JPH061358B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material containing a magenta coupler which forms a magenta dye pixel having high color-developing property and improved storability, particularly light fastness. Regarding materials. More specifically, it relates to a silver halide color photographic light-sensitive material containing a novel magenta coupler.

(Prior Art) Usually, in a silver halide color photographic light-sensitive material, exposed silver halide grains are reduced by an aromatic primary amine type color developing agent, and an oxidized product of the color developing agent is generated at this time. Dye images can be obtained by coupling with couplers that form yellow, magenta and cyan dyes.

The coupler which has been conventionally put to practical use for forming the magenta dye is a pyrazolone type coupler, which has unfavorable side absorption and is poor in storage stability, particularly resistance to formalin gas (formalin resistance). It has drawbacks.

In order to improve the above-mentioned drawbacks, various 1H-pyrazolo [3,2-C] -s-triazole magenta couplers have been proposed so far. For example, U.S. Patent 3,725,065,
It is described in British Patents 1,252,418 and 1,334,515. The compounds described in any of the patents are, of course, superior to the pyrazolone-based magenta couplers in terms of side absorption, but the improvement in formalin resistance is insufficient, and the improvement in color development and light fastness of the image is almost shown. Absent.

The compound described in Research Disclosure 12443 cannot be put to practical use at all in terms of color developability. The 1H-pyrazolo [3,2-C] -s-triazole type magenta couplers described in JP-A-58-42045 are remarkably improved in terms of improved formalin resistance and color development, but also improved light resistance. Is hardly done.

Further, the couplers described in JP-A-59-99437 and JP-A-59-1259732 have also been improved in color forming property, but in terms of light resistance of dye images based on the couplers described, the improvement is still observed. Absent.

In the latter case, the light fastness of the image is improved only by the additive used in combination therewith. However, regarding the coupler of the compound example 19 described in the former specification, the light resistance is slightly improved, but it is still insufficient.

That is, the 1H-pyrazolo-hydraulic [3,2-C] -s-triazole magenta coupler, which has hitherto attracted attention because it has no side absorption and has high formalin resistance, has almost no light resistance in dye images. It can be said that no improvements have been made.

(Object of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material having good light resistance and formalin resistance and high color forming property.

(Structure of the Invention) The above-described object of the present invention is to provide 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 has the following general formula: It is achieved by a silver halide color photographic light-sensitive material containing a magenta coupler represented by [I].

General formula [I] In the formula, R represents a hydrogen atom or a substituent, and A represents 5 to 6
Represents a group of atoms necessary for forming a heterocyclic ring of a member. Z represents a group of non-metal atoms capable of forming a nitrogen-containing heterocycle. (However, the nitrogen-containing heterocycle represented by Z does not further form a condensed ring.) Hereinafter, unless otherwise specified, a compound represented by the general formula [I] For convenience, the group represented by is simply represented by X here.

The substituent represented by R is specifically a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, Bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group,
Ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group,
It is an alkoxycarbofonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, or a heterocyclic thio group.

Next, the magenta coupler represented by the general formula [I] of the present invention will be described in more detail.

In the general formula [I], examples of the halogen atom represented by R include a chlorine atom and a bromine atom, and a chlorine atom is particularly preferable.

The alkyl group represented by R has a carbon number of 1 to 32, and the alkenyl group and the alkynyl group have a carbon number of 2 to 2.
32, a cycloalkyl group and a cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms,
The alkyl group, alkenyl group or alkynyl group may be linear or branched.

Further, these alkyl group, alkenyl group, alkynyl group, cycloalkyl group, and cycloalkenyl group are substituents [for example, aryl, cyano, halogen atom, heterocycle,
In addition to cycloalkyl, cycloalkenyl, spiro compound residue, bridged hydrocarbon compound residue, those substituted through carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, and further through hetero atom Those substituted through an oxygen atom such as hydroxy, alkoxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, nitro, amino (including dialkylamino, etc.), sulfa Those substituted via a nitrogen atom such as moylamino, alkoxycarbonylamino, aryloxycarbonylamino, amylamino, sulfonamide, imide and ureido, alkylthio, arylthio, heterocyclic thio, sulfonyl,
Those substituted through a sulfur atom such as sulfinyl and sulfamoyl, those substituted through a phosphorus atom such as phosphonyl, and the like].

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group,
1-hexylnonyl group, 1,1′-dipentylnonyl group, 2-chloro-t-butyl group, trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4 -Di-t-
Amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfoneaminophenoxypropyl group, 3-4 '-{α- [4 "(p-hydroxybenzenesulfonyl) phenoxy] dodecanoylamino} phenylpropyne Group, 3- {4 '-[α-
(2 ″, 4 ″ -di-t-amylphenoxy) butanamido] phenyl} -propyl group, 4- [α- (O-chlorophenoxy) tetradecanamidophenoxy] propyl group, allyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned.

The aryl group represented by R is preferably a phenyl group, and this aryl group may have a substituent (for example, an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, a phenyl group, a 4-t-butylphenyl group,
2,4-di-t-aminophenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4 '
Examples thereof include-[α- (4 "-t-butylphenoxy) tetradecanamide] phenyl group.

The heterocyclic group represented by R is preferably a 5- to 7-membered heterocyclic group, which may be substituted or condensed. Specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidyl group, a 2-benzothiazolyl group and the like.

Examples of the acyl group represented by R include an acetyl group,
Alkylcarbonyl group such as phenylacetyl group, dodecanoyl group, α-2,4-di-t-amylphenoxybutanoyl group, benzoyl group, 3-pentadecyloxybenzoyl group, arylcarbonyl group such as p-chlorobenzoyl group, etc. Is mentioned.

Examples of the sulfonyl group represented by R include an alkylsulfonyl group such as a methylsulfonyl group and a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-toluenesulfonyl group.

Examples of the sulfinyl group represented by R include an alkylsulfinyl group such as an ethylsulfinyl group, an octylfinyl group and a 3-phenoxybutylsulfinyl group, an arylsulfinyl group such as a phenylsulfinyl group and an m-pentadecylphenylsulfinyl group. To be

Examples of the phosphonyl group represented by R include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenylphosphonyl group. Arylphosphonyl groups such as

The carbamoyl group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N-methylcarbamoyl group, N, N-dibutylcarbamoyl group and N- (2-pentadecyl group. Examples include octylethyl) carbamoyl group, N-ethyl-N-dodecylcarbamoyl group, N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl group.

The sulfamoyl group represented by may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and for example, an N-propylsulfamoyl group, N, N-
Examples thereof include a diethylsulfamoyl group, an N- (2-pentadecyloxyethyl) sulfamoyl group, an N-ethyl-N-dodecylsulfamoyl group, and an N-phenylsulfamoyl group.

Examples of the spiro compound residue represented by R include spiro [3.3] heptan-1-yl and the like.

Examples of the bridged carbonized compound residue represented by R include, for example, bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1] decan-1-yl, 7,7-dimethyl- Bicyclo [2.2.1] heptan-1-yl etc. are mentioned.

The alkoxy group represented by R may be further substituted with the above-mentioned substituents for the alkyl group, and examples thereof include a methoxy group, a propoxy group, a 2-ethoxyethoxy group, a pentadecyloxy group and a 2-dodecyloxy group. Examples thereof include an ethoxy group and a phenethyloxyethoxy group.

As the aryloxy group represented by R, phenyloxy is preferable, and the aryl nucleus may be further substituted with the substituent or the atom described above for the aryl group, for example, a phenoxy group, pt-butylphenoxy group. Group, m-pentadecylphenoxy group and the like.

The heterocyclic oxy group represented by R is preferably one having a 5- to 7-membered heterocycle, and the heterocycle may further have a substituent, for example, 3,4,5,6-tetrahydro. Examples thereof include a pyranyl-2-oxy group and a 1-phenyltetrazole-5-oxy group.

The siloxy group represented by R may be further substituted with an alkyl group and the like, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group and a dimethylbutylsiloxy group.

Examples of the acyloxy group represented by R include an alkylcarbonyloxy group, an arylcarbonyloxy group and the like, which may further have a substituent, and more specifically, an acetyloxy group, α-chloroacetyl group. Examples thereof include an oxy group and a benzoyloxy group.

The carbamoyloxy group represented by R is an alkyl group,
It may be substituted with an aryl group and the like, and examples thereof include an N-ethylcarbamoyloxy group, an N, N-diethylcarbamoyloxy group and an N-phenylcarbamoyloxy group.

The amino group represented by may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include an ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, 2
-Chloro-5-hexadecanamide anilino group and the like.

Examples of the acylamino group represented by R include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and the like, which may further have a substituent, specifically, an acetamide group, α-
Examples thereof include an ethylpropanamide group, an N-phenylacetamide group, a dodecane amide group, a 2,4-di-t-amylphenoxyacetamide group, and an α-3-t-butyl-4-hydroxyphenoxybutanamide group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent. Specific examples thereof include a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonamide group, a p-toluenesulfonamide group, and a 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group represented by R may be an open chain type or a cyclic type, and may have a substituent, and examples thereof include a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, and glutar. Examples thereof include an imide group.

The ureido group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and for example, an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group, Np-tolyl ureido group etc. are mentioned.

The sulfamoylamino group represented by R may be substituted with an alkyl group, an aryl group (preferably a phenyl group) or the like, and examples thereof include N, N-dibutylsulfamoylamino group and N-methylsulfamoylamino. Group, N-phenylsulfamoylamino group and the like.

The alkoxycarbonylamino group represented by R may further have a substituent, and examples thereof include a methoxycarbonylamino group, a methoxyethoxycarbonylamino group and an octadecyloxycarbonylamino group.

The aryloxycarbonylamino group represented by R is
It may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group.

The alkoxycarbonyl group represented by R may further have a substituent, for example, a methoxycarbonyl group, a butyloxycarbonyl group, a dodecyloxycarbonyl group, an octadecyloxycarbonyl group, an ethoxymethoxycarbonyloxy group, a benzyloxycarbonyl group. Etc.

The aryloxycarbonyl group represented by R may further have a substituent, and examples thereof include a phenoxycarbonyl group, a p-chlorophenoxycarbonyl group, and a m-pentadecyloxyphenoxycarbonyl group.

The alkylthio group represented by R may further have a substituent, for example, an ethylthio group, a dodecylthio group,
Examples include octadecylthio group, phenethylthio group and 3-phenoxypropylthio group.

The arylthio group represented by R is preferably a phenylthio group and may further have a substituent, for example, a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group, a 3-octadecylphenylthio group, Two
Examples include -carboxyphenylthio group and p-acetaminophenylthio group.

The heterocyclic thio group represented by R is preferably a 5- to 7-membered heterocyclic thio group, and may further have a condensed ring,
It may have a substituent. Examples thereof include a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3,5-triazole-6-thio group.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a triazole ring and a tetrazole ring.

Further, the substituents (for example, R to R ₈ ) on the heterocycle in the general formula [I] and the general formulas [II] to [VIII] described later are Moieties (where R'and Z'are R in the general formula [I],
It is synonymous with Z and X is as described above. A), a so-called bis type coupler is formed, which is of course included in the present invention.

What is represented by the general formula [I] is more specifically represented by, for example, the following general formulas [II] to [VII].

General formula [II] General formula [III] General formula [IV] General formula [V] General formula [VI] General formula [VII] In the general formulas [II] to [VII], R to R ₈ and X
Is as defined for R in the above general formula [I], and X is as described above.

Among the general formulas [I], those represented by the following general formula [VIII] are preferable.

General formula [VIII] In the formula, R and X are Z. ₁ is R, X and Z in the general formula [II].
Is synonymous with.

Among the magenta couplers represented by the general formulas [II] to [VII], the magenta coupler represented by the general formula [II] is particularly preferable.

Regarding the substituents on the heterocycle in the general formulas [II] to [VIII], R in the general formula [I] and R in the general formulas [II] to [VIII] satisfy the following condition 1. It is preferable that the following conditions 1 and 2 are satisfied, and it is particularly preferable that the following conditions 1, 2 and 3 are satisfied.

 Condition 1 The root atom directly connected to the heterocycle is a carbon atom.

Condition 2 Only one hydrogen atom is bonded to the carbon atom
Yes, or not at all.

Condition 3 The bonds between the carbon atom and the adjacent atom are all single bonds.

The most preferable substituent R on the heterocycle is represented by the following general formula [IX].

General formula [IX] In the formula, R ₉ , R ₁₀ and R ₁₁ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group,
Heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, Siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group,
An imide group, an ureido group, a sulfamoylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, and a heterocyclic thio group, and R ₉ and R ₁₀ And at least two of R ₁₁ are not hydrogen atoms.

Also, two of R ₉ , R ₁₀ and R ₁₁ , such as R ₉ and R
₁₀ may combine with each other to form a saturated or unsaturated ring (eg, cycloalkane, cycloalkene, heterocycle), and R ₁₁ may bond to the ring to form a bridged hydrocarbon compound residue. Good.

The group represented by R _{2 to} R ₁₁ may further have a substituent, and specific examples of the group represented by R _{2 to} R ₁₁ and the substituent which the group may have include those described above. Formula [I]
Specific examples of the group represented by R in and the substituents.

Further, for example, a ring formed by combining R ₂ and R ₁₀ and R _{9 to} R ₉
Specific examples of the organic hydrocarbon compound residue formed by ₁₁ and the substituents which it may have include specific examples of the cycloalkyl, cycloalkenyl, and heterocyclic groups represented by R in the aforementioned general formula [I], and The substituent is mentioned.

Among the general formula [IX], (i) when two of R _{9 to} R ₁₁ are alkyl groups, (ii) one of R _{9 to} R ₁₁ , for example, R ₉ is a hydrogen atom. And when the other two R ₁₀ and R ₁₁ combine to form a cycloalkyl group with the root carbon atom.

Further preferred among (i) is 2 of R _{9 to} R _11.
One is an alkyl group and the other one is a hydrogen atom or an alkyl group.

Here, the alkyl, the cycloalkyl may further have a substituent, and specific examples of the alkyl, the cycloalkyl and the substituent thereof include alkyl represented by R in the general formula [I], cycloalkyl and the Specific examples of the substituents are given.

The heterocycle formed by A in the general formula [I] can be preferably represented by the following general formula [X].

General formula [X] Here, A ₂ represents a non-metal atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ₁₂ represents an alkyl group, an aryl group or an acyl group. Typical specific examples of the heterocycle represented by the above general formula [X] are shown below.

Pyrrolidinylidene, Pyrrolidinylidene, Indolinylidene, Pyridylidene, Quinolidene, Imidazolidinylidene, Imidazolidene, Pyrazolinilidene, Benzimidazolidylidene, Pyrimidinilidene, Quinazolinylidene,
Prinylidene, triazolylidene, tetrazolidene,
Oxazolidinylidene, oxazolilidene, benzoxazolilidene, thiazolidinylidene, thiazolilidene,
Examples thereof include benzthiazolilidene, oxadiazolilidene, thiadiazolylidene, and furazanilidene.

One of these heterocycles is a substituent such as an alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, nitro group, cyano group, hydroxyl group, thio group, halogen atom, carboxylic acid group or sulfonic acid group. In addition to those substituted above, those heterocycles also include those forming a condensed ring (for example, a heterocycle or an aromatic ring which is condensed) at an appropriate position.

Specific examples of the magenta coupler of the present invention represented by the above general formula [I] are shown below, but the present invention is not limited thereto.

Exemplified compound The typical synthesis method of the magenta coupler of the present invention is shown below.

Method (1)Method (2)In the formula, B is an alkyl group or a substituted alkyl group, and Y
Represents an anion of an acid. R, R₂, R₁₂, And A₂
Are synonymous with the above general formula [II] or [X], respectively.
It Also, the quaternizing agent is the target R₁₂Depending on various
Can be used.

Next, specific synthetic examples of these compounds will be shown. Journal
of the Chemical Society, Perkin I, 2047-2052 (197
7), British Patent 3,725,067, JP-A-58-102232, JP-A-58-102232
The synthesis was carried out with reference to No. 59-99437 and the like.

Synthesis of Compound Example (4) The reaction scheme is as follows.

Synthesis Example [Compound Example (4)] 13 g of 1,3-dimethylimidazolidine-2-thione and 20 g of ethyl bromoacetate were stirred for 3 hours while heating at 120 ° C. After cooling, the reaction solution was washed with ethyl acetate to obtain 22 g of oily 1,3-dimethyl-2-ethoxycarbonylmethylthioimidazolidinium bromide.

22 g of the bromine salt and 7-amino-6-methyl-3-
[(2-dodecylsulfonyl-1-methyl) ethyl]-
1H-pyrazolo [3,2-C] -s-triazole 30
g was dissolved in 500 ml of ethanol, 20 ml of triethylamine was further added, and the mixture was heated under reflux for 2 hours under a nitrogen stream. After cooling, the solvent was distilled off under reduced pressure. The residue was dissolved in ethyl acetate, washed with 1N hydrochloric acid, the organic layer was concentrated under reduced pressure, and purified by silica gel column chromatography using a hexane / ethyl acetate concentrated solvent. 28 g of the desired product was obtained. The structure of the target product was confirmed by NMR, IR, and mass spectrum.

The magenta coupler according to the present invention is added to the photographic light-sensitive material of the present invention in an amount of 1.5 × 10 ⁻³ mol to 1 mol of silver.
The range of 7.5 × 10 ^-1 mol is preferable, and 1 × 1 is more preferable.
It is in the range of 0 ^-2 mol to 5 x 10 ^-1 mol.

The silver halide photographic light-sensitive material of the present invention can be, for example, a negative and a positive film of a color negative, a color photographic paper, and the like. In particular, when the color photographic paper used for direct viewing is used, the method of the present invention can be used. The effect of is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention, including this color photographic paper, may be monochromatic or polychromatic. In the case of a multi-color silver halide photographic light-sensitive material, it is usually used as a photographic coupler in order to perform color reduction method color reproduction.
A silver halide emulsion layer containing magenta, yellow and cyan couplers, and a non-photosensitive layer are laminated on a support in an appropriate number and order of layers. The order may be appropriately changed depending on the priority performance and purpose of use.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes, as the silver halide, ordinary silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride. Any of those used in emulsions can be used.

The silver halide grains used in the silver halide emulsion of the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halogen ions and silver ions may be mixed at the same time, or while one of them is present, the other may be mixed. Also, taking into consideration the critical growth rate of silver halide crystals, halide ions and silver ions are added in a p
It may be produced by sequentially adding H and PAg while controlling them. After the growth, the conversion method may be used to change the halogen composition of the grains.

The grain size, grain shape, grain size distribution and grain growth rate of the silver halide grains can be controlled by using a silver halide solvent, if necessary, during the production of the silver halide emulsion of the present invention.

The silver halide grains used in the silver halide emulsion of the present invention have a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt, a rhodium salt or a complex salt in the step of forming and / or growing the grain. , Metal salt can be added to the inside of the particle and / or the surface of the particle by inclusion of iron salt or complex salt, and reduced to the inside and / or the surface of the particle by placing in a suitable reducing atmosphere. A sensitizing nucleus can be provided.

In the silver halide emulsion of the invention, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the soluble salts may be contained therein. The salts can be removed by the method described in Research Disclosure No. 17643.

The silver halide grains used in the silver halide emulsion of the present invention may be composed of a layer having a uniform inside and surface,
It may consist of different layers.

The silver halide grain used in the silver halide emulsion of the present invention 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 used in the silver halide emulsion of the present invention may have a regular crystal form, or may have an irregular crystal form such as a sphere or a plate. In these particles, any ratio of [1,0,0] plane to [1,1,1] 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 silver halide emulsion of the present invention may be used as a mixture of two or more kinds of silver halide emulsions which are separately formed.

The silver halide emulsion of the present invention is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
The sulfur sensitization method using active gelatin, the selenium sensitization method using a selenium compound, the reduction sensitization method using a reducing substance, the noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Is also good.

The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
A silver halide emulsion during and after the chemical ripening and / or after the chemical ripening for the purpose of preventing fog during storage or photographic processing and / or keeping the photographic performance stable. By the time of coating, compounds known as antifoggants or stabilizers in the photographic industry can be added.

As the binder (or protective colloid) of the silver halide emulsion of the invention, it is advantageous to use gelatin,
In addition, hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer of the light-sensitive material using the silver halide emulsion of the present invention, and other hydrophilic colloid layers can be obtained by crosslinking the binder (or protective colloid) molecules to increase the film strength. It is dura. The hardener is preferably added in an amount capable of hardening the photosensitive material to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

A plasticizer may be added for the purpose of increasing the flexibility of the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention.

A photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains a dispersion (latex) of a water-insoluble or sparingly-soluble synthetic polymer for the purpose of improving dimensional stability. Can be done.

In the color development processing, the emulsion layer of the silver halide color photographic light-sensitive material of the present invention is subjected to a coupling reaction with an oxidant of an aromatic primary amine developer (for example, p-phenylenediamine derivative or aminophenol derivative). Dye-forming couplers are used that do the above to form dyes. The dye-forming coupler is usually selected so that a dye that absorbs the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer, and a yellow dye-forming coupler is formed in the blue-light-sensitive emulsion layer. A coupler, a magenta dye-forming coupler is used for the green light-sensitive emulsion layer, and a cyan dye-forming coupler is used for the red light-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

Examples of yellow dye-forming couplers include acylacetamide couplers (for example, benzoylacetanilides and pivaloylacetanilides), and magenta dye-forming couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, and pyrazoloside couplers in addition to the couplers of the present invention. There are triazoles, open-chain acylacetonitrile couplers and the like, and cyan dye forming couplers include naphthol couplers and phenol couplers.

It is desirable that these dye-forming couplers have a group having a carbon number of 8 or more, which makes a coupler called a ballast group non-diffusible in the molecule. In addition, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye, but only need to reduce 2 molecules of silver ions even if they are 4-equivalent. Either of two equivalents may be used.

For the hydrophobic compound such as a dye-forming coupler which does not need to be adsorbed on the silver halide crystal surface, various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used. Can be appropriately selected according to the chemical structure of the hydrophobic compound such as The oil-in-water emulsion dispersion method can be applied to a conventionally unknown method of dispersing a hydrophobic additive such as a coupler, and is usually a high-boiling organic solvent having a boiling point of about 150 ° C. or higher, and if necessary, a low boiling point and / or Alternatively, a water-soluble organic solvent is used in combination to dissolve, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution and emulsified by using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flowgit mixer, and a long-wave device. After dispersion, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As the high boiling point oil agent, a phenol derivative, a phthalic acid ester, a phosphoric acid ester, which does not react with the oxidized product of the developing agent,
Boiling point of citric acid ester, benzoic acid ester, alkylamide, fatty acid ester, trimesic acid ester, etc. 15
An organic solvent having a temperature of 0 ° C. or higher is used.

Dissolving a hydrophobic compound in a solvent having a low-boiling point solvent alone or in combination with a high-boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, a cation A cationic surfactant can be used.

Between the emulsion layers of the color photographic light-sensitive material of the present invention (same color-sensitive layers and / or different color-sensitive layers), an oxidant of a developing agent or an electron transfer agent moves to cause color turbidity or sharpness. An anti-foggant is used to prevent deterioration and conspicuous graininess.

The color antifoggant may be used in the emulsion layer itself, or may be used in the intermediate layer by providing an intermediate layer between adjacent emulsion layers.

An image stabilizer which prevents deterioration of a dye image can be used in a color light-sensitive material using the silver halide emulsion of the present invention.

The protective layer of the light-sensitive material of the present invention, a hydrophilic colloid layer such as an intermediate layer is provided with an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the light-sensitive material due to friction or the like and to prevent deterioration of an image by UV light. It may be included.

The color light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and / or an antiirradiation layer. In these layers and / or emulsion layers, dyes which may be bleached or bleached from the color light-sensitive material during development processing may be incorporated.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the silver halide light-sensitive material using the silver halide emulsion of the present invention, the writing sensitivity for reducing the gloss of the light-sensitive material is increased, and the sticking of the light-sensitive materials to each other is prevented. A matting agent can be added for the purpose.

A lubricant can be added to reduce the sliding friction of the light-sensitive material using the silver halide emulsion of the present invention.

An antistatic agent for the purpose of antistatic can be added to a light-sensitive material using the silver halide emulsion of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used to protect the emulsion layer and / or the emulsion layer on the side of the support other than the emulsion layer. It may be used for the colloid layer.

In the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material using the silver halide emulsion of the present invention, the coating property is improved,
Various surfactants are used for the purpose of preventing static charge, improving slipperiness, emulsifying and dispersing, preventing adhesion and improving photographic properties (such as acceleration of development, hardening, and sensitization).

The light-sensitive material using the silver halide emulsion of the present invention is a photographic emulsion layer, the other layers are a baryter layer or a paper laminated with α-olefrein polymer, a flexible reflective support such as synthetic paper, cellulose acetate, nitric acid. Cellulose, polystyrene,
It can be applied to films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide, and rigid bodies such as glass, metal and pottery.

The silver halide material of the present invention may be directly or after (corresponding to the adhesiveness of the support surface, antistatic property, dimensional stability, resistance to corrosion, etc.) after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. It may be applied via one or more subbing layers) to improve wear, hardness, antihalation, frictional properties and / or other properties.

When coating a photographic light-sensitive material using the silver halide emulsion of the present invention, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in the spectral region where the emulsion layer constituting the light-sensitive material of the present invention has sensitivity. As the light source, natural light (sunlight), tungsten electric lamp, fluorescent lamp, xenon arc lamp, carbon arc lamp,
Xenon flash lamp, cathode ray tube flying spot,
Various laser light, light emitting diode light, electron beam, X-ray, γ
Any known light source such as light emitted from a phosphor excited by a ray or an α ray can be used.

The exposure time is, of course, from 1 millisecond to 1 second which is usually used in a camera, and it is also possible to use exposure shorter than 1 microsecond, for example, 100 microsecond to 1 microsecond using a cathode ray tube or a xenon flash lamp. However, exposure longer than 1 second is possible. The exposure may be performed continuously or intermittently.

The silver halide photographic light-sensitive material of the present invention can form an image by color development known in the art.

The aromatic primary amine color developing agent used in the color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers include aminophenol-based and p-phenylenediamine-based derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. Also, these compounds are generally used at a concentration of about 0.1 g to about 30 g for color developer 1, preferably about 1 g to about 1.5 g for color developer 1.

Examples of the aminophenol-based developer include O-aminophenol, p-aminophenol, 5-amino-2-
Oxytoluene, 2-amino-3-oxytoluene, 2
-Oxy-3-amino-1,4-dimethylbenzene and the like are included.

Particularly useful primary aromatic amino color developing agents are N, N '.
It is a -dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted with any substituents. Among them, examples of particularly useful compounds include N, N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N, N'-diethylaniline, 4,
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developing solution used in the processing of the present invention contains various components which are usually added to the color developing solution in addition to the primary aromatic amine color developing agent, such as sodium hydroxide and sodium carbonate. An alkali agent such as potassium carbonate, an alkali metal sulfite salt, an alkali metal bisulfite salt, an alkali metal thiocyanate salt, an alkali metal halide, benzyl alcohol, a water softening agent and a thickening agent can be optionally contained. The pH value of this color developer is usually 7 or more, and most commonly about 10
It is about 13.

In the present invention, after color development processing, processing is carried out with a processing solution having fixing ability. When the processing solution having fixing ability is a fixing solution, bleaching processing is carried out before that. As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it to silver halide, and at the same time, acts to color the uncolored part of the color former. And has a structure in which a metal ion such as iron, cobalt, or copper is coordinated with an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes a polycarboxylic acid or an aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these.

[1] Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminodiacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] Nitrilotritri Sodium acetate salt The bleaching agent used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide, a metal salt or a chelating agent. In addition, it is possible to appropriately add pH buffers such as borate, oxalate, acetate, carbonate, and phosphate, and those known to be added to ordinary bleaching solutions such as alkylamines and polyethylene oxides. it can.

Further, the fixer and the bleach-fixer are ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid A single pH buffer or two or more pH buffers composed of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be contained.

When the bleach-fixing solution (bath) is replenished with a bleach-fixing replenisher in the process of the present invention, the bleach-fixing solution (bath) may contain a thiosulfate, a thiocyanate or a sulfite. The bleach-fixing replenisher may contain these salts and be replenished to the processing bath.

In the present invention, in order to increase the activity of the bleach-fixing solution, air may be blown or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or a suitable oxidizing agent is used. For example, hydrogen peroxide, bromate, persulfate or the like may be added as appropriate.

EXAMPLES Next, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

Example 1 0.1 mol of each of the magenta coupler and the comparative coupler of the present invention as shown in Table 1 was taken with respect to 1 mol of silver.
Tricresyl phosphate in an amount 1 times the weight of the coupler and ethyl acetate in the amount 3 times the weight of the coupler were added, and the mixture was heated to 60 ° C. to be completely dissolved. This solution was added to 120 ml of a 5% aqueous solution of alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
Was mixed with 1200 ml of a 5% gelatin aqueous solution containing and was emulsified and dispersed by an ultrasonic disperser to obtain an emulsion. Then, 4 kg of this dispersion was added to a green-sensitive silver iodobromide emulsion (containing 6 mol% of silver iodide).
And a 2% solution of 1,2-bis (vinylsulfonyl) ethane as a hardening agent (water: methanol = 1: 1) 120m
1 was added, and the mixture was applied onto a transparent polyester base which was subbed and dried to prepare Samples 1-1 to 1-14. (Amount of coated silver 20 mg / 100 cm ² ) The sample thus obtained was subjected to wedge exposure according to a conventional method, and then the following development processing was performed.

[Development process] The composition of the treatment liquid used in each treatment step is as follows.

[Color developer composition] [Bleaching composition] [Fixer composition] [Stabilizing liquid composition] 1) The specific sensitivity is the reciprocal of the exposure amount that gives a density of fog +0.1, and the sample No. 100 using the comparative coupler 1) was set to 100.

2) The temperature is adjusted to 30 ° C. and 62% RH, and the sample is placed in a closed container containing 6 cc of a so-called moistened 0.9% formalin aqueous solution for 3 days, and then color development is performed. For comparison, a sample not treated with formalin is developed together. The formalin pressure resistance was calculated according to the following equation.

3) The sample after color development was irradiated on a xenon fade meter for 5 days, and% dye remained at initial density = 1.0.
showed that.

Comparison coupler 1) Comparison coupler 2) From Table 1, the coupler of the present invention shows that the coupler of the present invention has color developability, formalin resistance
It is clear that it has excellent photoluminescent property.

[Example-2] Samples 1-1 to 1-9 in Example-1 were similarly wedge-exposed and subjected to the following development processing. The results are shown in Table 2. In addition, insensitivity and light resistance were measured in Example-1
The same method was used.

[Development processing step] Color development 38 ° C 3 minutes 30 seconds Bleaching fixing 33 ° C 1 minute 30 seconds Stabilization treatment / or water washing treatment 25-30 ° C 3 minutes Drying 75-80 ° C 2 minutes Treatment used in each processing step The liquid composition 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'-diaminostilbenzsulfonic 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 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Water adjusted to pH 7.1 with potassium carbonate or glacial acetic acid Is added to bring the total amount to 1.

[Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g Ethylene glycol 10 g As is clear from the results in Table 2, Samples 2-4 to 2-14 containing the coupler of the present invention are superior in sensitivity, color developability and light resistance to the comparative sample.

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 as silver content, 8 mg of yellow coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved 3
Layer containing mg di-octyl phthalate coupler solvent (2) Containing 2 mg dibutyl phthalate UV absorber solvent in which 12 mg gelatin, 0.5 mg 2,5-di-t-octyl hydroquinone and 4 mg UV absorber are dissolved. Middle tier.

(3) 18 mg gelatin, 4 mg green sensitive silver chlorobromide emulsion, and 5 mg magenta coupler and 0.2 mg.
2,5-di-t-octylhydroquinone was dissolved.
Layer containing 2.5 mg of 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 as silver content, 3.5 mg of cyan coupler and 0.1 mg of 2,5-di-t-octylhydroquinone were dissolved 2.
Amount containing 0 mg of tricresyl phosphate coupler solvent.

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

A coating aid was added to each of the layers (1) to (6), and a gelatin crosslinking agent was added to each of the layers (4) and (6).

As the ultraviolet absorbers (2) and (4), U having the following structure is used.
V-1 and UV-2 were mixed and 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 thereof.

Each sample was measured for magenta density after white exposure.

The specific sensitivity and light resistance were measured in the same manner as in Example 1.

From Table 3, it is clear 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 Y-coupler C-coupler

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Matsunaga No. 1 Sakura-cho, Hino-shi, Tokyo Photo Konishi Roku Photo Industry Co., Ltd. (56) Reference JP-A-59-99437 (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 has the following general formulas [II] to [VII]. ] A silver halide color photographic light-sensitive material containing at least one magenta coupler represented by General formula [II] General formula [III] General formula [IV] General formula [V] General formula [VI] General formula [VII] [In the formula, R, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a substituent, and X is Represents a group (wherein A represents an atomic group necessary to form a 5- or 6-membered heterocycle). ]