JPH07140608A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and color fastness of a dye image, storage stability of a raw stock, and to reduce quality fluctuation due to processing fluctuation by incorporating a specified dye image forming coupler and a specified compound in a photosensitive layer. CONSTITUTION:At least one of the photosensitive layers contains at least one kind of dye-forming coupler represented by formula I and at least one kind of compound represented by formula II, and in formulae I and II, A is an aromatic group, tertiary alkyl, secondary or tertiary cycloalkyl, bicycloalkyl, or an aliphatic amino; B is an aromatic or heterocyclic group, Z is H or a group to be released by coupling with the oxidation product of an aromatic primary amine developing agent, at least one of A, B, and Z has a partial structure represented by formula II, each of R<1> and R<2> is H, an aliphatic, aromatic, or heterocyclic group, or alkoxy, or the like, and R<3> is an aliphatic, aromatic, or heterocyclic group, amino, alkoxy, acyl, or the like.

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. More specifically, it is excellent in color reproducibility of dye images and image fastness, and has little storability and quality variation due to difference in processing. The present invention relates to a silver halide color photographic light-sensitive material excellent in stability and a color image forming method using the same.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials have the characteristics of high image quality and excellent economical efficiency, and are the most commonly used methods for reproducing color images. is there. A large number of researches for high image quality have been continued in order to further pursue the characteristics of the silver halide color photographic light-sensitive material. To improve the image quality of color print materials, the color reproducibility of the color print produced after development is excellent, the image is sharp and has no bleeding (high sharpness), and the dye cloud fine particles forming the image Is an image quality performance required to be visually inconspicuous (excellent in graininess). Further, it has been strongly desired that the dye image formed in this manner is fast against light, heat, and humidity and does not fade forever when stored for a long period of time. The fastness of dye images has been remarkably improved in recent years, and it has become possible to store color prints for a long period of time.

The most commonly used color image forming method in silver halide color photographic light-sensitive materials is to use an exposed aromatic silver halide as an oxidizing agent and an oxidized aromatic primary amine type color developing agent. By reacting with a coupler, indophenol, indoaniline, indamine,
A method for forming azomethine, phenoxazine, phenazine and similar pigments. In such a method, a method of reproducing a color image by a subtractive color method is used, and generally, three methods of yellow, magenta and cyan are used.
A color image is formed by changing the amount of color dye produced. Among these, pivaloyl type yellow couplers and benzoyl type yellow couplers have been most commonly used as yellow couplers. The former has a drawback that the formed dye image is excellent in fastness but low in color developability, and there has been a limit in responding to the demand for rapid processing and low replenishment, which have been strongly demanded in recent years. Further, the hue of the produced dye has not reached a sufficiently satisfactory level. On the other hand, the latter has a serious drawback in that although the color development is high, the hue of the dye formed is worse and the fastness of the dye image is extremely low. In the coupler for color printing, the hue and fastness of the resulting dye are important, and a pivaloyl type yellow coupler is generally used. However, even a pivaloyl type yellow coupler is not at a sufficiently satisfactory level in terms of hue, and further improvement has been desired. In order to improve the color reproducibility of a color print, a pivaloyl acetanilide type coupler having an alkoxy group at the ortho position of the anilide ring has been attracting attention. Although this coupler is certainly improved to some extent in terms of color reproducibility, it still has a problem in terms of fastness of dye image.

Recently, in order to improve color reproducibility and color development, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure described in European Patent 0,447,969A1, Same 0,482,552A
A malondianilide type yellow coupler having a cyclic structure described in No. 1 and an acylacetanilide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 have been proposed. Although these couplers are greatly improved in terms of color reproducibility, they are not sufficiently satisfactory in terms of image fastness. Therefore, attempts have been made to improve the image fastness by using a so-called anti-fading agent such as a radical scavenger and a singlet oxygen quencher together with these couplers. For example, examples of amide compounds are described in JP-A-5-2248 and JP-A-5-188546. All of these compounds had a certain improvement effect on the light fastness of the conventionally known publicly known yellow couplers. However, the improvement effect was not always at a satisfactory level. Further, among compounds having a relatively large effect of improving light fastness, many have unfavorable adverse effects such as a decrease in color density, a change in sensitivity, and a deterioration in hue, and problems to be solved in practical use remain. It was

On the other hand, as yellow couplers having a phosphoryl group as an oil-solubilizing group, examples of pivaloyl-type couplers and benzoyl-type couplers are described in US Pat. No. 4,026,709. Nothing is mentioned, nor is there any mention of photographic properties when used in combination with an amide compound.

[0006]

The present invention has been made under the circumstances described above. Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having good color reproducibility. A second object of the present invention is to provide a silver halide color photographic light-sensitive material in which the resulting dye image is fast and is resistant to discoloration or fading. A third object of the present invention is to provide a silver halide color photographic light-sensitive material which has stable photographic quality with little fluctuation in photographic characteristics due to differences in the composition of the processing solution and the use conditions. A fourth object of the present invention is to provide a silver halide color photographic light-sensitive material which is improved in the fluctuation of photographic characteristics (raw storability) depending on the storage condition of an unused light-sensitive material. A fifth object of the present invention is to provide a rapid and simple color image forming method using the above silver halide color photographic light-sensitive material.

[0007]

The above objects of the present invention have been achieved by the following silver halide color photographic light-sensitive material and color image forming method. (1) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion-containing light-sensitive layer on a support, at least one light-sensitive layer represented by the following general formula [Y]
A silver halide color photographic light-sensitive material comprising at least one dye-forming coupler represented by the formula (1) and at least one compound represented by the following general formula (A).

[0008]

[Chemical 4]

(In the formula, A is an aromatic group, a tertiary alkyl group,
It represents a secondary or tertiary cycloalkyl group, bicycloalkyl group, aliphatic amino group, aromatic amino group or heterocyclic group, B represents an aromatic group or a heterocyclic group, and Z is a hydrogen atom or an aromatic group. It represents a group capable of splitting off by a coupling reaction with an oxidized product of a primary amine developing agent. However, A, B or Z
At least one of the groups represented by the following general formula [P-I]
It has a partial structure represented by. )

[0010]

[Chemical 5]

[0011]

[Chemical 6]

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an acylamino group or an acyl group, and R 1 ³ represents an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, wherein R ¹ and R ² or R ¹ and R ³ are mutually They may be combined to form a 5- to 7- or 5- to 8-membered ring, respectively.) (4) The silver halide color photographic light-sensitive material according to claim 1 is exposed for 10 ^-4 seconds per pixel. A color image forming method characterized by exposing by a shorter scanning exposure method, and then performing color development.

The present inventors have searched for new acylacetanilide type couplers, and have investigated the general formula [PI] of the present invention.
It has been found that a coupler having a partial structure represented by is an excellent coupler in terms of hue and color developability. Further, when the coupler of the present invention is used in combination with the compound represented by the general formula (A) of the present invention which has been conventionally known, the light fastness is of course improved, but the effect is expected. It became clear that it was bigger than I did. Furthermore, it was revealed that the heat fastness under high humidity conditions was also improved. Also,
When the above compound is used in combination with a known yellow coupler, the color density is lowered and the hue is deteriorated, which is a serious problem in practical use. It has been found that such an adverse effect is remarkably improved only when the above compound is combined with the coupler of the present invention. Hereinafter, the content of the present invention will be described in detail.

The yellow coupler represented by the general formula [Y] will be described in more detail. In addition, when each group described in the present specification includes an aliphatic moiety, the aliphatic moiety may be linear, branched or cyclic, and may be saturated or unsaturated, It may be unsubstituted or substituted and has about 1 to 50 carbon atoms. Examples include alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl. When each group described in the present specification includes an aromatic moiety, the aromatic moiety represents an aromatic hydrocarbon moiety (aryl), which may be a single ring or a condensed ring and is unsubstituted. Or, it may be substituted and has about 6 to 50 carbon atoms. When each group mentioned in this specification contains a heterocyclic moiety, the heterocyclic moiety is a heteroatom in the ring, for example, a nitrogen atom,
It has an oxygen atom, a sulfur atom, a phosphorus atom, etc., and may be a saturated ring or an unsaturated ring, may be a monocyclic ring or a condensed ring, and may be unsubstituted or substituted. Well, the carbon number is about 1 to 50. General formula [P-
In the phosphoryl group represented by I], one or two of the three free bonds (bonds) may be bonded to a hydrogen atom or a monovalent organic residue, respectively, or a plurality of bonds. A hand may combine with a divalent or trivalent organic residue to form a 5- to 7-membered cyclic structure. In addition, these organic residues and 5
The 7-membered ring may be substituted with a substituent as described below.

The divalent to trivalent organic residue is a group obtained by removing 2 or 3 hydrogen atoms from a compound composed of an aliphatic, aromatic, heterocyclic and functional group, and examples thereof include methylene, ethylene, Pentamethylene, propylene, 1,2,3-propanetriyl, p-phenylene, o-phenylene, naphthalene-1,4,5-triyl, biphenyl-4,4 '.
-Diyl, methylenedioxy, ethylenedioxy, carbonyldioxy, oxalyl, malonyl, maleoyl,
Phthaloyl, 2,3,5-hexatricarbonyl, ureylene, thio, oxy, sulfonyl, 2-oxobutane-1,3-diyl, methylene-1,4-phenylene, piperazine-1,4-diyl, 1,3,3. 5-triazine-
2,4,6-triyl and the like can be mentioned.

Examples of the above-mentioned substituent include an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic acyl group, an aromatic acyl group, an aliphatic acyloxy group, an aromatic acyloxy group,
Aliphatic acylamino group, aromatic acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, sulfamoyl group, fat Group sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, sulfonamide group, aliphatic amino group, aromatic amino group, heterocyclic amino group, aliphatic thio group, aromatic thio group, heterocyclic ring Thio group, sulfamoylamino group, cyano group, nitro group, sulfo group,
Examples thereof include a carboxyl group, a hydroxyl group, a ureido group, a hydroxyamino group, an unsubstituted amino group, a formyl group and a halogen atom, and these groups may be further substituted with the same group, for example, a sulfamoyl group. Is an unsubstituted sulfamoyl group, N-aliphatic sulfamoyl group, N-aromatic sulfamoyl group, N-aliphatic acylsulfamoyl group, N-aliphatic sulfonylsulfamoyl group, N-carbamoylsulfamoyl group. It may be a group or the like. Similarly, the carbamoyl group may be an unsubstituted carbamoyl group, an N-aliphatic carbamoyl group, an N-
It may be an aromatic carbamoyl group, an N-aliphatic acylcarbamoyl group, an N-aliphatic sulfonylcarbamoyl group, an N-sulfamoylcarbamoyl group or the like.

When A represents an aromatic group, it preferably represents an aromatic group which may be substituted and has a total of 6 to 30 carbon atoms, and examples of the substituent include a halogen atom, an alkyl group and an alkoxy group. , Carbonamide group, sulfonamide group and the like. Particularly preferred as A is a phenyl group or a phenyl group substituted with an alkoxy group.

When A represents a tertiary alkyl group, it preferably represents a tertiary alkyl group having 4 to 30 carbon atoms which may be substituted, and examples of the substituent include a halogen atom, an alkyl group, There are aryl groups, alkoxy groups, alkylthio groups, aryloxy groups, arylthio groups, amino groups and acylamino groups. Particularly preferably as A,
It is a t-butyl group.

When A represents a cycloalkyl group or a bicycloalkyl group, it preferably represents a tertiary cycloalkyl group, particularly preferably one represented by the following general formula (a).

[0020]

[Chemical 7]

In the general formula (a), R ¹ represents a substituent, and Q ¹ represents a nonmetallic atom group necessary for forming a 3- to 6-membered carbocycle or heterocycle with C. R ¹ may be a divalent group and combine with Q ¹ to form a bicyclo ring. R ¹ is preferably a halogen atom, a cyano group, an optionally substituted organic group having 1 to 30 carbon atoms [eg, an alkyl group (eg, methyl, ethyl, propyl), an alkylthio group, an alkoxy group, an alkenyl group]. Base,
Aryl group, aralkyl group (eg, benzyl, phenethyl), aryloxy group, arylthio group].

Examples of the 3- to 6-membered carbon ring or hetero ring in which Q ¹ is formed together with C in the general formula (a) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and 1,3-dithiolan-2-yl. ,
1,3-dioxolan-2-yl, oxolan-2-yl, 1,3-dioxan-2-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, thiolane-2- Examples of the bicyclo ring formed by yl etc. by R ^{1 and} Q ¹ include adamantyl, bicyclo [2,2,1] heptyl, bicyclo [1,1,1] pentyl, 2,6,7. -Trioxabicyclo [2,2,2]
Octan-4-yl, 2,6,7-trioxa-1-phosphabicyclo [2,2,2] octane-1-on-4
-Ill and the like. Among the groups represented by the general formula (a), particularly preferable groups are 1-methylcyclopropyl group, 1-ethylcyclopropyl group, 1-benzylcyclopropyl group, 1-phenylthiocyclopropyl group, 1
Examples include -methoxycyclopropyl group and adamantyl group.

When A represents an aliphatic amino group (eg, substituted amino group, alkyl-substituted amino group), aromatic amino group (eg, anilino group) or heterocyclic group, A is preferably the following general formula (b). ) Or (c).

[0024]

[Chemical 8]

In the formula, R ² and R ³ may be the same or different and each represents an aliphatic group, an aromatic group or a heterocyclic group. Q ² represents an organic residue (eg, indolenine ring residue) necessary for forming a nitrogen-containing heterocycle with the nitrogen atom. In the general formulas (b) and (c), when R ² and R ³ represent an aliphatic group, the number of carbon atoms is 1 to 50, preferably 1 to
30, more preferably 1 to 20 linear, branched, cyclic, substituted or unsubstituted aliphatic groups. Examples of aliphatic groups are methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl, isobutyl, dodecyl, 2
-Hexyldecyl. When R ² and R ³ represent a heterocyclic group, the number of carbon atoms is 1 to 50, preferably 1 to 30,
More preferably 1-20, containing at least one or more nitrogen atom, oxygen atom or sulfur atom as a hetero atom, a 3- to 12-membered ring, preferably a 5- to 6-membered ring, saturated or unsaturated, substituted or unsubstituted. It is a substituted, monocyclic or condensed-ring heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl, 2-furyl, 2-imidazolyl, 1,2,4
-Triazol-3-yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3-imidazolidin-5-yl, pyranyl and the like can be mentioned. When R ² and R ³ represent an aromatic group,
It represents a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, preferably 6 to 30, more preferably 6 to 20 carbon atoms. Typical examples of the aromatic group are phenyl and naphthyl. Among the groups represented by the general formula (b), those in which R ² is an alkyl group are preferable, and an alkyl group having 1 to 10 carbon atoms is particularly preferable. R ³ is preferably an alkyl group or an aromatic group.

The nitrogen-containing heterocyclic group formed by Q ² together with> N- has a carbon number of 1 to 50, preferably 1 to 30, more preferably 1 to 20, other than a nitrogen atom as a hetero atom, such as oxygen. May contain an atom or a sulfur atom, 3 to
It is a 12-membered ring, preferably a 5- or 6-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic or condensed heterocyclic group. Examples of this heterocyclic group include pyrrolidino,
Piperidino, morpholino, 1-piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinoline-1
-Yl, 1-imidazolidinyl, 1-pyrazolyl, 1-
Pyrrolinyl, 1-pyrazolidinyl, 2,3-dihydro-
1-indazolyl, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazin-S, S-dioxo-4-yl or benzoxazin-4-yl can be mentioned. A 1-indolinyl group is particularly preferable depending on Q ² .
Each group defined by the general formulas (a) to (c) may be further substituted with a substituent and may be condensed with a carbocycle, an aromatic ring or a heterocycle.

When B represents an aromatic group, it has 6 to 5 carbon atoms.
0, preferably 6-30, more preferably 6-20,
It is a substituted or unsubstituted aryl group. For example, a phenyl group and a naphthyl group are typical examples. When B represents a heterocyclic group, B has the same meaning as explained when R ² and R ³ represent a heterocyclic group. Each group defined by B may be further substituted with a substituent. As a preferred substituent, at least one is a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aliphatic or aromatic sulfonyl group, an N-aliphatic or aromatic sulfamoyl group, an N-aliphatic or aromatic group. Carbamoyl group, N-aliphatic or aromatic sulfonylsulfamoyl group, N-carbamoylsulfamoyl group, N-aliphatic or aromatic acylsulfamoyl group, N-aliphatic or aromatic sulfonylcarbamoyl group, N- When it is a sulfamoylcarbamoyl group, an aliphatic or aromatic acylamino group, or an aliphatic or aromatic sulfonamide group. B is preferably an aromatic group, and particularly preferably a phenyl group having at least one substituent in the ortho position. The substituent at the ortho position is particularly preferably an alkoxy group, a halogen atom, an amino group, an aluroxy group, an arylthio group or an alkylthio group.

Z may be a hydrogen atom or a conventionally known leaving group. Preferable Z is a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, an aromatic oxy group, an aromatic thio group, a heterocyclic oxy group, a heterocyclic thio group, an acyloxy group, a carbamoyloxy group, an alkylthio group or A halogen atom is mentioned. More preferable Z is a nitrogen-containing heterocyclic group or aromatic oxy group which is bonded to the coupling position at a nitrogen atom. These leaving groups are
Non-photographic useful group or photographic useful group or its precursor (for example, development inhibitor, development accelerator, desilvering accelerator, fogging agent, dye, hardener, coupler, developing agent oxidant scavenger, fluorescent dye, development It may be either a main drug or an electron transfer agent. When Z is a photographically useful group, those conventionally known are useful. For example, U.S. Pat. Nos. 4,248,962, 4,409,323, 4,438,193, 4,421,845, 4,618,571, and 4,652. No. 516, No. 4,861,701, No. 4,782,012, No. 4,857,440, No. 4,847,185, No. 4,477,563, No. 4,438,193. No. 4,628,024, No. 4,618,571, No. 4,741,994, European Published Patent No. 193,389.
No. A, No. 348, 138A or No. 274, 573
The photographically useful group described in No. A or a leaving group (for example, a timing group) for releasing the group is used.

When Z represents a nitrogen-containing heterocyclic group bonded to the coupling position at the nitrogen atom, it preferably has 1 to 5 carbon atoms.
5, more preferably 1 to 30, still more preferably 1 to 15
And a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed ring heterocyclic group. The hetero atom may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino, 1,2,4-triazol-2-yl, 1,2,3-triazole-2.
-Yl, benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, oxazolidin-2,4-dione-3-yl, 1,2,3-triazolidine-3,5-dione- 4-yl, imidazolidin-2,4,5-trion-3-yl, 2-imidazolinone-1-yl, 3,5-dioxomorpholino or 1-indazolyl can be mentioned. When these heterocyclic groups have a substituent, examples of the substituent include the substituents enumerated as the substituents which the group represented by R ¹ may have. Among them, preferred substituents are
One of the substituents is an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aluroxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, an aryl group, a nitro group, a carbamoyl group, a cyano group or a sulfonyl group. It's time.

When Z represents an aromatic oxy group, it is preferably a substituted or unsubstituted aromatic oxy group having 6 to 50 carbon atoms, more preferably 6 to 30 carbon atoms, and further preferably 6 to 10 carbon atoms. Particularly preferably, it is a substituted or unsubstituted phenoxy group. When it has a substituent, examples of the substituent include the substituents listed as the substituents which the group represented by R ¹ may have. Among them, a preferable substituent is a case where at least one substituent is an electron-withdrawing substituent, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group, and a nitro group. Examples thereof include a cyano group and an acyl group.

At least one of the groups represented by A, B or Z
The partial structure represented by the general formula [P-I] which one has will be described. Among the groups represented by general formula [P-I],
The preferable one is represented by the following general formula [P-II].

[0032]

[Chemical 9]

In the formula, X is an oxygen atom, a sulfur atom or --N
(R ^N1) - represents, R ^N1 represents a hydrogen atom, an aliphatic group or an aromatic group. X is particularly preferably an oxygen atom.
L ¹ is a linking group with a coupler residue (ketomethylene skeleton), a linking group formed by combining at least one of —CO— or —SO ₂ — with —NH—, —CO— or —
Represents COO- *. * Represents a bond to L ² . L ² represents an alkylene group or an arylene group. k, h, and n each represent 0 or 1. m ₂ represents an integer of 0, 1 to 3. m ₀ and m ₁ respectively represent 0 or 1, m ₀ ,
The sum of m ₁ and m ₂ is always 3. R ^P1 and R ^P2 may be the same or different and each 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 L ² and R ^P1 and R ^P2 may be bonded to each other to form a ring.

As L ¹ , -NHCO- *, -CON
_{H - *, - NHSO 2 -} *, - SO 2 NH - *, - NH
_{CONH - *, - SO 2 NHCO} - *, - SO 2 NHS
O _2- *, -SO ₂ NHCONH- *, -CONHSO
₂ NH- *, -CONHCO- *, -CO- *, -CO
O- * etc. are mentioned. As the alkylene group for L ² ,
It is preferably a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, and the arylene group is preferably a phenylene group having 6 to 36 carbon atoms. When m ₂ is 2 or 3, a plurality of [(X) _n − (L ² ) _h − (L ¹ )
_k ] may be the same or different.

More specifically, R ^P1 and R ^P2 are each an aliphatic group (preferably having 1 to 40 carbon atoms, more preferably 1 to 40 carbon atoms).
30. For example, butyl, t-butyl, 2-ethylhexyl, pentyl, dodecyl, cyclohexyl, aromatic group (preferably having 6 to 36 carbon atoms, more preferably 6 to 2 carbon atoms).
6. For example, phenyl, 4-t-butylphenyl), an aliphatic oxy group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30. For example, ethoxy, isopyropyroxy, butoxy, t-butoxy, hexyloxy, 2-ethylhexyloxy, decyloxy, dodecyloxy,
Cyclohexyloxy), an aromatic oxy group (preferably having a carbon number of 6 to 36, more preferably 6 to 26. For example, phenoxy, 4-t-butylphenoxy), an aliphatic amino group (preferably having a carbon number of 1 to 40, further Preferably 1-3
0. For example, octylamino, dihexylamino, dibutylamino) or an aromatic amino group (preferably having 6 carbon atoms).
-40, more preferably 6-30. For example, phenylamino, 2,4-dibutylphenylamino) is represented.

In the present invention, the group represented by the general formula [P-II] is preferably a partial structural formula of A or B in the general formula [Y], and more preferably a partial structure of B. preferable. The compound examples of the coupler represented by the general formula [Y] of the present invention are shown below, but the compounds of the present invention are not limited thereto.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

[Table 8]

[0045]

[Table 9]

[0046]

[Table 10]

[0047]

[Table 11]

[0048]

[Table 12]

[0049]

[Table 13]

[0050]

[Table 14]

[0051]

[Table 15]

[0052]

[Table 16]

[0053]

[Table 17]

[0054]

[Table 18]

The coupler represented by the general formula [Y] of the present invention can be synthesized by a generally known method or a method similar thereto. For example, it can be synthesized by the following synthesis route.

[0056]

[Chemical 10]

12 g of methyl methacrylate (1), 50 g of tris (2-ethylhexyl) phosphite (2) and 11.2 g of phenol were mixed and reacted at 110 ° C. for 2 hours. Compound (3) extracted by vacuum distillation was used as 1
An oily compound (4) was synthesized by treating with an equal amount of potassium hydroxide. The compound (4) was chlorinated with oxalyl chloride in dichloromethane to obtain the corresponding acid chloride compound (compound (5)), and then the compound (6) was reacted in acetonitrile in the presence of triethylamine. Post-treatment by a conventional method and purification by column chromatography gave an oily compound (7).
The compound (7) was chlorinated with sulfuryl chloride in dichloromethane, and the reaction solution was evaporated under reduced pressure to give an oil. In addition to this, triethylamine and 5-ethoxy-1
-Benzylhydantoin was added in an amount of 2 equivalents each, and dimethylformamide was added as a solvent, followed by purification by column chromatography to obtain the objective Exemplified coupler 17. Next, the compound represented by formula (A) of the present invention, which is used in combination with the yellow coupler of the present invention, will be described in detail. The compound of the present invention is a compound that prevents fading of a dye image formed from a yellow coupler and is a non-color forming compound. The non-color-forming compound is a compound that gives substantially no dye when processed with a color developing solution.

In the general formula (A), R ^{1 and} R ² are each independently a hydrogen atom, an aliphatic group (an alkyl group having 1 to 25 carbon atoms, for example, methyl, ethyl, i-propyl, t-butyl). , Cyclohexyl, 2-ethylhexyl, etc., aromatic groups (aromatic groups having 1 to 25 carbon atoms, such as phenyl, naphthyl, 4-t-octylphenyl,
2-chlorophenyl, 2,4,6-trimethylphenyl, etc.), heterocyclic group (eg, 2-pyridyl, etc.), alkoxy group (alkoxy group having 1 to 25 carbon atoms, for example,
Methoxy, butoxy, octyloxy, dodecyloxy, t-butoxy, benzyloxy, etc., an aryloxy group (an aryloxy group having 1 to 25 carbon atoms, for example, phenoxy, 4-t-octylphenoxy, 2,4
-Di-t-butylphenoxy, etc.), amino group (amino group having 1 to 35 carbon atoms, for example, dimethylamino, dibutylamino, N-methyl-N-hexadecylamino, N
-Methyl-N-phenylamino, etc.), an acylamino group (for example, acetamide, benzoylamino, N-methyl-N-myristoylamino, etc.) or an acyl group (an acyl group having 1 to 25 carbon atoms, for example, acetyl, pivaloyl, Benzoyl, 2- (2,4-di-t-amylphenoxy) -butanoyl and the like). In the general formula (A), R ³ is an aliphatic group, an aromatic group, a heterocyclic group, an amino group,
Alkoxy group, acyl group, carbamoyl group (eg, diethylcarbamoyl, dioctylcarbamoyl, N-methyl-N-hexadecylcarbamoyl, N-methyl-N
-Phenylcarbamoyl etc.), an alkoxycarbonyl group (eg ethoxycarbonyl, 2-ethylhexyloxycarbonyl etc.) or an aryloxycarbonyl group (eg 2-phenylethoxycarbonyl etc.), and specific examples thereof include R ¹ and R ^2. The same groups as those mentioned above can be mentioned. R ¹ , R ² and R ³ may be further substituted with a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, Examples thereof include an acylamino group, a sulfonamide group, an acyl group, an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a cyano group, a sulfonyl group, and a sulfoxide group. In formula (A), R ¹ and R ² may combine with each other to form a 5- to 7-membered ring. Specific examples thereof include a piperidine ring, a piperazine ring, a morpholine ring, a pyrrolidine ring, and a 4,4-dioxo-4-thiazine ring. In formula (A), R ¹ and R ³ may combine with each other to form a 5- to 8-membered ring. General formula (A)
In, a more preferable structure is the following general formula (AI),
It is represented by (A-II) or (A-III).

[0059]

[Chemical 11]

[0060]

[Chemical 12]

[0061]

[Chemical 13]

In the general formula (AI), R ¹ and R ²
Are respectively synonymous with R ¹ and R ² in the general formula (A). In formula (AI), R ⁴ is an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group,
Amino group, anilino group, sulfonyl group, phosphoryl group,
It represents an oxycarbonyl group or a carbamoyl group, and R ⁵ represents a hydrogen atom, an aliphatic group or an aromatic group. General formula (A-
In II), R ³ and R ³ 'are R in the general formula (A).
^It is synonymous with ³ and may be the same as or different from each other. Z ¹ and Z ² are each an alkylene group having 1 to 3 carbon atoms, which may be the same or different from each other,
Further, it may have a substituent having 1 to 20 carbon atoms. In formula (A-III), R ³ has the same meaning as R ³ in the general formula (A). R ⁶ represents a hydrogen atom, an aliphatic group or an aromatic group. X ¹ is a group capable of substituting on the benzene ring, and examples thereof include a halogen atom, an aliphatic group, an aromatic group, an alkoxy group, an amino group, an acyl group, a cyano group, an acyloxy group,
Examples include an acylamino group, an oxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a sulfonyl group, a urethane group, and a ureido group. n is an integer of 0 to 3, and when n is 2 or more, a plurality of X ^1's may be the same as or different from each other.

In the general formula (AI), R ⁴ is preferably an alkyl group, an alkoxy group, an aryloxy group, a sulfonyl group or a phosphoryl group, more preferably an alkyl group or an aryloxy group. R ⁵ is preferably a hydrogen atom or an alkyl group, most preferably an alkyl group. Among the compounds represented by the general formula (AI), more preferred are the compounds represented by the following general formula (A-IV).

[0064]

[Chemical 14]

In the general formula (A-IV), R ¹ , R ² and R ⁵ are respectively R ¹ , R ² in the general formula (AI).
And R ⁵ have the same meaning. Further, X ² is represented by the general formula (A-III
) Is the same as X ¹ . Y represents an alkylene group having a carbon chain length of 1 to 6 which may have a substituent. Examples of the group capable of substituting for Y include the same groups as those mentioned for X ¹ in formula (AI). n is an integer of 0-3. In formula (A-IV), R ¹ and R ² are each preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably an alkyl group. It is also preferable that R ¹ and R ² are linked to each other to form a 5- to 7-membered ring, and more preferably a piperidine, piperazine or morpholine ring. Y is preferably an alkylene group having a carbon chain length of 1 to 3, more preferably a methylene group or a propylene group, still more preferably a methylene group. When Y is a methylene group, Y is preferably substituted with an alkyl group having 1 to 25 carbon atoms, and the alkyl group is more preferably 1 to 1 carbon atoms.
12 alkyl groups, more preferably an ethyl group, a butyl group or a hexyl group. X ² is preferably a halogen atom or an alkyl group, more preferably a chlorine atom or a secondary or tertiary alkyl group, and still more preferably a chlorine atom or a tertiary alkyl group, and a t-butyl group, t-
Most preferred is an amyl group or a t-octyl group. n is preferably an integer of 1 to 3, more preferably 1 or 2. When n is 2, two X ² are preferably substituted at the 2-position and 4-position of the phenoxy group, respectively.

In the general formula (A-II), R ³ and R ³ ′ are preferably an aliphatic group, an aromatic group, an oxycarbonyl group or a carbamoyl group, more preferably an aliphatic group.
When R ³ or R ³ 'is an aliphatic group, it is a linear or branched alkyl group which may have a substituent, but is a secondary or tertiary alkyl group, or an aryloxy group. More preferably, it is an alkyl group substituted with a group.
Z ¹ and Z ² are preferably alkylene groups having 2 to 3 carbon atoms, and more preferably ethylene groups.

In the general formula (A-III), preferred R is
³ is the same group as preferred R ³ in formula (A-II). R ⁶ is preferably a hydrogen atom, an alkyl group, an alkoxy group or an amino group, more preferably an alkyl group. X ¹ is preferably a halogen atom, an alkyl group, an alkoxy group, an acyloxy group, an amino group, an acylamino group or a sulfonamide group, more preferably an alkoxy group, an acyloxy group, an amino group or an acylamino group. Among the compounds represented by the general formula (A-III), the compound represented by the following general formula (A-V) or (A-VI) is particularly preferable.

[0068]

[Chemical 15]

[0069]

[Chemical 16]

In the general formula (A-V), R ³ and R
⁶ is R ³ and R ⁶ in the general formula (A-III), respectively.
It is synonymous with and the preferable partial structure is also the same. R ⁷ represents an aliphatic group, an aromatic group or an acyl group, and is preferably an alkyl group. In formula (A-VI), R ³ and R ³ ′, and R ⁶ and R ⁶ ′ have the same meanings as R ³ and R ⁶ in formula (A-III), respectively, and the preferred partial structures are also the same.

Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0072]

[Chemical 17]

[0073]

[Chemical 18]

[0074]

[Chemical 19]

[0075]

[Chemical 20]

[0076]

[Chemical 21]

[0077]

[Chemical formula 22]

[0078]

[Chemical formula 23]

[0079]

[Chemical formula 24]

[0080]

[Chemical 25]

[0081]

[Chemical formula 26]

[0082]

[Chemical 27]

[0083]

[Chemical 28]

[0084]

[Chemical 29]

[0085]

[Chemical 30]

[0086]

[Chemical 31]

[0087]

[Chemical 32]

When the yellow coupler of the present invention is applied to a silver halide color photographic light-sensitive material, at least one layer containing the coupler of the present invention may be provided on a support. The layer containing the coupler of the present invention may be any layer as long as it is a hydrophilic colloid layer on a support,
It is preferably used in a blue-sensitive silver halide emulsion layer.

The preferable amount of the yellow coupler represented by the general formula [Y] of the present invention in the silver halide color photographic light-sensitive material is 0.01 to 10 mmol / m ² .
The range is more preferably 0.05 to 5 mmol / m ² , and most preferably 0.1 to ² mmol / m ² . Of course, two or more couplers represented by general formula [Y] may be used in combination. Further, it can be used in combination with a coupler other than the coupler represented by the general formula [Y]. In this case, the usage rate of the coupler of the present invention is preferably 30 mol% or more. The silver halide emulsion in the silver halide emulsion layer in which the coupler of the present invention is used is preferably used in an amount of 0.5 to 50 times, more preferably 1 by mol, based on the coupler.
-20 times, most preferably 1.5 to 10 times.

The amount of the compound represented by the general formula (A) used in the present invention varies depending on the type and amount of the yellow coupler used and is preferably 1 to 300% by weight based on the coupler used. And more preferably,
The range is 5 to 200% by weight, more preferably 10 to 100% by weight.

In the present invention, various known methods can be used for adding the coupler and the compound of the present invention to the hydrophilic colloid layer. Usually, it can be added by an oil-in-water dispersion method known as an oil protect method. That is, it is a method in which the coupler and the compound of the present invention are dissolved in a high-boiling point organic solvent such as a phosphoric acid ester or a phthalic acid ester and a low-boiling point auxiliary solvent, and then dispersed in a gelatin aqueous solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant, and phase inversion may be performed to form an oil-in-water dispersion. For the alkali-soluble coupler, a dispersion method known as Fischer dispersion method can be used. In order to remove the low boiling point organic solvent from the resulting dispersion, it is also preferable to use a method such as distillation, noodle washing, or ultrafiltration. The dispersion medium of such a coupler has a dielectric constant of 2 to 20 (25 ° C.) and a refractive index of 1.
High boiling organic solvents of 4-1.7 are preferred. In the present invention, the weight ratio of the dispersion medium to the coupler of the present invention is preferably 0.0 to 10, more preferably 0.1 to 5, and still more preferably 0.3 to 3. As the compound used as the dispersion medium, phosphoric acid esters, phthalic acid esters, benzoic acid esters, and fatty acid esters are generally used. Among them, phosphoric acid esters and phthalic acid esters are more preferable in terms of color forming property. From the viewpoint of color reproducibility, alkylphosphoric acid esters, phosphonic acid esters, phosphinic acid esters, and phosphine oxides are particularly preferable. From the viewpoint of image fastness, the amide compounds, epoxy compounds and solid esters described in JP-A-5-188546 are preferable.

Further, in terms of image fastness, in addition to the yellow coupler of the present invention, in addition to those disclosed in JP-A-4-350854 and JP-A-4-350854.
350650, 5-2247, 5-2248, 5
It is preferable to use the anti-fading agents described in JP-A No. 19427 and 5-61165 together.

The coupler of the present invention has the general formula (A) of the present invention.
It is preferable to use a water-insoluble polymer soluble in an organic solvent together with the compound represented by. Specific examples of the water-insoluble polymer include WO 88/00723 and JP-A-63.
-44658 and JP-A-5-107701. Particularly preferred as a polymer to be combined with the coupler of the present invention is a polymer composed of an acrylamide derivative or a methacrylamide derivative, but a polymer of acrylamide or methacrylamide having an aromatic group is preferable in terms of image fastness under high humidity. More preferable. The water-insoluble polymer can be dissolved in an organic solvent together with the coupler when the coupler dispersion is prepared, and dispersed in an aqueous gelatin solution. The amount of the water-insoluble polymer added is preferably in the range of 2 to 200% with respect to the weight of the coupler, more preferably 10 to 150% by weight, still more preferably 20 to 100%.
% By weight.

In the color light-sensitive material of the present invention, a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer are coated on a support having a reflective layer. It can be installed and configured. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. However, the order may be different from this. That is, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size comes to the uppermost layer, or from the viewpoint of storability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The support used in the present invention may be any support as long as it can be coated with a photographic emulsion layer such as glass, paper and plastic film, but is preferably a transparent support of triacetyl cellulose or polyethylene terephthalate, or the following. The reflective support described in detail below. Of these, the most preferable is a reflective support.
The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example, polyethylene coated paper, polyethylene terephthalate coated paper,
Polypropylene-based synthetic paper, transparent support provided with a reflective layer, or in combination with a reflective material, for example, glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, Vinyl chloride resin etc. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer, and it is preferable that at least one of the water resistant resin layers contains white pigment fine particles. The white pigment fine particles are preferably contained at a density of 12% by weight or more, and more preferably 14% by weight or more. As the light-reflecting white pigment particles, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and the surface of the pigment particles should be 2 to 4
It is preferable to use a product treated with a dihydric alcohol.
It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles, and the size of the distribution is determined by the occupation area ratio (%) (Ri) of the fine particles projected on a unit area. It can be measured and obtained. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable. In the present invention, a support having a surface of diffuse reflection of the second kind is preferably used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second-class diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of the surface irregularities is preferably 0.1 to 2000 cycles / mm for irregularities having a roughness of 0.1 μm or more, and more preferably 50 to 600 cycles / mm. For more information on such supports, see
It is described in JP-A-2-239244.

In the present invention, the silver halide grains may be emulsions of any halogen composition such as silver chloride, silver chlorobromide, silver bromide and silver iodobromide, but 95 mol% or more is silver chloride. It is preferred to use silver chloride, silver chlorobromide, or silver chloroiodobromide grains. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains,
The so-called uniform structure grains that have the same composition in any part of the silver halide grains, and the halogen composition that differs between the core inside the silver halide grains and the shell (shell) surrounding it (one or more layers) A so-called layered structure grain or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grain (in the case of being on the grain surface, a structure in which a portion having a different composition is bonded to the edge, corner or face of the grain) Particles and the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%,
More than 20 mol% is more preferable. The silver bromide content of the silver bromide localized layer is analyzed using an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen). can do. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate. ) Those having a crystalline form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the present invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver salt (bromide) bromide emulsion used in the present invention is P.Gl.
Chimie et Phisique Photographique (Paul by afkides
Montel, 1967), by GF Duffin Photographi
c Emulsion Chemistry (Focal Press, 1966
,) By VL Zelikman et al Making and Coating Phot
It can be prepared using the method described in, for example, ographic Emulsion (Focal Press, Inc., 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains different metal ions or complex ions thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions.
Ions mainly selected from iridium, rhodium, iron, etc. or their complex ions in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, complex ions thereof can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing a metal ion in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, European Patent 0,44
5-arylamino-1, described in 7,647
A 2,3,4-thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
York, London] 1964). As specific examples of compounds and spectral sensitization methods, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-12 is known.
The spectral sensitizing dye described in No. 3340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, European patent 0,420,0
No. 11, page 4, line 21 to page 6, line 54, EP 0,42
0,012, page 4, line 12 to page 10, line 33, EP 0,443,466, U.S. Pat. No. 4,975,362.
The sensitizing dyes described in No. 1 are preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, No. 4427555, No. 57-2208
As described in US Pat. No. 9,822,135, US Pat.
As described in No. 5, etc., an aqueous solution or a colloidal dispersion in which a surfactant coexists may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid to be added to the emulsion. JP-A-53-102
No. 733 and No. 58-105141, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, it is added at the same time as the chemical sensitizer to obtain a spectral spectrum. The sensitization can be carried out simultaneously with the chemical sensitization, or can be carried out prior to the chemical sensitization as described in JP-A-58-113928, and it can be added before the completion of silver halide grain precipitation. Spectral sensitization can also be started. Furthermore, US Pat. No. 422566
Adding the spectral sensitizing dyes separately as taught in No. 6, i.e. adding a portion prior to the chemical sensitization,
The balance can be added after chemical sensitization and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column can be used in combination. preferable. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are contained in an amount of 0.5 × 10 ^-5 mol to 5 mol per mol of silver halide.
0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.
An amount of 0 × 10 ⁻³ mol is used, and 0.1 to 10000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous amount used in the range of 0 times.

The light-sensitive material of the present invention is used in a printing system using an ordinary negative printer, in addition to a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, it is less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

The light-sensitive material according to the present invention has a hydrophilic colloid layer for the purpose of preventing irradiation and halation and improving safety of safelight, etc., see pages 27 to 76 of EP 0337490A2. It is preferable to add the dyes described above, which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes). Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating the color separation, there are EP 0,53
The water-soluble dyes described in JP-A-9-978A1, JP-A-5-127325 and JP-A-5-127324 are preferable.

In the present invention, a colored layer which can be decolorized by treatment is used instead of the water-soluble dye or in combination with the water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (from 400 nm to 70 in normal printer exposure).
In the visible light region of 0 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure), the optical density value at the wavelength having the highest optical density is preferably 0.2 or more and 3.0 or less. It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at a pH of 6 or lower but is substantially water-soluble at a pH of 8 or higher is disclosed in Japanese Patent Laid-Open No. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 p
It is preferable to use low calcium gelatin of pm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band 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 exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing.
Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied to process the light-sensitive material. As the additives for treatments, those described in the following patent publications, particularly in the specification of European Patent No. 0,355,660A2 (JP-A-2-139544) are preferably used.

[0117]

[Table 19]

[0118]

[Table 20]

[0119]

[Table 21]

[0120]

[Table 22]

[0121]

[Table 23]

Cyan couplers and magenta couplers are impregnated with a loadable latex polymer (eg US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the table above. Alternatively, it is preferable to dissolve it together with a water-insoluble and organic solvent-soluble polymer and emulsify and disperse it in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent No. 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler, a pyrrolotriazole coupler, or the yellow coupler of the present invention. That is, the compound and / or the color development processing in the above-mentioned European Patent Specification which chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound. Use of the compounds in the above-mentioned European patent specification, which are chemically bonded with an oxidized product of an aromatic amine-based color developing agent remaining behind to form a chemically inactive and substantially colorless compound, 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.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent No. 0,333,185A
3-hydroxypyridine cyan couplers described in No. 2 (among others, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples), and European Patent No. 0,456,226A1. , A pyrrolopyrazole-type cyan coupler, EP 0,484,
It is preferable to use the pyrroloimidazole type cyan couplers described in No. 909 and the pyrrolotriazole type cyan couplers described in European Patent Nos. 0,488,248 and 0,491,197A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents in the above table are used. Among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6 position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 0,226,8
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 49A and No. 0,294,785A. Further, as a 5-pyrazolone-based magenta coupler, International Publication WO92
/ 18901, WO92 / 18902 and WO9
The 5-pyrazolone-based magenta coupler capable of releasing arylthio described in 2/18903 is preferable in terms of image storability and little change in image quality due to processing.

Examples of the coupler which can be used in combination with the yellow coupler of the present invention include known acylacetanilide couplers which are not included in the present invention. Among these, preferred are pivaloyl acetanilide type, benzoyl acetanilide type, 1-alkylcyclopropane-1-carbonyl type and indoline-1-carbonyl type yellow couplers. At this time, the amount of the acylacetanilide coupler used together is preferably 50 mol% or less with respect to all the yellow couplers from the viewpoint of color reproducibility.

The method for processing the color light-sensitive material of the present invention is as follows:
In addition to the methods described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A 4-97355, page 5, upper left column, line 17 to 18 The processing materials and processing methods described in the lower right column, line 20 are preferable.

[0128]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constituent layers were further coated, A multilayer color photographic printing paper (000) having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 140.0 g, color image stabilizer (Cpd-2) 20.0 g, color image stabilizer (Cpd-3)
16.0 g, color image stabilizer (Cpd-5) 20.0 g,
Solvent (Solv-2) 20 g, solvent (Solv-5) 4
0 g, solvent (Solv-10) 10 g, solvent (Solv-10)
-11) Dissolved in 10 g of ethyl acetate and 180 ml of ethyl acetate, this solution was emulsified and dispersed in 1000 g of a 10% aqueous gelatin solution containing 60 ml of 10% sodium dodecylbenzenesulfonate to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, 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). The variation coefficient of grain size distribution is 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide were locally contained in a part of the grain surface based on silver chloride for each size emulsion). In this emulsion, blue-sensitive sensitizing dyes A, B and C shown below were contained in an amount of 1.4 × 10 ^-4 mol for each large-sized emulsion A per mol of silver, and for each small-sized emulsion A. , 1.7 × 10 ⁻⁴ mol, respectively. 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 a coating amount equivalent to 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. In addition, Cpd-12 and Cp are added to each layer.
The total amount of d-13 was 25.0 mg / m ² and 50.
It was added at 0 mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0131]

[Chemical 33]

(1.4 × 10 ⁻⁴ mol each for a large-sized emulsion and 1.7 × 10 ⁻⁴ mol each for a small-sized emulsion, per mol of silver halide). ) Green-sensitive emulsion layer

[0133]

[Chemical 34]

(Sensitizing dye D per mol of silver halide, 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mol added. ) Red-sensitive emulsion layer

[0135]

[Chemical 35]

(1 mol of silver halide was added to the large-sized emulsion in an amount of 5.0 × 10 ⁻⁵ mol, and to the small-sized emulsion was added in an amount of 6.0 × 10 ⁻⁵ mol. )

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0138]

[Chemical 36]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)
-5-Methylcaptotetrazole was added in an amount of 3.5 x 10 ^-4 mol, 3.0 x 10 ^-3 mol and 2.5 x 10 ^-4 mol per mol of silver halide, respectively. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ⁻⁴ mol was added. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0140]

[Chemical 37]

(Layer Structure) The layer structure of each layer is shown below. The numbers represent the coating amount (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) The Silver Chlorobromide Emulsion A 0.27 Gelatin 1.65 Yellow Coupler (ExY) 0.70 Color Image Stabilizer (Cpd-2) 0.10 Color Image Stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.10 Solvent (Solv-2) 0.10 Solvent (Solv-5) 0.20 Solvent (Solv-10) 0.05 Solvent (Solv -11) 0.05

Second Layer (Color Mixing Prevention Layer) Gelatin 1.20 Color mixing inhibitor (Cpd-4) 0.10 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of silver bromide 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) 0.18 UV Absorber (UV-2) 0.16 Color Image Stabilizer (Cpd-2) 0.03 Color Image Stabilizer (Cpd-5) 0.10. Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.08 Color image stabilizer (Cpd-10) 0.02 Solvent ( Solv-3) 0.13 solvent (Solv-4) 0.39 solvent (So v-6) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.80 Color mixing inhibitor (Cpd-4) 0.07 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

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 (silver molar ratio) The variation coefficients of the grain size distribution are 0.09 and 0.11, respectively, and in each size emulsion 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride). 0.20 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-9) 0.02 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-7) ) 0.22

Sixth Layer (UV Absorbing Layer) Gelatin 0.65 UV Absorber (UV-1) 0.45 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.06

Seventh Layer (Protective Layer) Gelatin 1.00 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

[0150]

[Chemical 38]

[0151]

[Chemical Formula 39]

[0152]

[Chemical 40]

[0153]

[Chemical 41]

[0154]

[Chemical 42]

[0155]

[Chemical 43]

[0156]

[Chemical 44]

[0157]

[Chemical formula 45]

[0158]

[Chemical formula 46]

With respect to the sample 000 prepared as described above, the yellow coupler of the first layer (blue sensitive layer) was used as shown in Table-A below.
Samples 001 to 048 were prepared by substituting the coupler shown in Table 1 and adding the anti-fading agent of the present invention as shown in Table-A. At this time, the coating amount of the coupler was changed so that the magnification (mol%) described in Table-A was obtained with respect to the sample 000. The amount of coated silver was also adjusted so that the molar ratio with the coupler was constant. Further, the compound represented by the general formula (A) of the present invention has a coating amount shown in Table-A in% by weight when the coupler is 1.0. Each sample after coating is 5 ℃
After storing for 2 weeks in the following, the following tests were conducted.

The above sample 000 was processed into a roll having a width of 127 mm, exposed imagewise using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd., and was replenished to twice the tank capacity for color development in the following processing steps. A continuous process (running process) was performed.

Treatment process Temperature Time Replenisher * Color development 38 ℃ 45 seconds 73 ml Bleaching and fixing 35 ℃ 45 seconds 60 ml ** Rinse (1) 35 ℃ 30 seconds ――Rinse (2) 35 ℃ 30 seconds ――Rinse ( 3) 35 ℃ 30 seconds 360 ml Dry 80 ℃ 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} light-sensitive 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 1-Hydroxyethylidene-1,1-diphosphonic acid (60%) 0.8 ml 0.8 ml Lithium sulfate (anhydrous) 2.7 g 2.7 g Triethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g-potassium bromide 0.03g-potassium carbonate 27.0 g 27.0 g diethylhydroxylamine 4.6 g 9.2 g sodium sulfite 0.1 g 0.2 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline・ 3/2 Sulfuric acid ・ monohydrate 5.0 g 11.5 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g Water added 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) ) 10.00 11.00

Bleach-fix solution (tank solution and replenisher are the same) Tank solution Replenisher Water 600 ml 150 ml Ammonium thiosulfate (750 g / liter) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Iron diamine tetraacetate 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water added 1000 ml 1000 ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.8 5.6

Rinse solution (same as tank solution and replenisher solution) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

Next, each sample after aging was subjected to gradation exposure with a light source that passed a blue filter and treated with the above-mentioned running treatment liquid. The optical density of the sample after the treatment was measured with blue light (intermediate wavelength 440 nm), and the maximum color density (Dmax) is shown in Table-A.

[0166]

[Table 24] (Table-A-1)

[0167]

[Table 25] (Table-A-2)

[0168]

[Table 26] (Table-A-3)

The structures of the comparative coupler and the coupler of the present invention used in this example are as follows.

[0170]

[Chemical 47]

[0171]

[Chemical 48]

[0172]

[Chemical 49]

[0173]

[Chemical 50]

[0174]

[Chemical 51]

Next, the above sample was irradiated with a xenon light source of 80,000 lux for 20 days to perform a fading test. The light fastness is evaluated by the residual ratio (%) of the color image at the initial density of 2.0,
The results are shown in Table-A. In addition, the above sample was placed at 80 ° C-7
The sample was stored under 0% RH for 20 days and then subjected to a fading test under high temperature and high humidity. The wet heat fastness was evaluated by the residual ratio (%) of the color image at the initial density of 2.0, and the results are also shown in Table-A. The value in parentheses in the table indicates the difference with respect to the sample to which the compound of the present invention was not added. Regarding the maximum color density, the smaller the absolute value of this value, the smaller the decrease in color density and the more excellent the photosensitive material. Regarding the image fastness, it is shown that the larger the value in (), the greater the effect of improving the fastness. From Table-A,
In the sample using the comparative coupler ExY-1, although the light fastness was improved by adding the compound A-17, A-31 or A-34 of the present invention, the color density was significantly reduced. I understand. Further, it can be seen that at this time, the wet heat fastness is slightly improved. On the other hand, in the coupler Y-1 of the present invention, the light fastness is also improved by adding the compound of the present invention, but at this time, the color density is hardly reduced. Further, the effect of improving the light fastness is obviously greater than that of ExY-1. Further, the wet heat fastness is also improved, and the effect is obviously larger than that of ExY-1. Coupler Y-2 of the present invention
Similarly to Y-5, structurally corresponding comparative couplers ExY-2 to ExY-5 also have a large effect of improving light fastness and wet heat fastness, and almost no decrease in color density is observed. A-17, A-31 and A-
It is clear from Table-A that the compounds of the present invention other than 34 have almost the same effects as described above. As described above, when the compound represented by the general formula (A) of the present invention is used in combination with the coupler of the present invention, the light fastness and the wet heat fastness can be improved without impairing the color developability. it can.

Example 2 The composition of the first layer of the sample 000 of Example 1 was changed as follows, and the kinds and coating amounts of the yellow coupler (ExY) and the compound of the present invention are shown in Table-B. Samples 101 to 120 in exactly the same manner as Sample 000 except that
Was produced.

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A 0.25 Gelatin 1.65 Yellow-Coupler (ExY) 0.72 Color Image Stabilizer (Cpd-2) 0.04 Color Image Stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-14) 0.12 Solvent (Solv-5) 0.20 Solvent (Solv-12) 0.20

For each sample, the maximum color density (Dmax), light fastness (color image residual rate,%) and wet heat fastness (color image residual rate,%) were evaluated in the same manner as in Example 1, and the results are shown. −
Shown in B. However, both light fastness and wet heat fastness were measured at an initial concentration of 2.0.

[0179]

[Table 27] (Table-B-1)

From Table-B, in the comparative coupler ExY-1, the light fastness can be improved when the compound A-19 of the present invention is added, but at the same time, the color density is largely decreased. I understand. When the addition amount of the compound of the present invention is increased, the color density is further reduced. In addition, improvement in wet heat fastness is also seen, but it is slight. On the other hand, when combined with the coupler Y-1 of the invention, by adding the compound A-19 of the invention, a greater effect of improving light fastness with respect to the comparative coupler was obtained. Further, at the same time, the wet heat fastness is also improved, and it can be seen that the improvement effect is obviously greater than that of the comparative coupler. Further, it can be seen that even when the amount of the compound A-19 of the present invention added was increased, the decrease in color density was extremely small. Also,
It is clear from Table-B that the same results as above were obtained in the comparison between the comparative coupler ExY-7 and the coupler Y-7 of the present invention. As described above, by using the coupler of the present invention in combination with the compound of the general formula (A) of the present invention, the light fastness and the wet heat fastness can be simultaneously improved without impairing the color developability.

Example 3 (Scanning Exposure) The same evaluations as in Example 2 were carried out except that the following exposure was carried out for each of the light-sensitive materials produced in Example 2. The results obtained were similar to those of Example 2. (Exposure) YAG solid-state laser (oscillation wavelength, 946 nm) using semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as excitation light source for wavelength conversion with KNbO3 SHG crystal, 473 nm, semiconductor laser GaAlAs (oscillation wavelength) , 808.7 nm) as the excitation light source and wavelength-converted the YVO4 solid-state laser (oscillation wavelength 1064 nm) by the KTP SHG crystal.
2 nm, AlGaInP (oscillation wavelength, about 670 nm: Toshiba type No. TOLD9211) was used. The laser light is an apparatus capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this apparatus, the amount of light was changed to determine the relationship D-logE between the density (D) of the photosensitive material and the amount of light (E). At this time, the laser light of three wavelengths was modulated in light quantity using an external modulator to control the exposure quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ^-8 seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature.

[0182]

By using the yellow coupler of the present invention in combination with the compound represented by the general formula (A) of the present invention, a silver halide color excellent in color reproducibility, image fastness and raw storage stability is obtained. A photographic light-sensitive material can be provided.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive layer containing a silver halide emulsion on a support, wherein at least one light-sensitive layer has a dye-forming coupler represented by the following general formula [Y]. And a compound represented by the following general formula (A), and a silver halide color photographic light-sensitive material. [Chemical 1] (In the formula, A represents an aromatic group, a tertiary alkyl group, a secondary or tertiary cycloalkyl group, a bicycloalkyl group, an aliphatic amino group, an aromatic amino group or a heterocyclic group, and B is an aromatic group. Or a heterocyclic group, Z represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidation product of an aromatic primary amine developing agent, provided that at least a group represented by A, B or Z is present. One has a partial structure represented by the following general formula [P-I].) [Chemical 3] (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, an acylamino group or an acyl group, and R ³ is a fatty group. Group, aromatic group, heterocyclic group, amino group,
It represents an alkoxy group, an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group.
R ¹ and R ² or R ¹ and R ³ may be bonded to each other to form a 5- to 7- or 5- to 8-membered ring, respectively. ) 2. A color characterized in that the silver halide color photographic light-sensitive material according to claim 1 is exposed by a scanning exposure method in which an exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then color development is performed. Image forming method.