JPH07281372A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproduction performance and sharpness by using a yellow coupler sharp in spectral absorption and forming a white pigment layer between a support and a silver halide emulsion layer. CONSTITUTION:The photosensitive material contains a white pigment in a hydrophobic polymer layer formed between the support and the silver halide emulsion layer and the photographic yellow coupler represented by one of formulae I-III in which R1 is alkyl or cycloalkyl; R2 is alkyl or aryl; R3 is straight chain unsubstituted alkyl; Z is a group to be released by a coupling reaction; R11 is a monovalent substituent except H; Q is a nonmetallic atomic group; R12, is H, amino, or the like; R13 is a group substitutable on a benzene ring; Z2 is a group to be released by a coupling reaction; each of R21 and R22 is alkyl, aryl, or a heterocyclic group; R23 is aryl or a heterocyclic group; and Z3 is a group to be released by a coupling reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent color reproducibility and sharpness, and has excellent adhesiveness to a support or a silver halide emulsion layer and after processing. A silver halide color photographic light-sensitive material that has excellent photographic performance, such as excellent drying properties and no fog, etc.
Also referred to as a color photosensitive material).

[0002]

2. Description of the Related Art With the spread of color photographic materials, the demand for high quality images is increasing. Particularly in recent years, in the case of color print light-sensitive materials, there has been an increasing demand from users for improving the color reproducibility and sharpness of dye images obtained.

With respect to color reproducibility, since the absorption characteristics of the dye image obtained are very important, research into couplers having good absorption characteristics has recently been actively conducted.

For example, JP-A-63-123047 and JP-A-4-9051
No. 4, pivaloylacetanilide yellow coupler having an alkoxy group in the anilide portion described in JP-A-4-124661 and the like, and a pivaloylacetanilide yellow coupler having a cycloalkyl group in the acyl portion described in JP-A-4-218042 and The asymmetric malondiamide yellow couplers described in JP-A-4-174428, JP-A-4-184434, JP-A-5-11416 and the like have a sharp absorption of a color forming dye and an improved color reproducibility.

On the other hand, various techniques for improving sharpness have been proposed. Irradiation and halation are generally known as factors affecting sharpness. The former is brought about by the incident light being scattered by oil droplets such as silver halide grains and couplers dispersed in the gelatin film, and mainly the amount of gelatin, the amount of silver halide,
The degree depends on the amount of oil droplets, and the latter depends on the degree of light reflection from the support, and the reflectance and refractive index of the support.

For prevention of irradiation, dyes have been improved. For example, JP-A-50-145125 and 52-20.
830, 50-111641, 61-148448, 61-151650
No. 62, No. 62-275562, No. 62-283336, etc., for improvement methods.

Further, as a method for preventing halation, a method of providing an antihalation layer is known, for example, Japanese Patent Laid-Open No.
Improved techniques are described in 55-33172, 59-193447, 62-33448 and the like.

However, in these methods, the sharpness is improved and the sensitivity is remarkably lowered, and it is difficult to improve the sharpness while maintaining the practically sufficient sensitivity only by such means.

For these techniques, Japanese Patent Publication No. 59-820,
The technique described in JP-A-58-60738, in which a white pigment-containing layer is provided between the support and the silver halide emulsion layer, is preferable because it reduces the sensitivity. It is preferable to use a hydrophobic binder for the white pigment layer in terms of drying.

In order to further improve the color reproducibility and the sharpness, we have investigated the above-mentioned technique, and between a yellow coupler having a very sharp spectral absorption and a support and a silver halide emulsion layer. It was found that the color reproducibility and the sharpness are synergistically improved by the combination of the techniques of providing the white pigment layer on the above, and the present invention has been accomplished.

[0011]

Therefore, a first object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility. The second object is to provide a silver halide color photographic light-sensitive material excellent in sharpness.

[0012]

The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support having resin coating layers on both sides of a base paper. The material comprises a hydrophobic polymer layer containing at least one white pigment between the support and the silver halide emulsion layer, and at least one of the silver halide emulsion layers has the general formula (Y -I) to (Y-III)
A silver halide color photographic light-sensitive material characterized by containing at least one photographic yellow coupler represented by any of the above. It should be noted that the presence of voids in the hydrophobic polymer layer produces a greater effect.

The details of the present invention will be described below.

First, the yellow coupler represented by formula (Y-I) will be described in detail.

The alkyl group represented by R ₁ in the general formula (YI) is a linear or branched alkyl group such as methyl, ethyl, i-propyl, t-butyl, dodecyl and 1-hexylnonyl. Groups. Examples of the cycloalkyl group represented by R ₁ include groups such as cyclopropyl, cyclohexyl and adamantyl.

The alkyl group and cycloalkyl group represented by R ₁ may further have a substituent, and examples of the substituent include a halogen atom (eg chlorine, bromine etc.), a cyano group, a nitro group, an aryl group. (Eg, phenyl, pt-octylphenyl, 2,4-di-t-amylphenyl, etc.), hydroxyl group, alkoxy group (eg, methoxy, 2-ethoxyethoxy, etc.), aryloxy group (eg, phenoxy, 2,4-diphenyl) -t-amylphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy etc.), heterocyclic oxy group (eg 4-pyridyloxy, 2-hexahydropyranyloxy etc.), carbonyloxy group (eg acetyloxy, pivaloyloxy etc.) Alkylcarbonyloxy groups, benzoyloxy and other aryloxy groups, etc.), sulfonyloxy groups (eg methanesulfone) Alkylsulfonyloxy groups such as nyloxy, trifluoromethanesulfonyloxy and dodecanesulfonyloxy, arylsulfonyloxy groups such as benzenesulfonyloxy and p-toluenesulfonyloxy), carbonyl groups (eg alkylcarbonyl groups such as acetyl and pivaloyl, benzoyl, 3 An arylcarbonyl group such as 5,5-di-t-butyl-4-hydroxybenzoyl), an oxycarbonyl group (eg, methoxycarbonyl, cyclohexyloxycarbonyl,
Alkoxycarbonyl group such as dodecyloxycarbonyl, aryloxycarbonyl group such as 2,4-di-t-amylphenoxycarbonyl, 2-pyridyloxycarbonyl,
Heterocyclic oxycarbonyl groups such as 1-phenylpyrazolyl-5-oxycarbonyl etc.), carbamoyl groups (eg dimethylcarbamoyl, 4- (2,4-di-t-amylphenoxy))
An alkylcarbamoyl group such as butylaminocarbonyl,
Phenylcarbamoyl, arylcarbamoyl groups such as 1-naphthylcarbamoyl), sulfonyl groups (eg, alkylsulfonyl groups such as methanesulfonyl and trifluoromethanesulfonyl, arylsulfonyl groups such as p-toluenesulfonyl), sulfamoyl groups (eg, dimethylsulfamoyl, Alkylsulfamoyl groups such as 4- (2,4-di-t-amylphenoxy) butylaminosulfonyl, arylsulfamoyl groups such as phenylsulfamoyl, and acylsulfones such as acetylsulfamoyl and ethylcarbonylaminosulfonyl. Famoyl group), amino group (eg, alkylamino group such as dimethylamino, cyclohexylamino, dodecylamino, arylamino group such as anilino, pt-octylanilino, etc.), sulfonamide group (eg, methanesulfonamie) , Heptafluoropropanesulfonamide, hexadecylsulfonamide, etc. alkylsulfonamide groups, p-toluenesulfonamide, pentafluorobenzenesulfonamide, etc. arylsulfonamide groups), acylamino groups (eg, acetylamino, myristoylamino, etc. alkylcarbonyl groups) Amino groups, arylcarbonylamino groups such as benzoylamino), alkylthio groups (eg methylthio, t-octylthio, etc.), arylthio groups (eg phenylthio) and heterocyclic thio groups (eg 1-phenyltetrazole-5-thio, 5-methyl) -1,3,4-oxadiazole-2-thio etc.) and the like.

R ₁ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

Examples of the alkyl group and cycloalkyl group represented by R ₂ include the same groups as the alkyl group and cycloalkyl group represented by R ₁ .
Moreover, examples of the aryl group represented by R ₂ include a phenyl group and a 1-naphthyl group. The alkyl group, cycloalkyl group and aryl group represented by R ₂ may have a substituent, and examples of the substituent include R
There can be mentioned groups group having the same meaning as described above as alkyl groups and substituents of the cycloalkyl groups represented by the alkyl group and cycloalkyl group as defined group and R ₁ represented by _1.

R ₂ is preferably an alkyl group, more preferably an unsubstituted alkyl group, and particularly preferably a methyl group.

The group capable of splitting off upon coupling with the oxidized product of the developing agent represented by Z ₁ is a nitrogen-containing heterocyclic group, an aryloxy group, an arylthio group or a heterocycle, which is bonded to the coupling position at a nitrogen atom. Oxy group, heterocyclic thio group,
Examples thereof include an acyloxy group, a carbamoyloxy group, an alkylthio group and a halogen atom.

When Z ₁ represents a nitrogen-containing heterocyclic group bonded to the coupling position at a nitrogen atom, the nitrogen-containing heterocyclic group has 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms. A 5- or 6-membered, substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed ring heterocyclic group are preferred.
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,
3-triazol-2-yl, 1,2,3-triazol-1-yl,
Benzotriazolyl, benzimidazolyl, imidazolidin-2,4-dione-3-yl, oxazolidine-2,4-dione-
3-yl, 1,2,4-triazolidine-3,5-dione-4-yl, imidazolidin-2,4,5-trione-3-yl, 2-imidazolinone-1-yl, 3,5- Examples include dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, the substituent is not particularly limited, but as a preferred substituent, one of the substituents is an alkyl group, an alkoxy group,
It is a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl 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.

When Z ₁ represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms. A substituted or unsubstituted phenoxy group is particularly preferable. When it has a substituent, preferred substituents are:
This is the 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, a nitro group, a cyano group or an acyl group.

When Z ₁ represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When it has a substituent, at least one substituent is preferably an alkyl group, an alkoxy group,
It is a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When Z ₁ represents a heterocyclic oxy group, the heterocyclic group moiety has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
3 to 12, preferably 5 to 6, containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom.
It is a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group having a member ring. Examples of the heterocyclic oxy group include a pyridyloxy group, a pyrazolyloxy group or a furyloxy group. When it has a substituent, one substituent is preferably an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group. , A nitro group, a carbamoyl group or a sulfonyl group.

When Z ₁ represents a heterocyclic thio group, the heterocyclic group part has at least a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. It is a substituted or unsubstituted, saturated or unsaturated, and monocyclic or condensed-ring heterocyclic group having 3 to 12, preferably 5 to 6 membered ring containing one or more. Examples of the heterocyclic thio group include a tetrazolylthio group, a 1,3,4-thiadiazolylthio group, a 1,3,4-oxadiazolylthio group, a 1,3,4-triazolylthio group, a benzimidazolylthio group and a benzo group. Examples thereof include a thiazolylthio group and a 2-pyridylthio group.
When it has a substituent, at least one of the substituents is preferably an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group or a sulfone. It is an amide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When Z ₁ represents an acyloxy group, the acyloxy group preferably has 6 to 10 carbon atoms and is a monocyclic ring or a condensed ring. A substituted or unsubstituted aromatic acyloxy group, or a carbon number of 2 to 30, preferably 2 to 20
Which is a substituted or unsubstituted aliphatic acyloxy group. These may further have a substituent.

When Z ₁ represents a carbamoyloxy group, this carbamoyloxy group is an aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. is there. For example, N, N-diethylcarbamoyloxy, N-phenylcarbamoyloxy,
1-imidazolyl carbonyloxy or 1-pyrrolo carbonyloxy is mentioned.

When Z ₁ represents an alkylthio group, the alkylthio group is a linear, branched, saturated or unsaturated, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. These may further have a substituent.

Preferred examples of Z ₁ include groups represented by the following general formulas (I), (II) and (III).

General formula (I) -OR ₄ General formula (II) -OCOR ₄

[0031]

[Chemical 4]

In the above general formulas (I) and (II), R ₄
Represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ₄ include the same groups as the alkyl group, cycloalkyl group, and aryl group represented by R ₂ in the general formula (YI). be able to. Examples of the heterocyclic group represented by R ₄ include groups such as 4-pyridyl and 2-hexahydropyranyl. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₄ may have a substituent, and examples of the substituent include the alkyl represented by R ₂ in the general formula (YI). Examples thereof include groups having the same meanings as those mentioned as the substituents for the group, cycloalkyl group and aryl group.

Of these alkyl groups, cycloalkyl groups, aryl groups and heterocyclic groups represented by R ₄ , aryl groups are preferred. The substituent of R ₄ is an electron-withdrawing group (for example, oxycarbonyl group such as carboxyl, methoxycarbonyl or i-propyloxycarbonyl, acyl group such as acetyl or benzoyl, trifluoromethanesulfonyl group or 4-hydroxyphenylsulfonyl group). Such as sulfonyl group, nitro group, cyano group,
A halogen atom, a sulfamoyl group such as dimethylsulfamoyl, an acylamino group such as acetylamino or pentafluorobenzoylamino, and a sulfonamide group such as methanesulfonamide) are preferable.

In the above general formula (III), X ₁ represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Examples of the atomic group necessary for forming a non-metallic atomic group, such as methylene, methine, substituted methine _{-CO -, - N (R 5} ) - (R 5 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic Represents a ring group), -N =, -O- and -S
(O) u- (u represents an integer of 0 to 2) and the like.

Z ₁ is particularly preferably the following general formula (I
It is a group represented by V).

[0036]

[Chemical 5]

In the above general formula (IV), Y ₁ is --N (R ₆ ).
- (R ₆ represents a group as defined for groups represented by R ₅ in the general formula (III)), - the O- and -S (O) r- (r 0~2
Represents an integer of) or the like, or a hetero atom represented by -C (O)
_{-, - C (R 7)} (R 8) - (R 7 and R ₈ is an alkyl group represented by R ₂ in the hydrogen atom or the general formula (I),
Represents a group having the same meaning as the group mentioned as the substituent of the cycloalkyl group and the aryl group) and -C (R ₉ )-(R ₉ is a hydrogen atom or represented by R ₂ in the general formula (Y-I). Represents a group having the same meaning as the group mentioned as the substituent of the alkyl group, cycloalkyl group and aryl group) and the like.

X ₂ represents a non-metal atom group necessary for forming a 5- or 6-membered ring in cooperation with -Y ₁ -N-CO-. Here, examples of the atomic group necessary for forming the non-metallic atomic group include an atomic group having the same meaning as the atomic group represented by X ₁ in the general formula (III).

R ₃ represents an unsubstituted alkyl group having 11 to 21 carbon atoms, preferably a straight chain.

The 2-equivalent yellow coupler represented by formula (Y-I) may be bonded at any substituent to form a bis form, tris form, tetrakis form or polymer form.

The yellow coupler represented by the general formula (Y-I) uses a commercially available compound that is easily available as a starting material, and a conventionally known method, for example, JP-A-63-123047,
It can be easily synthesized according to the method described in JP-A-4-9051 and JP-A-4-124661.

Specific examples of the yellow coupler represented by (Y-I) are shown below.

[0043]

[Chemical 6]

[0044]

[Chemical 7]

Next, the yellow coupler represented by formula (Y-II) will be described.

In the general formula (Y-II), R ₁₁ is preferably a halogen atom, a cyano group or a monovalent aliphatic group having 1 to 30 carbon atoms which may be substituted (for example, an alkyl group or an alkoxy group). ) Or a monovalent aromatic group having 6 to 30 carbon atoms (for example, an aryl group, an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group,
Alkoxy group, nitro group, amino group, acylamino group,
Examples thereof include a sulfonamide group and an acyl group.

Q is preferably a hydrocarbon ring having 3 to 30 carbon atoms, which may be substituted with any of 3 to 5 members together with C, or at least one hetero atom selected from N, S, O and P. It is a group of non-metal atoms necessary for forming a heterocycle having 2 to 30 carbon atoms contained therein. The ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane, cyclobutane, cyclopentane, cyclopropene, cyclobutene, cyclopentene,
There are rings such as oxetane, oxolane, 1,3-dioxolane, thietane, thiolane and pyrrolidine. Examples of the substituent which may have include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group.

R ₁₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or an alkyl group having 0 to 30 carbon atoms. It represents an amino group, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

R ₁₃ is preferably a halogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or 2 to 30 carbon atoms.
Alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 acylamino group, C1-30 sulfonamide group, C1-30 carbamoyl group, C0-30 Sulfamoyl group, carbon number 1
~ 30 alkylsulfonyl group, C6-30 arylsulfonyl group, C1-30 ureido group, C0
30 sulfamoylanomy group, C2-C30 alkoxycarbonylamino group, C1-C30 heterocyclic group, C1-C30 acyl group, C1-C30 alkylsulfonyloxy group, carbon The arylsulfonylkioxy group of the formulas 6 to 30 is represented, and the substituent thereof is, for example, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group. , Heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group, nitro group, Acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfo Aryloxy group, and an arylsulfonyloxy group.

The substitution position of R _{13 in} the general formula (Y-II) is the benzene ring of anilide.

[0051]

[Chemical 8]

Z ₂ represents the same group as Z ₁ in the above general formula (YI).

Next, particularly preferred substituents in formula (Y-II) will be described.

Particularly preferably, R ₁₁ is a halogen atom,
An alkyl group, most preferably a methyl group.
Q is particularly preferably a group of nonmetallic atoms in which the ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example,

[0055]

[Chemical 9]

R ₁₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms (for example, methyl, trifluoromethyl, ethyl, i-propyl, t-butyl etc.), a carbon atom having 1 to 8 carbon atoms. An alkoxy group (eg methoxy,
Ethoxy, methoxyethoxy, butoxy) or an aryloxy group having 6 to 24 carbon atoms (eg phenoxy, p-tolyloxy, p-methoxyphenoxy etc.), most preferably a chlorine atom, a methoxy group or a trifluoromethyl group. .

R ₁₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, and most preferably an alkoxy group, an alkoxycarbonyl group, It is an acylamino group or a sulfonamide group.

Z ₂ is particularly preferably a group represented by the general formula (IV) described in the general formula (YI).

The yellow coupler represented by the general formula (Y-II) is prepared by using a commercially available compound which is easily available as a starting material, according to a conventionally known method, for example, a method described in JP-A No. 4-218042. It can be easily synthesized.

Specific examples of the yellow coupler represented by formula (Y-II) are shown below.

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical 12]

[0064]

[Chemical 13]

[0065]

[Chemical 14]

Next, the coupler represented by formula (Y-III) will be described in detail.

When R ₂₁ and R _{22 in the} general formula (Y-III) represent an alkyl group, they have 1 to 30 carbon atoms, preferably 1 to 20 linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted. It is a substituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t-octyl, i-butyl, dodecyl, 2-hexyldecyl and the like.

When R ₂₁ and R ₂₂ represent a heterocyclic group, the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms,
A 3- to 12-membered ring, preferably a 5- to 6-membered, saturated or unsaturated, substituted or unsubstituted, and monocyclic or condensed ring containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. Is a heterocyclic group. Examples of the heterocyclic group include 3-pyrrolidinyl, 1,2,4-triazol-3-yl, 2-pyridyl, 4-pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4-dioxo-1,3- Imidazolidine-5-
And yl or pyranyl.

When R ₂₁ and R ₂₂ represent an aryl group, they represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Typical examples of the aryl group are phenyl and naphthyl.

The nitrogen-containing heterocyclic group which R ₂₁ and R ₂₂ may combine to form together with N has 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms.
15 is a 3- to 12-membered ring, which may contain, for example, an oxygen atom or a sulfur atom in addition to a nitrogen atom as a hetero atom, preferably a 5- to 6-membered ring, substituted or unsubstituted, saturated or unsaturated, and monocyclic. It is a heterocyclic group having a ring or a condensed ring. Examples of this heterocyclic group are pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-indolinyl, 1,
2,3,4-Tetrahydroquinolin-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.

When R ₂₁ and R ₂₂ represent a substituted alkyl group, an aryl group or a heterocyclic group, and when R ₂₁ and R ₂₂ are bonded to each other, the nitrogen-containing heterocyclic group formed with N is substituted. When having a group, examples of those substituents include the following. Halogen atom (for example, fluorine, chlorine), alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl), acylamino group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, acetamide, tetradecanamide, 2- (2,4-di-t-amylphenoxy) butanamide, benzamide), sulfonamide group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methanesulfonamide, Dodecanesulfonamide, hexadecanesulfonamide, benzenesulfonamide),
Carbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N-butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, N- Mesylcarbamoyl, N-dodecylsulfonylcarbamoyl), sulfamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, N-butylsulfamoyl, N-dodecylsulfamoyl, N-hexadecylsulfamoyl, N- 3- (2,4-di-t-amylphenoxy) butylsulfamoyl, N, N-diethylsulfamoyl),
Alkoxy group (C1-30, preferably 1-20. For example, methoxy, hexadecyloxy, i-propoxy), aryloxy group (C6-20, preferably 6-10. For example, phenoxy, 4-methoxyphenoxy. , 3-t-butyl-4
-Hydroxyphenoxy, naphthoxy), an aryloxycarbonyl group (having 7 to 21 carbon atoms, preferably 7 to 11 carbon atoms, for example, phenoxycarbonyl), an N-acylsulfamoyl group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms). N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl), sulfonyl group (having 1 to 30 carbon atoms, preferably 1 to 30 carbon atoms)
20. For example, methanesulfonyl, octanesulfonyl, 4-
Hydroxyphenylsulfonyl, dodecanesulfonyl), alkoxycarbonylamino group (C1-C30,
Preferably 1 to 20. For example, ethoxycarbonylamino), cyano group, nitro group, carboxyl group, hydroxyl group, sulfo group, alkylthio group (having 1 to 30 carbon atoms, preferably 1 to 20. For example, methylthio, dodecylthio, dodecylcarbamoylmethylthio), ureido group (carbon Number 1 to 30, preferably 1 to 20. For example, N-phenylureido, N-hexadecylureido), aryl group (having 6 carbon atoms)
-20, preferably 6-10. For example, phenyl, naphthyl,
4-methoxyphenyl), a heterocyclic group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, containing at least one or more nitrogen, oxygen or sulfur as a hetero atom, a 3 to 12 membered ring, preferably 5 to 6 Membered ring, monocyclic or condensed ring, for example, 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl, 2,4-dioxo-1,3-
Imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl), alkyl groups (1-30, preferably 1-20, straight-chain, branched or cyclic, and saturated or unsaturated alkyl, such as Methyl, ethyl, i-
Propyl, cyclopropyl, t-pentyl, t-octyl,
Cyclopentyl, t-butyl, sec-butyl, dodecyl, 2-
Hexyldecyl), an acyl group (having 1 to 30 carbon atoms, preferably 2 to 20. For example, acetyl, benzoyl), an acyloxy group (having 2 to 30 carbon atoms, preferably 2 to 20. For example, propanoyloxy, tetradecanoyloxy). , An arylthio group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, for example, phenylthio, naphthylthio), a sulfamoylamino group (having 0 to 30 carbon atoms, preferably 0 to 20 carbon atoms, such as N-butylsulfamoylamino, N -Dodecylsulfamoylamino, N-
Phenylsulfamoylamino) or N-sulfonylsulfamoyl group (having 1 to 30, preferably 1 to 20 carbon atoms. For example, N-mesylsulfamoyl, N-ethanesulfonylsulfamoyl, N-dodecanesulfonylsulfamoyl) , N-hexadecanesulfonylsulfamoyl) and the like.

The above-mentioned substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

Preferred substituents in the above are alkoxy groups, halogen atoms, alkoxycarbonyl groups, acyloxy groups, acylamino groups, sulfonyl groups, carbamoyl groups, sulfamoyl groups, sulfonamide groups, nitro groups, alkyl groups or aryl groups. Is mentioned.

In the general formula (Y-III), the aryl group represented by R ₂₃ has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
Is a substituted or unsubstituted aryl group. For example, a phenyl group and a naphthyl group are typical examples.

In formula (Y-III), the heterocyclic group represented by R ₂₃ has the same meaning as described above when R ₂₁ or R ₂₂ represents a heterocyclic group.

When R ₂₃ represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include the substituents enumerated above as examples when R ₂₁ has a substituent. As a preferred example of the substituent which R ₂₃ has, one of the substituents is a halogen atom, an alkoxycarbonyl group,
Sulfamoyl group, carbamoyl group, sulfonyl group, N-
A sulfonylsulfamoyl group, an N-acylsulfamoyl group, an alkoxy group, an acylamino group, an N-sulfonylcarbamoyl group, a sulfonamide group or an alkyl group.

A particularly preferred example of R ₂₃ is a phenyl group having at least one substituent in the ortho position.

In the general formula (Y-III), the group represented by Z ₃ includes the same groups as Z _{1 in the} general formula (Y-I), and particularly preferably the group represented by the general formula (IV). Is a group that is

Next, a particularly preferred range of the coupler represented by formula (Y-III) is described below.

The group represented by R ₂₁ in formula (Y-III) is preferably an alkyl group. Particularly preferably, it is an alkyl group having 1 to 10 carbon atoms.

The group represented by R ₂₃ in formula (Y-III) is preferably an aromatic group. Particularly preferably,
A phenyl group having at least one substituent at the ortho position. Examples of the substituent include those listed above as the substituent that may be possessed when R ₂₃ is an aryl group.
The example of a preferable substituent is also the same.

The group represented by Z ₃ in the general formula (Y-III) is preferably a nitrogen-containing heterocyclic group bonded to a coupling position at a 5- to 6-membered nitrogen atom, an aryloxy group, 5 to 6
And a 5-membered heterocyclic thio group.

Among the couplers represented by the general formula (Y-III), a particularly preferred coupler is the following general formula (Y-III).
a), a coupler represented by (Y-IIIb) or (Y-IIIc).

[0084]

[Chemical 15]

In the formula, Z ₃ is Z in the general formula (Y-III).
₃ in the above formula, R ₂₄ represents an alkyl group, R ₂₅ represents an alkyl group or an aromatic group, Ar represents a phenyl group having at least one substituent in the ortho position, X ₃ is -C
(R ₂₆ ) (R ₂₇ ) -N <represents an organic residue forming a nitrogen-containing heterocyclic group (monocyclic or condensed ring), and X ₄ represents -C (R ₂₈ ) = C.
(R ₂₉₎ represents an organic residue forming a -N nitrogen-containing Hajime Tamaki together with <(monocyclic or condensed), each _{R 2 6, R 27, R} 28 and R ₂₉ are a hydrogen atom or a substituent Represent

In the general formulas (Y-IIIa) to (Y-IIIc), detailed description and preferred ranges of the groups represented by R _{24 to} R ₂₉ , X ₃ , X ₄ and Ar are shown in the general formula (Y-III )
In the explanations given above, it has the same meaning as the explanation of the corresponding group. When R _{26 to} R ₂₉ represent a substituent, the examples of the substituents that the nitrogen-containing heterocyclic group formed by R ₂₁ and R ₂₂ in combination with N may have are listed.

Particularly preferred couplers in formulas (Y-IIIa) to (Y-IIIc) are represented by formulas (Y-IIIb) or (Y
-IIIc) is a coupler.

The coupler represented by the general formula (Y-III) has two groups represented by R ₂₁ , R ₂₂ , R ₂₃ and Z _3.
Dimers or higher multimers (eg telomers or polymers) that are linked to each other via valent or higher groups may be formed. In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

The coupler represented by formula (Y-III) is preferably a diffusion resistant coupler. The diffusion resistant coupler is a coupler having a group (diffusion resistant group) in the molecule that increases the molecular weight sufficiently in order to immobilize the molecule in the added layer. As the diffusion resistant group, an alkyl group having a total carbon number of 8 to 30, preferably 10 to 20 or a total carbon number of 4 is usually used.
An aryl group having -20 substituents is used. These diffusion resistant groups may be substituted anywhere in the molecule,
Moreover, you may have two or more.

The yellow coupler represented by the general formula (Y-III) is prepared by using a commercially available compound which is easily available as a starting material, and a conventionally known method, for example, JP-A-4-174428.
It can be easily synthesized according to the methods described in Nos. 4-184434 and 5-11416.

Specific examples of the yellow coupler represented by formula (Y-III) are shown below, but the invention is not limited thereto.

[0092]

[Chemical 16]

[0093]

[Chemical 17]

[0094]

[Chemical 18]

[0095]

[Chemical 19]

[0096]

[Chemical 20]

Among the yellow couplers represented by the general formulas (Y-I) to (Y-III) of the present invention, the yellow coupler represented by the general formula (Y-I) is most preferable.

The yellow couplers represented by formulas (Y-I) to (Y-III) of the present invention can be used in the range of 1.0 to 1.0 × 10 ^-3 mol per mol of silver halide.
It is preferably 5.0 × 10 ^{−1 to} 5.0 × 10 ⁻² mol, more preferably 4.0 × 10 ^{−1 to} 2.0 × 10 ⁻² mol.
The addition amount of the yellow coupler is preferably 0.70 g / m ² or less, particularly preferably 0.65 g / m ^2.

The hydrophobic polymer layer according to the present invention can be formed by various methods. As a preferable method, a white pigment surface-treated with a high molecular compound as described in JP-A-62-187846 is used. And a method of forming a hydrophobic layer by coating and drying a polymer soluble in an organic solvent and a white pigment described in JP-A-5-289235. Examples of the method for forming voids in the hydrophobic polymer layer include a method described in JP-A-5-313301, in which a hydrophobic binder is dissolved in a solvent, a poor solvent is added, and the resulting solution is coated and dried.

As the monomer forming the polymer according to the present invention, ethylene, propylene, 1-butene, dicyclopentadiene, butadiene, isoprene, chloroprene, isobutylene, vinyl chloride, vinylidene chloride, vinyl acetate, 1,4-pentadiene, Olefins such as 1,4-hexadiene, 1-allyl-1-cyclopentene and 1,5-hexadiene, styrene derivatives such as styrene, methylstyrene and p-methoxystyrene, methyl acrylate, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate Acrylic acid derivatives such as cyanoethyl acrylate, acrylamide, methyl acrylamide, cyclohexyl acrylamide, phenyl acrylamide, dimethyl acrylamide, methyl methacrylate,
Methacrylic acid derivatives such as ethylmethacrylate, butylmethacrylate, hydroxyethylmethacrylate, methacrylamide, methylmethacrylamide, butylmethacrylamide, benzylmethacrylamide, vinyl acetate, vinyl butyrate, vinyl chloroacetate vinyl benzoate, vinyl salicylate, etc. Vinyl esters, crotonic acid esters such as butyl croton, maleic acid esters such as dimethyl itaconate, fumaric acid esters such as diethyl fumarate, allyl compounds such as allyl acetate and allyl benzoate, methyl vinyl ether, butyl Vinyl ethers such as vinyl ether and dimethylaminoethyl vinyl ether, vinyl ketones such as methyl vinyl ketone and methoxyethyl vinyl ketone, vinyl pyridine N- vinylimidazole, N- vinyl triazole, vinyl heterocyclic compounds such as N- vinylpyrrolidone, glycidyl acrylate, glycidyl esters such as glycidyl methacrylate, acrylonitrile,
Unsaturated nitriles such as methacrylonitrile, divinylbenzene, methylenebisacrylamide, polyfunctional monomers such as ethylene glycol dimethacrylate, and further acrylic acid, methacrylic acid, itaconic acid, maleic acid and the like are preferable. It is preferable that the polymer contains at least one of 5 to 95% by weight.
Further, the polymer may contain a crosslinkable monomer in the range of 0.05 to 20% by weight. Preferred crosslinkable monomers include divinylbenzene, allyl acrylate, allyl methacrylate, allyloxyethyl acrylate, diallyl phthalate, diallyl itaconate, ethylene glycol and dimethacrylate.

The white pigment used in the hydrophobic polymer layer containing the white pigment according to the present invention is, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin. Etc. can be used, but titanium dioxide is preferable among them for various reasons.

The coating amount of the white pigment is preferably 1 to 50.
in the range of g / m ^2, more preferably from 3 to 20 g / m ^2.

The hydrophobic polymer layer containing the white pigment according to the present invention has a porosity of 5 relative to the hydrophilic colloid layer.
It is preferably about 35% by weight. The porosity is obtained from the specific gravity, the film thickness and the like. In addition to the white pigment, a colorant such as yellow, gray, blue, and black colloidal silver, an inorganic colored pigment, an organic colored pigment, or a dye may be added to the hydrophobic polymer layer containing the white pigment according to the present invention. I can. The hydrophobic polymer layer containing the white pigment according to the present invention can be provided between the support and the silver halide emulsion layer closest to the support. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing hydrophobic polymer layer, if necessary, an undercoat layer on the support or an intermediate layer at any position. It is possible to provide a non-photosensitive hydrophilic colloid layer.

A colorant-containing hydrophilic colloid layer can be coated between the hydrophobic polymer layer containing the white pigment according to the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs only light in a certain partial region. It can be selected according to. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, particularly preferably 30% or less.

The support used in the present invention is a paper support having resin coating layers on both sides, and the resin layer on the side coated with the silver halide emulsion layer may contain a white pigment. The base paper used in the paper support of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for composite paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any paper such as neutral paper and acid paper may be used. The paper thickness is preferably 40 to 250 μm.

In the above support, a sizing agent, a fixing agent, a tension enhancer, an antistatic agent, a dye, which is generally used in papermaking,
Additives such as antifoggants may be added, and
A surface sizing agent, a surface tension agent, an antistatic agent, etc. may be appropriately applied to the surface. As a method of coating a resin coating layer on a support, a method of laminating a polyolefin resin or a polyethylene terephthalate resin is known. The olefin resin mainly used for laminating can be selected from ethylene, α-olefins and a mixture of at least two kinds thereof. Among them, the widely used polyolefin resin is low density polyethylene, high density polyethylene or a mixture thereof.

In general, a resin laminate can be formed by melt-extruding a resin composition on a support and coating it. In order to carry out this melt extrusion coating method, usually, a resin composition is melt-extruded and coated in the form of a single layer or a plurality of layers on a support running through a slit die of an extruder. Usually, the melt extrusion temperature is preferably 200 to 250 ° C. The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

In the present invention, examples of the white pigment used in the resin coating layer of the support include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like. Although it can be used, titanium dioxide is particularly preferable. Even if titanium dioxide is surface-treated with aluminum hydroxide, alcohol, surfactant, etc.,
Further, it may not be surface-treated. These white pigments are contained in an amount of 3 to 25% by weight, preferably 5 to 20% by weight, based on the resin of the resin coating layer on the side of the reflective support on which the photographic emulsion is coated.

In the silver halide emulsion according to the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver iodochlorobromide or the like is used as a photosensitive silver halide. obtain.

Heavy metal ions can be contained in the silver halide emulsion according to the present invention. Examples of the heavy metal ions used include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and lead, Examples include rhenium, molybdenum, tungsten, and chromium ions. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
No. 756, No. 4,225,666, JP-A-55-26589, JP-B-55-4
The octahedron, the tetradecahedron, the dodecahedron by the method described in the literature such as No. 2737 and The Journal of Photographic Science (J.Photogr.Sci.) 21, 39 (1973). It is also possible to prepare particles having the same shape and use them. Further, grains having twin planes may be used. As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed.

The particle size of the silver halide grains is not particularly limited, but in view of other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm, more preferably 0.2
The range is up to 1.0 μm. The particle size can be measured by various methods generally used in the technical field. Typical methods include Loveland's "Particle Size Analysis Method" (ASTM. Symposium on Light Microscopy, pages 94-122, (1955)) or "Theory of Photographic Processes, Third Edition" (Mies And James, co-authored, Chapter 2, Macmillan, 1966). This particle size can be measured using the projected area of the particle or an approximate diameter. When the particles have a substantially uniform shape, the particle size distribution can be represented fairly accurately as a diameter or a projected area. The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

As the apparatus and method for preparing the silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method is preferable. preferable. As one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 can be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The coating silver amount of the color light-sensitive material of the present invention is preferably 0.9 g / m ² or less from the viewpoint of suitability for rapid processing, and is preferably
It is 0.7 g / m ² or less, particularly preferably 0.6 g / m ² or less. For the silver halide emulsion, a sensitization method using a sulfur compound, a sensitization method using a gold compound, and a sensitization method using a sulfur compound and a gold compound in combination can be used. Preferred sulfur sensitizers include thiosulfate, allylthiocarbamidourea, allylisothiocyanate, cystine, p-
Toluenethiosulfonic acid, rhodanine, inorganic sulfur and the like can be mentioned.

Preferred gold sensitizers include chloroauric acid and gold sulfide, as well as various gold complexes and the above-mentioned gold compounds.

The silver halide emulsion contains a known antifoggant for the purpose of preventing fog occurring during the process of manufacturing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog occurring during development. Agents can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: (IIa-1) to (IIa-) described on page 8 of the same publication.
8), compounds (IIb-1) to (IIb-7), and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. be able to. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

The color light-sensitive material of the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm in combination with a yellow coupler, a magenta coupler and a cyan coupler. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Useful sensitizing dyes include cyanine dyes,
Examples include merocyanine dyes and complex merocyanine dyes.

As the coupler used in the color light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent is used. Can also be used, but a typical product is 350-500 nm
Yellow coupler with spectral absorption maximum at 500-600nm
Magenta coupler with spectral absorption maximum at 600-750nm
The one known as a cyan coupler having a spectral absorption maximum is typical.

As the magenta dye-forming coupler, 5-pyrazolone type couplers, pyrazolone benzimidazole type couplers, pyrazoloazole type couplers, open chain acylacetonitrile type couplers and the like can be used.

Examples of magenta couplers that can be preferably used in the present invention include couplers represented by formulas (M-I) and (M-II) described on page 12 of JP-A-4-114154. . Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same publication. Among them, the coupler represented by the general formula (MI) is particularly preferable in order to enhance the effects of the present invention, and the MC described in pages 15 to 16 of the same publication as a specific compound.
-8 to MC-11 can be mentioned, but the present invention is not limited thereto.

As the cyan dye forming coupler, a naphthol type coupler, a phenol type coupler, an imidazole type coupler and the like can be used.

Examples of cyan couplers that can be preferably used in the present invention include couplers represented by the general formulas (C-I) and (C-II) described on page 17 of JP-A-4-114154. it can. Specific compounds are disclosed in the same publications 18 to 21.
The compounds described as CC-1 to CC-14 on the page can be mentioned, but the invention is not limited thereto.

When the oil-in-water type emulsion dispersion method is used for adding the coupler to the color light-sensitive material, the boiling point is usually 15
It is dissolved in a water-insoluble high-boiling point organic solvent at 0 ° C or higher, if necessary, in combination with a low-boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. . As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. A step of removing the low boiling point organic solvent may be added after or at the same time as the dispersion. As the high boiling point organic solvent for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent as needed to prepare a gelatin aqueous solution. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be adopted. At this time, examples of the water-insoluble polymer soluble in an organic solvent include poly (Nt-butylacrylamide).

The compound (d-11) described in JP-A-4-114154, page 33, for the purpose of shifting the absorption wavelength of the color forming dye,
Compounds such as the compound (A'-1) described on page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in No. 7 can also be used.

In the present invention, gelatin is used as the binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, single or co-polymers. Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as polymers can also be used in combination with gelatin. The gelatin used may be lime-processed gelatin, acid-processed gelatin, or may be gelatin produced from any one of cow bone, cow hide, pig skin, etc., but preferably cow bone, It is a lime-processed gelatin made from pig skin.

In the present invention, a photosensitive silver halide emulsion layer from the support closest to the side on which the silver halide emulsion layer is coated to the hydrophilic colloid layer farthest from the support, From the viewpoints of suitability for rapid processing and sensitivity, the total amount of gelatin contained in the non-photosensitive hydrophilic colloid layer is preferably 7.5 g or less, more preferably 4 g or more and less than 7 g per 1 m ^{2 of} the light-sensitive material.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material include N-nitroethylmorpholine compounds, isothiazolone compounds, phenol compounds, phenoxyethanol compounds, etc. for the purpose of preventing the decay of hydrophilic colloids such as gelatin. A fungicide can be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material are hardened by crosslinking a binder (or protective colloid) molecule to increase the film strength, either alone or in combination.

In addition to the above compounds, various photographic additives can be added to the light-sensitive material. Such examples include, for example, ultraviolet absorbers (eg, benzophenone compounds, benzotriazole compounds, etc.), development accelerators (eg, 1-aryl-3-pyrazolidone compounds, etc.), water-soluble anti-irradiation dyes (eg, azo compounds). Compounds, styryl compounds, oxonol compounds, etc.), film physical property improving agents (liquid paraffin, polyalkylene glycol, etc.),
Anti-turbidity agent (diffusion-resistant hydroquinone compound, etc.),
There are color image stabilizers (for example, hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble fluorescent whitening agents, and background color adjusting agents. In addition to these, competitive couplers, fogging agents, development inhibitor releasing couplers (so-called DI
R couplers), development inhibitor releasing compounds and the like can be added.

When the silver halide emulsion layer and the hydrophilic colloid layer are coated on the support used in the present invention, a thickener may be used to improve the coating property. As a coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are useful.

To form a photographic image using the color light-sensitive material of the present invention, the image recorded on the negative may be optically imaged and printed on the light-sensitive material to be printed. After the image is once converted into digital information, the image may be imaged on a CRT (cathode ray tube), and the image may be imaged and printed on a photosensitive material to be printed. It is also possible to print by changing the intensity of the laser light based on the above and scanning.

The color light-sensitive material of the present invention can form an image by performing color development processing known in the art.

As the aromatic primary amine type developing agent used in the present invention, known compounds can be mentioned. Representative examples of these compounds are shown below.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4: 4-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5: 2-Methyl-4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD -6: 4-amino-3-methyl-N-ethyl-N- {β- (methanesulfonamide) ethyl} aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD- 8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N -(β-Ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline Color developing agents are usually 1 x 10 per liter of image liquid
It is used in the range of ^{-2 to} 2 x 10 ^-1 mol, and from the viewpoint of rapid processing, it is 1.5 x 10 ^-2 to 2 x 10 ^-1 per liter of color developer.
It is preferably used in moles. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developer may contain the following developer components in addition to the above components. For example, as alkali agents, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation and stabilize pH. It can be used in combination within a range that maintains the effect. Furthermore, because of the necessity of preparation,
Alternatively, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like can be used for the purpose of increasing the ionic strength. If necessary, inorganic and organic antifoggants can be added. Although halide ions are often used for the purpose of suppressing development, chloride ions are mainly used and potassium chloride, sodium chloride and the like are mainly used for completing development in a very short time. The amount of chloride ions is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^-2 , per liter of color developing solution.
It is about 5.0 × 10 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ or less, per liter of color developing solution. Is desirable.

If necessary, a development accelerator can be used. Examples of the development accelerator include U.S. Pat.
No. 4, No. 3671247, various pyridinium compounds represented by JP-B-44-9503, and other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Patents 2,533,990, 2,531,832
No. 2, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No.
Polyethylene glycol and derivatives thereof, nonionic compounds such as polythioethers, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like described in JP-B-44-9509. Further, phenethyl alcohol described in US Pat. No. 2,304,925 and acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin,
In addition, the compounds described in JP-B-47-33378 and JP-B-44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

It is also possible to use an auxiliary developer together with the developing agent. Examples of the auxiliary developer include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p
-Aminophenol hydrochloride, N, N, N ', N'-tetramethyl-
P-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1 per liter of the developing solution.
0 g is used.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, it can be prepared by adding a plurality of components, each of which can coexist stably, in a small container prepared in advance in a concentrated aqueous solution or a solid state to water and stirring.

In processing the color light-sensitive material of the present invention, the color developing solution can be used in any pH range, but from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0.
It is more preferably used in the range of pH 9.8 to 12.0. The processing temperature for color development is preferably 15 to 45 ° C, and particularly preferably 20 to 45 ° C.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is within 1 minute. Furthermore, it is preferable to perform the treatment within 50 seconds.

In the present invention, when the color light-sensitive material is subjected to the running process while continuously replenishing the color developing solution, in order to reduce the overflow solution of the color developing solution and the environmental destruction due to the waste solution, Replenishment amount is 1
It is preferably 20 to 150 ml per m ² . Furthermore, it is more preferable to set the replenishment amount so that waste liquid due to overflow is not substantially generated.
It is particularly preferable that the amount is 20 to 60 ml per m ^{2 of the} light-sensitive material. Under such conditions, the performance of the light-sensitive material tends to change, but the color light-sensitive material according to the present invention can be used particularly advantageously under such conditions.

The color light-sensitive material is subjected to bleaching processing and fixing processing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Further, as a substitute for the washing treatment, a stabilizing treatment may be performed. As a development processing apparatus used for the development processing of the photosensitive material of the present invention, even if it is a roller transport type in which the photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, the photosensitive material is fixed and conveyed on a belt. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the processing solution. A web method by contact with a carrier impregnated with, a method by a viscous treatment liquid, and the like can also be used.

[0149]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of paper pulp having a basis weight of 180 g / m ² . However, on the side where the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support.

Photosensitive material sample 1 was prepared by coating each layer having the following constitution on this reflective support. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-
5) 3.34 g, stain inhibitor (HQ-1) 0.33 g, compound A 5.0 g and high boiling organic solvent (DBP) 5.0 g were dissolved by adding ethyl acetate 60 cc, and this solution was dissolved in 20% surfactant (SU). -1) 220cc of 10% gelatin aqueous solution containing 7cc
A yellow coupler dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

As for the coating solutions for the second to seventh layers, each coating solution was prepared so as to have the coating amounts shown in Tables 1 and 2 similarly to the coating solution for the first layer.

Further, as a hardening agent (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension.
Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0155]

[Table 1]

[0156]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) -sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine
Sodium Compound A: pt-octylphenol HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl hydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone

[0158]

[Chemical 21]

[0159]

[Chemical formula 22]

[0160]

[Chemical formula 23]

[0161]

[Chemical formula 24]

[0162]

[Chemical 25]

(Preparation of blue-sensitive silver halide emulsion) In one liter of a 2% gelatin aqueous solution kept at 40 ° C., the following (A
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over a period of time, and further add the following (C liquid) and (D liquid)
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was carried out at 60 ° C. to obtain a comparative blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (Preparation of green-sensitive silver halide emulsion) Addition time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
A monodisperse cubic emulsion EMP-2 having an average particle size of 0.43 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) Addition time of (A liquid) and (B liquid) and (C liquid) and (D liquid)
A monodisperse cubic emulsion EMP-3 having an average particle size of 0.50 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained in the same manner as in EMP-1, except that the addition time was changed.

The following compounds were used for EMP-3.
Optimal chemical sensitization was performed at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ^-4 mol / mol AgX sensitizing dye RS-2 1 × 10 ^-4 mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1- Phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0171]

[Chemical formula 26]

The yellow coupler of the first layer of Sample 1 is shown in Table 3.
Samples 2 to 7 are the same as sample 1 except that
Was produced.

Samples 8 to 14 were prepared in the same manner as Samples 1 to 7. However, an S-1 layer having the following constitution was applied between the support and the first layer.

S-1 layer (white pigment layer) To 500 g of the aqueous dispersion (A), 2.0 ml of a 2% aqueous solution of 2,4-dichloro-6-oxy-S-triazine sodium was added as a hardener to give a white pigment. The S-1 layer was applied so as to have a weight of 35 g / m ² .

Production of Water Dispersion (A) 40 g of anatase type titanium oxide (Anatase LW-S, manufactured by West Germany "Chat Leben") is dispersed in 450 ml of pure water, and hydroxypropyl cellulose (cps 1000-4000 manufactured by Wako Pure Chemical Industries, Ltd.). 1
A solution of 30 mg in 50 ml of water was added with stirring, this was heated to 55 ° C, stirred at 55 ° C for 30 minutes and cooled. This suspension is an ultrafiltration device (3 with a filter molecular weight of 1 million).
(Using a membrane). After heating this suspension to 50 ° C., blowing nitrogen gas for 30 minutes, and then adding a solution of 0.4 g of potassium persulfate in 20 ml of water, followed by adding 3 g of n-butyl acrylate, 10 g of styrene, and 2 g of hydroxymethyl methacrylate. The mixture was added dropwise over about 1 hour. After completion of dropping, the mixture was cooled 23 hours later to obtain an aqueous dispersion (A). Of the solid content of this water dispersion (A), 39
v% is a white pigment.

The following evaluations were performed using the samples thus produced.

<Evaluation of Color Reproducibility> Each sample was wedge-exposed with blue light by an ordinary method, and then developed in the following developing process. The obtained yellow image is Hitachi
The measurement was performed using a color analyzer 607 manufactured by Co., Ltd.
At the time of measurement, the concentration of the maximum absorption wavelength was standardized to 1.0.
The ΔE value was calculated from the difference ΔL *, Δa *, Δb * of the distance between the samples 2 to 14 and the sample 1 in the L * a * b * color coordinate space by the following formula.

[0178]

[Equation 1]

<Evaluation of Sharpness> A resolution test chart was printed on each sample with blue light, and the following development processing was performed. Then, the obtained yellow image was recorded on a microdensitometer PDM-5D (manufactured by Konica Corporation). ), The density was measured, and the value represented by the following formula was defined as the sharpness (CTF).

Sharpness (%) = (Dmax-Dmin of 5 lines / mm dense line print image) / (Dmax-Dmin in large area) where Dmax: maximum density Dmin: minimum density The better the sharpness is.

(Development processing conditions) Processing process Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach-fix 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 C. 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0g 10.0g N, N-diethylhydroxylamine 6.8g 6.0g triethanolamine 10.0g 10.0g diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g fluorescence Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank solution had a pH of 10.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Add water to make the total volume 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to bring the total volume to 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

The results are shown in Table 3.

[0186]

[Table 3]

In the samples using the yellow couplers other than the present invention, ΔE due to the provision of S-1 layer and S-2 layer
Although the increase in the value is small, the sample using the coupler of the present invention has a larger ΔE value than the samples using the yellow couplers other than the present invention, and the S-1 layer and S-
By providing two layers, a larger increase in ΔE value was obtained. The sample of the present invention, which uses a yellow coupler that produces a dye having a sharp spectral absorption and is provided with a white pigment layer, shows a color difference to the extent that a difference can be sufficiently recognized with respect to Sample 1, and the color reproducibility is low. It can be seen that it has improved significantly.

In addition, in the sample using the coupler of the present invention,
It can be seen that by providing the S-1 layer and the S-2 layer, the increase range of the CTF value is large and the sharpness is significantly improved. Example 2 Each sample of Example 1 was exposed and developed in the same manner except that the processing steps changed as described below were used.

Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 25 seconds 81cc Bleach-fix 35.0 ± 0.5 ℃ 25 seconds 54cc Stabilization 30-34 ℃ 25 seconds 150cc Dry 60-80 ℃ 30 seconds Development processing The composition of the liquid is shown below.

Color developer tank solution and replenisher tank solution Replenisher solution Pure water 800cc 800cc Diethylene glycol 10g 10g Potassium bromide 0.01g-Potassium chloride 3.5g-Potassium sulfite 0.25g 0.5g N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3.5 g 6.0 g Triethanolamine 10.0 g 10.0g Diethylenetriaminepentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter, and the tank liquid is pH = Ten.
Adjust to 10 and replenisher to pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetate ammonium ferric dihydrate 100g 50g diethylenetriamine pentaacetic acid 3g 3g ammonium thiosulfate (70% aqueous solution) 200cc 100cc 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 cc 25 cc Add water to make the total volume 1 liter. Add potassium carbonate or glacial acetic acid to the tank solution at pH = 7.0 and the replenisher to pH = 6.5. adjust.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g PVP 1.0g Ammonia water (25% ammonium hydroxide solution) 2.5g Ethylenediaminetetraacetic acid 1.0g Ammonium sulfite (40% solution) Add 10 cc water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

When the treated sample was evaluated in the same manner as in Example 1, it was confirmed that the effect of the present invention could be obtained even by the rapid treatment.

Example 3 Sample 15 was prepared in the same manner as in Sample 14 except that the S-1 layer of Sample 14 of Example 1 was changed to the S-2 layer shown below. did.

S-2 layer (white pigment layer) 100 parts by weight (solid content) of a copolymer composed of 10 parts by weight of vinylidene chloride, 70 parts by weight of vinyl chloride, 15 parts by weight of vinyl acetate and 5 parts by weight of maleic anhydride, and anatase. 100 parts by weight of type titanium oxide and 300 parts by weight of ethyl acetate were mixed and dispersed using a ball mill. 100 parts by weight of n-propanol was added to this solution, and coating was performed so that the coating amount of titanium oxide after drying was 10 g / m ² . The drying temperature was 20 ° C. Sample 15 was evaluated in the same manner as in Example 1, and the results are shown in Table 3
It is shown in No.15.

From these results, it can be seen that the presence of voids in the hydrophobic polymer layer further enhances the effect of the present invention.

Example 4 Polyethylene was laminated on one side of a paper support, and polyethyleneethylene containing titanium oxide was laminated on the other side on the side of the first layer. The support having a thickness of 110 μm was coated with each layer having the following constitution. Then, a multilayer color photographic light-sensitive material was prepared.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.42 μm
The shell was formed until At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.
An 18 μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so that a cube was obtained as a particle shape. An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method to obtain average grains. Diameter 0.25μ
The shell was formed to m. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue Sensitive Emulsion EM-B) EM-1
After sensitizing the dye by adding the sensitizing dye D-1, to 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-B.

(Preparation of Green Sensitive Emulsion EM-G) A green sensitive emulsion EM-G was prepared in the same manner as the blue sensitive emulsion except that the sensitizing dye D-2 was added to EM-2 for color sensitization.

(Preparation of red-sensitive emulsion EM-R) Red-sensitive emulsion EM-R was prepared in the same manner as blue-sensitive emulsion except that sensitizing dyes D-3 and D-4 were added to EM-2 for color sensitization. It was made.

(Preparation of pan-sensitive emulsion EM-P) Same as the blue-sensitive emulsion except that sensitizing dyes D-1, D-2, D-3 and D-4 were added to EM-1 for color sensitization. Pan-sensitive emulsion EM-
P was prepared.

T-1: 4-hydroxy-6-methyl-1,3,3a,
7-Tetrazaindene

[0207]

[Chemical 27]

Using the above EM-B, EM-G and EM-R, a color photographic light-sensitive material 4-1 having the following constitution was produced. The first to ninth layers were coated on the front surface of the support in the following constitution, and the tenth layer was coated on the back surface side. SA-1 and SA-2 are used as coating aids, and H is used as a hardening agent.
Sample 4-1 was prepared using -1 and H-2.

SA-1: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester / Sodium H-1: 2,4-dichloro-6-hydroxy-s-triazine
Sodium H-2: Tetrakis (vinylsulfonylmethyl) methane layer composition Coating amount (g / m ² ) Ninth layer gelatin 0.78 (UV absorbing layer) UV absorber (UV-1) 0.065 UV absorber (UV-2 ) 0.120 UV absorber (UV-3) 0.160 Solvent (SO-2) 0.1 Silica matting agent 0.03 Eighth layer Gelatin 1.43 (Blue sensitive layer) Blue sensitive emulsion EM-B (Coating silver amount) 0.4 General sensitive emulsion EM-P (Amount of coated silver) Yellow coupler (Y-1) 0.82 Anti-staining agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, ST-2, T-1) Seventh layer gelatin 0.54 ( Intermediate layer) Anti-color mixing agent (AS-1, 3, 4, 5, 6 equivalents)) 0.055 Solvent (SO-2) 0.072 6th layer gelatin 0.42 (Yellow yellow colloidal silver 0.1 colloidal silver layer) Anti-color mixing agent (AS -1, 3, 4, 5, 6 equivalents) 0.04 Solvent (S O-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 Anti-irradiation dye (AI-3) 0.03 Fifth layer Gelatin 0.54 (Intermediate layer) Color mixture inhibitor (AS-1, 3, 4, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 Fourth layer Gelatin 1.43 (Green-sensitive layer) Green-sensitive emulsion EM-G (coated silver amount) 0.40 Pan-sensitive emulsion EM-P (coated silver amount) 0.10 Magenta coupler (MC-1) 0.25 Yellow coupler (YC-2) 0.06 Anti-stain agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, ST-2, T-1) Third layer Gelatin 0.75 (Intermediate layer) Color mixture prevention Agent (AS-1, 3, 5, 6 equivalents) 0.055 Solvent (SO-2) 0.072 Anti-irradiation dye (AI-1) 0.01 Anti-irradiation dye (AI-2) 0.01 Second layer gelatin 1.38 ( Red-sensitive layer) Red-sensitive emulsion EM-R (coated silver amount) 0.3 0 Pan-sensitive emulsion EM-P (coated silver amount) 0.06 Cyan coupler (CC-2) 0.44 Solvent (SO-1) 0.31 Anti-stain agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-) 1) 1.0 1st layer Gelatin 1.0 (white pigment layer) Anatase type titanium dioxide 3.0 10th layer Gelatin 6.0 (backside matte layer) Silica matting agent 0.65 The amount of silver coated is in terms of silver.

SO-1: trioctyl phosphate SO-2: dioctyl phosphate AS-1: 2,4-di-t-octylhydroquinone AS-2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N-benzyladenine

[0211]

[Chemical 28]

[0212]

[Chemical 29]

[0213]

[Chemical 30]

[0214]

[Chemical 31]

[0215]

[Chemical 32]

Sample 4-2 was prepared in the same manner as Sample 1-1, except that the yellow coupler in the eighth layer of Sample 4-1 was changed as shown in Table 4. Further, 4-3 and 4-4 were prepared in the same manner as the samples 4-1 and 4-2. However, the support and the first
An S-1 layer having the same structure as in Example 1 was applied between the layers.

Sample No. Y coupler White pigment layer 4-1 Y-1 No 4-2 I-7 〃 4-3 Y-1 Yes 4-4 I-7 〃 Sample 1 obtained as described above On the other hand, among the original halftone dots, a black plate and a cyan plate were brought into close contact with each other and exposed under the following exposure condition-1. Then, the black plate and the magenta plate were brought into close contact with each other and exposed under the exposure condition-2 shown below. Further, the black plate and the yellow plate were brought into close contact with the sample, and the exposure conditions shown below-3
Exposed.

(Exposure condition-1) When exposing each light-sensitive material to a white light through a red filter (Ratten No. 26) and an ND filter, the ND filter density is adjusted so that the red light density after the development processing becomes the minimum. Exposure for 0.5 seconds with the minimum exposure amount.

(Exposure condition-2) When exposing each light-sensitive material to white light through a green filter (Ratten No. 58) and an ND filter, the ND filter density is adjusted to minimize the green light density after development processing. Exposure for 0.5 seconds with the minimum exposure amount.

(Exposure condition-3) When exposing each light-sensitive material to white light through a blue filter (Ratten No. 47B) and an ND filter, the ND filter density is adjusted so that the blue light density after the development processing becomes the minimum. Exposure for 0.5 seconds with the minimum exposure amount.

A daylight fluorescent lamp was used as the light source under the exposure conditions 1 to 3. The exposed sample was processed under the following processing condition-1 to obtain an image.

The conditions of the developing treatment and the prescription of the treatment liquid are as follows.

Processing Step-1 Temperature Time Immersion (Developer) 37 ° C 12 seconds Fog exposure-12 seconds (1 lux) Development 37 ° C 95 seconds Bleach-fixing 35 ° C 45 seconds Stabilization 25-30 ° C 90 seconds Dry 60- 85 ° C 40 seconds Processing solution composition (color developer) Benzyl alcohol 15.0ml Cerium sulfate 0.015g Ethylene glycol 8.0ml Potassium sulfite 2.5g Potassium bromide 0.6g Sodium chloride 0.2g Potassium carbonate 25.0g T-1 0.1g Hydroxylamine Sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) 4.5 g Aniline sulfate Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Water Potassium oxide 2.0 g Diethylene glycol 15.0 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.15.

(Bleach-fixing solution) Diethylenetriamine pentaacetate ferric ammonium 90.0 g Diethylenetriamine pentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4-triazole Adjust the pH to 7.1 with 0.15 g potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

(Stabilizing Solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Water Ammonium oxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide or Adjust the pH to 7.5 with sulfuric acid. The stabilization process is 2
A counter-current system with a tank configuration was adopted.

The formulation of the replenisher for running is shown below.

(Color development replenisher) benzyl alcohol 18.5 ml cerium sulphate 0.015 g ethylene glycol 10.0 ml potassium sulfite 2.5 g potassium bromide 0.3 g sodium chloride 0.2 g potassium carbonate 25.0 g T-1 0.1 g hydroxylamine sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) 5.4 g Aniline sulfate Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to make the total volume 1 liter and adjust to pH 10.35.

(Bleach-fixing solution replenishing solution) Same as the above-mentioned bleach-fixing solution.

(Stabilizer Replenisher) Same as the above stabilizer.

The replenishing amount of the developer replenishing solution, the bleach-fixing solution and the stabilizing solution was 320 ml per square meter of the light-sensitive material.

The following evaluations were performed using the samples thus prepared.

(Evaluation of Color Reproducibility) Of the obtained images,
The image of the 100% yellow portion was measured using a Color Analyzer Model 607 manufactured by Hitachi, Ltd. At the time of measurement, the concentration of the maximum absorption wavelength was standardized to 1.0. Sample 4-
ΔE was calculated in the same manner as in Example 1 from the difference ΔL *, Δa *, and Δb * in the distances in the L *, a *, and b * color coordinate spaces of 2 to 4-4 and Sample 4-1.

(Evaluation of small dot reproducibility) Of the obtained image, the small dot portion of the Y halftone dot test chart was observed with a loupe,
The dot reproducibility was evaluated by the value of the smallest halftone dot reproduced.

Sample No. ΔE Small point reproducibility 4-1-4% Comparison 4-2 1.6 4% 〃 4-3 1.8 4% 〃 4-4 4.3 2% The present invention From this result, only the sample of the present invention is colored. It can be seen that the reproducibility is good and the small point reproducibility is greatly improved.

[0235]

According to the present invention, a silver halide color photographic light-sensitive material excellent in color reproducibility and sharpness can be provided.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support comprising a base paper and resin coating layers provided on both sides thereof, the support and the silver halide. A hydrophobic polymer layer containing at least one white pigment is contained between the emulsion layers, and at least one of the silver halide emulsion layers has the following general formula (Y-
A silver halide color photographic light-sensitive material comprising at least one photographic yellow coupler represented by any one of I) to (Y-III). [Chemical 1] [In the formula, R ₁ represents an alkyl group or a cycloalkyl group, R ₂ represents an alkyl group, a cycloalkyl group or an aryl group, and R ₃ represents a straight-chain unsubstituted alkyl group. Z ₁ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. ] [Chemical 2] [In the formula, R ₁₁ represents a monovalent substituent except a hydrogen atom, and Q
Is required to form a 3- to 5-membered hydrocarbon ring with C, or to form a 3- to 5-membered heterocycle containing at least one hetero atom selected from N, S, O and P in the ring. Represents a non-metallic atomic group. R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an amino group, and R ₁₃ represents a group capable of substituting on the benzene ring. Z ₂ represents a hydrogen atom or a group capable of splitting off during the coupling reaction with the oxidized product of the developing agent. ] [Chemical 3] [In the formula, R ₂₁ and R ₂₂ each represent an alkyl group, an aryl group or a heterocyclic group, and R ₂₃ represents an aryl group or a heterocyclic group. Z ₃ represents a hydrogen atom or a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent. R ₂₁ and R ₂₂ may combine with each other to form a nitrogen-containing heterocycle with N. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein voids are present in the hydrophobic polymer layer.