JPH0625860B2 - Color photographic light-sensitive material having improved stability of cyan image to light - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color photographic light-sensitive material containing a phenolic cyan coupler. More specifically, it is excellent in color developability and stability of a formed cyan dye image to light. Relates to a color photographic light-sensitive material having improved

[Prior art]

As is well known, the color-reducing method color photograph shows an oxidation product of a color developing agent produced by reducing an exposed silver halide grain by an aromatic primary amine color developing agent, and a yellow, cyan, and magenta dye. By oxidatively coupling the coupler to be formed in the silver halide emulsion layer,
Form a dye image. As the yellow coupler forming the yellow dye, a compound having an open chain methylene group is generally used, and as the magenta coupler forming the magenta dye, a pyrazolone-based, pyrazolinobenzimidazole-based or imidazolone-based compound is used. . As a cyan coupler forming a cyan dye, a compound having a phenol or naphtholic hydroxyl group is used.

Each coupler is dissolved in a substantially water-insoluble high-boiling organic solvent or, if necessary, an auxiliary solvent in combination, and added to the silver halide emulsion, or dissolved in an alkaline aqueous solution to form an emulsion. Added to. The former is the oil droplet dispersion method and the latter is the alkali dispersion method, but it is generally said that the former is superior to the latter in light resistance, heat resistance, moisture resistance, graininess, and sharpness of color. .

As the basic properties required for each coupler, excellent color development is most important, and further high solubility in high-boiling organic solvents or alkaline aqueous solutions, and dispersion in silver halide photographic emulsions. It is desired to have various properties such as good properties and stability, good spectral absorption characteristics, and good color reproducibility and fastness of the obtained dye image.

Particularly in a color photographic light-sensitive material used for printing, it is strictly required that the fastness of a dye image obtained from each coupler is good.

Many attempts have been made to improve the fastness of dye images obtained from each coupler.

For example, U.S. Patents 3,432,300, 3,574,627 and 3,57
No. 3,050, Japanese Patent Publication No. 47-47245, No. 48-32728, No. 51-3046
2, JP-A-48-26133, 49-134326, 50-6338
No. 50, No. 23822, No. 51-123642, No. 51-124926, No. 51-124926
52-35633, 52-147433, 52-152224, 53-126
No. 53, No. 53-20327, No. 53-53321, No. 53-70822, No. 53
-77526, 53-77527, 54-48538, 54-62826
No. 54, No. 54-82234, No. 54-82385, No. 54-147038, No. 5
4-154345, 55-65954, 55-124141, 56-3951
No. 4, No. 56-159644, No. 56-167138, No. 57-204037,
58-105147, 59-3433, 59-125732, 60-21
No. 1455, No. 60-263149, No. 61-2151, No. 61-4041,
No. 61-4045 and the like disclose methods for improving the fastness of dye images, and among them, many techniques have been put to practical use.

Many of the above-mentioned techniques are aimed at improving the fastness of magenta dye images to light, and few techniques are aimed at improving the fastness of yellow and cyan dye images. Is limited.

However, recently, a technique aiming at improving the fastness of a cyan dye image has been gradually developed. For example, JP-A-59
-3433, 59-42541, 59-87456, 59-124340
No. 60-222853 and the like, a technique is disclosed in which a specific phenol compound is used in combination with a cyan coupler to improve the fastness of a cyan dye image.

However, although the fastness of the cyan dye image is improved to some extent by these techniques, it is still not sufficient, and in addition, the above-mentioned phenolic compound has a serious drawback that the coloring property of the cyan coupler is significantly reduced. Was confirmed. In particular, it shortens the color developing time, lowers the pH of the color developing solution, develops components in the color developing solution (for example, organic solvents such as benzyl alcohol and phenethyl alcohol, and sodium hydroxide and potassium carbonate). If you decrease the concentration of alkaline inorganic salts),
The decrease in the coloring property of the cyan coupler due to the coexistence of the phenolic compound was more remarkably observed.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color photographic light-sensitive material containing a cyan coupler having excellent color forming properties.

A second object of the present invention is to provide a color photographic light-sensitive material having improved cyan dye image stability, particularly fastness to light.

[Structure of Invention]

The above object of the present invention is to provide a color photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one coupler selected from the phenolic cyan dye image-forming couplers represented by the following general formulas [I] and [II] in at least one of the silver halide emulsion layers and the following general formula [III] This is accomplished by including at least one compound.

General formula [I] General formula (II) In the formula, R ₁ , R ₂ and R ₄ each represent an aliphatic group, an aryl group or a heterocyclic group, R ₃ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group or an acylamino group,
R ₅ represents an alkyl group. R ₂ and R ₃ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. Z ₁ and Z ₂
Each represents a hydrogen atom or a coupling-off group. n
Is 0 or 1.

General formula (III) In the formula, R ₇ represents an alkyl group, an alkenyl group, an aryl group or a cycloalkyl group, and R ₈ is a halogen atom, a hydroxyl group, a cyano group, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, an alkoxy group or an aryl. It represents an oxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acylamino group, a carbamoyl group, a sulfonamide group or a sulfamoyl group. However, R ₈ is not simultaneously substituted at the 2- and 6-positions of the hydroxyl group, and represents 0 or an integer of 1 to 4.

Hereinafter, the present invention will be described more specifically.

First, the cyan couplers represented by formulas [I] and [II] according to the present invention will be described in more detail.

In the present invention, the “aliphatic group” may be linear, branched or cyclic and includes saturated and unsaturated groups such as alkyl groups, cycloalkyl groups, alkenyl groups and alkynyl groups. It may also be replaced.

In the general formulas [I] and [II], R ₁ , R ₂ and
R ₄ is an aliphatic group having 1 to 31 carbon atoms (eg, methyl group, butyl group, octyl group, tridecyl group, hexenyl group, i
-Hexadecyl group, cyclohexyl group, etc.), aryl group (for example, phenyl group, naphthyl group, etc.), heterocyclic group (for example, 2-pyridyl group, 2-thiazolyl group, 2-imidazolyl group, 2-furyl group, 6- Quinolyl group), and these are alkyl groups, aryl groups, heterocyclic groups,
Alkoxy group (eg, methoxy group, 2-methoxyethoxy group, tetradecyloxy group, etc.), aryloxy group (eg, 2,4-di-t-amylphenoxy group, 2-
Chlorophenoxy group, 4-cyanophenoxy group, 4-butanesulfonamidephenoxy group etc.), acyl group (eg acetyl group, benzoyl group etc.) ester group (eg ethoxycarbonyl group, 2,4-di-t-amylphenoxy group) Carbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, butanesulfonamide group, dodecylbenzenesulfonamide group, dipropylsulfamoylamino group, etc.), Carbamoyl group (eg, dimethylcarbamoyl group, ethylcarbamoyl group, etc.), sulfamoyl group (eg, butylsulfamoyl group, etc.), imide group (eg, succinimide group, hydantonyl group, etc.), ureido group (eg, phenylureido group) Dimethylureido group etc.), sulfonyl group (eg methanesulfonyl group, carboxymethanesulfonyl group, phenylsulfonyl group etc.), aliphatic or aromatic thio group (eg butylthio group, phenylthio group etc.), hydroxyl group, cyano group, It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom and the like. When they have two or more substituents, they may be the same or different.

Further, in the above general formula [I], R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group, or a nonmetallic atom group forming a nitrogen-containing 5- or 6-membered ring with R ₂ .

Further, in the general formula [II], R ₅ represents an alkyl group,
Preferably, it may have a substituent with an alkyl group having 1 to 24 carbon atoms. As a specific substituent, an aliphatic group, an aryl group,
Examples thereof include a heterocyclic group, an aliphatic oxy group, an aliphatic thio group, an aryloxy group, an arylthio group and an acylamino group. More preferably, R ₅ is an alkyl group having 1 to 14 carbon atoms, and particularly preferably a lower alkyl group having 1 to 4 carbon atoms.

In the general formula [II], R ₆ is a hydrogen atom, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), a lower alkyl group (eg, methyl group, ethyl group, i-propyl group, butyl group, etc.). ) Represents an aryl group (eg, phenyl group, naphthyl group) or an acylamino group (eg, acetylamino group, benzamide group, etc.).

Z ₁ in the general formula [I] and Z ₂ in the general formula [II] represent a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.). ), An alkoxy group (for example, an ethoxy group, a dodecyloxy group, a methoxyethylcarbamoylmethoxy group, a carboxypropyloxy group, a methylsulfonylethoxy group, etc.), an aryloxy group (for example, a 4-chlorophenoxy group, a 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy group etc.), sulfonyloxy group (eg methanesulfonyloxy group, toluenesulfonyloxy group etc.), amide group (eg , Dichloroacetylamino group, heptaph Orobutyrylamino group, methanesulfonylamino group, toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group, etc.) ), An aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), imide group (eg, succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.), etc. is there. These leaving groups may include photographically useful groups.

Further, preferable examples of the cyan coupler represented by the above general formula [I] or [II] are as follows.

In the general formula [I], preferably R ₁ is an aryl group or a heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group; an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group,
Sulfonyl group, sulfamide group, oxycarbonyl group,
More preferably, it is an aryl group substituted with a cyano group. In the general formula [I], when R ₂ and R ₃ do not form a ring, R ₂ is preferably a substituted or unsubstituted alkyl group,
An aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In the general formula [II], R ₄ is preferably a substituted or unsubstituted alkyl group, and particularly preferably an alkyl group substituted with a substituted aryloxy.

Preferred R ₅ in the general formula [II] is an alkyl group having 1 to 4 carbon atoms as described above.

Preferred R ₆ in the general formula [II] is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

In the general formula [II], R ₆ is a chlorine atom and R ₅ has 1 to 1 carbon atoms.
Particularly preferred is a lower alkyl group of 4.

Preferred Z ₁ and Z _{2 in the} general formulas [I] and [II]
Are each a hydrogen atom, a halogen atom, an alkoxy group which may have a substituent, an aryloxy group or a sulfonamide group.

In the general formula [II], Z ₂ is preferably a halogen atom, particularly preferably a chlorine atom and a fluorine atom.

When n = 0 in the general formula [I], Z ₁ is more preferably a halogen atom, particularly preferably a chlorine atom or a fluorine atom.

In the present invention, the most preferable cyan coupler is a coupler represented by the following general formula [Ia].

General formula (Ia) R _1, R ₂ and Z ₁ in formula (Ia), and R _1, R ₂ and Z ₁ in formula (I), have the same meanings, it is as described above for the specific example of preferred groups .

Specific examples of the cyan coupler compounds represented by the above general formulas [I] and [II] are listed below, but the present invention is not limited thereto.

(I-1) (I-2) (I-3) (I-4) (I-5) (I-6) (I-7) (I-8) (I-9) (I-10) (I-11) (I-12) (I-13) (I-14) (I-15) (I-16) (I-17) (I-18) (I-19) (I-20) (I-21) (I-22) (I-23) (I-24) (I-25) (I-26) (I-27) (I-28) (I-29) (I-30) (I-31) (I-32) (I-33) (I-34) (I-35) (I-36) (II-1) (II-2) (II-3) (II-4) (II-5) (II-6) (II-7) (II-8) (II-9) (II-10) (II-11) (II-12) (II-13) (II-14) (II-15) (II-16) (II-17) (II-18) (II-19) (II-20) (II-21) (II-22) (II-23) (II-24) Cyan couplers represented by the general formulas [I] and [II] of the present invention (hereinafter referred to as couplers of the present invention) are disclosed in US Pat. Nos. 2,369,929, 2,772,162, 2,895,826,
No. 3,311,476, No. 3,446,622, No. 3,758,308, No. 3,88
0,661, 3,996,253, Japanese Patent Publication No. 49-11572, 56-651
34, JP-A-55-163537, JP-A-56-29235, JP-A-56-80045.
No. 56, No. 56-104333, No. 56-116030, No. 57-136650,
57-157246, 57-204543, 57-204544, 57-
No. 204545, No. 58-105229, No. 59-31953, No. 59-31954
No. 59-69755, No. 59-166956 and the like, and can be synthesized according to the synthetic method described.

To incorporate the coupler of the present invention in a silver halide emulsion, a conventionally known method may be used. For example, the coupler of the present invention is dissolved in a mixture of a known high-boiling solvent and a low-boiling solvent such as butyl acetate and butyl propionate, and then mixed with an aqueous gelatin solution containing a surfactant, and then mixed with a high-speed rotating mixer or a colloid mill. Alternatively, a silver halide emulsion can be prepared after emulsification with an ultrasonic disperser. Known high boiling point solvents include phthalic acid esters (eg, dibutyl phthalate), phosphoric acid esters (eg, tricresyl phosphate), N-substituted acid amides (eg, N, N-diethyllaurylamide). ), Phenols (eg, 2,5-di-t-amylphenol, etc.) and the like.

The coupler of the present invention usually contains 1 × 10 5 mol / mol of silver halide.
It can be used in the range of ^{-3 to} 5 x 10 ^-1 mol, preferably 1 x 10 ^{-2 to} 5 x 10 ^-1 mol.

The coupler of the present invention can also be used in combination with other types of cyan couplers.

When the color photographic light-sensitive material according to the present invention is used as a multicolor color photographic light-sensitive material, a yellow coupler and a magenta coupler which are commonly used in the industry in addition to the coupler of the present invention can be used in a usual manner. it can. Also,
A colored coupler having a color correction effect may be used if necessary. The above couplers may be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for a light-sensitive material, or the same compound may be added in two or more different layers.

A compound which is used in combination with the cyan coupler of the present invention to improve the color developability of the cyan coupler and to improve the fastness of the resulting cyan dye image to light is p-hydroxyphenyl represented by the above general formula [III]. It is a thioether compound.

General formula (III) In the general formula [III], the alkyl group represented by R ₇ may be linear or branched, and is preferably an alkyl group having 1 to 24 carbon atoms (for example, methyl group, i-propyl group, butyl group,
t-butyl group, octyl group, t-octyl group, decyl group, dodecyl group, octadecyl group and the like). R ₇
Examples of the alkenyl group represented by are propenyl group, pentenyl group, hexenyl group and the like, examples of the aryl group include phenyl group and naphthyl group, and examples of the cycloalkyl group include cyclopentyl group and cyclohexyl group.

Each of the groups listed above may be further substituted with other substituents. Examples of this substituent include a halogen atom,
Hydroxyl group, alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group, arylamino group, acylamino group, carbamoyl group, carbonamido group, sulfamoyl group, sulfone Examples thereof include an amide group.

In the general formula [III], examples of the alkyl group, alkenyl group, aryl group or cycloalkyl group represented by R ₆ include the groups described for R ₇ . R ₈ is a halogen atom (eg, chlorine atom, bromine atom, etc.), hydroxyl group, cyano group, alkoxy group (eg, methoxy group, 2-methoxyethoxy group, tetradecyloxy group, etc.), aryloxy group (eg, , 2-chlorophenoxy group, 4-cyanophenoxy group, 2,4-di-t-amylphenoxy group, 4-butanesulfonamidophenoxy group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, tetra Decyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group, 2,4
-Di-t-amylphenoxycarbonyl group), an acyl group (e.g., acetyl group, benzoyl group, etc.), an acylamino group (e.g., acetamide group, tetradecanamide group, 4-chlorobenzamide group, etc.), carbamoyl group (e.g., A dimethylcarbamoyl group, an ethylcarbamoyl group, etc.), a sulfonamide group (eg, butanesulfonamide group, dodecylbenzenesulfonamide group, etc.) and a sulfamoyl group (eg, butylsulfamoyl group, phenylsulfamoyl group, etc.) and the like.

Each of the above-mentioned groups may be further substituted with other substituents, if necessary, and the substituent may be an alkyl group represented by R ₇ , an alkenyl group, an aryl group or a cycloalkyl group. Examples of the group include the groups described above. l represents 0 or an integer of 1 to 4, and when n is 2 to 4, a plurality of R ₈ 's may be the same or different, but are not simultaneously substituted at the 2- and 6-positions of the hydroxyl group. .

In the general formula [III], it is preferable that R ₇ is an alkyl group or an aryl group, and n is 0 or 1 (when n = 1, R ₈ is preferably an alkyl group), and n is particularly preferably 0. . Therefore, the preferred embodiment of the general formula [III] is represented by the general formula [IIIa], and the most preferred embodiment is represented by the general formula [IIIb].

General formula (IIIa) In the formula, R ₉ represents an alkyl group or an aryl group, and R ₁₀ represents an alkyl group. The alkyl group and aryl group represented by R ₉ are synonymous with the alkyl group and aryl group represented by R ₇ in the general formula [III], and the alkyl group represented by R ₁₀ is the alkyl group represented by R ₈ . Is synonymous with. In the general formula [IIIa], the total number of carbon atoms of R ₉ and R ₁₀ is 6 to 2
More preferably, it is 4.

General formula (IIIb) Wherein, R ₉ has the same meaning as R ₉ in the general formula [IIIa]. In the general formula [IIIb], it is particularly preferred that R ₉ has 6 to 24 carbon atoms.

Typical examples of these compounds are shown below, but the compounds used in the present invention are not limited thereby.

(III-1) (III-2) (III-3) (III-4) (III-5) (III-6) (III-7) (III-8) (III-9) (III-10) (III-11) (III-12) (III-13) (III-14) (III-15) (III-16) (III-17) (III-18) (III-19) (III-20) (III-21) (III-22) The compound represented by the general formula [III] of the present invention (hereinafter referred to as the compound of the present invention) is described in Journal of the American Chemical Society (J. Am. Chem. Soc.), 51.
Volume 1526-1536 (1929), Chemiche Berichte (C
hem.Ber.), Vol. 87, pp. 947-955 (1954), Choat. Chem. Acta., Vol. 29, 277-2.
P. 85 (1957), compounds described in JP-A Nos. 50-6339 and 52-72225, etc. can be included and can be synthesized according to the synthetic method described.

The amount of the compound of the present invention used is preferably 5 to 300 mol%, more preferably 10 to 200 mol%, based on the cyan coupler of the present invention. The compounds of this invention are always used in the same layer as the cyan couplers of this invention. The compound represented by the general formula [III] of the present invention includes a part of the compounds described in JP-A-50-6339 and JP-A-52-72225. General formula (II
It is described that the compound contained in [I] has a property of improving the fastness to light of a magenta dye image formed from a 3-anilino-5pyrazolone-based magenta coupler, but the compound represented by the general formula [I] of the present invention is described. There is no suggestion that it has the effect of improving the color-forming property of the cyan coupler and the color-forming property of the cyan coupler represented by [II] and the fastness of the cyan dye image obtained from the coupler to light. .

As a result of earnest studies, the present inventors have found that the general formula [II
The compound represented by the formula I] cannot be expected to improve the color developability of the cyan couplers represented by the formulas [I] and [II] of the present invention and the fastness to light of a cyan dye image obtained from the cyan coupler. We have found that they have a remarkable effect.

The color photographic light-sensitive material of the present invention can be, for example, a color negative and positive film, and a color photographic paper. Especially, when the color photographic paper used for direct viewing is used, the effect of the method of the present invention can be obtained. Is effectively demonstrated.

The color photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multicolor color photographic light-sensitive material, a silver halide emulsion layer containing a magenta, yellow and cyan coupler as a photographic coupler and a non-light-sensitive layer are usually supported in order to reproduce a color by a subtractive method. Although it has a structure in which it is laminated on the body in an appropriate number of layers and layer order, the number of layers and layer order may be appropriately changed depending on the priority performance and the purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, as a silver halide, a conventional halogenated silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like. Any of those used for silver emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or one of them may be present while the other is mixed. In addition, while considering the critical growth rate of silver halide crystals, the halide ion and silver ion are mixed in the p
It may be grown by sequentially adding H and pAg while controlling them. After growth, it may be used in a conversion method to change the silver halide composition of the grains.

During the production of the silver halide of the present invention, a silver halide solvent may be used, if necessary, to control the grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Iron salt or complex salt,
Can be added to the inside of the grain and / or included in the surface of the grain, and by placing in a suitable reducing atmosphere, reduction sensitized nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. When removing the salts,
It can be performed based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may be composed of a layer having a uniform inside and surface,
It may consist of different layers.

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

The silver halide grains used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a spherical shape or a plate shape. In these particles, any ratio of {100} face to {111} face can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The silver halide emulsion of the present invention may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
During chemical ripening for the purpose of preventing fog during storage or during photographic processing and / or keeping photographic performance stable,
And / or at the end of the chemical ripening, and / or after the completion of the chemical ripening, a compound known as an antifoggant or a stabilizer in the photographic art can be added before coating the silver halide emulsion.

As the binder (or protective colloid) of the silver halide emulsion of the present invention, it is advantageous to use gelatin,
Other than that, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other hydrophilic colloid layers can be obtained by crosslinking the binder (or protective colloid) molecules to increase the film strength. It is dura. The hardener is preferably added in an amount such that the light-sensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added for the purpose of enhancing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. You can

In the color development processing, the emulsion layer of the silver halide color photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative). To form a pigment. Dye-forming couplers are used. The dye-forming couplers are usually selected so that for each emulsion layer a dye is formed which absorbs the light in the light-sensitive spectrum of the emulsion layer, and the blue-light-sensitive emulsion layer contains a yellow dye-forming coupler. However, a magenta dye-forming coupler is used in the green light-sensitive emulsion layer and a cyan dye-forming coupler is used in the red light-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

Yellow dye-forming couplers are acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and magenta dye-forming couplers are 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazoles, open-chain acylacetonitrile couplers. Examples of cyan dye forming couplers include naphthol couplers and phenol couplers other than those of the present invention.

It is desirable that these dye-synthesizing couplers have a group having a carbon number of 8 or more, which makes a coupler called a ballast group non-diffusible in the molecule. Further, these dye-forming couplers are required to reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalents, only 2 molecules of silver ions need to be reduced. Either equivalence may be used.

For the hydrophobic compound such as a dye-forming coupler which does not need to be adsorbed on the surface of the silver halide crystal, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used. Can be appropriately selected according to the chemical structure of the hydrophobic compound such as The oil-in-water emulsion dispersion method can be applied by a conventionally known method of dispersing a hydrophobic additive such as a coupler, usually, a high boiling point organic solvent having a boiling point of about 150 ° C. or higher, a low boiling point if necessary, and / or Alternatively, it is dissolved by using a water-soluble organic solvent together and emulsified by using a dispersing agent such as a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. in a hydrophilic binder such as gelatin aqueous solution. After dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high-boiling point oil agent, a phenol derivative that does not react with an oxidized product of a developing agent, a phthalic acid ester, a phosphoric acid ester, a citric acid ester, a benzoic acid ester, an alkylamide,
Boiling point of fatty acid ester, trimesic acid ester, etc. 150 ℃
The above organic solvents are used.

A hydrophobic compound is dissolved in a solvent having a low-boiling point solvent alone or in combination with a high-boiling point solvent, and as a dispersion aid when dispersed in water using a machine or ultrasonic waves, an anionic surfactant, a nonionic surfactant, a cationic Surfactants can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity or sharpness. An anti-foggant is used to prevent deterioration and conspicuous graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is provided with an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction or the like and to prevent deterioration of an image by UV light. May be included.

The color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an anti-halation layer, and / or an anti-irradiation layer. In these layers and / or in the emulsion layer, a dye which flows out or is bleached from the color light-sensitive material during the development processing may be contained.

A silver halide emulsion layer of a silver halide light-sensitive material using the silver halide emulsion of the present invention, and / or other hydrophilic colloid layer to enhance the writing property for reducing the gloss of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used for protection of the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion, and improvement of photographic properties (such as acceleration of development, hardening, and sensitization).

A photographic emulsion layer of a light-sensitive material using the silver halide emulsion of the present invention, and other layers include a baryter layer or a paper laminated with an α-olefin polymer, a flexible reflective support such as synthetic paper, cellulose acetate, nitric acid. Cellulose, polystyrene,
It can be applied to a film made of a semi-synthetic or synthetic polymer such as polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, or a rigid body such as glass, metal and pottery.

The silver halide light-sensitive material of the present invention, if necessary after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc.,
Directly or on the surface of support, antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property,
And / or 1 or 2 for improving other properties
It may be applied via the above-mentioned undercoat layer.

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

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As a light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, various laser light, light emitting diode light, electron beam,
Any known light source such as light emitted from a phosphor excited by X-rays, γ-rays, α-rays or the like can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and is shorter than 1 microsecond, for example, 100 microseconds to 1 using a cathode ray tube or a xenon flash lamp.
Microsecond exposure can be used, and exposure longer than 1 second or longer is also possible. The exposure may be performed continuously or intermittently.

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

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably at a concentration of about 1 g to about 1.5 g for color developer 1.

Examples of the aminophenol-based developer include -aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-
Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amino color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride and N.
-Methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5- (N-ethyl-N-dodecylamino) -toluene,
N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate, N-ethyl-N
-Β-hydroxyethylaminoaniline, 4-amino-
3-methyl-N, N-diethylaniline, 4-amino-
Examples thereof include N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate.

In the present invention, after color development processing, it is processed with a processing solution having a fixing ability. When the processing solution having a fixing ability is a fixing solution, a bleaching process is carried out before it, which is used in the bleaching step. As the bleaching agent, a metal complex salt of an organic acid is used, and the metal complex salt has an action of oxidizing metal silver produced by development to convert it to silver halide and simultaneously developing an uncolored portion of the color former. The structure is such that an amino acid such as aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be given as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, borate, oxalate, acetate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

When the processing of the present invention is carried out while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenisher, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like, The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

In the present invention, in order to increase the activity of the bleach-fixing solution, air may be blown in, or oxygen may be blown in the bleach-fixing bath and the storage tank of the bleach-fixing replenisher, if desired, or a suitable oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

〔Example〕

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

On a paper support which has been both sides laminated with Example 1 Polyethylene, cyan coupler ^{I-18 (4.8mg / 100cm 2} ) and 2,5-di -t- octyl dibutyl hydroquinone (0.4mg / 100cm ²⁾ of the present invention Dissolved in phthalate (4.0 mg / 100 cm ² ), gelatin (14.0 mg /
100 cm ² ) emulsified and dispersed in an aqueous solution, then mixed with a silver chlorobromide emulsion (containing 80 mol% of silver bromide) to give a silver amount of 3.5 mg / 100 cm ^2, and dried to obtain a monochromatic color photographic light-sensitive material. It was created and used as Sample 1.

In the above sample 1, the compounds III-2, III-3, III- of the present invention were added.
9, III-11, III-15, and III-16 were added to each of Samples 2, 3, 4, in which 1/2 mol of the cyan coupler was added.
5, 6 and 7 were obtained. Similarly, compound a outside the invention,
Samples 8, 9, 10 and 4 were also prepared in which b, c and f were added at 1/2 mol of the cyan coupler, respectively.

Comparative compounds a, b, c (all of which are described in JP-A-59-3433) (a) (b) (c) Comparative compound f (compounds described in JP-A-60-222853 and JP-A-59-124340) After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was performed in the next step.

The components of each treatment are as follows.

[Color developer] Benzyl alcohol 12m Diethylene glycol 10m Potassium carbonate 25g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g Hydroxylamine sulfate 2.5g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate
4.5g Add water to make 1 and adjust to pH 10.2 with sodium hydroxide.

[Bleach fixer] Ammonium thiosulfate 120 g Sodium metabisulfite 15 g Anhydrous sodium sulfite 3 g EDTA Ferric ammonium salt 65 g Water was added to adjust pH to 6.7-6.8.

The sensitivity and the maximum reflection density of Samples 1 to 10 processed above were measured by a photoelectric densitometer (PDA manufactured by Konishi Roku Photo Co., Ltd.
-60 type). The results are shown in Table 1.
However, the sensitivity is shown as a relative sensitivity when the sensitivity of Sample 1 is 100.

In addition, each treated sample was irradiated with a xenon fade meter for 15 days, and the light resistance of the dye image was examined. The results are also shown in Table 1. However, the evaluation of the light resistance of the dye image is as follows.

〔Survival rate〕

 Percentage of residual dye after light resistance test at initial density of 1.0.

As is clear from the results shown in Table 1, the samples (2
In all of Nos. 7 to 7), the maximum reflection density and the dye residual ratio are increased, and the color development of the cyan coupler and the light fastness of the cyan dye image are excellent. On the contrary, the samples (8-10 and 41) to which the comparative compound was added, although the light resistance of the cyan dye was improved to some extent, but the coloring property of the cyan coupler was deteriorated.

Example 2 Each sample was processed in exactly the same manner as in Example 1 except that benzyl alcohol was omitted from the composition of the color developing solution in the processing step. The results are shown in Table 2.

(* Presence / absence of benzyl alcohol represents presence / absence of benzyl alcohol in the color developing solution. The results with benzyl alcohol are quoted from those of Example 1. Sensitivity is 100 times that of sample 1 with benzyl alcohol. From Table 2, it can be seen that in the sample to which the comparative compound was added, the coloring rate was lowered by the treatment without benzyl alcohol, but in the case of the sample of the present invention, the benzyl alcohol was not present. It can be seen that the decrease in color developability is very small even with the treatment. Therefore, it is not necessary to include benzyl alcohol in the color developing solution when processing the sample of the present invention. This is also very advantageous in terms of pollution control.

Example 3 Samples 11 to 30 were prepared by combining couplers and additive compounds as shown in Table 3 and coating in the same manner as in Example 1.

Each sample was processed under the same conditions as in Example 2. Further, the treated sample was subjected to a light resistance test under the same conditions as in Example 1. The results are also shown in Table 3. The sensitivity in the table is for sample 11
Is the relative sensitivity when the sensitivity of is set to 100.

Comparative compounds d and e (both compounds described in JP-A-59-87456) (d) (e) The results in Table 3 also show that the combination of the coupler of the present invention and the compound of the present invention improves the color-forming property of the cyan coupler and the light fastness of the color-forming dye.

Example 4 On a paper support laminated on both sides with polyethylene, the following layers were sequentially coated from the support side to prepare a multicolor silver halide photographic light-sensitive material, and a sample 31 was obtained.

First layer: Blue-sensitive silver halide emulsion layer α-pivaloyl-α- (2,4 as a yellow coupler
6.8 mg of -dioxo-1-benzylimidazolin-3-yl) -2-chloro-5- [γ- (2,4-di-t-amylphenoxy) butyramide] acetanilide
/ 100cm ² , blue sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide)
Is converted to silver and 3.2 mg / 100 cm ² , dibutyl phthalate
3.5 mg / 100 cm ² and gelatin were coated so as to have a coating amount of 13.5 mg / 100 cm ² .

Second layer: intermediate layer 0.5 mg / 100 of 2,5-di-t-octylhydroquinone
cm ² , dibutyl phthalate was coated at 0.5 mg / 100 cm ^2, and gelatin was coated at 9.0 mg / 100 cm ² .

Third layer: green-sensitive silver halide emulsion layer 1- (2,4,6-trichlorophenyl) -3- (2-chloro-5-tetradecanamidoanilino) -5-pyrazolone as a magenta coupler 4.5 mg / 100 cm ^2. Convert the green-sensitive silver chlorobromide emulsion (containing 80 mol% of silver bromide) to silver
2.0 mg / 100 cm ^2, was coated with a dibutyl phthalate 3.0 mg / 100 cm ² and a gelatin as a 12.0 mg / 100 cm ^2.

Fourth layer: intermediate layer 2- (2-hydroxy-3-sec-butyl-5-t-butylphenyl) benzotriazole, which is an ultraviolet absorber, is added to 5.
0 mg / 100 cm ² , dibutyl phthalate 4.0 mg / 100 cm ² ,
2,5-di-t-octylhydroquinone 0.5 mg / 100
cm ² and gelatin were coated so as to be 12.0 mg / 100 cm ² .

Fifth layer: red-sensitive silver halide emulsion layer 5.0 mg / 100 cm ² of I-18 as a cyan coupler and a red-sensitive silver chlorobromide emulsion (containing 80 mol% of silver bromide) are converted into silver and converted into 3.
0mg / 100cm ² , tricresyl phosphate 3.5mg / 100c
m ² and gelatin were coated so as to be 11.5 mg / 100 cm ² .

Sixth layer: intermediate layer A layer having exactly the same composition as the fourth layer.

7th layer: Protective layer Gelatin was applied so as to have a concentration of 8.0 mg / 100 cm ² .

In the above Sample 31, the compound of the present invention was added to the fifth layer in a ratio as shown in Table 4 to prepare multilayer samples 32 to 40,
After exposure and treatment in the same manner as in Example 1, a light resistance test (exposure to a xenon fade meter for 16 days) was performed. The results are also shown in Table 4.

As is clear from the results in Table 4, the general formula [II of the present invention
The compound represented by the formula [I] is effective for stabilizing the dye image obtained from the cyan coupler of the present invention, and the effect becomes larger as the addition amount is increased.

[Effects of the Invention] According to a color photographic light-sensitive material containing the cyan coupler of the present invention and the compound represented by the general formula [III] in the same silver halide emulsion layer, it is possible to improve the coloring property of the cyan coupler and to form the same. The stability (fastness) to light of the cyan dye image to be formed can be improved. Moreover, even if benzyl alcohol, which is an environmentally harmful substance, is removed from the color developing solution in the color processing step, the color developability of the coupler is not substantially reduced, which is a great advantage in terms of pollution control.

Claims (1)

[Claims] 1. A 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 has the following general formula [I].
And at least one coupler selected from phenolic cyan dye image-forming couplers represented by [II],
A color photographic light-sensitive material containing at least one compound represented by the following general formula [III]. General formula [I] General formula (II) [In the formula, R ₁ , R ₂ and R ₄ each represent an aliphatic group, an aryl group or a heterocyclic group, and R ₃ and R ₆ each represent a hydrogen atom, a halogen atom, an alkyl group or an acylamino group, R ₅ represents an alkyl group. R ₂ and R ₃ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocycle. Z ₁ and Z ₂ each represent a hydrogen atom or a coupling-off group. n is 0 or 1. ] General formula [III] [In the formula, R ₇ represents an alkyl group, an alkenyl group, an aryl group or a cycloalkyl group, and R ₈ represents a hydrogen atom or an alkyl group. ]