JPH05303181A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide color photographic sensitive material improved in light resistance of a dye image and excellent in storage stability of an image by incorporating a specified pyrazolotriazole type magenta coupler. CONSTITUTION:The silver halide color photographic sensitive material contains at least one of the pyrazolotriazole type magenta couplers represented by formulae I and II in which each of R1-R3 and R5-R7 is alkyl; each of R4 and R8 is a substituent; each of L1 and L2 is alkylene: and each of X and Y is H or a group to be released by coupling with the oxidation product of a color developing agent. As a silver halide emulsion to be used, one such as silver bromide, iodide, iodochloride, chlorobromide, chloroiodobromide, or chloride, used for usual silver halide emulsions may be used. The silver halide grains may have a uniform silver halide composition and may be composed of core-shell type grains different in silver halide composition between the inside and the surface layer of each grain.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material excellent in image storability and color reproducibility.

[0002]

2. Description of the Related Art Conventionally, a combination of a yellow coupler, a magenta coupler and a cyan coupler is used in a color photographic paper which has been used for direct viewing. Many efforts have been made to date to improve the fastness of color dye images obtained from these couplers and to preserve and continue to utilize them for many years.

However, it is still not sufficient to meet the user's desire to prevent fading and discoloration of dye images in color photographs and to store high quality images semipermanently. In terms of storability in dark places such as albums, in recent years, significant improvements have been made as represented by "Konica Color 100 Years Print", and it has become possible to store photographic images for a long time that is satisfactory. On the other hand, the storage stability under the light (light resistance) under the condition of being exposed to light is still at an insufficient level, and improvement is desired. In particular, among the three color dyes of yellow, magenta, and cyan, the magenta dye has the weakest light resistance, and efforts have been made to improve it.

Further, the recently developed pyrazoloazole-based magenta couplers are different from 5-pyrazolone-based magenta couplers that have been conventionally used, and since the coloring dye has no secondary absorption around 430 nm, basically the color reproducibility is improved. It is known that the magenta dye obtained from the pyrazoloazole-based magenta coupler is inferior in light resistance to the magenta dye obtained from the 5-pyrazolone-based magenta coupler, though it is characterized by being advantageous to However, many improved techniques have been proposed. For example, JP-A-56-1
59644, 59-125732, 61-145552, 60-262159
No. 61-90155, JP-A-3-39956 and the like, and phenol or phenyl ether compounds, JP-A-61
-73152, 61-72246, 61-189539, 61-189540
Nos. 63-95439 and the like amine compounds, JP-A-61-140941, 61-145554, 61-158329, 62-
It is possible to use the metal complexes described in 183459, etc., the inclusion compounds described in JP-A No. 2-100048, the heterocyclic compounds and the like. However, when these compounds are used, the color density of the coupler is lowered, color contamination occurs during storage over time, color contamination occurs due to coloring of the added compound itself, and an undesirable change in color tone is caused. Or, the dispersibility of the dispersion containing the coupler may deteriorate, and the stability over time may deteriorate. Further, although the above-mentioned improved technology shows a great effect in improving the light resistance, the light resistance of the magenta dye is nevertheless improved. Is currently inferior to the light resistance of yellow dyes and cyan dyes, and as a result, the color balance of the image is disrupted during the fading process, causing the colors of the photograph to shift toward yellow and cyan, causing unnatural discoloration. There is a problem that it ends up. Further, a technique for improving light resistance by substituting a branched alkyl group having a large steric hindrance to the pyrazolotriazole skeleton is proposed in JP-A-61-65245 and the like, but in this case, light resistance is improved. There arise problems such as broad absorption of the generated dye and deterioration of color developability. Therefore, in order to improve the light resistance, it is strongly desired to develop a new technology.

[0005]

SUMMARY OF THE INVENTION It is, therefore, a first object of the present invention to provide a silver halide color photographic light-sensitive material which has improved light resistance of dye images and excellent image storability. A second object of the present invention is to provide a silver halide color photographic light-sensitive material excellent in color reproducibility.

[0006]

The above object of the present invention is to provide a compound represented by the following general formula [I]
Alternatively, it is achieved by a silver halide color photographic light-sensitive material characterized by containing at least one pyrazolotriazole type magenta coupler represented by the general formula [II].

[0007]

[Chemical 5]

[Wherein R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇
Represents an alkyl group, and R ₄ and R ₈ represent a substituent. L ₁ ,
L ₂ represents an alkylene group. X and Y represent a hydrogen atom or a group capable of splitting off in correspondence with the oxidized product of the color developing agent. ] More preferably, the general formula [I] or the general formula [II]
A silver halide color photographic light-sensitive material containing a magenta coupler-containing silver halide emulsion layer represented by the following formula and at least one compound represented by the following formula [III] or [IV].

[0009]

[Chemical 6]

[In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue.

[0011]

[Chemical 7]

Here, R ₂₁ a, R ₂₁ b and R ₂₁ c each represent a monovalent organic group. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆
Each represents a hydrogen atom, a halogen atom, or a group capable of substituting for a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- or 6-membered ring. ]

[0013]

[Chemical 8]

[In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring together with a nitrogen atom. The present invention will be described in more detail below.

The alkyl group represented by R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ may be linear, branched or cyclic, and may be substituted with another substituent. well,
Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, a neopentyl group, a chloromethyl group, a hydroxymethyl group and a methoxymethyl group.

Among the substituents represented by R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ , preferred is an alkyl group, and more preferred is a methyl group.

Examples of the group represented by X and Y and capable of splitting off upon reaction with the oxidation product of the color developing agent include, for example, a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen containing N atom Examples thereof include heterocyclic groups, alkyloxycarbonylamino, aryloxycarbonylamino, and carboxyl groups, with halogen atoms being preferred, and chlorine atoms being particularly preferred.

The substituent represented by R ₄ and R ₈ is not particularly limited, but typically, each group such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like is used. In addition to these, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxyfulvonylamino, alkoxycarbonyl, aryloxycarbonyl , Heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro, sulfonic acid, and other groups, and spiro compound residues,
Examples include bridged hydrocarbon compound residues.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group. Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group. Examples of the alkyl component and the aryl component in the alkylthio group and the aryl rethio group include the above alkyl groups and aryl groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 to 32 carbon atoms.
7 is preferable, and the alkenyl group may be linear or branched. The cycloalkenyl group is preferably one having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as a sulfamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, etc .; as an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; as a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; The ureido group is an alkylureido group, an arylureido group, etc .; The sulfamoylamino group is an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; Of these, 5- to 7-membered ones are preferable, and specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, l-tetrazolyl group and the like; heterocyclic oxy The group preferably has a 5- to 7-membered heterocycle, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group and the like; as a heterocyclic thio group Is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5triazole.
-6-thio group, etc .; siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group, succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc. Spiro [3.3] heptan-1-yl, etc. as spiro compound residues; bicyclo [2.2.l] heptan-1-yl, tricyclo [3.3.1.] As bridged hydrocarbon compound residues;
1 ^3.7 ) Decan-1-yl, 7,7-dimethyl-bi-cyclo (2.2.
1] heptane-l-yl and the like.

The alkylene group represented by L ₁ and L ₂ may be linear, branched or substituted and preferably has 1 to 30 carbon atoms.

The typical examples of the magenta coupler according to the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 9]

[0026]

[Chemical 10]

[0027]

[Chemical 11]

[0028]

[Chemical 12]

[0029]

[Chemical 13]

[0030]

[Chemical 14]

[0031]

[Chemical 15]

[0032]

[Chemical 16]

[0033]

[Chemical 17]

[0034]

[Chemical 18]

[0035]

[Chemical 19]

[0036]

[Chemical 20]

[0037]

[Chemical 21]

[0038]

[Chemical formula 22]

[0039]

[Chemical formula 23]

[0040]

[Chemical formula 24]

[0041]

[Chemical 25]

[0042]

[Chemical formula 26]

[0043]

[Chemical 27]

[0044]

[Chemical 28]

[0045]

[Chemical 29]

[0046]

[Chemical 30]

The couplers of the present invention are well known in the art, for example, JP-A-63 / 63
It can be synthesized according to the synthesis method described in -64046.

The synthetic examples of the compounds of the present invention are shown below.

[Synthesis Example] Synthesis of Exemplified Compound 54

[0050]

[Chemical 31]

Synthesis of (A) 52.2 g of β-alanine and 93.8 g of phthalic anhydride were placed in a 500 ml reactor and heated in an oil bath having a bath temperature of 160 ° C. for 1 hour. To the molten reaction product, 500 ml of ethanol was added, dissolved by heating, and then cooled to room temperature to precipitate crystals. The crystals were filtered to obtain 126,1 g of (A).

Synthesis of (B) To 8.7 g of (A), 60 ml of chloroform and 10 ml of thionyl chloride were added, and the mixture was heated under reflux for 2 hours and then concentrated under reduced pressure.
I got 0g.

Synthesis of (D) To 6.0 g of (C), 30 ml of an aqueous solution in which 100 ml of ethyl acetate and 3.3 g of sodium acetate were dissolved was added and suspended, and 8.5 g of (B) was added thereto and stirred at room temperature for 3 hours. .. The aqueous layer was removed, the ethyl acetate layer was washed twice with an aqueous sodium hydrogen carbonate solution, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain (D) 6.2g.

Synthesis of (F) To 6.0 g of (D) was added 100 ml of phosphorus oxychloride, and the mixture was heated under reflux for 3 hours. Then, the mixture was concentrated under reduced pressure, ethyl acetate and aqueous potassium hydrogen carbonate solution were added to the residue to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure to obtain (E). (E) proceeded to the next reaction without purification. 10 ml of concentrated sulfuric acid, 10 ml of water and 30 ml of acetic acid were added to 5.2 g of (E), and the mixture was heated under reflux for 6 hours. Water in which ethyl acetate and potassium carbonate were dissolved was added to the reaction solution to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain (F) (3 g).

Synthesis of (G) To 3.0 g of (F) was added 50 ml of chloroform, and 1.2 g of N-chlorosuccinimide was added over about 2 hours while stirring at room temperature. After reacting for 2 hours at room temperature, the mixture was concentrated under reduced pressure, ethyl acetate and water were added to the residue to adjust the pH to 7 to 8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give (G) 2.
8g was obtained.

Synthesis of (H) (G) 2.8 g ethanol 30 ml hydrazine hydrate 0.5 ml, water
1.3 ml was added and the mixture was heated under reflux for 6 hours. Then, it was cooled to room temperature and concentrated under reduced pressure. 50 ml of water and 5 ml of concentrated hydrochloric acid were added to the residue, and the mixture was heated under reflux for 2 hours. After cooling to room temperature, the precipitated by-product was filtered, and the third liquid was concentrated under reduced pressure. Add 15 ml of acetonitrile to the residue and keep it suspended under ice cooling.
After stirring for 30 minutes, the crystal was filtered to obtain 1.4 g of (H).

Synthesis of Exemplified Compound 54 To 1.4 g of (H) was added 30 ml of ethyl acetate and 20 ml of an aqueous solution in which 0.4 g of sodium hydrogen hydroxide was completely dissolved, and the mixture was stirred at room temperature for 30 minutes. Further, 20 ml of an aqueous solution in which 0.4 g of sodium acetate was completely dissolved was added. 20 ml of ethyl acetate in which 1.6 g of (I) was completely dissolved was added dropwise thereto at room temperature, and after the addition, the mixture was stirred at room temperature for 1 hour. The aqueous layer was removed, and the ethyl acetate layer was added with an aqueous sodium hydrogen carbonate solution to adjust the pH
7-8, the aqueous layer was removed, and the ethyl acetate layer was concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 1.5 g of Exemplified compound 54. The structures of these compounds were confirmed by NMR, IR and mass spectra.

Other couplers according to the present invention can also be synthesized by a method similar to the above synthesis method. It is preferable that the silver halide emulsion layer containing the coupler of the present invention contains at least one of the compounds represented by the above general formula [III] or [IV].

In the general formula [III], the alkyl group represented by R ₂₁ is represented by R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ in the general formula [I] or [II]. The groups described as the alkyl group are exemplified. The aryl group and heterocyclic group represented by R ₂₁ are not particularly limited, but the aryl group is preferably a phenyl group, and the heterocyclic group is
5- to 7-membered ones are preferable, specifically 2-furyl group, 2-
Examples thereof include a thienyl group, a 2-pyridinyl group and a 2-benzothiazolyl group.

Examples of the monovalent organic group represented by R _21a , R _21b and R _21c include an alkyl group, an aryl group, an alkoxy group, an aryloxy group and a halogen atom.

R ₂₁ is preferably a hydrogen atom or an alkyl group. Examples of the group capable of substituting the benzene ring represented by R _{22 to} R ₂₆ include a hydrogen atom, a hydroxy group, alkyl, alkenyl, cycloalkyl, aryl, heterocycle, acylamino, halogen atom, sulfonyl, sulfinyl, phosphonyl, acyl, Carbamoyl, cyano, alkoxy, aryloxy, heterocyclic oxy, acyloxy, amino,
Anilino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbamoylamino, aryloxysulfamoylamino, alkoxycarbonyl, aryloxycarbonyl, arylsulfonyl,
Examples thereof include alkylthio, arylthio, heterocyclic thio, and carboxyl groups.

As R ₂₂ , R ₂₃ , R ₂₅ and R ₂₆ , a hydrogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group and an acylamino group are preferable, and R ₂₄ is an alkyl group and a hydroxy group. , Aryl groups, alkoxy groups, aryloxy groups, arylthio groups, and arylsulfonyl groups are preferable.

R ₂₁ and R ₂₂ may be ring-closed to each other to form a 5- or 6-membered ring, and at that time, R ₂₃ or R ₂₄ is preferably a hydroxy group, an alkoxy group or an aryloxy group. R ₂₁ and R ₂₂ may be closed to form a methylenedioxy ring. Furthermore, R ₂₃ and R ₂₄ may be closed to form a 5-membered hydrocarbon ring, and at that time, R ₂₁ is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

Specific examples of the compound represented by the general formula [III] are shown below.

[0065]

[Chemical 32]

[0066]

[Chemical 33]

In addition to the above specific examples, the above general formula [III]
Specific examples of the compound represented by: JP-A-60-262159
Exemplified Compounds A-1 to 1 described in pages 11 to 13 of the publication
A-28, the exemplified compounds PH-1 to PH-29 described on pages 8 to 10 of JP-A 61-145552, and the examples described on pages 6 to 7 of JP-A-1-306846. Compounds B-1 to B-
21, Exemplified compounds I-1 to I-13, I'-1 to I'-8, II-1 to II described on pages 10 to 18 of JP-A 2-958.
-12, II'-1 to II'-21, III-8 to III-14, IV-1
~ IV-24, V-13 to V-17, No. 3-39956, page 10 to 1
Exemplified compounds II-1 to II-33 described on page 1 may be mentioned.

Next, in the above general formula [IV], R ₃₁ represents an aliphatic group or an aromatic group, preferably an alkyl group,
An aryl group and a heterocyclic group are preferred, and an aryl group is most preferred. Examples of the heterocycle formed by Z together with the nitrogen atom include a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a thiomorpholine-1,1-dione ring and a pyrrolidine ring.

Specific examples of the compound represented by the general formula [IV] are shown below.

[0070]

[Chemical 34]

In addition to the above specific examples, specific examples of the compound represented by the above general formula [IV] include Exemplified Compound B-described on pages 8 to 11 of JP-A-2-167543. 1-B-
65, exemplary compounds (1) to (120) described on pages 4 to 7 of JP-A-63-95439, and the like.

The amount of the compound represented by the general formula [III] or [IV] added is 5 to 50 with respect to the coupler of the present invention.
0 mol% is preferable, and 20 to 200 mol% is more preferable.

Further, in the silver halide emulsion layer containing the coupler of the present invention and the non-color forming compound of the present invention, JP-A-61-158 is used.
The metal chelate compounds described in Nos. 329 and 62-183459 may be used. In order to incorporate the magenta coupler used in the present invention into the emulsion, a conventionally known method may be used. For example, tricresyl phosphate, a high boiling point organic solvent having a boiling point of 175 ° C. or higher such as dibutyl phthalate, or a low boiling point solvent such as ethyl acetate or butyl propionate is used alone or as a mixture thereof according to the present invention. The magenta coupler, alone or in combination, is dissolved, mixed with an aqueous gelatin solution containing a surfactant, and then emulsified with a high speed rotary mixer or a colloid mill, and then added to silver halide for use in the present invention. A silver halide emulsion can be prepared.

The magenta coupler according to the present invention is usually 1 × 10 ^-3 to 1 mol, preferably 1 ×, per mol of silver halide.
It can be used in the range of 10 ⁻² to 8 × 10 ⁻¹ mol.

The magenta coupler according to the present invention can be used in combination with other types of magenta couplers.

The silver halide composition preferably used in the present invention is silver chloride, silver chlorobromide or silver chloroiodobromide. Further, it may be a combination mixture such as a mixture of silver chloride and silver bromide.

The silver halide emulsion used in the present invention is a conventional silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Any of the above can be used.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

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

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used.

Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The grain size of silver halide grains is preferably from 0.05 to 30 μm, more preferably from 0.1 to 20 μm.

The silver halide emulsion having any grain size distribution can be used. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The couplers used in the present invention include a development inhibitor, a development accelerator, a bleaching accelerator, a developer and a silver halide solvent by coupling with a colored coupler having a color correcting effect and an oxidized product of a developing agent. , Toning agents, hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers, which release photographically useful fragments. Of these, a so-called DIR compound which releases a development inhibitor with development and improves the sharpness of images and the graininess of images may be used.

In this DIR compound, a compound in which an inhibitor is directly bonded to the coupling position and a compound in which the inhibitor is bonded to the coupling position via a divalent group and which is separated by the coupling reaction A compound (referred to as a timing DIR compound) that is bound so as to release the inhibitor by an intramolecular nucleophilic reaction or an intramolecular electron transfer reaction is included. Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application.

A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can be used in combination with a dye-forming coupler.

Examples of yellow couplers preferably used in the present invention include known acylacetanilide type couplers. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds can be advantageously used.

Examples of cyan couplers preferably used in the present invention include phenol or naphthol type couplers.

Between the emulsion layers of the light-sensitive material (the same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity or deterioration of sharpness. Also, a color antifoggant can be used to prevent the graininess from being conspicuous.

An image stabilizer which prevents deterioration of a dye image can be used in the light-sensitive material of the present invention. Compounds which can be preferably used are those described in Item VII J of RD17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the light-sensitive material contain a UV inhibitor in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction and the like and to prevent deterioration of the image by UV rays. You can leave.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

The present invention can be preferably applied to color negative films, color papers, color reversal films and the like.

Color negative films, color papers, and color reversal films are generally composed of a blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer. There are no restrictions on the arrangement of the layers.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is carried out after exposure.

The color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step, and a stabilizing processing step if necessary, and a processing step using a bleaching solution and a processing using a fixing solution. Instead of the steps, the bleach-fixing treatment step can be carried out using a one-bath bleach-fixing solution, or the monobath treatment step using the one-bath developing bleach-fixing solution can be carried out for color development, bleaching and fixing. ..

[0097]

EXAMPLES The present invention will now be described based on examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a support having polyethylene laminated on one side of a paper support and polyethylene containing titanium oxide on the other side, titanium oxide was applied to each layer having the constitution shown in Tables 1 and 2 below. By coating on the side of the contained polyethylene layer, a multilayer silver halide color photographic material sample 101 was prepared. The coating liquid was prepared as follows.

First layer coating solution Yellow coupler (EY-1) 26.7 g, dye image stabilizer (ST-1) 10.0 g, dye image stabilizer (ST-2)
60 ml of ethyl acetate was added to 6.67 g, 0.67 g of stain inhibitor (HQ-1) and 6.67 g of high boiling organic solvent (DNP) to dissolve, and this solution was dissolved in 7 ml of 20% surfactant (SU-2).
A yellow coupler dispersion was prepared by emulsifying and dispersing it in 220 ml of a 10% gelatin aqueous solution containing the above using an ultrasonic homogenizer.

This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension. Below, Table 1,
Table 2 shows each configuration in detail.

[0102]

[Table 1]

[0103]

[Table 2]

The structural formulas of the compounds used in the above layers are shown below.

[0105]

[Chemical 35]

[0106]

[Chemical 36]

[0107]

[Chemical 37]

[0108]

[Chemical 38]

[0109]

[Chemical Formula 39]

Blue-Sensitive Silver Halide Emulsion (Em-B) Monodisperse cubic emulsion with average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5 mol% Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / Mol AgX stabilizer STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX green-sensitive Silver halide emulsion (Em-G) Monodisperse cubic emulsion with average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5 mol% Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stability Agent STAB-1 6 × 10 ^-4 mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX Red-sensitive silver halide emulsion (Em-R) Average grain size 0.50 μm, coefficient of variation = 0.08, Monodisperse cubic emulsion with a silver chloride content of 99.5 mol% Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer The structural formula of the TAB-1 6 × 10 ^-4 mol / mol AgX Sensitizing dye RS-1 1 × 10 ^-4 mol / compound used in the monodispersed cubic emulsion in mol AgX below.

[0111]

[Chemical 40]

Next, the third layer coupler EM-1 of Sample 101 was used.
Were replaced with equimolar couplers of the present invention shown in Table 3 below to prepare Samples 102 to 120. In addition, the third dye image stabilizer
Samples 121-130 were prepared without addition to the layers.

The thus-prepared sample was wedge-exposed with green light according to a conventional method, and then processed according to the following processing steps.

Processing process Temperature Time Color development 35.0 ± 0.3 ℃ 45 seconds Bleach-fixing 35.0 ± 0.5 ℃ 45 seconds Stabilization 30-34 ℃ 90 seconds Dry 60-80 ℃ 60 seconds Composition of each processing solution is as follows. Show.

The replenishing amount of each processing solution is 80 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material.

Color developing solution tank solution Replenishing solution Pure water 800 ml 800 ml Triethanolamine 10 g 18 g N, N-diethylhydroxylamine 5 g 9 g Potassium chloride 2.4 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g 1.8 g N-ethyl -N-β-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Water In addition, the total volume is set to 1000 ml, and the pH of tank liquid is
Adjust the pH to 10.10 and the replenisher to pH 10.60.

Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Add water Adjust the total volume to 1000 ml and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid (tank liquid and replenishing liquid are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.5 g Water is added to bring the total volume to 1000 ml, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide. Adjust to.

The following evaluations were performed using each sample after the continuous treatment.

<Light resistance> The obtained sample was irradiated with a xenon fade meter for 14 days, and the residual ratio (%) of the dye image at the initial density of 1.0 was determined.

<Λmax> represents the maximum absorption wavelength of the wedge at the reflection optical density of 1.0.

<Abs600> Absorbance of wedge at 600 nm (absorption of λmax is 1.0
And)).

<Dmax> represents the maximum color density.

The results are shown in Table 3.

[0125]

[Table 3]

As is clear from Table 3, each sample using the magenta coupler of the present invention has a markedly reduced absorbance at 600 mm, the color reproducibility is improved, and the light fastness of the present invention is also improved. It can be seen that the examples are greatly improved by using the dye image stabilizer of the present invention as compared with the comparative examples.

Example 2 Dye image stabilizer III- of the third layer of Sample 101 of Example 1
Samples 201 to 221 were prepared by replacing 8 with III-2 and IV-2 (the molar ratio to the coupler was 1 respectively). Samples 222 to 230 were prepared in which the dye image stabilizer was not added to the third layer.

The same evaluation as in Example 1 was performed using each of the obtained samples. The results are shown in Table 4.

[0129]

[Table 4]

As can be seen from Table 4, the sample Nos. (203 to 221) of the present invention have excellent color reproducibility and light resistance of the comparative sample as in Example 1. Further, it was found that the light resistance was more effective than that of Example 1.

Example 3 The dye image stabilizer III-8 in the third layer of the sample 101 of Example 1 was added.
Samples 301 to 321 were prepared by substituting two kinds of III-10 and IV-2 (each having a molar ratio to the coupler of 1), and the same evaluation as in Example 1 was performed using each sample. The results are shown in Table 5.

[0132]

[Table 5]

As is clear from Table 5, the embodiment of the present invention has the same effect as that of the embodiment 1, and further has the light resistance more than that of the embodiment 2.

As shown in the above results (Tables 3 to 5), the color reproducibility is all the same, but the light fastness is improved by using two kinds of dye image stabilizers in combination. It turned out that the result was obtained.

[0135]

It has been found that the silver halide color photographic light-sensitive material of the present invention has excellent effects on image storability and color reproducibility.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one pyrazolotriazole magenta coupler represented by the following general formula [I] or general formula [II]. [Chemical 1] [In the formula, R ₁ , R ₂ , R ₃ , R ₅ , R ₆ and R ₇ represent an alkyl group, and R ₄ and R ₈ represent a substituent. L ₁ and L ₂ represent an alkylene group. X and Y represent a hydrogen atom or a group capable of splitting off in correspondence with the oxidized product of the color developing agent. 2. A silver halide emulsion layer containing a magenta coupler represented by the general formula [I] or the general formula [II] and at least a compound represented by the following general formula [III] or the general formula [IV]. The silver halide color photographic light-sensitive material according to claim 1, wherein one of them is contained. [Chemical 2] [In the formula, R ₂₁ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or the following residue. [Chemical 3] Here, R ₂₁ a, R ₂₁ b and R ₂₁ c each represent a monovalent organic group. R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ each represent a hydrogen atom, a halogen atom or a group capable of substituting for a benzene ring. R _{21 to} R ₂₆ may combine with each other to form a 5- or 6-membered ring. ] [Chemical 4] [In the formula, R ₃₁ represents an aliphatic group or an aromatic group, and Z represents a nonmetallic atom group necessary for forming a 5- to 7-membered ring with a nitrogen atom. ]