JPH0467142A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide colorphotographic sensitive material superior in color reproduction and color development performances and remarkably improved in lightfastness of a magenta dye image by incorporating a pyrazoloazole type magenta coupler having at least one specified group. CONSTITUTION:The silver halide color photographic sensitive material contains the pyrazoloazole type magenta coupler having at least one group represented by formula I in which J is a divalent bonding group; A is arylene; and Y is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring together with an nitrogen atom, thus permitting the obtained silver halide color photographic sensitive material to be superior in color reproduction and development performances and remarkably improved in the lightfastness of the magenta dye image.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler, and more specifically, the present invention relates to a silver halide color photographic light-sensitive material containing a magenta coupler. The present invention relates to a silver halide color photographic light-sensitive material that has excellent reproducibility and color development, and further provides dye images that are stable against heat and light.

[Prior Art] Couplers commonly used in silver halide color photographic materials include yellow couplers made of open-chain ketomethylene compounds, magenta couplers made of pyrazolone compounds, pyrazoloazole compounds, phenol compounds, and naphthols. Cyan couplers made of such compounds are known. Conventionally, 5-pyrazolone compounds have been frequently used as magenta couplers.

Known pyrazolone magenta couplers are described in U.S. Pat. No. 2,600,788, U.S. Pat.

However, The Theory of the Photographic Fist Process (The Theory of the P
photographic Process), 7th edition, Cumilan Publishing, 4th edition (1977).

As described in pages 356-358, Fine Chemicals, published by CMC, Volume 14, No. 8, pages 38-41, Abstracts of the 1985 Annual Conference of the Photographic Society of Japan, pages 108-110. The dye formed from pyrazolone magenta coupler has undesirable side absorption, and improvement thereof is desired.

As described in the previous literature, dyes formed from pyrazoloazole magenta couplers have no side absorption. The fact that this coupler is a good coupler can be found in US Pat. No. 3,725,067, US Pat.
No. 309, No. 3,810,761, etc.

[Problems to be Solved by the Invention] However, the azomethine dyes formed from these couplers have extremely low fastness to light, which significantly impairs the performance of color photographic materials, especially print-type color photographic materials.

Research has been conducted to improve the fastness to light. For example, JP-A No. 59-125732, No. 6
No. 1-282845, No. 61-292639, No. 61
JP-A No. 61-72246, JP-A No. 62-208048, JP-A No. 62-157031, JP-A No. 62-157031, JP-A-279855 describes a technique of using a pyrazoloazole magenta coupler in combination with a phenol compound or a phenyl ether compound.
No. 3-163351 discloses a technique in which an amine compound is used in combination.

Further, JP-A-63-24256 proposes a pyrazoloazole magenta coupler having an alkyloxyphenyloxy group.

However, even with the above technology, the fastness of the magenta dye image to light is insufficient, and there has been a strong desire for improvement.

The present invention has been made to solve the above problems,
SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which has excellent color reproducibility and color development, and which has significantly improved light fastness of magenta dye images.

[Means for Solving the Problems] The above object of the present invention is to provide a silver halide color photograph characterized by containing a pyrazoloazole magenta coupler having at least one group represented by the following general formula [I]. This was achieved using photosensitive materials.

General formula "[I] [In the formula, J represents a divalent linking group, A represents an arylene group, and Y represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle with a nitrogen atom. ] The present invention will be explained in more detail below.

The pyrazoloazole magenta coupler used in the present invention has a group represented by the above general formula [I]. The pyrazoloazole ring connected to J in the general formula [I] is represented by, for example, the following general formula [■].

General formula [■] In the formula, Z represents a nonmetallic atom 8T necessary to form a nitrogen-containing heterocycle, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

Moreover, R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes alkyl, aryl, acylamino,
Examples include sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, etc., but also halogen atoms, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, Aryloxy, heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino,
imide, ureido, sulf7moylamino, alkoxycarbonylamino, aryloxycarbonylamino,
Also included are alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R preferably has 1 to 32 carbon atoms, and may be linear or branched.

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide F group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc. Phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, Acyl groups such as arylphosphonyl groups include alkylcarbonyl groups; carbamoyl groups such as allylcarbonyl groups include alkylcarbamoyl groups and arylcarbamoyl groups; sulfamoyl groups include alkylsulfamoyl groups;
Acyloxy groups such as arylsulfamoyl groups include alkylcarbonyloxy groups,
Arylcarbonyloxy groups, etc./Carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, allylureido groups, etc.; sulfamoylamino groups include alkylsulfamoylamino groups, aryl Sulfamoylamino group, etc. The heterocyclic group is preferably a 5- to 7-membered one, specifically 2-furyl group, 2-thienyl group, 2-pyriminyl group,
The heterocyclic oxy group such as 2-benzothiazolyl group is 5-
Those having a 7-membered heterocycle are preferred, such as 3, 4,
5.6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazol-5-oxy group, etc.; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, such as 2-pyridylthio group, 2-pyridylthio group, etc. -penzothiazolylthio group, 2,4-diphenoxy 1,3,5-triazole-6 monothio group, etc.; as siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; as imide group, succinate Spiro compound residues such as acid imide group, 3-hephtadecylsuccinimide group, phthalimide group, and glutarimide group include spiro[3,3]hebutane-
As a bridged hydrocarbon compound residue such as 1-yl, bicyclo[2゜21]
Heptan-1-yl, trinculo [3°3.1.137
] Decane-1-yl, 7,7-dimethyl-bicyclo[2
,2,1]butan-1-yl and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atoms,
bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy,
Alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alcoquinoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxy carbonylamino, aryloxycarbonylamino, carboxyl, (R1' is the same as the above R, Z' is the same as the above Z, R, / and R3' are a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) ), but preferably a halogen atom, especially a chlorine atom.

As the nitrogen-containing heterocycle formed by Z or Z',
Examples include a pyrazole ring, an imidazole ring, a triazole ring, a tetra, and a zole ring, and examples of the substituents that the nitrogen-containing heterocycle formed by Z or Z' may have include those described for R above.

Moreover, among the general formulas [n], the following general formulas [n] are preferable:
IX].

In the formula, R1X and Zl have the same meanings as R, X and Z in the general formula [n].

More specifically, those represented by the general formula [■] are represented by, for example, the following general formulas [I11] to [■].

General formula [I111 General formula [IV] General formula [V] General formula ['/II General formula [■1 General formula [■J] In the above general formulas [III] to [■], R1 to RL2 and X are the above R and It is synonymous with X.

In addition, R5 of couplers represented by general formulas [m] to [■]
-R12 or X may become a divalent group to form a bis body, and may also be polymerized by introducing an unsaturated double bond.

Among the magenta couplers represented by the general formulas [I[I] to [■], particularly preferred are the magenta couplers represented by the general formulas [I11] and [■].

The divalent linking group represented by J in the general formula [I1 includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, Phosphonyl, acyl, carbamoyl, sulfamoyl, alkoxy, aryloxy, heterocyclicoxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxy It represents a divalent group derived from carbonyl, a heterocyclic thio group, and a divalent group that can be formed by combining these divalent groups, and is preferably represented by the following general formula [X].

General formula [X] 1 + R 13 items 4 items R work 1 item L 2 items R 4 children, -R in the formula
The 1j side is bonded to the pyrazoloazole ring.

R, , R, and R+6 in the general formula [X] each independently represent an alkylene group, an arylene group, or an aralkylene group having 1 to 12 carbon atoms. The alkylene group may be linear or branched, and examples thereof include a methylene group, methylmethylene group, dimethylene group, decamethylene group, etc., and examples of the arylene group include a phenylene group, a naphthylene group, and an aralkylene group. The alkylene group, arylene group, or aralkylene group represented by R, 3, R, and RL5 may have a substituent, and the substituent may include R of general formula [II]
Examples include each substituent represented by the following.

Also, in the general formula [XJ, L□, R2 and R3 are R, , R
16 -NGO--CON--0CO coo--s=-5o--so□-S and t are O
Or represents an integer of 1.

The arylene group represented by 8 in the general formula [I] includes a phenylene group, a naphthylene group, etc., and these arylene groups can have a substituent represented by R in the general formula [I1].

In the general formula [I], a non-R group represented by Y.

R□7 and R18 each independently represent a hydrogen atom, an alkyl group or an aryl group, and n represents an integer of O to 2.

tg Represents SO,N-. However, R16 represents a hydrogen atom, an alkyl group or an aryl group. p, q, r.

The 7-membered heterocycle may be saturated or unsaturated, but an unsaturated ring is preferred. Further, these heterocycles have the general formula [I
[I] may have a substituent represented by R.

A group having a heterocycle represented by the general formula [I] is a group having a heterocycle represented by the general formula [I].
R of the pyrazoloazole ring represented by I11] to [■]
s, R6, R7+ Rs, Re, R1゜+
At least one of R11+R12 and X is substituted.

Typical specific examples of magenta couplers according to the present invention are shown below, but the present invention is not limited thereto.

Exemplary coupler M-6 Cσ C I 2 H 2 S C1xH*s(II) Shingoshi■2t12sLnノC Im H tips (nl M-18 M-19 -σ M-34 Less than millstone ~ --1゜m-・;; The pyrazoloazole magenta coupler according to the present invention is described in the Journal of the Chemical Society (
Journal of the Chemical 5
ociety), Perkin; I
(1977), 2047-2052, U.S. Patent 3
, No. 725,067, JP-A-59-99437, No. 5
No. 8-42045, No. 59-162548, No. 59-
No. 171956, No. 60-33552, No. 60-43
No. 659, No. 60-172982, No. 60-1907
No. 79, No. 61-189539, No. 61-24175
No. 4, No. 63-163351, No. 62-157031
Those skilled in the art can easily synthesize it by referring to No.

Next, a typical synthesis example of the pyrazoloazole magenta coupler according to the present invention will be shown below.

Synthesis example (1) of Nadomari illustrative coupler scheme (M-6) (IV) (V) (Vl) (II) 10.0 g of compound (1), 92 g of potassium carbonate and ethyl α-bromuraurate (n ) 17.6g was added to 250mR of acetonitrile and heated under reflux for 10 hours,
The precipitated potassium bromide was filtered off by hot filtration.

The filtrate was distilled off under reduced pressure, and the residue was extracted with 200 ml of ethyl acetate. After washing with water, it was dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. This pale yellow residue was recrystallized from acetonitrile to obtain 15.2 g of compound (III). However, the yield of compound (III) was 76%, and the mp was 39-40.
It was ℃.

9.1 g of the above compound (III) was mixed with 4 ml of ethyl alcohol.
After dissolving in 5 ml of water, a solution of 16 g of sodium hydroxide dissolved in 5 d of water was added, and the mixture was heated under reflux for 3 hours. After the reaction, the alkali was neutralized with hydrochloric acid, and the ethyl alcohol was distilled off under reduced pressure. The residue was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. 40 g of chloroform and 48 g of thionyl chloride were added to the obtained oily compound (rV), and the mixture was heated under reflux for 3 hours. After the reaction,
Chloroform and excess thionyl chloride were distilled off under reduced pressure to obtain 8.4 g of compound (V) as a pale brown part (exemplary coupler M-6).

Second, Compound (VI) 6.0g and Viridi: z2.1g
was added to 60 d of ethyl acetate. A solution prepared by dissolving 8.4 g of the compound (V) in 16 d of ethyl acetate was added dropwise to this solution under water cooling, and the mixture was stirred at room temperature for 3 hours. After the reaction,
The ethyl acetate solution was washed with water, dried over magnesium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using ethyl acetate-n-hexane as a developing solvent to obtain 102 g of white amorphous exemplary coupler M-6. However, the yield is 77%,
The structure of the compound was confirmed by IR, mass spectrum, nuclear magnetic resonance spectrum and elemental analysis.

In order to incorporate the magenta coupler used in the present invention into an emulsion, a conventionally known method may be followed.

For example, the present invention may be applied to a high boiling point organic solvent having a boiling point of 175°C or higher such as tricresyl phosphate or dibutyl phthalate, or a low boiling point solvent such as ethyl acetate or butyl propionate, or a mixture thereof as necessary. After dissolving the magenta coupler alone or in combination,
It can be mixed with an aqueous gelatin solution containing a surfactant, then emulsified in a high-speed rotary mixer or colloid mill, and then added to silver halide to prepare the silver halide emulsion used in the present invention.

The magenta coupler according to the invention usually has a content of 1X10-' to 1 mole per mole of silver halide, preferably IX10-'
"~8 x 10-' moles can be used.

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

The pyrazoloazole magenta coupler according to the present invention can be used together with an image stabilizer represented by the following general formula [A] and/or general formula [B].

General formula [A] 22 in R23 In the general formula [A], R21 represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, Straight chain or branched alkyl groups such as n-octyl group, tert-octyl group, benzyl group, and hexadecyl group can be mentioned.

Moreover, this alkyl group may have a substituent. Examples of the alkenyl group represented by R2□ include allyl, hexenyl, and octenyl groups.

Furthermore, the aryl group of R2□ includes multiple groups such as phenyl and naphthyl. This aryl group can have a substituent, and specific examples include a methoxyphenyl group and a chlorophenyl group.

Furthermore, specific examples of the heterocyclic group represented by R2□ include a tetrahydropyranyl group, a pyrimidyl group, and the like.

In the general formula [A], R221Rts, R2B and R2@ represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a benzyl group or an acylamino group, and among these, an alkyl group, For alkenyl groups and aryl groups, R2
The same alkyl groups, alkenyl groups, and aryl groups mentioned for L can be mentioned.

Examples of the halogen atom include fluorine, chlorine, and bromine.

Furthermore, specific examples of the alkoxy group include a methoxy group, an ethoxy group, a benzyloxy group, and the like. Further, the acylamino group is Rz v CON H-
Here, R2□ is an alkyl group (e.g., multiple groups such as methyl, ethyl, n-propyl, n-butyl, n-octyl, tert-octyl, benzyl, etc.), an alkenyl group (e.g., allyl, octenyl, oleyl). It can represent an aryl group (e.g., phenyl, methoxyphenyl, naphthyl, etc.) or a heterocyclic group (e.g., pyridinyl, pyrimidyl).

In the general formula [A], R24 represents an alkyl group, a hydroxy group, an aryl group, an alkoxy group, an alkenyloxy group, or an aryloxy group, and among these, the alkyl group and aryl group are represented by R7□ Specific examples include the same alkyl groups and aryl groups. Regarding the alkoxy group of R24, the above R
2! l R231 The same alkoxy groups mentioned for R28 and R26 can be mentioned.

Further, R21 and R2□ may be ring-closed with each other to form a 5- or 6-membered heterocycle, and R23 and R24 may be further ring-closed to form a 5-membered ring.

Typical specific examples of the compound represented by the general formula [A] are shown below, but the present invention is not limited thereto.

Hereinafter, the compounds of the present invention will be described in the Journal of the Chemical
Society (Journal of the Ch.
chemical 5ociety), No. 415-417
Page (1962) No. 2904-2914 (1965)
The Journal of Organic Chemistry
hemistry), Vol. 23, pp. 75-76: Tetrahedron, Vol. 26, pp. 4143-4751 (1970);
Chem, Lett), (4), No. 315-3
16 pages (1972); Journal of the Chemical Society of Japan, No. 10
．． Pages 1987-1990 (1972) ・Nyanal of Chemical Society (Journal
of the Chemical S.

ciety), pp. 415-417 (1962)
; Bulletin of Chemical Society of Japan, Vol. 53, pp. 555-556 (198
It can be easily synthesized by the method described in 0).

General formula [B Koshi-111] In the general formula [B], R31 represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group, or an aryl group, and R32 represents a halogen atom,
It represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and n represents an integer of O to 3.

Y represents s, so, so2 or an alkylene group.

The secondary or tertiary alkyl group or secondary or tertiary alkenyl group represented by R, tll preferably has 3 to 32 carbon atoms, particularly 4 to 12 carbon atoms, and specifically, , t-butyl, S-butyl, t-amyl, S-
Examples include groups such as amyl, t-octyl, i-propyl, i-propenyl, and 2-hexenyl.

The alkyl group represented by Rs2 preferably has 1 to 32 carbon atoms, and the alkenyl group preferably has 2 to 32 carbon atoms.
These are preferable, and both may have a substituent and may be linear or branched. Specific examples include groups such as methyl, ethyl, t-butyl, pentadecyl, 1-hexynonyl, 2-chlorobutyl, benzyl, 24-di-t-amylphenoxymethyl, 1-ethoxytridecyl, allyl, and isopropenyl.

The cycloalkyl group represented by R31 and R32 is preferably one having 3 to 12 carbon atoms, such as cyclohexyl,
Examples include groups such as 1-methylcyclohexyl and cyclopentyl.

As the aryl group represented by R31 and R82, phenyl and naphthyl groups are preferable, including those having a substituent. A
Specific examples include phenyl, 4-nitrophenyl, 4-t-butylphenyl, 24-di-amylphenyl, 3-hexadecyloxyphenyl, and α-naphthyl.

The alkylene group represented by Y preferably has 1 to 12 carbon atoms, and specific examples thereof include methylene, ethylene, propylene, butylidene, hexamethylene, and the like. These groups may have substituents.

Substituents that Rsl, Ra□ and Y may have include:
For example, halogen atoms and nitro, cyano, amide,
Examples include groups such as sulfonamide, alkoxy, aryloxy, alkylthio, arylthio, and acyl.

Typical specific examples of general formula [B] are shown below, but the present invention is not limited thereto.

The compound represented by the general formula [B] is disclosed in U.S. Patent No. 2807
．． No. 653, Journal of the Chemical Society Parkin I (J, Chem, 5ocP
Arkin I) p. 1712 (1979).

The amount of the image stabilizer represented by the general formula [A] and general formula [B] to be used is preferably 5 to 400 mol%, respectively, based on the pyrazoloazole magenta coupler according to the present invention. , more preferably 10 to 250 mol%
It is.

Although the pyrazoloazole magenta coupler of the present invention and the image stabilizer are preferably used in the same layer, the image stabilizer may be used in a layer adjacent to the layer in which the coupler is present.

Silver halide compositions preferably used in the present invention include silver chloride, silver chlorobromide, and silver chloroiodobromide. Furthermore, a combination mixture such as a mixture of silver chloride and silver bromide may be used.

The silver halide emulsion used in the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any used in silver emulsions can be used.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and the surface layer of the grain.

The silver halide grains may be such that a latent image is mainly formed on the surface, or may be such that a latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the 1100) plane to the flll1 plane can be used.

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

The grain size of the silver halide grains is preferably 0.
．． 05 to 30μ, more preferably (1.1 to 20μ) can be used.

Silver halide emulsions having any grain size distribution can be used. Emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used singly or in combination. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used. The coupler used in the present invention includes a colored coupler having a color correction effect and a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, and a toning agent by coupling with an oxidized form of a developing agent. agent, hardening agent, fogging agent, anti-capri agent, chemical sensitizer,
Compounds that release photographically useful fragments such as spectral sensitizers and desensitizers are included.

Among these, a so-called DIR compound may be used, which releases a development inhibitor during development and improves image clarity and image graininess.

These DIR compounds include those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and the intramolecular demand for the group separated by the coupling reaction is Those bound in such a way that the inhibitor is released by nuclear reactions, intramolecular electron transfer reactions, etc. (timing DI
It is called R compound. ) is included. Also, there are two types of inhibitors: those that are diffusible after withdrawal, and those that are not diffusible.
They can be used alone or in combination depending on the purpose.

A colorless coupler (also referred to as a competitive coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler (51).

Yellow couplers preferably used in the present invention include known acylacetanilide couplers. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used.

Cyan couplers preferably used in the present invention include phenol or naphthol couplers.

The oxidized form of the developing agent or the electron transfer agent moves between the emulsion layers of the photosensitive feed (between the same color-sensitive layers and/or between different color-sensitive layers), causing color turbidity and deterioration of sharpness. A color antifoggant may also be used to prevent graininess from becoming noticeable.

The light-sensitive material of the present invention may contain an image stabilizer that prevents deterioration of the dye image. Compounds that can be preferably used are those described in Section 2 J of DR17643.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain an ultraviolet inhibitor to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent deterioration of images due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in 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 generally consist of a blue-sensitive, green-sensitive, or red-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer.
The present invention is not subject to any limitations on the arrangement of these layers on the support.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing.

Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleaching solution and the process using a fixing solution. In addition, a bleach-fixing process can be carried out using a -bath bleach-fixing solution, or a monobath process can be carried out using a monobath developing, bleaching-fixing solution for color development, bleaching and fixing.

[Example] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these embodiments.

Example 1 Multilayer color photographic material samples No. 1 to No. 10 were prepared by sequentially coating the following layers on polyethylene resin-coated paper containing anatase-type titanium oxide.

Note that the amount added in the photosensitive material is per 100 crrr.

(1) 20 mg of gelatin, 5 mg of blue-sensitive silver chlorobromide emulsion (silver bromide content: 80 mol%), 8 mg of Y
- A layer containing 1,0,1 mg of 2,5-di-tert-octylhydroquinone and 3 μm of dioctyl phthalate.

(2) A layer containing 12+ng gelatin, 0.5 mg 2,5-di-t-octylhydroquinone, 4 mg UV absorber'' and 2 mg dibutyl phthalate.

(3) 18 mg of gelatin, 4 mg of silver in a green-sensitive silver chlorobromide emulsion (silver bromide content: 70 mol%), 5 mg of the magenta coupler shown in Table 1, and 0.2 mg of 2.5-di-t- Layer containing octyl hydroquinone and 2.5 mg dioctyl phthalate.

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

(5) 16 mg of gelatin, 4 mg of silver as red-sensitive silver chlorobromide emulsion (silver bromide content 70 mol%), 3.5 m
g of C-1,0.1 mg of 2,5-di-t-octylhydroquinone and 2.0 mg of tricresyl phosphate.

(6) Protective layer containing 9 mg of gelatin.

As the ultraviolet absorbers in (2) and (4), UV-1 and UV-2 having the structures described below were mixed (mixing ratio 1:1) and used.

After the above-mentioned multilayer photosensitive material was subjected to wedge exposure according to a conventional method, the following development treatment was performed.

Each sample was exposed to white light and then measured for magenta density. The light resistance was also evaluated as follows.

(Evaluation of light resistance) The light resistance was evaluated by irradiating the sample after the color development treatment with a xenon fade meter for 5 days and showing the percentage of dye remaining after the treatment at the initial density D=1.0.

The above results are shown in Table-1.

(Development processing process) Color development 38°C 3 minutes 30 seconds Bleach fixing 38°C 1 minute 30 seconds Stabilization processing/
Or washing with water at 25°C to 30°C for 3 minutes, drying at 758°C to 80°C for 2 minutes, and the composition of the treatment liquid used in each treatment step is as follows.

(Color developer) Benzyl alcohol 15d Ethylene glycol 151g Potassium sulfite
2.0g potassium bromide
0.7g sodium chloride
0.2g potassium carbonate 3
0.0g Hydroxylamine sulfate 30g
Polyphosphoric acid (TPPS) 2.5g3-
Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl) Aniline sulfate 5.5g Optical brightener (4,4'-aminostilbenesulfonic acid derivative) 10g Potassium hydroxide 2. Add 0 g of water to bring the total volume to 12, and adjust the pH to 11.08.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100d ammonium sulfite (40%
% solution) 27.5d glacial acetic acid
10.0 pH 7.1 with potassium carbonate or glacial acetic acid
and add water to bring the total volume to 12.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g 1-hydroxyethylidene-11 disulfonic acid 2.0 g Water was added, the temperature was raised to 1°C, and p! was added with sulfuric acid or potassium hydroxide. -17,
Adjust to 0.

Ultraviolet absorber comparative coupler 1 Comparative coupler 2 Cρ Table 1 From the results in Table 1, the dye image of the sample of the present invention has excellent light resistance, high maximum density, and excellent performance. I understand.

Example 2 Silver halide color photographic materials No. 11 to No. 024 were prepared by sequentially coating the following layers on a paper support laminated on both sides with polyethylene from the support side.

Layer 1...1.2g, /r+? Seratin, 0.
Blue-sensitive silver chlorobromide emulsion (silver chloride content: 993 mol%), 0.50 g/rn
0.80g/rr dissolved in dioctyl phthalate of
A layer containing a yellow coupler (Y-1) of r.

Layer 2...0, 70g/resistant gelatin, 0.5
mg of 2.5-di-t-octylhydroquinone, 2m
Intermediate layer consisting of g of dibutyl phthalate, 30 mg/rrl' of anti-irradiation dye (A l-1), 20 mg/d of (AI-2).

Layer 3...1.25g/rr? gelatin, 0.
25 g/i green-sensitive silver chlorobromide emulsion (silver chloride content 99.
0.74 g/m of the magenta coupler shown in Table 2 dissolved in dioctyl phthalate (5 mol%) and 0.30 g/m
% and a layer containing an image stabilizer shown in Table 2.

However, the image stabilizer was added in an amount of 100 mol % based on the coupler.

Layer 4 - = - 1.02 g/rn'' gelatin, 0.
5 mg of 2,5-di-t-octylhydroquinone, 2
Intermediate layer consisting of mg dibutyl phthalate.

Layer 5...1.20g/m gelatin, 0.30
g/rr? red-sensitive silver chlorobromide emulsion (silver chloride content: 99%)
．． 7 mol%), 0.46 g/rrr of cyan coupler (C-
A layer containing 1).

Layer 6...1.00g/rr? of gelatin and 0
．． 0 dissolved in 20g/rrr of dioctyl phthalate
, 30g/rr? (U used in Example 1)
A layer containing a mixture of V-1 and UV-2 (1=1).

Layer 7: A layer containing 0.50 g/nr of gelatin.

Comparative coupler Cσ l-1 AI In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-s-trianne sodium was added in layer 2, layer 4, and layer 7 at a concentration of 0.017 g per 1 g of gelatin, respectively. It was added as follows.

The obtained sample was passed through a photosensitive needle KS-7 type (manufactured by Konica Corporation).
After wedge exposure using the following color development process, the highest density of the green-sensitive emulsion layer (
D max) was measured.

Further, the light resistance was evaluated by irradiating the obtained sample with a xenon fade meter for 5 days and determining the residual rate (%) of the magenta dye image at an initial density of 10.

The results are shown in Table-2.

[Processing process] Color development, bleaching, fixing, stabilization, drying, drying temperature 347±03°C 347±05°C 30-34°C 60-80°C Time 45 seconds 50 seconds 90 seconds 60 seconds <Color developer> Pure water 800 mQ Triethanolamine 8gN, N-
Diethylhydroxylamine 5g Potassium chloride
2g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 = aminoaniline sulfate 5g sodium tetrapolyphosphate 2g potassium carbonate
30g potassium sulfite
0.2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to bring the total volume to 12, and adjust the pH to 10.2.

<Bleach-fix solution> Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100d ammonium sulfite (40% solution 1 (k)
) 27. pH with h+N potassium carbonate or glacial acetic acid
Adjust to 5.7 and add water to bring the total volume to 12.

<Stabilizing liquid> 5-chloro-2-methyl-4=isothiazolin-3-one Igl-hydroquinethylidene-1 1-one phosphonic acid Add 2 g of water to make 1 sieve, and adjust the pH to 70 with sulfuric acid or potassium hydroxide. Adjust to.

1 Comparative coupler 1゜Table 2 2 is the same as that used in Example 1 From the results in Table 2, the dye image of the sample of the present invention was further improved in light resistance by using an image stabilizer (Jl). It turned out that it was possible to make some significant improvements.

Furthermore, it was found that the coloring density was sufficient and excellent coloring properties were exhibited.

Example 3 Sample 25 of a multilayer color photographic abrasive material was prepared by sequentially coating each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Incidentally, the amount added in the silver halide photographic light-sensitive material is expressed per unit unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

1st layer; antihalation layer (HC) Gelatin layer containing black colloidal silver.

Second layer: Intermediate layer (IL) Gelatin layer containing an emulsified dispersion of 2.5-di-t-octylhydroquinone.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL) average grain size 030 μm, AgBr containing 16.0 mol% Ag
Monodispersed emulsion consisting of 1 (emulsion ■)...silver coating amount 1.8
g/ir? Sensitizing dye I... 6X 10-' moles per mole of silver Sensitizing dye ■ 1. OX 10-1' Molar cyan coupler (C-2)... 006 mol per mol of silver Colored cyan coupler (CC-1)... 0003 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver DIR compound (D-2)... 0002 mol per mol of silver 4th layer; High sensitivity red-sensitive silver halide emulsion layer (RH) average grain size 05 μm, AgBrI containing 7.0 mol% Agl
Monodispersed emulsion (emulsion ■) consisting of...silver coating! 1.3g
/B Sensitizing dye I... 3X per mole of silver 10-I1 mole Sensitizing dye ■・1. OX 10-'Morsian coupler (C-2)... 0.02 mol per mol of silver Colored cyan coupler (CC-1)... 0.0015 mol DIR compound (D -2)... 0.001 mol per mol of silver Fifth layer; Intermediate layer (IL) A gelatin layer with the same composition as the second layer.

6th layer: Low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion ■... Coated silver amount 1.5 g/rd Sensitizing dye ■... 2.5X 10-I' mol per 1 mol of silver Sensitizing dye■
... 1.2X 10-' mole magenta coupler (comparative coupler 4) per mole of silver ...0.050 mole colored magenta coupler (CM-1) per mole of silver - per mole of silver 0009 mol DIR compound (D-1)... o, ooto mol per mol of silver DIR compound (D-3) 0.0030 mol per mol of silver 7th layer; High sensitivity green sensitivity/N Silver halogenide emulsion layer (GH) emulsion■ Coated silver amount L4g/sensitizing dye■... 1.5X 10-' mol per mole of silver Sensitizing dye■ 1.5x per mole of silver. OX 10-' mol Magenta coupler (comparative coupler 3 used in Example 2)...0020 mol per mol of silver Colored magenta coupler (CM-1)...0002 mol per mol of silver DIR compound (D-3)... 0.0010 mol per mol of silver 8th layer: Yellow filter layer Seratin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer: Low-speed blue-sensitive silver halide emulsion layer (BL) Monodispersed emulsion (emulsion ■) consisting of AgBrI with an average grain size of 0.48 μm and containing 16 mol% of Ag...Amount of silver coated: 0.9 g/
m Sensitizing dye V... 1.3X 10-' mol per mol of silver Yellow coupler (Y-2) 029 mol per mol of silver 10th layer; High sensitivity blue-sensitive emulsion layer (BH) average grain Diameter 08μ
m, Monodisperse emulsion (emulsion ■) consisting of AgBrI containing 15 mol% of AgI... Silver coating amount: 0.5 g/Go sensitizing dye V... 1. OX 10-' mol Yellow coupler (Y-2)... 0.08 mol per mol of silver DIR compound (D-2)... 0.0025 mol per mol of silver 11th layer, 1 protective layer (Pro-1) Silver iodobromide (Heg 11 mol% average particle size 07 μm)...Amount of silver coated 0.5 g/m Ultraviolet absorber UV-1UV-2 used in Example 1 (1:
Gelatin layer containing '1).

12th layer; second protective layer (Pro-2) Gelatin layer containing polymethyl methacrylate particles (average particle size 15 μm) and formalin scavenger (I(S-1)).

In addition to the above ingredients, each layer contains a gelatin hardening agent (H
-1) and a surfactant were added.

Furthermore, Samples 26 to 32 were prepared in the same manner as Sample 25, except that the comparative coupler 3 contained in Layer 6 and Layer 7 in Sample 11 was changed to the coupler shown in Table 2.

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 ■・Anhydro-9-ethyl-3,3'- (
3-sulfopropyl)-4 5,4',5'-benzothiacarbocyanine hydroxide sensitizing dye■ Anhtrow 55'-diphenyl9-ethyl-3,3'-di(3sulfopropyl)oxacarbocyanine hydroxy Sensitizing dye
-sulfopropyl)-5 6,5',6'-dibenzoxavalent lupocyanine hydroxyto sensitizing dye; Cyanine hydrocoxide D-1 0M-1 ('ρ (,4 C1σ Comparative coupler I-1 Comparative coupler Comparative coupler 2 Samples 25 to t, 'I32 obtained as in 2) were measured using white light. After wedge exposure, the following development process was performed.Then, the specific sensitivity and maximum density were determined for each sample.However, the specific sensitivity is the reciprocal of the exposure amount that slopes the density of fog density + 01, and sample 25 is taken as 100. (It is shown as a relative value when 7.

The results are shown in Table-3.

Processing process (38℃) Processing time Color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Washing with water for 6 minutes and 30 seconds Stabilization for 3 minutes and 15 seconds Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) Aniline sulfate 475g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate
37.5 g sodium bromide
1.3 g nitrilotriacetic acid trisodium salt (monohydrate) 25 g potassium hydroxide 1.0 g Add water to bring the mixture to 1, and adjust to pH 10 using potassium hydroxide or 20% sulfuric acid.
Adjust to 06.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid
10.0m, add 1 g of water!
Then adjust the pH to 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1/l
and adjust the pH to 6.0 using acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 15 ml Konidax (manufactured by Konica) 7.5 J Add water to make one volume.

As is clear from the results in Table 3, the sample of the present invention had higher sensitivity and maximum density than the comparative sample, and was found to have excellent color development. Ta.

[Effects of the Invention] As explained in detail above, the present invention provides a silver decagenide color photographic light-sensitive material that has excellent color reproducibility and color development, and has significantly improved light fastness of magenta dye images. I was able to do that.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a pyrazoloazole magenta coupler having at least one group represented by the following general formula [I]. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, J represents a divalent linking group, A represents an arylene group, and Y forms a 5- to 7-membered heterocycle with the nitrogen atom. Represents a group of nonmetallic atoms necessary to ]