JP2909504B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide light-sensitive material which is suitable for rapid processing, has excellent coloring properties, and has improved fastness of a dye image.

(Prior Art) In order to form a dye image using a silver halide photographic light-sensitive material, usually, an aromatic primary amine-based color developing agent is used,
When reducing silver halide grains in the exposed silver halide photographic light-sensitive material, itself is oxidized, and this oxidized product is
It is carried out by reacting with a coupler previously contained in a silver halide photographic light-sensitive material to form a dye. Usually, three types of couplers that form three dyes of yellow, magenta, and cyan are used to perform color reproduction by a subtractive color method.

In the recent photographic industry, in order to reduce the time required for the development process when forming the dye image, a high p
High activity development processing such as H, high temperature, and high concentration of color developing agent and simplification of processing steps are generally performed. In particular, in order to shorten the development processing time by the high activity development processing, it is extremely important to improve the development speed in color development.

It is known that the shape, size and composition of silver halide emulsion grains greatly affect the development speed, etc., and particularly the halogen composition has a large effect, especially when high chloride silver halide is used. It is known to indicate the development speed.

However, speeding up of the silver development itself alone is not sufficient, and development of couplers that rapidly and effectively form dyes by reacting with the oxidized form of the developing agent that occurs during silver development, and technology for using the couplers. Was required.

Other basic properties required for couplers include: first, high solubility in high-boiling organic solvents, etc .; good dispersion and dispersion stability in silver halide emulsions; Excellent absorption characteristics, good color tone, a clear dye image in a wide color reproduction range is formed, and the obtained dye image is light,
It has fastness to heat, moisture and the like. In particular, in a coupler used for a color print material, from the mission of recording and preserving a photographic image, it is desired that both the light fastness and the preservability in a dark place (dark discoloration) of the obtained dye image be enhanced as much as possible. .

Attempts made in the past to improve photobleaching and darkfading can be broadly divided into two directions.

One is to develop new couplers that can form dye images with less fading, and the other is to develop new additives that can prevent fading.

Many phenolic cyan couplers that form cyan dyes are known in the past. For example, U.S. Pat.
2- [α-2,4-di-tert-amylphenoxybutanamide] -4,6-dichloro-5 described in No. 1,171
Methyl phenol has a disadvantage that the coloring dye formed therefrom has good light resistance, but has poor heat resistance.

Further, cyan couplers in which the 3- or 5-position of phenol is substituted with an alkyl group having 2 or more carbon atoms are described in, for example, JP-B-49-11572, JP-A-60-209735, JP-A-60-209735 and JP-A-6-209735.
No. 0-205447. Although the heat resistance of cyan images produced from these couplers is improved to some extent, it is still insufficient.

Further, 2,5-diacylaminophenol-based cyan couplers in which the 2-position and 5-position of phenol are substituted with an acylamino group are described in, for example, U.S. Pat. Nos. 2,369,929 and 2,772,1.
No. 62, 2,895,826, JP-A-50-112038, 53-109
Nos. 630 and 55-163537.

These 2,5-diacylaminophenol-based couplers have good heat resistance of the formed cyan image, but are inferior in the coloring property of the coupler, the photobleaching property of the formed cyan image, and the yellowing due to the light of the unreacted cyan coupler. There is a disadvantage that. Further, further heat resistance is also required.

Also, 1-hydroxy-2 described in JP-A-56-104333.
-Acylaminocarbostyrilcyan couplers have good fastness to light and heat, but the spectral absorption characteristics of the formed color image are not preferable for color reproduction of a color photograph, There are problems such as generation of stains.

Also, U.S. Patent No. 3,767,412, JP-A-59-65844,
No. 59-86048, No. 59-40643, No. 61-35444, No. 61-5
Cyan polymer couplers described in JP-A Nos. 249 and 61-39044 certainly have excellent heat resistance under dry conditions, but have a drawback of insufficient color development.

Also, JP-A-60-221752, JP-A-60-221753, JP-A-60-221175
No. 242457, No. 61-27540, etc. disclose an improvement technique using a coupler in combination, but the improvement level is insufficient.

Furthermore, techniques for improving photobleaching and thermal fading with various additives have been proposed. For example, JP-A-59-105645,
Nos. 60-205447, 62-129853, 62-196657 and the like, an improved technique using a coupler-dispersed oil, JP-A-60-222853.
Nos. 62-87961, 62-118344, 62-178962
No. 62-210465, etc.
Furthermore, JP-A-61-167953 and JP-A-62-198859 disclose improvement techniques by using a coupler-dispersed oil and a discoloration inhibitor in combination, but all have only a partial effect or a low improvement level. At present, satisfactory technical development has not yet been achieved.

In U.S. Pat. No. 4,203,716, a hydrophobic substance such as an oil-soluble coupler is dissolved in a water-miscible organic solvent, and this liquid is mixed with a loadable polymer latex to impregnate the polymer with the hydrophobic substance. A method is disclosed. However, the method using such a loadable polymer latex has a problem that the light fastness of a cyan image is particularly poor as compared with the case of using a high-boiling coupler solvent immiscible with water. Another drawback is that a large amount of polymer must be used in order to sufficiently impregnate the coupler and obtain a sufficient maximum color density.

Further, oil-soluble couplers, water-insoluble, organic solvent-soluble polymer containing a dispersion of a photosensitive material containing a film quality improvement and image fastness improvement technology, for example, U.S. Pat.
No. 195, 4,201,589, 4,120,725, JP-A-51-195
Nos. 34, 51-134627 and 55-64236. However, none of them had high image fastness and satisfactory color development.

U.S. Pat. No. 4,120,725 describes the use of a polymer having a specific structure in combination with a water-soluble desilvering-promoting polymer. When applied, it not only greatly inhibits rapid development, but also reduces photographic sensitivity. (In general, in high silver chloride, the sensitizing dye has weak adsorption power to the silver halide emulsion, and the sensitizing dye is a polymer for accelerating desilvering. It is presumed that the desilvering occurs poorly (it is presumed that the desilvering promoting polymer is adsorbed on the emulsion).

(Problems to be Solved by the Present Invention) An object of the present invention is to provide a silver halide light-sensitive material which is suitable for rapid processing, has excellent coloring properties, and has improved fastness of a dye image.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have made the following (1),
It has been found that the above object can be effectively achieved by the silver halide color light-sensitive material of (2) or (3).

(1) On a support, at least one of a diffusion-resistant oil-soluble cyan coupler which couples with an oxidized form of an aromatic primary amine developing agent to form a substantially non-diffusible dye, A mixed solution in which at least one compound represented by the general formula [I] and at least one polymer which is insoluble in water and soluble in an organic solvent and has a relative fluorescence quantum yield (K value) of 0.2 or more, is dissolved. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a dispersion obtained by the above method.

General formula [I] (2) The silver halide color as described in (1), wherein one or more compounds of the general formula [I] contained in the mixed solution have a melting point of 85 ° C. or less. Photosensitive material.

(3) The above item (1) or (1), wherein at least one of the silver halide emulsion layers contains silver halide grains substantially containing no silver iodide and containing 80 mol% or more of silver chloride. (2) The silver halide color photographic light-sensitive material as described in (2) above. (Here, the term "silver halide grains substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.1 mol% or less.
The silver halide grains are 5 mol% or less, more preferably 0 mol%. Hereinafter, the present invention will be described in detail.

Preferred polymers used in the silver halide photographic light-sensitive material according to the present invention are those having a relative fluorescence yield K value of 0.25 or more, more preferably 0.3 or more. The larger this value is, the better.

The K value is a relative fluorescence quantum yield in a polymer of the compound A having the following structural formula, which is a kind of dye often used as a so-called fluorescent probe, and is defined by the following formula.

Compound A Here, Φa and Φb are the fluorescence quantum yields of compound A in polymers a and b, for example, Macromolec
ules, 14 , 587 (1981). Specifically, a polymer thin film having a concentration of Compound A of 0.5 mmol / kg (note: the thickness of the thin film is
was measured at room temperature using a spin-coating method on a slide glass so that the absorbance at ^max was 0.05 to 0.1).
a, Φb. Further, in the case of the present invention, it is the K value when polymethyl methacrylate (number average molecular weight: 20,000) is used as the polymer b.

Here, it is not clear why the larger the K value, the greater the effect of improving the heat fastness of cyan is, but in the first place, the higher the fluorescence yield of the fluorescent probe, the finer the polymer. It is said that visual motility is bound [Jour
nal of Physical Chemistry, 86 , 4205 (1982), etc.)
The following are presumed from the fact that That is,
Cyan dye diffuses in oil droplets by heat,
It is presumed that the fading reaction is promoted for some reason, and that the polymer of the present invention coexists with the cyan dye, thereby restricting the diffusion (movement) of the cyan dye and improving the heat fastness.

2- (2 ') represented by the general formula [I] used in the present invention.
(Hydroxyphenyl) benzotriazole-based compound may be solid or liquid at room temperature, but its melting point or the melting point of a mixture of two or more thereof is preferably 85 ° C or lower, more preferably 60 ° C or lower, and particularly preferably 25 ° C or lower. C. or lower (ie, liquid) is preferred. In the case of a mixture,
It is preferred that the individual compounds that constitute it are themselves liquids.

Specific examples in the case of a liquid include JP-B-55-36984 and JP-B-55-1.
No. 2587 and JP-A-58-214152.

The compound represented by the general formula (I) may be a single compound or a mixture. As the mixture, those composed of a group of structural isomers can be preferably used.
(Structural isomers are described in U.S. Pat. No. 4,587,346.) For details of the compound represented by the general formula (I),
Other JP-A-58-221844, JP-A-59-46646, JP-A-59-109
No. 055, Japanese Patent Publication No. 36-10466, No. 42-26187, No. 48-549
No. 6, No. 48-41572, U.S. Pat.No. 3,754,919, No. 4,22
No. 0,711. Preferred specific examples of the compound of the formula (I) are shown below, but it should not be construed that the invention is limited thereto.

(UV-1) to (UV-33) are liquid at room temperature.

Hereinafter, the polymer according to the present invention will be described with reference to specific examples, but the present invention is not limited thereto.

(A) Vinyl polymer The monomers forming the vinyl polymer of the present invention include:
Acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, sec-butyl acrylate, t
ert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
Octyl acrylate, tert-octyl acrylate,
2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate,
Dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ) Ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9),
1-bromo-2-methoxyethyl acrylate, 1,1-
And dichloro-2-ethoxyethyl acrylate. In addition, the following monomers can be used.

Methacrylates: Specific examples thereof include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, and n-methacrylate.
Butyl methacrylate, isobutyl methacrylate, se
c-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate,
Cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy)
Ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol mono Methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-
Propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate ( Additional mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt, and the like.

Vinyl esters: Specific examples thereof include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and saturyl acid. Acrylamides: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethyl Acrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetone acrylamide, tert
-Octylacrylamide and the like; methacrylamides: for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert
-Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide,
Dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide,
N- (2-acetoacetoxyethyl) methacrylamide and the like; Olefins: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3- Dimethyl butadiene, etc .; styrenes:
For example, styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, methyl vinyl benzoate; vinyl ethers: for example , Methyl vinyl ether,
Butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, and the like; butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate , Dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone,
Examples include methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl acrylate, glycidyl methacrylate, N-vinyloxazolidone, N-vinylpyrrolidone, acrylonitrile, methacrylonitrile, methylenemalononitrile, vinylidene, and the like.

As the monomer (for example, the above-mentioned monomer) used in the polymer of the present invention, two or more kinds of monomers are used as comonomers for various purposes (for example, for improving the solubility). Further, for the purpose of controlling color development and solubility, as long as the copolymer does not become water-soluble, a monomer having an acid group as exemplified below may be used as a comonomer.

Acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate, for example, monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, and the like; monoalkyl maleate, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate Citraconic acid; styrenesulfonic acid; vinylbenzylsulfonic acid; vinylsulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, and the like; methacryloyloxyalkylsulfonic acid For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc .; Amides alkylsulfonic acids, e.g., 2-acrylamido-2-methyl-ethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methyl butanoic acid and the like; methacrylamide alkyl sulfonic acids, for example,
2-methacrylamide-2-methylethanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, and the like; these acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions.

When a hydrophilic monomer (here, one that becomes water-soluble when formed into a homopolymer) among the vinyl monomers mentioned above and other vinyl monomers used in the present invention is used as a comonomer, As long as the copolymer does not become water-soluble, the ratio of the hydrophilic monomer in the copolymer is not particularly limited, but is usually preferably 40
Mol% or less, more preferably 20 mol% or less, further preferably 10 mol% or less. When the hydrophilic comonomer copolymerized with the monomer of the present invention has an acid group, from the viewpoint of image preservation as described above, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol. %Less than,
Preferably, it is at most 10 mol%, most preferably when no such comonomer is present.

The monomers of the invention in the polymer are preferably methacrylate, acrylamide and methacrylamide. Particularly preferred are acrylamide and methacrylamide.

(B) Polymer by condensation polymerization and polyaddition reaction As a polymer by condensation polymerization, a polyamide by diamine and dibasic acid and ω-amino-ω'-carboxylic acid is used. As a polymer by polyaddition reaction, diisocyanate and dihydric alcohol are used. Are known.

Specific examples of the diamine used in the present invention include hydrazine, methylene diamine, ethylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, dodecyl methylene diamine, 1,4-diaminocyclohexane, 1,4-diaminomethylcyclohexane, o-aminoaniline, p-aminoaniline, 1,4
-Diaminomethylbenzene and di (4-aminophenyl) ether.

Glycine and β-amino-ω-carboxylic acids
Alanine, 3-aminopropanoic acid, 4-aminobutanoic acid, 5-aminopentanoic acid, 11-aminododecanoic acid,
-Aminobenzoic acid, 4- (2-aminoethyl) benzoic acid and 4- (4-aminophenyl) butanoic acid.

As the diisocyanate, ethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate,
p-xylene diisocyanate, 1,5-naphthyl diisocyanate and the like.

(C) Others For example, polyamide obtained by ring-opening polymerization In the formula, m represents an integer of 4 to 7. —CH ₂ — may be branched. Examples of such a monomer include α-pyrrolidone and α-piperidone.

In addition, a polymer represented by the following general formula can also be used.

During AB _n type, A is an ether bond and -SO ₂ - represents a repeating unit having a bond selected from coupled to at least one main chain. Where B is Ether bond, Represents a repeating unit or a single bond having at least one bond selected from a —SO ₂ — bond and an ester bond, which may be the same or different from A. R represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, which may be substituted or unsubstituted. n represents an integer of 5 or more.

Two or more of the polymers of the present invention described above may be used in combination.

The molecular weight and the degree of polymerization of the polymer of the present invention have substantially no significant effect on the effects of the present invention, but as the molecular weight increases,
It takes a long time to dissolve in the auxiliary solvent, and it is difficult to emulsify and disperse due to the high solution viscosity, resulting in coarse particles. And other problems are likely to occur. Reducing the viscosity of the solution by using a large amount of an auxiliary solvent as a countermeasure causes a new process problem. From the above viewpoint, the viscosity of the polymer is preferably 5000 cps or less, more preferably 2000 cps or less, when 30 g of the polymer is dissolved in 100 cc of the auxiliary agent used. The molecular weight of the polymer usable in the present invention is preferably 150,000 or less, more preferably 100,000 or less.

The water-insoluble polymer in the present invention is a polymer in which the solubility of the polymer in 100 g of distilled water is 3 g or less, preferably 1 g or less.

The ratio of the polymer of the present invention to the auxiliary solvent varies depending on the type of the polymer used, and varies over a wide range depending on the solubility in the auxiliary solvent, the degree of polymerization, the solubility of the coupler, and the like. Usually at least a coupler,
High-boiling coupler solvent and polymer are dissolved in co-solvents. A co-solvent is used in an amount necessary to obtain a sufficiently low viscosity so that the solution is easily dispersed in water or aqueous hydrophilic colloid. Is done. The higher the degree of polymerization of the polymer, the higher the viscosity of the solution, so it is difficult to uniformly determine the ratio of the polymer to the co-solvent regardless of the type of polymer, but it is usually about 1: 1 to 1:50 ( (Polymerization ratio) is preferable. The ratio of the polymer of the present invention to the coupler (polymerization ratio) is 1:20
To 20: 1, more preferably 1:10 to 10: 1.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited thereto.

(P-1) Polymethyl methacrylate P-2) Polyethyl methacrylate P-3) Polyisopropyl methacrylate P-4) Polymethylchloroacrylate P-5) Poly (2-tert-butylphenyl acrylate) P-6) Poly (4-tert-butylphenyl acrylate) P-7) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) P-8) Methyl methacrylate-acrylonitrile copolymer (65:35) P-9) Methyl Methacrylate-styrene copolymer (90:10) P-10) N-tert-butyl methacrylate-methyl methacrylate-acrylic acid copolymer (60:30:10) P-11) Methyl methacrylate-styrene-vinyl Sulfonamide copolymer (70:20:10) P-12) Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50) P-13) Methyl methacrylate-acrylic acid copolymer (95: 5) P-14) Methyl methacrylate-r-butyl methacrylate copolymer (65:35) P-15) Methyl methacrylate-N -Vinyl-2-pyrrolidone copolymer (90:10) P-16) poly (N-sec-butylacrylamide) P-17) poly (N-tert-butylacrylamide) P-18) polycyclohexyl methacrylate-methyl Methacrylate copolymer (60:40) P-19) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (20:70:10) P-20) diacetone acrylamide-methyl methacrylate copolymer (20:80) P-21) N-tert-butylacrylamide-methyl methacrylate copolymer (40:60) P-22) Poly (Nn-butylacrylamide) P-23) tert-butyl methacrylate-N-tert-butyl acrylamide copolymer (50:50) P-24) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-25) poly (N-tert- Butyl methacrylamide) P-26) N-tert-butyl acrylamide-methyl methacrylate copolymer (60:40) P-27) Methyl methacrylate-acrylonitrile copolymer (70:30) P-28) Methyl methacrylate Styrene copolymer (75:25) P-29) Methyl methacrylate-hexyl methacrylate copolymer (70:30) P-30) Poly (4-biphenyl acrylate) P-31) Poly (2-chlorophenyl acrylate) ) P-32) Poly (4-chlorophenyl acrylate) P-33) Poly (pentachlorophenyl acrylate) P-34) Poly (4-ethoxycarbo) P-35) Poly (4-methoxycarbonylphenyl acrylate) P-36) Poly (4-cyanophenyl acrylate) P-37) Poly (4-methoxyphenyl acrylate) P-38) Poly (3,5-dimethyladamantyl acrylate) P-39) Poly (3-dimethylaminophenyl acrylate) P-40) Poly (2-naphthyl acrylate) P-41) Poly (phenyl acrylate) P-42) Poly (N, N-dibutylacrylamide) P-43) Poly (isohexylacrylamide) P-44) Poly (isooctylacrylamide) P-45) Poly (N-methyl-N-phenylacrylamide) P-46) Poly (Adamantyl methacrylate) P-47) Poly (sec-butyl methacrylate) P-48) N-tert-butyl acrylamide- Acrylic acid copolymer (97: 3) P-49) Poly (2-chloroethyl methacrylate) P-50) Poly (2-cyanoethyl methacrylate) P-51) Poly (2-cyanomethylphenyl) P-52) Poly (4-cyanomethylphenyl methacrylate) P-53) Poly (cyclohexyl methacrylate) P-54) Poly (2-hydroxypropyl methacrylate) P-55) Poly (4-methoxy) P-56) Poly (3,5-dimethyladamantyl methacrylate) P-57) Poly (phenyl methacrylate) P-58) Poly (4-butoxycarbonylphenyl methacrylamide) P-59) Poly (4-carboxyphenyl methacrylamide) P-60) poly (4-ethoxycarbonylphenyl methacrylamide) P-61) Poly (4-methoxycarbonylphenylmethacrylamide) P-62) Poly (cyclohexylchloroacrylate) P-63) Poly (ethylchloroacrylate) P-64) Poly (isobutylchloroacrylate) P-65) Poly ( Isopropyl chloroacrylate) P-66) Poly (N-phenylacrylamide) P-67) Poly (N-phenylmethacrylamide) P-68) Poly (N-cyclohexylacrylamide) P-69) Poly (N -Cyclohexyl methacrylamide) Synthesis example (1) Synthesis of methyl methacrylate polymer (P-1) 50.0 g of methyl methacrylate, 0.5 g of sodium polyacrylate, and 200 ml of distilled water were put into a 500 ml three-necked flask,
The mixture was heated to 80 ° C. with stirring in a nitrogen stream. 500 mg of dimethyl azobisisobutyrate was added as a polymerization initiator to initiate polymerization.

After polymerization for 2 hours, the polymerization solution was cooled, and the polymer in the form of beads was filtered and washed with water to obtain 48.7 g of P-1.

Synthesis Example (2) Synthesis of t-butylacrylamide polymer (P-17) A mixture of 50.0 g of t-butylacrylamide and 250 ml of toluene was placed in a 500 ml three-necked flask, and heated to 80 ° C. with stirring in a nitrogen stream. 10 ml of a toluene solution containing 500 mg of azobisisobutyronitrile as a polymerization initiator was added to initiate polymerization.

After polymerization for 3 hours, the polymerization liquid was cooled, hexane 1 was poured, and the precipitated solid was filtered off, washed with hexane and heated and stirred under reduced pressure to obtain 47.9 g of P-17.

In the present invention, cyan couplers that are advantageously used include the following general formulas (IIa) and (IIb).

[In the general formulas (IIa) and (IIb), R ₁ , R ₂ and R ₄ represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, and R ₃ , R ₅ and R ₆ represent a hydrogen atom , A halogen atom, an aliphatic group, an aromatic group or an acylamino group, and R ₃ may represent a non-metallic atomic group forming a 5- or 6-membered nitrogen-containing ring together with R ₂ . Y ₁ and Y _{2 each} represent a hydrogen atom or a group capable of leaving during a coupling reaction with an oxidized form of a developing agent, and n represents 0 or 1. In the cyan couplers of the general formulas (IIa) and (IIb), preferred aliphatic groups for R ₁ , R ₂ and R ₄ include, for example, methyl, butyl, tridecyl, cyclohexyl, allyl and the like having 1 to 32 carbon atoms. Examples of the aryl group include phenyl and naphthyl, and examples of the heterocyclic group include 2-pyridyl, 2-imidazolyl, 2-furyl, and 6
-Quinolyl and the like. These groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (e.g., methoxy, 2-methoxyethoxy), an aryloxy group (2,4-di-tert-amylphenoxy, 2-chlorophenoxy, 4-chlorophenoxy). Cyanophenoxy, etc.), alkenyloxy group (2-propenyloxy, etc.), acyl group (acetyl, benzoyl, etc.), ester group (butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl, toluenesulfonyloxy, etc.), amide group (Acetylamino, methanesulfonamide, dipropylsulfamoylamino, etc.), carbamoyl group (dimethylcarbamoyl, ethylcarbamoyl, etc.), sulfamoyl group (butylsulfamoyl, etc.), imide group, (succinimide, hydantoinyl, etc. ), Ureido groups (phenylureido, dimethylureide, etc.), aliphatic or aromatic sulfonyl groups (methanesulfonyl, phenylsulfonyl, etc.), aliphatic or aromatic thio groups (ethylthio, phenylthio, etc.), hydroxy group, cyano group, carboxy It may be substituted with a group selected from a group, a nitro group, a sulfo group, a halogen atom and the like.

When R ₃ and R ₅ in the general formula (IIa) are substitutable substituents, they may be substituted with the substituents described for R ₁ .

R ₅ in the general formula (IIb) is preferably an aliphatic group, and methyl, ethyl, propyl, butyl, pentadecyl, tert-butyl, cyclohexyl, cyclohexylmethyl, phenylthiomethyl, dodecyloxyphenylthiomethyl, butanamide Methyl, methoxymethyl and the like can be mentioned.

In the general formulas (IIa) and (IIb), Y ₁ and
Y ₂ represents a hydrogen atom or a coupling-off group (including a coupling-off group; the same applies hereinafter), and examples thereof include a halogen atom (fluorine, chlorine, bromine, etc.)
Alkoxy group (ethoxy, dodecyloxy, methoxyethylerbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, etc.), aryloxy group (4-chlorophenoxy, 4-methoxyphenoxy group, 4-carboxyphenoxy, etc.), acyloxy group (acetoxy , Tetradecanoyloxy, benzoyloxy, etc.), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy, etc.), amide group (dichloroacetylamino, heptafluorobutyrylamino, methanesulfonylamino, toluenesulfonylamino, etc.), alkoxycarbonyl Oxy groups (ethoxycarbonyloxy, benzyloxycarbonyloxy, etc.), aryloxycarbonyloxy groups (phenoxycarbonyloxy, etc.), Aliphatic or aromatic thio group (ethylthio, phenylthio, etc. tetrazolylthio), an imido group (succinimide, etc. hydantoinyl), and the like aromatic azo group (such as phenylazo).
These leaving groups may include photographically useful groups.

Preferred R ₁ in the general formula (IIa) is an aryl group or a heterocyclic group, and is 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.

When R ₃ and R ₂ do not form a ring in formula (IIa), R ₂ is preferably a substituted or unsubstituted alkyl group,
It is an aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, and R ₃ is preferably a hydrogen atom.

In formula (IIb), R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group.

In the general formula (IIb), preferred R ₅ is an alkyl group having 1 to 15 carbon atoms and a methyl group having a substituent having 1 or more carbon atoms. As the substituent, an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, Alkyloxy groups are preferred.

In the general formula (IIb), R ₅ is more preferably an alkyl group having 1 to 15 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms.

 Most preferably, it is an ethyl group.

In formula (IIb), preferred R ₆ is a hydrogen atom or a halogen atom, and a chlorine atom and a fluorine atom are particularly preferred.

In the general formulas (IIa) and (IIb), preferred Y ₁ and
Y ₂ is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group, respectively.

In formula (IIb), Y ₂ is preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

When n = 0 in the general formula (IIa), Y ₁ is more preferably a halogen atom, and particularly preferably a chlorine atom or a fluorine atom.

Hereinafter, specific examples of the oil-soluble cyan coupler according to the present invention will be described, but the present invention is not limited thereto.

The color light-sensitive material of the present invention may contain a yellow coupler or a magenta coupler in addition to the cyan coupler.

As the yellow coupler, a pivaloylacetanilide-based coupler or a benzoylacetanilide-based coupler is preferably used, and the former is more preferable in terms of the fastness of a color image. Among them, couplers having a nitrogen-releasing type coupling-off group are more preferable in that they have high activity (high color development).

Further, as the magenta coupler, 3-anilino-5
-Pyrazolone couplers, 3-acylamino-5-pyrazolone couplers, pyrazolotriazole couplers and the like are preferably used. Among them, pyrazolotriazole couplers are more preferable because they have less side absorption on the short wavelength side and have excellent color image fastness.

In a light-sensitive material in which a cyan coupler is dispersed according to the present invention, in order to maintain a good color balance of three colors of yellow, magenta and cyan when a color image is faded by light and heat, a pivaloylacetoanilide-based yellow coupler and It is particularly preferable to use a pyrazolotriazole-based magenta coupler.

Specific examples of the oil-soluble magenta and the yellow coupler that can be used in the present invention are listed below, but are not limited thereto.

Useful high-boiling solvents used in the present invention are compounds represented by the following general formulas (III) to (VIII).

In the formula, W ₁ , W ₂ and W ₃ each represent a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, and W ₄ represents W ₁ , O-
W ₁ or SW ₁ , wherein n is an integer of 1 to 5, and when n is 2 or more, W ₄ may be the same as or different from each other; ₁ and W ₂ may be linked together to form a condensed ring.

W ₆ represents a substituted or unsubstituted alkyl group or aryl group, and the total number of carbon atoms constituting W ₆ is 12 or more.

In the present invention, the amount of the high-boiling coupler solvent used varies in a wide range depending on the type and amount of the coupler and the polymer, but in terms of weight ratio, the high-boiling coupler solvent / coupler ratio is:
Preferably, 0.05 to 20, more preferably 0.1 to 10, and the high boiling coupler solvent / polymer ratio is preferably 0.
02 to 40, more preferably 0.05 to 20. The high-boiling coupler solvents may be used alone or in combination of two or more.

Among the compounds represented by the general formulas (III) to (VIII), the general formulas (III), (IV) and (VIII) are preferable.

Particularly preferred are compounds represented by the general formula (III),
And compounds represented by the following general formula (IX) or (X) among the compounds included in the general formula (IV) or (VII).

In the formula, n is an integer of 3 to 15, and W ₇ represents a substituted or unsubstituted alkyl group having 4 to 15 carbon atoms.

W ₈ , W ₉ , W ₁₀ and W ₁₁ each represent an alkyl group having 1 to 40 carbon atoms or a substituted alkyl group (an alkyloxycarbonyl group, an alkylcarbonyloxy, an arylcarbonyloxy, an alkyloxy or an aryloxy as a substituent; And a substituted or unsubstituted alkoxycarbonyl group having 1 to 40 carbon atoms (substituents are the same as the above-mentioned substituted alkyl group substituents), or a hydrogen atom. W ₈ , W ₉ , W ₁₀ and W ₁₁ are not simultaneously hydrogen atoms, and the total number of carbon atoms of W ₈ , W ₉ , W ₁₁ and W ₁₁ is 8 to 60, preferably 8 to 45. It is. further
W ₈ , W ₉ , W ₁₀ and W ₁₁ may be the same or different, and may form a ring.

Among the compounds represented by the general formula (I), particularly preferred are those represented by the general formula (XI).

Although W _8, W ₉ and W ₁₀ in the above is as shown by the general formula (X), at least any one of the alkoxycarbonyl group of the W _8, W ₉ or W _10, aryloxycarbonyl group, Or 8 to 40 carbon atoms substituted with an aryloxy group (count carbon atoms including substituents)
Shows an alkyl group.

The total number of carbon atoms of W ₈ , W ₉ and W ₁₀ is 8 to 60, more preferably 8 to 45. W ₈ and W ₁₀ may form a ring.

Specific examples of the substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group represented by W _{1 to} W ₆ in the general formulas (III) to (VIII) The groups exemplified for (IIa) and (IIb) are applicable.

Hereinafter, specific examples of the high boiling point coupler solvent used in the present invention will be shown, but the present invention is not limited thereto.

The dispersion of lipophilic fine particles of the present invention containing the cyan coupler, the compound of the formula (I) and the polymer is typically prepared as follows.

The polymer of the present invention, which is a so-called linear polymer which has not been crosslinked and is synthesized by a solution polymerization method, emulsion polymerization, suspension polymerization or the like, a compound of the general formula (I), a high-boiling coupler solvent, and an auxiliary organic solvent After completely dissolving them together, the solution is dispersed in water, preferably in a hydrophilic colloid aqueous solution, more preferably in a gelatin aqueous solution, with the aid of a dispersing agent, by ultrasonic waves, in the form of fine particles by a colloid mill or the like, It is contained in a silver halide emulsion. Alternatively, water or a hydrophilic colloid aqueous solution such as a gelatin aqueous solution is added to a dispersing aid such as a surfactant, the polymer of the present invention, the compound of the general formula (I), a high boiling coupler solvent and an auxiliary organic solvent containing a coupler, It may be an oil-in-water dispersion with phase inversion. After removing the auxiliary organic solvent from the prepared dispersion by a method such as distillation, noodle washing or ultrafiltration, the dispersion may be mixed with a photographic emulsion. The auxiliary organic solvent referred to here is an organic solvent useful at the time of emulsification and dispersion, a drying step at the time of coating, and one that is finally removed from the photosensitive material substantially by the above-described method and the like, and has a low boiling point. An organic solvent or a solvent that has some solubility in water and can be removed by washing with water. Examples of the auxiliary organic solvent include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, and the like.

Further, if necessary, an organic solvent that is completely miscible with water,
For example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, and the like can be partially used in combination.

These organic solvents can be used in combination of two or more.

The average particle diameter of the lipophilic fine particles thus obtained is preferably from 0.04 μm to 0.4 μm, and more preferably from 0.06 μm to 0.2 μm, from the viewpoints of color development and rapid processing. The particle size of the lipophilic fine particles can be measured by, for example, a measuring device such as Nanosizer manufactured by Coulter, UK.

The content of the coupler used in the present invention in the silver halide emulsion layer is usually from 0.01 to 2.
It is in the range of 0 mol, preferably in the range of 0.1 to 1.0 mol.

The high-boiling coupler solvent that can be used in the present invention is a compound that is immiscible with water having a melting point of 150 ° C. or less and a boiling point of 140 ° C. or more other than the compounds of the above general formulas (III) to (IX). Any solvent can be used. The melting point of the high boiling coupler solvent is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. The boiling point of the high boiling coupler solvent is preferably 160 ° C.
And more preferably 170 ° C. or higher.

Examples of the coupler solvent including the coupler and the like include gelatin and the like containing an anionic surfactant such as alkylbenzenesulfonic acid and alkylnaphthalenesulfonic acid and / or a nonionic surfactant such as sorbitan sesquioleate and sorbitan monolaurate. It can be mixed with an aqueous solution containing a hydrophilic binder, emulsified and dispersed by a high-speed rotation mixer, a colloid mill or an ultrasonic dispersing device, and added to a silver halide emulsion for use.

In the present invention, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the silver halide. Since the present invention aims at rapid processing, silver chlorobromide containing preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 98 mol% or more of silver chloride is preferable. This silver chlorobromide may contain a small amount of silver iodide,
It is preferable not to include it at all.

The average grain size of the silver halide grains in the photographic emulsion (the grain size in the case of a sphere or a sphere-like grain, and the ridge length in the case of a cubic grain, expressed as an average based on the projected area) is particularly important. However, 2 μm or less is preferable, and 0.2 to 1.5 μm is particularly preferable.

The silver halide grains in the photographic emulsion layer may be those having regular crystals such as cubic, tetradecahedral or octahedral (normal crystal emulsions) or irregular such as spherical or tabular. It may have a crystalline form or a composite form of these crystalline forms. It may consist of a mixture of particles of different crystal forms. Among them, the use of the above-mentioned normal crystal emulsion is preferred.

Further, an emulsion may be used in which tabular silver halide grains having a grain diameter of 5 times or more the thickness thereof occupy 50% or more of the total projected area.

The silver halide emulsion contained in at least one layer of the photosensitive layer preferably has a coefficient of variation (a value obtained by dividing a statistical standard deviation by an average grain size and expressed as a percentage) of 15% or less (more preferably). Is 10% or less).

Such a monodisperse emulsion may be an emulsion having the above-mentioned coefficient of variation by itself, but in particular, separately having two or more kinds of different coefficients of variation having an average grain size of 15% or less (preferably 10% or less). The emulsion may be a mixture of the prepared monodispersed emulsion. The grain size difference or the mixing ratio can be arbitrarily selected, but preferably an emulsion having an average grain size difference of 0.2 μm or more and 1.0 μm or less is used.

For the definition and measurement method of the coefficient of variation, see James, "Theory of The Photographic Process, The Macmilan".
It is described on page 39 of the llan Company, 3rd edition (1966).

The silver halide grains may have different phases between the inside and the surface layer. Further, the particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle. The latter grains are particularly useful as direct positive emulsions.

Cadmium salts, zinc salts, thallium salts, lead salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts may be coexistent in the course of silver halide grain formation or physical ripening.

Silver halide emulsions are usually chemically sensitized. A conventional method can be applied to the chemical sensitization method, and details thereof are described in JP-A-62-2152.
No. 72, page 12, lower left column, line 18 to lower right column, line 16; Silver halide emulsions are usually spectrally sensitized. For spectral sensitization, a usual methine dye can be used, and details thereof are described in JP-A-62-215272, No. 22.
It is described in the third line from the bottom right corner of the page to page 38 and on the attached sheet of the Procedure Amendment dated March 16, 1987.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole, (especially 1-phenyl-5-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazine Thioketo compounds such as oxadolinthione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene), pentaazaindenes Etc. Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc., can be added.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamide phenol derivative and the like as a color fogging inhibitor or a color mixing inhibitor. May be.

Various fading inhibitors can be used in the light-sensitive material of the present invention. That is, hydroquinones as organic fading inhibitors for cyan, magenta and / or yellow images,
6-hydroxychromans, 5-hydroxycoumarins, spirochromans, p-alkoxyphenols,
Representative examples include hindered phenols, mainly bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives in which the phenolic hydroxyl group of each of these compounds is silylated or alkylated. As an example. Further, metal complexes represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

Specific examples of the organic anti-fading agent are described in the specifications of the following patents.

Hydroquinones are disclosed in U.S. Pat.Nos. 2,360,290 and 2,4
No. 18,613, No. 2,700,453, No. 2,701,197, No. 2,
No. 728,659, No. 2,732,300, No. 2,735,765, No.
No. 3,982,944, No. 4,430,425, UK Patent No. 1,363,921
No., U.S. Pat.Nos. 2,710,801 and 2,816,025,
6-Hydroxychromans, 5-hydroxycoumarins, and spirochromans are described in U.S. Pat.
No. 3,573,050, No. 3,574,627, No. 3,698,909, No. 3,764,337, JP 52-152225, etc. UK Patent 2,0
No. 3,700,455, hindered phenols are disclosed in U.S. Pat.
JP-A-52-72225, U.S. Pat.No. 4,225,235, JP-B-52-6623, and the like, gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Pat. No. 32,886, JP-B-56-21144, and the like, hindered amines are disclosed in U.S. Pat.
No. 4,268,593, British Patent No. 1,326,889, No. 1,354,
No. 313, No. 1,410,846, JP-B-51-1420, JP-A-58
Nos. 1,14036, 59-53846, 59-78344 and the like, ethers and ester derivatives of phenolic hydroxyl groups are described in U.S. Pat.Nos. 4,155,765, 4,174,220 and 4,254,216.
No. 4,264,720, JP-A-54-145530, JP-A-55-632
No. 1, No. 58-105147, No. 59-10539, Japanese Patent Publication No. 57-3785
No. 6, U.S. Pat.No.4,279,990, Japanese Patent Publication No. 53-3263, and the like, metal complexes are described in U.S. Pat.Nos. 4,050,938 and 4,241,155.
And British Patent No. 2,027,731 (A). These compounds can achieve their purpose by adding 5 to 100% by weight, based on the corresponding color coupler, to the photosensitive layer, usually by co-emulsifying the coupler with the coupler.

Prefabrication of M Stain Inhibitor In the present invention, the following compounds are preferably used together with the above-mentioned coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inactive and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Preferred as the compound (F) is a secondary reaction rate constant k2 with p-anisidine (in trioctyl phosphate at 80 ° C.) of from 1.0 l / mol · sec to 1 × 10 ⁻⁵ l / mol · sec. It is a compound that reacts. The secondary reaction rate constant can be measured by the method described in JP-A-63-158545.

If k2 is larger than this range, the compound itself becomes unstable, and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent, which is the object of the present invention, may not be prevented.

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

In the formula, R1 and R2 each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which forms a chemical bond by reacting with an aromatic amine-based developer, and X represents a group which is eliminated by reacting with an aromatic amine-based developer. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes addition of an aromatic amine-based developing agent to the compound of the general formula (FII). Represents a group. Here, R1 and X, Y and R2 or B may be combined with each other to form an existing structure.

Representative methods of chemically bonding with the residual aromatic amine-based developing agent are a substitution reaction and an addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545, JP-A-62-283338, Japanese Patent Application No. 62-158342, Japanese Patent Application No. 63-18439, and the like. Are preferred.

On the other hand, the compound (G) which forms a chemically inactive and colorless compound by chemically bonding to an oxidized form of an aromatic amine-based developing agent remaining after the color development processing is more preferably represented by the following general formula (GI) ).

Formula (GI) RZ In the formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group which decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is a nucleophilic ⁿ CH ₃ I value of Pearson (RGPearson,
etal., J. Am. Chem. SOC., 90 , 319 (1968)) or a group derived therefrom is preferred.

Specific examples of the compound represented by the general formula (GI) are described in EP-A-255722, JP-A-62-143048 and JP-A-62-143048.
Nos. 229145, 63-18439, 63-136724, 62
Preferred are those described in JP-A-214681 and JP-A-62-158342.

The details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

In order to prevent the deterioration of the cyan dye image due to heat and especially light, it is more effective to introduce an ultraviolet absorber into both layers adjacent to the cyan coloring layer.

Among the anti-fading agents, spiroindanes and hindered amines are particularly preferred.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, a benzotriazole compound substituted with an aryl group (for example, US Pat. No. 3,533,794)
), 4-thiazolidone compounds (for example, those described in U.S. Patent Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, those described in JP-A-46-2784), cinnamate compounds (for example, US Patent 3,70
Nos. 5,805 and 3,707,375), butadiene compounds (for example, those described in U.S. Pat. No. 4,045,229), and benzooxide compounds (for example, U.S. Pat.
700,455) can be used. An ultraviolet-absorbing coupler (for example, an α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted to a specific layer.

The light-sensitive material of the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes,
Hemioxonol and merocyanine dyes are useful. Details of useful oxonol dyes are described in JP-A-62-215272.
On page 158, upper right column to page 163.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, gelatin is lime-treated,
Either one treated with an acid may be used. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin, (Academic Press, 1964).

As the support used in the present invention, usually, a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, which are used for a photographic light-sensitive material, In addition, there are a laminate thereof, a thin glass film, paper and the like. Paper coated or laminated with a polymer of an α-olefin having 2 to 10 carbon atoms, such as a baryta or α-olefin polymer, especially polyethylene, polypropylene, ethylene butene copolymer, a vinyl chloride resin containing a reflective material such as TiO ₂ , A support such as a plastic film whose surface is roughened to improve the adhesion to other polymer substances as shown in JP 47-19068 also gives good results. Further, an ultraviolet curable resin can also be used.

These supports are selected from transparent and opaque ones according to the purpose of the light-sensitive material. It is also possible to add a dye or a pigment to make it transparent and colored.

The opaque support was originally opaque such as paper, or a transparent film to which a dye or a pigment such as titanium oxide was added, or surface-treated by a method shown in JP-B-47-19068. Plastic films and the like are also included.
The support is usually provided with an undercoat layer. In order to further improve the adhesiveness, the surface of the support may be subjected to a preliminary treatment such as corona discharge, ultraviolet irradiation, or flame treatment.

The color light-sensitive material applicable to the production of the color photograph of the present invention is an ordinary color light-sensitive material such as a color negative film, a color paper, a reversal color paper, a color reversal film and the like, and a color light-sensitive material for printing is particularly preferable.

In the development of the light-sensitive material of the present invention, a black-and-white developer and / or
Alternatively, a color developing solution is used. The color developing solution is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N, N-diethylaniline. Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Can be These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a benzimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catechol sulfonate, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Fogging agents such as sodium borohydride, auxiliary phenomena such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids,
Alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, 'N'-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof It can be raised as a representative example.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 l or less per square meter of the light-sensitive material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area between the processing tank and air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (VI) and copper (II), peracids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex salts are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and the prebath thereof, if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,
No. 988, JP-A-53-32,736, JP-A-53-57,831, JP-A-53-3
No. 7,418, No. 53-72,623, No. 53-95,630, No. 53-95,
No. 631, No. 53-104,232, No. 53-124,424, No. 53-14
Compounds having a mercapto group or a disulfide group described in JP-A Nos. 1,623 and 53-28,426 and Research Disclosure No. 17,129 (July 1978);
Thiazolidine derivatives described in No. 140,129; JP-B-45-8,5
No. 06, JP-A-52-20832, JP-A-53-32,735, and thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,1
27,715; iodides described in JP-A-58-16,235; polyoxyethylene compounds described in West German Patent Nos. 966,410 and 2,748,430; polyamine compounds described in JP-B-45-8836; -42,434, 49-59,644, 53
-94,927, 54-35,727, 55-26,506, 58-
No. 163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Patent No. 3,893,858, West German Patent No. 1,290,812, and
Compounds described in -95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, a large amount of iodide salts, and the use of thiosulfates is common.
In particular, ammonium thiosulfate can be used most widely.
As a preservative of the bleach-fixing solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the rinsing water temperature,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in the Journal of the Society of Motion Picturs and T
It can be determined by the method described in elevisoin Engineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria are propagated, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium ion described in Japanese Patent Application No. 61-131,632,
The method of reducing magnesium ions can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc.
Sanitizing agents described in "Sterilization, disinfection and fungicide technology of microorganisms" edited by the Sanitary Technology Society, and "Encyclopedia of antibacterial and antifungal agents" edited by the Japan Society of Antifungals and Fungi can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-9.
And preferably 5-8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like, but in general, the range is 20 seconds to 10 minutes at 15 to 45 ° C, preferably 30 seconds to 5 minutes at 25 to 40 ° C. Is done. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned water washing. In such a stabilization process, Japanese Unexamined Patent Publication No.
All known methods described in -8,543, 58-14,834 and 60-220,345 can be used.

In some cases, a stabilization process is further performed after the water washing process. For example, the stabilization process is used as a final bath of a color light-sensitive material for photography. Examples include a stabilizing bath containing formalin and a surfactant. Various chelating agents and anti-shrinking agents can also be added to this stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135,628 can be mentioned.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64,339, JP-A-57-144,457 and JP-A-58-144,457.
No. 115,438 and the like.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Hereinafter, the present invention will be described specifically with reference to Examples.
Embodiments of the present invention are not limited thereby.

Example (1) Sample 101 of the present invention was prepared as follows.

8 g of the exemplary polymer (P-1) of the present invention and the exemplary coupler (C
-3) A solution consisting of 10 g, 8 g of the exemplary compound mixture represented by the general formula (I) (UV-42 / UV-43 / UV-44 = 4/2/5; weight ratio) and 50 ml of ethyl acetate was heated at 50 ° C. After warming to gelatin 15
g and 1.0 g of sodium dodecylbenzenesulfonate were added to an aqueous solution 100, and a fine particle emulsified dispersion was obtained with a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho).

This emulsified dispersion was mixed with a photographic emulsion consisting of silver chlorobromide (98 mol% of silver chloride), the pH was adjusted to 6.0, and then, on a paper support laminated on both sides with polyethylene, as shown in Table 1. Sample 101 of the present invention was prepared using the layer structure and the main component composition described above. (Here, 4.6-dichloro-hydroxy-s-triazine-sodium salt was used as a gelatin crosslinking agent.

Similarly, samples 102 to 105 were prepared. Here, the species and amount of the polymer and the compound of the general formula (I) and the coupler species are as follows:
The results are as shown in Table 2, and other than that are the same as the samples shown in Table 1.

The average particle diameter of the coupler-containing lipophilic fine particles used in Samples 101 to 105 was generally between 0.10 and 0.17 µ.

These samples were subjected to continuous tone exposure through an optical wedge for sensitometry, and then subjected to the following treatment (A).

1. Color development 35 ° C 45 seconds 2. Bleaching and fixing 35 ° C 1 minute 00 seconds 3. Rinse 25 ° C to 30 ° C 2 minutes 30 seconds Here, the composition of each processing solution in the color development processing step (A) is as follows. is there.

Color developer (A) Water 800 cc Ethylenediaminetetraacetic acid 1.0 g Sodium sulfite 0.2 g N, N-diethylhydroxylamine 4.2 g Potassium bromide 0.01 g Sodium chloride 1.5 g Triethanolamine 8.0 g Potassium carbonate 30 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 4.5g 4,4'-diaminostilbene-based fluorescent whitening agent (Sumitomo Chemical Co., Ltd. Whitex4) 2.0g Add water and 1000ml with KOH pH10.25 bleach-fixing solution ammonium thiosulfate _{(54Wt%) 150ml Na 2 SO} 3 15g NH 4 [Fe (III) (EDTA)] 55 g EDTA · 2Na 4g glacial acetic acid 8.61g water in the added total amount 1000 ml pH 5.4 rinse liquid EDTA・ 2Na ・ 2H ₂ O 0.4g Water was added and the total volume was 1000ml. PH 7.0 The following tests were performed for each of the developed samples for light fastness, heat fastness, and wet heat fastness. When the sample was left in a dark place at 100 ° C. for 5 days and when it was left in a dark place at 80 ° C. and 70% RH for 12 days, the degree of fading was expressed as a density reduction rate at an initial density of 1.5. It is shown in Table 2.

As is clear from Table 2, by using the polymer having the K value of the present invention and the compound of the general formula (I) in accordance with the present invention,
It can be seen that a synergistic improvement effect (super additive effect) on dark fading is observed.

Example (2) In Sample 101 of Example (1) (see Table 1), the type and amount of the coupler solvent, polymer and compound of the formula (I) were changed as shown in Table 3. Sample 101 other than
Samples 201 to 214 similar to those shown in Table 1 were prepared.

These film samples were subjected to continuous tone exposure using a wedge for sensitometry, and experiments of processing (A) and processing (B) were performed.

The contents of the processing (A) and the processing (B) are as follows: benzyl alcohol is contained in the color developer (A) 1 used in Example (1).
The one containing 15 ml is the color developer (B), and the other processing contents are the same.

The test according to Example (1) was conducted for the heat fastness of each sample treated with the color developer (A).
Table 3 shows the results of the degree of the fading expressed as a density reduction rate at an initial density of 1.5, and the maximum densities of each sample in the treatments (A) and (B).

As is evident from Table 3, the samples in which the polymer of the present invention and the compound of the general formula (I) are used in combination have excellent heat fastness and color development in any of the couplers. In particular, when the ultraviolet absorber of the present invention having a low (co) melting point is used, the coloring properties are more excellent, and it is understood that the effect is remarkable in the treatment containing no benzyl alcohol. Further, it can be seen that the sample containing the coupler solvent even without containing the compound of the general formula (I) has high color development, but is inferior in heat fastness.

Example (3) Silver chlorobromide (98 mol% of silver chloride) was replaced with silver chlorobromide (70 mol% of silver bromide) in sample 101 of Example (1) (see Table 1).
In the same manner as in Sample 101 (see Table 1) except that the kind and amount of the coupler species, coupler solvent, compound of the general formula (I) and polymer were changed as shown in Table 4,
Created ~ 311.

These film samples were subjected to continuous tone exposure to a sensitometric wedge, and subjected to the following processing.

Color development process 1. Color development 33 ° C 3 minutes 30 seconds 2. Bleaching and fixing 33 ° C 1 minute 30 seconds 3. Washing 28 ° C to 35 ° C 3 minutes 00 seconds Color developing solution Diethylenetriamine pentaacetic acid 1.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Na ₂ SO ₃ 2.0 g KB _r 0.5 g hydroxylamine sulfate 3.0 g 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30 g Optical brightener (4,4'-diaminostilbene) 1.0 g Add water to make up to 1 liter (pH 10.1) Bleach-fix solution Ammonium thiosulfate (70 wt%) 150 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (EDTA)] 55 g EDTA · 2Na 4 g Add water to make 1 liter (pH 6.9) Heat fastness and wet heat fastness of each developed sample according to Example (1) All tests were performed. Table 4 shows the results of expressing the degree of the fading by the density reduction rate at the initial density of 1.5.

As is apparent from Table 4, according to the present invention in which the polymer having a K value of 0.2 or more of the present invention is used in combination with the compound represented by the general formula (I), the polymer which does not satisfy the K value of the present invention is used. It can be seen that the effect of improving the heat fastness and wet heat fastness of the cyan image is remarkably large as compared with the case where is used.

Also, U.S. Pat.No. 4,201,589 and JP-A-51-134,627.
It can be seen that Comparative Polymers D and E in Table 4 described in the examples of the present invention have poor heat fastness as compared with the polymers of the present invention. In particular, the comparative polymer E containing an acid group does not show the effect of improving heat fastness as compared with the case where no polymer is added,
It turns out that it worsens.

Example (4) A multilayer color photographic paper 401 having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of first layer coating solution Ethyl acetate 2 was added to 19.1 g of yellow coupler (Y-17) and 4.4 g of color image stabilizer (Cpd-1) and 1.8 g of (Cpd-7).
7.2 cc and 4.1 g of each of the solvents (S-10) and (S-67) were added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (80.0 mol% silver bromide, cubic, average grain size 0.85μ, variation coefficient 0.08) and silver bromide 80.0 mol%, cubic, average grain size 0.62μ, variation coefficient 0.07 Was mixed at a ratio of 1: 3 (Ag mole ratio) and sulfur-sensitized, and a blue-sensitive sensitizing dye shown below was added in an amount of 5.0 × 10 ⁻⁴ mol per mol of silver. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
As a gelatin hardener for each layer, 1-oxy-3.5-dichloro-s-triazine sodium salt was used.

 The following were used as spectral sensitizing dyes for each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
4.0 × 10 ^-6 mol, 3.0 × 10 ^-5 mol, 1.0 × 10 ^-5 mol, and 2-methyl-5-t-octylhydroquinone in an amount of 8 × 10 ^-3 mol and 2 × 10 ^-3 mol per mol of silver halide, respectively. ^-2 ,
2 × 10 ^{-2 was} added.

Also, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1.2 × 10 ^-2 mol, 1.1 × 10
^-2 mol was added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first polyethylene contains white pigment (TiO ₂ ) and blue dye (ultramarine)] First layer (blue-sensitive layer) Silver chlorobromide emulsion described above (AgBr: 80 mol%) 0.26 Gelatin 1.83 Yellow coupler (Y-17) 0.83 Color image stabilizer (Cpd-1) 0.19 Color image stabilizer (Cpd-7) 0.08 Solvent (S-10) 0.18 Solvent (S-67) 0.18 Second layer (mixed colors) Inhibitor layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (S-25) 0.16 Solvent (S-16) 0.08 Third layer (green sensitive layer) Silver chlorobromide emulsion (AgBr 90 mol%, 0.16 cube, average A mixture of particles with a particle size of 0.47μ and a coefficient of variation of 0.12 mixed with AgBr 90 mol%, cubic, with an average particle size of 0.36μ and a coefficient of variation of 0.09 at a ratio of 1: 1 (Ag molar ratio) Gelatin 1.79 Magenta coupler ( M-5) 0.32 Color image stabilizer (Cpd-3) 0.20 Color image stabilizer (Cpd-6) 0.03 Color image stabilizer (Cpd-4) 0.0 1 Color image stabilizer (Cpd-7) 0.04 Solvent (S-7) 0.16 Solvent (S-16) 0.16 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorbing agent (Cpd-8) 0.47 Color mixing inhibitor (Cpd- 5) 0.05 solvent (S-69) 0.24 Fifth layer (red sensitive layer) 0.23 Silver chlorobromide (AgBr 70 mol%, cubic, average grain size 0.49μ, variation coefficient 0.08, AgBr 70 mol%, A mixture of a cube, an average particle size of 0.34μ, and a coefficient of variation of 0.10 was mixed at a ratio of 1: 2 (Ag mole ratio). Gelatin 1.34 Cyan coupler (C-3) 0.17 Cyan coupler (C-11) 0.13 General formula ( Compound of I) (UV-18) 0.30 Dispersing polymer (P-17) 0.30 Solvent (S-67) 0.20 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing agent (Cpd-8) 0.16 Color mixing inhibitor (Cpd) -5) 0.02 Solvent (S-69) 0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic of polyvinyl alcohol 0.17 Modified copolymer (Modification degree 17%) Liquid paraffin 0.03 In the red-sensitive layer of Sample 401, Samples 402 to 414 were prepared in the same manner as in Sample 401, except that the kind of the polymer for dispersion, the compound of the formula (I) and the kind of the coupler solvent were changed according to Table 6. (The K value of the used polymer is 5th.
Shown in the table) After imagewise exposure of the above photosensitive material, continuous processing (running test) was performed using a Fuji Color Paper Processing Machine PP600 until the replenishment of the tank volume for color development was doubled in the following processing steps.

Rinse solution Ion-exchanged water (3 ppm or less for each of calcium and magnesium) The following tests were conducted on the heat fastness, wet heat fastness and light fastness of each sample processed when the replenishment amount of the color developer was twice the tank capacity. Was done. When left in a dark place at 100 ° C for 8 days, in a dark place at 80 ° C and 70% RH for 10 days, and irradiated with light for 7 days using a xenon fading tester (about 100,000 lux) About each time you do
Tables 7 and 8 show the results of expressing the degree of fading in terms of the density reduction rate for each of the cyan, magenta and yellow colors. (The initial concentration of 1.5 for heat and wet heat test and 1.0 for light test.
From the concentration decrease from ) As is clear from Tables 7 and 8, Example (1)
Also, as shown in Example (2), it can be seen that the combined use of the polymer having the K value of the present invention and the compound of the general formula (I) significantly improves the heat and wet heat fastness of the cyan dye. Also, it can be seen that the light fastness is improved at the same time.

Further, according to the present invention, when a pivaloylacetanilide-based yellow coupler and a benzotriazole-based magenta coupler are used, the overall discoloration balance of yellow, magenta, and cyan is good. It turns out that it is excellent.

Example (5) In the photosensitive materials 401 to 414 used in Example (4), the emulsions of the first, third and fifth layers were respectively EM-1, EM-
Samples 501 to 514 were prepared in which Samples 2 and EM-3 were replaced.
The emulsions used are as follows.

The above photosensitive material was exposed through an optical wedge and processed in the following steps.

 Processing process Temperature Time Color development 35 ° C 45 seconds Bleaching and fixing 30-36 ° C 45 seconds Stable 30-37 ° C 20 seconds Stable 30-37 ° C 20 seconds Stable 30-37 ° C 20 seconds Stable 30-37 ° C 30 seconds Drying 70 8585 ° C. for 60 seconds (4 tank counter-current system to stable →) The composition of each processing solution is as follows.

Color developer Water 800 ml Ethylenediaminetetraacetic acid 2.0 g Triethanolamine 8.0 g Sodium chloride 1.4 g Potassium carbonate 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g N , N- diethylhydroxylamine 4.2 g 5,6-dihydroxybenzene-1,2,4-sulfonic acid 0.3g fluorescent whitening agent (4,4' Jiaminosuchi Ruben system) 2.0 g water to make 1000 ml pH (25 10.1 Bleaching and fixing solution Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 18g Iron (III) ethylenediaminetetraacetate 55g Disodium ethylenediaminetetraacetate 3g Glacial acetic acid 8g Add water 1000ml pH (25 ℃) 5.5 Stabilizer Formalin (37%) 0.1 g Formalin-sulfite adduct 0.7 g 5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4- Isothiazolin-3-one 0.01 g Copper sulphate 0.005 g Water was added to 1000 ml pH (25 ° C) 4.0 Samples 501 to 514 which had been treated were subjected to the same heat fastness test as in Example (4). The same results as in Example (4) were obtained, indicating that the sample of the present invention was excellent in heat fastness regardless of the type of silver halide emulsion or the type of development processing.

Example (6) A multilayer color photographic paper 601 having the following layer constitution was produced on a paper support laminated on both sides with polyethylene. The coating solution was prepared as follows.

Preparation of First Layer Coating Solution To 19.1 g of yellow coupler (Y-17), 4.4 g of color image stabilizer (Cpd-1) and 0.7 g of color image stabilizer (Cpd-7), 27.2 cc of ethyl acetate and solvent (S-10) were added. ) 8.2 g was added and dissolved, and this solution was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution containing 8 cc of 10% sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (cubic mean grain size 0.88
mu, variation coefficient 0.08 of particle size distribution, a blue-sensitive sensitizing dye shown below was added 2.0 × 10 ^-4 mol, respectively per mol of silver contained 0.2 mol% of silver bromide on the grain surface) as a percentage of the total particles A product which was later subjected to sulfur sensitization was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the following composition. Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer.
As the gelatin hardener for each layer, 1-oxy-3, 5-
Dichloro-s-triazine sodium salt was used.

 The following were used as the spectral sensitizing dyes in each layer.

The following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer per mole of silver halide.
8.5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol and 2.5 × 10 ^-4 mol were added.

The following dyes were added to the emulsion layer to prevent irradiation.

(Layer Configuration) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.

Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive layer) Silver chlorobromide emulsion described above 0.30 Gelatin 1.86 Yellow coupler ( Y-17) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (S-10) 0.35 Dispersing polymer (P-17) 0.06 Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture inhibitor (Cpd-5) 0.08 Solvent (S-25) 0.16 Solvent (S-16) 0.08 Third layer (Green sensitive layer) Silver chlorobromide emulsion (cubic, 0.55μ and 0.39μ with average particle size of 1: 3 mixed (Ag (Molar ratio), the coefficient of variation of the particle size distribution is 0.10 and 0.08, respectively, and 0.8 mol% of AgBr is contained locally on the surface of the particles. 0.12 Gelatin 1.24 Magenta coupler (M-5) 0.27 colors Image stabilizer (Cpd-3) 0.15 Color image stabilizer (Cpd-6) 0.02 Color image stabilizer (Cpd-7) 0.03 Solvent S-7) 0.32 Solvent (S-16) 0.22 Fourth layer (ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (Cpd-9) 0.47 Color mixture inhibitor (Cpd-5) 0.05 Solvent (S-69) 0.24 Fifth layer (Red Sensitive Layer) Silver chlorobromide emulsion (cube, average particle size of 0.58μ and 0.45μ mixed at 1: 4 (Ag molar ratio), variation coefficient of particle size distribution is 0.09 and 0.11, respectively. 0.2 mol% of AgBr, each containing 0.6 mol% of AgBr localized in part of the particle surface) 0.23 Gelatin 1.34 Cyan coupler (C-1) 0.13 Cyan coupler (C-14) 0.16 Color image stabilizer (Cpd-8) 0.04 Compound of formula (I) (UV-8) 0.13 Dispersing polymer (P-17) 0.13 Solvent (S-9) 0.10 Solvent (S-71) 0.10 Sixth layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorbing Agent (Cpd-9) 0.16 Color mixture inhibitor (Cpd-5) 0.02 Solvent (S-69) 0.08 Seventh layer (protective layer) Gelatin 1.33 Poly Acrylic of vinyl alcohol 0.17 Modified copolymer (modification degree 17%) Liquid paraffin 0.03 In the red-sensitive layer of Sample 601,
Samples 602 to 607 similar to Sample 601 were prepared except that the compound of the general formula (I) was changed according to Table 10.

(The K value of the polymer used is shown in Table 9.) After processing the light-sensitive material in the same step as the processing used in Example (5), the processed sample was heated at 100 ° C. for 8 hours.
The sample was stored under conditions of 80 days and 70% RH for 10 days, and the same evaluation as in Example (4) was performed.

 Table 11 shows the results.

As is evident from Table 11, this example also shows that the sample of the present invention is superior in both heat fastness and wet heat fastness to the comparative example.

Similar results were obtained with the sample 601 of Example (6) in which the coupler in the green sensitive layer was replaced with M-17, M-18, M-33, and M-34.

(Results of the Invention) According to the present invention, a color photograph having more excellent heat fastness, wet heat fastness and light fastness can be obtained.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Tomokazu Yasuda 210 Nakanuma, Minamiashigara-shi, Kanagawa Fujisha Shin Film Co., Ltd. (56) References JP-A-60-140344 (JP, A) JP-A-58- 149038 (JP, A) JP-A-58-95736 (JP, A) JP-A-62-75447 (JP, A) JP-B-51-39853 (JP, B2)

Claims (3)

(57) [Claims] 1. A method according to claim 1, wherein the support comprises at least one nondiffusible oil-soluble cyan coupler which couples with an oxidized aromatic primary amine developing agent to form a substantially nondiffusible dye. A mixed solution in which at least one compound represented by the following general formula [I] and at least one polymer which is insoluble in water and soluble in an organic solvent and has a relative fluorescence quantum yield (K value) of 0.2 or more, is dissolved. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing a dispersion obtained by emulsification and dispersion. General formula [I] 2. A compound represented by the general formula [I] contained in the mixed solution:
2. The silver halide color photographic light-sensitive material according to claim 1, wherein the melting point of one or a mixture of two or more of the above compounds is 85 ° C. or lower. 3. The silver halide emulsion layer according to claim 1, wherein at least one of said silver halide emulsion layers contains silver halide grains substantially containing no silver iodide and containing at least 80 mol% of silver chloride. Item or the silver halide color photographic light-sensitive material according to Item (2).