.S. Pat. No. 3,457,07
Gallic acid derivatives described in US Pat. No. 4,332,332
Methylenedioxybenzenes described in 886; Aminophenols described in JP-B-56-21144; U.S. Pat. Nos. 3,336,135 and 4,268,593;
British Patent Nos. 1,326,889 and 1,354,31
No. 3, No. 1,410,846, Japanese Examined Patent Publication No. 51-1420
And JP-A-58-114036 and JP-A-59-53846.
And hindered amines described in JP-A-59-78344; U.S. Patent Nos. 4,050,938 and 4,241.
Examples thereof include metal complexes described in No. 155 and British Patent No. 2,027,731 (A). These compounds are usually used in an amount of 5 to 100 relative to the corresponding color coupler.
The object can be achieved by co-emulsifying the weight% with the coupler and adding it to the photosensitive layer.

In order to prevent the 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 to the cyan coloring layer.

As the ultraviolet absorber, a benzotriazole compound substituted with an aryl group (for example, those described in US Pat. No. 3,533,794) and a 4-thiazolidone compound (for example, US Pat. No. 3,314,794) are used. No. 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamic acid ester compounds (for example, US Pat.
705,805 and 3,707,395), butadiene compounds (US Pat. No. 4,045,22).
9) or a benzoxazole compound (for example, US Pat. Nos. 3,406,070 and 4,27).
Those described in No. 1,307) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer. Above all, a benzotriazole compound substituted with the above-mentioned aryl group is preferable.

To apply the present invention to multilayer silver halide color photographic light-sensitive materials, a blue-sensitive silver halide emulsion layer containing a yellow coupler and a green-sensitive silver halide emulsion layer containing a magenta coupler are provided on a support. Although at least one red-sensitive silver halide emulsion layer containing a cyan coupler and a cyan coupler can be applied in this order, the order may be different. Further, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength region and a color coupler which forms a dye having a complementary color with the light to be exposed, thereby performing color reduction by the subtractive color method. be able to. However, the photosensitive emulsion layer and the color hue of the color coupler may not have the above correspondence.

The compounds of the present invention can be applied to, for example, color papers, color reversal papers, direct positive color photographic materials, color negative films, color positive films and color reversal films. Above all, it is preferably applied to a color light-sensitive material having a reflective support (for example, color paper, color reversal paper) or a color light-sensitive material for forming a positive image (for example, direct positive color light-sensitive material, color positive film, color reversal film).

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 the processing method and processing addition applied for processing the light-sensitive material. Examples of the agent include patent publications shown in Tables 1 to 5 below, particularly European Patent EP 0,355,660A2.
Those described in Japanese Patent Application No. 1-107011 are preferably used.

[0225]

[Table 1]

[0226]

[Table 2]

[0227]

[Table 3]

[0228]

[Table 4]

[0229]

[Table 5] Further, as the cyan coupler, in addition to the diphenylimidazole-based cyan coupler described in JP-A-2-33144, a cyan coupler described in European Patent EP 0,333,185A2
-Hydroxypyridine cyan couplers (among others, couplers (42) listed as specific examples, 4-equivalent couplers obtained by imparting a chlorine leaving group to 2-equivalent couplers, and couplers (6) and (9) are particularly preferred) and JP-A-64-322
No. 60, a cyclic active methylene cyan coupler (among others, coupler examples 3, 8, and
34 is particularly preferred).

As the silver halide used in the present invention, for example, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide and silver iodobromide can be used, but especially for the purpose of rapid processing. Contains 90 mol% of silver chloride containing substantially no silver iodide
It is preferable to use a silver chlorobromide or silver chloride emulsion of 95% or more, especially 98% or more.

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer is used in order to improve the sharpness of an image and the like, as described in European Patent EP 0,337,490A2.
Dyes that can be decolorized by the treatment described on page 76 (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, or 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) of titanium oxide surface-treated with a dihydric or tetrahydric alcohol (eg, trimethylolethane).

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 EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, compound (F) and // which chemically bond with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable 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 the oxidant thereof with the coupler during storage after processing.

In order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-mold property as described in JP-A-63-271247. It is preferable to add an agent.

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. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.3 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 5 to 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. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In exposing, US Pat. No. 4,88
It is preferable to use the band stop filter described in U.S. Pat. This removes light mixing,
The color reproducibility is significantly improved.

The light-sensitive material according to the present invention is described in Research Disclosure No. 17643, pages 28-29, and ibid. Development can be carried out by a usual method described in the left column to the right column of page 615 of 18716. For example, a color developing process, a desilvering process, and a washing process are performed. In the desilvering process, instead of the bleaching process using a bleaching agent and the fixing process using a fixing solution, a bleach-fixing processing process using a bleach-fixing solution can be performed, or a bleaching process step, a fixing process step, The bleach-fixing steps may be combined in any order. A stabilizing step may be performed instead of the water washing step, or a stabilizing step may be performed after the water washing step. Further, a monobath processing step using a one-bath development bleach-fix processing solution in which color development, bleaching and fixing are performed in one bath can also be performed. In combination with these treatment steps, for example, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step, an adjusting step, and an intensifying step may be performed. An intermediate washing step may be optionally provided between the above steps. In these processes, a so-called activator process may be performed instead of the color development process.

[0239]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1 16.1 g of yellow coupler Y-1 was weighed, 16.1 g of high boiling organic solvent dibutyl phthalate was added, and 24 ml of ethyl acetate was further added to dissolve the solution. This solution was added with sodium dodecylbenzenesulfonate 1 This was emulsified and dispersed in 200 g of a 10 wt% gelatin aqueous solution containing 0.5 g.

The total amount of this emulsified dispersion was adjusted to a high silver chloride emulsion 24.
7 g (silver 70.0 g / kg emulsion, silver bromide content 0.5 mol%), and coated on a triacetate film base provided with an undercoat layer so that the coated silver amount was 1.73 g / m ^2. Sample 101 was prepared by providing a gelatin layer as a protective layer on the coating layer so that the dry film thickness was 1.0 μm. As a gelatin hardener, 1-oxy-
3,5-Dichloro-s-triazine sodium salt was used.

In the same manner as in Sample 101, a coupler and a color image stabilizer as shown in the following Table A (100 mol% relative to the coupler) were added when the above-mentioned emulsion dispersion was prepared.
Samples were prepared by co-emulsifying with the combination of No. 1, and applied in the same manner as Sample 101 to prepare Samples 102 to 156.

Each sample thus obtained was subjected to wedge exposure and then developed in the following processing steps.

[Processing Step] [Temperature] [Time] Color development 35 ° C. 45 seconds Bleach fixing 30-35 ° C. 45 seconds Rinse (1) 30-35 ° C. 20 seconds Rinse (2) 30-35 ° C. 20 seconds Rinse ( 3) 30 to 35 ° C. for 20 seconds Drying 70 to 80 ° C. for 60 seconds The composition of each treatment liquid is as follows. [Color developer] water 800ml ethylenediamine -N, N, N ', N ' - tetramethylene phosphonic acid 1.5g Potassium bromide 0.015g Triethanolamine 8.0g sodium chloride 1.4g potassium 25 g N-ethyl carbonate - N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N, N-bis (carboxymethyl) hydrazine 5.5 g Optical brightener (WHITEX 4B, manufactured by Sumitomo Chemical Co., Ltd.) 1 0.0 g Water was added 1000 ml pH (25 ° C) 10.05 [bleach-fixing solution] 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 Bromide Ammonium 0 g water was added to 1000 ml pH (25 ° C.) 6.0 [rinse solution] Ion-exchanged water (calcium and magnesium were each 3 ppm or less) In each sample of 101 to 156 in which the dye image was formed in this manner, 400 nm or less It was exposed to a xenon tester (illuminance: 200,000 lux) for 15 days with an ultraviolet absorption filter manufactured by Fuji Photo Film Co., Ltd., which cuts light. The yellow density (stain) of the unexposed area of each sample was measured and the density residual rate at the initial density of 2.0 was determined.

The measurement was carried out with a Fuji Denshi Densitometer.

The obtained results are shown in Table A shown in Tables 6 to 7 below.

[0247]

[Table 6]

[0248]

[Table 7] The structural formula of the yellow coupler Y-1 is shown below.
The structural formulas of the comparative couplers a to c are shown below and the structural formula of the comparative compound (a) is shown below.

[0249]

Embedded image

[0250]

Embedded image

[0251]

Embedded image From these results, the general formulas (a-I), (a-II) of the present invention,
The compounds represented by (a-III), (a-IV) and (a-V) have a color image fastness when used in combination with the yellow dye-forming coupler represented by the general formula (I) of the present invention. Significant improvements, the magnitude of which is unexpected from the prior art.

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 prepare a A multilayer color photographic paper having the layer structure shown was produced. The coating solution was prepared as follows.

Preparation of fifth layer coating solution Cyan coupler (ExC) 32.0 g, color image stabilizer (C
pd-2) 3.0 g, color image stabilizer (Cpd-4) 2.0
g, color image stabilizer (Cpd-6) 18.0 g, color image stabilizer (Cpd-7) 40.0 g and color image stabilizer (Cpd-
8) To 5.0 g, 50.0 cc of ethyl acetate and solvent (S
olv-6) was added and dissolved, and this solution was added to 500 cc of a 20% aqueous gelatin solution containing 8 cc of sodium dodecylbenzenesulfonate, and then emulsified and dispersed with an ultrasonic homogenizer to prepare an emulsified dispersion. on the other hand,
Silver chlorobromide emulsion (cubic, 1: 4 of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm)
Mixture (Ag mole ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and AgBr was used for each size emulsion.
0.6 mol% was locally contained in a part of the particle surface). This emulsion contained the following red-sensitive sensitizing dye E per mol of silver at a concentration of 0.9 × 10 ⁻⁴ per mol of silver emulsion.
Moles, and 1.1 × 10 ^-4 moles for small size emulsions. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and the red-sensitive silver chlorobromide emulsion were mixed and dissolved to prepare a fifth layer coating solution having the following composition.

Coating solutions for the first to fourth layers, the sixth layer and the seventh layer were prepared in the same manner as the fifth layer coating solution. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In addition, the preservatives Cpd-10 and Cpd were added to each layer.
The total amount of -11 is 25.0 mg / m ² and 50.0 mg, respectively.
/ M ² .

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. [Blue Sensitive Emulsion Layer] Sensitizing Dye A shown in Chemical Formula 92 below.

[0257]

Embedded image And sensitizing dye B shown in the following chemical formula 93

[0258]

Embedded image (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] Sensitizing dye C shown in Chemical formula 94

[0259]

Embedded image (Per mol of silver halide, 4.0 × 10 ^-4 mol for large size emulsion, 5.6 × for small size emulsion)
10 ⁻⁴ mol) and a sensitizing dye D represented by Chemical Formula 95 below.

[0260]

Embedded image (Per mol of silver halide, for the 7.0 × 10 ^-5 mol to the small size emulsion to the large size emulsion 1.
0 × 10 ⁻⁵ mol) [Red-sensitive emulsion layer] Sensitizing dye E shown in Chemical formula 96 below.

[0261]

Embedded image (0.9 × 10 ⁻⁴ mol for a large-sized emulsion, and 1.
1 × 10 ⁻⁴ mol) Further, the compound represented by the following Chemical formula 97 was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0262]

Embedded image Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 8.5 × 10 ^-5 mol per mol of silver halide, respectively. 7.7 x 10 ^-4 mol, 2.5 x
10 ⁻⁴ mol was added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol, respectively, per mol of silver halide.

In order to prevent irradiation, the dye shown in the following chemical formula 98 is added to the emulsion layer (the amount in parentheses represents the coating amount).
Was added.

[0265]

Embedded image (Layer constitution) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [Polyethylene on the first layer side contains white pigment (TiO ₂ ) and bluish dye (ultraviolet)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average grain size 0 3: 8 mixture of large size emulsion of 0.88 μm and small size of 0.70 μm (silver molar ratio) Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, and bromide for each size emulsion (Silver 0.3 mol% is locally contained in a part of the particle surface) 0.30 Gelatin 1.86 Yellow coupler (EXY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0.06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-5) 0.08 Solvent (Solv) -1) 0.16 Solvent (Solv -4) 0.08 Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion having average grain size 0.55 μm and small size emulsion 0.39 μm (Ag) (Mole ratio). Coefficients of variation of particle size distribution are 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is locally contained in a part of particle surface in each size emulsion) 0.12 Gelatin 1.24 Magenta coupler (EXM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd) -9) 0.02 Solvent (Solv-2) 0.40 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (red-sensitive emulsion ) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.58 μm and small size emulsion of 0.45 μm (Ag mole ratio). Coefficient of variation of grain size distribution is 0.09 And 0.11, and AgBr 0.6 mol% was locally contained in a part of the grain surface in each size emulsion. 0.23 Gelatin 1.34 Cyan coupler (EXC) 0.32 Color image stabilizer (Cpd-2) ) 0.03 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-6) 0.18 color image stabilizer (Cpd-7) 0.40 color image stabilizer (Cpd-8) 0 .05 solvent (Solv-6) 0.14 sixth layer (ultraviolet absorbing layer) gelatin 0.53 ultraviolet absorber (UV-1) 0.16 color mixing inhibitor (Cpd-5) 0.02 solvent (Solv-5) ) 0.08 7th layer (protective layer) Gelatin 1. 3 Acrylic modified copolymer of polyvinyl alcohol (modification degree 17%) 0.17 shows the structure of each compound was used on liquid paraffin 0.03 by Formula 99 to reduction 107.

[0266]

Embedded image

[0267]

Embedded image

[0268]

Embedded image

[0269]

Embedded image

[0270]

Embedded image

[0271]

Embedded image

[0272]

Embedded image

[0273]

[Chemical formula 106]

[0274]

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 each sample, and gradation exposure of a three-color separation filter for sensitometry was performed. The exposure at this time is 2 seconds with an exposure time of 0.1 second.
The exposure was performed so that the exposure amount became 50 CMS.

The exposed samples were subjected to continuous processing (running test) using a paper processor using the solutions having the following processing steps and compositions until replenishment of twice the tank capacity for color development.

Treatment process Temperature Time Replenisher ^* Tank capacity (ml) (liter) Color development 35 ℃ 45 seconds 161 17 Bleach fixing 30-35 ℃ 45 seconds 215 17 Rinse (1) 30-35 ℃ 20 seconds -10 Rinse (2) 30-35 ° C 20 seconds -10 Rinse (3) 30-35 ° C 20 seconds 350 10 Dry 70-80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material Rinsing is from (3) to (2), A three-tank countercurrent system from (2) to (1) was adopted.

The composition of each processing solution is as follows. [Color developer] Tank solution Replenisher Water 800 ml 80 0 ml Ethylenediamine -N, N, N ', N ' - tetramethylene phosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g - 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 40 g 5.0 g N, N-di (sulfoethyl) hydroxylamine 1Na 4.0 g 5.0 g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Water was added. 1000 ml 1000 ml pH (25 ° C) 10. 05 10.45 [bleach-fixing solution] (tank solution and replenisher are the same) Water 400 ml Ammonium thiosulfate (70%) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water 1000 ml pH (25 ° C.) 6.0 [rinse solution] (same as tank solution and replenisher) ion-exchanged water (calcium and magnesium are 3 ppm or less for each) The sample thus obtained is designated as 1A, Layer yellow coupler and color image stabilizer (color image stabilizers Cpd-1, C
Other samples 2A to 22A were prepared in the same manner as sample 1A, except that the pd-7 was additionally added) and the mixture was co-emulsified as shown in Table B shown in Table 8 below. The addition amount was 50 mol% with respect to the yellow coupler.

A fading test was conducted on each sample thus formed with a dye image. To evaluate the effect of preventing fading, the yellow density residual rate at the initial density of 2.0 after 15 days of exposure with a xenon tester (illuminance: 200,000 Lux) was obtained. The results obtained are shown in Table B.

[0279]

[Table 8] As is clear from Table B, the sample of the present invention also exhibits an excellent preventing effect even in a multi-layered silver halide color photographic light-sensitive material, and the effect is remarkably superior to the conventionally known techniques and is expected. It was a fleeting thing.

Example 3 Sample 101 of Example 1 described in JP-A-2-854.
The yellow coupler of the blue-sensitive layer is a coupler having an acyl group represented by the general formula (I) of the present invention, YY-5, YY-
6, YY-13, YY-16, YY-17 or YY
-22 (addition amount is 40 mol% replaced), and the coupler and the general formulas (a-I), (a-II) of the present invention,
Compound (a-III), (a-IV) or (a-V), A-12, B-9, C-7, D-10 or E-
9 (the addition amount is 25 mol% with respect to the coupler) was co-emulsified and added, and a sample was prepared in the same manner as sample 101,
When exposed to light and developed, examined for photographic characteristics and subjected to a brown test, the sample of the present invention showed excellent photographic characteristics and an effect of preventing browning.

Example 4 In the color photographic light-sensitive material of Example 2 described in JP-A-1-158431, the yellow coupler in the blue sensitive layer was replaced by a coupler having an acyl group represented by formula (I) of the present invention. , YY-1, YY-3, YY-7 or YY-2
9 (addition amount was 40 mol% replaced), and the coupler and the general formulas (a-I), (a-II) and (a) of the present invention were changed.
-III), (a-IV) or (a-V) compound,
A-19, B-29, C-7, D-10 or E-9
(Amount of addition is 50 mol% with respect to the coupler) was added after co-emulsification, and other samples were prepared in the same manner, subjected to exposure and development processing, examined for photographic characteristics, and subjected to a brown test. The above sample showed excellent photographic characteristics and an effect of preventing browning.

[0282]

The yellow dye-forming coupler represented by the general formula (I) of the present invention, the general formula (a-I) of the present invention,
(A-II), (a-III), (a-IV) and (a-V)
The silver halide color photographic light-sensitive material in which the compound represented by the formula (1) is combined exhibits a higher fastness than the conventionally known combination of silver halide color photographic light-sensitive materials.

[107]

Claims (1)

(57) [Claims] 1. An acylacetamide type yellow dye-forming coupler having an acyl group represented by the following general formula (I) and at least one general formula (a-I) represented by the following general formulas 2 to 6. ), (A-II), (a-III),
A silver halide color photographic light-sensitive material comprising at least one selected from compounds represented by (a-IV) and (a-V). Embedded image (In the general formula (I), R ¹ represents a monovalent group,
Is a 3- to 5-membered hydrocarbon ring together with C or N, S, O,
It represents a group of non-metal atoms necessary for forming a 3- to 5-membered heterocycle having at least one heteroatom selected from P in the ring. However, R ¹ is not a hydrogen atom and does not bond with Q to form a ring. ) (In the general formula ( _aI ), R _a1 is —C (O) —R.
_a21 , -S (O) _n3 -R _a21 , -C (O) OR _a21 ,-
P (O) (R _a22 ) (R _a23 ), -C (O) N
(R _a21 ) (R _a24 ), and —S (O) _n4 N (R _a21 ).
_Represents (R _a24 ). Z _a1 and Z _{a2, which} may be the same or different, each represents a divalent linking group bonding to the nitrogen atom and a carbon atom, and X _a1 is —O— or —S.
_{(O) n5 -, - N} (R a25) - and -C (R _{a26)
Represents} (R _a27 )-. R _a21 represents an aliphatic group, an aromatic group or a heterocyclic group, R _a22 and R _a23 may be the same or different, and each of them may be an aliphatic group, an aromatic group, an aliphatic oxy group or an aromatic group. Represents an oxy group, R _a24
Represents a hydrogen atom, an aliphatic group and an aromatic group. R _a25
Is synonymous with an aliphatic group and R _a1 , R _a26 and R _a1
a27 may be the same or different, a hydrogen atom, an aliphatic group, an aliphatic oxy group, an aromatic oxy group,
It represents an aliphatic acyloxy group or an aromatic acyloxy group. n3 and n4 represent 1 or 2, and n5 represents 0, 1 or 2. R _a22 and R _a23 , R _a21 and R
_a24 and R _a26 and R _a27 may be bonded to each other to form a 5- to 8-membered ring. However, the nitrogen-containing heterocycle represented by Z _a1 , Z _a2 , X _a1 and a nitrogen atom is a 5- to 8-membered ring, and when a piperidine ring is formed, the carbon atom bonded to the nitrogen atom is -C. (O)-or -CH
(R _a28 ) −. Here, R _a28 represents an aliphatic group or an aromatic group. R _a1 may form a dimer or higher multimer. ) (In the general formula (a-II), X _a2 and X _a3 may be the same or different, and -N (R _a36 )
(R _a32 ), -C (O) N (R _a31 ) (R _a32 ), -S
(O) _n6N ( _Ra31 ) ( _Ra32 ) or -P (O) (R
_a33 ) N (R _a31 ) (R _a32 ) is represented. Z _a3 represents a mere bond or a divalent aliphatic group having 7 or less atoms contributing to the bond distance between X _a2 and X _a3 . n6 represents 1 or 2. R _a36 is —C (O) R _a34 , —S (O) _n7 R
_a34 and represent _{-P (O) (R a34)} (R a35).
R _a31 is _{-C (O) R a34, -S} (O) n7 R a34, -P
_{(O) (R a34) (} R a35), represents an aromatic group and an aliphatic group. Here, R _a34 represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group or an aromatic amino group, and R _a35 represents an aliphatic group, an aromatic group or an aliphatic oxy group. And an aromatic oxy group. n7 is 1
Or 2 is represented. R _a32 represents a hydrogen atom, a heterocyclic group or a group defined by R _a31 . R _a33 represents an aliphatic group, an aromatic group, an aliphatic oxy group or an aromatic oxy group. When Z _a3 is a single bond, R _a31 or R _a32 may form a dimer or higher multimer. The total number of carbon atoms of X _a2 and X _a3 is 6 or more. R _a36 and R _a32 , R _a31
And R _a32 may combine with each other to form a 5- to 8-membered ring, but they do not form a 2,2,6,6-tetramethylpiperidine ring. In addition, X _a2 and X _a3 are simultaneously -C
When it is (O) N (R _a31 ) (R _a32 ), Z _a3 cannot be methylene or monosubstituted methylene. ) [Chemical 4] (In the general formula (a-III), R _a2 is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —C (O) R _a41 or —S
(O) _n8 R _a41 and -P (O) (R _a41 ) (R _a42 ).
And R _a3 is —C (O) R _a41 , —S (O) _n8 R
_a41 and -P (O) ( _Ra41 ) ( _Ra42 ).
R _a4 is a hydrogen atom, an aliphatic group, an aromatic group, —C (O) R
represent _a43 and -S (O) _n9 R _a43. Z _a4 is -O-
Or represents -S-. R _a41 is an aliphatic group, an aromatic group,
It represents an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group and an aromatic amino group, and R _a42 represents an aliphatic group, an aromatic group, an aliphatic oxy group and an aromatic oxy group. n
8 represents 1 or 2. R _a43 represents an aliphatic group, an aromatic group, an aliphatic amino group or an aromatic amino group, and n
9 represents 1 or 2. The total number of carbon atoms of R _a2 , R _a3 and R _a4 is 8 or more, and R _a2 , R _a3 or R _a4 may form a dimer or higher multimer. R _a2 and R _a3 may combine with each other to form a 5- to 8-membered ring,
It does not form a 2,6,6-tetramethylpiperidine ring. ) (In the general formula (a-IV), _Ra5 is -C (O).
_Ra51 , -S (O) _{n10 Ra51} , -P (O) ( _Ra51 )
(R _a52 ), R _a6 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or a group defined by R _a5 . R
_a7 is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a nitro group, a cyano group, -C (O) R _a53 and -S (O).
_n11 represents _R53 . n1 represents an integer of 1 to 3, n
2 represents an integer of 0, 1 to 4, and n1 + n2 is an integer of 6 or less. R _a51 and R _a53 represent an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group and an aromatic amino group, and R _a52 represents an aliphatic group, an aromatic group, an aliphatic oxy group. Represents a group and an aromatic oxy group. n10 and n11 represent 1 or 2. R _a5
And R _a6 is bonded to each other, may form a 5- to 8-membered ring, n2 is when two or more bonded, if R _a7, may form a 5- to 8-membered ring, R _a5 or R _A7 may form a dimer or higher multimer. ) (In the general formula ( _aV ), R _a8 and R _a9 are a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —C (O)
R _a61 , -S (O) _n12 R _a61 , -P (O) (R _a61 )
(R _a62 ), and Z _a5 represents 5 to 5 together with two nitrogen atoms.
It represents a group of non-metal atoms necessary for forming an 8-membered heterocycle. However, the total number of carbon atoms of R _a8 and R _a9 is 6 or more.
R _a61 represents an aliphatic group, an aromatic group, an aliphatic oxy group, an aromatic oxy group, an aliphatic amino group or an aromatic amino group, and R _a62 represents an aliphatic group, an aromatic group, an aliphatic oxy group or an aromatic group. Represents a group oxy group. R _a8 or R _a9 may form a dimer or higher multimer. n12 represents 1 or 2. )