JPH0339958A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve light fastness, processability at high temp. and color tone by forming at least one silver halide emulsion layer contg. a specified compd. and a specified yellow coupler. CONSTITUTION:A silver halide emulsion layer contg. a compd. represented by formula I and a yellow coupler represented by formula II is formed on a support. In the formula I, each of R1 and R2 is H or alkyl, each of R3 and R4 is H, alkyl, a heterocyclic group, etc., each of R5 and R6 is H, alkyl, aryl, etc., X is a divalent group contg. C as a constituent atom of the 6-membered ring and n is 0, 1 or 2. In the formula II, R1 is alkyl or cycloalkyl, R2 is alkyl, cycloalkyl, etc., R3 is a group substitutable on the benzene ring, n is 0 or 1, Y is a monovalent ballast group and Z is H or an atom or group releasable at the time of coupling. Heat processability, light fastness and yellow hue can be improved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic material and a processing method thereof, and more specifically, a silver halide color photographic material with good image storage stability, high temperature processability, and color tone. Regarding materials.

[Prior art]

The yellow magenta and cyan couplers used in silver halide color photographic materials used for direct viewing, such as color photographic paper, are required to have basic performance such as dye image storage stability. In recent years, there has been an increasing demand for improved color reproducibility in order to faithfully reproduce the colors of objects.

Yellow couplers have the disadvantage that color reproduction of yellow and orange is insufficient due to unnecessary absorption of the coloring dye at wavelengths of 500 nm or more.

To address these problems, various improvements to couplers and addition of color tone improvers have been investigated. For example, time opening F@63-2
41547 and No. 63-256952 have been proposed, and show good color tone.

However, the above method alone provides insufficient light resistance and requires the addition of an anti-fading agent. Various methods have been proposed as anti-fading agents.

If an anti-fading agent is added, the above-mentioned color tone improvement effect may be reduced, or the density of the yellow image may increase during heat treatment (laminating and pasting of color prints are heat treated). A problem arises in that only some parts become yellowish.

Therefore, it has been desired to propose a method that provides yellow images with good color tone, good light resistance, and no increase in density due to heat treatment. Therefore, as a result of various studies, the present inventors found that
It has been found that all of the above problems can be improved by using a specific yellow coupler and an anti-fading agent together.

[Purpose of the invention]

A first object of the present invention is to provide a silver halide photographic material which has less unnecessary absorption on the long wavelength side and which forms a yellow dye image without an increase in density upon heat treatment.

A second object of the present invention is to provide a silver halide photographic material in which a yellow dye image has good light fastness and a good yellow hue.

[Structure of the invention]

The above object is achieved by a silver halide color photographic light-sensitive material having the following structure.

A silver halide color characterized by having at least one silver halide emulsion layer containing a compound represented by the following general formula [T] and a yellow coupler represented by the following general formula (Y-1) on a support. Photographic material.

General formula (T) In the formula, R and R3 represent a hydrogen atom or an alkyl group, Rs
, R4 is a hydrogen atom, an alkyl group, an aryl group or a haheterocyclic group R1+ R@ is a hydrogen atom, an alkyl group,
Aryl group, acyl group or alkoxycarbonyl group,
X is 2 having a carbon atom as a constituent atom of the above 6-membered ring
In the valence group, n represents o, 1 or 2.

General formula [Y-1) In the formula, R1 represents an alkyl group or a cycloalkyl group,
R8 represents an alkyl group, cycloalkyl group, acyl group, or aryl group, R3 represents a group that can be substituted with benzene, n represents O or l, Y represents a monovalent ballast group, and 2 represents hydrogen. Represents an atom or an atom or group that can be separated during coupling.

The compound represented by the general formula [T] will be explained in detail below.

The alkyl group represented by R1 or R8 is preferably a methyl group.

The alkyl group represented by R1-R has 1 to 4 carbon atoms.
The aryl group is preferably a phenyl group.

The heterocyclic group represented by R3 or R4 is preferably a thienyl group.

The alkoxycarbonyl group represented by Rs and Rs is preferably one having 2 to 19 carbon atoms, and the acyl group is preferably an acetyl group or a benzoyl group.

The polygroup represented by R3-R6 includes those having a substituent, and when R3*R4 is phenyl, preferred substituents include a halogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, a cyclohexyl group, Examples include alkoxy groups having 1 to 18 carbon atoms, phenylalkyl groups having 7 to 9 carbon atoms, and hydroxyl groups. When R6゜R, is an alkyl group, preferred substituents include hydroxyl groups, phenyl groups, and phenylalkyl groups having 1 to 9 carbon atoms. 12 alkoxy groups, benzoyloxy groups, and alkylcarbonyloxy groups having 2 to 18 carbon atoms.

Preferred divalent groups represented by X) C-NN
Examples include H-acyl.

Here, R7 is a hydrogen atom, alkyl having 1 to 4 carbon atoms, R8
is a hydrogen atom, a methyl group, a phenyl group, -P(OXOdeall)2 (alkyl has 1 to 4 carbon atoms), an allyloxy group, a benzyloxy group, an alkoxy group with a carbon number of 1 to 12, R is a hydrogen atom ,OH,7! J ruoxy group, benzyloxy group, alkoxy group having 1 to 12 carbon atoms, acyloxy group, acylamino group, Ro. represents a hydrogen atom or an acyl group, R11 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and CB! OR14, R1! is a hydrogen atom, carbon number l~4
R14 represents a hydrogen atom or an acyl group.

The acyl group represented by R1, the acyl group in the acylamino group, the acyl group represented by R1゜, the acyl group represented by Ro, and the acyl group in the C-NNH-acyl group represented by In addition to the alkylcarbonyl groups represented by 2 to I8, preferred examples include 4.

Here, R, -R6,n has the same meaning as above, and Q,
m is O or l, m≧Q, R13 is a simple bond, a divalent bonding group (for example, a C1-14 alkylene group (p is 0 or l)), Rls is a hydrogen atom, an alkyl group (preferably an alkyl group having 1 to 8 carbon atoms), an acyl group, an alkoxyoxalyl group, a sulfonyl group, or a carbamoyl group, R1□R17 is a hydrogen atom, an alkyl group, or an aryl group, R18 is water, and RIF is the one mentioned above. RI represents -0-21 atom, alkyl group].

) represents.

Specific examples of compounds represented by the general formula () below 13 - 14 T-30 T-31 The compound represented by the general formula [T] can be made into synthetic leather by a known method. For example, a method of acylating a 4-hydroxytetrahydrothiopyran compound with an acid chloride, a method of reacting a 4-ketotetrahydrothiopyran compound with a diol, and 1,5-dioxa-9-thia-spiro[5,5]-undecane. A method for obtaining a l,4-dioxa-8-thia-spiro[4,51-decane-based compound, etc. can be used.

The compound represented by the general formula (T) is added to a silver halide emulsion layer containing a yellow coupler in a light-sensitive material, and the method of addition is described in U.S. Pat.
, 801.170, 2,801.171, 2,
272.191 and 2,304.940, in which it is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, and then added to the hydrophilic colloid solution after being dispersed. At this time, there is no problem in using a coupler hydroquinone derivative, an ultraviolet absorber, a known dye image fading inhibitor, etc., as necessary. For example,
Known pigment image fading inhibitors include JP-A-61-14
Examples include compounds described in No. 3754 and the like. At this time, there is no problem even if two or more kinds of compounds of the present invention are mixed.

The additive amount of the compound represented by the general formula (T) is preferably 1.5 g or less per 1I112, particularly preferably 0.01 to 0.6 g.

General formula (Y-1) In the above formula, R4 represents an alkyl group or a cycloalkyl group, R2 represents an alkyl group, cycloalkyl group, acyl group, or aryl group, and R8 represents a group that can be substituted on the benzene ring. , n represents 0 or 1, Y represents a monovalent ballast group, and 2 represents a hydrogen atom or an atom or group that can be separated during coupling.

In general formula (Y-1), the alkyl group represented by R3 may be linear or branched, and examples thereof include methyl, ethyl, isopropyl, t-butyl, and dodecyl groups. These alkyl groups include those having further substituents, and examples of the substituents include halogen atoms and polygroups such as aryl, alkoxy, aryloxy, alkylsulfonyl, acylamino, alkoxy, and hydroxy.

Examples of the cycloalkyl group represented by R3 include cyclopropyl, cyclohexyl, and adamantyl groups.

Preferably, Ro is a branched alkyl group.

Examples of the alkyl group and cycloalkyl group represented by R2 include the same groups as R, and examples of the aryl group include a phenyl group. The alkyl group, cycloalkyl group, and aryl group represented by R1 include those having the same substituents as R. Examples of the acyl group include acetyl, propionyl, butyryl, hexanoyl, and benzoyl groups.

R1 is preferably an alkyl group or an aryl group, more preferably an alkyl group.

R1 is not particularly limited as long as it is a group that can be substituted on the benzene ring, but specifically includes a halogen atom (e.g. chlorine atom), an alkyl group (e.g. ethyl, i-propyl, t-butyl group)
, alkoxy groups (e.g. methoxy groups), aryloxy groups (e.g. phenyloxy groups), acyloxy groups (e.g. methylcarbonyloxy, benzoyloxy groups), acylamino groups (e.g. acetamido, phenylcarbonylamino groups), carbamoyl groups (e.g. N- methylcarbamoyl, N-7enylcarbamoyl group), alkylsulfonamide group (e.g. ethylsulfonylamino group),
Arylsulfonamide groups (e.g. phenylsulfonylamino groups), sulfamoyl groups (e.g. tbaN-propylsulfamoyl, N-7znylsulfamoyl groups) and imide groups (e.g. succinimide, glutarimide groups)
Examples include.

In the general formula (Y-1), 2 represents a group that leaves during the coupling reaction with the oxidized form of the developing agent, for example, a group represented by the following general formula (Y, -2) or (Y-3). represents.

-oRro (y-2) In the general formula (Y-2), RIll represents an aryl group or a heterocyclic group including those having a substituent.

N 2 , -22, (Y-3) In general formula (Y-3), 2 works with the nitrogen atom to form 5
Represents a group of nonmetallic atoms necessary to form a 6-membered ring.

Examples of the atomic groups necessary to form the nonmetallic atomic group include methylene, methine, -o-, -5+, -502-, and the like.

The cyan dye-forming coupler of the present invention represented by the general formula (Y-1) is usually lXl0 per mole of silver halide.
-'mol-1 mol, preferably lXl0-2 mol-8X
A range of 10-' moles can be used.

Next, the high boiling point organic solvent represented by the above general formula (Y-1) and used for dispersing yellow coupler, etc., refers to an organic solvent with a boiling point of 150°C or higher, and the type thereof is not particularly limited, such as phthalate. Examples include esters such as acid esters, phosphoric esters, and benzoic esters, organic acid amides, ketones, and hydrocarbon compounds.

Among high boiling point organic solvents, the dielectric constant at 30°C is 6.
Those having a dielectric constant of 6.0 or less and 1.9 or more and a vapor pressure of 0.5 mmHg or less at 100° C. are more preferable, and heptatalic acid esters or phosphoric acid esters are particularly preferable.

Further, two or more types of high boiling point organic solvents may be used in combination.

Examples of phthalic acid esters advantageously used in the present invention include those represented by the following general formula (S-1).

General Formula (S-1) In the formula, R' and R2 each represent an alkyl group, an alkenyl group, or an aryl group. However, the total number of carbon atoms in the groups represented by R1 and R2 is 12 to 32. More preferably, the total number of carbon atoms is 16 to 24, and still more preferably 18 to 24.

In the present invention, R1 and R1 of the general formula (S-1)
The alkyl group represented by may be linear or branched, such as butyl group, pentyl group, hexyl group, 2-ethylhexyl group, 3.5.5-1-limethylhexyl group,
These include octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and the like.

The aryl group represented by R1 and R1 is, for example, a phenyl group, a naphthyl group, etc., and the alkenyl group is, for example, a hexenyl group, a heptenyl group, an octadecenyl group, etc.

These alkyl groups, alkenyl groups and aryl groups are
Substituents for alkyl and alkenyl groups include, for example, halogen atoms, alkoxy groups, aryl groups, aryloxy groups, alkenyl groups, alkoxycarbonyl groups, etc. Examples of substituents of the group include halogen atoms,
Examples include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkenyl group, and an alkoxycarbonyl group.

In the above, R' and R2 are preferably alkyl groups, such as 2-ethylhexyl group, 3.5.5-trimethylhexyl group, n-octyl group, n-nonyl group, etc.

Phosphoric esters advantageously used in the present invention include those represented by the following general formula (s-2).

General formula (S-2) In the formula, R", R' and R6 each represent an alkyl group, an alkenyl group or an aryl group. However, R'R' and R
The total number of carbon atoms in the group represented by 5 is 24 to 54, preferably 27 to 36.

The alkyl group represented by R'R' and Rs in general formula (S-2) is, for example, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the alkenyl group include a hexenyl group, a heptenyl group, and an octadecenyl group.

These alkyl groups, alkenyl groups and aryl groups are
It also includes those having single or multiple substituents. Preferably R3R4 and R1 are alkyl groups, for example 2-
Ethylhexyl group, n-octyl group, 3.5.5-trimethylhexyl group, n-nonyl group, n-decyl group, 5e
Examples include c-decyl group, 5ec-dodecyl group, and -octyl group.

Typical specific examples of high boiling point organic solvents preferably used in the present invention are shown below, but the present invention is not limited thereto.

yuyousho-1 S-5 -7- -11 CHIC) lc. HI C t H & -13 -15 -17 -19 -21 -14 -16 -18 -20 -22 The high boiling point organic solvents advantageously used in the present invention are further represented by the following general formula [TO] Things can be mentioned.

General formula [TO] In the formula,

The alkyl group represented by R , , R 2 and R in the above general formula [TO] may be linear, branched or cyclic, and the alkyl group may have a substituent. .

Examples of unsubstituted alkyl groups include alkyl groups having 1 to 20 carbon atoms, preferably 1 to 18 carbon atoms, such as ethyl group, butyl group, pentyl group, cyclohexyl group, octyl group, dodecyl group, heptadecyl group, octadecyl group, etc. .

Examples of the substituent of the substituted alkyl group include an aryl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group.

The aryl group represented by Rr, R2 and R3 in the above general formula (TO) is a phenyl group or a naphthyl group, which may have a substituent, for example, a carbon number t-t.
up to a, preferably an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an amine group mono- or di-substituted with an alkyl group having 1 to 12 carbon atoms, and an amine group having 1 to 1 carbon atoms.
Amino group substituted with up to 2 acyl groups, halogen atom,
These include hydroxy groups and amino groups.

Specific examples of the compound represented by the general formula (To) used in the present invention are shown below, and the present invention applies to these compounds (T.

1) (To-3) (To-5) (To-6) (To-8) (T O-10) (To-2) (To-4) (To-7) (To-9) (To-11) (To-12) (T O-14) (T O-16) (T.

18) (T O-20) (T O-13) (To-15) (To-17) (To-19) (To-21) 21'l5 (To-22) (To-24) (T O-26) (To-28) (T O-23) (To-25) (T O-27) Shif13 (T O-29) (To-30) (To-31) (T O-33) (T O-35) (T O-32) (To-34) (T O-36) (To-37) (To-38) (To-39) (To-40) (To-41) (To-42) I'+1 (T O-43) (To-44) (T O-45) (T O-46) (To-47) し2tIs (T O-48) (To-49) (T O-50) (To-51) (To-52) (T O-53) (T.

54) (T O-55) (T O-56) (TO-57) (To-58) 1 (C,H,0CO(CH,)+ o)rP-OCiHs
(T O-59) 1 ((C4Hste"NC0(C)It)a3"rP O
C+zHts(T O-60) (To -61) (To -62) (cans-Thp-.

CCaH*su “P-0 (To-63) (To-64) (i c4ush-P proverb 0 CCsH+ +b-P-0 (TO-65) (T.

66) (csn+akp-.

(CaH+yte'P-0 (To-67) (To -68) (To -69) (TO-70) (Ct.H5P-0 (i (+sH□te'P-0 (T O- 71) (T O-72) (C+xHz1P=0 (CI48 -78) (TO-79) (TO-80) ((CzHs)zNco(CHxtei"i+)sP-0
(To-81) (To-82) (To-83) (To-84) (To-85) (To-86) (To-87) (To-89) As the amount of high-boiling organic solvent used is preferably 0-1-1011+12, particularly 0.1-5 per 1 g of coupler.
mQ is preferred.

Examples of high-boiling organic solvents that may be used in combination with the above-mentioned high-boiling organic solvents include phenol derivatives that do not react with oxidized developing agents, phthalic esters, phosphoric esters, citric esters, benzoic esters, alkylamides, fatty acid esters, An organic solvent having a boiling point of 150°C or higher, such as trimesic acid ester, is used.

When the light-sensitive material of the present invention is used for multiple colors, a pyrazolone type magenta coupler can be used, and a phenol type or naphthol type can be used as a cyan coupler.

The arrangement of each silver halide emulsion layer is, in order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive silver halide emulsion layer containing a cyan coupler. Preferably, it is a silver emulsion layer, and in the light-sensitive material as a whole, essential layers on the support include, in order from the support side, a blue-sensitive silver halide emulsion layer containing a yellow coupler, and a green-sensitive silver halide emulsion containing a magenta coupler. A non-photosensitive intermediate layer containing a UV absorber, a red-sensitive silver halide emulsion layer containing a cyan coupler and the compound of the present invention, a non-photosensitive layer containing a UV absorber, and a protective layer are preferably arranged.

As the support, a resin-coated paper support or a polyethylene terephthalate support containing a white pigment is preferably used.

As the ultraviolet absorber, those represented by the following general formula CU-1) are preferred.

General formula (U) 2 (In the above general formula [U], R3, R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group,
Represents a nitro group or a hydroxyl group. ) The multiple groups represented by R1-R1 include those having substituents.

Among the groups represented by R1 and R2, a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group are preferred, and a hydrogen atom, an alkyl group, and an alkoxy group are particularly preferred in tFF.

Among the groups represented by R1, hydrogen atoms, halogen atoms, alkyl groups, and alkoxy groups are particularly preferred.

At least one of R3-R3 is preferably an alkyl group, and more preferably at least two are alkyl groups. Further, it is preferable that at least one of RI-R1 is a branched alkyl group.

A typical example is shown below.

The amount of the compound represented by the general formula (tJ) added is preferably 0.1 to 300% by weight, more preferably 1 to 200% by weight, based on the binder of the layer to which the compound is added.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any material used in emulsions can be used, but those with a silver chloride content of 90 mol % or more are particularly preferred, a silver bromide content of 10 mol % or less, and a silver iodide content of 0.
It is preferably 5% mole or less. More preferably,
It is silver chlorobromide with a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

Furthermore, in the silver halide emulsion layer of the present invention containing silver halide grains having a silver chloride content of 90 mol % or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is The proportion of silver halide grains of 90 mol% or more is 60% by weight or more, preferably 80% by weight or more.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The particle diameter of the silver halide grains of the present invention is not particularly limited, but in consideration of other photographic performance such as rapid processing properties and sensitivity, it is preferably 0.2 to 1.6 μm1, and more preferably 0.2 μm to 1.6 μm.
It is in the range of 25 to 1.2 μm. The above particle size can be measured by various methods commonly used in the technical field. Typical methods include Loveland's ``Particle Size Analysis Method'' (A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122) or ``Theory of Photographic Processes'' ( Co-authored by Mies and James, 3rd edition, published by Macmillan (
1966), Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less in the grain size distribution. Here, the coefficient of variation is
This is a coefficient indicating the breadth of particle size distribution, and is defined by the following formula.

Here, ri represents the particle diameter of each particle, and ni represents the number thereof.

The grain size here refers to the diameter in the case of spherical silver halide grains, or the diameter when the projected image is converted into a circular image of the circumferential area in the case of grains with shapes other than cubic or spherical. represent.

The silver halide grains used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the ammonia method. The particles may be elongated all at once, or may be grown after forming seed particles.

The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as a form of simultaneous mixing method,
The pAg-chondrold-double jet method described in No. 48521 and the like can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether may be used. Further, compounds such as mercapto group-containing compounds, nitrogen-containing heterocyclic compounds, or sensitizing dyes may be added during the formation of silver halide grains or after the completion of grain formation.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183.756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
No. 737, The Journal of 7 Photographic Science (J, Photogr, Sci,), 2
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literature such as 1.39 (1973) and used. Furthermore, particles having twin planes may be used. The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added to the inside of the particles and/or on the surface of the particles using complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the unnecessary soluble salts may be left in the emulsion. . In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion of the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

The emulsion of the present invention is chemically sensitized by conventional methods.

After exposure, the light-sensitive material of the present invention can be subjected to a process including at least a color development process and a desilvering process to give a dye image, but preferably, after exposure, a color development process is performed, and then a bleach-fixing process is performed. This treatment method involves washing with water or stabilizing.

In the color development process, a color developing agent is usually contained in a color developing solution, but some or all of the color developing agent is incorporated into a color photographic light-sensitive material, and color development with or without a color developing agent is carried out. It also includes processing with a developer.

The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenylenediamine derivatives, with p-phenylenediamine derivatives being particularly preferred. These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used.

These compounds are generally used in color developers 1 (approximately 0 for 2).
．． 1 to about 30 g, more preferably a color developer l
A concentration of about 1 g to about 15 g of Q is used.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phenylenediamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N~methyl-p-7enylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2- Amino-5-(N-ethyl-N-totecylamino) to toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoalinine, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline -p-toluenesulfonate and the like can be mentioned.

Further, the above color developing agents may be used alone or in combination of two or more. Further, the color developing solution may contain commonly used alkaline agents such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium metaborate, or borax, and may further contain various additives. agents, such as alkali metal halides, such as potassium bromide or potassium chloride, or development regulators, such as citradinic acid, and preservatives, such as hydroxylamine, polyethyleneimine, glucose or sulfites, such as sodium salts, potassium salts, etc. May be contained. Furthermore, various antifoaming agents and surfactants,
Methanol, N,N-dimethylformamide, ethylene glycol, diethylene glycol or dimethyl sulfoxide, benzyl alcohol, etc. can be contained, but in the present invention, benzyl alcohol is substantially not included, and 2 x 10-'' mol/Q It is preferable to process with a color developing solution containing the following sulfite. The sulfite concentration is more preferably 1 x 10-' to 1.7 x 10-" mol/1 mole, particularly 5 x 10-3-I
X 10-"mol/Q is preferable. Also, "substantially free of benzyl alcohol" means that the concentration is 0.5m+2/Q
It is preferable that it not be contained at all.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

Further, the temperature of the processing solution in the color developing tank is preferably 101 to 65.
℃, more preferably 25°C to 45°C.

The developing time is preferably within 2 minutes and 30 seconds, more preferably within 2 minutes.

After color development, silver halide color photosensitive materials are usually bleached. The bleaching treatment may be performed simultaneously with the fixing treatment (bleaching and fixing) or separately, but it is preferable to use a bleach-fixing bath that processes bleaching and fixing in one bath. The bleach-fix solution preferably has a pl of 4.5 to 6.8, particularly preferably 4.5 to 6.0.

The bleaching agent that can be used in the bleach-fix solution is preferably a metal complex salt of an organic acid, particularly a complex salt of an organic acid such as aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid coordinated with a metal ion such as iron, cobalt or copper. Preferably.

Additives added to the bleach-fix solution include, in particular, alkali halides or ammonium halides, rehalogenating agents such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, metal salts, chelating agents, etc. It will be done.

Also, the pH of @ acid salts, oxalates, acetates, carbonates, phosphates, etc.
Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions can be added as appropriate.

Furthermore, the bleach-fix solution contains sulfites such as ammonium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, and sodium metabisulfite, as well as boric acid, borax, and hydroxide. Contains one or more pH buffers consisting of various salts such as sodium, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. I can do it.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A solution in which a coupler and, if necessary, a dye image stabilizer and stain inhibitor were dissolved in a high boiling point organic solvent and ethyl acetate was added to an aqueous gelatin solution containing a dispersion aid and dispersed using an ultrasonic homogenizer. A gelatin solution for coating and a photosensitive silver halide emulsion were added to the obtained dispersion to prepare an emulsion layer coating solution.

Each layer having the structure shown in Table 1 was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side, and multilayer silver halide color photographic exposure was performed. Material sample 1 was created.

The silver halide emulsion used was prepared as follows.

[Preparation method of blue-sensitive silver halide emulsion The following (liquid A) was added to a 2% gelatin aqueous solution of 10,100 O kept at 140°C.
and (Solution B) were simultaneously added over 30 minutes while controlling the pAg = 6.5 and pH = 3.0, and the following (Solution C) and (Solution D) were added at a pAg of -7.3 and pH -5. , 5 over 180 minutes.

At this time, pAg was controlled by the method described in JP-A-59745437, and pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Liquid A) N a CQ 3.42
gK B r O,0
Add 3gH, O and 200m
12 (Liquid B) A g N Os 10
Add gH, O and 200tQ
(Liquid C) N a CQ 102.
7gK B r 1.
Add OgH and O to 600f
lIQ (liquid D) A g N O, 300 g H, O was added, and after the completion of the addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate. Mix with gelatin aqueous solution to obtain an average particle size of 0.85μ
m, coefficient of variation (S/r) -0.07, silver chloride content 99
．． A 5 mol % monodispersed cubic emulsion EMPl was obtained.

The following compound was used for the above emulsion E M P-1, and 5
Chemical ripening was performed at 0°C for 90 minutes to obtain a blue-sensitive silver halide emulsion (EmA).

Sodium thiosulfate 0.8 mg 1 mol 1 mol A Auric acid 0.5II 1 g 1 mol A
gx stabilizer 5B-56XIO-'mol 1 mol AgX
Sensitizing dye D-15XlO-' 1 mol AgX Same as EMP-1 except that the average particle size was 0.43 μm.
, coefficient of variation (S/”r) -0.08, silver chloride content 99
．． A 5 mol % monodisperse cubic emulsion EMP-2 was obtained.

E M P-2 was chemically ripened at 55°C for 120 minutes using the following compound to form a green-sensitive silver halide emulsion (E
mB) was obtained.

Sodium thiosulfate 1.5a+g1 mol Ag
X Chloroauric acid 1. Oag1 molAg
X stabilizer 5B-56X10-'mol 1 molAgX sensitizing dye D-24,OX IQ-'mol/% Ag
X [Preparation method 1 of red-sensitive silver halide emulsion (A solution) and (
The procedure was the same as EMP-1 except that the addition time of B solution) and the addition times of (C solution) and (D solution) were changed, and the average particle size was 0.
A monodispersed cubic emulsion E M P-3 having a coefficient of variation (S/r) of 50 μm 1 and −0.08 and a silver chloride content of 99.5 mol % was obtained.

E M P-3 was chemically ripened at 60°C for 90 minutes using the following compound to form a red-sensitive silver halide emulsion (E M
C) was obtained.

Sodium thiosulfate 1.8 mg 1 mol 1 mol A Auric acid 2.0 mg 1 mol 1 mol A fixative S B -56X 10-' mol/mol A
gX-1 -3 B-5 Table-1 (1) Table-1 (2) -1 T- ■ T-2 (Dibutyl 7-talate) VP (Polyvinylpyrrolidone) Q-1 A B- O-1 This sample After exposure to blue light according to a conventional method, the treatment was carried out according to the following processing steps.

Processing process Temperature Time Development color development 35.0±0.3℃ 45 seconds Bleach fixing 35.0±0.5℃ 45 seconds stabilization 30
~34°0 90 seconds dry 60~80°0 6
0 second processing solution composition [color developer] Triethanolamine 10gN,
N-diethylhydroxylamine 5g Potassium bromide 0.02g Potassium chloride 2g Potassium sulfite
0.3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1.0g catechol-3,5-disulfonic acid disodium salt 1.0gN-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Add potassium carbonate water to bring the total volume to 14.

[Bleach-fix solution] Ferric ammonium ethylenediaminetetraacetate dihydrate, ammonium thiosulfate ethylenediaminetetraacetate (70% aqueous solution), ammonium sulfite (40% aqueous solution), add water to bring the total volume to 14, and adjust to pH-5 with potassium carbonate glacial acetic acid. Adjust to 7.

[Stabilizing liquid] 5-chloro-2-methyl-4-inthiazolin-3-one ethylene glycol ■-hydroxyethylidene-1. l- Adjust to pH-10,10 4.5 g 1, Og 7 g 0 g 3 g 00 mQ 27.5 m12 Rum or 1.0 g 1.0 g Diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0g ammonium sulfite 3.0g optical brightener (4,4'
-diaminostilbendisulfonic acid derivative)
Add 1.5 g of water to bring the total volume to IQ, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

The above sample was designated as Sample 1, and then the yellow coupler and high boiling point organic solvent in the first layer of Sample 1 were changed as shown in Table 2, and the additives (dye image stabilizer) were added as shown in Table 2. A sample was prepared in the same manner, and exposed and processed in the same manner as Sample 1.

All samples with yellow dye images after processing were evaluated as follows.

[Light fastness test]: Initial concentration when exposed to sunlight for 14 days using an underglass outdoor sunlight exposure table: 1.
A fading rate of 0 was determined.

Fading rate - (1,0 - concentration after fading) x 100 [Takamaro processability] = After being left in a constant temperature bath at 85% RH for one day, the initial concentration was 1.
, 0 was determined.

[Color tone]: Measure the visible absorption spectrum of the part where the density is 1.0 at the maximum absorption wavelength, measure the wavelength (λ,) on the long wavelength side that indicates a density of 0.5, and measure the end of the long wavelength side. evaluated.

Table HBS: The amount of high boiling point organic solvent additive is expressed as the number of moles per mole of Cobra in the same layer TCP: Tricresyl phosphate*: Sample excluding 5T-2 in the first layer**: S-S The mixing ratio of and To-66 is 1:l (weight)
As is clear from Table 2, the samples of the present invention have good light fastness, high temperature processability, and color tone.

Furthermore, when a high boiling point organic solvent with a low dielectric constant is used, the results are even better when the compound of the present invention is used in combination with another dye image stabilizer. Furthermore, it can be seen that the use of the compound represented by -Matagi (TO) provides even better color tone.

In addition, instead of To-66 of sample 19, To-68°TO
-86, To-55, TO-4 samples, sample 1
Sample using Its-12 instead of S-5 in 2, Sample 1
Y-1-9, Y-・1-10 instead of Y-1-3 in 6
．． Each sample using Y-1-16, T-24 of sample 13
The effects of the present invention were also observed for each sample using T-20, T-29, and T-31 instead of T-20, T-29, and T-31.

Claims (1)

[Scope of Claims] It is characterized by having at least one silver halide emulsion layer containing a compound represented by the following general formula [T] and a yellow coupler represented by the following general formula [Y-1] on a support. A silver halide color photographic light-sensitive material. General formula [T] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms or alkyl groups, R_3 and R_4 are hydrogen atoms, alkyl groups, aryl groups or heterocyclic groups, R_6 represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, or an alkoxycarbonyl group, X represents a divalent group having a carbon atom as a constituent atom of the 6-membered ring, and n represents 0, 1 or 2. ] General formula [Y-1] ▲ Numerical formulas, chemical formulas, tables, etc. , R_3 represents a group that can be substituted on the benzene ring, n represents 0 or 1, Y represents a monovalent ballast group, and Z represents a hydrogen atom or an atom or group that can be separated during coupling. ]