JPH08201977A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance sharpness and stability against change of development processing conditions by incorporating specified dispersed fine solid particles in a photographic constituent layer and specifying a ratio of the total coated gelatin amount to the total film silver amount in the photographic constituent layers. CONSTITUTION: The silver halide color photographic sensitive material has each at least one yellow, magenta, and cyan coupler containing photosensitive silver halide emulsion layers and the photographic constituent layers comprising at least one nonphotosensitive layer on a support, and at least one of the photographic constituent layers has the ratio of the total coated gelatin amount to the total film silver amount of 3.8-7.8, and contains the dispersed fine solid particles of a dye represented by the formula in which D is a compound residual group having a chromophore; X is a dissociable H atom or a group having it and combined directly or via a divalent bonding group with D; and Y is an integer of 1-7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, and more specifically, it has high sharpness and stability in performance against changes in development processing conditions. The present invention relates to a silver halide photographic light-sensitive material which is excellent in stability and is excellent in stability during production.

[0002]

2. Description of the Related Art The sharpness is an important characteristic among the factors that determine the image quality of silver halide photographic light-sensitive materials. As is well known in the literature of photographic science and reports to the literature, etc., it is the reflection and scattering characteristics of light of the photosensitive material that influence the sharpness, and the blurring and bleeding of light that occurs during exposure. It deteriorates the sharpness.

The diffusion of light that occurs when the light incident on the light-sensitive material is reflected by the interface between the support and the emulsion layer, the surface of the support on the side opposite to the emulsion layer or the surface of the emulsion layer is called halation. Diffusion caused by scattering by silver halide grains in the emulsion layer is called irradiation. Various techniques have been proposed for a long time to prevent such halation and iranitation. In particular, anti-halation that absorbs light that has passed through the emulsion layer on the side opposite to the incident direction of light to the emulsion layer (usually the lower side). A method of providing a colored layer called a layer, a method of dyeing an emulsion layer with a dye (anti-irradiation dye) that absorbs light in a wavelength range corresponding to the photosensitive wavelength of the layer, and the like are practically used as effective methods. .

Organic dyes are often used for coloring the antihalation layer and dyeing for preventing irradiation. Dyes used for such purposes are required to have various characteristics as described below in order to be incorporated into a light-sensitive material. (1) It has absorption characteristics suitable for a desired wavelength range. (2) Photochemically inactive, that is, incorporation into a light-sensitive material does not adversely affect photographic characteristics. (3) Do not leave detrimental or elution in the course of photographic processing to leave harmful coloring on the processed light-sensitive material. (4) For the purpose of coloring or dyeing a specific photographic constituent layer, do not diffuse or transfer to other layers. (5) It should be possible to provide stable performance in which discoloration occurs due to the manufacturing process of photographic light-sensitive materials and the storage of products after manufacture.

Among these characteristics, (3) and (4) are contradictory characteristics of the dye. That is, since a dye having a good decolorizing property and a good elution property is usually selected, it is often necessary to use a dye having a high diffusibility. As a result, it is difficult to limit the presence of dyes in a particular photographic layer. On the other hand, most of recent photographic systems using silver halide are colorized and are put to practical use for various purposes. Although various color image forming methods have been proposed, the most widely used one at present is a cup with an oxidation product of an aromatic primary amine developing agent which is produced when a photosensitive silver halide grain is developed. This is a system using a so-called color coupler capable of forming a dye by a ring reaction. By using a coupler that forms yellow, magenta and cyan dyes in this reaction, it is possible to obtain a full-color surface image by a subtractive method using these as the three primary colors.

In general color light-sensitive materials, mainly blue,
A light-sensitive emulsion layer comprising a combination of light-sensitive silver halide emulsions spectrally sensitized separately in the green and red regions and a dye-forming coupler corresponding to each complementary color is provided as a separate layer. A non-photosensitive emulsion layer is also provided for the purpose of separating the color development between the photosensitive emulsion layers or protecting the surface of the photosensitive material.

The dyes used for the purpose of improving the sharpness as described above are incorporated in the above-mentioned light-sensitive emulsion layer or non-light-sensitive emulsion layer. At this time, coloring a specific layer of the photographic constituent layer is a very important technique, and particularly when it is used as an antihalation layer, it is limited to a desired layer in order to maximize its effect. The presence of dye is essential. The reason is that in order to prevent halation, it is necessary to provide a layer having a high light absorption rate under the photosensitive emulsion layer, and the dye for this purpose moves,
This is because the effect is reduced by diffusion, and further, the moved photosensitive emulsion layer is adversely affected such as desensitization. For this reason, many reports have been made on techniques for preventing the diffusion of dyes.

Among them, a solid fine particle dispersion obtained from a dye of a type which has various characteristics, particularly high absorbance and immobilization property and which becomes diffusible or non-diffusible depending on the difference in pH, is disclosed in Japanese Patent Laid-Open No. HEI-3. -7931.

[0009]

However, when the present inventors prepared a color light-sensitive material using a solid fine particle dispersion obtained from a dye of the above type and examined various performances, serious problems were found. It became clear.
That is, it has been found that the photosensitive material in which the above-mentioned dye dispersion is incorporated in the antihalation layer has a large fluctuation in photographic performance due to changes in development processing conditions, which is a practical problem.

The magnitude of this variation also depends on the color coupler used, so that the color balance of the dye image varies due to changes in processing conditions, which is not preferable. Further, it has been found that such a problem becomes more serious as the grain size of the silver halide emulsion used becomes smaller. The grain size of silver halide grains contained in the light-sensitive material greatly affects the graininess of the obtained image. That is, the larger the particle size, the coarser the grain, and the smaller the particle, the finer the grain. Therefore, in order to form a light-sensitive material excellent in graininess, it is desired to use silver halide grains having a grain size as small as possible. However, if the above problems occur, the graininess and the processing stability are not compatible with each other, which is a practical problem.

Further, the coating liquid containing the solid fine particle dispersion of the dye is not sufficiently stable over time due to changes in the conditions during the production of the photosensitive material, which causes problems such as deterioration of image quality. Therefore, the stability of the coating liquid containing the solid fine particle dispersion of the dye is desired. As is clear from the above,
A first object of the present invention is to have a solid dispersion of a dye capable of limiting and coloring a specific layer of a photographic light-sensitive material,
It is an object of the present invention to provide a silver halide color photographic light-sensitive material having excellent sharpness and stability against changes in development processing conditions. A second object of the present invention is to provide a stable silver halide color photographic light-sensitive material, the performance of which does not fluctuate even when the conditions during manufacturing of the light-sensitive material are changed.

[0012]

The above objects of the present invention are as follows. At least one yellow coupler-containing photosensitive silver halide emulsion layer, a magenta coupler-containing photosensitive silver halide emulsion layer and a cyan coupler-containing photosensitive silver halide emulsion layer, and at least one non-photosensitive layer on the support. In a silver halide photographic light-sensitive material having a photographic constituent layer, the solid fine particle dispersion of the dye represented by the general formula (VII) is contained in at least one of the photographic constituent layers. A silver halide color photographic light-sensitive material, characterized in that the ratio of the total gelatin coating amount to the total coating silver amount is 3.8 to 7.8.

[0013]

[Chemical 10]

In the formula, D represents a compound residue having a chromophore, X represents a dissociative hydrogen bonded to D directly or through a divalent linking group or a group having a dissociative hydrogen, and Y represents 1 Represents an integer from 1 to 7. 2. 1) The solid fine particle dispersion of the dye is contained after a heat treatment step at 40 ° C. or higher.
The described silver halide color photographic light-sensitive material. 3. The solid fine particle dispersion of the dye contains a compound represented by the following general formula (VIII).
Alternatively, the silver halide color photographic light-sensitive material described in 2.

[0015]

[Chemical 11]

In the formula, R represents a hydrogen atom, a hydrophobic group or a hydrophobic polymer, P contains at least one of the following structural units A, B and C, and the polymerization degree of P is 10 or more and 3500 or less. Represents a polymer. m represents 0 or 1, and n represents 1 or 2.

[0017]

[Chemical 12]

R ¹ is a hydrogen atom or has 1 to 6 carbon atoms.
Represents an alkyl group of R ² is a hydrogen atom or a carbon number of 1 to
10 represents an alkyl group, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom, a methyl group, a carboxymethyl group (including ammonium or a metal salt) or a cyano group, and X represents a hydrogen atom or a carboxyl group. Represents a group (including ammonium or metal salt) or a carbamoyl group,
Y is a carboxyl group (including ammonium or metal salt), a sulfo group (including ammonium or metal salt),
Sulfoxy group (including ammonium or metal salt), sulfomethyl group (including ammonium or metal salt),-
_{CONHC (CH 3) 2 CH 2} SO ( including ammonium or metal salts) ₃ H group or -CONHCH ₂ CH ₂ CH ₂
It represents an N ⁺ (CH ₃ ) ₃ Cl ⁻ group. 4. The solid fine particle dispersion of the dye is represented by the following general formula (IX-a)
Alternatively, the silver halide color photographic light-sensitive material described in the above 1, 2 or 3 containing at least one of the compounds represented by (IX-b).

[0019]

[Chemical 13]

Where a and b are each 5 to 500
Represents the integer. 5. 5. The light-sensitive material as described in 1 to 4 above, wherein the dye is represented by the following general formula (X-a) or (X-b).

[0021]

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6. 5. The light-sensitive material described in 1 to 4 above, wherein the dye is represented by the following general formula (XI).

[0023]

[Chemical 15]

7. At least one coupler represented by the following general formula (I) or (II) as a yellow coupler, at least one coupler represented by the following general formula (III) or (IV) as a magenta coupler, and as a cyan coupler 7. The light-sensitive material described in 1 to 6 above, which contains at least one coupler represented by the following general formula (V) or (VI). Was effectively achieved by

[0025]

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[0026]

[Chemical 17]

[0027]

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In the present invention, the ratio of the total gelatin coating amount on the photosensitive emulsion layer coating side to the total coating silver amount must be 3.8 to 7.8 by weight. When the amount of gelatin exceeds the above range, the processing variation becomes large when the solid disperse dye of the present invention is used. The smaller the amount of gelatin, the smaller the variation in the treatment. Therefore, preferably this ratio is between 4.0 and
7.3, more preferably 4.0 to 6.8.

When a color coupler or the like is dissolved in a high boiling point organic solvent and dispersed in fine particles to be contained in a light-sensitive material, the emulsion film may be easily mechanically broken if the amount of gelatin is excessively reduced. However, when the light-sensitive material is stored under high temperature and high humidity conditions, there arises a problem that an oil content leaches out. Therefore, the amount of gelatin is 3.8 or more.

In the present invention, the smaller the grain size of the silver halide grains used in the light-sensitive material, the more noticeable the effect of the invention. The use of a silver halide emulsion having a smaller grain size is more advantageous for graininess. On the other hand, as described above, conventionally, when a dye having a high absorbance and an excellent fixability is used instead of the range layer, the sharpness is improved, but the fluctuation of the photographic performance due to the change of the development processing condition becomes large. In particular, the fluctuation of photographic performance becomes more remarkable as the grain size of the silver halide emulsion becomes smaller.

On the other hand, according to the present invention, even if the grain size of silver halide grains is small, excellent sharpness and graininess,
And it becomes possible to achieve processing stability. The grain size of the silver halide grains to be contained in the photosensitive emulsion layers is 0.
It is preferably 6 μm or less, more preferably 0.5 μm or less. Most preferably, it is 0.45 μm or less. There is no particular lower limit to the particle size, but it is selected so as to obtain the required sensitivity. Therefore, the particle size is preferably 0.05 μm or more.

The silver halide emulsion used is preferably a monodisperse emulsion having a small variation coefficient of grain size distribution. The standard of monodispersity is that the coefficient of variation of particle size distribution is 20% or less, preferably 1
It is 5% or less. It is also possible to mix different monodisperse emulsions and use them in the same layer to obtain the desired photographic properties. Even in such a case, the average grain size of the silver halide grains used in the same layer is 0.6 μm.
The following are preferred.

When the light-sensitive material of the present invention is formed on a transparent support, a color image having excellent sharpness and graininess can be obtained, which is very useful in preparing a print film for projection. .

Next, the dye represented by the general formula (VII) will be described. The dye represented by the general formula (VII) of the present invention is characterized by having dissociative hydrogen in the molecular structure.

The compound residue having a chromophore in D is
It can be selected from many well known dyes. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.

X represents a dissociative hydrogen bonded to D directly or via a divalent linking group or a group having a dissociative hydrogen. Divalent linking group between X and D is an alkylene group, an arylene group, a heterocyclic _{residue, -CO -, - SO n -} (n
= 0, 1, 2), -NR- (R represents a hydrogen atom, an alkyl group, an aryl group), -O-, and a divalent group combining these linking groups, and they are an alkyl group. It may have a substituent such as an aryl group, an alkoxy group, an amino group, an acylamino group, a halogen atom, a hydroxyl group, a carboxy group, a sulfamoyl group, a carbamoyl group or a sulfonamide group. Preferred examples - (CH _{2)
n - (n = 1,2,3),} - CH 2 CH (CH 3) CH
_2- , 1,2-phenylene, 5-carboxy-1,3-
Phenylene, 1,4-phenylene, 6-methoxy-1,
3-phenylene, -CONHC ₆ H ₄ -, and the like.

The dissociative hydrogen or the group having a dissociative hydrogen represented by X is not dissociated when the dye represented by the formula (VII) is added to the silver halide photographic light-sensitive material of the present invention. Therefore, it has the property of making the dye of formula (VII) substantially water-insoluble, and dissociates to make the compound of formula (VII) substantially water-soluble in the step of developing the photosensitive material. Have characteristics. Examples of the group having a dissociative hydrogen represented by X include a group having a carboxylic acid group, a sulfonamide group, a sulfamoyl group, a sulfonylcarbamoyl group, an acylsulfamoyl group, a phenolic hydroxyl group and the like. Examples of the dissociative hydrogen represented by X include hydrogen of the enol group of the oxonol dye.

The preferable range of y is 1 to 5, and the particularly preferable range is 1 to 3.

Among the compounds represented by the formula (VII), preferred are those in which the group having a dissociative hydrogen in X is a group having a carboxylic acid group, and particularly an aryl group substituted with a carboxyl group. Compounds are preferred. Further, among the compounds represented by the formula (VII), more preferred are the compounds represented by the above general formula (Xa) or the general formula (Xb).

The general formulas (Xa) and (Xb) will be described in detail below. The acidic nucleus represented by A ¹ and A ² is preferably one derived from a cyclic ketomethylene compound or a compound having a methylene group sandwiched by electron withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Pyridine,
Mention may be made of hydroxypyridone, pyrazolidinedione and 2,5-dihydrofuran. These may have a substituent.

The compound having a methylene group sandwiched by electron-withdrawing groups can be represented by Z ¹ CH ₂ Z ² .
Here, Z ¹ and Z ² are —CN, —SO ₂ R ¹¹ , and
-COR ¹¹ , -COOR ¹² , -CONHR ¹² , -SO ₂
NHR ¹² or -C [= C (CN) ₂ ] R ¹¹ is represented. R
¹¹ represents an alkyl group, an aryl group, or a heterocyclic group,
R ¹² represents a hydrogen atom or a group represented by R ¹¹ , and these may each have a substituent.

Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine,
Mention may be made of quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxodiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and coumarone. it can.
Each of these may have a substituent.

The methine group represented by L ¹ , L ² and L ³ is
It may have a substituent and the substituents may be linked to each other to form a 5- or 6-membered ring (eg, cyctopentene, cyclohexene).

The substituents which each of the above-mentioned groups may have are compounds represented by the formulas (VII), (Xa) and (Xb).
There is no particular limitation as long as it is a substituent that is substantially soluble in H5 to pH7 water. For example, the following substituents can be mentioned. Carboxylic acid group, sulfonamide group having 1 to 10 carbon atoms (for example, methanesulfonamide, benzenesulfonamide, butanesulfonamide, n-octanesulfonamide), unsubstituted or alkyl- or aryl-substituted sulfamoyl group having 0 to 10 carbon atoms (For example,
Unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, naphthylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (eg, methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl) , An acylsulfamoyl group having 1 to 10 carbon atoms (eg, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a linear or cyclic alkyl group having 1 to 8 carbons (For example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl, benzyl, phenethyl,
4-carboxybenzyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl,
Allyl), alkoxy groups having 1 to 8 carbon atoms (eg, methoxy, ethoxy, butoxy), halogen atoms (eg,
F, Cl, Br), an amino group having 0 to 10 carbon atoms (eg, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), an ester group having 2 to 10 carbon atoms (eg, methoxycarbonyl), carbon number 1-1
0 amide group (eg, acetylamino, benzamide), carbamoyl group having 1 to 10 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl) , Hydroxyphenyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4
-Butanesulfonamidophenyl), an aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy, naphthoxy), an alkylthio group having 1 to 8 carbon atoms (eg, methylthio, ethylthio, octylthio). An arylthio group having 6 to 10 carbon atoms (eg, phenylthio, naphthylthio), an acyl group having 1 to 10 carbon atoms (eg, acetyl, benzoyl, propanoyl), a sulfonyl group having 1 to 10 carbon atoms (eg, methanesulfonyl, benzene) Sulfonyl),
Ureido group having 1 to 10 carbon atoms (for example, ureido, methylureido), urethane group having 2 to 10 carbon atoms (for example,
(Methoxycarbonylamino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxybenzoxazole ring), pyridine ring, sulfolane ring, pyrrole ring, pyrrolidine ring, morpholine ring, piperazine ring, pyrimidine Ring, furan ring).

Further, more preferable compounds among the compounds represented by the general formula (Xb) are the compounds represented by the above general formula (XI). The compound represented by the general formula (XI) has hydrogen of an enol group as dissociative hydrogen.

In the formula (XI), the alkyl group represented by R ¹ includes an alkyl group having 1 to 4 carbon atoms, a 2-cyanoethyl group, a 2-hydroxyethyl group and a carboxybenzyl group, and an aryl group includes a phenyl group. 2-methylphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,6-dicarboxyphenyl group, 2-hydroxyphenyl group, 3
-Hydroxyphenyl group, 4-hydroxyphenyl group,
Examples thereof include a 2-chloro-4-carboxyphenyl group and 4-methylsulfamoylphenyl group, and examples of the heterocyclic group include groups described in Chemical formula 19 below.

[0047]

[Chemical 19]

Examples of the alkyl group of R ² include an alkyl group having 1 to 4 carbon atoms, a carboxymethyl group, a 2-hydroxyethyl group and a 2-methoxyethyl group, and an aryl group is a 2-carboxyphenyl group and a 3-carboxyphenyl group. Examples thereof include a carboxyphenyl group, a 4-carboxyphenyl group and a 3,6-dicarboxyphenyl group, and examples of the heterocyclic group include the following
Group described in 0, -COR ⁴ includes an acetyl group, and -SO ₂ R ⁴ includes a methanesulfonyl group.

[0049]

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Examples of the alkyl group of R ³ , R ⁴ , R ⁵ and R ⁶ include alkyl groups having 1 to 4 carbon atoms. R ³ , R ⁴ , R
Examples of the aryl group of ⁵ and R ⁶ include a phenyl group and a methylphenyl group. In the present invention, R ¹ is preferably a carboxyl-substituted phenyl group (eg, 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 3,6-dicarboxyphenyl).

The following is a general formula (VI) used in the present invention.
Specific examples of the compounds represented by I), (X-a), (X-b) and (XI) will be described, but the present invention is not limited thereto.

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

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[0062]

[Chemical 31]

[0063]

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[0064]

[Chemical 33]

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

[Chemical 38]

[0070]

[Chemical Formula 39]

[0071]

[Chemical 40]

The dyes used in the present invention are those described in International Patent WO
88/04794, European Patent EP027472
3A1, 276566, 299435, JP-A-52-92716, 55-155350, 5
5-155351, 61-205934, 48
-68623, U.S. Pat. Nos. 2,527,583, 348.
No. 6897, No. 37465939, No. 3933798
No. 4130429, No. 4040841, No. 3-282244, No. 3-7931, and No. 3-167.
It can be synthesized according to the method described in the specification or publication such as No. 546 or according to the method.

The solid fine particle dispersion of the dye used in the present invention can be prepared by a known method. Details of the production method are described in functional pigment application technology (published by CMC, 1991) and the like. Media distribution is one of the common methods. In this method, a dye in a wet state with water or an organic solvent called dye powder or its wet cake is made into an aqueous slurry, and a known pulverizer (for example, ball mill, vibration ball mill, planetary ball mill, vertical sand mill, roller mill, pin mill, Grind by mechanical force in the presence of dispersion media (steel balls, ceramic balls, glass beads, alumina beads, zirconia silicate beads, zirconia beads, Ottawa sand, etc.) using a coball mill, caddy mill, horizontal sand mill, attritor, etc.) To do. Of these, the average diameter of the beads is preferably 2 mm to 0.3 mm, more preferably 1 mm to 0.3 mm, still more preferably 0.5 mm to 0.3 mm.
The mm one is used. In addition to these methods, a method of pulverizing with a jet mill, a roll mill, a homogenizer, a colloid mill or a dissolver, or a pulverizing method with an ultrasonic disperser can be used.

Further, as disclosed in US Pat. No. 2,877,0012, after dissolving in a uniform solution, a poor solvent is added to precipitate solid fine particles. For example, JP-A-3-1827.
As disclosed in No. 43, a method of precipitating solid fine particles by lowering the pH after dissolving in an alkaline solution can also be used.

When these solid fine particle dispersions are prepared, it is preferable to add a dispersion aid. As the dispersion aids which have been conventionally disclosed, alkylphenoxyethoxy sulfonate, alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate ester salt, alkyl sulfosuccinate, sodium oleyl methyl tauride, naphthalene sulfonic acid Formaldehyde degenerate, polyacrylic acid, polymethacrylic acid, maleic acid acrylic acid copolymer, anionic dispersant such as carboxymethyl cellulose, cellulose sulfate, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Examples of the nonionic dispersant, cationic dispersant and betaine dispersant include those represented by the following general formula (IX-a) or (IX-
It is particularly preferable to use the polyalkylene oxide represented by b).

[0076]

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In the general formulas (IX-a) and (IX-b), a and b each represent a value of 5 to 500. Preferred a
And b are 10 to 200, respectively, and more preferable a and b.
The value of each is 50 to 150. It is preferable that the values of a and b are in this range from the viewpoint of improving the uniformity of the coated surface. In the above dispersion aid, the weight ratio of the polyethylene oxide part is preferably 0.3 to 0.9, more preferably 0.7 to 0.9, and further preferably 0.8 to 0.9. The average molecular weight of the above dispersion aid is preferably 1,000 to 30,000, more preferably 5,000 to 40,000, and even more preferably 8.0.
It is from 00 to 20,000. Further, the HLB (hydrophilic / lipophilic balance) of the above dispersion aid is preferably 7 to 30, more preferably 12 to 30, and further preferably 18 to 30. A value within this range is preferable from the viewpoint of improving the uniformity of the coated surface.

These compounds are available as commercial products, such as Pluronic manufactured by BASF.

In the following, the general formula (IX-
Specific examples of the compound represented by a) or (IX-b) will be described.

[0080]

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In the present invention, the amount of the dispersion aid used with respect to the dye of the present invention is preferably 0.05 to 0.5, more preferably 0.1 to 0.3 by weight ratio.
When the amount of the dispersion aid used is within this range, it is preferable in terms of improving the uniformity of the coated surface. Further, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, for the purpose of stabilizing and lowering the viscosity of the dispersion of solid fine particles,
Hydrophilic colloids such as polysaccharides and gelatin can also coexist. In the present invention, it is particularly preferable that the compound of the general formula (VIII) coexists.

The solid fine particle dispersion of the dye of the present invention is heat-treated before, during or after the dispersion by the method disclosed in JP-A-5-216166.

The heat treatment which is preferably applied to the dye dispersion in the present invention is a method which is carried out before the step of finely dispersing the dye powder into a solid state such as heating in a solvent, and a method in which the dye is added in the presence of a dispersant. There are a method of performing dispersion without cooling or temperature at the time of dispersing in water or another solvent, and a method of heat-treating a liquid or a coating liquid after dispersion, but it is particularly preferable to perform after dispersion.

When a plurality of solid fine particle dispersions containing the dye of the formula (VII) are used in a specific layer, at least one kind may be heat-treated.

The pH during the dispersion and during the heat treatment after the dispersion may be any condition as long as the dispersion is stably present, and is preferably the pH.
2.0 or more and 8.0 or less, more preferably 2.0 or more and 6.
It is 5 or less, more preferably 2.5 or more and less than 4.5.
When the pH during heat treatment is within this range, it is preferable from the viewpoint of improving the film strength of the coated product. The pH of the dispersion can be adjusted by using, for example, sulfuric acid, hydrochloric acid, acetic acid, citric acid, phosphoric acid, oxalic acid, carbonic acid, sodium hydrogencarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide or a buffer solution thereof. .

The temperature for the heat treatment varies depending on the heat treatment step, the size and shape of the powder or particles, the heat treatment conditions, the solvent and the like. However, in the case of heat treatment with powder, 40 ° C. to 200 ° C. is suitable, preferably 50 ° C. to 150 ° C., and when heat treating in a solvent, 40 ° C. to 150 ° C., preferably 50 ℃ to 150 ℃, 4 when heat treatment during dispersion
0 ° C. to 90 ° C. is suitable, preferably 50 ° C. to 90 ° C., and 40 ° C. when heat-treating the dispersion liquid after dispersion.
To 100 ° C is suitable, preferably 50 ° C to 95 ° C. If the temperature of the heat treatment is lower than 40 ° C, the effect is poor and it is not preferable.

When the heat treatment is carried out in a solvent, the kind of the solvent is not limited as long as it does not substantially dissolve the dye, and for example, water, alcohols (for example, methanol, ethanol, isopropyl alcohol, butanol). , Isoamyl amylcol, octanol, ethylene glycol, diethylene glycol, ethyl cellosolve), ketones (eg, acetone, methyl ethyl ketone), esters (eg, ethyl acetate, butyl acetate), alkylcarboxylic acids (eg, acetic acid, propionic acid), Examples thereof include nitriles (eg acetonitrile), ethers (eg dimethoxyethane, dioxane, tetrahydrofuran), amides (eg dimethylformamide) and the like.

Further, even when the dye is dissolved by these solvents alone, it can be used if the dye is not substantially dissolved by mixing with water or another solvent or adjusting the pH.

The time for heat treatment cannot be unequivocally stated. A low temperature requires a long time, and a high temperature requires a short time. The heat treatment can be arbitrarily set so that the heat treatment can be realized within a range that does not affect the production process, but it is usually preferably 1 hour to 4 days.

The photographic light-sensitive material is provided with a layer containing fine particles of a dye, after the fine particles thus obtained are dispersed in a suitable binder to prepare a solid dispersion of substantially uniform particles. It can be provided by coating it on a desired support. The binder is not particularly limited as long as it is a hydrophilic colloid that can be used in the photosensitive emulsion layer or the non-photosensitive layer, but gelatin or a synthetic polymer such as polyvinyl alcohol or polyacrylamide is usually used.

The fine particles in the solid dispersion have an average particle diameter of 0.
005 μm to 10 μm, preferably 0.01 μm to 5 μm, more preferably 0.01 μm to 1.5
It is preferably μm. Within this range, it is preferable in terms of non-aggregation of fine particles and light absorption efficiency.

The solid fine particle dispersion of the compound of the general formula (VII) used in the present invention can be used alone or in combination with a plurality of solid fine particle dispersions. Furthermore, the hydrophilic colloid layer to which the solid fine particles are added may be a single layer,
It may have multiple layers. For example, when a single solid fine particle dispersion is added to only one layer, when dividedly added into a plurality of layers, when a plurality of solid fine particle dispersions are simultaneously added to one layer, and when added to separate layers, etc. Examples include, but are not limited to:

The solid fine particle dispersion is preferably contained in various non-photosensitive hydrophilic colloid layers (for example, an antihalation layer, a yellow filter layer, etc.) according to its purpose, and a plurality of the nonphotosensitive layers are provided. In the light-sensitive material of the aspect described above, these plural layers can be contained. Further, the solid fine particle dispersion may be incorporated in an amount necessary for an antihalation layer, and may be added to a photosensitive silver halide emulsion layer for preventing irradiation.

The solid fine particle dispersion of the dye used in the present invention is contained in the non-photosensitive hydrophilic colloid layer in the silver halide photographic light-sensitive material according to the hue of the dye. In the light-sensitive material department of the aspect described above, it may be contained in these plural layers. The concentration of the dye in the solid fine particle dispersion of the present invention is suitably 0.1 to 50% by weight, preferably 2 to 30% by weight. The dye concentration in this range is preferable from the viewpoint of the viscosity of the dispersion.

The solid fine particle dispersion of the present invention can be contained in, for example, the photographic light-sensitive material described in JP-A-2-282244. In the present invention, it is preferable to contain the compound represented by the general formula (VIII) together with the solid fine particle dispersion in the same photographic constituent layer.

When the compound represented by the formula (VIII) is used in combination with the solid fine particle dispersion of the dye, the interaction between the dye and the bander (gelatin etc.) makes the coating difficult and has a desired absorption. This is preferable because it can solve the problem that a coating layer is difficult to obtain.

Compounds (VII) preferably used in the present invention
It is preferable that I) has a relatively higher molecular weight than the surfactants conventionally used in the field of photography (molecular weight 10
00 or more). Further, the hydrophilic group of the conventional surfactant is usually one nonionic alkylene oxide group such as ethylene oxide, anionic group such as carboxyl group, sulfone group, phosphoric acid group, and cationic group such as quaternary ammonium group. On the other hand, the hydrophilic group of the compound (VIII) has one of a repeating structure of a monomer unit containing an OH group, a repeating structure of an anionic group and a repeating structure of a cationic group. It is necessary to have the above.

The compound (VIII) can also be used as a coating aid, an antistatic agent, a surface friction modifier and a surface hydrophobizing agent.

Examples of the hydrophobic group represented by R in the general formula (VIII) include an aliphatic group (eg, alkyl group, alkenyl group, alkynyl group, etc.), aromatic group (eg, phenyl group, naphthyl group, etc.) and alicyclic group. Yes, these include those that have been replaced. As the substituent, an aliphatic group, an aromatic group,
Alicyclic group, heterocyclic group, halogen atom, hydroxyl group, cyano group,
Examples thereof include a nitro group, an N-substituted sulfamoyl group, a carbamoyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxy group, an aryloxy group, an aralkyl group and an acyl group.

When the hydrophobic group represented by R in the general formula (VIII) is an alkyl group, it has 3 to 70 carbon atoms, preferably 4 to 4 carbon atoms.
50, especially 8-24 is preferable. Furthermore, when R is a substituted or unsubstituted alicyclic group, aromatic hydrocarbon group or hydrophobic polymer, R has a greater effect of enhancing dispersion stability.

When R in the general formula (VIII) is a hydrophobic polymer, polystyrene and its derivative, polymethacrylic acid ester (eg polymethylmethacrylate) and its derivative, polyacrylic acid ester and its derivative, polybutene, Water-insoluble vinyl polymers and vinyl copolymers typified by polyvinyl acetate and polyvinyl versatate, and water-insoluble polyoxyalkylenes such as polyoxypropylene and polyoxytetramethylene,
Further, water-insoluble polymers such as polyamide and polyester can be used. In particular, polystyrene and its derivatives, polymethacrylic acid esters and their derivatives, polyacrylic acid esters and their derivatives, and polyvinyl chloride are preferably used. The degree of polymerization of the hydrophobic polymer is 2 or more and 500 or less, preferably 2 or more and 200 or less, and more preferably 2 or more and 100 or less.

Specific examples of the case where R in the general formula (VIII) is a hydrophobic group are shown below, but the invention is not limited thereto.

[0103]

[Chemical 43]

[0104]

[Chemical 44]

[0105]

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[0106]

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[0107]

[Chemical 47]

[0108]

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[0109]

[Chemical 49]

[0110]

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With respect to the compound represented by the general formula (VIII) of the present invention, P is a polymer containing at least one of the structural units A, B and C. Specific examples of the structural unit A include vinyl alcohol, α-methyl vinyl alcohol, α-propyl vinyl alcohol and the like. Examples of the structural unit B include vinyl acetate, vinyl formate, vinyl propionate and their α-substituted products.

Further, as the structural unit C, acrylic acid, methacrylic acid or crotonic acid (each containing an ammonium salt or a metal salt such as Na or K), maleic acid or itaconic acid (each a monoalkyl ester, an ammonium salt or Na) is used. , Metal salts such as K), vinylphosphonic acid, vinylsulfuric acid, acrylsulfonic acid, methacrylsulfonic acid, 2-acrylamido-3-methylpropanesulfonic acid or 2-methacrylamido-3-methylpropanesulfonic acid (each ammonium). Salt, or a metal salt such as Na or K), acrylamidopropyltrimethylammonium chloride or methacrylamideamidopropyltrimethylammonium chloride, and other monomer units that ionically dissociate in water.

Of these, the structural unit A contains a vinyl alcohol unit, the structural unit B contains a vinyl acetate unit, and the structural unit C contains a carboxylic acid (ammonium salt or a metal salt such as Na or K). ) Or sulfonic acid (including an ammonium salt or a metal salt such as Na or K) is a more preferable unit.

The content of the structural units A, B and C is not particularly limited, but when the content of the structural unit C is 1 mol% or less, the polymer represented by the general formula (VIII) is water-soluble or water-soluble. In order to be dispersible, the content of the structural unit A is preferably 50 mol% to 100 mol%.

The general formula (VII) preferably used in the present invention is
The compounds represented by I) include a wide range of compounds from water-soluble to water-dispersible. As long as the compound represented by the general formula (VIII) preferably used in the present invention is water-soluble or water-dispersible, it does not matter that P contains a structural unit other than the structural units A, B and C. Examples of these structural units include ethylene, propylene, isoptene, acrylonylolyl, acrylamide, methacrylamide, N-vinylpyrrolidone, vinyl chloride or vinyl fluoride units.

The degree of polymerization of P is 10 to 3500, preferably 10 to 2000, more preferably 10 to 1000, and particularly preferably 10 to 500.

The lower alkyl group for R ² in the structural units A and B includes an alkyl group having 1 to 10 carbon atoms, and a methyl group is particularly preferable. Further, the alkyl group may be substituted with a hydroxyl group, an amide group, a carboxyl group, a sulfonic acid group, a sulfinic acid group, a sulfonamide group or the like.

As the binder of the hydrophilic colloid layer, gelatin is most commonly used because of its photographic properties, production suitability and physical properties. When the compound represented by the general formula (VIII) is mixed in gelatin at a ratio of 1% by weight or more, a compound having a composition compatible with gelatin is preferable. As such a compound, when the structural unit B is 50 mol% or less, the structural unit C contains a carboxyl group and the number of the carboxyl group is 1 per unit, the content is 5 mol% or more, preferably 10 mol% or more. It is particularly preferably 15 mol% or more, and when the number of the carboxyl groups is n per unit, the content thereof is preferably 1 / n above. As the compound represented by the general formula (VIII) which is particularly preferable from the viewpoint of compatibility with gelatin, structural unit A is vinyl alcohol having a content of 50 mol% or more, and structural unit B is vinyl acetate having 40 mol% or less, Structural unit C is itaconic acid (ammonium salt,
Alternatively, it is a polymer containing 2 mol% or more of (including metal salts such as Na and K).

The photographic element usually has a multilayer structure of a hydrophilic binder, but depending on the layer structure, the compound represented by the general formula (VIII) can be used alone as a binder for a certain layer. As the gelatin, those having insufficient compatibility with gelatin can be used.

The compound represented by the general formula (VIII) has different optimum chemical compositions, molecular weights, etc. of P and R constituting the sensitive material of the present invention, but for any purpose,
It is particularly preferable that the weight ratio of P and R is 0.001 ≦ R / P ≦ 2, more preferably 0.01 ≦ R / P ≦ 1.

Specific examples of the compound represented by the general formula (VIII) in the present invention are shown in Table-A, but the invention is not limited thereto.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

[0125]

[Table 4]

The amount of the compound of the general formula (VIII) used in the present invention varies depending on the physical properties and amount of the solid fine particle dispersion used, but is usually 0.001 g / m ^{2 to} 10 g / m ² , preferably 0.002 g. / M ^{2 to 5} g / m ² . This range is preferable from the viewpoint of improving the uniformity of the coated surface. In the present invention, the compound represented by the general formula (VIII) may be used as a dispersant when preparing a dispersion, may be allowed to coexist after dispersion, or may be allowed to coexist immediately before coating.

The compounds represented by the general formula (VIII) are described in, for example, JP-A Nos. 62-288643 and 61-25423.
No. 7, No. 61-254238, No. 61-254239
No. 61-254240, and the like. In addition, the general formula (VIII)
When R in the polymer is an alkyl group, it is available as a commercial product (for example, MP- manufactured by Kuraray Co., Ltd.
103, MP-203, MP102, etc.).

Formula (I) preferably used in the present invention:
The content of each coupler represented by (VI) is preferably 1 × 10 ⁻³ mol to 1 mol per mol of silver.

In the general formulas (I) and (II), the coupling leaving group represented by Y is preferably a nitrogen-containing heterocyclic group having a nitrogen atom as a leaving atom or an aryl having an oxygen atom as a leaving atom. An oxy group is mentioned. More preferably, the above-mentioned nitrogen-containing heterocyclic group is preferable. The preferred examples of the compounds represented by formulas (I) and (II) are shown below, but the invention is not limited thereto.

[0130]

[Chemical 51]

[0131]

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[0132]

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[0133]

[Chemical 54]

[0134]

[Chemical 55]

In the general formula [III], the substituent of the substituted phenyl group represented by R ¹ and R ² is a linear, branched or cyclic aliphatic group (eg, methyl group, butyl group, hexadecyl group). Group, cyclohexyl group, propenyl group, 2-octadecenyl group, propargyl group, etc.),
Aromatic group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc.), alkoxy group (eg, methoxy group) Group, 2-methoxyethoxy group),
Aryloxy group (eg, phenoxy group, 2,4-di-tert-aminophenoxy group, 2-chlorophenoxy group, etc.), carboxyl group, acyl group (eg, acetyl group, benzoyl group, etc.), ester group (eg, Methoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group,
Toluenesulfonyloxy group etc.), amide group (eg acetylamino group, benzoylamino group etc.), silyl group (trimethylsilyl group etc.), silyloxy group,
Silylamino group, carbamoyl group, alkylcarbamoyl group (eg, methylcarbamoyl group, ethylcarbamoyl group, etc.), dialkylcarbamoyl group (eg, dimethylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group), aliphatic sulfonamide group ( For example, methanesulfonamide group), aromatic sulfonamide group (for example, phenylsulfonamide group),
Sulfamoyl group, alkylsulfamoyl group (for example, ethylsulfamoyl group), dialkylsulfamoyl group (for example, dimethylsulfamoyl group), mono- or dialkylamino group, sulfamide group (for example,
Dipropylsulfamoylamino group etc.), imide group (eg succinimide group, hydantoinyl group etc.), ureido group (eg phenylureido group, dimethylureido group etc.), aliphatic sulfonyl group (eg,
Methanesulfonyl group etc.), aromatic sulfonyl group (eg phenylsulfonyl group etc.), aliphatic or aromatic thio group (eg ethylthio group, phenylthio group etc.), hydroxy group, cyano group, thiocyanato group, nitro group and halogen Atom (for example, chlorine atom, bromine atom,
Iodine atom) and the like, and when they have two or more substituents, they may be the same or different from each other.

When Z ¹ represents a group capable of splitting off during a coupling reaction with an oxidized product of a developing agent, specific examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom) and an alkoxy group. (For example, an epoxy group, a dodecyloxy group, a methoxyethylcarbamoylmethoxy group,
Carboxypropyloxy group, methylsulfonylethoxy group etc.), aryloxy group (eg 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, Benzoyloxy group etc.), an aliphatic or aromatic sulfonyloxy group (eg methanesulfonyloxy group, toluenesulfonyloxy group etc.), an acylamino group (eg dichloroacetylamino group, heptafluorobutyrylamino group etc.),
Aliphatic or aromatic sulfonamide group (eg, methanesulfonamide group, p-toluenesulfonylamino group, etc.), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, Phenoxycarbonyloxy group etc.), aliphatic / aromatic or heterocyclic thio group (eg ethylthio group, phenylthio group, tetrazolylthio group etc.), carbamoylamino group (eg N-methylcarbamoylamino group, N-phenylcarbamoylamino group etc.) 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, 1,2-dihydro-2-oxo-1-pyridyl group, etc.), imide group (for example, succiniyl group) De group, and hydantoinyl group),
There are aromatic azo groups (eg, phenylazo group, etc.), and these groups may be further substituted with a substituent when R ¹ and R ² represent a substituted phenyl group. Also,
A bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom is also included.

Among the above, a more preferable leaving group is a halogen atom, an alkoxy group, an aryloxy group, a sulfonyloxy group or an acylamino group. In the general formula [III], when R ¹ , R ² or Z ¹ is a divalent or lower polyvalent group to form a dimer or lower multimer, or a polymer main chain The case where they are linked to form a polymeric coupler is also included.

Among the pyrazolone couplers represented by the general formula [III], the effect of the present invention is more effectively exerted on the pyrazolone coupler represented by the following general formula [IIIa].

[0139]

[Chemical 56]

In the formula, R ⁷ is R in the general formula [III].
^{When 1} and R ² represent a substituted phenyl group, it has the same meaning as the substituent. Among the compounds represented by the general formula [III], Z ¹ is a substituted or unsubstituted arylthio group in a particularly preferred magenta coupler. General formula (III)
Examples of the compound represented by the formula (1), synthetic method, etc. are described in, for example, JP-A-49-111631, JP-A-54-48540, and JP-A-55-55.
-62454, 55-118034, 56-380.
43, 56-80045, 56-126833, 57-4044, 57-35858, 57-947.
52, the same 58-17440, the same 58-50537, the same 5
8-85432, 58-117546, 58-12
6530, 58-145944 and 58-20515.
1, JP-A Nos. 54-170, 54-10491 and 54
-21258, same 53-46452, same 53-4645
3, 57-36577, JP-A-58-110596,
58-132134, 59-26729, U.S. Pat. Nos. 3,227,554, 3,432,521 and 4,310,61.
8, No. 4,351,897 and the like.

Typical examples of the magenta coupler represented by the formula [III] included in the present invention are shown below, but the invention is not limited thereto.

[0142]

[Chemical 57]

[0143]

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[0144]

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[0145]

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Among the couplers represented by the general formula [IV], preferred compounds are 1H-imidazo [1,2-b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,5]. 1-C] [1,2,4] triazoles, 1H-pyrazolo [1,5-b] [1,2,
4] triazoles, 1H-pyrazolo [1,5-d] tetrazoles and 1H-pyrazolo [1,5-a] benzimidazoles, and particularly preferred compounds among them are [IVa] and [IVb]. .

[0147]

[Chemical formula 61]

The substituents R ¹¹ and R ¹² of the above general formulas [IVa] and [IVb] will be described in detail. R ¹¹ and R ¹² represent an aliphatic group, an aromatic group or a heterocyclic group. These groups are further substituted (for example, halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, sulfonyloxy group, acyl group, sulfonyl group, carboxyl group,
Sulfo group, hydroxyl group, amino group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, ureido group, sulfinyl group, alkylthio group, arylthio group, cyano group, etc.) Things are also included. R ¹¹ , R ¹² and R ^{13 each} further represent a hydrogen atom or a substituent below the halogen atom in the above (), and among these, an alkyl group, an aryl group, a carbonamido group, a sulfonamide group and a ureido group are preferable. Is.

Z ² has the same meaning as described for Z ¹ in the general formula [III]. When Z ² represents a coupling-off group, more preferred is a halogen atom,
An alkoxy group, an aryloxy group, a sulfonyloxy group, and an acylamino group. In addition, as a leaving group bonded via a carbon atom, aldehydes or ketones
There is a bis type coupler obtained by condensing two molecules of an equivalent coupler.

When any one of R ¹¹ , R ¹² , R ^{13 and} Z ² becomes a divalent or higher polyvalent group and forms a dimer or a multimer, or is linked to a polymer main chain. ,
It also includes the case of forming a polymeric coupler. Above (IV
Examples of compounds of the couplers represented by the general formulas a] and [IVb], synthetic methods, and the like are described in the following documents.

The compound of the general formula [IVa] is represented by JP-B-47-
No. 27411, etc., compounds of general formula [IVb] are described in JP-A-59-171956, JP-A-60-172982, etc.
Each is listed. Also, JP-A-58-4204
5, JP-A-59-214854 and JP-A-59-17755.
3, ibid. 59-177554 and ibid. 59-177557.
The highly chromogenic ballast group described in each item or the like is applied to any of the compounds of the above general formulas [IVa] and [IVb].

Specific examples of the pyrazoloazole-based coupler used in the present invention are shown below, but the invention is not limited thereto.

[0153]

Embedded image

Next, the general formula (V) representing the cyan coupler used in the present invention will be described in detail. R ₃ and R ₄
Is an aliphatic group having 1 to 31 carbon atoms (eg, methyl group, butyl group, octyl group, tridecyl group, iso-hexadecyl group, cyclohexyl group), aryl group (eg, phenyl group, naphthyl group, 2-pyridyl group) , 2-thiazolyl group, 2-imidazolyl group, 2-furyl group, 6-quinolyl group, etc., and these are alkyl group, aryl group, heterocyclic group, alkoxy group (for example, methoxy group, 2
-Aryloxy group such as methoxyethoxy group and tetradecyloxy group (for example, 2,4-di-tert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group, 4-butanesulfonamidophenoxy group, etc.), Acyl group (eg, acetyl group, benzoyl group, etc.), ester group (eg, ethoxycarbonyl group, 2,
4-di-tert-amylphenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc., amide group (for example, acetylamino group, butanesulfonamide group, dodecylbenzenesulfonamide group, diprothyl group) Pilsulfamoylamino group etc.), carbamoyl group (eg dimethylcarbamoyl group, ethylcarbamoyl group etc.), sulfamoyl group (eg butylsulfamoyl group etc.), imide group (eg succinimide group, hydantonyl group etc.), ureido group (Eg, phenylureido group, dimethylureido group, etc.), sulfonyl group (eg, methanesulfonyl group, carboxymethanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, butyl group) O group, a phenylthio group), a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo group, may be substituted with a group selected from among a halogen atom. When having two or more substituents, they may be the same or different from each other.

In the above general formula (V), R ₅ is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an acylamino group or a non-metal atom group forming a nitrogen-containing 5- or 6-membered ring together with R _4. Represent. Further, preferable examples of the cyan coupler represented by the general formula (V) are as follows.

In the general formula (V), R ₃ is preferably an aryl group or a heterocyclic group, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group; an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group. More preferably, it is an aryl group substituted with a group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or a cyano group.

In the general formula (V), when R ₅ and R ₄ do not form a ring, R ₄ is preferably a substituted or unsubstituted alkyl group or aryl group, and particularly preferably a substituted aryloxy-substituted alkyl group. And R ₅ is preferably a hydrogen atom. Hereinafter, specific examples of the cyan coupler used in the present invention will be exemplified.

[0158]

[Chemical formula 63]

[0159]

[Chemical 64]

In the general formula [VI], the aliphatic group represented by R ₁ may be linear or cyclic, preferably has 1 to 32 carbon atoms, may be saturated or unsaturated, and may be a methyl group. , Butyl group, hexadecyl group,
Typical examples are an allyl group, a cyclohexyl group, a propenyl group, a propargyl group, and the like. Examples of the aryl group represented by R ₁ are a phenyl group and a naphthyl group, which are represented by R _1. Typical examples of the heterocyclic group include a 2-pyridyl group, a 2-furyl group, a 6-quinolyl group, and the like. These groups include a substituent group (including a substituted atom, the same applies hereinafter) as enumerated below. You may have one or more. As the permissible substituents, an aliphatic group (eg, methyl group, allyl group, cyclopentyl group, etc.), aromatic group (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 2-imidazolyl) Group, 2-furyl group, 6-quinolyl group, etc., aliphatic oxy group (eg, methoxy group, 2-methoxyethoxy group, 2-propenyloxy group, etc.), aromatic oxy group (eg, 2,4-di-tert) -Amylphenoxy group,
4-cyanophenoxy group, 2-chlorophenoxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group (eg butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluene) Sulfonyloxy group, etc.), amide group (eg acetylamino group, methanesulfonamide group, ethylcarbamoyl group, diethylcarbamoyl group, butylsulfamoyl group etc.), imide group (eg succinimide group, hydantoinyl group etc.), ureido group (eg For example, phenylureido group, dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, phenylthio group, ethylthio group, etc.) ), A hydroxyl group, a cyano group, a carboxyl group, a dichloro group, a sulfonic acid group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), and when there are two or more substituents, they are the same or different. You may

In the general formula [VI], R ₂ represents a methyl group having a substituent, and the substituent here may be a substituent allowed by R ¹ . In the general formula [VI], the alkyl group, aryl group, alkoxy group and acylamino group of R ₃ may be substituted with a substituent allowed by R ₁ . R ₃
May form a ring with R ₂ .

In the general formula [VI], preferred R ₁ is an alkyl group which may have a substituent, and a substituted aryloxyalkyl group is particularly preferred. Preferred R ₂ in the general formula [VI] is an alkyl group having 2 or more carbon atoms, or an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an arylseleno group. Is an alkyl group substituted with (particularly preferably a methyl group). An ethyl group is particularly preferable.

In the general formula [VI], R ₃ is preferably a hydrogen atom or a halogen atom, and particularly preferably a chlorine atom. In the general formula [VI], when Y ₁ represents a coupling-off group (hereinafter referred to as a leaving group), the leaving group is a coupling activated carbon, an aliphatic group, or an aliphatic carbon group via an oxygen, nitrogen, sulfur or carbon atom. Group, aromatic group, heterocyclic group,
Aliphatic / aromatic or heterocyclic sulfonyl group, aliphatic /
A group that bonds with an aromatic or heterocyclic carbonyl group, a halogen atom, an aromatic azo group, etc., and the aliphatic, aromatic or heterocyclic group contained in these leaving groups is
R ₁ may be substituted with a permissible substituent, and when two or more of these substituents are the same or different, these substituents may be further substituted with R _1. May have.

Specific examples of the coupling-off group will be given below.
Halogen atom (eg fluorine atom, chlorine atom, bromine atom etc.), alkoxy group (eg ethoxy group, dodecyloxy group, methoxyethylcarbamoylmethoxy group, carboxylpropyloxy group, methylsulfonylethoxy group etc.), aryloxy group (eg 4 -Chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group etc.), acyloxy group (eg acetoxy group, tetradecanoyloxy group, benzoyloxy group etc.), aliphatic or aromatic sulfonyloxy group (eg methanesulfonyl group) Oxy group, toluenesulfonyloxy group etc.), acylamino group (eg dichloroacetylamino group, heptafluorobutylamino group etc.), aliphatic or aromatic sulfonamide group (eg methanesulfonamino group, p Toluenesulfonylamino group etc.), alkoxycarbonyloxy group (eg ethoxycarbonyloxy group, benzyloxycarbonyloxy group etc.), aryloxycarbonyloxy group (eg phenoxycarbonyloxy group etc.), aliphatic / aromatic or heterocyclic thio group (Eg, ethylthio group, phenylthio group, tetrazolylthio group, etc.), carbamoylamino group (eg, N-methylcarbamoylamino group, N-phenylcarbamoylamino group, etc.), 5-membered or 6-membered nitrogen-containing heterocyclic group (eg, imidazolyl group) , A pyrazolyl group, a triazolyl group, a tetrazolyl group, a 1,2-dihydro-2-oxo-1-pyridyl group), an imide group (for example, a succinimide group, a hydantoinyl group, etc.),
There are aromatic azo groups (for example, phenylazo group, etc.) and the like, and these groups may be further substituted with a group acceptable as the substituent for R ₁ . Further, there is a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.
The leaving group of the present invention may contain a photographically useful group such as a development inhibitor and a development accelerator. Preferred combinations of leaving groups in each general formula will be described later.

Preferred Y ₁ in the general formula [VI] is a hydrogen atom, a halogen atom, and a chlorine atom is particularly preferred. Specific preferred examples of the coupler represented by formula (VI) are shown below, but the invention is not limited thereto.

[0166]

Embedded image

[0167]

[Chemical formula 66]

[0168]

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Next, the photographic layers of the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention includes a color negative film, a reversal film, a color negative film for movies, a color positive film, a positive film for movies, a general-purpose color light-sensitive material for movies, a black and white negative film, a microfilm, and X-. It can be applied to black-and-white light-sensitive materials such as ray films.

There are no particular restrictions on various additives and development processing methods used when the present invention is applied to black and white light-sensitive materials. For example, JP-A-2-68539 and JP-A-5-11389.
The following relevant parts of JP-A No. 2-58041 and JP-A No. 2-58041 can be preferably used.

1. Silver halide emulsion and its production method
2-68539, page 8, lower right column, line 6 from bottom to page 10 upper right column, line 12 2. Chemical sensitization method: Page 10, upper right column, line 13 to lower left column 16
Line, selenium sensitization method described in JP-A-5-11389. 3. Antifoggant / stabilizer: JP-A-2-68539, No. 10
Page 17, lower left column, line 17 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes: page 4, lower right column, line 4 to page 8, lower right column, and JP-A-2-58041, page 12, lower left column, line 8 to lower right column, line 19. 5. Surfactant / antistatic agent: JP-A-2-68539
Page 1, upper left column, line 14 to page 12, upper left column, line 9 and JP-A-2-5
No. 8041, page 2, lower left column, line 14 to page 5, line 12 6. Matting agent / Plasticizer / Slipping agent: page 12, upper left column, line 10 to upper right column, line 10 and JP-A-2-58041, page 5, lower left column, line 13 to page 10, lower left column, line 3 Eye. 7. Hydrophilic colloid: JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener: Page 12, lower left column, line 17 to page 13, upper right column 6
Line. 9. Development method: Same as page 15, upper left column, line 14 to same, lower left column 13
Line.

When the present invention is applied to a color photographic material, at least one photosensitive layer may be provided on the transparent support. As a typical example, at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities is provided on a transparent support.
It is a silver halide photographic light-sensitive material. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, in the case of a reflective color light-sensitive material, the order of installation is reversed. Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These include couplers and DIRs described below.
A compound, a color mixing inhibitor, etc. may be contained. The multiple silver halide emulsion layers constituting each unit photosensitive layer are DE 1,1
It is preferable to arrange two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in JP 21,470 or GB 923,045 so that the sensitivities are gradually lowered toward the support. Also,
JP-A-57-112751, 62-200350, 62-206541, 62-20
As described in each of the 6543 publications, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

The preferred silver halide used in the photographic light-sensitive material is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 0.5 mol% to about 30 mol% silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Further, preferred silver halides used for the reflective type light-sensitive material and the color positive film for motion pictures are silver chlorobromide and silver chloride, and particularly, the silver chloride content is 95 mol% or more and the rest is silver bromide (silver iodide) Are preferred.

The silver halide grains in a photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No.17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and
No.18716 (November 1979), p.648, No.307105 (November 1989)
Mon), pp. 863-865, and "Graphics and Chemistry" by Graphide, published by Paul Montel (P. Glafkides, Chemie e.
t Phisique Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal
Press, 1966), "Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman, et al.,
Making and Coating Photographic Emulsion, Focal P
ress, 1964) and the like.

US 3,574,628, US 3,655,394 and GB 1,41
The monodisperse emulsions described in 3,748 are also preferred. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14, 248
~ 257 (1970); US 4,434,226, 4,414,310, 4,4
It can be easily prepared by the method described in 33,048, 4,439,520 and GB2,112,157.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed inside the grain, or a type having a latent image both on the surface and inside. Must be a type of emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used, and the preparation method is described in JP-A-59-133542. . The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are RD No.17643 and RD No.187.
16 and No. 307105, and the relevant parts are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

US Pat. No. 4,082,553, the surface of which is covered with silver halide grains, US Pat. No. 4,626,498, and JP-A-59-214852.
It is preferable to apply the internally fogged silver halide grains and colloidal silver described in (4) above to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is US 4,626,498, JP-A-59-2
14852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, especially 0.05.
˜0.6 μm is preferred. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

The coated silver amount of the light-sensitive material of the present invention is 6.0 g / m 2.
^It is preferably ² or less, and most preferably 4.5 g / m ² or less.

The photographic additives that can be used in the present invention are also described in RD, and the relevant portions are shown in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer Page 23 Page 648 Right column Page 866 2. Sensitivity enhancer Page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 866 to 868, supersensitizer, to page 649, right column 4. Whitening agent Page 24 Page 647 Right column Page 868 5. Light absorber, pages 25 to 26, page 649, right column, page 873, filter dye, page 650, left column, ultraviolet absorber 6. Binder 26 pages 651 left column 873 to 874 7. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 8. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 9. Antistatic agent Page 27 Page 650 Right column Page 876-877 10. Matting agent pp. 878-879

Other couplers described below can be used in the light-sensitive material of the present invention. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); A coupler represented by the general formula (I) of claim 1 of 307248; US 5,066,576.
The coupler represented by the general formula (I) on lines 45 to 55 of column 1 of the above; the coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; in claim 1 on page 40 of EP 498, 381A1. The couplers described (especially D-35 on page 18); EP 447,969 A1 4
Couplers represented by formula (Y) on page (especially Y-1 (page 17), Y-54
(P. 41)); US Pat. No. 4,476,219, column 7, lines 36-58, formula (II).
~ (IV) couplers (especially II-17, 19 (column 1
7), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57)
(Page 11, lower right), L-68 (Page 12, lower right), L-77 (Page 13, lower right)); EP
456, 257 A-4 -63 (134 pages), A-4 -73, -75 (139 pages); EP 4
86, 965 M-4, -6 (page 26), M-7 (page 27); JP-A-6-43611, paragraph 0024, M-45; JP-A-5-204106, paragraph 0036, M-1;
M-22 of paragraph 0237 of 4-362631. Cyan coupler: CX-1, 3, 4, 5, 11, of JP-A-4-204843
12, 14, 15 (pages 14 to 16); C-7, 10 (35 of JP-A-4-43345)
Page, 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); represented by the general formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. A coupler. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

As couplers in which the color forming dye has an appropriate diffusibility, US 4,366,237, GB 2,125570, EP 96,873B, D
Those described in E 3,234,533 are preferable. The coupler for correcting the unwanted absorption of the color forming dye is a yellow colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially page 84). YC-86),
Yellow colored magenta coupler ExM-7 described in the EP
(Page 202, EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8) described in US 4,833,069, CC-13 (column 10), US 4,837,136 (2 ) (Column 8),
The colorless masking couplers represented by formula (A) of claim 1 of W092 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound:
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP 378, 236A1 (particularly T-101 (page 30), T-104 (page 31), T-
113 (36 pages), T-131 (45 pages), T-144 (51 pages), T-158 (58 pages)),
EP 436,938 A2, page 7 of the compound represented by formula (I) (especially D-49 (page 51)), JP-A-5-307248 represented by formula (1) (especially (23) ), 5 of EP 440,195A2
Compounds represented by formulas (I), (II) and (III) described on pages 6 to 6 (particularly I- (1) on page 29); Bleach accelerator releasing compound: EP 310,1
Compounds represented by formulas (I) and (I ') on page 5 of 25A2 (especially 61
(60), (61) on page and compounds of formula (I) of claim 1 of JP-A-6-59411 (particularly (7) of paragraph 0022); Ligand-releasing compounds: described in claim 1 of US 4,555,478 A compound represented by LIG-X (in particular, a compound on lines 21 to 41 of column 12);
Leuco dye releasing compounds; compounds 1 to 6 in columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: compounds represented by COUP-DYE in claim 1 of US 4,774,181 (especially column 7)
10 to compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22 of column 25) ) And EP 450,63
7A2, ExZK-2, page 75, lines 36-38; compounds that release a dye group only after elimination: a compound of formula (I) in claim 1 of US 4,857,447 (especially Y- in columns 25-36). 1-Y
-19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3, 5, JP-A-62-215272
16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93
(Pages 140-144); Latex for impregnation of oil-soluble organic compounds: U
Latex described in S 4,199,363; Oxidized developer scavenger: US Pat. No. 4,978,606, column 2, lines 54 to 62, formula (I)
A compound represented by the formula (especially I-, (1), (2), (6), (12) (columns 4 to 5), a formula of column 5, lines 5 to 10 of US 4,923,787 (especially compound 1 (column 3) ); Stain inhibitors: Formulas (I) to (III) on page 4, lines 30 to 33 of EP 298321A, especially I-47, 72, III-1, 27.
(Pages 24-48); Anti-fading agent: EP 298321A, A-6, 7, 20, 21,
23, 24, 25, 26, 30, 37, 40, 42, 48, 63, 90, 92, 9
4, 164 (pages 69-118), US 5,122,444 columns 25-38 II-1
~ III-23, especially III-10, EP 471347A, pages 8-12, I-1 ~ I
II-4, especially II-2, US 5,139,931 columns 32-40 A-1-4
8, especially A-39, 42; Materials that reduce the amount of color-enhancing agent or color-mixing inhibitor used: I-1 to II- on pages 5 to 24 of EP 411324A
15, especially I-46; formalin scavenger: EP 477932A
24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A-1-
214845, page 17, H-1, 4, 6, 8, 14, US 4,618,573, columns 13 to 23, compounds represented by formulas (VII) to (XII) (H-1 to 5
4), compounds (H-1 to 76) represented by the formula (6) on the lower right side of page 8 of JP-A-2-214852, particularly compounds described in claim 1 of H-14, US 3,325,287; development inhibitor precursor: JP 62-16813
9 P-24, 37, 39 (pages 6-7); Compounds as claimed in claim 1 of US 5,019,492, in particular column 7 28-29; preservatives, fungicides: US 4,923,790 columns 3-15 I. -1 to III-43, especially II-1, 9, 10, 18, III-25; Stabilizer, antifoggant: U
S 4,923,793 columns 6-16 I-1 ~ (14), especially I-1, 60,
(2), (13), US 4,952,483 columns 25-32 compounds 1-6
5, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: JP-A-3-156
450 pages 15-18 a-1 to b-20, especially a-1, 12, 18, 27, 35,
36, b-5, V-1 to 23 on pages 27 to 29, especially V-1, EP 445627A
FI-1 to F-II-43 on pages 33 to 55, especially FI-11, F-II-8, EP 45
7153A, pages 17-28, III-1 to 36, especially III-1, 3, W088 / 047
94, 8 to 26, Dye-1 to 124, microcrystalline dispersion, EP 319999A, pages 6 to 11, compounds 1 to 22, especially compound 1, EP 519306A formula
Compounds D-1 to 87 represented by (1) to (3) (pages 3-28), US
Compounds 1 to 22 (columns 3 to 10) represented by formula (I) of 4,268,622, compound (1) represented by formula (I) of US 4,923,788
To (31) (columns 2 to 9); UV absorber: compounds (18b) to (18r), 101 to 427 (6 to 6) represented by formula (1) of JP-A-46-3335.
Page 9), compounds (3) to (6) represented by formula (I) of EP 520938A.
6) (pages 10-44) and compounds of formula (III) HBT-1-10
(Page 14), compounds (1) to (3 represented by formula (1) of EP 521823A.
1) (columns 2-9).

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and 16 μm or less. Particularly preferred. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds. It is defined as
The film thickness means the film thickness measured under a humidity condition of 25 ° C. and a relative humidity of 55% (2 days), and T _1/2 is A. Green et al.'S Photographic Science and Engineering. (Photogr. Sci. Eng), Vol. 19, 2, 124-129. It can be measured by using a swellometer of the type described. T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is
150 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) /
It can be calculated by the film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
In this back layer, the above-mentioned light absorber, filter dye,
It is preferable to add an ultraviolet absorber, an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is 150-500%
Is preferred.

The support which can be used in the silver halide light-sensitive material of the present invention includes a glass plate, paper (paper obtained by laminating neutral paper or acidic paper with a resin such as polyethylene or polyester, baryta paper, polypropylene paper). Etc.), plastic films or sheets (polyethylene terephthalate, polyethylene-2,6-naphthalene dicarboxylate, polyesters such as cellulose triacetate and cellulose nitrate; resins such as polyvinyl chloride), etc.
Any transparent, semi-transparent, or reflective support can be used as long as it can be coated with the hydrophilic colloid layer.

A transparent plastic support pair is preferably used for a positive film for motion pictures to which the present invention is preferably applied.

[0192]

【Example】

Example 1 An undercoated polyethylene terephthalate film support (having a thickness of 120 μm and having a resin layer containing carbon fine particles coated on the side opposite to the emulsion surface so as to have a transmission density of 1.0) was prepared as follows. Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver halide.

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 1 mol% / 99 mol%, gold-sulfur sensitized emulsion B1 having an average grain size of 0.7 μm) 0.4 μm gold-sulfur sensitizing emulsion B2 in a 1: 3 mixture (molar ratio of silver.) 0.50 gelatin 2.49 yellow coupler (ExY) 1.10 solvent (Solv-1) 0.13 solvent (Solv) -2) 0.13 (Cpd-1) 0.0016 (Cpd-2) 0.0006 (Cpd-3) 0.006 (Cpd-4) 0.03 Second layer (color mixing prevention layer) Gelatin 0.60 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03

Third Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, average halogen composition Br / Cl = 25 mol% / 75 mol%, gold-sulfur sensitized emulsions R1 and 0 having an average grain size of 0.25 μm) 0.1 μm gold-sulfur 1: 3 mixture of silver sensitized emulsion R2 (molar ratio of silver) 0.44 gelatin 3.18 cyan coupler (ExC) 0.97 (Cpd-6) 0.18 (Cpd-5) 0 .015 Solvent (Solv-5) 0.50 Solvent (Solv-6) 0.32 (Cpd-7) 0.0002 (Cpd-8) 0.003 (Cpd-2) 0.003 Fourth layer (preventing color mixture) Layer) Gelatin 0.60 (Cpd-5) 0.03 Solvent (Solv-3) 0.03 Solvent (Solv-4) 0.03 Fifth layer (green sensitive emulsion layer) Silver chlorobromide emulsion (cubic, average) Halogen composition Br / Cl = 25 mol% 75 mol%, 1: 3 mixture of gold-sulfur sensitized emulsion G1 having an average grain size of 0.25 μm and gold-sulfur sensitized emulsion G2 of 0.1 μm (silver mole ratio) 0.52 gelatin 1.94 magenta coupler ( ExM) 0.61 (Cpd-9) 0.001 (Cpd-5) 0.012 Solvent (Solv-3) 0.15 (Cpd-10) 0.003 (Cpd-11) 0.002 (Cpd-12) 0.003 Sixth layer (protective layer) Gelatin 1.47 Polyvinyl alcohol acrylic modified copolymer 0.05 (17% conversion) Liquid paraffin 0.02 The compounds used here are shown below.

[0195]

[Chemical 68]

[0196]

[Chemical 69]

[0197]

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[0198]

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[0199]

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[0200]

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As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0202]

[Chemical 74]

Next, with respect to Sample 101, multilayer color photosensitive materials of Samples 102 to 106 were prepared by changing the color coupler used for each photosensitive emulsion layer and the coating amount of silver halide emulsion as shown in Table 1. In addition, Table 1 shows the total gelatin coating amount / total coating silver amount ratio (gelatin / silver ratio) of the samples. However, samples 102, 103, 104, 105 and 106
The yellow coupler of the blue-sensitive layer of Samples 101, 102, 103, 104 and 10 has the same molar coating amount as that of EXY of Sample 101
The cyan couplers of the red-sensitive layers of 5 and 106 are sample 10
Samples 102, 103, with the same molar coating amount as EXC 1
The magenta couplers of the green-sensitive layers of 104, 105 and 106 were coated so as to have the same molar coating amount as the EXM of sample 101.

Then, the resin layer on the back surface of the support used for Samples 101 to 106 was removed, and instead of
A hydrophilic colloid layer containing a conductive polymer (0.05 g / m ² ) and tin oxide fine particles (0.23 g / m ² ) is provided, while a solid having the following composition is provided between the surface of the support and the first layer. Samples 107 to 112 differing only in that a layer containing a fine particle dispersed compound (antihalation layer) was newly provided.

[0205]

[Chemical 75]

[0206]

[Table 5]

[0207]

[Chemical 76]

[0208]

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[0209]

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The total gelatin coating amount / total coating silver amount ratio (gelatin / silver ratio) of the obtained samples was as follows: Sample 107, 109, 110, 111 = 8.10 Sample 108 = 6.19 Sample 112 = 8.96 there were. On the other hand, the amount of gelatin used in each layer was proportionally reduced and adjusted to adjust the sample 113 shown in Table 2.
To 124 were created. [Antihalation Layer Composition] Gelatin 1.55 g / m ² Dye solid dispersion (X-42) (solid content) 0.025 〃 〃 (XI-1) (solid content) 0.140 〃 Exemplified compound (IX- 12) 0.033 〃 〃 (P-2) 0.005 〃

Method for preparing solid fine particle dispersion A wet cake of the exemplified compound (XI-1) was weighed so that the net amount of the compound was 240 g, and 48 g of the dispersion aid exemplified compound (IX-12) was weighed. Was added to make 4000 g. "Distribution type sand grinder mill (UVM-
2) "(made by IMEX KK) was filled with 1.7 L of zirconia beads (0.5 mm diameter), and the discharge rate was 0.5 L / mi.
It was crushed for 2 hours at n ⁻¹ and a peripheral speed of 10 m / s. The dispersion was diluted to a compound concentration of 3% by weight. The mixture was heat-treated at 90 ° C. for 10 hours, and P-2 was added to the compound in a weight ratio of 3%.

A dispersion of the compound (X-42) was prepared in the same manner, mixed with the above dispersion and used for the antihalation layer.

[0213]

[Table 6]

The photographic characteristics of each of the obtained samples were evaluated as follows. First, each sample was exposed through a wedge having a rectangular pattern with a spatial frequency stepwise changed for sharpness evaluation and B, G and R filters, and was exposed by Eastman Kodak Company.
Color development processing was performed according to the -2B process. By measuring the color density pattern of the sample after the treatment with a micro densitometer, the attenuation of the density difference of the rectangular pattern was obtained.
The TF value was calculated. CTF as an index of sharpness of each trial
The spatial frequency giving a value of 0.8 was used.

Next, each sample was exposed to light through an optical wedge for sensitometry and B, G and R filters, and subjected to the same color development processing as described above. At this time, the processing time of the color developing solution was changed by ± 30 seconds with respect to the standard setting value of 3 minutes, and the change in color density with respect to changes in processing conditions was also tested. The color densities of yellow, magenta and cyan of the processed sample were measured using a densitometer to obtain so-called characteristic curves. From these characteristic curves, sensitivity, contrast, and Dmax were obtained. The sensitivity was represented by the reciprocal of the exposure amount that gives a density higher than the fog density by 1.0, and was shown as a relative value with the value of the sample after the standard development time treatment being 100. The contrast is 0.4 and 2.
It was expressed by the difference in logarithm of the exposure amount giving 5.

The results are summarized in Table 3.

[0219]

[Table 7]

[0218]

[Table 8]

[0219]

[Table 9]

[0220]

[Table 10]

From the results, the effect of the present invention is clear.
That is, in contrast to Samples 101 to 106, Sample 10 using the solid dispersion of the dye of the present invention in the antihalation layer
Nos. 7 to 124 show sharpness equal to or higher than that when a resin layer is used on the back surface of the support. However, when the antihalation layer having a solid disperse dye is introduced instead of the range layer, the process variation is significantly deteriorated. On the other hand, comparison of samples 112, 118 and 124, and samples 107 and 11
As is clear from the comparison of Nos. 3 and 119, the gelatin coating amount was adjusted so that the ratio of the gelatin coating amount to the coated silver amount was 7.
By setting it to 8 or less, this process variation can be improved.

On the other hand, the effect of improving the processing fluctuation is more remarkable when the couplers of the general formulas (I) to (VI) are used, and a photosensitive material having both high sharpness and excellent processing stability. Can be provided. (For example, sample 11
Sample 108 for sample 3 and sample 11 for sample 113
5. Sample 116 against sample 113) By applying the present invention, good sharpness is maintained even when the resin back layer, which requires a large amount of washing water during the treatment, is removed, and the treatment stability is excellent. It is possible to provide a light-sensitive material.

Reference Example Preparation of Solid Dispersion of Dye A wet cake of Exemplified Dye Compound XI-1 was weighed so that the net amount of the compound was 8.0 g, and the dispersion aid of the present invention or a comparative dispersion aid was prepared. Add agent (Table 4), add water and add 13
The amount was set to 2 g and put in a "batch type sand grinder mill" (manufactured by IMEX Co., Ltd.). Zirconia beads (0.5mm
(Diameter) was added, and the content was crushed for 4.5 hours at a peripheral speed of about 5 m / s.

The beads were removed by filtration, and the dispersion was taken out and diluted to a compound concentration of 3% by weight. Then, the dispersion was heated under the conditions of Table 4, and the compound of the present invention was added according to Table 4. Gelatin (57.0 g) and distilled water were added to the obtained dispersion, diluted so that the total gel concentration was 6.0% by weight, and the pH was adjusted to 5.1.
To prepare an anti-halation layer coating solution.

In order to test the stability of the dye dispersion during production, a sample was prepared by applying the obtained coating solution within 20 minutes after preparation, and a sample was prepared by leaving it at 40 ° C. for 8 hours after preparation. . A triacetyl cellulose transparent support was used for test coating, and the coating amount was adjusted so that the coating amount of the dye was 150 mg / m ² . The change in absorption over time of the coating solution was examined by measuring the transmission density of the sample after coating. The results are summarized in Table 4. As is clear from this, in the preparation of the antihalation layer using the solid dispersion of the dye in the present invention, the dispersion aid of the general formula (IX-a) or (IX-b) is used at the time of dispersion. It can be seen that it is preferable to heat-treat and to add the compound of the general formula (VIII) in order to enhance the stability over time of the coating liquid containing the dye dispersion. In addition, the uniformity of the coated surface is improved by increasing the temporal stability of the coating liquid.

[0226]

[Table 11] Table 4 Dispersion Dispersion aid ^* Heating conditions Compound (VIII) Dye absorption spectrum change with time 1 a ^** None None Accepted 2 IX-12 None None Somewhat small 3 IX-12 90 ° C-10hr None Small 4 IX-12 70 ℃ -3d None Small 5 IX-12 None P-2 Small 6 IX-12 90 ℃ -10hr P-2 Almost not observed 7 IX-12 70 ℃ -3d P-2 Almost not recognized * 20% by weight of the dispersion aid was added to the dye, and 3% by weight of the compound (VIII) was added to the dye. ** a is sodium polynaphthalene sulfonate

[0227]

INDUSTRIAL APPLICABILITY The present invention has a solid dispersion of a dye capable of limiting and coloring a specific layer of a photographic light-sensitive material, and has excellent sharpness and stability against changes in development processing conditions. An excellent silver halide color photographic light-sensitive material can be provided. Further, the present invention can provide a stable silver halide color photographic light-sensitive material, the performance of which does not fluctuate even when the conditions during manufacturing of the light-sensitive material are changed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/00 530 7/34 7/36 7/38

Claims (7)

[Claims] 1. A support comprising at least one yellow coupler-containing photosensitive silver halide emulsion layer, a magenta coupler-containing photosensitive silver halide emulsion layer and a cyan coupler-containing photosensitive silver halide emulsion layer. A silver halide photographic light-sensitive material having a photographic constituent layer comprising a non-photosensitive layer, wherein at least one of the photographic constituent layers contains a solid fine particle dispersion of a dye represented by the general formula (VII). A silver halide color photographic light-sensitive material, characterized in that the ratio of the total coating amount of gelatin in the photographic constituent layer to the total coating amount of silver is 3.8 to 7.8. Embedded image In the formula, D represents a compound residue having a chromophore, X represents a dissociative hydrogen bonded to D directly or via a divalent linking group or a group having a dissociative hydrogen, and Y represents 1 to 7 Represents an integer. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the solid fine particle dispersion of the dye is contained after a heat treatment step at 40 ° C. or higher. 3. A silver halide color photograph according to claim 1, wherein the solid fine particle dispersion of the dye contains at least one compound represented by the following general formula (VIII). Photosensitive material. Embedded image In the formula, R represents a hydrogen atom, a hydrophobic group or a hydrophobic polymer, P contains at least one of the following structural units A, B and C, and a polymer having a degree of polymerization of P of 10 or more and 3500 or less. Represent m represents 0 or 1, and n represents 1 or 2. Embedded image Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ² represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom or a methyl group, R ⁴
Represents a hydrogen atom, a methyl group, a carboxymethyl group (including ammonium or metal salt) or a cyano group, X represents a hydrogen atom, a carboxyl group (including ammonium or metal salt) or a carbamoyl group, and Y represents a carboxyl group ( Ammonium or metal salt), sulfo group (including ammonium or metal salt), sulfoxy group (including ammonium or metal salt), sulfomethyl group (including ammonium or metal salt), -CONHC
(CH ₃₎ (including the ammonium or metal salts) ₂ CH ₂ SO ₃ H group or ^{_{-CONHCH 2 CH 2 CH 2 N +}} (C
H ₃ ) ₃ Cl ⁻ group. 4. The solid fine particle dispersion of said dye contains at least one compound represented by the following general formula (IX-a) or (IX-b). Silver halide color photographic light-sensitive material. [Chemical 4] In the formula, a and b each represent an integer of 5 to 500. 5. The method according to any one of claims 1 to 4, wherein the dye is represented by the following general formula (X-a) or (X-b).
The light-sensitive material according to any one of 1. Embedded image 6. The light-sensitive material according to any one of claims 1 to 4, wherein the dye is represented by the following general formula (XI). [Chemical 6] 7. A yellow coupler which is at least one of the couplers represented by the following general formula (I) or (II), and a magenta coupler which is at least one of the couplers represented by the following general formula (III) or (IV). And a cyan coupler containing at least one of the couplers represented by the following general formula (V) or (VI). [Chemical 7] Embedded image [Chemical 9]