JPH0749546A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To efficiently improve color fog without lowering max. density or deteriorating image preservability and to provide a silver halide color photographic sensitive material giving an excellent finish. CONSTITUTION:In this silver halide color photographic sensitive material with at least one photosensitive silver halide emulsion layer on the base, a coupler and a stain inhibitor are contained in the photosensitive silver halide emulsion layer closest to the base and the stain inhibitor is contained by 1-5mol% of the amt. of the coupler. A specified yellow coupler is preferably contained as a coupler in the emulsion layer closest to the base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which is excellent in color developability and image storability and has improved color fog.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. These couplers are required to have basic properties such as color developability, storage stability, color reproducibility of an obtained dye image, and image storability, and are particularly suitable for direct appreciation of color photographic paper. In a color photographic light-sensitive material, a white background is regarded as important, and it is required to suppress stain such as color fog as much as possible.

An antistaining agent such as a hydroquinone derivative is used to suppress color fog. Before the oxidized product of the developing agent, which is generated in the unexposed area for some reason, undergoes the coupling reaction with the coupler, the stain inhibitor scavenges the oxidized product to suppress color fog. As expected from such a mechanism, when a large amount of stain inhibitor is used, color development of the coupler is hindered, so that problems such as reduction in maximum density and softening occur. In addition, as described in JP-A-62-275261,
When a large amount of stain resist is used, there is a problem that the light resistance of the dye image is deteriorated. In order to efficiently improve the color fog in this way, there has been a dilemma that the maximum density is lowered and the light resistance is deteriorated.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide color photograph which efficiently improves color fog and gives an excellent finish without causing a decrease in maximum density and deterioration of image storability. To provide a light-sensitive material.

[0005]

The above object of the present invention is to provide a light-sensitive halogen closest to a support in a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on the support. A silver halide color photographic light-sensitive material (hereinafter, simply referred to as "color light-sensitive material" or "color It is also described as "sensitive material").

As a result of careful examination of the amount ratio of the anti-stain agent to the coupler, the present inventors have found that in the light-sensitive silver halide emulsion layer closest to the support, the amount of the anti-stain agent to the coupler is specified. It has been discovered that by defining the range, the occurrence of fog can be sufficiently suppressed without causing deterioration of image storability and reduction of maximum density.

In the light-sensitive silver halide emulsion layer located farther from the support, if the stain inhibitor is reduced to the range of the present invention, fog cannot be sufficiently suppressed. The reason for this is not clear, but in rapid processing, it takes time for the processing solution to penetrate into the light-sensitive material, so the photosensitive silver halide emulsion layer closest to the support is compared with other silver halide emulsion layers. It is considered that the start of development was delayed, and as a result, the generation of fog could be sufficiently suppressed even if the amount of the anti-staining agent was reduced, and the above dilemma could be resolved.

The stain inhibitor used in the color light-sensitive material of the present invention is a compound capable of scavenging the oxidant of the developing agent, preferably a reducing agent capable of cross-oxidizing with the oxidant. Preferred are hydroquinone derivatives, gallic acid derivatives, 2,4-disulfonamidophenol derivatives and hydrazine derivatives, and particularly preferred are compounds represented by the following general formula [HQ-I].

[0009]

[Chemical 2]

In the general formula [HQ-I], R ¹ , R ² ,
R ³ and R ⁴ are each a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkylacylamino group, an arylacyl. Amino group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfonamide group, arylsulfonamide group, alkylsulfamoyl group, arylsulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, cyano group, alkoxycarbonyl group Represents an aryloxycarbonyl group, an alkylacyloxy group or an arylacyloxy group.

In the atom or group represented by R ¹ , R ² , R ³ and R ⁴ , examples of the halogen atom include fluorine, chlorine and bromine atoms, and examples of the alkyl group include methyl and ethyl. , Propyl, i-propyl, butyl,
Each group such as t-butyl, amyl, i-amyl, octyl, dodecyl, octadecyl and the like can be mentioned, particularly having 1 to 32 carbon atoms.
Alkyl groups of are preferred.

The alkenyl group includes, for example, allyl, octenyl, oleyl, etc., and especially has 2 to 2 carbon atoms.
32 alkenyl groups are preferred.

Examples of the aryl group include phenyl and naphthyl.

Examples of the acyl group include acetyl, octanoyl, lauroyl and the like.

Examples of the cycloalkyl group include cyclohexyl and cyclopentyl.

The alkoxy group is, for example, methoxy, ethoxy, dodecyloxy, etc., the aryloxy group is, for example, phenoxy, the alkylthio group is, for example, methylthio, butylthio, dodecylthio, etc., the arylthio group is, for example, phenylthio, and the alkylacylamino group is, for example. Acetylamino, arylacylamino groups such as benzoylamino, alkylcarbamoyl groups such as methylcarbamoyl, arylcarbamoyl groups such as phenylcarbamoyl, alkylsulfonamide groups such as methylsulfonamide, arylsulfonamide groups such as phenyl. Examples of sulfonamide and alkylsulfamoyl groups include methylsulfamoyl and arylsulfamoyl groups. Phenylsulfamoyl, alkylsulfonyl group such as methylsulfonyl, arylsulfonyl group such as phenylsulfonyl, alkyloxycarbonyl group such as methyloxycarbonyl, aryloxycarbonyl group such as phenyloxycarbonyl, alkylacyloxy group Examples of acetyloxy and arylacyloxy groups include benzoyloxy and the like, respectively.

These groups include those having a substituent,
As the substituent, an alkyl group, an aryl group, an aryloxy group, an alkylthio group, a cyano group, an acyloxy group,
Examples thereof include an alkoxycarbonyl group, an acyl group, a sulfamoyl group, a hydroxyl group, a nitro group, an amino group and a heterocyclic group.

At least one of R ¹ and R ³ is a group having a total number of carbon atoms of 6 or more including the above-mentioned substituents.

The above-mentioned general formula [HQ-
Of the compounds represented by the following general formula [HQ-II]
Compounds represented by are particularly preferable.

[0020]

[Chemical 3]

In the formula, R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group or a heterocyclic group. However, R ¹¹ and R ¹²
At least one of them is a group having a total number of carbon atoms of 6 or more.

Examples of the alkyl group represented by R ¹¹ and R ¹² include methyl, ethyl, propyl, i-propyl, butyl, t-butyl, amyl, i-amyl, octyl, dodecyl and octadecyl groups. Among them, an alkyl group having 1 to 32 carbon atoms is particularly preferable.

The alkenyl group includes, for example, allyl, octenyl, oleyl, etc., and particularly has 2 to 2 carbon atoms.
32 alkenyl groups are preferred.

Examples of the aryl group include phenyl and naphthyl.

Examples of the acyl group include acetyl, octanoyl and lauroyl, examples of the cycloalkyl group include cyclohexyl and cyclopentyl, and examples of the heterocyclic group include imidazolyl, furyl, pyridyl, triazinyl and thiazolyl. .

In the general formula [HQ-II], R ¹¹ and R ¹²
It is preferable that at least one of the groups has a total number of carbon atoms of 8 or more, more preferably both R ¹¹ and R ¹² are groups having a total number of carbon atoms of 8 to 18, and most preferably , R ¹¹ and R ¹² both have a total number of carbon atoms of 8
To 18 are the same alkyl groups.

The above-mentioned general formula [HQ-
Specific examples of the compound represented by the formula [I] are shown below, but of course the present invention is not limited thereto.

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

In the present invention, the coupler contained in the light-sensitive silver halide emulsion layer closest to the support may be a yellow coupler, a magenta coupler or a cyan coupler, but a yellow coupler is preferred.

Various acylacetanilide type couplers can be preferably used as the yellow coupler.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. A coupler represented by the following general formula [I] is particularly preferable.

[0035]

[Chemical 9]

In the formula, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkyl group, a cycloalkyl group or an aryl group. R ₃ represents a group capable of substituting on the benzene ring, and m represents an integer of 0-4. However, when m is 2 or more, a plurality of R ₃ may be the same or different. Z represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized product of a developing agent.

Next, the coupler represented by the above general formula [I] will be described in detail.

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

The alkyl group and cycloalkyl group represented by R ₁ may further have a substituent, and examples of the substituent include a halogen atom (chlorine, bromine, etc.), a cyano group, a nitro group, an aryl group ( Phenyl, pt-octylphenyl, 2,4-di-t-amylphenyl, etc.), hydroxyl group, alkoxy group (methoxy, 2-ethoxyethoxy, etc.), aryloxy group (phenoxy, 2,4-di-t-amyl) Phenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy, etc.), heterocyclic oxy group (4-pyridyloxy, 2-
Hexahydropyranyloxy, etc.), carbonyloxy group (acetylcarbonyl, alkylcarbonyloxy group such as pivaloyloxy, arylcarbonyloxy group such as benzoyloxy), sulfonyloxy group (methanesulfonyloxy, trifluoromethanesulfonyloxy, dodecanesulfonyloxy, etc.) Alkylsulfonyloxy group, benzenesulfonyloxy, p-toluenesulfonyloxy, and other arylsulfonyloxy groups), carbonyl group (acetyl, pivaloyl, and other alkylcarbonyl groups,
Benzyl, arylcarbonyl groups such as 3,5-di-t-butyl-4-hydroxybenzoyl), oxycarbonyl groups (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), carbamoyl groups (dimethylcarbamoyl, 4- (2,4-di-t-amylphenoxy) butylcarbamoyl and other alkylcarbamoyl groups, phenylcarbamoyl, 1 -Arylcarbamoyl group such as naphthylcarbamoyl), sulfonyl group (alkylsulfonyl group such as methanesulfonyl and trifluoromethanesulfonyl, arylsulfonyl group such as p-toluenesulfonyl), sulfamoyl group (dimethylsulfamoyl, 4- (2,4 -Di-t-amylphenoxy) butylsulfamoyl and other alkylsulfamoyl groups, phenylsulfamoyl and other arylsulfamoyl groups, acetylsulfamoyl, ethylcarbonylsulfamoyl and other acylsulfamoyl groups) , Amino group (dimethylamino Cyclohexylamino, alkylamino groups such as dodecyl amino, anilino,
pt-octylanilino and other arylamino groups), sulfonamide groups (methanesulfonamide, heptafluoropropanesulfonamide, hexadecylsulfonamide and other alkylsulfonamide groups, p-toluenesulfonamide, pentafluorobenzenesulfonamide, etc.) Aryl sulfonamide group), acylamino group (alkylcarbonylamino group such as acetylamino, myristoylamino, arylcarbonylamino group such as benzoylamino), alkylthio group (methylthio, t-octylthio, etc.), arylthio group (phenylthio) and heterocycle Thio group (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 in the general formula [I] include the same groups as the alkyl group and cycloalkyl group represented by R ₁ above. 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 a group having the same meaning as the alkyl group and cycloalkyl group represented by R ₁ ; Examples thereof include the groups having the same meanings as the groups described as the substituents of the alkyl group and cycloalkyl group represented by R ₁ .

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

Examples of the group substitutable on the benzene ring represented by R ₃ in the general formula [I] include substituents of the alkyl group, cycloalkyl group and aryl group represented by R _2. The groups having the same meanings as the existing groups can be mentioned.

R ₃ is preferably an acylamino group, a sulfonylamino group, an oxycarbonyl group and a sulfamoyl group. m represents an integer of 0 to 4, preferably 1.

The group capable of splitting off upon coupling with the oxidized product of the developing agent represented by Z in the general formula [I] is represented by, for example, the following general formulas [II], [III] and [IV].

[0046]

[Chemical 10]

In the above general formulas [II] and [III],
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 [I]. it can. Examples of the heterocyclic group represented by R ₄ include 4-pyridyl and 2-hexahydropyranyl. These R
_The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by ₄ may have a substituent, and examples of the substituent include an alkyl group represented by R ₂ in the above general formula [I], Examples thereof include groups having the same meanings as the groups described as the substituents of the cycloalkyl group and the aryl group.

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

In the above general formula [IV], Z ₁ represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring in cooperation with a nitrogen atom. Here, as an atomic group necessary for forming a non-metallic atomic group, for example, methylene, methine, substituted methine -C (O) -, - N (R 5) -, (R 5 is a hydrogen atom, an alkyl group, An aryl group or a heterocyclic group), -N =, -O- and -S (O) u- (u represents an integer of 0 to 2) and the like.

Of the compounds represented by the above general formula [I], the compounds represented by the following general formula [V] are preferable.

[0051]

[Chemical 11]

In the formula, R ₁ and R ₂ each represent a group having the same meaning as the group represented by R ₁ and R ₂ in the above formula [I]. Z ₂ represents a group having the same meaning as the group represented by Z in the above formula [I]. W is a group represented by the following general formula [VI].

[0053]

[Chemical 12]

In the formula, X represents a carbonyl group or a sulfonyl group, and preferably a carbonyl group.

L represents an alkylene group or an arylene group, for example, a linear or branched alkylene group (for example, methylene, ethylene, 2,3-propylene, 1,2-cyclohexylene group), 1,4-phenylene group, 1 , 2-naphthylene group, 9,10
-Anthranylene group and the like can be mentioned. Of these, an alkylene group having 1 to 6 carbon atoms is preferable.

Y represents a divalent linking group, for example, a sulfinyl group, a sulfenyl group, a sulfonyl group, a sulfamoyl group, a carbonyl group, a carbonyloxy group, a carbamoyl group, an oxy group, an oxycarbonyl group, an amino group, an acylamino group, Examples thereof include sulfonamide groups. Of these linking groups, a sulfonyl group, a sulfamoyl group, a carbonyloxy group, a carbamoyl group, an oxy group, an oxycarbonyl group, and an acylamino group are preferable, and a sulfonyl group, an oxy group, an oxycarbonyl group, and a carbamoyl group are particularly preferable.

N represents 0 or 1.

R ₆ represents an alkyl group, a cycloalkyl group or an aryl group. Examples of the alkyl group, cycloalkyl group or aryl group represented by R ₆ include the same groups as the alkyl group, cycloalkyl group and aryl group represented by R ₂ in the above formula [I]. .
The alkyl group, cycloalkyl group or aryl group represented by R ₆ may have a substituent, and examples of the substituent include the alkyl group represented by R ₂ in the above formula [I] and the cycloalkyl group. The group and the group mentioned as the substituent of the aryl group may be the same as those described above.

The substituent represented by Z ₂ in the general formula [V] is preferably the following general formulas [VII], [VIII] and [I]
X], [X], [XI] or [XII] is a substituent.

[0060]

[Chemical 13]

General formulas [VII], [VIII], [IX], [X]
And [XI], R ₇ , R ₈ and R ₉ each represent a substitutable group on the azole ring, for example, the above general formula [I]
In the above, there may be mentioned groups having the same meanings as the groups mentioned as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R ₂ .

In the general formula [XI], R ₁₀ is, for example, a group having the same meaning as the alkyl group, cycloalkyl group and aryl group represented by R ₄ in the general formulas [II] and [III], a carbonyl group and a sulfonyl group. Represents a group such as a group.

In the general formulas [X] and [XI], Z ₃ is-
N (R ₁₁ )-(R ₁₁ represents a group having the same meaning as the group represented by R ₅ in the general formula [IV]), -O-, or -S (O) v- (v is 0 ~ Represents an integer of 2).

In the general formula [XII], Y ₁ is-(R ₁₂ )-
(R ₁₂ represents a group having the same meaning as the group represented by R ₅ in the general formula [IV]), —O— and —S (O) r— (r represents an integer of 0 to 2) and the like. A hetero atom represented, or -C (O)-,
—C (R ₁₃ ) (R ₁₄ ) — (R ₁₃ and R ₁₄ are each a hydrogen atom or a substituent of an alkyl group, a cycloalkyl group or an aryl group represented by R ₂ in the above formula [I]. its dependent represents a group as defined for group) and _{-C (R 15) - (R} 15
Represents a hydrogen atom or a carbon atom represented by the above-mentioned general formula [I] and a group having the same meaning as the group mentioned as the substituent of the alkyl group, cycloalkyl group and aryl group represented by R ₂ ) Represent

In the above general formula [XII], Z ₄ is -Y _1-
It represents a group of non-metal atoms necessary for forming a 5- or 6-membered ring in cooperation with 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 Z ₁ in the above general formula [IV].

Among the compounds represented by the above general formula [V], the compounds represented by the following general formula [XIII] are preferable.

[0067]

[Chemical 14]

In the formula, R ₁ and R ₂ have the same meanings as the groups represented by R ₁ and R ₂ in the above formula [I].

Z ₅ represents a group having the same meaning as the group represented by the above general formula [XII], but in the state represented by the following general formula [XII '] (the general formula [X by the reaction with the oxidized product of the developing agent]. XIII] is a group having a molecular weight of 235 or less in the state where a hydrogen atom is added to Z ₅ desorbed from the compound represented by XIII].

[0070]

[Chemical 15]

In the general formula [XIII], W ₁ is a group represented by the following general formula [XIV], [XV] or [XVI].

[0072]

[Chemical 16]

In the general formulas [XIV] and [XVI], R ₁₆
Represents an alkyl group or a cycloalkyl group, and examples thereof include a group having the same meaning as the alkyl group and cycloalkyl group represented by R ₁ in the above formula [I]. The alkyl group and cycloalkyl group represented by R ₁₆ may have a substituent, and examples of the substituent include an alkyl group represented by R ₂ in the above formula [I], a cycloalkyl group, and an aryl group. The same groups as those mentioned as the substituents of can be mentioned. Of these alkyl groups or cycloalkyl groups represented by R ₁₆ , an unsubstituted alkyl group is preferable.

In the general formula [XV], R ₁₇ represents a substitutable group on the benzene ring, for example, a substituent of the alkyl group, cycloalkyl group or aryl group represented by R ₂ in the general formula [I]. The same groups as those mentioned above can be mentioned.

R ₁₇ is preferably an unsubstituted alkyl group, more preferably an unsubstituted branched alkyl group, and particularly preferably an unsubstituted branched alkyl group having 3 to 12 carbon atoms.

K represents an integer of 0 to 5, and when k is 2 or more, a plurality of R _17's may be the same or different.
k is preferably 2.

In the general formulas [XV] and [XVI], L ₁ and L ₂ each represent an alkylene group, for example, the same as the group mentioned as the alkylene group represented by L in the above general formula [VI]. The following groups can be mentioned.

L ₁ is preferably an alkylene group having 3 to 7 carbon atoms, more preferably 1,3-propylene group, 1,1-propylene, 1,1-pentylene group and 1,1-hexylene group, and 1.3-
Propylene groups and 1,1-propylene groups are particularly preferred. L
₂ is preferably an alkylene group having 3 to 7 carbon atoms, and 1,3-
A propylene group, a 2,2-propylene group, a 2,3-propylene group and a 1,1-propylene group are more preferable, and a 1,3-propylene group and a 2,3-propylene group are particularly preferable.

Among the compounds represented by the above general formula [XIII], the compounds represented by the following general formula [XVII] are preferable.

[0080]

[Chemical 17]

[0081] In the formula, R ₁ and R ₂ in the general formula (I) and the group represented by R ₁ and R _2, are each synonymous.

In the general formula [XVII], W ₂ represents a group represented by the following general formula [XVIII] or [XIX].

[0083]

[Chemical 18]

In the above general formula [XVIII], R ₁₈ represents a linear or branched unsubstituted alkyl group having 11 to 21 carbon atoms.

In the general formula [XIX], R ₁₉ represents a hydrogen atom or a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, and preferably ethyl, butyl or hexyl. R ₂₀ and R ₂₁ are each a hydrogen atom or a carbon atom having 4 to 4 carbon atoms.
Represents 12 branched alkyl groups. However, the total number of carbon atoms of R ₂₀ and R ₂₁ is 4 to 16.

In the above general formula [XVII], Z ₆ represents a group having the same meaning as the group represented by the above general formula [XII], but in the state represented by the above general formula [XII '] (oxidation of the developing agent). (A state in which a hydrogen atom is added to Z ₆ released from the compound represented by the general formula [XVII] by a reaction with a body), the molecular weight is 160 or less.

Of the compounds represented by the general formula [XVII],
Preferred are compounds represented by the following general formula [XX].

[0088]

[Chemical 19]

[0089] In the formula, R ₁ and R ₂ in the general formula (I) and the group represented by R ₁ and R _2, are each synonymous.

R ₂₂ represents a straight-chain unsubstituted alkyl group having 11 to 21 carbon atoms.

Z ₇ represents a group having the same meaning as the group represented by the above general formula [XII], but the state represented by the above general formula [XII '] (the general formula [by the reaction with the oxidation product of the developing agent] XX] is a group having a molecular weight of 128 or less in a state where a hydrogen atom is added to Z ₇ desorbed from the compound represented by [XX].

The 2-equivalent yellow coupler represented by the above general formula [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 [I] uses a commercially available compound which is easily available as a starting material, and is disclosed in a conventionally known method such as JP-A-63-123047 and JP-A-2-245949. It can be easily synthesized according to the method described.

Specific examples of the leaving group Z in the general formula [I] of the present invention are shown below. The molecular weight in the state where a hydrogen atom is added to Z which is eliminated from the compound represented by the general formula [I] by the reaction with the oxidized product of the developing agent is shown in parentheses.

[0095]

[Chemical 20]

[0096]

[Chemical 21]

Specific examples of the substituent R ₃ in the general formula [I] of the present invention are shown below.

[0098]

[Chemical formula 22]

[0099]

[Chemical formula 23]

The typical examples of the two-equivalent yellow couplers represented by the general formula [I] used in the present invention (referred to as the yellow couplers of the present invention) are shown below, but the present invention is not limited thereto.

[0101]

[Chemical formula 24]

[0102]

[Chemical 25]

In the present invention, the coating amount of the yellow coupler of the present invention is 0.75 g / m ² or less, preferably 0.71 g / m ²
It is the following. The amount of the stain inhibitor added is 1 to 5 mol% with respect to the yellow coupler, but preferably 2 to 4
Mol%.

The magenta and cyan couplers used in the color light-sensitive material according to the present invention form a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm by coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as typical examples, known as a magenta coupler having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm and a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm. Some of them are listed.

As a magenta coupler which can be preferably used in the color light-sensitive material according to the present invention, there is disclosed in JP-A-4-
No. 114154, page 12, general formulas (M-I) and (M-II)
Examples of the specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same publication.

As a cyan coupler which can be preferably used in the color light-sensitive material of the present invention, JP-A-4-114154 is known.
The couplers represented by the general formulas (C-I) and (C-II) described in No. 17 on page 17 can be mentioned.
It is described as CC-1 to CC-9 on pages 18 to 21 of the same specification. One of these preferably used cyan couplers is a 2-acylamino-5-ethylphenol cyan coupler, which is a compound described in JP-A-2-251845, page 5, lower right column to page 6, upper left column. Examples thereof include coupler Nos. II-1 to II-20 on page 6, upper right column to page 7, upper left column. The most preferred of these is
It is a compound represented by II-4. Another type of cyan coupler that is preferably used is a 2,5-diacylaminophenol cyan coupler, which is disclosed in JP-A 2-25.
Nos. 1845, page 3, upper left column, line 7 to lower right column, line 4; specific examples thereof include coupler No. I-1 on page 4 upper left column to page 5 lower left column. I-31 can be mentioned. Of these, the most preferably used is I-2.
Is a compound represented by.

When the oil-in-water emulsion dispersion method is used to add the coupler used in the light-sensitive material of the present invention,
Usually, it is dissolved in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C or higher, if necessary, in combination with a low-boiling point and / or water-soluble organic solvent, and a surfactant is used in a hydrophilic binder such as a gelatin aqueous solution. Emulsify and disperse. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. It is preferable to include a step of removing the low boiling point organic solvent after or simultaneously with the dispersion.

As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler (and the photographically useful organic compound such as an ultraviolet absorber and a color turbidity preventing agent described below), 10
A high boiling point organic solvent having a vapor pressure of 0.5 mmHg or less at 0 ° C. is preferable, and a compound having a dielectric constant of 6.0 or less is more preferable. The dielectric constant indicates the dielectric constant at 30 ° C. Specific examples of compounds include compound examples II-1 to II described in JP-A-63-103245.
-9, III-1 to III-6, compound examples described in JP-A No. 1-196048 H-1 to H-22, compound examples described in JP-A No. 64-66646
II-1 to II-38 can be preferably used. Of these, dioctyl phthalate, dinonyl phthalate, di-i
-A phthalic acid ester such as dodecyl phthalate and a phosphoric acid ester such as tricresyl phosphate are particularly preferable.

Ethyl acetate is preferably used as the low boiling point organic solvent. In addition, as a preferred surfactant used at the time of dispersion, a hydrophobic group having 8 to 30 carbon atoms in one molecule and -SO ₃ M group or -OSO ₃ M (M represents a hydrogen atom or a cation) The compound which has both can be mentioned. Specific examples of preferable surfactants include the anionic surfactants A-1 to A-11 described in JP-A 64-26854, pp. 55-56, more preferably A-11 and A-8. Is mentioned. Further, a surfactant having a fluorine atom substituted in the alkyl chain is also preferably used.

It is also preferable to add these surfactants to the coating liquid. These dispersions are usually added to a coating solution containing a silver halide emulsion and then coated, but it is preferable that the dispersion is added to the coating solution within 10 hours, more preferably within 3 hours, most preferably 20 minutes. Is to be added within.

The compound (d-11) described on page 33 of JP-A-4-114154, 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 specification can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compounds described in No. 187 can also be used.

[0112] The coating amount of the coupler, if it is possible to obtain a sufficiently high concentration is not particularly limited, preferably 1 mol of silver halide per 1 × 10 ^-3 to 5 mol, more preferably 1 × 10 ^- It is used in the range of ² to 1 mol.

An anti-fading agent is preferably used in combination with the magenta coupler used in the present invention. The first of these compounds is a phenyl ether compound represented by the general formulas I and II described in JP-A-2-66541, page 3. Specific examples of the compound include Compound I described on pages 3 to 5 of the specification.
-1 to I-32 and II-1 to II-18. Among these, more preferable compounds are the compounds represented by I-13 and II-9.

The second anti-fading agent preferably used in combination is a phenolic compound represented by the general formula IIIB described in JP-A-3-174150. Of these, compounds III-1, III-12, III-13, and III-14 described in the same specification are more preferable, and the compound represented by III-14 is particularly preferable.

A third type of anti-fading agent preferably used in combination is an amine compound represented by the general formula A shown in JP-A-64-90445. Specific examples of compounds include A-1 to A-15 described in the upper right column of the same specification. Of these, the more preferred compound is A-3.

An anti-fading agent is preferably used in combination with the yellow coupler and the cyan coupler according to the present invention. Among these, preferred anti-fading agents are compounds represented by the general formula I ′ described in JP-A 1-196049, page 8, and Japanese Patent Application No. 3-185.
The compounds described in No. 113 are mentioned. More preferable compounds are the compounds represented by I-10 and I-13 described on page 9 of the same specification. The anti-fading agent used in combination with these magenta, yellow and cyan couplers is preferably added in the same oil oil droplet as the coupler at a ratio of 0.1 to 3 mol, and more preferably 0.5 to 1.5 mol, per mol of the coupler. More preferably, it is added in a ratio of. As the anti-fading agent, it is preferable to use different kinds of compounds in combination. The anti-fading agent is represented by the general formula IIIB described in JP-A-3-17450 and the general formulas I and II described on page 3 of JP-A-2-66541. A preferred example is the combined use of a phenyl ether compound. Further, a combined use of the phenolic compound represented by the general formula IIIB described in JP-A No. 3-17450 and the amine compound represented by the general formula A described in JP-A No. 64-90445 is also a preferable combination example.

Examples of the ultraviolet absorber used in the present invention include compounds having a spectral absorption maximum wavelength in the ultraviolet region (400 nm or less) and a molecular extinction coefficient of 5000 or more. Examples of preferred compounds include the compounds represented by the general formula III-3 described in JP-A 1-250944 and the compounds represented by the general formula I described in JP-A 4-1633. Specific examples of compounds include IIIc-1 to IIIc-1 described in JP-A 1-250944.
7, III-1 to III-24 and 63-18 described in JP-A-64-66646
UV-1L to UV-22L described in 7240, UV-1S to UV-19S described in the same specification, and compounds I-1 to I-23 described in JP-A No. 4-1633 can be mentioned. Among them, particularly preferable compounds include IIIc-7 and IIIc-12 described in JP-A 1-250944, page 15, upper left column, and liquid UV absorber UV-23L described in JP-A-63-187240. These UV absorbers are preferably added by the above-mentioned dispersion method, but in the present invention, the high-boiling organic solvent used in the UV absorber layer is 0.3-by weight ratio to the UV absorber.
It is added at a rate of 0. The ratio is preferably 0.1 to 0, and most preferably 0. As the high boiling point organic solvent, the compound used for dispersing the coupler is preferably used. In the present invention, the ultraviolet absorber is preferably contained in the non-photosensitive layer. Further, it is separated from the non-photosensitive intermediate layer further apart from the silver halide emulsion layer farthest from the support and the emulsion layer farthest away from the support, and second away from the emulsion layer. It is a light-insensitive layer intermediate to the emulsion layer in position.

In the present invention, it is preferable to add a fine particle powder (so-called matting agent) to the surface layer or the layer farthest from the support. As a matting agent, JP-A-2-7325
The compounds described in No. 0, page 4, lines 9 to 20, are preferable, and crystalline or amorphous silica is most preferable. These may be used alone or in combination of two or more. Regarding the particle size of the matting agent, the average particle size is 1 to 10 μm.
m is preferable, and 2 to 7 μm is more preferable. The amount of the matting agent applied is 0.021 to 0.1 g / m ² , and more preferably 0.025.
~ 0.08 g / m ² .

Further, it is preferable to add a high boiling point organic solvent to the surface layer. As a preferable high boiling point organic solvent to be added to the surface layer, a high boiling point organic solvent having a vapor pressure at 100 ° C. of 0.5 mmHg or less is preferable, and a compound having a dielectric constant of 6.0 or less is more preferable. As specific examples of compounds, those described in the dispersion of the coupler can be mentioned as they are. The addition amount is 1 to 100 mg / m ² , and preferably 10 to 50 mg / m ² .

To the light-sensitive material according to the present invention, a fluorine-containing surfactant or an organopolysiloxane is added for the purpose of improving surface properties such as gloss, stickiness, sticking resistance, slipperiness and scratch resistance. You may. Preferable fluorine-containing surfactants include compounds represented by the general formulas (I), (II) and (III) described in Japanese Patent Application No. 4-270425. Among them, particularly preferred are FI-55, FI-81, FK-
5, FK-13 and FK-23. Preferable organopolysiloxanes include compounds represented by the general formulas (S1), (S2), (I), (II) and (III) described in Japanese Patent Application No. 4-270425. Among them, particularly preferable compounds include the compounds represented by S-7 and S-19.

In the present invention, it is preferable to use an oil-soluble dye. An oil-soluble dye has a solubility in water at 20 ° C of 0.01
The following organic dyes are referred to, and compounds having a molecular absorption coefficient of 20,000 or more at the maximum absorption wavelength at a wavelength of 400 nm or more are preferable. Preferred compounds include the compounds of the general formulas II and III shown on page 26 of JP-A-2-842. Examples of preferable specific compounds include compounds 1 to 27 described on pages 29 to 32 of the same specification. Of these, compounds 4 and 9 are particularly preferable. The oil-soluble dye is preferably added to the non-photosensitive layer, and is preferably added in an amount of 0.05 to 5 mg / m ² .

In the present invention, it is preferable to add a fluorescent whitening agent to the light-sensitive material. As a fluorescent whitening agent, JP-A-2-
A compound represented by the general formula II described in No. 232652 is preferable,
Specific examples of compounds include compounds 1 to 6 described on pages 18 to 20 of the same specification. Of these, compound No. 3,1,
The compound represented by 5 is particularly preferable. These optical brighteners are preferably added to the non-photosensitive layer. The amount added is preferably 0.001 to 0.3 mg / m ^{2, and} more preferably 0.1 to 0.2 mg / m ^2.
Is more preferable.

In the present invention, it is preferable to add a water-soluble polymer compound which complements the above-mentioned optical brightening agent and enhances the optical brightening effect. Preferred compounds include polyvinylpyrrolidone and polymers containing vinylpyrrolidone as a repeating unit. These are preferably contained in the ultraviolet absorber-containing layer farthest from the support and / or in a layer further distant from the layer.

For the color light-sensitive material of the present invention, it is preferable to use water-soluble dyes having absorption in various wavelength regions for the purpose of preventing irradiation and halation.
As a preferable anti-irradiation dye, JP-A-62-62
The compound represented by the general formula II described in JP-A-253146 (specific examples of the compound include compound II-1 to 12-13 described in the same specification).
II-19), compounds represented by the general formula I described in JP-A No. 64-26850 (specific examples of compounds are Compound Nos. 1-85 described on pages 7 to 11 of the specification), JP-A-2-97940. No. 1 to 103 described in No. 1 to 103 described on page 5 in the lower section of the same specification as specific compound examples, page 3 of Japanese Patent Application No. 4-182885. The compounds described in the 22nd line to 5th page, 2nd line are mentioned. Of these, particularly preferred compounds include compound No. 47 represented by general formula I described in JP-A No. 64-26850, compound No. 54 represented by general formula I described in JP-A No. 2-97940, 1, 4, 6, described in Japanese Patent Application No. 4-182885
It is a compound represented by 7, 9.

As the anti-irradiation dye, it is preferable to use a dye having different maximum absorption wavelengths in combination,
It is preferable to use a dye having a maximum absorption at 00 nm, a dye having a maximum absorption wavelength at 500 to 600 nm, and a dye having a maximum absorption wavelength at 400 to 500 nm in combination. These dyes may be added to any layer, but are preferably added to the non-photosensitive layer. The addition amount, preferably for each of the compounds 1 to 100 mg / m ^2, more preferably from 3~60mg / m ^2.

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.

As a mode of reacting the soluble silver salt and the soluble halide, a forward mixing method, a back mixing method, a simultaneous mixing method,
Any combination thereof may be used, but those obtained by the simultaneous mixing method are preferable. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one form of the simultaneous mixing method.

Further, a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and 57-92524, German Published Patent 2921164, etc., an apparatus for continuously changing the concentration of a water-soluble silver salt and a water-soluble halide aqueous solution, and the reaction mother liquor was taken out of the reactor as described in JP-B-56-501776, etc. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by a filtration method.

Further, 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.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be kept contained. Research Disclosure 17
It can be performed based on the method described in No. 643.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a {100} plane as a crystal surface. or,
U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26589
Issue, Japanese Examined Japanese Patent Publication No. 55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) Volume 21
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron are prepared by the method described in the literature such as page 39 (1973),
It can also be used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The particle size of the silver halide grains is not particularly limited, but considering other photographic properties such as rapid processing property and sensitivity, it is preferably 0.1 to 1.6 μm, more preferably 0.2 to 1.2 μm.
It is in the μm range. The particles can be measured by various methods generally used in the technical field. The particle size can be obtained by using the projected area of the particle or an approximate diameter value.

When the particles are substantially uniform in shape,
The particle distribution can be represented fairly accurately using diameter or projected area. The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Monodispersed silver halide having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain distribution of silver halide grains is preferable. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following.

Coefficient of variation = S / R (where S is the standard deviation of the grain size distribution and R is the average grain size.) The grain size as used herein means the diameter of spherical silver halide grains. Also, in the case of a particle having a shape other than a cube or a sphere, it represents the diameter when the projected image is converted into a circular image having the same area.

The silver halide grain emulsion according to the present invention is silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver bromide or silver chloride, but preferably substantially contains silver iodide. Not more than 90 mol% is silver chlorobromide grains or silver chloride consisting of silver chloride. The content of substantially no silver iodide means that the silver iodide content is 0.
It is 5 mol% or less, preferably 0.1 mol% or less, more preferably not contained at all. The silver chloride content is preferably 95 mol% or more, more preferably 98 mol% or more, still more preferably 99 mol% or more.

When the silver halide grains according to the present invention are silver chlorobromide containing silver bromide, core / shell grains having a different composition within the silver halide grains or a silver bromide localized phase are provided on the grain surface. Alternatively, the grains may be inside, but silver halide grains having a uniform composition from the inside to the surface are preferable.

The silver halide emulsion according to the present invention contains various metal salts in the course of grain formation or physical ripening, or
A metal complex salt can be introduced.

The metal used is the first in the periodic law.
VIB group, VIIB group, VIII group, IIB group, IIIA group,
Group IVA can be mentioned, and among them, those preferably used are Mn, Fe, Co, Ni, Zn, Ga, Ge, Mo, Ru, Pd, C.
It is a salt or complex salt of d, In, Sn, W, Re, Os, Ir, Pt, Tl, Zn, Au. These may be used alone or in combination.

A preferred metal salt or complex salt is Japanese Patent Application No. 2-1623.
No. 32, No. 2-253667, No. 3-109173, No. 4-251468, No.
4-82250, JP-A-4-125629, 4-251469, 4-253
No. 081 and the like.

The addition amount of these compounds can be varied over a wide range depending on the kind of the compound or the purpose.
10 ^-11 to 10 ^-3 mol is preferably used with respect to the mol.

The silver halide grain emulsion according to the present invention can be used in combination with a gold sensitizing method using a gold compound and a (sulfur) sensitizing method using a chalcogen sensitizer.

As the gold sensitizer, chloroauric acid, gold chloride, gold thiosulfate, and various gold complexes can be added. Examples of the oxidizing compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole.

The amount of the gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of gold compound, the ripening conditions, etc., but is usually 1 × 10 ^-9 to 1 × per mol of silver halide.
10 ⁻⁴ mol is preferable, and more preferably 1 × 10 ⁻⁸ to 1 × 10 5.
^-5 mol.

As the chalcogen sensitizer, a sulfur sensitizer,
Although a selenium sensitizer and a tellurium sensitizer can be used,
Sulfur sensitizers are preferred. Examples of the sulfur compound include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenesulfonate, rhodanine, and inorganic sulfur.

The light-sensitive material of the present invention can be subjected to reduction sensitization. Known methods are known for reduction sensitization. For example, a method of adding various reducing agents, a method of aging under conditions of high silver ion concentration, a method of aging under conditions of high pH, and the like can be used.

Examples of the reducing agent used for reduction sensitization include stannous salts such as stannous chloride, boranes such as tri-t-butylamine borane, sulfites such as sodium sulfite and potassium sulfite, and reductones such as ascorbic acid. Examples thereof include thiourea dioxide and the like. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to the silver halide emulsion for ripening, or they are added during the formation of silver halide grains to reduce and increase them simultaneously with grain formation. You may feel.

The amount of these reducing agents added needs to be adjusted according to the pH of the silver halide emulsion, the concentration of silver ions, etc., but generally 10 mol per mol of the silver halide emulsion is used.
^-7 to 10 ^-2 mol is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of the compound used for such purpose include
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, thiosulfinic acid, and hydrogen peroxide solution.

A silver halide solvent may be added to the silver halide emulsion according to the present invention in the process of sensitization. The silver halide solvent preferably used is thiocyan compounds, and examples thereof include potassium thiocyanate, sodium thiocyanate, calcium thiocyanate, magnesium thiocyanate, silver thiocyanate and ammonium thiocyanate.

The pH and pAg at the time of sensitization are not particularly limited.
It is performed in the range of H4.0-11.0 and pAg4.5-8.5.

The silver halide emulsion according to the present invention has a known fog for the purpose of preventing fog during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog during development. Inhibitors and stabilizers can be used. Examples of compounds used for such purpose include compounds represented by the following general formula [S].

[0155]

[Chemical formula 26]

In the formula, Q represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and M represents a hydrogen atom or an alkali metal atom.

The 5-membered heterocyclic ring represented by Q is, for example, imidazole ring, tetrazole ring, thiazole ring, oxazole ring, selenazole ring, benzimidazole ring,
A naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring and the like can be mentioned. The 6-membered heterocyclic ring represented by Q includes a pyridine ring, a pyrimidine ring,
Examples thereof include a quinoline ring, and these 5- or 6-membered heterocycles include those having a substituent. Examples of the alkali metal atom represented by M include a sodium atom and a potassium atom.

A more preferable structure of the mercapto compound represented by the general formula [S] is described in Japanese Patent Application No. 4-330655, paragraphs [0016].
As described in paragraph 0032. Further, specific compounds include S-described in paragraphs 0034 to 0039 of the same application.
1-1 to S-4-8 can be mentioned. In addition, Japanese Patent Application No. 4-80948
The compound represented by the general formula [I] is also preferred, paragraph 002
Specific examples are given as 1 to 49 in 6 to paragraph 0028.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention. As a blue-sensitive sensitizing dye, Japanese Patent Application No. 2-5112
BS-1 to 8 described in No. 4, pages 108 to 109 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used.

When the light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, I described in Japanese Patent Application No. 3-73619, pages 12 to 14
The dyes RS-1 to 11 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

When the light-sensitive material according to the present invention is exposed using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the luminous flux in the case of scanning exposure with laser light. In the spatial variation of the intensity of the light, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, the line parallel to the scanning line and passing through the point where the light intensity is maximum and the outer edge of the light flux. When the distance between two intersecting points is the ray of the light beam, it can be considered as the exposure time per pixel by (the ray of light beam) / (scanning speed). As the exposure time per pixel becomes shorter, the relationship between the exposure time and the color density tends to become more complicated, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used.

A laser printer device which is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-407.
1, 59-11062, 63-197947, JP-A-2-74942
No. 2-236538, Japanese Patent Publication No. 56-14963, No. 56-40822,
European Wide Area Patent 77410, Technical Report of Department of Electronic Communication 80
Volume 244 and movie television technical magazine 1984/6 (382) pages 34-36.

As the red-sensitizing sensitizing dye, cycyanine dyes represented by the following general formulas [2] and [3] are preferably used.

[0164]

[Chemical 27]

In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group, an alkenyl group or an aryl group. L ₁ ,
L ₂ , L ₃ , L ₄ and L ₅ each represent a methyl group. Z ₁ ,
Z ₂ , Z ₃ and Z ₄ each represent an atom or a group of atoms necessary for completing a 5- or 6-membered heterocyclic nucleus. Z ₅ represents an atomic group necessary for forming a 6-membered carbocycle. m ₁ , m ₂ , m ₃ and m ₄ each represent 0 or 1. n represents 0 or 1. X ^-
Represents an acid anion. Y ₁ and Y ₂ each represent 0 or 1, and when the compound forms an intramolecular salt, Y ₁ and Y ₂ are
Each represents 0.

Examples of the supersensitizer used in the silver halide emulsion according to the present invention include stilbene, azaindene,
A compound such as a mercapto heterocyclic compound or a condensate of thiourea or phenol and hexamethylenetetramine can be used, but it is preferable to use a 9-membered or more cyclic compound containing a heterocycle.

From the viewpoint of effect, the cyclic compound is preferably one having an aliphatic ring and / or an aromatic ring and an ether bond, and the aliphatic ring forming the cyclic compound is preferably 4 or less, and has an aromatic ring. Macrocyclic compounds are more preferred.

Typical compounds are crown ethers, and specific examples of these cyclic compounds include S-1 to S-39 described in paragraphs 0049 to 0055 of Japanese Patent Application No. 4-330655.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder for dispersion and coating liquid.

For the production method of gelatin, for example, TH Jame
s; The Theory of The Photographic Process, 4th ed. (19
77) page 55 and the basics of photographic engineering, silver halide photography, pages 119 to 124. As the raw material, cow bone (ossein) cowhide (hide) and pig skin (pig skin) are used, preferably prepared from cow bone, but even if two or more kinds of them are mixed, Good.

As the treatment, alkali treatment, acid treatment, oxygen treatment and the like are carried out, but alkali-treated gelatin is preferred. The isoelectric point of the alkali-processed gelatin is preferably 4.5 or higher, more preferably 5 or higher. Although gelatin can be usually subjected to ion exchange treatment, in the present invention, cation, anion and gelatin subjected to both ion exchange treatment can be appropriately selected depending on the use, but gelatin subjected to both ion exchange is preferred. Gelatin treated with hydrogen peroxide is also preferably used.

The hydrogen peroxide treatment may be carried out in any of the gelatin preparation steps. For example, it may be performed directly on ossein, during the alkali treatment, after the alkali treatment, or after extraction as a gelatin solution. In the present invention, gelatin prepared by adding hydrogen peroxide solution during alkali treatment is preferable. Hydrogen peroxide is added in the range of 1 to 100 g as pure H ₂ O ₂ per 1 kg of ossein. The reaction with hydrogen peroxide is preferably carried out at pH 9.0 or higher.

The composition of gelatin is preferably such that the low molecular weight component is small and the high molecular weight component is large. For the measurement method of high and low molecular weight components, see JP-A 1-265247.
The method described on page 2, lower left column, line 15 to page 3, upper left column, line 8 can be used. It is more preferable that the high-molecular weight component is 30% or more and / or the low-molecular weight component is 40% or less, according to the method. The molecular weight of gelatin is preferably 10,000 to 200,000.

The jelly strength of gelatin is preferably high, and more preferably 250 or more. Particularly preferred is 270 or more.

The content of ions as impurities contained in gelatin is preferably as low as possible. For example, the calcium ion content is preferably 5000 ppm or less, more preferably 2000 ppm or less. However, depending on the emulsion, the presence of 4000 to 5000 ppm of calcium may be preferable.

Heavy metal ions such as iron and copper ions are preferably 500 ppm or less in total, and 10 ppm or less for each component. In particular, the iron ion content is 5 ppm or less, more preferably 3 ppm or less.

Further, the higher the specific optical rotation of gelatin is, the more preferable it is, and the more preferable value is 150 or more. When used for the top layer,
A specific rotation of 210 or more is preferable.

The less the coloring of gelatin is, the better it is. The transmittance of a 10% by weight aqueous solution of gelatin at 420 nm is 50%.
Above, preferably 60% or more, more preferably 70% or more gelatin is advantageous for the present invention. In order to increase the transmittance of gelatin, selection of raw materials, hydrogen peroxide treatment, ion exchange, adsorption with a chelate resin, etc. are appropriately performed.

The total amount of gelatin contained in the light-sensitive material of the present invention is 10.0 g / m ² or less, preferably 7.0 g / m ² or less. The lower limit is not limited, but it is generally from the viewpoint of physical properties or photographic performance. It is preferably 3.0 g / m ² or more.
The amount of gelatin is determined by the water content measurement method described in the Pagui method.
It is calculated in terms of the weight of gelatin containing 11.0% water.

In the present invention, a binder hardener is used. As the hardener, vinyl sulfone type hardeners and chlorotriazine type hardeners are preferably used. As the vinyl sulfone type hardener, compounds described in JP-A No. 61-249054, page 25, upper right column, line 13 to page 27, upper right column, line 2 can be preferably used. Furthermore, the compound H-12 described on page 26 of the same specification is more preferable. As the chlorotriazine type hardener, JP-A-61-245153, page 3, lower left column, line 1 to 3
4th line from the lower right column of the page and 4th line from the lower right column of the page 3 to 5
The compounds described in the lower left column of the page are preferably used. Further, the compound represented by XII-1 described on page 4 of the same specification is more preferable. These hardeners are preferably used in combination with different compounds, and may be added to any layer. The hardener is preferably used in an amount of 0.1 to 10% by weight based on the binder.

In the present invention, it is preferable to add a mildew proofing agent to either layer. Preferred compounds include
The compound represented by the general formula II described in Japanese Patent Application No. 1-298092, page 9, is preferable. Specific examples of compounds include the same specification 69-
Compound examples No. 9 to 22 described on page 70 are mentioned. Of these, the compound shown as No. 9 is particularly preferable.

In the present invention, a preservative and a fungicide can be used. As a preferred example, Japanese Patent Laid-Open No. 3-1576
There are compounds described in No. 46, page 17, lower right column, line 16 to page 19, lower left column.

As the reflective support according to the present invention, any material may be used, including white pigment-containing polyethylene-coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used for the reflective support, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, fine silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, oxidation Examples thereof include zinc, talc, and clay, but barium sulfate and titanium oxide are preferable. The white pigment may be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support is preferably 10% by weight or more, more preferably 13% by weight as the content in the waterproof resin layer.
It is preferably not less than 15% by weight, more preferably not less than 15% by weight. The dispersity of the white pigment in the waterproof resin layer of the paper support is
It can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and further preferably 0.10 or less as the coefficient of variation described in the above publication. The surface of the paper support is preferably smoother, and the central average roughness (SRa) is 1.0 μm.
The following is preferable. The calculation method of SRa is Japanese Patent Application No. 3-2.
Calculated by the formula described on page 6 of No. 576.

The base paper used for the support of the present invention is selected from commonly used materials. That is, bleached softwood pulp by sulfuric acid method (NBKP), bleached hardwood pulp by sulfuric acid method (LBK)
P), sulfite bleached softwood pulp (NBSP), sulfite bleached hardwood pulp (LBSP), and other natural pulps may be used alone or in combination of two or more. When used in combination, the desirable pulp mixture ratio is hardwood pulp /
The ratio of softwood pulp is 95/5 to 60/40.

In the present invention, it is preferable to add various additives shown below to the base paper to enhance paper strength such as water resistance. For example, as a sizing agent, alkyl ketene dimer fatty acid salt, rosin, maleated rosin, alkenyl succinate,
Alkyl succinate and polysaccharides are used, but alkyl ketene dimer fatty acid salt is preferably used. It is preferable to use 0.2 to 2% of these per pulp. As the dry paper strengthening agent, cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol and the like are used, but cationized starch and anionized polyacrylamide are preferable. Further, as the wet paper strength enhancer, melamine resin, urea resin, epoxidized polyamide resin and the like are used, but epoxidized polyamide resin is preferable. Also, generally, the surface of the pulp is tab-sized or size-pressed with a liquid containing a water-soluble polymer additive. As the water-soluble polymer, cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide, gelatin and the like can be used, but cationized starch and polyvinyl alcohol are preferable.

As the antifoggant, there is disclosed in JP-A-55-103549.
Water-soluble iodine compounds described in JP-A No. 56-43637, weak acid salts or oxides of magnesium, calcium or zinc described in JP-A-56-43637, urea compounds having a molecular weight of 150 or less described in JP-A-56-97343, The magnesium compounds described in 19405 are used. Of these compounds, magnesium hydroxide, magnesium oxide, calcium oxide, and zinc oxide are preferable, and are used in an amount of 0.1 to 10% by weight based on the pulp. Further, as the inorganic electrolyte, salt, mirabilite or the like is used, but salt is preferable. Glucerin, polyethylene glycol, etc. are used as hygroscopic substances, and hydrochloric acid, sodium hydroxide, sodium carbonate, etc. are used as pH adjusters.
In addition, additives such as a dye (preferably a blue dye and ultramarine), a fluorescent whitening agent, an antistatic agent and an antifoaming agent are used in combination. After the pulp is appropriately crushed, it becomes a pulp slurry containing the above additives as required, and is made into paper by a paper machine such as a Fourdrinier paper machine and dried and supercalendered. Surface sizing is performed before or after this drying.

The support is preferably one obtained by coating both sides of the base paper obtained as described above with a polyolefin resin. Examples of the polyolefin resin include polyethylene,
Homopolymers of α-olefins such as polypropylene and mixtures of these polymers, particularly preferred polyolefins are high-density polyethylene, low-density polyethylene or mixtures thereof. The molecular weight of these polyolefins is not particularly limited, but polyolefins in the range of 20,000 to 200,000 are generally used. There is also no particular limitation on the thickness of the polyolefin resin coating layer, and usually about 15 to
It is 50 μm thick. When the support is a paper support, various forms of support can be used, for example, thin base paper having a support thickness of 80 to 180 μm, utility model 64-29550.
The peel-adhesive type and the thick base paper described in Japanese Patent No. 312058 can also be used. When a support such as polypropylene or polyethylene terephthalate is used, it can be produced by adjusting the amount of white pigment applied to each of transparent, translucent and opaque types. The oxygen permeability of the support is preferably 2.0 cc / m ² · hr · atm or less.

As a reflective support according to the present invention, a photographic paper support having a resin composition layer containing an inorganic and / or organic white pigment and cured by electron beam irradiation on at least one side of a substrate is also highly smooth. It has high sharpness and is preferably used.

The electron beam curable coating liquid used in the present invention contains at least one organic compound capable of forming a cured resin by an electron beam and a pigment, preferably an inorganic pigment, as main components, and if necessary, other additives are added. It contains an agent.

Organic compounds which are polymerized and cured by electron beam irradiation are unsaturated compounds containing two or more carbon-carbon double bonds in one molecule, such as acrylic and methacrylic oligomers, polyfunctional acrylic and methacrylic compounds. Monomers and unsaturated compounds containing at least one carbon-carbon double bond in one molecule, such as monofunctional acrylic monomers, methacrylic monomers and vinyl monomers are included.

These unsaturated organic compounds generate radicals by electron beam irradiation to polymerize, and form cross-links due to intermolecular and intramolecular cross-linking reactions to be cured to form a cured resin.

A typical resin has an acryloyl or methacryloyl group at both ends and a skeleton of polyester,
There are compounds that are polyurethanes, polyethers and polycarbonates.

The acrylic and methacrylic oligomers include acrylic acid or methacrylic acid ester of polyurethane, acrylic acid or methacrylic acid ester of polyether alcohol, acrylic acid or methacrylic acid ester of bisphenol A, maleic acid or fumarate ester of polyester. And so on. Further, as the polyfunctional acrylic monomer and methacrylic monomer, 1,6-hexanediol diacrylate, neopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, glycerol trimethacrylate, polyethylene glycol diacrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol pentaacrylate, neopentyl glycol diacrylate, isocyanalic acid diacrylate, isocyanalic acid triacrylate, trimethylolpropane triacrylate Acrylate, propylene oxide modified trimethylo , And the like Le propane polyacrylate. In addition, monofunctional acrylic monomer,
As the methacrylic monomer and the vinyl monomer, methyl acrylate, ethyl acrylate, butoxyethyl acrylate, benzyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, phenoxyethyl acrylate, N, N-diethylaminoethyl methacrylate,
Examples thereof include styrene, N-vinylpyrrolidone, polyoxyethylenephenol acrylic acid ester, and 2-ethylhexyl acrylate.

As commercially available products, for example, Aronix M-5700 and M-6100 (polyester acrylate), Aronix M-1100 and M-
1200 (urethane acrylate), Aronix M-10
1,102 (monofunctional acrylate), Aronix M-21
Examples thereof include 0, 215 (multifunctional acrylate, all manufactured by Toa Gosei Co., Ltd.) and GE-510 (epoxy compound: manufactured by Mitsubishi Gas Co., Ltd.).

The coating liquid contains a pigment, usually a white inorganic pigment, uniformly mixed with the electron beam-curable organic compound dissolved or dispersed in an organic solvent. As the white inorganic pigment, the white pigment used for the reflection support can be used as it is.

The content of the white inorganic pigment in the coating liquid is preferably set to 20 to 80% by weight based on the total solid weight of the cured resin coating layer. When the content is less than 20% by weight, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and when the content exceeds 80% by weight, the flexibility of the obtained cured resin coating layer is deteriorated. , Film cracks will occur. To disperse the white inorganic pigment in the electron beam curable unsaturated organic compound, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill),
Cowles dissolver, homomixer, sand grinder, ultrasonic disperser, etc. can be used.

As the organic solvent, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene, ethylene chloride, carbon tetrachloride, chloroform, dichlorobenzene or the like can be used. .

As a coating method, a roller coating method may be used, or alternatively, a general method used for coating a sheet, for example, a bar coating method, an air doctor coating method, a blade coating method or a squeeze coating method. Any of an air knife coating method, a reverse roll coating method, a transfer coating method and the like may be used. A fountain coater or slit orifice coater system can also be used.

There is no particular limitation on the electron beam irradiation apparatus used in the present invention, and in general, as such an electron beam irradiation electron beam accelerator, a curtain beam type that is relatively inexpensive and can obtain a large output is used. Used effectively. The acceleration voltage during electron beam irradiation is preferably 100 to 300 kV, and the absorbed dose is preferably 0.5 to 10 Mrad.

The thickness of the coating layer is 3 to 100 μm, preferably 5 to 50 μm. If the amount is out of this range, coating unevenness occurs, a large amount of energy is required for curing, and curing becomes insufficient, which is not preferable in terms of quality.

If necessary, the surface of the coating liquid may be smoothed with a mirror-finished roll or cured, or the surface may be matted with a matte roll such as a silk roll.

The support substrate used in the present invention includes
Generally, any material used for a photographic support can be used, but paper is usually used. Examples of the paper used as the sheet substrate include natural pulp paper, synthetic pulp paper, mixed paper of natural pulp and synthetic pulp, and various types of combined paper. These paper substrates may be mixed with additives such as sizing agents, paper strengthening agents, fixing agents, fillers, antistatic agents, pH adjusters, pigments and dyes which are generally used in papermaking. . Further, a surface sizing agent, a surface paper strength agent, or an antistatic agent may be applied on the surface.

The photosensitive material according to the present invention is directly or undercoated (adhesiveness, antistatic property of the surface of the support) after corona discharge, ultraviolet irradiation, flame treatment and the like on the surface of the support, if necessary. It may be applied via one or more undercoat layers) to improve dimensional stability, abrasion resistance, hardness, antihalation properties, friction properties and / or other properties.

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are particularly useful.

The printed light-sensitive material thus produced is exposed through a processed negative film. Various types of negative films can be used. Also, negative films having various spectral sensitivities can be used. A preferred negative film is Konica Color Super DD100. More preferably, Konica Impressa50 and Fuji Riara are mentioned. Further, the exposure time is in the wide range of several tens of milliseconds to several tens of seconds. As the exposure method at this time, various methods which are usually carried out at a developing station can be used. Examples of devices preferably used as printers include Konica Printer CRP-5N2, SCP-8015, KCP-7N3, Gretag
3141 Printer, Agfa MSP Printer, Kodak CLA
Examples include S35 printers. It is also preferable to produce a large-sized print using a stretcher and an enlarging machine.

In the present invention, the time from exposure to development may be any time, but a shorter time is preferable in order to shorten the overall processing time. Further, the light-sensitive material according to the present invention has a small change in image density even when the time from exposure to development is 30 seconds or less, and a high quality image can be stably obtained.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. Representative compound examples 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- (N-ethyl-N-β-hydroxyethylamino)
Aniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-6: 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) 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- (β-Butoxyethyl) aniline CD-12: 4- (N-ethyl-N- (β-hydroxypropylamino) aniline These color developing agents may be used alone or in the known p-phenylenediamine. You may use together with a derivative.

The color developing agent is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the developing solution, and from the viewpoint of rapid processing, it is 1.5 x 10 per liter of the color developing solution.
It is preferably used in the range of ^{−2 to} 2 × 10 ⁻¹ mol.

As the color developing agent used in the present invention, CD-5, CD-6 and CD-9 are preferable.

These p-phenylenediamine derivatives are
It is generally used in the form of a salt such as sulfate, hydrochloride, sulfite, nitrate, p-toluenesulfonate.

The preferred developer of the present invention preferably contains substantially no benzyl alcohol. Here, the term "substantially free" means that benzyl alcohol is 2 cc / liter or less, and it is most preferred that the present invention does not include benzyl alcohol at all.

The color developer may contain the following developer components in addition to the above components. As an alkaline agent,
For example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicate or the like may be used alone or in combination to prevent precipitation and maintain the pH stabilizing effect. It can be used in combination within the range. Further, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate and the like can be used for the necessity of preparation or for the purpose of increasing ionic strength.

In the present invention, it is preferable that the color developing solution contains chlorine ions in an amount of 2.5 × 10 ^{-2 to} 5 × 10 ^-1 mol / liter. In addition, bromide ion is 2.0 × 10 ^-5 ~ 2.0
It is preferable to contain ^{x10 -2} mol / liter.

Here, the chlorine ion and the bromine ion may be added directly to the developing solution or may be eluted from the light-sensitive material to the developing solution during the development processing. When directly added to the color developing solution, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, cadmium chloride and the like can be mentioned as chloride ion supplying substances, but preferred among them are Are sodium chloride and potassium chloride.
Further, it may be supplied from an optical brightener added to the developing solution.

Sodium bromide, potassium bromide, ammonium bromide, lithium bromide as a bromide ion-supplying substance,
Nickel bromide, magnesium bromide, manganese bromide, calcium bromide, cadmium bromide, cerium bromide, thallium bromide and the like can be mentioned. Among them, preferred are sodium bromide and potassium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

Further, in the color developing solution, instead of hydroxylamine which has been conventionally used as a preservative, JP-A-63-1 is used.
46043, 63-146042, 63-146041, 63-146040
No. 63-135938, No. 63-118748, and No. 63-179351.
And hydroxylamine derivatives described in JP-A-64-6
2639 and JP-A-1-303438, etc., hydroxamic acids, hydrazines, hydrazides, phenols, α-
Preferred as organic preservatives are hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed amines. Used.

These compounds may be used in combination with the conventionally used hydroxylamine and the above organic preservatives, but it is preferable not to use hydroxylamine from the viewpoint of developing characteristics.

If necessary, a development accelerator can be used. Examples of the development accelerator include U.S. Pat.
No. 4, 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. Issue 2,53
1,832, 2,950,970, 2,577,127 and JP-B-44-
Polyethylene glycol and its derivatives described in 9504, nonionic compounds such as polythioethers, JP-B-44-950
Organic solvents and organic amines described in No. 9, ethanolamine,
Examples include ethylenediamine, diethanolamine, triethanolamine and the like. Further, phenethyl alcohol described in U.S. Pat. No. 2,304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, if necessary, ethylene glycol,
Methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, p-toluenesulfonic acid, and other compounds described in JP-B-47-33378 and 44-9509 are dissolved aids for increasing the solubility of the developing agent. It can be used as an agent.

Further, an auxiliary developing agent can be used 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 1.0 g per liter of the developing solution. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (DIR couplers), development inhibitor-releasing compounds and the like can be added, if desired.

Further, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be 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, a color developing solution may be prepared by adding a plurality of components which can coexist stably in a concentrated aqueous solution, or a solid container prepared in advance in a small container into water and stirring. it can.

The sulfite concentration in the color developer is 1 × 10 ^-2.
It is preferably not more than mol / liter. Especially including 0 7 × 10 ^-3
It is favorable when the amount is less than mol / liter, and particularly preferably 5 × 10 ⁻³ mol / liter or less including 0.

In the present invention, the color developing solution is adjusted to an arbitrary pH.
Although it can be used in the range, it is preferably pH 9.5 to 13.0, and more preferably 9.8 to 12.0, from the viewpoint of rapid processing.

The processing temperature for color development is preferably 25 to 70 ° C. The higher the temperature, the shorter the treatment is possible, which is preferable, but it is preferable that the temperature is not too high from the stability of the treatment liquid.
Treatment at 25 to 50 ° C is preferred. Color development time is
It must be 70-240 seconds. If it is shorter than 70 seconds, the maximum density during continuous processing becomes unstable, and if it is longer than 240 seconds, sludge is likely to be generated in the color developing solution. It is preferably in the range of 90 to 220 seconds.

The replenishing amount of the color developer is preferably 200 cc or less, more preferably 20 to 180, per liter of the light-sensitive material.
cc, particularly preferably 20 to 165 cc.

The processing step essentially comprises a color developing step, a bleach-fixing step, and a water washing step (including a stabilizing treatment as an alternative to water washing), but the steps may be added or have the same meaning as long as the finishing effect is not impaired. It can be replaced with a process. For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or a bleaching step can be placed before the bleach-fixing step. As the processing step of the color light-sensitive material of the present invention, it is preferable to provide a bleach-fixing step immediately after the color development step.

The bleaching agent that can be used in the bleach-fixing solution is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating a polycarboxylic acid, an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these compounds include compounds 2 to 20 described in JP-A 1-205262, pages 58 to 59.

These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution.

As the bleach-fixing solution, a solution containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution comprising a composition containing a large amount of a halide such as ammonium bromide in addition to an ethylenediaminetetraacetic acid iron (III) salt bleaching agent and a silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (III) A special bleach-fix solution having a composition comprising a combination of a salt bleach and a large amount of a halide such as ammonium bromide can be used.

As the above-mentioned halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or thiosulfate. Typical examples thereof include thiosulfates such as sodium and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether.

These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally 70 to 250 g.

The bleach-fixing solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid,
Various pH buffering agents such as sodium acetate and ammonium hydroxide can be contained alone or in combination of two or more kinds. Further, various optical brighteners, antifoaming agents or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, organic solvents such as methanol, dimethylformamide and dimethylsulfoxide. And the like can be appropriately contained.

The bleach-fixing solution is described in JP-A-46-280,
45-8506, 46-556, Belgian Patents 770,910, Japanese Patent Publications 45-8836, 53-9854, JP-A-54-71634 and 49.
Various bleaching accelerators described in JP-A-42349 and the like can be added.

The bleach-fixing solution is used at a pH of 4.0 or higher, but is generally used in the range of 4.0 to 9.5, preferably 4.
Used in 5-8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. The treatment temperature is 80 ° C or lower, preferably 55 ° C or lower, and the evaporation is suppressed to use. Bleach-fix processing time
240 seconds or less is preferable.

In the development processing according to the present invention, color development and bleach-fixing are followed by water washing treatment. A preferred embodiment of the water washing treatment will be described below.

Examples of compounds preferably used in the washing solution include chelating agents having a chelate stabilizing constant for iron ions of 8 or more. Here, the chelate stabilization constant is the value of "Stability Constan" by LG Sillen & A.E.
ts of Metalion Complexes '', The Chemical Society, Lo
ndon (1964) and S. Chaberek & A.E. Martell, "Organic Se
questering Agents ”, Wiley (1959) and others.

The chelate stability constant for iron ions is 8
Examples of the chelating agent described above include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds and the like. In addition, the said iron ion means a ferric ion. Specific examples of the chelating agent having a chelate stability constant with ferric ion of 8 or more include the compounds described in JP-A 1-205162, page 63, line 15 to page 64, line 17. .

The amount of the chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution. Further, an ammonium compound is particularly preferable as the compound added to the washing solution. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A 1-205162, page 65, line 5 to page 66, line 11.

The amount of the ammonium compound added was 1
It is preferably 1.0 × 10 ^-5 mol or more per liter, more preferably in the range of 0.001 to 5.0 mol, particularly preferably
It is in the range of 0.002 to 1.0 mol.

Further, it is desirable that the washing solution contains sulfite within a range where bacteria are not generated. The sulfite contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite and bisulfite. Ammonium sulfate, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite,
Ammonium metabisulfite and hydrosulfite,
Examples thereof include glutaraldehyde bis sodium bisulfite and succinic acid aldehyde bis sodium bisulfite.

It is preferable that at least 1.0 × 10 ^-5 mol of sulfite be added to 1 liter of the washing solution, and 5 × 10 5
^{-5 to} 1.0 × 10 ^-1 mol is more preferable. The method of addition may be such that it is added directly to the washing solution, but it is preferably added to the washing replenisher.

The washing solution used in the present invention preferably contains a mildew-proofing agent, which prevents sulfurization.
It is possible to improve image storability. Examples of such antifungal agents include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds. , Isoxazole-based compounds, propanolamine-based compounds, sulfamide-based compounds, pyronone-based compounds and amino-based compounds. Specific compounds include:
Examples thereof include compounds described in JP-A 1-205162, page 68, line 10 to page 72, line 16. Among these compounds, thiazole compounds, sulfamide compounds, and pyronone compounds are particularly preferably used.

The addition amount of the antifungal agent to the washing liquid is preferably in the range of 0.001 to 30 g, and more preferably 0.003 to 5 g, per liter of the washing liquid.

The water washing solution according to the present invention preferably contains a metal compound in combination with a chelating agent. Such metal compounds include Ba, Ca, Ce, Co, In, La, Mn, Ni and B.
Examples thereof include compounds of i, Pb, Sn, Zn, Ti, Zr, Mg, Al and Sr. These metal compounds can be supplied as inorganic or organic salts such as halides, sulfates, carbonates, phosphates and acetates, hydroxides or water-soluble chelate compounds.

The amount of these compounds added is preferably 1.0 × 10 ^{-4 to} 1.0 × 10 ^-1 mol, and more preferably 4.0 × 10 ^{-4 to} 2.0 × 10 ^-2 mol, per liter of the washing solution.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution. Specific compounds include Exemplified Compounds 1 to 32 described on pages 73 to 75 of JP-A 1-205162.

The compound having an aldehyde group is preferably used in an amount of 0.1 to 50 g, and particularly preferably 0.5 to 10 g, per liter of the washing water.

As the washing water according to the present invention, ion-exchanged water treated with an ion-exchange resin may be used.

The pH of the wash water applicable to the present invention is 5.5 to 10.
The range is 0. As the applicable pH adjuster, any of commonly known alkali agents and acid agents can be used. The treatment temperature of the water washing treatment is preferably 15 to 60 ° C,
The range of 20 to 45 ° C is more preferable. Also, the washing time is 24
0 second or less is preferable. When the washing treatment is carried out in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. In particular, it is preferable to sequentially perform the treatment with the treatment time increased by 20 to 50% in the previous tank.

In the case of the multi-tank counter flow current system, the method of supplying the washing liquid in the washing treatment step is preferably such that the washing liquid is supplied to the post-bath and allowed to overflow into the pre-bath. Of course,
It can also be processed in a single tank. As a method of adding the compound, various methods such as adding as a concentrated solution to the washing tank, or adding the above compound and other additives to the washing solution supplied to the washing tank, and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, especially 0.5 to 30 times, the amount carried in the pre-bath (normal bleach-fixing solution or fixing solution) per unit area of the light-sensitive material.
Double is preferred.

The washing tank in the washing treatment is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As a developing device for the photosensitive material, any known type of device may be used. Specifically, it may be a roller transport type in which a photosensitive material is sandwiched between rollers arranged in a processing tank and conveyed, or an endless belt method in which a photosensitive material is fixed to a belt and conveyed, A method of forming a tank in a slit shape, supplying a processing solution to the processing tank and conveying a photosensitive material,
It is also possible to use a spray method in which the treatment liquid is atomized, a web method in which a carrier impregnated with the treatment liquid is brought into contact, a method using a viscous treatment liquid, and the like.

In the present invention, a large amount of light-sensitive material is processed and run in these color development to drying steps to elute components from the light-sensitive material into the processing solution, contamination between processing tanks and evaporation of the processing solution are saturated, The effect is particularly exerted when the treatment is carried out after being stabilized.

These exposure-drying processes are carried out, for example, by a color automatic developing machine for a large laboratory. As a specific example of preferable equipment, for example, Noritsu PRV2-40
6, PRV2-212, PRV2-416. Further, it may be processed by a minilab system, and preferable devices include, for example, Konica Nice Print System NPS-602QA, Noritsu QSS-1401, Fuji FA-120 and the like.

[0261] In addition, due to environmental friendliness, the Konica Nice Print System FriendlyS, which allows recycling of waste liquid with ACR-40
It may be processed by the QA-Z system.

[0262]

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 Canadian Standard Freeness (JIS P-8121-7
6) 20% of softwood sulfite bleached pulp (NBSP) beaten until 250cc was mixed with 80% of hardwood sulfite bleached pulp (LBSP) beaten to the above-mentioned freeness of 280cc, and the concentration was 1
% Pulp chiller was prepared.

Cationized starch, alkyl ketene dimer resin, anionic polyacrylamide resin and polyamide polyamine epichlorohydrin resin were added to this pulp chiller. After being sufficiently dispersed, magnesium hydroxide was added thereto so that the final content after papermaking was 5% by weight based on the total solid content.

[0265] Paper is made from the slurry of the above raw materials, and the rice is weighed 17
A 0 g / m ² paper substrate was produced.

After performing corona discharge treatment on both the front and back surfaces of the paper substrate, high density polyethylene and low density polyethylene were extrusion coated on the back surface at a resin temperature of 330 ° C. to form a back surface resin coating layer having a thickness of 30 μm.

Each layer having the constitution shown in Table 1 and Table 2 was coated on this reflective support to prepare a multilayer color light-sensitive material. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, (ST-2) 6.67 g, stain inhibitor (HQ-7) 0.67 g and High boiling organic solvent (DNP) 6.6
To 7 g, 60 cc of ethyl acetate was added and dissolved, and this solution was dissolved in 10% gelatin solution containing 7 cc of 20% surfactant (SU-1).
An emulsion was dispersed in 220 cc using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions.
A layer coating solution was prepared.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.

As a hardening agent, the second and fourth layers (H
-1) and (H-2) were added to the 7th layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension.

[0271]

[Table 1]

[0272]

[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

[0274]

[Chemical 28]

[0275]

[Chemical 29]

[0276]

[Chemical 30]

[0277]

[Chemical 31]

[0278]

[Chemical 32]

(Preparation of Blue-Sensitive Silver Halide Emulsion) The following (A) was added to 1 liter of a 2% gelatin aqueous solution kept at 40 ° C.
30) while controlling the liquid) 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 performed 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 a sulfuric acid or sodium hydroxide aqueous solution.

(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 performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (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) (solution A) and solution B
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for the above 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) (solution A) and (solution B)
A monodisperse cubic emulsion EMP with an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1, except that the addition time of (C liquid) and the addition time of (C liquid) and (D liquid) are changed.
-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out 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 Supersensitizer RSS-1 3 × 10 ⁻³ mol / mol AgX The sample thus obtained is referred to as Sample 101 (for comparison).

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0288]

[Chemical 33]

[0289] In the manufacture of the sample 101, the first layer and the fifth layer
Samples 102 to 105 were prepared in the same manner except that the amount of the stain inhibitor in the layer was changed and added as shown in Table 3. Further samples
Sample 10 in which the first layer and the fifth layer of 101 to 105 were replaced and applied.
6-110 were also produced.

Each sample was subjected to white light wedge exposure in the usual way, and then processed according to the following development processing steps. 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 ℃ 30 seconds Composition of developing solution Is shown below.

Color developer tank solution and replenisher tank solution Replenisher solution Pure water 800cc 800cc Triethylenediamine 2g 3g Diethyleneglycol 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 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter.
At 0, the replenisher is adjusted 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) 27.5cc Add water to make the total volume 1 liter, and adjust to pH = 6.5 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 make the total volume 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

The color fog, maximum color density and light fastness of the obtained color sample were measured as follows. The results are shown in Table 3.

<Color Fog> The minimum reflection density (D
^B min and D ^R min) were measured using a PDA-65 densitometer (manufactured by Konica Corporation).

<Light resistance> Each of the samples was measured with a PDA-65 densitometer for blue light and red light reflection densities before and after fading when exposed to sunlight for 50 days using an underglass outdoor exposure table. did. The degree of fading due to light (fading rate) was determined as follows.

Fading rate (%) = (D ₀ −D / D ₀ ) × 100 where D ₀ = density before light exposure (1.0) D = density after light exposure

[0298]

[Table 3]

D ^B min of samples 101-105 and D ^R m of 106-110
By comparing in, it is found that in the light-sensitive silver halide emulsion layer closest to the support, color fog can be sufficiently suppressed even if the amount of the stain inhibitor is reduced to the range of the present invention. On the other hand, D ^R min and 106-1 of samples 101-105
From a comparison of D ^B min of 10, it can be seen that in the fifth layer away from the support, color fog cannot be adequately suppressed when the amount of anti-stain agent is reduced to the range of the present invention. Further, by reducing the amount of the stain inhibitor within the scope of the present invention, the maximum color density and the light resistance can be improved.

It can be seen that the effect of the present invention is greater when the coupler of the first layer is a yellow coupler.

Example 2 Yellow coupler of the first layer of the photosensitive material sample of Example 1,
Samples 201 to 232 were prepared in the same manner except that the stain inhibitor / yellow coupler ratio and the dye image stabilizer were changed and added as shown in Table 2.

After exposing each sample to blue light wedge exposure according to a conventional method,
The same processing was performed, and the resulting yellow color-developed sample was evaluated for color fog, maximum color density, light resistance test and color reproducibility. The results are shown in Table 4.

<Color Reproducibility> The color reproducibility of the yellow image was evaluated according to the following two grades.

◯: Good Δ: Yellow with orange tint

[0305]

[Table 4]

[0306]

[Chemical 34]

ST-6: pt-octylphenol ST-7: Di (2-dodecyloxycarbonylethyl) sulfide ... Compound PD-1 described in Japanese Patent Application No. 51-1891 As shown in Table 4, prevention of stains By setting the ratio of the agent to the yellow coupler within the range of the present invention, it is possible to sufficiently suppress the generation of fog without significantly deteriorating the light resistance or decreasing the maximum density.

By comparing Samples 206 to 210, it can be seen that the overall performance of color fog, light fastness and maximum color density is preferable when the ratio of the stain inhibitor to the coupler is in the range of 2 to 4 mol%.

Further, it is understood that the effects of the present invention can be obtained even if the yellow coupler is changed. Among them, the general formula [I]
The sample using the coupler shown in has good color reproducibility,
In addition, the effects of the present invention are also greatly exhibited, which is preferable.

Example 3 (Preparation of blue-sensitive silver halide emulsion) EMP-of Example 1
In the preparation of No. 1, K ₂ IrCl ₆ and K ₄ Fe (CN) _{6 in} (C liquid)
EM-A to F were manufactured in the same manner except that was changed as follows.

Emulsion name K ₂ IrCl ₆ alternative K ₄ Fe (CN) ₆ alternative EM-A K ₂ IrCl ₆ K ₄ Ru (CN) ₆ EM-B K ₂ IrBr ₆ K ₄ Os (CN) ₆ EM-C K ₂ IrCl ₆ PbNO ₃ EM-D K ₂ IrBr ₆ KInCl ₃ EM-E K ₂ IrBr ₆ / K ₂ IrCl ₆ GaNO ₃ (equimolar mixture) EM-F K ₂ IrBr ₆ / K ₂ IrCl ₆ GeNO ₃ (equimolar mixture) Each of the above EM-A to F was chemically sensitized in the same manner as in the method for preparing the blue-sensitive silver halide emulsion of Example 1 to obtain EM-.
a to f were obtained.

(Preparation of Green-Sensitive Silver Halide Emulsion) In the preparation of EMP-1 of Example 1, K ₂ IrCl ₆ in (solution C) was used.
And EM-G to L were produced in the same manner except that K ₄ Fe (CN) ₆ was changed as follows.

Emulsion name K ₂ IrCl ₆ alternative K ₄ Fe (CN) ₆ alternative EM-G K ₂ IrCl ₆ K ₄ Ru (CN) ₆ EM-H K ₂ IrBr ₆ K ₄ Os (CN) ₆ EM-I K ₂ IrCl ₆ PbNO ₃ EM-J K ₂ IrCBr KInCl ₃ EM-K K ₂ IrBr ₆ / K ₂ IrCl ₆ GaNO ₃ (equimolar mixture) EM-L K ₂ IrBr ₆ / K ₂ IrCl ₆ GeNO ₃ (Equimolar mixture) Each of the above EM-G to L was chemically sensitized in the same manner as in the method for preparing the green-sensitive silver halide emulsion of Example 1, and Em-.
g-1 was obtained.

(Preparation of Red-Sensitive Silver Halide Emulsion) In the preparation of the red-sensitive silver halide emulsion of Example 1, the emulsion used, the sensitizing dye and the supersensitizer were changed as follows. A red sensitive silver halide emulsion was prepared.

Red-sensitive emulsion Emulsion used Sensitizing dye Supersensitizer EmR-11 EM-G RS-1 RSS-1 EmR-12 EM-G RS-2 RSS-2 EmR-13 EM-G RS-3 RSS -3 EmR-14 EM-H RS-4 RSS-4 EmR-15 EM-H RS-1 RSS-3 EmR-16 EM-H RS-3 RSS-5 EmR-17 EM-I RS-2 RSS-4 EmR-18 EM-J RS-3 RSS-2 EmR-19 EM-K RS-2 RSS-2 EmR-20 EM-K RS-3 RSS-3 EmR-21 EM-K RS-4 RSS-3 EmR- 22 EM-L RS-1 RSS-5 EmR-23 EM-L RS-2 RSS-2 EmR-24 EM-L RS-4 RSS-4

[0316]

[Chemical 35]

[0317]

[Chemical 36]

Blue-sensitive silver chlorobromide emulsion Em in Example 1
-B to Em-a to f, green-sensitive silver chlorobromide emulsion Em-G to Em-g to 1, and red-sensitive silver chlorobromide emulsion Em-R to E.
Samples were prepared in the same manner except that they were replaced with mR-11 to 14.

The same tests as in Example 1 were carried out and the same evaluations were carried out, and it was confirmed that the effects of the present invention were more effectively obtained with the samples of the present invention.

Example 4 The same sample as in Example 1 was prepared except that in Example 1, two blue-, green-, and red-sensitive emulsions were used in combination with two kinds of monodispersed emulsions having different grain sizes and exposure performance characteristics. . The same tests and evaluations as in Example 1 were performed, and it was confirmed that the effect of the present invention was obtained more effectively with the sample of the present invention.

Example 5 Using each of the light-sensitive materials obtained in Example 1, the same evaluation was carried out using the equipment of the minilab system. As equipment,
Konica Minilab Color Paper Process CPK2-20 (C
PK-20QA-M) (Developer replenisher20P-1, Developer
starter20P-1S, Bleach-fix & replenisher20P-2, Super
Stabilizer & replenisher 20P-2) was used. Also, as processed negatives, Konica Impreza 50, SuperDD100,
Fujiriara was used. Before the test, each print photosensitive material of the present invention was used for running processing until the total amount of replenisher liquid in each tank of the processor became three times the initial amount of each tank liquid. or,
Separately from this, a running test was similarly performed using Konica Color QA Paper Type A5 before the test. The same test as in Example 1 was conducted, and it was confirmed that the sample of the present invention more effectively obtained the effect of the present invention.

Example 6 The same treatment as in Example 2 was carried out with the following modifications.

Evaluation was carried out in the same manner as in Example 1, and it was confirmed that the effects of the present invention were effectively obtained.

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 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-methanesulfonamide Ethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxyamine 3.5 g 6.0 g triethanolamine 10.0 g 10.0 g 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. Ten.
Adjust pH to 10 and replenisher to pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetic acid ammonium ferric dihydrate 100 g 50 g diethylenetriamine pentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 cc 100 cc 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0g 1.0g Ammonium sulfite (40% aqueous solution) 50cc 25cc 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. Prepare.

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 ammonia water.

Example 7 An electron beam curable coating liquid having the following composition was prepared.

Urethane / acrylate resin 25% Epoxy / acrylate resin 25% Titanium dioxide (anatase type) 50% While rotating the above coating liquid at a line speed of 30 m / min,
Coating amount (solid content) of 6g using a slit orifice coater on the peripheral surface of a rotating drum having a high gloss mirror surface.
/ M ² so that a 175 g / m ² weighed base paper for photographic printing paper support that runs in conjunction with the drum rotation speed is laminated and pressed onto this coating liquid layer, and an electron beam is applied from the back of the base paper. The coating liquid layer was cured by irradiating it with an accelerating voltage of 175 kV and an absorbed dose of 1 Mrad, and the obtained laminate was peeled off from the peripheral surface of the drum.

In this way, the same sample as in Example 1 was prepared except that the prepared support was used.

The same tests and evaluations as in Example 1 were carried out, and it was confirmed by the tests of the present invention that the effects of the present invention were obtained more effectively.

[0332]

According to the present invention, it is possible to obtain a color photographic material which is excellent in color developability and image storability and in which color fog is suppressed.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein a coupler and an anti-staining agent are provided in the light-sensitive silver halide emulsion layer closest to the support. A silver halide color photographic light-sensitive material containing the anti-staining agent in an amount of 1 to 5 mol% based on the coupler. 2. A silver halide color photographic light-sensitive material according to claim 1, wherein the coupler contained in the light-sensitive silver halide emulsion layer closest to the support is a yellow coupler. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the yellow coupler is a compound represented by the following general formula [I]. [Chemical 1] [In the formula, R ₁ represents an alkyl group or a cycloalkyl group, and R ₂ represents an alkyl group, a cycloalkyl group or an aryl group. R ₃ represents a group capable of substituting on the benzene ring, and m
Represents an integer of 0 to 4. However, when m is 2 or more, a plurality of R ₃ may be the same or different. Z represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized product of a developing agent. ]