JPH1115114A - Silver halide color photographic sensitive material and its treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To decrease the use amt. of a yellow coupler and to improve adaptability for fast treatment by incorporating a specified dye image forming coupler and a polyhydric alcohol into at least one silver halide emulsion layer. SOLUTION: This silver halide color photographic sensitive material has at least one silver halide emulsion layer on a supporting body, and at least one layer of silver halide emulsion layers contains a dye image forming coupler expressed by the formula and a polyhydric alcohol. In the formula, RA is an alkyl group, RB is a halogen atom or alkoxy group, RC is -COORD1 , -COORD2 COORD1 , -NHCORD2 SO2 RD1 , -N(RD3 )SO2 RD1 or -SO2 N(RD3 )RD1 , RD1 is a univalent org. group RD2 is an alkylene group, RD3 is an alkyl or aralkyl group or hydrogen atom, YA is a univalent org. group, (n) is 0 or 1, and RE, RF are hydrogen atoms or alkyl groups.

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 a processing method therefor, and more particularly, to a silver halide color photographic light-sensitive material having excellent color development in color development processing and rapid processing suitability. It relates to the processing method.

[0002]

2. Description of the Related Art Silver halide photographic materials have been widely and practically used today because of their high sensitivity, excellent gradation and sharpness. There is a silver halide color photographic light-sensitive material. In a silver halide color photographic light-sensitive material, a dye-forming coupler of yellow, magenta, or cyan is usually used as a color-forming agent for forming a dye image. The basic performance required for these couplers includes color developability, image storability, image sharpness, color reproducibility and the like.

The development processing of these silver halide color light-sensitive materials is a so-called wet processing, which requires a lot of time to adjust the processing solution, generates stains, generates waste liquids containing various chemicals, and requires work in a dark place. And the like.

However, since silver halide color photographic materials have the above-mentioned advantages, a method in which a skilled technician concentrates from color negatives to color prints in a small number of large developing laboratories has been adopted. The above-mentioned drawbacks in the development process have been compensated for.

In recent years, so-called mini-labs, which can consistently perform from the development of color negatives to the production of color prints in a small space such as the store of a photo shop, have rapidly become widespread. However, it has become possible to develop silver halide color photographic materials. Under such circumstances, there is an increasing demand for environmental conditions such as a further reduction in development processing time and a reduction in photographic waste liquid processing.

[0006] In order to achieve the rapid processing of shortening the processing time, approaches are made from two aspects of the processing means and the photosensitive material. Improvements in the processing means include color development processing at high pH and color development processing. Attempts have been made from photographic processing solutions, such as raising the temperature and increasing the concentration of the color developing agent.

However, the rapid processing means using the above-mentioned processing solution is more susceptible to the effects of fluctuations in the pH, temperature, and color developing agent concentration of the processing solution, resulting in a decrease in the maximum color density, an increase in fog, and a change in gradation. This greatly affects the image quality characteristics.

[0008] Approaches from the light-sensitive material for shortening the processing time include reduction of the amount of binder applied and reduction of the amount of coupler and silver halide required for the color-forming reaction. In particular, in the case of a color paper having a reflective support layer, it is common to use a yellow coupler having a lower molar extinction coefficient as compared with a magenta coupler or a cyan coupler, and the yellow coupler coating amount due to improvement in yellow color developing property is generally used. There is a strong demand for the development of reduction technologies.

JP-A-47-26133 discloses an image forming method for processing a silver halide photographic light-sensitive material in the presence of acetamide in which the α-position is substituted with a diacylamino group or an aliphatic acyl group and a color developing agent. And a compound having a leaving group and a diffusion-resistant group represented by the general formula (Y-I) is disclosed. JP-A-56-30126 discloses a photosensitive material containing a yellow or magenta coupler having an aryloxycarbonylaryl group, and exemplifies a compound represented by the general formula (Y-I). Nothing is said about the effects that can be obtained in combination with the requirements.

JP-A-63-11935 and JP-A-63-60
No. 446 discloses a technique for improving dispersion stability by using a polyhydric alcohol as a surfactant. Also, JP-A-55-56867, JP-A-49-66329, and JP-A-63-66329.
169369, JP-A 1-260437, 2-9
Nos. 6743 and 4-131839 each contain a polyhydric alcohol as an example of a nonionic surfactant. However, in any case, polyhydric alcohols are used as surfactants, and the effects thereof are limited to those utilizing the properties as surfactants.

Further, Japanese Patent Application Laid-Open No. 4-265975 discloses a method for improving the stability of a developing solution against a change in pH by adding a monohydric alcohol to a silver halide photographic material. However, it was found that it had no effect on the improvement of the coloring property.

JP-A-6-266076 and JP-A-7-209
Nos. 829 and 7-209829 disclose a silver halide color photographic light-sensitive material containing a dye image-forming coupler and a polyhydric alcohol, the effect of which is obtained by a combination of a magenta coupler and a polyhydric alcohol. No mention is made of the effects that can be seen in combination with the constituent requirements of the present application, which are improvement in stability over time of dispersion, improvement in manufacturing suitability, and improvement in image storability.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce the amount of yellow coupler used by utilizing the optical property that a higher reflection density can be obtained with a smaller amount of yellow image dye, and to achieve rapid processing suitability. An object of the present invention is to provide an excellent economical silver halide color photographic light-sensitive material and a processing method therefor.

[0014]

The above object of the present invention has been attained by the following constitutions.

(1) In a silver halide color photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is represented by the following formula (Y-I). A silver halide color photographic light-sensitive material comprising a dye image-forming coupler to be used and a polyhydric alcohol.

[0016]

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[Wherein, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _C represents —CO
OR _D1 , -COOR _D2 COOR _D1 , -NHCOR _D2 SO
_{2 R D1, -N (R D3} ) SO 2 R D1 or -SO ₂ N (R _D3)
Represents R _D1 . R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an alkyl group, an aralkyl group, or a hydrogen atom. Y _A represents a monovalent organic group, n represents 0 or 1, R _E and R _F is each represents a hydrogen atom or an alkyl group. (2) The polyhydric alcohol is contained in the same silver halide emulsion layer in a weight ratio of 0.1 to 8.0 with respect to the dye image-forming coupler represented by formula (Y-I). The silver halide color photographic light-sensitive material as described in (1), wherein the light-sensitive material contains:

(3) The silver halide color photographic material as described in (1) or (2), wherein the polyhydric alcohol is represented by the following general formula (I).

Formula [I] R _A1 —O—R _A2 wherein R _A1 represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R _A2 represents an alkyl group, an alkenyl group or a cycloalkyl group. , a cycloalkenyl group, - (O =) C- R A3, -SO 2 -R A4, - (O
=) P <(- _ORA5 ) ( _-ORA6 ),-(O =) P
_{<(R A7) (R A8} ), - represents a _{CON <(R A9) (R} A10) or _{-SO 2 N <(R A11)} (R A12).

Here, R _{A3 to} R _A9 and R _A11 represent an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group or aryl group, respectively, and R _A10 and R _A12 represent a hydrogen atom or an alkyl group, an alkenyl group, Represents a cycloalkyl group, a cycloalkenyl group, or an aryl group.

[0021] However, alkyl groups represented by R _A1, alkenyl group, cycloalkyl group, cycloalkenyl group and / or an alkyl group represented by R _A2, alkenyl group, cycloalkyl group, cycloalkenyl group and / or R _A3 to R _A12 And at least one position on the carbon atom of the alkyl group, alkenyl group, cycloalkyl group or cycloalkenyl group represented by is substituted with a hydroxyl group, and the total number of alcoholic hydroxyl groups in the molecule is 2 or more. Further, R _A1 and R _A2 do not condense with each other to form a ring. (4) The polyhydric alcohol is represented by the following general formula [II] or [III] (1) or (2).
The silver halide color photographic light-sensitive material described in the above.

[0022]

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Wherein R _A21 , R _A22 , R _A23 and R _A24 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group; Represents a sulfamoyl group.

However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all of them are hydrogen atoms. (5) The silver halide color photographic material as described in (1) or (2), wherein the polyhydric alcohol is represented by the following general formula [IV].

[0025]

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Wherein R _A41 , R _A42 and R _A43 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a carbamoyl group, and L represents an alkylene group or an arylene group. Represents, Y
_A is a hydrogen atom or a carbamoyl group, a sulfamoyl group,
Represents an acyl group, and m represents 0 or 1. (6) The silver halide color photographic material as described in (1) or (2), wherein the polyhydric alcohol is represented by the following general formula [V].

[0027]

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[In the formula, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, and R ₅₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group; R ₅₁ and R ₅₂ may be fused with each other to form a lactone ring. (7) The silver halide color photographic material as described in (1) or (2), wherein the polyhydric alcohol is represented by the following general formula [VI].

[0029]

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Wherein R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group or a sulfamoyl group. , P represents an integer of 1 to 20. When p is 2 or more, a plurality of R ₇₃ may be the same or different. However, p is 1
When R represents any two of R ₇₁ , R ₇₂ and R ₇₃ are hydrogen atoms, and when p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms. And not all are hydrogen atoms. (8) The silver halide color photograph according to (3), wherein the polyhydric alcohol represented by the general formula [I] is a compound represented by the following general formula [VII] or [VIII]. Photosensitive material.

[0031]

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Wherein R _{81 to} R ₈₄ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group;
To 20 and when q is 2 or more, a plurality of R ₈₃ ,
R ₈₄ may be the same or different. Where q
R ₈₁ but when representing a 1, R _82, at least two of R ₈₃ and R ₈₄ are hydrogen atoms, and not that all of them are hydrogen atoms, when q is 2 or more, R _81, R _At least two of ₈₂ , the plurality of R _83, and the plurality of R ₈₄ are hydrogen atoms, and not all are hydrogen atoms. ]

[0033]

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[Wherein R _{91 to} R ₉₆ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. Where R
₉₁ at least two hydrogen atoms of to R _96, and will not be all hydrogen atoms. (9) The silver halide color photographic light-sensitive material according to any one of claims 1 to 8, wherein the total processing time from the color development step to the drying step is within 4 minutes. A method for processing a silver halide color photographic light-sensitive material.

Hereinafter, the present invention will be described in detail.

The silver halide color photographic light-sensitive material of the present invention comprises a dye image forming coupler represented by the above formula (Y-I) (hereinafter a yellow color coupler represented by the formula (Y-I), A yellow coloring coupler of the formula (Y-I),
(Also referred to as a yellow coupler of the general formula (Y-I)). The following formula (Y-I)
The yellow color coupler represented by the formula (1) will be described.

In the general formula (YI), the alkyl group represented by R _A is a linear, branched or cyclic alkyl group, for example, a methyl group, an ethyl group, an i-propyl group, a t-butyl group. Group, dodecyl group, 1-hexylnonyl group, cyclopropyl group, cyclohexyl group, adamantyl group and the like.

These alkyl groups may be further substituted. Examples of the substituent include a halogen atom (eg, a chlorine atom and a bromine atom), an aryl group (eg, a phenyl group,
pt-octylphenyl group, etc.), alkoxyl group (eg, methoxy group, etc.), aryloxy group (eg, 2,
4-di-t-pentylphenoxy group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), acyl group (eg,
Acetyl group, benzoyl group, etc.), sulfonylamino group (eg, dodecanesulfonylamino group, etc.), hydroxyl group and the like.

As R _A , a branched alkyl group is preferable, and a t-butyl group is particularly preferable.

As the alkoxyl group represented by R _B ,
A straight-chain or branched alkoxyl group, for example, methoxy group, ethoxy group, 1-methylethyloxy group, t-butyloxy group, dodecyloxy group, 1-hexylnonyloxy group and the like can be mentioned. Among them, a methoxy group is preferable.

[0041] As the halogen atom represented by R _B is, for example, a chlorine atom, a bromine atom, may be mentioned a fluorine atom, a chlorine atom is preferable.

-COOR _D1 and -COOR represented by R _{C
D2 COOR D1, -NHCOR D2 SO 2} R D1, -N
In (R _D3) SO ₂ R _D1 or _{-SO 2 N (R D3) R} D1, as the monovalent organic group represented by R _D1, is preferably a group having a function as a diffusion-resistant group, for example, the number of carbon atoms 10 or more linear or branched alkyl groups (for example, dodecyl group,
An octadecyl group or the like) or an aryl group (a 2,4-dipentylphenyl group or the like) is preferable, and a linear or branched alkyl group having 14 or more carbon atoms is more preferable. R _D2
As the alkylene group represented by, for example, a propylene group, a trimethylene group and the like are preferable. The alkyl group represented by R _D3 is preferably a linear or branched alkyl group such as a methyl group, an ethyl group, an i-propyl group, and the like, and the aralkyl group is, for example, a benzyl group.

As R _C , a —COOR _D1 group is preferable.

The alkyl group represented by R _E and R _F is a straight-chain or branched alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, i-propyl, butyl, hexyl. And a methyl group is particularly preferred.

Examples of the monovalent organic group represented by Y _A include an alkyl group (for example, an ethyl group, an i-propyl group,
t-butyl group, etc.), alkoxyl group (eg, methoxy group, etc.), aryloxy group (eg, phenyloxy group, etc.), acyloxy group (eg, methylcarbonyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetamido group, phenyl group) A carbamoyl group (eg, N-methylcarbamoyl group, N-
Phenylcarbamoyl group, etc.), alkylsulfonylamino group (eg, ethylsulfonylamino group), arylsulfonylamino group (eg, phenylsulfonylamino group), sulfamoyl group (eg, N-propylsulfamoyl group, N-phenylsulfamoyl) Group) and an imide group (for example, a succinimide group and a glutarimide group).

Next, specific examples of the yellow color coupler represented by formula (YI) will be shown, but the present invention is not limited thereto.

[0047]

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[0048]

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The yellow color coupler represented by the formula (YI) can be synthesized by a conventionally known method. Further, the yellow-coloring coupler (compound) represented by the general formula (Y-I) may be used in combination, or the yellow-coloring coupler of the general formula (Y-I) and other couplers may be used as long as the effects of the present invention are not impaired. May be used in combination.

The coating amount of the yellow color coupler in the silver halide photographic light-sensitive material of the present invention is 0.50 × 10 ⁻³ to 1.
It is preferably 10 × 10 ⁻³ mol / m ² , and particularly preferably from 0.60 × 10 ^{−3 to} 1.00 × 10 ⁻³ mol / m.
² is preferred. The coating amount of the coupler referred to herein means the total amount of the yellow coloring coupler, and is represented by the general formula (Y
It is not the amount of only the yellow color coupler represented by -I).

Next, the polyhydric alcohol used in the present invention will be described.

In the present invention, the polyhydric alcohol means a compound having two or more alcoholic hydroxyl groups in a molecule, and is an aliphatic compound, an alicyclic compound or a heterocyclic compound having no aromaticity. It is a compound having two or more hydroxyl groups substituted by carbon atoms in the molecule.

The polyhydric alcohol of the present invention preferably has a total of 6 or more carbon atoms.

The polyhydric alcohol of the present invention has a molecular weight of 5,000.
The following are preferred, and those which are liquid at room temperature are preferred.

The polyhydric alcohol of the present invention preferably has a hydroxyl value of 50 or more.

The polyhydric alcohol of the present invention is preferably
It has a gP value of 3 or more.

The polyhydric alcohol of the present invention is preferably a compound represented by the following formulas [I] to [VIII].

Formula [I] R _A1 —O—R _A2 wherein R _A1 represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R _A2 represents an alkyl group, an alkenyl group or a cycloalkyl group. , a cycloalkenyl group, - (O =) C- R A3, -SO 2 -R A4, - (O
=) P <(- _ORA5 ) ( _-ORA6 ),-(O =) P
_{<(R A7) (R A8} ), - represents a _{CON <(R A9) (R} A10) or _{-SO2N <(R A11) (R} A12).

Here, R _{A3 to} R _A9 and R _A11 represent an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, respectively, and R _A10 and R _A12 represent a hydrogen atom or an alkyl group, an alkenyl group, Represents a cycloalkyl group, a cycloalkenyl group, or an aryl group.

[0060] However, alkyl groups represented by R _A1, alkenyl group, cycloalkyl group, cycloalkenyl group and / or an alkyl group represented by R _A2, alkenyl group, cycloalkyl group, cycloalkenyl group and / or R _A3 to R _A12 And at least one position on the carbon atom of the alkyl group, alkenyl group, cycloalkyl group or cycloalkenyl group represented by is substituted with a hydroxyl group, and the total number of alcoholic hydroxyl groups in the molecule is 2 or more. Further, R _A1 and R _A2 do not condense with each other to form a ring. ]

[0061]

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[In the general formulas [II] and [III], R _A21 , R _A22 , R _A23 and R _A24 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, Represents an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group.

However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all of them are hydrogen atoms. ]

[0064]

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Wherein R _A41 , R _A42 and R _A43 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a carbamoyl group, and L represents an alkylene group or an arylene group. Represents, Y
_A is a hydrogen atom or a carbamoyl group, a sulfamoyl group,
Represents an acyl group, and m represents 0 or 1. ]

[0066]

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[In the formula, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, R ₅₂ represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group; R ₅₁ and R ₅₂ may be fused with each other to form a lactone ring. In the general formulas [I] to [V], R _{A1 to} R _A12 , R _A21 to
The alkyl group represented by R _A24 , R _{A41 to} R _A43, and R ₅₂ may be linear or branched, and preferably has 1 to 32 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group,
Representative examples thereof include a t-butyl group, a dodecyl group, a heptadecyl group, a 2-ethylhexyl group, and the like.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
_A43 and alkenyl group represented by R ₅₂ may be linear or branched, preferably it has 2 to 32 carbon atoms, such as vinyl group, propenyl group, 11-undecenyl group, a 1-methyl-propenyl group whose typical examples It is listed as.

The substituted alkyl group or substituted alkenyl group having two or more hydroxyl groups represented by R ₅₁ is the above-mentioned R _A1 to R _A1 .
Any two or more carbon atoms of the alkyl and alkenyl groups of R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 and R ₅₂ (including those further substituted by substituents) are substituted by a hydroxyl group. Typical examples thereof include a 1,2-dihydroxypropyl group and a 1,1-dihydroxymethylethyl group.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
The cycloalkyl groups represented by _A43 and R _52, preferably has 3 to 12 carbon atoms, in particular 5-7, may have a branched structure, such as cyclohexyl group, a cyclopentyl group, a cyclopropyl group, A representative example thereof is a 2-methylcyclopropyl group.

R _{A1 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
The cycloalkenyl groups represented by _A43 and R _52,
Those having 3 to 12 carbon atoms, particularly those having 5 to 7 carbon atoms, are preferred, and may have a branched structure. Examples thereof include a 1-cyclohexenyl group and a 2-cyclopentenyl group.

R _{A3 to} R _A12 , R _{A21 to} R _A24 , R _{A41 to} R
The aryl group represented by _A43 and R _52, carbon atoms 6
To 14 are preferable, and typical examples thereof include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

The above-mentioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group and aryl group may be further substituted by a substituent. Examples of the substituent include the following.

Alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Each group such as alkenyl, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, Examples include aryloxycarbonyl, heterocyclic thio groups, spiro compound residues, bridged hydrocarbon compound residues, and hydroxyl groups.

The acyl group represented by R _{A21 to} R _A24 and Y _A includes-(O =) C-R _A3 (R _A3 is as described above)
Is preferred.

The sulfonyl group represented by R _{A21 to} R _A24 is preferably —SO ₂ —R _A4 (R _A4 is as described above).

The phosphonyl groups represented by R _{A21 to} R _A24 include-(O =) P <(-O-R _A5 ) (-O-R _A6 )
(R _A5 and R _A6 are as described above).

The carbamoyl group represented by R _{A21 to} R _A24 , R _{A41 to} R _A43 and Y _A is -CON <(R _A9 )
( _RA10 ) ( _RA9 and _RA10 are as defined above) are preferred.

The sulfamoyl groups represented by R _{A21 to} R _A24 and Y _A include —SO ₂ N <(R _A11 ) (R _A12 )
(R _A11 and R _A12 are as described above).

The alkylene group represented by L preferably has 1 to 32 carbon atoms and may be linear or branched.
The arylene group represented by L is preferably a phenylene group. The alkylene group and the arylene group represented by L may further have a substituent, and the substituent may be the aforementioned R _A1
To R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ and R ₅₂
And the substituents mentioned above.

In the general formula [I], R _A1 and R _A2 do not condense with each other to form a ring, but R _A5 and R _A6 ,
R _A7 and R _A8 , R _A9 and R _A10, and R _A11 and R _A12 may be fused with each other to form a ring.

Particularly preferred among the polyhydric alcohols of the present invention are the compounds represented by the above general formulas [II] and [III] and the following general formulas [VI] to [VIII].

[0083]

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[Wherein, R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. , P represents an integer of 1 to 20. When p is 2 or more, a plurality of R ₇₃ may be the same or different. However, p is 1
When R represents any two of R ₇₁ , R ₇₂ and R ₇₃ are hydrogen atoms, and when p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms. And not all are hydrogen atoms. ]

[0085]

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[Wherein R _{81 to} R ₈₄ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group;
To 20 and when q is 2 or more, a plurality of R ₈₃ ,
R ₈₄ may be the same or different. Where q
R ₈₁ but when representing a 1, R _82, at least two of R ₈₃ and R ₈₄ are hydrogen atoms, and not that all of them are hydrogen atoms, when q is 2 or more, R _81, R _At least two of ₈₂ , the plurality of R _83, and the plurality of R ₈₄ are hydrogen atoms, and not all are hydrogen atoms. ]

[0087]

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Wherein R _{91 to} R ₉₆ are each a hydrogen atom,
Represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. Where R
₉₁ at least two hydrogen atoms of to R _96, and will not be all hydrogen atoms. In the general formulas [VI] to [VIII], R _{71 to} R ₇₃ and R ₈₁ to
Alkyl group represented by R ₈₄ and R ₉₁ to R _96, an alkenyl group, a cycloalkyl group, a cycloalkenyl group,
R _{A1 to} R in the general formulas [I] to [V], respectively.
_A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ and R ₅₂ , an alkyl group, alkenyl group, cycloalkyl group,
Those described as the cycloalkenyl group may be mentioned.

[0089] The above alkyl group, alkenyl group, cycloalkyl group and cycloalkenyl groups, as a further may be substituted by a substituent, the substituent R _A1
To R _A12 , R _{A21 to} R _A24 , R _{A41 to} R _A43 , R ₅₁ and R ₅₂
And the substituents mentioned above.

The acyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include-(O =) C-R _A3 (R _A3
Is as described above).

The sulfonyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include -SO ₂ -RA ₄ (RA ₄
Is as described above).

The phosphonyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include-(O =) P <(-O
-R _A5 ) (-O-R _A6 ) (R _A5 and R _A6 are as defined above).

The carbamoyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include -CON <(R _A9 )
( _RA10 ) ( _RA9 and _RA10 are as defined above) are preferred.

The sulfamoyl groups represented by R _{71 to} R ₇₃ , R _{81 to} R ₈₄ and R _{91 to} R ₉₆ include —SO ₂ N <(R
_A11 ) ( _RA12 ) ( _RA11 and _RA12 are as defined above).

The polyhydric alcohol of the present invention preferably has a total of 6 or more carbon atoms.

The polyhydric alcohol of the present invention has a molecular weight of 5,000.
The following are preferred, and those which are liquid at room temperature are preferred.

The polyhydric alcohol of the present invention preferably has a hydroxyl value of 50 or more.

The polyhydric alcohol of the present invention is preferably
It has a gP value of 3 or more.

Hereinafter, typical specific examples of the polyhydric alcohol of the present invention will be shown, but the present invention is not limited thereto.

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In the present invention, the yellow coupler represented by the general formula (Y-I) (hereinafter referred to as a yellow coupler of the general formula (Y-I)) and the polyhydric alcohol of the present invention are preferably blue. It is contained in at least one of the light-sensitive silver halide emulsion layers.

In order to incorporate the yellow coupler of the general formula (Y-I) and the polyhydric alcohol into the silver halide emulsion layer, a conventionally known method, for example, the yellow coupler of the general formula (Y-I) according to the present invention is used. If necessary, dissolve the coupler and the polyhydric alcohol in a mixture of a known high-boiling solvent such as dibutyl phthalate or tricresyl phosphate and a low-boiling solvent such as butyl acetate or ethyl acetate, or a solvent containing only a low-boiling solvent. After that, mixed with a gelatin aqueous solution containing a surfactant, and then emulsified and dispersed using a high-speed rotating mixer or a colloid mill or an ultrasonic disperser,
A method of adding to the emulsion can be adopted. Also,
After setting the above emulsified dispersion, shredded, washed with water,
This may be added to the emulsion.

In the present invention, the yellow coupler of the general formula (YI) and the polyhydric alcohol according to the present invention may be separately dispersed by the above-mentioned dispersion method and added to the silver halide emulsion. A method in which the compounds are simultaneously dissolved, dispersed, and added to the emulsion is preferred.

The polyhydric alcohol of the present invention may be added in the same general formula (Y) in the same silver halide emulsion layer.
It is necessary that the weight ratio with respect to the yellow coupler of -I) is 0.1 or more, preferably 0.1 or more.
0 or less, more preferably 0.1 or more and 2.0 or less. The polyhydric alcohol of the present invention may be used alone or in combination of two or more.

When two or more of the polyhydric alcohols of the present invention are used in combination, the total amount of the plurality of polyhydric alcohols of the present invention is more than the total amount of the polyhydric alcohol of the present invention with respect to the yellow coupler of the general formula (YI) according to the present invention. The weight ratio may be 0.1 or more.

Next, typical specific examples of magenta couplers that can be used in combination include compounds described in JP-A-4-313951, pages 52 to 58, and the like.

Other magenta couplers that can be used in combination are, for example, US Pat. No. 3,684,514, British Patent 1,183,515, Japanese Patent Publication No. 40-6031,
Nos. 40-6035, 44-15754, 45-
Nos. 40757 and 46-19032 and JP-A-50-1
No. 3041, No. 53-129035, No. 51-376
No. 46, No. 55-62454, U.S. Pat.
No. 067, British Patents 1,252,418 and 1,33
4,515, JP-A-59-171956, and 59-
No. 162548, No. 60-43659, No. 60-33
No. 552, Research Disclosure No. 246
26 (1984), Japanese Patent Application No. 59-243007, 5
9-243008, 59-24309, 59
No. 243012, No. 60-70197, No. 60-7
No. 0198 and the like, and can be synthesized according to the methods described therein.

Next, typical specific examples of cyan couplers that can be used in combination include, for example, C-1 to C-24 described in JP-A-4-313951, pages 59 to 61.

Other than these, cyan couplers which can be used in combination include, for example, US Pat.
Nos. 801 and 171 and JP-A-50-112038 and 5
No. 0-134644, No. 53-109630, No. 54
-55380, 56-65134, 56-80
No. 045, No. 57-155538, No. 57-2045
No. 45, No. 58-98731, No. 59-31953, and the like, and can be synthesized according to the methods described therein.

In the present invention, a high-boiling organic solvent is a solvent having a boiling point of 1
It is an organic solvent having a temperature of 50 ° C. or higher and may be a solid at room temperature as long as it is sufficiently compatible with the coupler. The high boiling point organic solvent in the present invention preferably has a vapor pressure of 0.5 mmHg or less at 100 ° C., and has a solubility in water of 25 ° C.
Is preferably 1% or less.

In the present invention, the high-boiling organic solvent added to the silver halide emulsion layer containing the yellow coupler of the general formula (Y-I) has a weight ratio of 0 to the yellow coupler of the general formula (Y-I). It is preferably 0.05 or more, more preferably 0.05 or more and 8.0 or less, and still more preferably 0.05 or more and 2.0 or less.

As the high boiling point organic solvent used in the present invention, those represented by the following formulas (H-1) to (H-4) are preferable.

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In the formula, R _H1 , R _H2 and R _H3 each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. In the following formula (H-4), R _H1 and R _H2 may be bonded to each other to form a ring.

Specific examples of the high boiling point organic solvent used in the present invention are shown below, but the present invention is not limited to these.

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In addition to the above-mentioned compounds, examples of high boiling organic solvents used in the present invention include exemplified compounds II-1 to II-29 and 14 to 14 described in JP-A-1-196048, pp. 8-9.
Exemplified compounds H-1 to H-22 described on page 15;
Exemplified compounds S-1 to 209446 described on pages 3 to 7
S-69, Exemplified compounds I-1 to I-95 described on pages 10 to 12 of JP-A-63-253943, JP-A-4-147.
No. 136, pages 6 to 9 for exemplary compounds S-1 to S-74
And the like.

Using these high-boiling organic solvents, if necessary, a low-boiling and / or water-soluble organic solvent is used in combination to dissolve a hydrophobic compound such as a dye-forming coupler, and to dissolve in a hydrophilic binder such as an aqueous gelatin solution. A stirrer using a surfactant,
After homogenizer, colloid mill, flow jet mixer, emulsified and dispersed using a dispersing means such as an ultrasonic device,
What is necessary is just to add to the target hydrophilic colloid layer.

Further, in the silver halide photographic light-sensitive material, the weight ratio of the polyhydric alcohol to the dye-forming coupler (polyhydric alcohol / dye-forming coupler) may be 0.5 or more and 5 or less. preferable.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention contains 95 to 99.95 of silver chloride.
Mol%, and silver chlorobromide containing substantially no silver iodide is preferred. Silver chloride content is 97-9
9.9 mol% is more preferred. In order to reduce the development time and the replenishment amount of the color developing solution in a shorter time, 99.5 to 99.5 may be used.
More preferably, it is 99.9 mol%.

The silver halide grains used in the light-sensitive material of the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
No. 225666, Japanese Patent Application Laid-Open No. 55-26589, Japanese Patent Publication No. 5
No. 5-42737 and The Journal of Photographic Science (J. Photogr. Sc.
i. ) Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Furthermore,
Particles having twin planes may be used.

As the silver halide grains used in the light-sensitive material of the present invention, grains having a single shape may be used.
Particles of various shapes may be mixed.

The particle size of the silver halide grains used in the light-sensitive material of the present invention is not particularly limited. However, considering other photographic properties such as rapid processing property and sensitivity, it is preferable that
0.1 to 1.2 μm, more preferably 0.2 to 1.0
It is in the range of μm. The particle size can be measured by various methods generally used in the technical field. A typical method is described in Loveland's “Particle Size Analysis Method” (ASTM Symposium on Right Microscopy, pp. 94-122, 1955).
Alternatively, the method described in “Theory of Photographic Process, Third Edition” (co-authored by Mies and James, Chapter 2, published by Macmillan, Inc., 1966) can be mentioned.

The particle size can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the light-sensitive material of the present invention may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less, are preferred. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size referred to here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a 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 an acidic method, a neutral method and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

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

For the reduction sensitization of the silver halide emulsion according to the present invention, a known method can be used. For example,
It is also possible to use a method of adding various reducing agents,
A method of ripening under high silver ion concentration conditions and a method of ripening under high pH conditions can be used.

The reducing agent used for the reduction sensitization of the silver halide emulsion according to the present invention includes stannous salts such as stannous chloride, borane such as tri-t-butylamine borane, sodium sulfite, potassium sulfite and the like. And reductones such as ascorbic acid, thiourea dioxide and the like. Of these, thiourea dioxide, ascorbic acid and its derivatives, and sulfites 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 the above-described reducing agent is preferable because of its excellent reproducibility.

These reducing agents are dissolved in a solvent such as water or alcohol and added to a silver halide emulsion for ripening, or added during the formation of silver halide grains to increase the reduction at the same time as the formation of the grains. You may feel.

The amount of these reducing agents to be added must be adjusted according to the pH, silver ion concentration and the like of the silver halide emulsion.
It is preferably from 0 ^-7 to 10 ^-2 mol.

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

The silver halide emulsion according to the present invention is subjected to reduction sensitization and can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like can be mentioned.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes such as chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used is
Although it is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., it is usually preferably 1 × 10 ^-4 mol to 1 × 10 ^-8 mol per mol of silver halide. More preferably, 1 × 10 ⁻⁵ mol to 1 × 1
^0-8 mol.

The silver halide emulsion according to the present invention is intended to prevent fogging during the preparation process of the silver halide photographic light-sensitive material, to reduce performance fluctuation during storage, and to prevent fogging during development. And known antifoggants and stabilizers can be used. Examples of the compound which can be used for such a purpose include a compound represented by the general formula (II) described in the lower column on page 7 of JP-A-2-14636, and specific compounds thereof include: (IIa-1) to (IIa-8) described on page 8 of the publication,
Compounds of (IIb-1) to (IIb-7) and 1- (3-
(Methoxyphenyl) -5-mercaptotetrazole and the like. These compounds are added in a step of preparing silver halide emulsion grains, a step of chemical sensitization, at the end of the step of chemical sensitization, a step of preparing a coating solution or the like according to the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol / mol to 1 mol of silver halide is used.
It is preferably used in an amount of about 5 × 10 ⁻⁴ mol. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide,
1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol is more preferable. In the step of preparing a coating solution, when adding to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 ×
An amount of about 10 ^-1 mol is preferable, and 1 x 10 ^-5 mol to 1 x
10 ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × 1
0 amount of about ^-9 mol to 1 × 10 ^-3 mol are preferred.

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

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compounds can be used.
No. 1124, pages 108 to 109, BS-
1 to 8 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include 110
GS-1 to GS-5 described on the page are preferably used. As the red-sensitive sensitizing dye, RS-1 to 8 described in pages 111 to 112 of the same specification are preferably used. When exposing the silver halide photographic light-sensitive material according to the present invention to a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, and as the infrared-sensitive sensitizing dye, Japanese Patent Application No. 3-73619 specification 12-14
The dyes IRS-1 to 11 described on the page are preferably used. It is preferable to use supersensitizers SS-1 to SS-9 described on pages 14 to 15 in combination with these dyes.

In the silver halide photographic light-sensitive material of the present invention,
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, as dyes having absorption in the visible region, AI-1 to 11 described in Japanese Patent Application No. 2-51124, pp. 117-118, can be used. Dyes are preferably used, and as the infrared absorbing dye, compounds represented by general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 have preferable spectral characteristics. However, it is preferable that the silver halide photographic emulsion has no influence on the photographic characteristics and that there is no contamination due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column on page 3 to page 5 in the same specification.

As the coupler used in the silver halide photographic light-sensitive material of the present invention, a coupling reaction with an oxidized form of a color developing agent is carried out to form a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm. Although any compound obtained can be used, particularly typical ones are a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, and a wavelength range of 500 to 600 nm.
Representatively, a magenta coupler having a spectral absorption maximum wavelength and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm are typical.

As a yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention, a coupler represented by formula (Y-I) described in page 8 of Japanese Patent Application No. 234208/1990 is preferred. Can be mentioned.
Specific compounds are described in pages 9 to 11 of the same specification.
To YC-9. Among them, YC described on page 11 of the same specification
-8 and YC-9 are preferable because they can reproduce yellow of a preferable color tone.

The cyan couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include those represented by formulas (C-I) and (C-II) described in Japanese Patent Application No. 2-234208, p. And a coupler represented by the following formula: Specific compounds include those described as CC-1 to CC-9 on pages 18 to 21 of the same specification.

When an oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually necessary to use a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. In accordance with the above, a low boiling point and / or water-soluble organic solvent is used in combination to dissolve and emulsify and disperse in a hydrophilic binder such as an aqueous gelatin solution using a betaine-based surfactant or another surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 234208/1990 and the compound (A'-1) described on page 35 of the specification are disclosed. And the like. In addition, a fluorescent dye-releasing compound described in U.S. Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but is preferably 1 × 10 ^{−3 to} 5 mol, more preferably 1 × 10 ⁻³ mol per mol of silver halide. It is used in the range of × 10 ^-2 to 1 mol.

In the silver halide photographic light-sensitive material of the present invention,
It is advantageous to use gelatin as a binder, but if necessary, other gelatin, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, a homopolymer or a copolymer A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

Further, the total amount of gelatin used as a binder is preferably 10.0 g / m ² or less,
Further, it is preferably 7.0 g / m ² or less because the effects of the present invention can be realized more. There is no particular lower limit, but generally 3 g from the viewpoint of physical properties or photographic performance.
/ M ² or more.

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

As the white pigment used for the reflective support according to the present invention, an inorganic and / or organic white pigment can be used, and preferably, an inorganic white pigment is used.
For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the water-resistant resin layer on the surface of the reflective support according to the present invention is preferably at least 10% by weight in the water-resistant resin layer.
Further, the content is preferably 13% by weight or more,
More preferably, it is 15% by weight or more. The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention 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 more preferably 0.10 or less, as the variation coefficient described in the above publication. Is more preferred.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, charging, etc.). (1 or 2 or more undercoating layers for improving the antistatic property, dimensional stability, friction resistance, hardness, antihalation property, frictional properties and / or other properties). .

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material of the present invention include aminophenol and p-phenylenediamine widely used in various color photographic processes. Compounds are used. In particular, aromatic primary amine color developing agents are preferably used.

The aromatic primary amine developing agents include (1) N, N-dimethyl-p-phenylenediamine hydrochloride (2) N-methyl-p-phenylenediamine hydrochloride (3) 2-amino-5- ( N-ethyl-N-dodecylamino) toluene (4) N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate (5) N-ethyl-N- (β- Hydroxyethyl) -3
-Methyl-4-aminoaniline sulfate (6) 4-amino-3-methyl-N, N, -diethylaniline (7) 4-amino-N- (β-methoxyethyl) -N-
Ethyl-3-methylaniline / p-toluenesulfonate (8) 4-amino-N-ethyl-N- (γ-hydroxypropyl) -3-methylaniline / p-toluenesulfonate These color developing agents are 1 × 1 per liter of developer
It is preferably used in the range of 0 ^{-3 to} 2 × 10 ^-1 mol, and more preferably in the range of 5 × 10 ^-3 to 2 × 10 ^-1 mol.

To the color developing solution, known developing solution component compounds can be added in addition to the above color developing agents. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

As the alkaline agent used in the color developing solution for a silver halide photographic light-sensitive material of the present invention, potassium carbonate, potassium borate, trisodium phosphate and the like are used. Sodium, potassium hydroxide and the like are used. The pH of the color developing solution is 9 to
It is generally 12, and preferably between 9.5 and 11.

For the purpose of suppressing development, halide salt ions are often used. However, in the image forming method according to the present invention, it is necessary to complete the development in a very short time, so that chloride ions are mainly used. Potassium chloride, sodium chloride, and the like. The amount of chloride ions is preferably about 3.0 × 10 ^-2 mol or more, more preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ⁻² mol per liter of the color developing solution.
0 × 10 ⁻¹ mol. The bromide ion can be used in a range that does not impair the effects of the present invention, but has a large effect of suppressing development, and is preferably about 1.0 × 10 ⁻³ mol or less per liter of the color developing solution, more preferably, It is desirable to be 5.0 × 10 ⁻⁴ or less.

Examples of preservatives include hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids,
Particularly effective organic compounds are hydrazines, hydrazide amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines. It is a preservative. Particularly, dialkyl-substituted hydroxylamines such as diethylhydroxyamine and alkanolamines such as triethanolamine are preferably used.

As the chelating agent used in the color developer according to the present invention, compounds such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid are used. Particularly, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, 1
-Hydroxyethylidene-1,1-diphosphonic acid is preferably used.

The color development temperature is usually 15 ° C. or higher, generally in the range of 20 to 50 ° C. In addition, it is preferable to carry out at 30 ° C. or higher for rapid processing.

The color development processing time is generally from 10 seconds to 4 minutes, but is preferably in the range of from 5 seconds to 45 seconds in the present invention. It is preferably performed in a range of from 25 to 25 seconds, more preferably in a range of from 5 to 15 seconds.

The replenishment amount of the color developing solution when performing the running process while continuously replenishing the color developing solution is as follows.
Considering the recent environmental pollution caused by the waste liquid of the developing solution, it is preferable that the overflow does not substantially occur during running. Specifically, the replenishing amount of the developing solution is preferably 20 to 60 ml per 1 m ² of the photosensitive material.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed.

The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the photographic material is conveyed between rollers arranged in a processing tank, and a photosensitive material may be applied to the belt. An endless belt system in which the material is fixed and conveyed may be used. In particular, a system in which a processing tank is formed in a slit shape, and a processing solution is supplied to the processing tank and the photosensitive material is conveyed may be used.

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EXAMPLES Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of silver halide emulsion> Three kinds of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method. Each silver halide emulsion was prepared by adding STB-1 as an emulsion stabilizer at the end of chemical sensitization in an amount of 2 × 1 per mol of silver halide.
^0-4 moles were added.

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[Table 1]

<Preparation of color light-sensitive material> The structures shown in Tables 2 and 3 below were prepared on a paper support in which polyethylene was laminated on one side and polyethylene containing titanium oxide was laminated on the other side on the first layer side. Were coated to prepare a multilayer color photosensitive material 101 (comparative sample).

First coating liquid: 26.7 g of yellow coupler (YC-1), 0.67 g of stain inhibitor (HQ-1), dye image stabilizer (ST)
-1) To 60 g of ethyl acetate was added and dissolved in 10.0 g of 6.7 g of (ST-2) and 6.7 g of high boiling point solvent (DNP), and this solution was dissolved in 10% sodium alkylnaphthalenesulfonate (SU-1). A 10% aqueous gelatin solution containing 10 ml was emulsified and dispersed using a homogenizer to prepare a yellow coupler dispersion. To this dispersion was added a blue-sensitive silver chlorobromide emulsion (Em-1 was converted to silver, 10 g).
And a gelatin solution for coating to prepare a first layer coating solution.

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

As the hardener, (H-1) was added to the second layer and the third layer, and (H-2) was added to the seventh layer. SU-1 and SU-2 (surfactant) were added as coating aids to adjust the surface tension.

[0197]

[Table 2]

[0198]

[Table 3]

The structures (formulas) of the compounds used in Tables 2 and 3 are shown below.

[0200]

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[0201]

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[0202]

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[0203]

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The sample 101 was manufactured as described above.

Next, the high boiling solvent DN in the first layer of the sample 101 was used.
P is the polyhydric alcohol of the present invention described in Table 4;
No. 01 in the first layer was replaced with an equimolar number of yellow couplers of the present invention shown in Table 4 and samples 102 to 1 were used.
27 were produced.

The thus-prepared sample was subjected to wedge exposure with blue light according to a conventional method, and then developed according to the following processing steps.

<< Development Processing >> Processing Step Temperature Time Replenishment Color Development 35.0 ± 0.3 ° C. 45 seconds 120 ml Bleaching and Fixing 35.0 ± 0.3 ° C. 45 seconds 51 ml Stability 30-34 ° C. 90 seconds 250 ml (3 (Tank cascade) Drying 60 to 80 ° C for 30 seconds The composition of the treatment liquid is shown below. The replenishment amount is an amount per 1 m ² of the photosensitive material. The stabilization treatment was replenished by a countercurrent method to the stabilization tank 3 → 1.

Color developing solution (processing step A) Tank solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium chloride 2 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1 g N-ethyl-N-β -Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4 g Potassium carbonate 27 g Add water to make 1 l, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

Replenisher Pure water 800 ml Triethanolamine 18 g N, N-diethylhydroxylamine 9 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl -4-Aminoaniline sulfate 8.2 g Potassium carbonate 27 g Add water to make 1 l, and adjust the pH to 10.60 with potassium hydroxide or sulfuric acid.

Bleach-fix tank solution and replenisher Ferric ammonium salt of ethylenediaminetetraacetic acid 53 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70%) solution 123 g Ammonium sulfite (40%) solution 51 g Aqueous ammonia or glacial acetic acid at pH 5.4 And add water to bring the total volume to 1 l.

Stabilizing tank solution and replenisher orthophenylphenol 0.1 g Juvitex (Ciba-Geigy) 1.0 g zinc sulfate-7-hydrate 0.1 g ammonium sulfite (40% solution) 5.0 ml 1-hydroxyethylidene- 1,1-Diphosphonic acid 3.0 g Ethylenediaminetetraacetic acid 1.5 g Adjust the pH to 7.8 with aqueous ammonia or glacial acetic acid, and add water to make the total volume 1 liter.

<< Evaluation Method >> The following evaluation was performed using the sample after the continuous treatment.

<Coloring Property> The reflection density was measured using a PDA-65 densitometer (manufactured by Konica Corporation), and the quantitative value (mmol / m ^{2) of the} amount of yellow image dye formed by color development processing using HPLC. ). Reflection density 0.1
The slope of (reflection density / quantity of yellow image dye) in the range of -1.0 was determined by linear regression, and the square of this slope was compared for each sample. The larger the square of the slope, the higher the reflection density per the same amount of the generated dye. It is represented by a ratio when the value of sample 101 (comparative example) is set to 1.

Table 4 shows the results.

[0215]

[Table 4]

As is evident from Table 4, it is found that the sample using the polyhydric alcohol of the present invention and the yellow coupler of the present invention in combination has excellent color developability.

The effects of the present invention were remarkably observed when the total time from color development to drying was within 4 minutes. Furthermore,
Even when the color development time was reduced from 45 seconds to 30 seconds, as in Table 4, it was observed that the samples using both the polyhydric alcohol of the present invention and the yellow coupler of the present invention had excellent color developability.

Further, a light-sensitive material in which only the silver amount in Example 1 was reduced to 1/5 was prepared, and hydrogen peroxide or a compound capable of releasing hydrogen peroxide described in JP-A-7-159960 was used. The same effect as in Table 4 was obtained by performing a development process using a processing method of image amplification using the same method and performing the same evaluation.

Example 2 The yellow coupler of the first layer of the sample 101 of Example 1 was replaced with an equimolar number of yellow couplers shown in Table 5, and the HBS of the first layer was changed to a high boiling point at a weight ratio shown in Table 5. The same color development processing and evaluation as in Example 1 were performed, replacing the solvent and the polyhydric alcohol. Table 5 shows the results.

[0220]

[Table 5]

As is clear from Table 5, even when the polyhydric alcohol of the present invention and the yellow coupler of the present invention are used in combination and the weight ratio of the polyhydric alcohol is 0.1 or more with respect to the yellow coupler, the coloring property is improved. It was found that the effect of improvement was remarkable. The same effects as described in Table 5 were also observed when the yellow coupler of the present invention not shown in Table 5 was used in combination with the polyhydric alcohol of the present invention.

As in Example 1, the effect of the present invention was remarkably observed when the total time from color development to drying was within 4 minutes. Further, the same effect was observed even when the color development time was reduced from 45 seconds to 30 seconds. Further, as in the case of Example 1, a photosensitive material in which only the silver amount was reduced to 1/5 was prepared.
Developing using the processing method of amplifying an image using hydrogen peroxide or a compound releasing hydrogen peroxide described in JP-A-7-159960 and the like, and performing the same evaluation, the same evaluation as in Table 5 was obtained. The effect was obtained.

[0223]

According to the present invention, the use of an optical property that a higher reflection density can be obtained with a smaller amount of image dye can be used to reduce the amount of the yellow coupler used, and it is excellent in rapid processing suitability and is a highly economical halogen. A silver halide color photographic light-sensitive material and a processing method thereof can be provided.

Claims (9)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is represented by the following general formula (Y-I). A silver halide color photographic light-sensitive material comprising a dye image-forming coupler and a polyhydric alcohol. Embedded image [Wherein, R _A represents an alkyl group, R _B represents a halogen atom or an alkoxyl group, and R _C represents —COOR _D1 , —C
_{OOR D2 COOR D1, -NHCOR D2 SO} 2 R D1, -N
(R _D3 ) SO ₂ R _D1 or —SO ₂ N (R _D3 ) R _D1 .
R _D1 represents a monovalent organic group, R _D2 represents an alkylene group, and R _D3 represents an alkyl group, an aralkyl group, or a hydrogen atom. Y _A represents a monovalent organic group, n represents 0 or 1, R _E and R _F is each represents a hydrogen atom or an alkyl group. ] 2. The weight ratio of the polyhydric alcohol to the dye image-forming coupler represented by formula (Y-I) contained in the same silver halide emulsion layer is 0.1 to 8. 2. The silver halide color photographic light-sensitive material according to claim 1, which contains 0 or less. 3. The polyhydric alcohol according to the following general formula [I]
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material is represented by the following formula: Formula (I) R _A1 —O—R _A2 wherein R _A1 represents an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, and R _A2 represents an alkyl group, an alkenyl group, a cycloalkyl group, or a cycloalkenyl group, - (O =) C- R A3, -SO 2 -R A4, - (O
=) P <(- _ORA5 ) ( _-ORA6 ),-(O =) P
_{<(R A7) (R A8} ), - represents a _{CON <(R A9) (R} A10) or _{-SO 2 N <(R A11)} (R A12). Where R
_A3 to R _A9 and R _A11 are each an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group or an aryl group, R _A10 and R _A12 is a hydrogen atom or an alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group Represents an aryl group. However, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group represented by R _A1 and / or an alkyl group, an alkenyl group represented by R _A2 ,
A cycloalkyl group, a cycloalkenyl group and / or R _A3
At least one position on the carbon atom of the alkyl group, alkenyl group, cycloalkyl group, or cycloalkenyl group represented by R _A12 is substituted with a hydroxyl group, and the total number of alcoholic hydroxyl groups in the molecule is 2 or more. And then R _A1 and R _A2
Does not condense with each other to form a ring. ] 4. The polyhydric alcohol has the following general formula [II]:
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material is represented by [III]. Embedded image Wherein R _A21 , R _A22 , R _A23 and R _A24 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group,
Represents a cycloalkenyl group, an aryl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. However, at least two of R _A21 , R _A22 , R _A23 and R _A24 are hydrogen atoms, and not all are hydrogen atoms. ] 5. The polyhydric alcohol according to the following general formula [IV]
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material is represented by the following formula: Embedded image Wherein R _A41 , R _A42 and R _A43 are each a hydrogen atom,
L represents an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, or a carbamoyl group;
Represents an alkylene group, an arylene group, Y _A represents a hydrogen atom or a carbamoyl group, a sulfamoyl group, an acyl group, m represents 0 or 1. ] 6. The polyhydric alcohol according to the following general formula [V]
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material is represented by the following formula: Embedded image [Wherein, R ₅₁ represents a substituted alkyl group or a substituted alkenyl group containing two or more hydroxyl groups, R ₅₂ represents an alkyl group,
Represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group, and may be condensed with R ₅₁ and R ₅₂ to form a lactone ring; ] 7. The polyhydric alcohol according to the following general formula [VI]
3. The silver halide color photographic light-sensitive material according to claim 1, wherein the material is represented by the following formula: Embedded image [Wherein, R ₇₁ , R ₇₂ and R ₇₃ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, a sulfamoyl group; 1 to 2
Represents an integer of 0. When p is 2 or more, a plurality of R ₇₃ may be the same or different. However, when p represents 1, R ₇₁ ,
When any two of R ₇₂ and R ₇₃ are hydrogen atoms and p is 2 or more, at least two of R ₇₁ , R ₇₂ and a plurality of R ₇₃ are hydrogen atoms, and all of them are hydrogen atoms Never be. ] 8. The silver halide color according to claim 3, wherein the polyhydric alcohol represented by the general formula [I] is a compound represented by the following general formula [VII] or [VIII]. Photosensitive material. Embedded image Wherein R _{81 to} R ₈₄ each represent a hydrogen atom, an alkyl group,
Represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group, q represents an integer of 1 to 20, and when q is 2 or more, a plurality of R ₈₃ , R ₈₄ may be the same or different. However, when q represents 1, at least two of R ₈₁ , R ₈₂ , R ₈₃ and R ₈₄ are hydrogen atoms, and not all hydrogen atoms.
When q is 2 or more, at least two of R ₈₁ , R ₈₂ , the plurality of R _83, and the plurality of R ₈₄ are hydrogen atoms, and not all are hydrogen atoms. [Formula 7] [Wherein, R _{91 to} R ₉₆ each represent a hydrogen atom, an alkyl group,
Represents an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an acyl group, a sulfonyl group, a phosphonyl group, a carbamoyl group, or a sulfamoyl group. However, at least two of R _{91 to} R ₉₆ are hydrogen atoms, and not all are hydrogen atoms. ] 9. The method according to claim 1, wherein the silver halide color photographic light-sensitive material is processed in a process in which the total processing time from the color development step to the drying step is within 4 minutes. Characteristic processing method of silver halide color photographic light-sensitive material.