JPH071385B2 - Silver halide color photographic light-sensitive material with excellent raw storage stability - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material excellent in raw storability, and relates to a silver halide color photographic light-sensitive material containing a novel pyrazolotriazole magenta coupler. Is.

BACKGROUND OF THE INVENTION Couplers generally used in silver halide color photographic light-sensitive materials include yellow couplers composed of closed ketomethylene compounds, magenta couplers composed of pyrazolone compounds and pyrazoloazole compounds, cyan couplers composed of phenol compounds and naphthol compounds, and the like. It has been known.

Conventionally, pyrazolone compounds are often used as magenta couplers. Known pyrazolone magenta couplers are described in U.S. Pat. Nos. 2,600,788, 3,519,429, JP-A-49-111631, and JP-A-57-35858.
However, the theory of the photographic proces
s.) Macmillan 4th Edition (1977) pages 356 to 358, Fine Chemical CMC, Volume 14, No. 8, pages 38 to 41, Annual Meeting of the Photographic Society of Japan 1985 (May 23, 1985) ,twenty four
As described on pages 108 to 110 of the abstracts of the lectures in Japan and the Institute of Private Science, dyes formed from magenta couplers composed of pyrazolone compounds have unfavorable side absorption, and their improvement is desired.

As described in the above-mentioned literature, the dye formed from the magenta coupler composed of the pyrazolotriazole compound has no side absorption. The fact that this coupler is a good coupler means that other than the above-mentioned documents, U.S. Pat.
58,309, 3,725,067, etc.

However, this excellent coupler is also not sufficient in terms of color developability, the raw storage stability such as formalin resistance is insufficient, and the light resistance (fastness to light) of the dye formed from the coupler is poor.

[Object of the Invention] An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a pyrazolotriazole-based magenta coupler having improved color-forming property and raw storability, and a dye having excellent light resistance. To provide a silver halide color photographic light-sensitive material containing a pyrazolotriazole-based magenta coupler.

[Structure of the Invention] The present invention has been made to achieve the above object, and a silver halide color photographic light-sensitive material according to the present invention is
In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I]
Is contained in at least one kind of magenta coupler.

General formula [I] [In the formula, R ₁ represents a branched alkyl group having 3 or more carbon atoms other than the α-position, R ₂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkylthio group, an alkylamino group,
It represents an arylamino group, an acylamino group, an alkoxy group or a heterocyclic group, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent. Also n
Represents 1 or 2. [Operation of the Invention] A coupler in which an alkylsulfone group or an arylsulfone group is linked to a pyrazolotriazole nucleus through an alkylene chain having 3 or more carbon atoms is disclosed in Japanese Patent Application Nos. 59-243012 and 60-60.
No. 70197, No. 60-70198, etc., it was found that the coupler of the present invention exhibited a higher color development than expected as compared with the coupler described above, and the above object could be achieved. Although its specific action is not clear, it is thought to be the action of a methylene group or an ethylene group and a branched alkyl group, and the effect was surprising.

[Specific Configuration of the Invention] Hereinafter, the present invention will be described in detail.

The formula [I] will be described in more detail. R ₁ represents a branched alkyl group having 3 or more carbon atoms other than the α-position, and more preferably a β-position branched alkyl group having 5 or more carbon atoms (for example, 2
-Methylbutyl group, 2-ethylhexyl group, 2-ethyloctyl group, 2-hexyldecyl group and the like).

R ₂ is a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, an i-propyl group, an octyl group, a stearyl group, etc.),
Cycloalkyl group (eg cyclohexyl group), aryl group (eg phenyl group, naphthyl group etc.), alkylthio group (eg methylthio group, ethylthio group, laurylthio group, stearylthio group etc.), alkylamino group (eg methylamino group, Dimethylamino group, butylamino group, dioctylamino group etc.), arylamino group (eg anilino group, β-naphthylamino group etc.), acylamino group (eg acetamino group, propionylamino group,
Hexanoylamino group, stearoylamino group, benzoylamino group, etc.), alkoxy group (eg, methoxy group,
An ethoxy group, a dodecyloxy group, etc.) and a heterocyclic group (eg, a pyrazolyl group, etc.), which include those having a substituent. Of these, an alkyl group having 1 to 30 carbon atoms is preferable, and an alkyl group having 1 to 15 carbon atoms is more preferable.

Z represents a hydrogen atom or a group that is released when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. Specifically, a halogen atom (eg chlorine, bromine, fluorine), an alkoxy group (eg ethoxy group, benzyloxy group etc.), an aryloxy group (eg phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group etc.), Acyloxy group (eg acetoxy group, myristoyloxy group, benzoyloxy group etc.), arylthio group (eg phenylthio group, 2-butoxy-5-octylphenylthio group, 2,5-dihexyloxyphenylthio group etc.), alkylthio group ( For example, a methylthio group,
Octylthio group, hexadecylthio group, benzylthio group), sulfonamide group, pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group and the like. Of these, a halogen atom is preferable.

n represents 1 or 2, preferably 2.

Typical examples of the magenta coupler of the present invention are shown below, but the present invention is not limited thereto.

[Exemplified compound] Next, specific synthesis examples of the compound of the present invention are shown below.

Synthesis Example 1 Synthesis of Exemplified Compound (2) (1) Synthesis of compound To 55 g of 2-hexyloctyl bromide and 19.7 g of β-mercaptopropionic acid, 90 ml of ethyl alcohol was added, 24.3 g of potassium hydroxide was further added, and the mixture was heated under reflux for 2 hours. The reaction solution was concentrated, washed with water, acidified with hydrochloric acid, and further washed with water to obtain 57.6 g of a compound. Yield 96.8
%.

Next, 100 ml of water was added to 50 g, heated to 80 ° C., and 45 ml of 35% hydrogen peroxide was slowly added dropwise while stirring. After the dropwise addition, heating was continued for 3 hours, and then ethyl acetate was added and the mixture was washed with water, washed with a 5% potassium hydrogen carbonate aqueous solution, and then 20 g of potassium hydrogen carbonate was added to remove the ethyl acetate layer. Concentrated hydrochloric acid was added to the remaining aqueous layer, ethyl acetate was further added, the mixture was washed with brine, and the ethyl acetate layer was concentrated to give the compound.
53g was obtained. Yield 96.8%.

Next, 68 g of thionyl chloride was added to 53 g, and the mixture was stirred at room temperature for several hours to give 3-methyl-4-ethoxycarbonyl-
5-hydrazine-1H-pyrazole 23.2 g toluene 130 ml
30 g of sodium acetate and 66 ml of water were added, and the mixture was added dropwise. After completion of dropping, the mixture was heated to 85 ° C. to dissolve the solid and remove the aqueous layer.

The toluene layer was cooled, the precipitated solid was filtered off, and recrystallized with 200 ml of ethyl acetate to obtain 53.5 g of a compound. yield
81.4%, melting point 153-155 ° C.

(2) Synthesis of Compound To 80 g of the compound was added 400 ml of distilled toluene, 23.2 g of phosphorus oxychloride was added, and the mixture was heated under reflux for 3 hours. Next, toluene was concentrated, 400 ml of ethyl acetate and 56 ml of water were added,
After removing the aqueous layer, 30.3 g of potassium hydrogen carbonate and 110 ml of water were added, and the mixture was stirred at 70 ° C. for 1 hour. Then, the aqueous layer was removed and the ethyl acetate layer was concentrated to obtain 75.6 g of the compound. To this compound were added 95% sulfuric acid (40 ml), water (40 ml) and acetic acid (80 ml), and the mixture was heated for 9 hours.

The reaction solution was poured into 400 ml of ice water, 240 ml of ethyl acetate was added, the aqueous layer was removed, and the mixture was neutralized with an aqueous potassium hydrogen carbonate solution, and then the ethyl acetate layer was concentrated. Toluene (160 ml) was added to the concentrate to cause precipitation to obtain 34 g of a compound. Yield 5
1.8%, melting point 108.5-110.5 ° C.

(3) Synthesis of Exemplified Compound (2) 50 g of the compound was added to 200 ml of ethyl acetate and 100 ml of chloroform, then 54.3 g of N-chlorosuccinimide was added, and the mixture was stirred at room temperature. After further adding 200 ml of ethyl acetate,
The reaction solution was washed with water, the ethyl acetate layer was concentrated, and recrystallized from 150 ml of acetonitrile to obtain the desired exemplary compound (2). Yield 81.0%, melting point 75-76 ° C.

The coupler of the present invention represented by the general formula [I] (hereinafter,
The coupler of the present invention) can be easily synthesized according to the above synthesis example.

The coupler of the present invention is preferably used alone, but 2
You may use together 1 or more types. The coupler of the present invention is a pyrazolotriazole-based magenta coupler which is not included in the present invention.
You may use together with 1 type or 2 or more types.

The amount of the coupler of the present invention to be used is not limited, but is preferably 0.005 to 2 mol, and more preferably 0.01 to 0.5 mol, per mol of silver halide.

The method for incorporating the coupler of the present invention into a silver halide emulsion layer or the like may be such that it is added as an alkaline solution when the coupler of the present invention is alkali-soluble, and when it is oil-soluble, for example, in the US Patents 2,322,027 and 2,8
01,170, 2,801,171, 2,272,191 and 2,30
No. 4,940 according to the method described in each specification, the coupler of the present invention is dissolved in a high-boiling point solvent, if necessary in combination with a low-boiling point solvent, dispersed in a hydrophilic colloid into fine particles and added to a silver halide emulsion. Preferably. Examples of hydrophilic colloids include gelatin, gelatin derivatives known as photographic binders, and gelatin graft polymers,
Various cellulose derivatives, polyvinyl alcohol partial oxides, sodium alginate, poly-N-vinylpyrrolidone and the like can be widely used. At this time, a hydroquinone derivative, an ultraviolet absorber, a browning inhibitor, etc. may be used in combination, if necessary. Further, two or more couplers of the present invention may be mixed and used. In addition to the above, latex dispersion and methods using other polymers are known.

The method of adding the coupler of the present invention to the silver halide emulsion which is preferable in the present invention will be described in detail. One or more of the couplers of the present invention may be optionally combined with other couplers, hydroquinone derivatives, and browning inhibitors. Acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially di-n-butyl phthalate, tri-cresyl phosphate, triphenyl phosphate, etc. Di-isooctyl azelate, di-n-butyl sebacate, tri-n
-Hexyl phosphate, N, N-di-ethyl-caprylamidobutyl, N, N-diethyllaurylamide, n-pentadecyl phenyl ether, di-n-octyl phthalate, di-iso-dodecyl phthalate, di-n-nonyl Phthalate, 2,4-di-tert-pentylphenol, n
-Nonylphenol, 3-pentadecyl phenyl ethyl ether, 2,5-di-sec-amyl phenyl butyl ether, monophenyl-di-o-chlorophenyl phosphate or a high boiling point solvent such as fluorine paraffin, and /
Or low boiling point of methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, diethylene glycol monoacetate, nitromethane, carbon tetrachloride, chloroform, cyclohexanetetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, etc. Dissolved in a solvent, anionic surfactants such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and / or nonionic surfactants such as sorbitan sesquioleate and sorbitan monolauric acid ester and / or cationic surfactants,
Mix with an aqueous solution containing a hydrophilic binder such as gelatin,
It is emulsified and dispersed by a high-speed rotary mixer, colloid mill, ultrasonic dispersion device, etc. and added to the silver halide emulsion.

In addition to the above, the latex dispersion method and its effects are described in JP-A-49-74538, JP-A-51-59943, JP-A-54-32552 and Research Disclosure, August 1976, No. 14850, 77.
~ P. 79.

Suitable latices include, for example, styrene, acrylates,
n-butyl acrylate, n-butyl methacrylate,
2-acetoacetoxyethyl methacrylate, 2- (methacryloyloxy) ethyltrimethylammonium methosulfate, 3- (methacryloyloxy) propane-1-sulfonic acid sodium salt, N-isopropylacrylamide, N- [2- (2-methyl-4) -Oxopentyl)] acrylamide, 2-acrylamido-2-
Homopolmers, copolymers and terpolymers of monomers such as methylpropanesulfonic acid and the like.

The coupler of the present invention is generally contained in the green-sensitive silver halide emulsion layer, but may be incorporated in an intermediate layer, a protective layer, or in a layer adjacent to the green-sensitive silver halide emulsion layer, if necessary. .

When the silver halide color photographic material of the present invention is constructed in full color, a red-sensitive and blue-sensitive silver halide emulsion layer is provided in addition to the green-sensitive silver halide emulsion layer containing the coupler of the present invention. The coupler contained in the emulsion layer may be a so-called 2-equivalent type or a 4-equivalent type coupler.

The yellow coupler to be contained in the blue-sensitive silver halide emulsion layer includes a closed ketomethylene compound, an active point-o-aryl substituted coupler, an active point-o-acyl substituted coupler, and an active point which are so-called 2-equivalent type couplers. Hydantoin compound-substituted couplers, active-point urazole compound-substituted couplers and active-point succinimide compound-substituted couplers, active-point fluorine-substituted couplers, active-point chlorine or bromine-substituted couplers, active-point-o-sulfonyl-substituted couplers, etc. Can be used. Specific examples of yellow couplers that can be used include U.S. Patents 2,875,057, 3,265,506 and 3,408,1.
No. 94, No. 3,551,155, No. 3,582,322, No. 3,725,072
No. 3,891,445, West German Patent 1,547,868, West German Application Publication No. 2,219,917, No. 2,261,361, No. 2,414,006, British Patent No. 1,425,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 47-26133.
No. 48, No. 48-73147, No. 51-102636, No. 50-6341, No. 50
-123342, 50-130442, 51-21827, 50-87650
No. 52-82424, No. 52-115219, No. 58-95346 and the like.

Further, examples of cyan couplers that can be used in the blue-sensitive emulsion layer of the present invention include phenol type and naphthol type couplers. And these cyan couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Specific examples of the cyan coupler include U.S. Pat.
2,434,272, 2,474,293, 2,521,908, 2,89
5,826, 3,034,892, 3,311,476, 3,458,315
No., No. 3,476,563, No. 3,583,971, No. 3,591,383,
3,767,411, 3,772,002, 3,933,494, 4,0
04,929, West German patent application (OLS) 2,414,830, 2,454,
329, JP-A-48-59838, 51-26034, 48-5055
No. 51, No. 51-146827, No. 52-69624, No. 52-90932, No. 5
Examples thereof include those described in 8-95346 and Japanese Patent Publication No. 49-11572.

Further, as the magenta coupler used in the green-sensitive silver halide emulsion layer according to the present invention, the coupler of the present invention is used, but a pyrazolone-based, pyrazolinobenzimidazole-based or indazolone-based compound may be used in combination. These magenta couplers may be not only 4-equivalent type couplers but also 2-equivalent type couplers like the yellow couplers. Furthermore, a pyrazolotriazole-based coupler other than the present invention can be used in combination. As examples of these, JP-A-59-162548, 59-171956, 60-33552, the same issue,
No. 60-43659, No. 60-191253, etc.

When the coupler of the present invention is used in combination with another coupler in the green-sensitive silver halide emulsion layer, the coupler of the present invention may be used in the range of 1 to 99%.

In the present invention, a non-diffusible DIR compound, a colored magenta or colored cyan coupler, a polymer coupler, a diffusible DIR is contained in a silver halide emulsion layer and other photographic constituent layers.
A coupler such as a compound may be used in combination. For the non-diffusible DIR compound, the colored magenta or the colored cyan coupler, the description in Japanese Patent Application No. 59-193611 by the present applicant,
Regarding the polymer coupler, Japanese Patent Application No.
Reference can be made to the descriptions in No. 59-172151.

For the method of adding a coupler other than the present invention which can be used in the present invention to a photographic constituent layer, the above-mentioned addition method of the coupler of the present invention can be referred to, and the addition amount is not limited, but it is 1 per 1 mol of silver. It is preferably in the range of x10 ^{-3 to} 5 mol, more preferably 1 x 10 ^{-2 to} 5 x 10 ^-1 mol.

The coupler of the present invention can be used in any of the silver halide photographic light-sensitive materials regardless of the type and application thereof, and is particularly advantageously used in, for example, a multilayer negative type color photographic light-sensitive material or color print photographic light-sensitive material. it can. The silver halide used at this time is, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide or silver chloroiodobromide, and these silver halide emulsions are known. Prepared by any method. The silver halide emulsion may be, for example, a so-called conversion emulsion, Lippmann emulsion, covered grain emulsion, or one which has been previously provided with an optical or chemical fog, which is dependent on the type and use of the photographic light-sensitive material. Is appropriately selected. Further, the type of silver halide, the content and mixing ratio of silver halide, the average grain size, the size distribution, etc. are also appropriately selected according to the type and use of the photographic light-sensitive material.

These silver halides are active gelatin: sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, etc .: selenium sensitizers: reduction sensitizers, such as stannous salt, polyamines: noble metal sensitizers, such as gold. Sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2
Sensitizers of aurosulfobenzothiazolemethochloride and the like or water-soluble salts such as ruthenium, rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparamaid, etc. Depending on the amount, it acts as a sensitizer or an antifoggant, etc.): By itself or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer are combined, a gold sensitizer and a selenium sensitizer are combined). It may be chemically sensitized by using together with a sensitizer.

Further, this silver halide can be optically sensitized to a desired wavelength range, and for example, a zero methine dye, a monomethine dye,
Optical sensitization can be carried out individually or in combination (for example, supersensitization) with an optical sensitizer such as a cyanine dye such as a dimethine dye or a trimethine dye, or a merocyanine dye.

As the support that can be used in the light-sensitive material of the present invention, paper, laminated paper (for example, a laminate of polyethylene and paper), glass, cellulose, acetate, cellulose nitrate, polyester, polycarbonate, polyamide, polystyrene, polyolefin, etc. The film-like or sheet-like substrate can be mentioned.
Then, these supports can be subjected to surface treatment such as various hydrophilic treatments for the purpose of improving adhesion to each constituent layer, for example, saponification treatment, corona discharge treatment, subbing treatment,
Processing such as setting processing is performed.

The silver halide photographic light-sensitive material according to the present invention is basically composed of at least a support and a light-sensitive layer provided on the support, but as described above, it is a layer suitable for various positions depending on the purpose. In general, a layer having a plurality of layers is provided. Further, the photosensitive layer itself is a multi-layer comprising a layer containing a relatively high-sensitivity silver halide and a layer containing a relatively low-sensitivity silver halide, which are sensitized in the same wavelength range or different wavelength ranges. It may be configured.

In the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye soluble in water or decolorized by a color development processing solution (AI dye) can be added.
Oxonol dyes, hemioxonol dyes, merocyanine dyes and azo dyes are included. Of these, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include British Patent 58
4,609, 1,277,429, JP-A-48-85130, 49-996
No. 20, No. 49-114420, No. 49-129537, No. 52-108115
No. 59, No. 25845, No. 59-111640, No. 59-111641, U.S. Patent Nos. 2,274,782, 2,533,472, 2,956,879,
3,125,448, 3,148,187, 3,177,078, 3,2
47,127, 3,260,601, 3,540,887, 3,575,70
No. 4, No. 3,653,905, No. 3,718,472, No. 4,071,312,
The thing described in the said 4,070,352 can be mentioned.

These AI dyes are generally 2x per mole of silver in the emulsion layer.
It is preferable to use 10 ^{−3 to} 5 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻² to 1 × 10 ⁻¹ mol.

The silver amount (silver coating amount) of the silver halide emulsion layer in the silver halide color photographic light-sensitive material of the present invention is not limited,
The total amount of the light-sensitive silver halide emulsion layer is preferably 0.3 to 1 g / m ² . That is, in order to obtain excellent image quality, the silver amount is preferably 1 g / m ² or less, while in order to obtain high maximum density and high sensitivity, the silver amount is 0.3 g / m ² or more. Is preferred.

The silver halide color photographic light-sensitive material of the present invention may further contain various photographic additives, for example, antifoggants, stabilizers, and ultraviolet absorbers described in Research Disclosure Magazine 17643. A color stain preventing agent, a fluorescent whitening agent, a color image fading preventing agent, an antistatic agent, a film hardening agent, a surfactant, a plasticizer, a wetting agent and the like can be used.

Specific examples of such photographic additives include stabilizers (mercury compounds, triazoles, azaindenes, quaternary benzothiazolium, zinc or cadmium salts, etc.): quaternary ammonium salts, polyethylene glycols, etc. Sensitizer: Physical property improver, for example, glycerin, dihydroxyalkane such as 1,5-pentadiol, ester of ethylenebisglycolic acid, bisethoxydiethyleneglycol succinate, amide of acrylic acid, polymer emulsion dispersion, etc. : Hardeners such as formaldehyde,
Halogen-substituted fatty acids such as mucochromic acid, mucobromic acid, compounds having acid anhydride groups, dicarboxylic acid chlorides, disulfonic acid chlorides, methanesulfonic acid biesters, dialdehydes in which the aldehyde groups are separated by 2-3 carbon atoms. Sodium bisulfite derivative of aldehyde, bisaziridine, ethyleneimines, etc .; Spreading agents such as saponin, lauryl or oleyl monoether of polyethylene glycol, sulfated and alkylated polyethylene glycol salts, etc .: Coating aids such as sulfosuccinate, etc. Various antistatic agents, antifoaming agents, anti-slip agents, matting agents and the like may be used alone or in combination.

As the ultraviolet absorber preferably used in the present invention, a benzophenone compound (for example, those described in JP-A-46-2784, US Pat. Nos. 3,215,530 and 3,698,907), a butadiene compound (for example, those described in US Pat. No. 4,045,229) ), 4-thiazolidone compounds (see, for example, US Pat.
Nos. 794 and 3,352,681), benzotriazole compounds substituted with an aryl group (for example, Japanese Patent Publication No. 36-1).
No. 0466, No. 41-1687, No. 42-26187, No. 44-29620,
48-41572, JP-A-54-95233, 57-142975, U.S. Patents 3,253,921, 3,533,794, 3,754,919,
Same 3,794,493, same 4,009,038, same 4,220,711, same 4,3
No. 23,633, Research Disclosure (Research.D
22519), benzooxide compounds (for example, those described in US Pat. No. 3,700,455), cinnamic acid ester compounds (for example, US Pat. No. 3,705,
No. 805, No. 3,707,375, and those described in JP-A No. 52-49029) can be used. In addition, U.S. Pat.
No. 2 and those described in JP-A-54-48535 can also be used. UV absorber couplers (for example, α-naphthol cyan dye forming couplers) and UV absorbing polymers (for example, JP-A Nos. 58-111942, 58-178351 and 58-181).
Nos. 041, 59-19945, and 59-23344) and the like can be used.

In the present invention, the light resistance can be further improved by using one or more of these ultraviolet absorbers.

The silver halide color light-sensitive material according to the present invention is generally developed with an aromatic primary amine type color developing agent. The color developing agent is an aromatic primary amine-based compound, and is typically a p-aminophenol-based or p-phenylenediamine-based compound, and specifically, for example, p-aminophenol or diethyl-p-phenylene. Diamine hydrochloride, monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-
5-diethylaminotoluene hydrochloride, 2-amino-5-
(N-ethyl-N-dodecylamino) -toluene, N-
Ethyl-N-β-methanesulfonamide ethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β
-Methanesulfonamidoethyl-4-aminoaniline,
4-N-ethyl-N-β-hydroxyethylaminoaniline, N-ethyl-N-β-methoxyethyl-3-methyl-4-aminoaniline, p-toluenesulfonate,
N-ethyl-N- [2- (2-methoxyethoxy) ethyl] -3-methyl-4-aminoaniline, p-toluenesulfonate, N-ethyl-N- {2- [2- (2-methoxy) Ethoxy) ethoxy] ethyl} -3-methyl-4
-Aminoaniline, p-toluenesulfonate, etc. may be mentioned.

The silver halide color photographic light-sensitive material of the present invention may contain the above-mentioned color developing agent or its precursor.

The above color developing agents may be used alone or in combination of two or more, and the color developing solution may contain various components which are usually added, for example, alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal sulfites and alkali metals. A bisulfite, an alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a thickening agent such as a water softening agent, a development regulator such as citrazinic acid, and the like can be optionally contained. The pH value of this color developing solution is usually 7 or higher, most commonly about 10 to about 13.

However, benzyl alcohol is preferably not added to the color developing solution. That is, benzyl alcohol has a high pollution load value of BOD and COD, and benzyl alcohol has a low water affinity, so diethylene glycol and triethylene glycol are newly required as solvents, but glycols also have BOD and COD. Since the COD is high, the processing liquid discarded due to overflow has a problem of environmental pollution. Further, benzyl alcohol has low solubility in a developing solution, and it takes a long time to prepare a developing solution or a replenishing solution, which is a problem in working. Further, when the replenishing amount is large, the number of times to prepare the replenishing liquid becomes large, which also becomes a work burden.

Therefore, it is very preferable that the color developing solution contains substantially no benzyl alcohol, because environmental pollution and working problems are solved.

The color developing solution used in the present invention can be used in combination with a black and white developing solution. The black-and-white developing solution is what is called a black-and-white first developing solution used in the processing of a commonly known silver halide color photographic light-sensitive material, or one used in the processing of a black-and-white light-sensitive material and is generally added to the black-and-white developing solution. Various well-known additives described above can be contained. A typical additive is 1-phenyl-3-
Developing agents such as pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, calcium bromide, 2-methylbenzimidazole, methylbenzthiazole. Examples thereof include an inorganic or organic inhibitor, a water softening agent such as polyphosphate, and a surface overdevelopment inhibitor composed of a trace amount of iodide or mercapto compound.

In the present invention, after the development treatment with the color developing solution, any treatment can be carried out, such as bleaching, fixing or bleach-fixing, stabilizing, washing with water and stopping.

As the bleaching agent added to the bleaching solution or the bleach-fixing solution,
A metal complex salt of aminopolycarboxylic acid such as an iron (II) complex salt of ethylenediaminetetraacetic acid is preferable. The color development processing may be performed twice or more as in the first and second steps.

The silver halide color photographic light-sensitive material of the present invention is disclosed in JP-A-58-1.
No. 4834, No. 58-105145, No. 58-134634 and No. 58-18631
And Japanese Patent Application Nos. 58-2709 and 59-89288, 61-7162
You may perform water washing alternative stabilization treatment as shown in No. 0 grade.

EFFECTS OF THE INVENTION According to the present invention, a magenta dye image that is fast against light can be obtained, the color developability is good, and the raw storability is good, so that it can be stored for a long time.

[Examples] Next, the present invention will be specifically described with reference to Examples.

Example-1 Magenta couplers of the present invention and comparative couplers as shown in Table 1 were taken in an amount of 0.1 mol per 1 mol of silver, respectively, and the amount of tricresyl phosphate was 1 times the weight of the coupler and the amount of acetic acid was 3 times the weight of the coupler. Ethyl was added and heated to 60 ° C. to completely dissolve it. This solution was added to 120 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
Was mixed with 1,200 ml of a 5% gelatin aqueous solution containing and was emulsified and dispersed by an ultrasonic disperser to obtain an emulsion. After that, 4 kg of this dispersion was added to a green-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide).
And 120 ml of a 2% solution of 1,2-bis (vinylsulfonyl) ethane (water: methanol = 1: 1) was added as a hardening agent, and the mixture was applied onto a transparent polyester base which had been sublimed and dried to obtain Sample 11 ~ 17 (silver coating amount 20mg / 100c
m ² ).

The sample thus obtained is subjected to wedge exposure according to a conventional method, and then the following development process is performed. The results are shown in Table 1.

[Development process] Color development 38 ℃ 3 minutes 15 seconds Bleach 38 ℃ 4 minutes 20 seconds Water wash 38 ℃ 3 minutes 15 seconds Fixing 38 ℃ 4 minutes 20 seconds Water wash 38 ℃ 3 minutes 15 seconds Stabilization 38 ℃ 1 minute 30 seconds Dry 47 ° C ± 55 ° C 16 minutes 30 seconds The composition of the processing solution used in each processing step is as follows.

[Color developer composition] Potassium carbonate 30.0g Sodium hydrogen carbonate 2.5g Potassium sulfite 5.0g Potassium bromide 1.3g Potassium iodide 2.0mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g Ethylenetriamine sodium pentaacetate 2.5g 3-Methyl- 4-amino-N-ethyl-N- (β-hydroxyethyl) -aniline sulphate 4.8g potassium hydroxide 1.2g Water was added to bring the total amount to 1 and potassium hydroxide or 20% sulfuric acid was added to pH 10.06. Adjust to.

[Bleaching composition] Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid 10.0g Ammonium bromide 150.0g Glacial acetic acid 40.0ml Sodium bromate 10.0g Add water to make 1 and use ammonia water or glacial acetic acid.
Adjust to pH 3.5.

[Fixing solution composition] Ammonium thiosulfate 180.0 g Anhydrous sodium sulfite 12.0 g Sodium metabisulfite 2.5 g Ethylenediaminetetraacetic acid disodium 0.5 g Sodium carbonate 10.0 g Add water to make 1.

[Stabilizer composition] Formalin (37% aqueous solution) 2.0 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 5.0 ml Add water to make 1.

1) The specific sensitivity was set to 100 for the sample No. 11 using the comparative coupler 1 by the number of teeth of the exposure amount giving the fog density + 0.19 density.

2) Put the sample in a closed container containing 6 ml of a 0.9% formalin aqueous solution whose temperature and humidity have been adjusted to 32 ° C. and 62% RH for 3 days, and then perform color development. For comparison, a sample not treated with formalin is developed together.

As is clear from Table 1, it was confirmed that the samples according to the present invention had a high maximum concentration without lowering the sensitivity, were excellent in formalin resistance, and had good raw storage stability.

Example-2 Sample Nos. 11 to 17 in Example-1 were similarly wedge-exposed and then subjected to the following development processing. The results are shown in Table 2.

[Development processing step] Color development 38 ° C 3 minutes 30 seconds Bleach-fixing 33 ° C 1 minute 30 seconds Stabilization treatment 25-30 ° C 3 minutes (or washing with water) Drying 75-80 ° C About 2 minutes In each processing step The composition of the treatment liquid used is as follows.

[Color developer] Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 0.7g Sodium chloride 0.2g Potassium carbonate 30.0g Hydroxylamine sulfate 3.0g Polyphosphoric acid (TPPS) 2.5g 3-Methyl-4-amino-N -Ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate 5.5g Optical brightener (4,4'-diaminostilbenz sulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1 And adjust the pH to 10.20.

[Bleach fixer] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.g Ethylenediaminetetraacetic acid 3.0g Ammonium thiosulfate (70% solution) 100.0ml Ammonium sulfite (40% solution) 27.5ml Glacial acetic acid 10.0ml Potassium carbonate or glacial acetic acid Adjust the pH to 7.1 with and add water to bring the total to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10.0 g Water is added to bring the total amount to 1.

1) The specific sensitivity was set to 100 for the sample No. 2-11 using the comparative coupler by the number of teeth of the exposure amount giving the fog density +0.11 density.

2) The sample after the color development treatment was irradiated on a xenon fade meter for 5 days, and the% dye remaining after the treatment at the initial density D = 1.0 was shown.

As is clear from Table 2, it was confirmed that the samples according to the present invention had a high maximum density without a decrease in sensitivity, excellent light resistance, no fading of magenta images, and good storage stability.

Example-3 A silver halide color photographic light-sensitive material was prepared by sequentially coating the following layers on a polyethylene resin-coated paper containing anatase type titanium oxide.

The following addition amounts are based on 100 cm ² .

(1) 20 mg of gelatin, 5 mg of silver-sensitive silver chlorobromide emulsion (containing 80 mol% of silver bromide), and 8 mg of yellow coupler ^* and 0.1 mg of 2,5-di-t-octylhydroquinone. , A layer containing 3 mg of di-octyl phthalate (coupler solvent).

(2) An intermediate layer containing 12 mg of gelatin, 0.5 mg of 2,5-di-t-octylhydroquinone, 4 mg of UV absorber ^* , and 2 mg of dibutyl phthalate (UV absorber solvent).

(3) 18 mg of gelatin, 4 mg of silver-sensitive silver chlorobromide emulsion (containing 70 mol% of silver bromide), 5 mg of magenta coupler ^* , 2 mg of antioxidant ^* and 0.2 mg of 2,5. A layer containing di-t-octylhydroquinone, 2.5 mg dioctyl phthalate (coupler solvent).

(4) An intermediate layer containing the same composition as (2).

(5) 16 mg of gelatin, 4 mg of silver-sensitive silver chlorobromide emulsion (containing 70 mol% of silver bromide), and 3.5 mg of cyan coupler ^* and 0.1 mg of 2,5-di-t-octyl. Layer containing hydroquinone, 2.0 mg tricresyl phosphate (coupler solvent).

(6) An intermediate layer containing the same composition as (2).

(7) A protective layer containing 9 mg of gelatin.

* As UV absorbers (2), (4), and (6), UV-1 and UV-2 having the following structures were mixed (mixing ratio 1: 1) and used.

* As the antioxidant of (3), di-t-pentylhydroquinone-di-octyl ether was used.

The above-mentioned multilayer photosensitive material was processed in the same manner as in Example-2.
Table 3 shows the yellow coupler, magenta coupler, and cyan coupler used in each layer, and the results.

Each sample was measured for magenta density after white exposure.

The specific sensitivity and light resistance were measured by the same method as in Example-2.

It is clear from Table 3 that the dye image of the coupler of the present invention is excellent in light fastness, and that it is further improved by using an ultraviolet absorber.

UV absorber Yellow coupler Cyan coupler Example-4 A multilayer color photographic light-sensitive material sample 51 was prepared by sequentially coating each layer having the composition shown below from the support side on a triacetyl cellulose film support. The addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Preparation of Sample 51 (Comparative) First layer: Antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size () 0.30 μm, AgBrI containing 6 mol% AgI Monodisperse emulsion (Emulsion I) ... Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-5): 1 mol of silver In contrast, 0.06 mol Colored cyan coupler (CC-1) ... 0.003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2) ... silver 1 0.002 mol per mol Fourth layer: High-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average particle size () 0.5 μm, AgI containing 7.0 mol% AgBrI monodisperse emulsion (Emulsion II) .. Silver coating amount 1.3 g / m ² Sensitizing dye I …… 3 × 10 ^-5 mol for 1 mol of silver Sensitizing dye II …… 1.0 × 10 ^-5 mol for 1 mol of silver Cyan coupler (C-5 ) …… 1 silver To 0.02 mol Colored cyan coupler (CC-1) ... 0.0015 mol to 1 mol of silver DIR compound (D-2) ... 0.001 mol to 1 mol of silver Fifth layer: intermediate layer (IL) A gelatin layer with the same composition as the two layers.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Silver coating amount 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per 1 mol silver Dye IV: 1.2 × 10 ^-5 mol / mol silver Magenta coupler (M-1): 0.050 mol / mol silver Colored magenta coupler (CM-1): 1 mol silver 0.009 mol DIR compound (D-1) ... 0.0010 mol per 1 mol of silver DIR compound (D-3) ... 0.0030 mol per 1 mol of silver Seventh layer: high-sensitivity green-sensitive silver halide emulsion layer ( GH-1) Emulsion-II …… Silver coating amount 1.4g / m ² Sensitizing dye III …… 1.5 × 10 ⁻⁵ mol per 1 mol silver Sensitizing dye IV …… 1.0 × 10 per 1 mol silver ^-5 mol magenta coupler (M-1) ...... silver mole with respect to 0.002 mol colored magenta coupler (CM-1) 0.020 mol of DIR compound against ...... silver mole (D-3) ...... silver 0.0010 mol eighth layer moles: Gelatin layer containing an emulsified dispersion of the yellow filter layer Yellow colloidal silver and 2,5-di -t- octylhydroquinone.

Ninth layer: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size () and 6.0 mol% AgI, silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ^-5 mol for 1 mol of silver Yellow coupler (Y-3): 0.29 mol for 1 mol of silver 10th layer: High-sensitivity blue-sensitive silver halide emulsion layer (BH -1) Average particle size () 0.8 μm, AgBrI containing 15 mol% AgI Monodisperse emulsion (Emulsion IV) Silver coating amount 0.5 g / m ² Sensitizing dye V: 1.0 × 10 1 mol of silver ^-5 mol Yellow coupler (Y-3) ... 0.08 mol to 1 mol of silver DIR compound (D-2) ... 0.0015 mol to 1 mol of silver 11th layer: first protective layer (Pro-1) Silver iodobromide (AgI 1 mol%, average particle size (r) 0.07μ
m) ... Silver coating amount 0.5g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2 (mixing ratio 1: 1).

12th layer: 2nd protective layer (Pro-2) Polymethylmethacrylate particles (average diameter 1.5 μm)
And a gelatin layer containing formalin scavenger (HS-1) In addition to the above composition, each layer contains a gelatin hardener (H
-1) and a surfactant were added.

Further, a sample was prepared in the same manner as the sample 51 except that the M-1 of the layers 6 and 7 in the sample 51 was changed to the coupler (2) of the present invention.
Created 52.

The compounds contained in each layer of each sample are as follows.

Sensitizing dye I: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II: Anhydro-9-ethyl-3,3 ′ -The-
(3-Sulfopropyl) -4,5,4 ', 5'-di-benzothiacarbocyanine hydroxide Sensitizing dye III: anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-Sulfopropyl) oxycarbocyanine hydroxide Sensitizing dye IV: anhydro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V: anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo- 5'-methoxythiacyanine The sample Nos. 51 to 52 thus obtained were subjected to wedge exposure using white light and then subjected to the following development processing.

[Development process] (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Processing solution used in each processing step The composition is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water and adjust to pH = 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

Formalin resistance of magenta images was determined for these samples in the same manner as formalin resistance was determined in Example-1. The results obtained are shown in Table 4.

As is clear from Table 4, the use of the magenta coupler of the present invention made it possible to obtain a light-sensitive material having extremely good formalin resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenzo Nakayama 1 Sakura-cho, Hino-shi, Tokyo Photo Konishi Roku Photo Industry Co., Ltd. (72) Katsutoshi Kato 1 Sakura-cho, Hino-shi, Tokyo Photo Roku Konishi Photo Co., Ltd. In-house (56) References JP 61-120152 (JP, A) JP 61-65245 (JP, A)

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one of the silver halide emulsion layers is represented by the following general formula [I]. A silver halide color photographic light-sensitive material containing at least one magenta coupler. General formula [I] [In the formula, R ₁ represents a branched alkyl group having 3 or more carbon atoms other than the α-position, and R ₂ hydrogen atom, an alkyl group, a cycloalkyl group,
It represents an aryl group, an alkylthio group, an alkylamino group, an arylamino group, an acylamino group, an alkoxy group or a heterocyclic group, and Z represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent. N is 1
Or represents 2. ]