JPH0452454B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to color photographic materials, particularly for printing. Prior art and its problems Conventionally, diacylamino-type phenol couplers having acylamino groups at the 2- and 5-positions have been known as cyan couplers for forming cyan dyes in color photographic materials for printing. . The cyan dye formed from this cyan coupler has very little dark fading compared to dyes formed from other cyan couplers, and the cyan color peculiar to cyan dyes fades, yellow increases, and the overall There is also less of a tendency for green to appear. Furthermore, there is little loss during color development, and the process stability is excellent. However, using this cyan coupler in accordance with a conventional method, a blue-sensitive silver halide emulsion layer containing a yellow coupler and a non-light-sensitive first emulsion layer were coated on a reflective support.
an intermediate layer, a green-sensitive silver halide emulsion layer containing a magenta coupler, a non-photosensitive second interlayer containing a UV absorber, a red-sensitive silver halide emulsion layer containing a cyan coupler, a non-photosensitive If a color photographic light-sensitive material for printing is constructed by coating the protective layers in this order, the light resistance will be poor and it will not be practically satisfactory. Purpose of the Invention The present invention was made in view of the above-mentioned circumstances, and its main purpose is to provide a color photographic material that has excellent dark fading resistance and light fading resistance, and has extremely good image storage stability. It is in. As a result of various studies for this purpose, the present inventors found that when using a diacylamino type phenol coupler, a silver halide emulsion layer on the side opposite to the support side, adjacent to the silver halide emulsion layer on the farthest side from the support. The present inventors have discovered that such objects can be achieved when a predetermined ultraviolet absorber is contained in the non-photosensitive layer of the present invention. That is, the present invention has a plurality of silver halide emulsion layers on a reflective support, and at least one of the silver halide emulsion layers contains a cyan coupler represented by the following general formula [], Moreover, a non-photosensitive layer is provided on the side opposite to the support adjacent to the silver halide emulsion layer on the farthest side from the support, and this non-photosensitive layer is formed by ultraviolet rays represented by the following general formula []. This is a color photographic material characterized by containing an absorbent. General formula [] {In the above general formula [], R ₁ and R ₂ each represent an optionally substituted alkyl group, aryl group, or alkenyl group, and Z ₁ represents an atom or group that leaves during coupling. } General formula [] {In the above general formula [], R ₃ , R ₄ and R ₅ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkenyl group, a nitro group or a hydroxyl group. } Specific constitution of the invention The color photographic light-sensitive material (hereinafter referred to as "sensitive material") of the present invention is
It has two or more silver halide emulsion layers, but in a typical embodiment, it has three types of light-sensitive silver halide emulsion layers with different spectral sensitivities, and each emulsion layer has diffusion-resistant yellow, magenta, and yellow emulsion layers. It contains one of three types of couplers: and cyan. In such a case, the combination of a light-sensitive silver halide emulsion layer and a coupler is usually a cyan coupler in the red-sensitive silver halide emulsion layer, a magenta coupler in the green-sensitive silver halide emulsion layer, Furthermore, a yellow coupler is respectively combined with the blue-sensitive silver halide emulsion layer. There is no particular restriction on the order in which the emulsion layers are laminated. However, normally, the emulsion layer containing a yellow coupler, the emulsion layer containing a magenta coupler, and the emulsion layer containing a cyan coupler are coated in this order from the reflective support side. The cyan coupler used in the present invention is one or more of the compounds represented by the above general formula []. To explain the above general formula [] in detail,
R ₁ and R ₂ are each preferably a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. At least one of R ₁ and R ₂ is preferably an alkyl group having a substituent or an aryl group having a substituent. Examples of such substituents include the following. -SO ₂ NR' −, −NR′SO ₂ −, −COO−, −OCO
-, -SO ₂ -, -O-, -NR'SO ₂ NR"- (where R', R" represents a substituted or unsubstituted alkyl group) is an unsubstituted or carboxylic acid group. A group to which an alkyl group substituted with a group, a halogen atom, a heterocyclic group, etc. is bonded, or a group to which an aryl group is bonded, which is unsubstituted or substituted by a carboxylic acid group, a halogen atom, a heterocyclic group, etc.; A plurality of substituted or unsubstituted alkylene groups, substituted or unsubstituted alkyl groups, substituted or unsubstituted arylene groups, or substituted or unsubstituted aryl groups -SO ₂ NR′−,−NR′SO ₂ −,−
COO−, −OCO−, −SO ₂ −, −O−, −NR′SO ₂
Divalent group represented by NR"- (R', R" are as above)
A group formed by connecting multiple . Furthermore, Z ₁ may be any of the atoms or groups that can be separated by various known couplings. Next, typical examples of the cyan coupler represented by the general formula [] will be given.

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[Table] ｜

C ₁₂ H ₂₅

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[Table] The magenta coupler used in the present invention is not particularly limited, but it is preferably one or more of the 5-pyrazolone type, more preferably 1-phenyl-5-pyrazolone type. Among these, one or more of those represented by the following general formula [] is particularly preferred. General formula [] In the above general formula [], X ₁ is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, alkoxy group, aryloxy group,
It represents an amide group, a hydroxy group, a cyano group, or a nitro group, and Y ₁ , Y ₂ and Y ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a nitro group, or an aryloxy group. W ₁ represents a hydrogen atom, a halogen atom or a monovalent organic group, and Z ₂ represents an atom or group that is separated upon coupling. To explain the above general formula [] in more detail, W ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group, and examples of the monovalent organic group include a nitro group, an alkyl group, an alkoxy group, and an acylamino group. group, sulfonamide group, alkylcarbamoyl group, arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, alkylsuccinimide group, alkoxycarboamide group, alkoxycarboalkyl group, each of which may have a substituent. An amino group, an aralkoxycarboalkylamino group, an alkylaminocarboalkylamino group, an arylaminocarboalkylamino group, an aralkylaminocarboalkylamino group, and the like are suitable. Further, Z ₂ may be an atom or group that is separated by various known couplings. Next, a typical example of a magenta coupler represented by the general formula [] will be given. These magenta couplers are known, for example, from US Patent No. 3,684,514, British Patent No. 1,183,515,
-6031, Special Publication No. 6035, Special Publication No. 15754, Special Publication No. 15754
No. 45-40757, 1975-19032, 13041-1981, 129035-129035, 129035-1980
It can be synthesized according to the method described in No. 51-37646 and JP-A No. 55-62454. The yellow coupler used in the present invention is not particularly limited, but is preferably an α-pivaloylacetanilide coupler. Among these, especially one represented by the following general formula []
It is preferable that there be more than one species. In the above general formula [], R ₆ represents a hydrogen atom, a halogen atom or an alkoxy group, and R ₇ is -NHCOR ₇₁ , -NHSO ₂
R ₇₁ , −COOR ₇₁ or

represents a group represented by the formula: (wherein R ₇₁ and R ₇₂ each represent an optionally substituted alkyl group), and Z ₃ represents an atom or group that leaves during coupling. To explain the above general formula [] in more detail, R ₇ is -NHCOR ₇₁ , -NHSO ₂ R ₇₁ , -
COOR ₇₁ or

In the group represented by [Formula], R ₇₁ and R ₇₂ may each be an unsubstituted alkyl group, or substituted aryloxy group, alkoxycarbonyl group, alkylsulfonyl group, sulfonic acid group, aryl It may be an alkyl group substituted with a group, a substituted alkylamide group, or the like. Furthermore, Z ₃ may be any atom or group that can be separated by various known couplings. Among these, it is preferable that Z ₃ is a nitrogen-containing double surface ring group having a bond on the N atom. Next, typical examples of the yellow coupler represented by the above general formula [] will be listed. These yellow couplers are disclosed in, for example, West German Published Patent No. 2057941, West German Published Patent No. 2163812,
JP-A-47-26133, JP-A-48-29432, JP-A-Sho
No. 50-65231, JP-A-51-3631, JP-A-51-
No. 50734, JP 51-102636, JP 51-33410
No., JP 48-66835, JP 48-94432, JP 49-1229, JP 49-10736, JP 52
It can be synthesized according to the method described in, for example, No.-25733. Each of these couplers is contained in the silver halide emulsion layer in an amount of about 0.05 to 1 mole per mole of silver halide. Among such silver halide emulsion layers, a non-photosensitive layer is formed on the emulsion layer furthest from the support, usually on the side opposite to the support of the cyan coupler-containing emulsion layer. This non-photosensitive layer consists of a hydrophilic binder, for example gelatin. This non-photosensitive layer contains an ultraviolet absorber. The ultraviolet absorber used is one or more benzotriazole compounds represented by the above general formula []. Next, typical examples of the ultraviolet absorbent represented by the above general formula [] will be shown. These benzotriazole compounds are disclosed in Japanese Patent Publications No. 36-10466, No. 42-26187, No. 48-5496,
No. 48-41572, U.S. Patent No. 3754919, U.S. Patent No. 4220711
No., etc. Such a UV absorber is contained in an amount of about 0.01 to 2 parts by weight per 1 part by weight of the binder in the non-photosensitive layer. The amount of binder applied in the non-photosensitive layer is usually about 0.1 to 3 g/m ² . In addition, it is preferable to further form a non-photosensitive layer consisting essentially of a binder on the non-photosensitive layer, adjacent to the side opposite to the support side. This greatly reduces the phenomenon known as perspiration, in which the surface loses its luster over time. The amount of binder applied in such a layer is
It is generally about 0.1 to 3 g/m ² . In addition, between the emulsion layer located at least on the support side and the intermediate emulsion layer, and between the intermediate emulsion layer and the emulsion layer located at the farthest side from the support, first and second non-photosensitive layers are provided, respectively. It is preferable to provide a neutral intermediate layer. The second intermediate layer on the side farthest from the support preferably contains the above-mentioned ultraviolet absorber. In this case, the amount of the ultraviolet absorber added is generally about 0.1 to 10 in weight ratio to the amount added in the non-photosensitive layer. This improves light resistance and the effect of preventing fog caused by static. Note that such first and second intermediate layers are
It also has a hydrophilic binder, but the amount of binder applied is preferably 0.1 to 3 g/m ² . On this premise, various methods can be used to disperse the diffusion-resistant coupler in the photosensitive material of the present invention, such as the so-called alkaline aqueous dispersion method, solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. This can be appropriately selected depending on the chemical structure of the diffusion-resistant coupler. In the present invention, a latex dispersion method and an oil-in-water emulsion dispersion method are particularly effective. These dispersion methods have been well known for a long time, and the latex dispersion method and its effects have been described in Japanese Patent Application Laid-open No. 74538/1983.
No. 51-59943, No. 54-32552 and research
Research Disclosure
Magazine, August 1976, No. 14850, pages 77-79. Suitable latexes include, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)
Ethyltrimethylammonium methosulfate, 3-(methacryloyloxy)propane-1
- homopolymers, copolymers and copolymers of monomers such as sulfonic acid sodium salt, N-isopropylacrylamide, N-[2-(2-methyl-4-oxopentyl)]acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, etc. It is a terpolymer. Conventionally known methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method, such as N-butylacetanilide, diethyl lauramide, dibutyl phthalate, tricresyl phosphate, N- One method is to dissolve the above-mentioned diffusion-resistant coupler in a high boiling point solvent such as dodecylpyrrolidone and finely disperse it in a hydrophilic colloid such as gelatin. The silver halide used in the silver halide emulsion layer of the light-sensitive material of the present invention includes conventional silver halides such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Any used in silver halide photographic emulsions are included. These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide. Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100] planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain. These silver halide grains can be prepared by known methods commonly used in the art. It is preferable that soluble salts be removed from the silver halide emulsions used in the light-sensitive materials of the present invention, but those in which soluble salts have not been removed can also be used. It is also possible to use a mixture of two or more silver halide emulsions prepared separately. As the binder for the silver halide emulsion layer or the non-photosensitive layer, conventionally known binders are used.
Suitable examples include gelatin derivatives such as gelatin, phenylcarbamylated gelatin, acylated gelatin, and phthalated gelatin. These binders can be used as a compatible mixture of two or more if desired. A silver halide photographic emulsion in which silver halide grains are dispersed in a binder liquid can be sensitized with a chemical sensitizer. Chemical sensitizers that can be advantageously used in combination in the present invention include noble metal sensitizers,
4 of sulfur sensitizers, selenium sensitizers and reduction sensitizers
It is roughly divided into species. As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium, and platinum can be used. In addition, when using a gold compound, ammonium thiocyanate and sodium thiocyanate can also be used together. As the sulfur sensitizer, in addition to activated gelatin, sulfur compounds can be used. As selenium sensitizers, active and inactive selenium compounds can be used. Examples of reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives. On the other hand, a conventionally known method may be used to incorporate the ultraviolet absorber into the non-photosensitive layer. That is, it is usually dissolved in a high-boiling organic solvent with a boiling point of about 175°C or higher, if necessary in combination with a low-boiling point solvent, and then finely dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. The dispersion may be added to the desired hydrophilic colloid layer. To be more specific, examples of high boiling point solvents include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., especially dimethyl phthalate, diethyl phthalate, dipropylphthalate, di-butyl phthalate, G-n-
Octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate,
Phthalate esters such as diisodecyl phthalate, phosphate esters such as tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl phosphate, triisononyl phosphate), dioctyl sebacate, di-( Sebacic acid esters such as 2-ethylhexyl) sebacate and diisodecyl sebacate, glycerin esters such as glycerol tripropionate and glycerol tributyrate, as well as adipic acid esters, glutaric acid esters, succinic acid esters, maleic acid esters, and fumaric acid. ester, citric acid ester, etc. Then, at the same time, a UV absorber is added to these high boiling point solvents, as necessary, with methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran. , methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, diethylene glycol, monoacetate, acetylacetone,
Dissolved in a low boiling point solvent such as nitromethane, nitroethane, carbon tetrachloride, chloroform (these high boiling point solvents and low boiling point solvents may be used alone or in combination), and alkylbenzene sulfonic acid and alkylnaphthalene sulfone. Anionic surfactants such as acids and/or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolaurate are mixed with an aqueous solution containing a hydrophilic binder such as gelatin, and mixed with a high-speed rotary mixer, colloid mill or It may be emulsified and dispersed using an ultrasonic dispersion device or the like and added to the hydrophilic colloid. In addition to the above-mentioned additives, the photosensitive material of the present invention may also contain stabilizers, development accelerators, hardeners, surfactants, antifouling agents, lubricants, DIR substances, fluorescent brighteners, mordants, or Various other additives useful for photographic materials may also be added. In addition to the silver halide emulsion layer and the non-photosensitive layer, the sensitive material of the present invention may be provided with a back layer or the like as appropriate. As the reflective support for the photosensitive material of the present invention, conventionally known ones such as plastic laminate paper, baryta paper, synthetic paper, etc. can be appropriately selected depending on the purpose of use, and these supports are generally used in the photographic emulsion layer. Various treatments are applied to strengthen the adhesion. Specific Effects of the Invention The light-sensitive material of the present invention is exposed to light through a negative light-sensitive material having an image made of a coupling product, and then subjected to color development processing. The color development process is performed by a normal color development method. That is, first, it is processed with a color developing solution containing a color developing agent. Alternatively, a color developing agent or its precursor is contained in the sensitive material, and this is
Treated with so-called activator liquid. Thereafter, a bleaching step and a fixing step are usually performed according to conventional methods. In this case, the color development process using a color developer or activator liquid, the bleaching process, and the fixing process may be performed independently, but instead of performing two or more processes independently, a process that has these functions is used. It is also possible to carry out once (one bath) using a liquid. For example, a one-bath processing method in which a color developer or activator solution contains both a bleaching agent and a fixing agent as described below, and a bleach-fixing method in which bleaching and fixing are carried out using a bleaching agent and a fixing agent after the color development step. Methods include using a bath. Furthermore, after processing with a color developer or activator solution, desilvering can be carried out by immediately processing with a bleach-fixing bath, etc., but an acid stopping step is provided between the color development step and the bleaching and fixing steps. You can also do that. For such an acidic stop bath, an aqueous solution of acetic acid, citric acid, etc. can be used. Further, steps such as predural mater, neutralization, washing with water, stabilization, etc. can be provided as necessary. Through such color development processing, a dye image is formed on the print sensitive material by a coupling reaction. The color developing agent for the photosensitive material of the present invention is typically an aromatic primary amine color developing agent. Aromatic primary amine color developing agents include aminophenol derivatives and P-phenylenediamine derivatives, and these compounds can be used in the free state or in the form of their hydrochloric acid groups, sulfates, P-toluenesulfonates, Tetraphenylborate, P
It can be used as an organic acid salt such as -(t-octyl)benzenesulfonate. Specific aromatic primary amine color developing agents include O-aminophenol, P-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino -1,4-dimethylbenzene, N,N-diethyl-P-phenylenediamine hydrochloride, N-methyl-P-phenylenediamine hydrochloride, N,N-
Dimethyl-P-phenylenediamine hydrochloride, N-
Ethyl-N-β-methanesulfonamidoethyl-
3-methyl-4-aminoaniline and its sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, N,N-diethyl-3-(β-methanesulfonamidoethyl)-4-aminoaniline hydrochloride, 4-amino-N-(2-methoxyethyl)
-N-ethyl-3-methylaniline-P-toluenesulfonate, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline tetraphenylborate, 4-amino- N-(2-methoxyethyl)-N-ethyl-3-
Methylaniline tetraphenylborate, P
Typical examples include -morpholinoaniline, P-piperidinoaniline, 4-amino-N,N-diethyl-3-chloroaniline, and the like. In some cases, the photosensitive material of the present invention may contain
A color developing agent precursor may also be included. A color developing agent precursor is a compound that can form a color developing agent under alkaline conditions;
Examples include a Schiff base type precursor with an aromatic aldehyde derivative, a polyvalent metal ion complex precursor, a phthalic acid imide derivative precursor, a phosphoric acid amide derivative precursor, a Schüger amine reactant precursor, and a urethane type precursor. Precursors for these aromatic primary amine color developing agents are, for example, U.S. Pat. No. 3,342,599, U.S. Pat.
Specifications of British Patent No. 803783, JP-A-53-
Publications No. 135628 and No. 54-79035, research
Disclosure Magazine No. 15159, No. 12146, No.
Described in No. 13924. These aromatic primary amine color developing agents are
It is usually contained in a color developing solution in an amount of about 1 to 20 g/approx. When it is contained as a precursor in a sensitive material, it is contained in an amount of about 0.5 to 3 moles per mole of silver halide. The color developing solution or activator solution used for the photosensitive material of the present invention includes alkaline agents such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, etc., and sulfurous acid. Sulfites such as sodium and potassium sulfite, sodium bromide, potassium bromide,
It contains bromide salts such as ammonium bromide. Furthermore, if necessary, a known development inhibitor,
Thiocyanates such as sodium thiocyanate, potassium thiocyanate, ammonium thiocyanate, salts such as ammonium chloride, potassium chloride, sodium chloride, ethylene glycol, diethylene glycol, methanol, ethanol, n-butanol, benzyl alcohol, acetone, dimethylformamide, etc. Contains organic solvents, amines such as hydroxylamine, ethanolamine, ethylenediamine, diethanolamine, water softeners such as sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and water-soluble fluorescent brighteners. It's okay. The color developer or activator solution used in the present invention may contain an auxiliary developer. As such an auxiliary developer, 1-aryl-3-virazolidone derivatives are preferred, and are used in an amount of 1 mg to 1 g, preferably 10 mg to 500 mg, per color developer or activator solution.
A typical auxiliary developer is 1-phenyl-3
-pyrazolidone, 4-methyl-1-phenyl-3
-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone,
4-Methyl-4-hydroxymethyl-1-(P-
and tolyl)-3-pyrazolidone. The color developing solution or activator solution used in the present invention is kept alkaline according to a conventional method, and its hydroxyl ion concentration is determined by the type and composition of the negative photosensitive material or print photosensitive material used in the present invention to be processed. The pH may be appropriately selected depending on the purpose and use, but the pH is generally 9.5 to 13.5. The color developing solution or activator solution used in the present invention is generally used within a certain temperature range. The temperature range can be appropriately selected depending on the type, composition, use, purpose, etc. of the printed photosensitive material according to the present invention to be processed, but is preferably 15°C to 70°C, more preferably 30°C to 50°C. As the bleaching agent used in the bleaching or bleach-fixing bath, known compounds can be used, such as ferric complex salts of aminopolycarboxylic acids such as ferric sodium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, Persulfates such as ammonium sulfate and sodium persulfate can be used. Further, as the fixing agent used in the fixing or bleach-fixing bath, known compounds can be used, such as thiosulfates such as sodium thiosulfate and ammonium thiosulfate, 3,6-dithia-
Water-soluble sulfur-containing diols such as 1,8-octanediol, 3,6,9,12-tetrathia-1,14-tetradecanediol, ethylene-bis-thioglycolic acid, ethylene-bis-thioglycolic acid sodium salt Water-soluble sulfur-containing dibasic acids such as the following can be used. Specific Effects of the Invention According to the present invention, a color photographic material is realized which has excellent cyan image fading resistance in both dark and bright colors and has extremely good image storage stability. Furthermore, the color balance in dark fading and bright fading is also good. Furthermore, fog due to static during high-speed coating or transportation within the printer is extremely low. Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown and the present invention will be explained in further detail. Example 1 Each of the following layers was sequentially placed on a support made of polyethylene-coated paper from the support side to produce each sample having the structure shown in Table 1 below. 1st layer Blue-sensitive silver halide emulsion containing yellow coupler (90 mol

[Table] A silver chlorobromide emulsion containing silver bromide containing 300 g of gelatin per mole of silver halide and containing 0.5 mole of exemplary coupler Y-7 dissolved and dispersed in dibutyl phthalate per mole of silver halide. Apply gelatin (2g/ ^m2 ) and dry. 2nd layer 1st intermediate layer (gelatin layer with coated gelatin 1.5g/m ² ) 3rd layer Green-sensitive silver halide emulsion containing magenta coupler (80 mol

[Table] Silver chlorobromide emulsion containing silver bromide, silver halide 1
A coating containing 400 g of gelatin per mole and 0.3 mole of exemplary compound M-22 per mole of silver halide dissolved and dispersed in dibutyl phthalate was coated in an amount of 2 g/m ² of gelatin and dried. 4th layer A second intermediate layer containing an ultraviolet absorber. Exemplary ultraviolet absorber UV-7 was dissolved in 20 g of dibutyl phthalate and dispersed in gelatin, and the amount of ultraviolet absorber was
Coat and dry so that the amount of gelatin is 0.6g/m ² and 1.5g/m ² . 5th layer Red-sensitive silver halide emulsion containing cyan coupler (80 mol

Exemplary coupler C-6, which is a silver chlorobromide emulsion containing silver bromide, containing 300 g of gelatin per mole of silver halide, dissolved and dispersed in dibutyl phthalate,
C-26, C-29 and the following comparative couplers (containing 0.4 mol per mol of silver halide) were coated and dried at a coating weight of 20 g/m ² of gelatin. comparison coupler 6th layer A protective layer containing an ultraviolet absorber. Exemplary UV absorber UV-7 is dissolved in dibutyl phthalate and decomposed into gelatin, which is coated and dried so that the amount of UV absorber is 0.4 mg/m ² and the amount of gelatin is 1.5 g/m ² . For comparison, a protective layer consisting only of gelatin layer containing no ultraviolet absorber was coated and dried so that the amount of gelatin was 1.5 mg/m ² .

[Table] Using a sensitometer (manufactured by Konishiroku Photo Industry, Model KS-7), samples 1 to 7 prepared in this way were examined.
After exposure to blue light, green light, and red light through a light wedge, a color development process was performed according to the following processing steps. Incidentally, the development processing conditions were as follows, and all were carried out in the same manner. Processing process (32.8℃) Processing time Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 3 minutes 30 seconds Drying Color developer composition N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 -Aminoaniline sulfate 4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2.0g Benzyl alcohol 10.0ml Polyethylene glycol (average degree of polymerization 400)
Add 3.0ml water to make 1, and adjust the pH to 10.0 using sodium hydroxide. Bleach-fix solution composition Ethylenediaminetetraacetic acid iron sodium salt
60.0g Ammonium thiosulfate 100.0g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to make 1, and adjust to PH7.0 using sulfuric acid. For each sample having a colored dye image formed by a method with an oxidation-reduction potential of -70 mV or more, a xenon fademeter (WEL-6X-HC model manufactured by Suga Test Instruments) was used.
A light fading test was conducted by exposing the material to xenon light for 500 hours. Also, in a dark place at 70℃80

[Table] A dark fading test was conducted by leaving the product in a constant temperature and humidity room at RH for 500 hours. Then, the dye residual rate (D/Do×
100) was measured using a Sakura color densitometer PDA-60 model (manufactured by Konishi Roku Photo Industries), yellow density was measured using a blue filter, magenta density was measured using a green filter, and cyan density was measured using a red filter. The results are shown in Table 2.

[Table] From the results shown in Table 2, the photosensitive material of the present invention has excellent bright and dark fading resistance for cyan images, and the balance of cyan, magenta, and yellow densities after bright and dark fading is also excellent. Overall, it can be seen that a color photographic material with extremely good image storage stability can be obtained. Example 2 In the same manner as Sample Nos. 5, 6, and 7 of Example 1, after sequentially installing from the support to the 6th layer, a protective layer consisting only of gelatin layer was added as a 7th layer on top of the support. Coat and dry to an amount of 1.0mg/ ^m2 .
Samples Nos. 8, 9, and 10 shown in Table 3 below were prepared.

[Table] Next, exposure and color development treatment was carried out in the same manner as in Example 1, a light fading test and a dark fading test were conducted, and the dye residual rate of the density after the test was measured. The results are shown in Table 4. In addition, after each test, the glossiness of the sample was measured using a glossmeter model VG-103 (Nippon Denshoku Kogyo Co., Ltd.). The results are shown in Table 5. Note that Table 5 also shows the results of Samples Nos. 1 to 5 in Example 1.

【table】

[Table] From the results shown in Tables 4 and 5, it is clear that by providing a protective layer consisting only of a gelatin layer as the seventh layer, a color photographic material with extremely good image storage stability and no loss of gloss over time can be created. You can see what you can get. Example 3 In the same manner as in Example 1 and Example 2, samples Nos. 11 to 17 shown in Table 6 were prepared by sequentially installing up to the 6th layer or the 7th layer. For each of these samples, after performing exposure and color development treatment in the same manner as in Example 1,
A light fading test and a dark fading test were conducted, and the coloring dye residual rate and gloss after the test were measured. The results are shown in Table 7.

【table】

[Table] From the results shown in Table 7, the photosensitive material of the present invention has excellent bright and dark fading resistance for cyan images;
The density of each yellow pigment is well balanced, and overall the image storage stability is very good.
It can be seen that if a protective gelatin layer is provided as a layer, the gloss will not deteriorate over time. Example 4 A sample having the same structure as Sample No. 5 of Example 1 except that the cyan coupler in the fifth layer and the ultraviolet absorbers in the fourth and sixth layers were changed as shown in Table 8. It was created.

[Table] Next, exposure and color development were carried out in the same manner as in Example 1, a light fading test and a dark fading test were conducted, and the residual dye density after the test was measured. The results are shown in Table-9.

[Table] From the results in Table 9, even if the cyan coupler and ultraviolet absorber are changed as shown in Table 8, all the samples according to the present invention have excellent bright and dark fading properties of cyan dye images. I know that there is. Comparative experiment The sixth layer of sample No. 1 of Example 1 was prepared by dissolving UV-7 in dibutyl phthalate and dispersing it in gelatin, and adding an amount of ultraviolet absorber of 0.4 mg/m ² and an amount of gelatin.
The same sample as Sample No. 1 was prepared, except that it was coated and dried to a concentration of 1.5 g/m ² . (Comparative sample No.
26) For the sixth layer of sample No. 1 of Example 1, UV-7 was dissolved in dibutyl phthalate and dispersed in gelatin, and the amount of ultraviolet absorber was 0.4 mg/m ² and the amount of gelatin.
The same sample as Sample No. ¹ was prepared, except that the fourth layer was coated and dried so that the amount of gelatin containing no ultraviolet absorber was 1.5 g/m 2 . (Comparative Sample No. 27) Sample No. 5 except that the fourth layer of Sample No. 5 of Example 1 was coated and dried so that the amount of gelatin containing no ultraviolet absorber was 1.5 g/m ² The same sample was prepared. (Comparative Sample No. 28) These comparative samples were treated in the same manner as in Example 1. The results are shown in the table below.

【table】

Claims (1)

[Scope of Claims] 1. In a color photographic light-sensitive material having a plurality of silver halide emulsion layers on a reflective support, the silver halide emulsion located on the farthest side from the support among the plurality of silver halide emulsion layers. The layer contains a cyan coupler represented by the following general formula [], and a non-photosensitive layer is provided adjacent to the silver halide emulsion layer on the support side and on the opposite side to the support side, respectively, A color photographic material characterized in that these non-photosensitive layers contain an ultraviolet absorber represented by the following general formula []. General formula [] {In the above general formula [], R ₁ and R ₂ are
Each represents an alkyl group or a phenyl group, which may be substituted, and Z ₁ represents an atom or group that is separated upon coupling. } General formula [] {In the above general formula [], R ₃ , R ₄ and R ₅
each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. }