JPH07140607A - Silver halide color photographic sensitive material 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 water-soluble polymer in a photosensitive layer. CONSTITUTION:At least one of the photosensitive layers contains at least one kind of water-soluble polymer and at least one kind of dye image forming coupler represented by formula I in which A is an aromatic group, tertiary alkyl, secondary or tertiary cycloalkyl, bicycloalkyl, an aliphatic or aromatic amino or heterocyclic group, 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, and at least one of A, B, and Z has a partial structure represented by formula II.

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 and image fastness of a dye image, and has good raw storability and quality fluctuation due to processing fluctuation. 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 required to have image quality performance that is required to be visually inconspicuous (excellent in graininess). Also,
It is required that the dye image produced in this manner is fast against light, heat, or humidity and does not fade forever. 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 that the color of the dye formed is worse and the fastness of the dye image is extremely low although the latter has a high color forming property. 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 of these couplers.

For example, the improvement of image fastness by a water-insoluble polymer is described in International Patent Publication WO88 / 0072.
No. 3 etc. Further, examples of using a water-insoluble polymer for the above-mentioned coupler having an improved hue are also described in JP-A-5-107701 and JP-A-5-2246. In this case, although the image fastness is certainly improved, the decrease in color density is a problem. In the case of a yellow coupler having a cycloalkyl group or an indoline ring residue as an acyl group of an acylacetanilide type yellow coupler, the color density reduction when a polymer is used tends to be improved, but it is not always a sufficient level, and further improvement is required. Was desired. On the other hand, as yellow couplers having a phosphonyl group in the oil-soluble group (ballast group) in the molecule, examples of pivaloyl type couplers and benzoyl type couplers are described in US Pat. No. 4,026,709, but they were produced. Nothing is said about the fastness of the dye image, and in combination with a water-insoluble polymer, further,
No mention is made of photographic properties when used in combination.

[0006]

The present invention has been made under the circumstances described above. Therefore, the first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in 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 robust 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 a stable photographic quality with little variation 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. That is, (1) in a silver halide color photographic light-sensitive material having at least one photosensitive layer containing a silver halide emulsion on a support, at least one layer of the photosensitive layer contains a dye represented by the following general formula [Y]. A silver halide color photographic light-sensitive material comprising at least one type of couplers formed and at least one type of water-insoluble polymer.

[0008]

[Chemical 3] (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. Represents a group or a heterocyclic group, Z is a hydrogen atom or an aromatic first group.
It represents a group capable of splitting off by a coupling reaction with an oxidized product of a primary amine developing agent. However, at least one of the groups represented by A, B, or Z has a partial structure represented by the following general formula [PI]. )

[0009]

[Chemical 4]

(2) The silver halide color photograph of item 1 above, wherein the water-insoluble polymer is contained in an amount of at least 20% by weight based on the dye-forming coupler represented by the general formula [Y]. Photosensitive material. (3) The silver halide color photographic light-sensitive material as described in 1 or 2 above, wherein the water-insoluble polymer is a polymer composed of a monomer unit having at least one kind of aromatic group. (4) The silver halide color photographic light-sensitive material as described in the above item 1, 2 or 3 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. Color image forming method.

The present inventors have found that the hue of the yellow coupler,
We have been searching for new acylacetanilide type couplers for the purpose of improving color formation and image fastness. Among them, it was found that the coupler having a partial structure represented by the general formula [P-I] of the present invention is a coupler excellent in hue, color developability and image fastness. Further, when the coupler is used in combination with a conventionally known water-insoluble polymer, the image fastness is naturally improved as expected, but the effect is larger than expected, and It was found that the reduction in color density and the deterioration in hue, which had been an obstacle, were remarkably improved. 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 ring 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. 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 a total of 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].

[0018]

[Chemical 5]

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 carbon ring 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 carbocycle or heterocycle in which Q ¹ is formed 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].

[0022]

[Chemical 6]

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].

[0030]

[Chemical 7]

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 of 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.

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

[Table 3]

[0038]

[Table 4]

[0039]

[Table 5]

[0040]

[Table 6]

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

[Table 9]

[0044]

[Table 10]

[0045]

[Table 11]

[0046]

[Table 12]

[0047]

[Table 13]

[0048]

[Table 14]

[0049]

[Table 15]

[0050]

[Table 16]

[0051]

[Table 17]

[0052]

[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.

[0054]

[Chemical 8]

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 water-insoluble polymer of the present invention will be described in detail. The water-insoluble polymer of the present invention is an organic solvent (for example, ethyl acetate, butyl acetate, metholethyl ketone,
Soluble in toluene etc., 100 g of distilled water (25
It may have any structure as long as the solubility in (° C.) is 3 g or less, preferably 1 g or less. Among them, a polymer obtained by polymerizing a vinyl monomer is preferable. As the vinyl monomer preferably used in the polymer of the present invention, two or more kinds of monomers are used as comonomers with each other according to various purposes (for example, solubility improvement). Further, for the purpose of adjusting color developability and solubility, a monomer having an acid group is also used as a comonomer within a range in which the copolymer does not become water-soluble. Also, crosslinkable 2
Monomers with one or more ethylenically unsaturated components can be used. As such a monomer, for example,
Those described in JP-A-60-151636 can be preferably used.

In the vinyl monomer used in the present invention, when a hydrophilic monomer (here, a monomer which becomes water-soluble when made into a homopolymer) is used as a comonomer, the copolymer is water-soluble. The ratio of the hydrophilic monomer in the copolymer is not particularly limited as long as it does not change, but it is usually preferably 40 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less. When the hydrophilic comonomer copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol% or less from the viewpoint of image storability. It is preferably 10 mol% or less, and most preferably the case where such a comonomer is not contained.

The monomers used in the present invention in the polymer are preferably methacrylate type, acrylamide type and methacrylamide type. Particularly preferred are acrylamide type and methacrylamide type. The number average molecular weight of the polymer that can be used in the present invention is preferably 50.
00 or more and 150,000 or less, more preferably 10,000 or more 1
It is less than 0,000. Some specific examples of the polymer used in the present invention are shown below, but the polymer used in the present invention is not limited thereto. The copolymerization ratio of the copolymer in the specific examples shown below is a molar ratio.

[0059]

[Chemical 9]

[0060]

[Chemical 10]

[0061]

[Chemical 11]

[0062]

[Chemical 12]

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 amount of the yellow coupler represented by the general formula [Y] of the present invention used in the silver halide color photographic light-sensitive material is preferably in the range of 0.01 to 10 mmol / m ² , more preferably 0.05 to. 5 mmol / m ² range, and most preferably from 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 amount of the silver halide emulsion in the silver halide emulsion layer in which the coupler of the present invention is used is preferably 0.5 to 50 times, more preferably 1 to 20 times, most preferably 1 to 20 times, in terms of silver mol, of the coupler. Preferably 1.5
It is in the range of 10 times.

In the present invention, various known methods can be used for adding the coupler 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, after dissolving the coupler in a high-boiling organic solvent such as a phosphoric acid ester or a phthalic acid ester and a low-boiling-point auxiliary solvent,
This is a method of dispersing 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. As a dispersion medium for such a coupler, a dielectric constant of 2 to 20 (25
C.) and a high boiling point organic solvent having a refractive index of 1.4 to 1.7 is preferable. Specific examples of the polymer of the present invention other than the above are described in columns 7 to 15 of US Pat. No. 4,857,449 and pages 12 to 30 of WO88 / 00723. There is. In the present invention, the weight ratio of the dispersion medium is in the range of 0 to 10 with respect to the coupler of the present invention, preferably 0.1 to 5, and more preferably 0.3 to 3. Organic substances used as the dispersion medium include 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, JP-A-4-350854, 4-350650, 5-2247 and 5-224.
It is preferable to use the anti-fading agents described in No. 8, No. 5-19427 and No. 5-61165 together.

The water-insoluble polymer of the present invention 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% by weight, more preferably 10% by weight, based on the weight of the coupler.
˜150% by weight, more preferably 20 to 100% by weight. In the color light-sensitive material of the present invention, at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer, and at least one cyan color forming silver halide emulsion layer are coated on a support having a reflective layer. Can be configured. In a general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler that 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 photosensitive layer and the coloring hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

As the support used in the present invention, any support can be used as long as it can be coated with a photographic emulsion layer, such as glass, paper, plastic film, etc., but preferably triacetyl cellulose or It is a transparent support of polyethylene terephthalate or a reflective support described in detail below. The most preferable among them is a reflective support. "Reflective support" used in the present invention
The term "reflective support" refers to a material that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes titanium oxide, zinc oxide, calcium carbonate, and sulfuric acid on the support. Examples include those coated with a hydrophobic resin containing a light reflecting substance such as calcium dispersed therein, and those using a hydrophobic resin itself containing a light reflecting substance dispersed therein as a support. For example, polyethylene-coated paper, polyethylene terephthalate-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or together with a reflective substance, such as a glass plate, polyethylene terephthalate, cellulose triacetate or cellulose nitrate. There are polyester film, polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, and the like.
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 fine particles, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a divalent to tetravalent alcohol. It is preferable that the white pigment fine particles are uniformly dispersed without forming an aggregate of particles in the reflective layer, and the size of the distribution is such that the occupied area ratio (%) (Ri) of the fine particles projected onto a unit area. Can be measured and obtained. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio of the standard deviation s of Ri to the average value (R) of Ri, s / R. 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, and particularly preferably 0.08 or less. 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 second-class diffuse reflective surface 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 surface irregularities is
The roughness of 0.1 μm or more is preferably 0.1 to 2000 cycles / mm, and further 50 to 60 cycles.
It is preferably 0 cycle / mm. Details of such a support are described in JP-A-2-239244.

In the present invention, the silver halide grains may be any silver halide emulsion having any halogen composition such as silver chloride, silver chlorobromide, silver bromide, 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 shorten 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 the high illuminance sensitivity, enhancing the spectral sensitization sensitivity, or enhancing the temporal stability of the photosensitive material,
High silver chloride grains containing 0.01 to 3 mol% of silver iodide on the emulsion surface as described in JP-A-3-84545 may be preferably used. The halogen composition of the emulsion may be different or the same between the grains, but if an emulsion having the same halogen composition among the 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 having the same composition in any portion of the silver halide grains, or the core inside the silver halide grains
Or a so-called layered structure grain in which the halogen composition is different between the shell (shell) and the surrounding layer (one or more layers), or
Particles with a structure that has a non-layered portion with different halogen composition inside or on the surface (if the surface of the particle has a structure in which different composition portions are bonded to the edges, corners, or surfaces), etc. are used by selecting as appropriate be able to. 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
It may be a clear boundary, an unclear boundary by forming a mixed crystal due to a difference in composition, or may be one which positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in the inside and / or on the surface of a silver halide grain in the form of a layer or a 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 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 the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1-2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, 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 photographic emulsions is regular (regu- lar) such as cubic, tetradecahedral or octahedral.
It is possible to use one having a lar) crystal form, one having an irregular crystal form such as a sphere or a plate, or one having a composite form thereof. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. 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 by the method described in ographic Emulsion (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method and a combination thereof is used. May be. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one type 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 or complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions mainly selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, complex ions thereof can be used in combination. In addition, 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 represented 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 may contain various compounds or precursors thereof for the purpose of preventing fog during production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. It 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 No. 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 in 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-3-2073.
No. 0, page 4, lower left column to page 15, lower left column, EP 0,42
No. 0,011, p. 4, line 21 to p. 6, line 54, id 0, 4
20,012, page 4, line 12 to page 10, line 33, 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 and US Pat.
As described in No. 06,025, an aqueous solution or colloidal dispersion in which a surfactant coexists may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent that is substantially immiscible with water, such as phenoxyethanol, and then dispersed in water or a hydrophilic colloid to be added to the emulsion. JP-A-53
It may be directly dispersed in a hydrophilic colloid as described in No. 102733 and No. 58-105141, and the dispersion may be added to the emulsion. The timing of addition to the emulsion is
It may be at any stage in the preparation of emulsions heretofore known to be useful. 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 the application, but it is described in US Pat. No. 3,628,9.
No. 69 and No. 4,225,666, it is also possible to add spectral sensitization at the same time as the chemical sensitizer as described in JP-A No. 58-113928. It can be carried out prior to chemical sensitization as described, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, the spectral sensitizing dyes may be added separately as taught in U.S. Pat. Addition is also possible 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 amount of these spectral sensitizing dyes to be added varies depending on the case and is 0.5 × per mol of silver halide.
The range of 10 ^{−6 to} 1.0 × 10 ⁻² mol is preferable. More preferably, it is in the range of 1.0 × 10 ^{−6 to} 5.0 × 10 ⁻³ mol. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, it is disclosed in JP-A-2-
It is preferable to use the compounds described in No. 157749, page 13, lower right column to page 22, lower right column. By using these compounds, the storability of the light-sensitive material, the processing stability, 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 used in an amount of 0.5 × 10 ^{−5 to} 5.0 × 10 ⁻² mol, preferably 5.0 × 10 ^{−5 to} 5.0 × 10 ⁻³ mol, per mol of silver halide. , 0.1 to 10,000 per mole of sensitizing dye
There is an advantageous amount of use in the range of double, preferably 0.5 to 5000 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer, but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or 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) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal.
In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used, 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, II-VI group semiconductor lasers in the green and blue regions have been confirmed to oscillate, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such cases, at least two layers should be 67
It becomes less necessary to have the spectral sensitivity maximum at 0 nm or more.

In such scanning exposure, the time for which the silver halide in the photosensitive 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 varies 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.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation and improving safety of safelight, etc., and it is described in EP No. 0,337,490A2, No. 27-No. It is preferable to add the dyes which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes) described on page 76. Among these water-soluble dyes, increasing the amount used may deteriorate color separation and safelight safety. As a dye that can be used without deteriorating the color separation, there are EP 0,53
9,978A1, JP-A-5-127325, and JP-A-5-127325.
The water-soluble dyes described in 127327 are preferred.

In the present invention, a colored layer that can be decolorized by treatment is used instead of the water-soluble dye or in combination with the water-soluble dye. The color layer that can be decolorized by the treatment used is
It may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a processing 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 7 in normal printer exposure).
The optical density value is preferably 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of 00 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure. 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, the dyes described in JP-A-2-282244, page 3, upper right column to page 8;
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, and a dye Examples thereof include a method of adsorbing to fine particles such as silver halide and fixing it 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 that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30
8244, pp. 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. A method for preparing colloidal silver as a light absorber is shown in US Pat. Nos. 2,688,601 and 3,459,563. 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 that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a mold preventive 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. Table 1 below shows the additives for treatment and treatment.
9 to the patent publications shown in Table 23, particularly European Patent No. 0,35
Those described in the specification of 5,660A2 (JP-A-2-139544) are preferably used.

[0090]

[Table 19]

[0091]

[Table 20]

[0092]

[Table 21]

[0093]

[Table 22]

[0094]

[Table 23]

The cyan 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. It is preferable to dissolve it with a water-insoluble and organic solvent-soluble polymer and to emulsify and disperse it in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are, for example, US Pat. No. 4,857,449, columns 7 to 15 and WO88 / 00723.
Homopolymers or copolymers described on pages 12 to 30 of the specification. 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 according to 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 type coupler, a pyrrolotriazole type coupler and the yellow coupler of the present invention. That is, the compound and / or the color development process in the above-mentioned European Patent Specification which chemically bonds with an aromatic amine-based developing agent remaining after the color development process to form a chemically inactive and substantially colorless compound. Using the compounds in the above-mentioned European patent specification, which form a chemically inactive and substantially colorless compound, chemically or in combination with the oxidation product of the aromatic amine type color developing agent which remains afterwards, either alone or in combination. 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 of 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. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A. Further, as a 5-pyrazolone-based magenta coupler, International Publication WO92 / 189
No. 01, No. 92/18902 and No. 92/1890
The arylthio-eliminating 5-pyrazolone-based magenta couplers described in No. 3 are 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. The amount of the acylacetanilide coupler used in combination at this time is preferably 50 mol% or less based on all the yellow couplers from the viewpoint of color reproducibility.

As the method for processing the color light-sensitive material of the present invention, in addition to the methods described in the above table, JP-A-2-20725 can be used.
No. 0, 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 page 18, lower right column, line 20 The method is preferred.

[0101]

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 Using the undercoated polyethylene terephthalate support, a single-layer photosensitive material 101 for evaluation of the layer constitution shown below was prepared. (Preparation of Coating Solution for Emulsion Layer) 1.85 mmol of coupler, 10 ml of ethyl acetate, tricresyl phosphate (solvent) and trioctyl phosphate (solvent) were added to the coupler in an amount of 30% by weight and dissolved. This solution was emulsified and dispersed in 33 g of a 14% gelatin aqueous solution containing 3 ml of 10% sodium dodecylbenzenesulfonate.
On the other hand, silver chlorobromide emulsion (cube, average grain size 0.88
3: 7 mixture of large size emulsion (μm) and small size emulsion (0.70 μm) (silver molar ratio). Coefficients of variation of particle size distribution are 0.08 and 0.10. For each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the grain surface). In this emulsion, blue-sensitizing dyes A and B (compounds common to those in Example 2) shown below were added in an amount of 2.0 × 10 ^-4 mol / mol of silver per mol of silver, respectively, and a small size. 2.5 × 10 ⁻⁴ mol of each was added to the emulsion. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion and this emulsion were mixed and dissolved to prepare an emulsion layer coating solution having the following composition. As a hardening agent, 1-oxy-3,5
-Sodium dichloro-s-triazinate was used. (Layer constitution) The layer constitution of the sample used in this experiment is shown below. (The numbers indicate the coating amount per m ^2. )

[Support] Polyethylene terephthalate support [Emulsion layer] Silver chlorobromide emulsion (above) 3.0 mmol Coupler (coupler described in Table A) 1.0 mmol Polymer of the present invention (compound in Table A Species and weight% based on coupler) 0.1 mmol Antifading agent (A-1) 0.1 mmol Antifading agent (A-2) 0.1 mmol Tricresyl phosphate (30% by weight relative to coupler) Trioctyl phosphate (30% by weight based on the coupler) Gelatin 5.5 g [Protective layer] Gelatin 2.5 g Polyvinyl alcohol acrylic modified copolymer (17% conversion) 0.15 g Liquid paraffin 0.03 g

The structures of the comparative coupler used in this example and the coupler of the present invention are shown below.

[0104]

[Chemical 13]

[0105]

[Chemical 14]

[0106]

[Chemical 15]

[0107]

[Chemical 16]

[0108]

[Chemical 17]

The above light-sensitive material was imagewise exposed using an optical wedge and then processed in the following processing steps. (Processing process) Processing process Temperature Time Color development 35 ℃ 40 seconds Bleach fixing 35 ℃ 60 seconds Water wash 35 ℃ 120 seconds

(Processing liquid composition) [Color developer] Distilled water 800 ml Triethanolamine 8.1 g Diethylhydroxylamine 4.2 g Potassium bromide 0.05 g Sodium chloride 0.5 g Sodium hydrogen carbonate 3.9 g Sodium sulfite 0.13 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g potassium carbonate 18.7 g Water was added to 1000 ml pH 10.15

[Bleach-fixing solution] Distilled water 400 ml Ammonium thiosulfate (700 g / l) 150 ml Sodium sulfate 18.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 55.0 g Sodium ethylenediaminetetraacetate 5.0 g Water was added to 1000 ml pH 6. 70

The yellow color density of the processed sample was measured with blue light (center wavelength 440 nm), and the maximum color density (D
_max ) was determined and shown in Table A (Tables 24 and 25 below). In addition, the maximum color density when the water-insoluble polymer was used for each coupler was taken as a standard (10
The coloring rate when the water-insoluble polymer is not used is shown in parentheses when it is set to 0%). Furthermore, after irradiating this sample with a xenon light source of 80,000 lux (5 hours light / 1 hour dark intermittent irradiation) for 14 days, the blue light density was measured again, and the residual ratio of the color image in the D _max region was measured. I asked. The results are also shown in Table A together.

[0113]

[Table 24]

[0114]

[Table 25]

From Table A, for the comparative coupler ExY-1,
It can be seen that the light fastness is improved by adding the polymer, but at the same time, the color density is reduced. For example, when the polymer P-1 was added, the color density was reduced by 17%. On the other hand, the comparison couplers ExY-2, Ex
For Y-3 and ExY-4, it can be seen that the decrease in color density when the polymer P-1 is added is improved to about 10 to 13%, but it cannot be said to be a satisfactory level. On the other hand, in the coupler of the present invention, it is also found that the light fastness is improved by adding the polymer P-1, and the degree of improvement is slightly larger than that of the comparative coupler. Further, it can be seen that in the coupler of the present invention, the decrease in color density caused by the addition of the polymer P-1 is 2 to 5%, which is a significant improvement over the case of the comparative coupler. In particular, the polymers P-7 and P-13, which are composed of acrylamide and methacrylamide having an aromatic group, have a low color density and a large effect of improving light fastness, and thus can be said to be a preferable combination.

Example 2 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multi-layer color photographic paper (100) having the layer constitution shown in was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 130.0 g, color image stabilizer (Cpd-2) 10.0 g, color image stabilizer (Cpd-3)
20.0 g, color image stabilizer (Cpd-5) 20.0 g,
Solvent (Solv-1) 20 g, solvent (Solv-5) 5
Dissolve this solution in 0 g and 180 ml of ethyl acetate and add 1 part of this solution.
An emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of a 10% gelatin aqueous solution containing 60 ml of 0% sodium dodecylbenzenesulfonate. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.88 μm and a small size emulsion A having a grain size of 0.70 μm (silver molar ratio). The variation coefficient of the grain size distribution is 0.08 each
And 0.10. 0.3 mol% silver bromide for each size emulsion,
(Partially contained on a part of the surface of the grain based on silver chloride)
Was prepared. In this emulsion, blue-sensitive sensitizing dyes A, B and C shown below were respectively added to the large size emulsion A per mol of silver at 1.4 × 10 ⁻⁴ mol, and the small size emulsion A was obtained.
In each case, 1.7 × 10 ⁻⁴ mol was added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the 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

[0119]

[Chemical 18]

(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

[0121]

[Chemical 19]

(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

[0123]

[Chemical 20]

(1 mol of silver halide was added to the large-sized emulsion at 5.0 × 10 ⁻⁵ mol, and to the small-sized emulsion at 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.

[0126]

[Chemical 21]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl) is used.
-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.

[0128]

[Chemical formula 22]

(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 [White pigment (TiO ₂ ; content 15
%) And bluish dye (ultra-blue)

First Layer (Blue Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion A 0.27 Gelatin 1.36 Yellow Coupler (ExY) 0.65 Color Image Stabilizer (Cpd-2) 0.05 Color Image Stabilizer (Cpd-3) 0.10 Color image stabilizer (Cpd-5) 0.10 Solvent (Solv-1) 0.10 Solvent (Solv-5) 0.25

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.08 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 coefficients of variation of the grain size distribution are 0.10 and 0.08, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride). 0.13 Gelatin 1.45 Magenta Coupler (ExM) 0.16 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 0.70 Color mixing inhibitor (Cpd-4) 0.06 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. 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 0.60 UV Absorber (UV-1) 0.39 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

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

[0138]

[Chemical formula 23]

[0139]

[Chemical formula 24]

[0140]

[Chemical 25]

[0141]

[Chemical formula 26]

[0142]

[Chemical 27]

[0143]

[Chemical 28]

[0144]

[Chemical 29]

In the sample 100 prepared as described above, the yellow coupler of the first layer (blue sensitive layer) was replaced with the coupler shown in Table B below, and the water-soluble polymer of the present invention was shown in Table B. Samples 101 to 120 added as described above were prepared. At this time, the coating amounts of the coupler and the water-insoluble polymer were changed so that the magnification (mol) shown in Table B with respect to Sample 100 was obtained. The amount of coated silver was also adjusted so that the molar ratio with the coupler was constant. 5 for each sample after coating
The following test was performed after storing at 0 ° C. for 2 weeks.

First, a sample 100 was used as a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd., color temperature of light source was 3200 ° K).
Was used to develop about 35% of the coated silver amount, and exposure was performed so as to give a gray color. The sample 100 was processed into a roll having a width of 127 mm, and imagewise exposed using a printer processor PP1820V manufactured by Fuji Photo Film Co., Ltd.
In the following processing steps, continuous processing (running processing) was performed until the tank capacity for color development was doubled.

Treatment process Temperature Time Replenisher ^* Color development 38.5 ° C. 45 seconds 73 ml Bleach fixing 35 ° C. 45 seconds 60 ml ^** Rinse (1) 35 ° C. 30 seconds ── Rinse (2) 35 ° C. 30 seconds ── Rinse (3) 35 ° C 30 seconds 360 ml Dry 80 ° C 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material ** In addition to the above 60 ml, light-sensitive material 1 m from rinse (1)
Pour 120 ml per ² pour. (Rinse was a three-tank counter-current system from (3) to (1))

The composition of each processing solution for processing A is as follows. Color developing solution Tank solution Replenishing solution 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 0.03 g 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, 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-fixing solution Tank solution Replenishing solution Water 600 ml 150 ml Ammonium thiosulfate (750 g / l) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid iron 5 g 12.5 g Nitric acid (67%) 30 g 65 g Water was 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, after the passage of time, each sample was subjected to gradation exposure with a light source that passed a blue filter, and each sample was treated with the above-mentioned running treatment liquid. It was visually confirmed that the sample using the coupler Y-1 of the present invention had less orange color than the sample using the comparative coupler ExY-1 and exhibited a bright and vivid yellow even in the high color density portion. . Similarly, it was confirmed that the sample using the coupler Y-5 of the present invention exhibited a bright and vivid yellow color as compared with the sample using the comparative coupler ExY-5. The optical density of these samples was measured with blue light (intermediate wavelength 440 nm). The results are shown in Table B (Table 26 below). Next, the sample was subjected to light irradiation for 14 days under a xenon light source of 80,000 lux (5 hours light / 1 hour dark intermittent irradiation), and a fading test was performed. The light fastness was evaluated by the residual ratio of the color image at the initial densities of 2.0 and 1.0, and the results are also shown in Table B.

[0151]

[Table 26]

From Table B, comparative couplers ExY-1, Ex
It can be seen that in the sample using Y-5, the light fastness is improved by adding the polymer as in Example 1, but the color density is greatly reduced with the increase of the addition amount.
On the other hand, in the samples using the couplers Y-1 and Y-5 of the present invention, the color density was slightly decreased even when the amount of the polymer P-1 added was increased, and the effect of improving the light fastness was also large. I understand. In particular, the couplers of this invention are polymers P-1
Without addition, the lightfastness in the high density range was excellent, but the lightfastness in the low density range was slightly inferior to the comparative coupler. However, by using the polymer of the present invention together, not only the light fastness in the high concentration region but also the light fastness in the low concentration region was greatly improved.

Example 3 For the sample 100 shown in Example 2, the yellow coupler (ExY) in the first layer and the water-insoluble polymer (Cpd-) were used.
Sample 100 except that 1), the type of solvent (Solv-1 and Solv-5) and the coating amount were changed as shown in Table C.
Samples 201 to 224 were manufactured in exactly the same manner as in. For each sample, one was aged at 5 ° C. for 14 days and the other was aged at 40 ° C.-80% RH for 14 days. These samples were also exposed and processed in the same manner as in Example 2. The yellow color density of the sample after the treatment was measured, and the maximum color density (D _max ) was determined and is shown in Table C (Table 27 below). Further, in parentheses, the coloring rate of 40 ° C.-80% RH aged product is shown with the refrigerated aged product as a reference (100%). Then, the refrigerated aged product was irradiated with light under a xenon light source of 80,000 lux (intermittent irradiation of 5 hours light / 1 hour dark) for 14 days, and a fading test was performed. The light fastness was evaluated by the residual ratio of the color image at the initial density of 1.5, and the results are shown in Table C.

[0154]

[Table 27]

From Table C, in the sample using the comparative coupler ExY-3, the color density was greatly decreased with the increase of the addition amount of the polymer, and the decrease of the color density was 40 ° C-80% RH.
It can be seen that the sample that has been aged for further enlargement. Also,
It can be seen that by reducing the amount of the high boiling point organic solvent used, the color density is further reduced in both the refrigerated aged product and the 40 ° C.-80% RH aged product. On the other hand, in the sample using the coupler Y-11 of the present invention, not only the decrease in color density when the polymer was added but also the amount of the high boiling point organic solvent used was reduced, 80% R
Even when it is aged with H, the decrease in color density is small. As described above, the coupler of the present invention can improve light fastness without causing a remarkable decrease in color density when used in combination with a water-insoluble polymer. further,
When the amount of the polymer used is increased or when the amount of the high boiling point organic solvent used is reduced, a greater improvement effect can be obtained.

Example 4 For the sample 100 shown in Example 2, the yellow coupler (ExY) of the first layer and the water-insoluble polymer (Cpd-) were used.
1), sample 100 except that the type of solvent (Solv-1 and Solv-5) and the coating amount were changed as shown in Table D.
Samples 301 to 328 were manufactured in exactly the same manner as in. These samples were also exposed and processed in the same manner as in Example 2. The yellow color density of the processed sample was measured to determine the maximum color density (D _max ). The light fastness of these samples was evaluated in the same manner as in Example 2. As a result, it was confirmed that the light fastness was improved by adding the polymer to the coupler of the present invention as in Example 2. Next, the sample is subjected to 80 ° C.-70% RH.
The sample was stored for 28 days under the condition (1), and a fading test was performed. 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 shown in Table D (Table 28 below).

[0157]

[Table 28]

As is clear from Table D, among the water-insoluble polymers of the present invention, polymers P-4, P-7, P-13, P-15 and P each consisting of a monomer having an aromatic group. -31
Shows that, in addition to the improvement in light fastness, the wet heat fastness is also improved.

Example 5 (Scanning Exposure) The same evaluations as in Example 2 were carried out on the respective light-sensitive materials prepared in Example 2 except that the following exposure was carried out. The results obtained were similar to those of Example 2. (Exposure) YAG solid-state laser (oscillation wavelength, 946 nm) using a semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as an excitation light source is KNbO ₃ SHG
A YVO ₄ solid-state laser (oscillation wavelength: 10 nm, 473 nm wavelength-converted by a crystal, semiconductor laser GaAlAs (oscillation wavelength: 808.7 nm) was used as an excitation light source.
The wavelength is 532 nm extracted from the KTP SHG crystal of 64 nm) and taken out by AlGaInP (oscillation wavelength, about 6
70 nm: Toshiba No. TOLD9211) was used. It is an apparatus that can sequentially scan and expose on a color photographic paper that moves in the direction perpendicular to the scanning direction by each rotating polygon of laser light. This device is used to change the amount of light to determine the relationship D between the density (D) and the amount of light (E) of the photosensitive material.
-LogE was determined. 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.

[0160]

By using the yellow coupler of the present invention and a water-insoluble polymer in combination, a silver halide color photographic light-sensitive material excellent in color reproducibility, image fastness and raw storability is provided. You can

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion-containing light-sensitive layer on a support, wherein at least one light-sensitive layer is a dye represented by the following general formula [Y]. A silver halide color photographic light-sensitive material comprising at least one type of couplers formed and at least one type of water-insoluble polymer. [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. Represents a group or a heterocyclic group, Z is a hydrogen atom or an aromatic first group.
It represents a group capable of splitting off by a coupling reaction with an oxidized product of a primary amine developing agent. However, at least one of the groups represented by A, B, or Z has a partial structure represented by the following general formula [PI]. ) [Chemical 2] 2. The silver halide color photograph according to claim 1, wherein the water-insoluble polymer is contained in an amount of at least 20% by weight based on the dye-forming coupler represented by the general formula [Y]. Photosensitive material. 3. The silver halide color photograph according to claim 1, wherein the water-insoluble polymer is a polymer composed of a monomer unit having at least one aromatic group. Photosensitive material. 4. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3 is exposed by a scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then color development is performed. And a color image forming method.