JPH0327034A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the rapid processability of a sensitive material and the sharpness of an image by incorporating prescribed planar silver halide particles having a high silver chloride content into an emulsion layer and providing a hydrophilic colloidal layer contg. a specified finely powdered dye between the emulsion layer and the reflective supporting body. CONSTITUTION:Planar particles having >=5 average aspect ratio are allowed to account for >=50% of the total projection area of silver halide particles in one or more of silver halide emulsion layers on the reflective supporting body and high silver chloride particles having >=80 mol% silver chlroide content are used as the silver halide particles. A hydrophilic colloidal layer contg. a finely powdered dye practically insoluble in water at pH<=6 but practically soluble in water at pH>=8, e.g., a compd. represented by the formula is formed between the supporting body and the planar silver halide emulsion layer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic print light-sensitive material with improved image sharpness. It is something. (Prior Art) Irradiation and halation are generally known as factors that affect the sharpness of images of silver halide color photographic materials. The former is caused by the scattering of incident light by silver halide particles dispersed in the gelatin film, and the latter is caused by light reflection from the support. A general explanation of these can be found in T. H. James
The Theory of the Photographic Process, by John S.
Photographic Process) J 4th edition, pages 578 to 591 are described in detail. Many studies have been conducted on the shape and size of silver halide grains in order to prevent the optical sharpness deterioration mentioned above. For example, JP-A No. 58-100845 describes a method in which normal crystals are used in the layer furthest from the support or the green-sensitive layer, and JP-A No. 58-126531 describes a method in which more than 80% of particles sensitive to the same spectrum are zero. A method using particles of .8 μ or larger and 0.65 μ or smaller is shown. However, in these methods, since the particle size is limited to a certain range, the sensitivity cannot be set freely, and the required sensitivity and the preferred sensitivity in terms of sharpness often do not necessarily match. Research Disclosure is a method of improving sharpness by changing the shape of particles.
ch Disclosure)No. 2 2 5
34 (January 1983). Here we show that the use of tabular silver halide emulsions with high average aspect ratios results in less scattering of light incident at right angles to the major planes of the plates and improved sharpness. ing. However, as described in JP-A No. 62-32448, when tabular grains are used and a transparent support is used, the sharpness is certainly improved, but when a substantially white reflective support is used. In some cases, the particles were no different from those of normal grains, or even worse, and it was found that there was no improvement in the printed photosensitive material having a reflective support. Therefore, in JP-A-62-32448, when a substantially white reflective support is used, silver chloroiodobromide (2 mol% or less of silver iodide), silver iodobromide (2 mol% or less of silver iodide), ), a photographic light-sensitive material coated with at least one layer of silver chlorobromide or a silver halide photographic emulsion containing tabular grains in which at least 50% of the total projected area of the silver bromide grains has an average aspect ratio of 5 or more. discloses a technique in which the sharpness is significantly improved by providing a layer containing a decolorizing column colorant in a photographic processing step between the reflective support and the tabular silver halide emulsion layer. On the other hand, in recent years there has been a strong demand for speeding up the development process for silver halide color photographic light-sensitive materials, especially light-sensitive materials for printing, and over the years, technological developments have been made one after another to shorten the process and have been introduced into the market. It has been. In particular, recently it has been known that increasing the silver chloride content or using pure silver chloride is effective for silver chlorobromide, which does not substantially contain silver iodide. The use of high silver chloride grains has been put into practical use.

On the other hand, a method for forming tabular grains with a high silver chloride content of 50 mol% or more is disclosed in U.S. Pat. No. 4,399,215.
No. 4,400,463, JP-A-62-2
No. 18959 and European Patent No. 0,288.949. However, the present inventors used tabular high-silver chloride grains, which are highly processable, and
Although I implemented the method described in the issue, I was not able to obtain a sufficient effect in improving sharpness. For example, when colloidal silver was used in the colored layer, the maximum density was significantly lower than when tabular high silver chloride grains were used, making it unusable. Furthermore, in most cases when a mordant and a dye were combined, the color did not decolor and was not usable.

It has also been found that the mere use of a water-soluble dye does not significantly improve sharpness compared to commonly used non-tabular grains.

(Problem to be Solved by the Invention) Therefore, the object of the present invention is to relate to a silver halide color photographic light-sensitive material which is excellent in processing speed and has greatly improved sharpness, and in particular, it relates to a silver halide color photographic material having a white reflective support. This is related to printed materials. (Means for Solving the Problem) It has been found that the object of the present invention can be achieved by the method shown below. That is, in a silver halide color photographic material having at least one silver halide emulsion layer on a reflective support, at least 50% of the total projected area of silver halide grains is present in at least one of the silver halide emulsion layers. Contains tabular grains with an average aspect ratio of 5 or more,
The silver halide grains are high silver chloride grains with a silver chloride content (average value) of 80 mol% or more, and at least one layer is provided between the reflective support and the tabular silver halide emulsion layer. A halogen characterized by having at least one hydrophilic colloid layer containing a finely powdered dye (hereinafter simply referred to as finely powdered dye) that is substantially water-insoluble at pH 6 or lower but substantially water-soluble at least at pH 8 or higher. This was achieved using silver oxide color photographic materials.

The fact that the fine powder dye used in the present invention is substantially water-insoluble at least at a pH of 6 or less means that the fine powder is dispersed at a pH of at least 6 or less.
A hydrophilic colloid of 6 or less, such as gelatin, means that it is insoluble to the extent that it can be retained in an aqueous solution. Preferably, the dye has a solubility in water of pH 6 at room temperature (24° C.) of 10% by weight or less, more preferably 5% by weight or less. In addition, "substantially soluble in water at pH 8 or above" means that the dye is dissolved to such an extent that the fine powder dispersion state cannot be maintained in an aqueous solution with pH 8 or above. Solubility at room temperature is 90
Dyes in excess of 95% by weight are preferred. The solid dyes of the present invention may be water-soluble or water-insoluble at pH 7, but are at least substantially water-insoluble at pH 6 or below, and substantially water-soluble at pH 8 or above. ．． As such a fine powder dye, at least one type of dye represented by the following general formulas (I) to (V) is preferably used.

General formula (1) A = L, - (L, = L3), A' General formula (IV) A-@Lx - No. L2 = B General formula (V) (In the formula, A and A' may be the same or different. each represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group.R
represents a hydrogen atom or an alkyl group, R. and R each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group; and R may be connected to form a 5- or 6-membered ring. R, and R. each represents a hydrogen atom, an alkyl group, a hydroxy group, a carboxyl group, an -alkoxy group, or a halogen atom; @ Ll % t, which represents the nonmetallic atomic group necessary to form
t and L each represent a methine group. m represents O or l, n and q each represent 0, 1 or 2, p represents O or l, when p is 0, R1 represents a hydroxy group or a carboxyl group, and R4 and Rs represent hydrogen Represents an atom. However, the compound represented by general formula (I), (■), (III), (IV) or (V) has a pKa in a mixed solution of water and ethanol in a volume ratio of 1:1 in one molecule. is 4~l
It has at least one dissociable group in the range of 1. > General formulas (I), (II), (III), (IV) and (V) will be explained in detail. The acidic nucleus represented by A or A' is preferably 2-birazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinesion, isoxazolidinone, barbituric acid, thiobarbituric acid, indandione. , represents pyrazoloviridine or hydroxypyridone. The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, penzoxazole, naphthoxazole or virol. A dissociative group having a pKa (acid dissociation constant) in the range of 4 to 1 liter in a mixed solution of water and ethanol at a volume ratio of 1 to 1 makes the dye molecule substantially water-insoluble at pH 6 or below.
There are no particular restrictions on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or higher, but preferably carboxyl groups, sulfamoyl groups,
Sulfonamide group, amino group, hydroxyl group,
More preferred is a carboxyl group. The dissociative group may be substituted not only directly on the dye molecule, but also via a divalent linking group (eg, alkylene group, phenylene group). Examples via a divalent linking group include 4-carboxyphenyl, 2-methyl-3-carpoxyphenyl, 2.4-dicarboxyphenyl, 3.5-dicarboxyphenyl, 3-carboxyphenyl, 2 .5-dicarboxyphenyl, 3-ethylsulfamoylphenyl,
4-phenylsulfamoylphenyl, 2-carpoxyphenyl, 2,4.6-trihydroxyphenyl, 3-
Benzenesulfonamidophenyl, 4-(p-cyamibenzenesulfonamido)phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carpoxyphenyl, 3-methoxy 4-carpoxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzene, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-disulfamoyl Examples include phenyl, carboxymethyl, 2-carboxyethyl, 3-carboxybrobyl, 4-carboxybutyl, 8-carboxyoctyl, and the like.
R,R. Or the alkyl group represented by R6 has 1 carbon number
-10 alkyl groups are preferred, such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like. The alkyl group represented by R+ and Rs is preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-butyl, n-octyl, n-octadecyl, isobutyl, isobrobyl),
Substituents [e.g., halogen atoms such as chlorine and bromine, nitro groups, cyano groups, hydroxy groups, carboxy groups, alkoxy groups (e.g., methoxy, ethoxy), alkoxy carbonyl groups (e.g., methoxy carbonyl, i-proboxyl groups) carbonyl), aryloxy groups (e.g. phenoxy), phenyl groups, amide groups (e.g. acetylamino, methanesulfonamide), carbamoyl groups (e.g.
methylcarbamoyl, ethylcarbamoyl), or sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl). The aryl group represented by R1 or R2 is preferably a phenyl group or a naphthyl group, and the substituents include the above R
．． The substituents of the alkyl group represented by and R include the groups and alkyl groups (eg, methyl, ethyl). ]. The acyl group represented by R or R2 has 2 to 10 carbon atoms.
Preferred are acyl groups such as acetyl, probionyl, n-octanoyl, n-decanoyl, isobutanoyl, and benzoyl. Examples of the alkylsulfonyl group or arylsulfonyl group represented by R1 or R include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl,
Examples include groups such as 0-carboxybenzenesulfonyl. R. Or the alkoxy group represented by R6 has 1 to 1 carbon atoms.
10 alkoxy groups are preferred, such as groups such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, imbroboxy, etc. can be mentioned. Examples of the halogen atom represented by R8 or R6 include chlorine, bromine, and fluorine. R, and R4 or R3 and R. An example of a ring formed by linking is a julolidine ring. Examples of the 5-1 or 6-membered ring formed by linking R and R2 include a viveridine ring, a morpholine ring, and a virolidine ring. Lt. The methine group represented by L- or Ls has a substituent (
For example, methyl, ethyl, cyano, phenyl, chlorine atoms,
H. The term is used to include those with the drug (droxybrovir). The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, probionyl, hebutanoyl, dodecanoyl, hexadecanoyl, 1-oxo-7-chlorohebutyl), arylcarbonyl group (arylcarbonyl group that may be substituted, such as benzoyl, 4
-ethoxycarbonylbenzoyl, 3-chlorobenzoyl), alkoxycarbonyl groups (alkoxycarbonyl groups that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-
Ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyshethoxycarbonyl,
2-methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), aryloxycarbonyl group (substituted For example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl,
4-fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl,
2,4-di(1-amyl)phenoxycarbonyl),
Carbamoyl group (carbamoyl group which may be substituted, for example, carbamoyl group, ethyl rubamoyl, dodecyl rubamoyl, phenylcarbamoyl, 4-methoxyphenyl rubamoyl, 2-promophenyl rubamoyl, 4-chlorophenyl rubamoyl, 4-Ethoxyluponylphenylcarbamoyl, 4-probylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2.4-di(t-amyl)phenyl Carbamoyl, 2-chloro3-(dodecyloxycarbonyl)phenylcarbamoyl, 3-(
hexyloxycarbonyl) phenylcarbamoyl),
Represents a sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), a sulfamoyl group (a sulfamoyl group that may be substituted, such as sulfamoyl, methylsulfamoyl). Next, specific examples of dyes used in the present invention will be given, but the present invention is not limited thereto. 1-1 1-2 1-3 {-4 1-9 1-5 1-6 l-7 1-8 ■-13 1-14 ■-15 ■-16 I-17 ■-18 ■-19 I- 20 ■-27 I-28 1-1 0 ■-21 Summer-22 ■-25 ! -26 ■-2 1-3 1-4 I-5 1-6 1-1 1-2! -3 Seal-4 1-9 1-10 1-11 ■-12 1-5 Summer-6 Mouth-7 1-8 Seal-13 Summer-14 Seal-15 1-16 ■-17 1-18 ■-19 ■-20 I-25! -21! -22 ■-23 I-24 ■-29 Seal-31 l-32 I-34 I-35 IV-7 C Spirit H. cy3 ff-2 ff-5 IV-10 ■-11 ff-12 ■-14 ■-15 V-t V-6 V-7 V-2 V-3 ■-4 V-5 Dyes used in the present invention International Publication W0 8 8/04
No. 794, European Patent (EP) 0274723A1
No. 276,566, No. 299,435, JP-A No. 52-92716, No. 55-155350, No. 55
-155351, 61-205934, 48-
68623, U.S. Patent No. 2,527,583, 3
．． No. 486,897, No. 3,746,539, No. 3,
No. 933,798, 4. No. 130,429, 4,
It can be easily synthesized by the method described in No. 040,841, etc., and according to that method. A method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-56-12639 and JP-A-55-1553.
No. 50, No. 55-155351, No. 63-27838
No. 63-197943, European Patent No. 15.601
No. 274,723, No. 276,566, No. 29
No. 9,435 and International Patent Application Publication WO 8 8/0
4 7 9 4 etc. However, it does not disclose the problem of sharpness in light-sensitive materials in which a high silver chloride emulsion layer consisting mainly of tabular grains is formed on a reflective support. In the present invention, a dye that is substantially insoluble in water having a pH of 6.0 or less is used as described in International Publication WO 88/0 4794,
European Patent (EP) No. 0276566 and JP-A-63
It is preferable to use it by dispersing it in a fine powder form in a colloid together with a dispersion aid according to the method described in Japanese Patent Application No. 197943. “In fine powder form” means its average particle size (projection,
circular approximation) is 1 μm or less, preferably 0.5 μm to 0
．． 01 μm, the colloid layer is substantially resistant to diffusion with respect to other adjacent layers, and is dispersed without coarsely agglomerating at 3 μm or more. cormorant. Examples of dispersion aids include ordinary nonionic surfactants, anionic surfactants, amphoteric surfactants, etc.
1 5272, page 201, lower left column to page 210, upper right column, the description of the cited patent specification and the specific compound W-
Compounds represented by 1 to w-99, Japanese Patent Publication No. 5
General formula [■] of No. 6-36415, Japanese Patent Publication No. 59-31-688, and Japanese Patent Application Laid-open No. 63-282738,
It is possible to select and use surfactants represented by the formulas [■] and [rX]. For example, (1) C-th H23CON-CH2 CH2 COONa spirit OH O-(CHz
Jx SO:+Na(x:y=j:f.X:Y-shape 6
J Also, a water-soluble organic solvent such as dimethylformamide, methyl alcohol, ethyl alcohol, dimethylsulfonylamide, etc. can be used as a dispersion aid. Hydrophilic colloids such as gelatin, casein,
Hydroxyl ethyl cellulose, poly-N-vinylpyrrolidone, polyacrylic acid, gelatin derivatives, and alkaline water can be used. The fine powder dispersion can be prepared by dissolving the solid dye in a water-soluble organic solvent and dispersing it in a colloidal aqueous solution having a neutral or acidic pH. Particularly preferably, the solid dye is wetted with water or an insoluble liquid, and then kneaded with a dispersion aid. A method in which solid dyes are made into fine particles in a mill and dispersed in a colloidal aqueous solution, a method in which the solid dye is made into a fine powder using ultrasound and then dispersed in a colloidal aqueous solution using a dispersion aid such as a surfactant, and an alkaline method. It can be produced by dissolving the dye in water and then decomposing it into an acidic aqueous colloid solution. It is preferable to use an organic acid, such as citric acid, oxalic acid, acetic acid, or tartaric acid, in combination with the dye or colloid aqueous solution. The fine powder dye used in the present invention may be fine crystals of the dye or
The particles may have a micellar structure or may be microagglomerated particles. The particle size of powder particles can be determined by observing a cross section of a colloid layer containing them using a transmission electron microscope.
It can be measured. In the present invention, the hydrophilic colloid layer containing fine powder dye refers to a non-photosensitive layer (e.g., antihalation layer, antiirradiation layer, filter layer, subbing layer, intermediate layer, color mixing prevention layer, ultraviolet absorption layer, protective layer) ) or a photosensitive layer (silver halide emulsion layer). The content of this fine powder dye is preferably 5 mg/rd-1000 mg/rt? , more preferably 10 mg/rrr to 200 m
g/rr? It is. The optical density of the colored layer (hydrophilic colloid layer containing finely powdered dye) used in the present invention is:
The transmittance at the absorption peak wavelength in the visible region is preferably set to 80% or less, more preferably 50% or less, particularly preferably 30% or less. The absorption wavelength of the colored layer can be selected depending on the purpose, such as one that absorbs only light in a certain visible region or one that absorbs light in the entire visible region. The silver halide emulsion used in the present invention is one in which 80 mol % or more of the total silver halide constituting the grains consists of silver chloride. Preferably 80
It is mol% or more and 99.5 mol% or less, more preferably 90 mol% or more and 99 mol% or less. The remaining silver halide is silver bromide, and silver iodide may also be included, but it is most preferable that it is not included. When silver iodide is included, it is preferably 1 mol % or less. Further, the silver halide emulsion used in the present invention includes tabular grains having an average aspect ratio of 5 or more.
It accounts for at least 50% of the total projected area of the silver halide grains. The term "aspect ratio" used in this specification refers to the ratio of diameter to particle thickness. The "diameter" of a grain refers to the diameter of a circle having an area equal to the projected area of the grain when the emulsion grain is observed under a microscope or an electron microscope. From a shaded electron micrograph of an emulsion sample, the thickness and diameter of each grain can be measured, and the aspect ratio of each tabular grain can be calculated. The average aspect ratio of the silver halide emulsion used in the present invention is determined as follows. That is, from among all the silver halide grains present in the emulsion, those with a diameter of 0.1 to 10 μ and a thickness of 0.3 μ or less are selected, and tabular grains with a large aspect ratio are selected from among the silver halide grains with a sum of projected areas. Collect as many particles as necessary to exceed 50%, calculate the average aspect ratio of the particles thus collected, and make sure that the value is 5 or more. The diameter of the tabular silver halide grains used in the present invention is:
As mentioned above, 0.1 to 10μ, preferably 0.2 to 5μ.
0μ, particularly preferably 0.3 to 2.0μ.
Further, the thickness of the particles is 0.3 μm or less.

Grain thickness is expressed as the distance between two parallel planes that make up a tabular silver halide grain. In the present invention,
More preferred tabular silver halide grains have a grain diameter of 0.
．． 2 μm or more, 5. 0μm or less, particle thickness 0.3
μm or less, and the aspect ratio (average diameter/average thickness) is 5 or more and 30 or less. More preferably, in the case of a silver halide photographic emulsion, grains having a grain diameter of 0.3 μm or more and 2.0 μm or less and an aspect ratio of 5 or more and 8 or less occupy 85% or more of the total projected area of all silver halide grains. be. If the aspect ratio exceeds 30, the silver halide becomes too easy to dissolve, which is undesirable. The size distribution of the tabular silver halide grains used in the present invention may be narrow or wide, but monodisperse emulsions are preferred, and the grain size distribution, which represents the degree of monodispersity, has a statistical standard deviation ( s) and the average particle size (1) (s/
d) is 0.25 or less, more preferably 0.23 or less, still more preferably 0.15 or less. The halogen composition of the tabular emulsion used in the present invention may be different or equal among the grains, but When an emulsion having an equal halogen composition is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition or distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and those surrounding it. A particle with a so-called layered structure in which the halogen composition differs between the shell (single layer or multiple layers), or a structure with a non-layered portion with a different halogen composition inside or on the particle surface (if it is on the particle surface, the edge of the particle , a structure in which parts of different compositions are joined on a corner or surface) can be selected and used as appropriate. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance.

When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. Alternatively, it may be one that actively has continuous structural changes.

In high silver chloride emulsions, the silver bromide localized layer is formed in a layered or non-layered manner inside silver halide grains and/or in a layered or non-layered manner as described above.
Or those with a structure on the surface are preferable. The halogen composition of the localized layer is at least 1 in terms of silver bromide content.
0 mol% is preferred, and more than 20 mol% is more preferred. And these localized layers are inside the particle,
It can be located on the surface of the particle, at the corner, or on the surface, but one preferred example is one in which epitaxial growth occurs on a part of the corner of the particle. On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, it is necessary to use grains with a uniform structure with a small distribution of halogen composition within the grains in a high silver chloride emulsion with a silver chloride content of 90 mol% or more. Also preferably done. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the processing solution. In such cases, the silver chloride content is 98 mol% or more.
Emulsions of nearly pure silver chloride, such as 100 mol %, are also preferably used. The silver halide grains used in the present invention are composed of two or more types of monodispersed silver halide emulsions with different grain sizes in an emulsion layer having substantially the same color sensitivity in order to satisfy the target gradation of the light-sensitive material. Can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions may be mixed or layered for use. The tabular silver halide emulsion used in the present invention is manufactured by Cugna
c, Chateau's report, and Puffin's ``Chemistry of Photographic Emulsions J''.
lsion Che+++istry) (Focal
Press, New York, 1966), pp. 66-72, and A. P. H. Trivelli,
W. F. Edited by Smith “Photo Magazine J”
．． Journal) 80 (1940), p. 285;
No. 8-111935, No. 58-111936, No. 58
-111937, 58-10853, 62-2
No. 18959, U.S. Pat. No. 4,399.215. Same 4
, 400,463, European Patent No. 0.288,9
It can be easily prepared by referring to the method described in No. 49. For example, in the presence of a pebutizer containing adenine and thioether bonds while maintaining a low pCβ of pc120.3,
It is obtained by simultaneously adding a NaCβ solution and an A g N O s solution to form pure silver chloride tabular grains, and then adding a KBr solution. The size of the tabular silver halide grains can be adjusted by controlling the temperature, selection of the type and quality of the solvent, the silver salt used during grain growth, the addition rate of the halide, etc.

When producing the tabular silver halide grains of the present invention, by using a silver halide solvent as necessary, grain size, grain shape (diameter/thickness ratio, etc.), grain size distribution,
The growth rate of particles can be controlled. The amount of the solvent used is preferably in the range of 10-' to 1.0% by weight of the reaction solution, particularly preferably in the range of 10-' to 10-'% by weight.In the present invention, as the amount of the solvent used increases, While it is possible to make the grain size distribution monodisperse and increase the growth rate, there is also a tendency for the thickness of the grains to increase with the amount of solvent used.In the present invention, known silver halide solvents can be used. Silver halide solvents that are often used include ammonia, thioethers, thioureas, thiocyanate salts, thiazolinthiones, and the like.

For thioethers, U.S. Pat. No. 3,271,15
No. 7, No. 3,574.628, No. 3,790,3
No. 87 etc. can be referred to. Regarding thioureas, JP-A-53-82408 and JP-A-55-777
No. 37, U.S. Pat. No. 2,2 for thiocyanate salts.
No. 22,264, No. 2,448,534, No. 3.
No. 320,069, and Japanese Patent Application Laid-open No. 144319/1989 can be referred to with respect to thiazolinthiones.

In the process of forming or physically ripening silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron acid or iron complex salts, etc. may coexist. .

When producing the tabular silver halide grains used in the present invention, a silver salt solution (for example, A
A method of increasing the addition rate, amount, and concentration of an aqueous alkali halide solution (e.g., an aqueous NaC 12 solution) and an aqueous NaC 12 solution is preferably used. These methods are described, for example, in British Patent No. 1.335.
No. 925, U.S. Patent No. 3,650,757, U.S. Pat.
672.900, 4,242,445, JP-A-55-142329, JP-A-55-158124, etc., may be referred to. After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting, chemical ripening, and spectral sensitization before being used for coating. To remove soluble silver salts from the emulsion after physical ripening, use Medel's water washing, flocculation sedimentation method, or ultrafiltration method. The tabular silver halide grains used in the present invention can be chemically sensitized if necessary. That is, sulfur-containing compounds that can react with activated gelatin and silver (e.g. thiosulfates, thioureas, merkabut compounds, rhodanines).
Sulfur sensitization method using reducing substances (e.g. stannous salts,
Reduction sensitization method using noble metal compounds (e.g., gold complex salts, pt, Ir.Pd, Ph%F)
A noble metal sensitization method using complex salts of metals of group Ⅰ of the periodic table such as e) can be used alone or in combination. Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, F. M. by Harmer, He
terocyclic compounds-Cyan
ine dies and related comp
ounds (John Wiley & Sons (N
ew York, London 1, 1964)
Examples include those listed in . Specific examples of compounds and spectral sensitization methods are described in the above-mentioned JP-A-62-
2 1 5272 Publication Specification, page 22, upper right column to 3rd page
The one described on page 8 is preferably used. The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used. The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the light to be exposed, namely yellow for blue, magenta for green, and cyan for red. By containing so-called color couplers, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above. The tabular emulsion used in the present invention may be contained in at least one of the light-sensitive layers (for example, a blue-sensitive layer or a red-sensitive layer), or may be contained in all the light-sensitive layers. When the tabular emulsion according to the present invention is contained in a plurality of photosensitive layers having different color sensitivities, a colored layer according to the present invention may be disposed between the photosensitive layer and the support, depending on the spectral wavelength. is preferable. Yellow couplers, magenta couplers, and cyan couplers, which produce yellow, magenta, and cyan colors, respectively, by coupling with oxidized products of aromatic amine color developers are commonly used in color photosensitive materials. The cyan coupler, magenta coupler and yellow coupler preferably used in the present invention have the following general formulas (C-1), (C-1), (MT), (M-1f).
and (Y). General formula (C-1) 0H General formula (C-n) General formula (M-1) General formula (M1) 0H Ytomi General formula (Y) General formula (C-1) and (C-11) In, R1,
R2 and R4 represent a substituted or unsubstituted aliphatic, aromatic or heterocyclic group, R,, RS and R represent a hydrogen atom, halogen atom, aliphatic group, aromatic group or acylamino group, R, is nitrogen-containing 5jii with Ro! !
! Alternatively, a group of nonmetallic atoms forming a 6-membered ring may be used.a Yl% Yt represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of a developing agent. n is 0
Or represents l. Rs in Formula 1a (C-11) is preferably an aliphatic group, such as a methyl group, ethyl group, proyl group, butyl group, pentadecyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, Examples include phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group. Preferred examples of the cyan coupler represented by the general formula (C-1) or (C-I1) are as follows. In general formula (C-1), preferred R. is an aryl group,
A heterocyclic group, including a balogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, and a cyano group. More preferably, it is an aryl group substituted with a group. In general formula (C-1), when R and Rz do not form a ring, R8 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably a substituted aryloxy-substituted alkyl group, R is preferably a hydrogen atom. In formula 1a (c-n), R is preferably an alkyl group of substituent or mztn, or an aryol group, and particularly preferably an alkyl group of substituted aryloxytta. - In formula (C-I1), R is preferably 2 carbon atoms.
It is a methyl group having an alkyl group of ~15 and a substituent having 1 or more carbon atoms, and the substituent is preferably an arylthio group, an alkylthio group, an acylamino group, an aryloxy group, or an alkyloxy group. In general formula (C-I1), RS is more preferably an alkyl group having 2 to 15 carbon atoms, particularly preferably an alkyl group having 2 to 4 carbon atoms. In the general formula (C-n), R4 is preferably a hydrogen atom, a halogen atom, a chlorine atom, a fluorine atom, etc. is particularly preferred. General formula (C-1) and (C-
Preferred Y and Yt in n) are a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, and a sulfonate group, respectively. In general formula CM-1), R7 and R represent an aryl group, and R. represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y represents a hydrogen atom or a leaving group. R, and I? ，
The permissible substituents for the aryl group (preferably phenyl group) include the substituent R. are the same as the substituents allowed for, and when there are two or more substituents, they may be the same or different. R. is preferably a hydrogen atom, an aliphatic acyl group or a sulfonyl group, and particularly preferably a hydrogen atom. Preferably h is of the type that leaves off with either sulfur, oxygen or nitrogen atoms, such as those disclosed in US Pat. No. 4,351.897 and International Publication W 0 88/04.
Particularly preferred are sulfur atom separation types, such as those described in No. 795. In general formula (M-n), R1. m represents a hydrogen atom or a substituent, Y4 represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred, Za,
Zb and Zc represent methine, f-reduced methine, 1N1, or 1Q-, and one of the Za-Zb bond and Zb-Zc bond is a double bond, and the other is a single bond. Z
When the b-Zc bond is a carbon-carbon double bond, m Rl including the case where it is part of an aromatic ring. or Y4
When forming a multimer of 2I or more, Za, zb
Alternatively, when Zc is a substituted methine, this includes the case where the IftA methine is used to form a multimer of lt-isomer or higher. Among the birazoloazole couplers represented by the general formula (M-n), imidazo-(1, 2-b) Preferred are pyrazoles,
Pyrazolo (1
, 5-b) (1.2,4] }Riazole is particularly preferred. In addition, a fractionated alkyl group as described in JP-A-61-65245 is placed at the 2, 3 or 6 position of the birazolotriazole ring. Directly linked birazolotriazole coupler, birazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246, alkoxyphenyl as described in JP-A-61-147254 Use of birazoloazole couplers with a sulfonamide ballast group or birazolotriazole couplers with an alkoxy or aryloxy group in the 6-position as described in EP 226.849 and EP 294.785. is preferable. In the general formula (Y), R. represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group,
R. represents a hydrogen atom, a halogen atom, or an alkoxy group. A is -NllCOR+3, -NHSOt-R+z,
-SOJHR+s, -COOR+x, -SOJ
-Lx1 R. represents. However, l? ts and I? +a represents an alkyl group, an aryl group or an acyl group, and ys represents a leaving group. R. and Rts, as a substituent of RI4,
The same substituents allowed for the leaving group Y.h.
is preferably a type that leaves off with either an oxygen atom or a nitrogen atom, and a nitrogen atom splitting type is particularly preferred. General formula (C-1), (C-11), (M-1), (M-
Specific examples of couplers represented by (2) and (Y) are listed below. (C-1) C, Hv (C-4) 0H (C-9) 0 ■ (C-5) (C-6) CxHs (C-7) (C-8) CJs (C-13) (C -14) (C-15) (C-16) (C-17) (C-18) (C-19) ■ (M-1) CI et al CM-2) Ct (M-3) (C- 20) (C-21) (C-22) (M-4) CM-6) (Y-1) (Y-2) (Y-5) (Y-6) (Y-3) (Y-4 ) (Y-7) (Y-8) (Y-9) The couplers represented by the above general formulas (C-1) to (Y) are:
The silver halide emulsion layer constituting the photosensitive layer usually contains 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol, per mol of silver halide. In the present invention, various known techniques can be applied to add the coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, in which it is dissolved in a solvent and then emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water dispersion through phase inversion. Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method; after removing the low-boiling point organic solvent from the coupler waste by distillation, noodle washing, or ultrafiltration, a photographic emulsion is prepared. May be mixed with As a dispersion medium for such a coupler, the dielectric constant (25℃〉
It is preferable to use a JIJ i9 medium with a high boiling point and/or a water-insoluble polymer compound having a refractive index (25°C) of 1.5 to 1.7. As the high boiling point organic solvent, preferably the following general formula (A) ~
A high boiling point II t9 medium represented by (E) is used. General formula (A) W. 0 wt-o-p So-called O General formula (B) W, -COO-Wt General formula (E) W+-0-At (In the formula, Wls te1 and 1, respectively, are substituted or unsubstituted alkyl groups, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, H4 is H,
01<, or S−L, n is an integer from ■ to 5, and when n is 2 or more, u4 may be the same or different from each other, and in general formula (E), H1 and Ka2 may take the form of a condensed ring. The high boiling point a solvent that can be used in the present invention also has a melting point of 1 other than -a formula (A) to (E).
It can be used as long as it is a water-immiscible compound with a boiling point of 140°C or lower and a temperature of 140°C or lower, and is a good solvent for couplers. The melting point of the high-boiling organic solvent is preferably 80°C or lower. The boiling point of the high boiling point solvent is preferably 160°C or higher, more preferably 170°C or higher. For details on these high boiling point organic solvents, please refer to JP-A-62
- Lower right column of page 137 of published specification No. 215272~
It is written in the upper right column of page 144. Additionally, these couplers can be applied to loadable latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer. Homopolymers or copolymers described on pages 12 to 30 of WO88/00723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an axianophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Silylation of spirochromans, p-alkoxyphenols, hindered phenols including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered millets, and the phenolic hydroxyl groups of these compounds. , alkylated ether or ester derivatives are typical examples. Further, metal complexes such as (bissalicylaldoximato)nickel complexes and (bis-N,N-dialkyldithiorubamato)nickel complexes can also be used. Specific examples of organic anti-fading agents are found in the following patents! It is written in one book.゜Hydroquinone neck is U.S. Patent No. 2,360.290,
2.418.613, 2.700, 453
No. 2,701,197, No. 2.728,65
No. 9, No. 2,732,300, No. 2,735.7
No. 65, No. 3.982,944, No. 4.430,
425, British Patent No. 1,363.921, US Patent No. 2.710.801, US Patent No. 2.816.028, etc., 6-hydroxychromans, 5-hydroxycoumarans, and spirochromans are U.S. Patent No. 3.432,3
No. 00, No. 3.573.050, No. 3,574.
No. 627, No. 3,698,909, No. 3,764
．． No. 337, JP-A-52-152225, etc., and spiroindanes are described in U.S. Pat. No. 4,360,589, p.
-Alkoxyphenols are US 4H'f No. 2.735
, 765, British Patent No. 2.066.975, Japanese Patent Application Publication No. 10539/1982, Japanese Patent Publication No. 19765/1983, etc., and hindered phenols are described in US Patent No. 3.100.4.
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,22
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457.079, U.S. Pat. 56-21144
U.S. Patent No. 3.336.
．． 135, British Patent No. 4.268,593, British Patent No. 1.326,889, British Patent No. 1.354.313, British Patent No. 1.410.846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. No. 58-114036, No. 59-53846,
Metal complexes are described in U.S. Patent No. 4.050.938, U.S. Patent No. 4,241.155, British Patent No. 2.027,731 (A), etc., respectively. ．． The purpose of these compounds can be achieved by co-emulsifying them with the respective color couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it. As ultraviolet absorbers, penzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314,794, U.S. Pat. No. 3,352,
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., U.S. Pat. No. 3,705.8)
05, 3.707.395), butadiene compounds (as described in U.S. Pat. No. 4.045.229), or benzoxide compounds (e.g., U.S. Pat. No. 3.406.070). 3,677,67
No. 2 and those described in No. 4,271.307) can be used. UV-absorbing couplers (e.g. α-
A naphthol-based cyan dye-type coupler) or an ultraviolet-absorbing polymer may also be used. These ultraviolet absorbers may be mordanted in a specific layer. Among these, the penzotriazole compounds substituted with the aforementioned aryl group are preferred. In addition, it is particularly preferable to use the following compounds together with the above-mentioned couplers. It is particularly preferred to use it in combination with a virazoloazole coupler. In other words, a compound (F
) and/or a compound (G
) is preferably used simultaneously or singly in order to prevent the generation of stains and other side effects due to the reaction of the color developing agent or its oxidized product in the film with the coupler during storage after processing.

A preferred compound (F) has a second-order reaction rate constant k! with p-anisidine. (in triocutinolephosphate at 80°C) is 1.0ffi/10!・sec~1
×10-J! /mol-sec. The second-order reaction rate constant is based on JP-A-63-158.
It can be measured by the method described in No. 545. If k2 is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k2 is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented. A more preferable compound (F) can be represented by the following general formula (F[) or (Fll). General formula (Fl) R, -(^). -X General formula (F■) Rt-C-Y 1 B In the formula, Rls Rx each represents an aliphatic group, an aromatic group, or a heterocyclic group. n represents l or 0. A represents a group that reacts with an aromatic amine developer to form a chemical bond, and X represents a group that reacts with an aromatic amine developer and leaves the group. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, or a sulfonyl group, and Y promotes the addition of an aromatic amine developing agent to the compound of general formula (FII) represents a group that I here? , and X
, Y and Rt or B may be bonded to each other to form a cyclic structure. Among the methods of chemically bonding with residual aromatic aene-based developing agents, the typical ones are substitution reactions and addition reactions. -IG For specific examples of compounds represented by formulas (FT) and (Fn), see JP-A-63-158545 and JP-A No. 63-158545.
2-283338, European Patent Publication No. 298321,
Those described in specifications such as No. 211589 are preferred. On the other hand, a more preferable compound (G) that chemically bonds with the oxidized aromatic amine developing agent remaining after color development processing to form a chemically inert and colorless compound is the following general formula ( Gl). General formula (G!) R - Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the photosensitive material to release a nucleophilic group. In the compound represented by the general formula (Gl), Z has Pearson's nucleophilicity "CH21 value (
R. G. Pearson, et al. , J.
Eight meters. Chess. Soc. , 90. 319 (1
A group in which 968)) is 5 or more, or a group in which =i is preferable. For specific examples of the compound represented by the general formula (Gl), see European Patent Publication No. 255722, Japanese Patent Application Publication Nos. 62-143048, 62-229145, Japanese Patent Applications 63-136724, 62-214681,
Those described in European Patent Publication Nos. 298321 and 277589 are preferred. Also, the above compound CG
) and compound (F) are described in European Patent Publication No. 277589. In addition to the above-mentioned dyes, water-soluble dyes or water-soluble dyes made by photographic processing may be added to the photosensitive material produced using the present invention, as filter dyes in the wood-philic colloid layer, or for various purposes such as prevention of eradication and halation. It may also contain a dye. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among these, useful are xonol dyes, xonol dyes, and merocyanine dyes. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin (Academic Press, 1964), written by Arthur Vuis. As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For the purpose of the present invention, the use of a reflective support is more preferred, and the "reflective support" used in the present invention is defined as a "reflective support" that enhances the reflectivity and sharpens the dye image formed in the silver halide emulsion layer. Such reflective supports include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those coated with a light-reflecting substance. This includes those using a dispersed hydrophobic resin as a support. Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with reflective layers or reflective materials, such as glass plates, polyester films such as polyethylene terephrate, cellulose triacetate, or cellulose nitrate. , polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, etc. As other reflective supports, supports with specular reflective or type 2 diffuse reflective metal surfaces can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to make the metal surface a phased surface or use metal powder to make it diffusely reflective. The metal may be aluminum, tin, aluminum, magnesium, or an alloy thereof, and the surface may be a metal plate, metal foil, or metal RSN surface obtained by rolling, vapor deposition, plating, or the like. Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate.

It is preferable to provide a layer of water-resistant resin, especially thermoplastic resin, on the metal surface. It is preferable to provide an antistatic layer on the opposite side of the support of the present invention from the side having the metal surface. For details of such a support, see, for example, JP-A-61-21
No. 0346, No. 63-24247, No. 63-2425
It is described in No. 1 and No. 63-24255. These supports can be selected as appropriate depending on the purpose of use. As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with tetrahydric alcohol. The occupied area ratio (%) of white pigment fine particles per defined unit area is calculated by dividing the observed area into adjoining unit areas of 64 x 6μ, and dividing the area of fine particles projected onto that unit area. It can be determined by measuring the occupied area ratio (%) CRL). The coefficient of variation of the occupied area ratio (%) is R. The average value (R) of R. It can be determined by the ratio s/R of the standard deviation S of . The number of target unit areas 1k (n) is preferably 6 or more. Therefore, the coefficient of variation s/R can be found as follows. In the present invention, the variation coefficient of the occupied area ratio (%) of pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles is substantially "uniform". It can be said that. The color photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately rather than in a bath as described above. The color developer used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples are p-phenylenediane derivatives, representative examples of which are shown below, but are not limited thereto. D-IN,N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotriene D-3 2-amino-5-(N-ethyl-N-laurylamino)toluene D-4 4-(N-ethyl-N- (β-hydroxyethyl)amino]aniline D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline D-6 4-amino-3-methyl-N-ethyl-N-[
β-(methanesulfonamido)ethyl]-aniline D-7 N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8 N,N-dimethyl-p-phenylenediamine D-9 4-amino-3-methyl-N =Ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-11 4-Afruit-3-Methyl-N-Ethyl-N
-β-Butoxyethylaniline Among the above p-phenylenediamine fj'EE forms, 4-amino-3-methyl-N-ethyl-N-[
β-(methanesulfonamido)ethyl]-aniline (exemplified compound D-6). In addition, these p-phenyl diamine derivatives and sulfates, hydrochlorides, sulfites, P-}
Salts such as luenesulfonate may also be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g per 12 developing solutions.
g to about 10 g. In carrying out the present invention, it is preferable to use a developer that does not substantially contain benzyl alcohol. Here, "substantially not containing" preferably means 2Ii#! More preferably, the benzyl alcohol concentration is 0.5 Jd/1 or less, and most preferably, no benzyl alcohol is contained at all. It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent, reducing the dye formation efficiency. Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" preferably means 3. OXIO
- The concentration of sulfite ions is less than 1 mol/l, and most preferably, no sulfite ions are contained at all. The very small amount of sulfite ions used to prevent oxidation in the kit is excluded. The developer used in the present invention preferably contains substantially no sulfite ions, and more preferably substantially no hydroxylamine. This is preferable because hydroxylamine has the function of a preservative for the developing solution and also has silver developing activity itself, and it is thought that fluctuations in the concentration of hydroxylamine greatly affect photographic properties. .The term "substantially free of hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-' mol/l or less, and most preferably no hydroxylamine at all.Used in the present invention It is more preferable that the developing solution contains an organic preservative in place of the hydroxyluane and sulfite ion.The organic preservative is added to the processing solution for color photographic materials. It refers to all organic compounds that reduce the deterioration rate of aromatic primary amine color developing agents.In other words, it refers to organic compounds that have the function of preventing color developing agents from being oxidized by air, etc. Among them, hydroxylamine derivatives (hydroxyl (excluding amines, the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, [
, monoamines ζ diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols,
Oximes, diamide compounds, and fused cyclic amines are particularly effective organic preservatives. These are JP-A-63
- No. 4235, No. 63-30845, No. 63-21
No. 647, No. 63-44655, No. 63-53551
No. 63-43140, No. 63-56654, No. 63-58346, No. 63-43138, No. 63-
No. 146041, No. 63-44657, No. 63-44
656, U.S. Patent No. 3,615.503, U.S. Patent No. 2,4
94,903, JP-A No. 52-143020, JP-B No. 48-30496, etc. Other preservatives include various types of gold xi, salicylic acids described in JP-A-59-180588, and JP-A-57-53749.
4-3532, polyethyleneimines as described in JP-A No. 56-94349, aromatic polyhydroxy compounds as described in U.S. Pat. No. 3,746,544, etc., as necessary. Also good. In particular, it is preferable to add alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives, or aromatic polyhydroxy compounds. Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
s27oQ, No. 63-9713, No. 63-97l4, No. 63-11300, etc. Further, it is more preferable to use the above-mentioned hydroxyluane ξ derivative or hydrazine derivative in combination with amines in terms of improving the stability of the color developer and further improving the stability during continuous processing. As the above-mentioned amines, JP-A-63
- Cyclic amines such as those described in JP-A No. 239447, amines such as those described in JP-A-63-128340, and other patent applications such as JP-A-63-9713 and JP-A-63-1130.
Examples include amines as described in No. 0. In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain XIO-" to 1.5 XIO゜■mol/l. Particularly preferably, it contains
-'mol/l. Chlorine ion concentration is 1.5X10-
If the amount is more than '~to-' mol/l, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5×101
If it is less than mol/It, it is not preferable in terms of preventing fog. In the present invention, 3.0% bromine ion is added to the color developer.
X 10-5 mol/fl-1. It is preferable to contain OX10″1 mol/l. More preferably, it contains 5.0
×10-' to 5X10-'mol/l. Bromine ion concentration is IXIO-'mol/j! If the amount is higher, development will be delayed and maximum density and sensitivity will be reduced; 3. OXIO-'
If it is less than mol/l, fogging cannot be sufficiently prevented. Here, chloride ions and bromine ions may be added directly to the developer, or may be eluted from the light-sensitive material into the developer during the development process. When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride. It may also be supplied from an optical brightener added to the developer. As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among them, potassium bromide and sodium bromide are preferred. When eluted from a light-sensitive material during development processing, both chloride ions and bromine ions may be supplied from the emulsion or from a source other than the emulsion. The color developer used in the present invention preferably has p119 to l2,
More preferably, it is 9 to 11.0, and the color developer may contain other known developer compound compounds. In order to maintain the above pH, it is preferable to use various buffers. RI street agents include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3.4 -dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2
-Methyl-1,3-propanediol salt, valine salt, broline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. Especially carbonates, phosphates, tetraborates, hydroxybenzoates are soluble, pH 9
．． It has excellent buffering ability in the high pH range of 0 or more, and even when added to color developers, there is no negative impact on photographic performance (fogging, etc.)
It is particularly preferable to use these street agents because they have the advantages of being free from carbon dioxide and being inexpensive. Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) , potassium 5-sulfo-2-hydroxybenzoate (5
-potassium sulfosalicylate). However, the present invention is not limited to these compounds. The amount of the Ffi street agent added to the color developer is preferably 0.1 mol/l or more, particularly 0.1 mol/l!
~0.4 mol/1! It is particularly preferable that In addition, various chelating agents can be used in the color developer to prevent precipitation of calcium and magnesium, or to improve the stability of the color developer. for example,
Nitrilotriacetic acid, diethylenetrianepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-}rimethylenephosphonic acid, ethylenediamine-N,N,N',N'-tetramethylenesulfonic acid, transsilohexanediaxipentaacetic acid Acetic acid, 1,2-diaξnopropane tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenyl acetic acid, 2-phosphonobutane-1.2.4
-}ricarbosiic acid, 1-hydroxyethylidene-1,1
-diphosphophone a, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and the like. child. These chelating agents may be used in combination with 211 or more if necessary. These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example lj
! The amount is about 0.1g to Log. If necessary, any development accelerator can be added to the color developer. As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 3B-7826, No. 44-1
No. 2380, No. 45-9019 and U.S. Patent No. 3.
813, 247, etc., JP-A-52-49829 and its so-tsss4
p-phenylenediamine-based compounds represented by No. JP-A-50-137726, JP-B No. 44-30074,
Quaternary ammonium salts disclosed in JP-A-56-156826 and JP-A-52-43429, U.S. Patent No. 2,
No. 494.903, 3. 128. No. 182, 4
, 230.796, 3.253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,54
No. 6, No. 2, 596, 926 and No. 3, 582
, No. 346, etc.;
No. 16088, No. 42-25201, U.S. Patent No. 3.
128. No. 183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532,501
Polyalkylene oxide represented by No. 1, etc., and others
-Phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary. In the present invention, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include penzotriazole, 6-nitrobenzimigzole, 5-nitroisoindazole, 5-methylhenzotriazole, 5-nitropensotriazole, 5-chloropenzotriazole, 2-thiazoli Typical examples include nitrogen-containing heterocyclic compounds such as lupenzimidazole, 2-thiazolylmethyl-benzidazole, indazole, hydroxyazaindolizine, and adenine. The color developer applicable to the present invention preferably contains a fluorescent color enhancer. As an optical brightener, 4.4'
-Diamino-2.21-disulfostilbene compounds are preferred. Addition amount is 0 to 5 g/l, preferably 0.1 g to
It is 4/l. Also, if necessary, alkyl sulfonic acid,
Various surfactants such as arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added. The processing temperature of the color phenomenon liquid applicable to the present invention is 20 to 50°C, preferably 30 to 40'C. Processing time is 20 seconds ~ 5
The time period is preferably 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 600 rI per rrr of photosensitive material.
I1 is suitable, preferably 50 to 300 IllI!
It is. More preferably 60 m to 200 m, most preferably 60 m to 150 m. Next, the desilvering process that can be applied to the present invention will be explained.
The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step. The bleaching solution, bleach-fixing solution, and fixing solution that can be applied to the present invention will be explained below. As the bleaching agent used in the bleach or bleach-fix solution, any bleaching agent can be used, but especially iron (
III) complex salts (e.g., complex salts with aminobocarboxylic acids such as ethylenediaξanetetraacetic acid and diethylenetriaminepentaacetic acid, aminobolyphosphonic acid, phosphonocarboxylic acid, and organic phosphonic acid) or citric acid, tartaric acid, malic acid Organic acids such as persulfates and hydrogen peroxide are preferred. Among these, complex salts of iron (Ill) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Anobocarboxylic acids useful for forming organic complex salts of iron (I[[),
Aminobolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, 1. Examples include 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methylylinoniacetic acid, iodinononiacetic acid, glycol ether diaminetetraacetic acid, and nitriacetic acid. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, the iron (nntt salt) of ethylenediaenetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methylynononiaacetic acid is preferred because of its high bleaching power. The ferric ion complex salts of may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferric ion complex salt may be formed in a solution by using a chelating agent such as aminobocarboxylic acid, aminobolyphosphonic acid, or phosphonocarboxylic acid. may be used in excess than the formal warning. Among the complexes, aminobolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/
L is preferably 0.05 to 0.50 mol/l. Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 30, Research Disclosure No. 17129
No. (July 1978 issue), compounds having a mercabuto group or disulfide bond, and
No. 8506, JP-A-52-20832, JP-A No. 53-32
Thiourea compounds described in No. 735 and US Pat. No. 3,706.561, and halides such as iodine and bromide ions are preferred because they have excellent bleaching power. In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, use borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. with PL+ buffering capacity.
inorganic acids, organic acids and alkalis thereof,
metal or ammonium salts or ammonium nitrate;
Corrosion inhibitors such as guanidine can be added. The fixing agent used in the bleach-fixing solution or the fixing solution is a known fixing agent, namely thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycan IJ Water-soluble silver halide solubilizers such as cholic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and 1,000-ureas;
It can be used as a species or as a mixture of two or more species. Further, a special bleach-fixing solution consisting of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354 may also be used.
In the present invention, it is preferable to use thiosulfates, especially ammonium thiosulfates. The amount of fixing agent per li is 0
．． The amount is preferably 3 to 2 mol, more preferably 0.5 to 1.
It is in the range of 0 mole. pHsI of bleach-fix solution or fix solution
The range is preferably 3 to IO, more preferably 5 to 9. Further, the bleach-fix solution may contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and other organic solvents. Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.). These compounds are approximately 0.0 in terms of sulfite ion.
The content is preferably 2 to 0.05 mol/l, more preferably 0.04 to 0.40 mol/l. As a preservative, sulfites are commonly added, but other
Ascorbic acid, carbonyl bisulfite adducts, carbonyl compounds, etc. may be added. Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary. After desilvering treatment such as fixing or bleach-fixing, washing and/or stabilization treatment is generally performed. The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of flushing tanks and the amount of water in the multistage countercurrent system is described in the Journal of the Society of Picture and Television Engineers (Journa 1 or the Society).
y or Motion Picture and T
elevi-sion Engineers) Volume 64, p. 248-253 (May 1955 issue). Generally, the number of stages in the multistage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4. According to the multi-stage countercurrent method, the amount of washing water can be greatly reduced, for example, to 0.5 ffi-If or less per 1 nf of photosensitive material, and the effect of the present invention is remarkable. As the time increases, problems arise such as bacteria multiplying and floating matter adhering to the photosensitive material. As a solution to such problems, Japanese Patent Application Laid-Open No. 62-28883
The method for reducing calcium and magnesium described in No. 8 can be used extremely effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in M61-120145,
Penzotriazole, copper ion, etc. described in JP-A No. 61-267761, “Chemistry of antibacterial and anti-mildew J” written by Hiroshi Horiguchi.
(1986) Sankyo Publishing, Hygiene Technology Society ``tI of microorganisms''
It is also possible to use the disinfectants described in "Bacteria, Sterilization, and Anti-Mold Technology" (1982), published by the Society of Industrial Engineers and the Japan Society of Anti-Bacterial and Anti-Mold Agents, "Dictionary of Antibacterial and Anti-Mold Agents J (1986)."Furthermore, For the washing water, a surfactant as a draining agent and a chelating agent such as EDTA as a water softener can be used.The washing water can be treated with a stabilizing solution following the above washing process or directly without going through the washing process. A compound having an image stabilizing function is added to the stabilizing solution, such as aldehyde compounds such as formalin, and tl suitable for dye stabilization.
Examples include buffers for ipH to iI and ammonium compounds. Furthermore, in order to prevent the proliferation of bacteria in the solution and to impart anti-mold properties to photographic materials after processing, the various disinfectants and anti-mold agents described above can be used. Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 60-220
All known methods described in No. 345 and the like can be used. In addition, it is also a preferable embodiment to use chelating agents such as (1)-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds. A so-called rinsing solution is also used as a washing solution or stabilizing solution after desilvering. The preferred pH of the water washing step or stabilization step is 4 to IO, more preferably 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but -a is 15 to 45
Preferably the temperature is 20 to 40°C. Although the time can be set arbitrarily, a shorter time is preferable from the standpoint of reducing processing time. Preferably the time is 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, wandering ttIi, ease of handling, etc. A specific preferred amount of replenishment is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or it is less than 1 liter per trrt of photosensitive material, preferably less than SooIi. Replenishment may be performed continuously or intermittently. The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is reducing the amount of waste liquid by using a multi-stage counter-current system to allow the overflow of washing water to flow into the bleach-fix bath, which is a pre-bath, and replenish the bleach-fix bath with concentrated liquid. (Examples) Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. Reference Example The emulsion used in the present invention was prepared as follows. 100
IN Ha S to 0 cc of 2.5% gelatin aqueous solution
8.7 cc of o4 1, 1 g of 2,4-thiazolidinone, and 222.0 g of NaCj were added. This solution was kept at 50°C and mixed with 320 cc of 37.5% A g N O s aqueous solution and 320 cc of 12.9% NaCn aqueous solution under strong stirring.
cc was added in 45 minutes by double jet method.

During this time, the amount of sodium chloride aqueous solution added was adjusted so that the initial pAg was maintained. Subsequently, 100 cc of a 1.68% KBr aqueous solution was added to the above emulsion over 10 minutes.

After removing soluble salts by a sedimentation method, gelatin was added to redisperse the mixture, and sodium thiosulfate was added for optimal chemical sensitization. The emulsion thus obtained is emulsion A.
Suppose that In Emulsion A, 80% of the total projected area of the silver halide grains contained was occupied by tabular grains, the average thickness of the tabular grains was 0.19 μm, and the average aspect ratio was 7. The average particle size was measured using a Coulter Counter Model TA-II manufactured by Coulter Electronics, and was found to be 0.80 μm. Further, as a result of measuring the X-ray diffraction of this grain before and after annealing, the average silver bromide content of the entire grain was 98 mol%, and ΔBr was 24 mol%. Let d be the diameter of a salt having an area equal to the projected area when the silver halide grains of emulsion A are dispersed on a plane, then the standard deviation S of d divided by the average value d of d is 100
The value multiplied by (this is called the coefficient of variation) was 20%. Emulsion B was obtained by appropriately changing the solution temperature, the amount of adenine sulfate added, and the addition time of the A g N O * aqueous solution in the formulation of Emulsion A. Emulsion B had a similar profile to Emulsion A, except that the average thickness of the tabular grains was 0.13 μm and the average grain size by Coulter Counter was 0.45 μm. In the formulation of emulsion A, by removing the step of adding KBr aqueous solution after adding A g N O s aqueous solution, emulsion C
I got it. Emulsion C had the same profile as Emulsion A, except that it had pure silver chloride grains. In the formulation of emulsion B,
Emulsion D was obtained by removing the step of adding the KBr aqueous solution after adding the A g N O s aqueous solution. Emulsion D had a similar profile to Emulsion B except that it had pure silver chloride grains.

Next, we will discuss the preparation method of the comparative emulsion. 1 000c
INHa SO4 1 in 2.5% gelatin solution of c
8.7 CC and 6.8 g of NaCn were added. Add this solution to 6
19.2% A g N O was incubated at 2°C and stirred vigorously.
30 cc of S aqueous solution 1 and 130 cc of 6.6% NaCJ2 aqueous solution were added for 60 minutes using a double jet method. 1
After 0 minutes, 285 cc of 35.1% A g N O s aqueous solution and 285 cc of 12.1% NaCI2 aqueous solution were added to this solution.
c was added over 25 minutes by double jet method. Subsequently, an aqueous solution containing 1.75 g of KBr was added to the above emulsion for 10 minutes.
Added within minutes. After precipitation and redispersion, this emulsion was optimally chemically sensitized with sodium thiosulfate. This emulsion is called Emulsion E. Emulsion E was cubic in shape, had an average grain size of 0.80 um by Coulter Counter, and had a coefficient of variation of 12%. The average silver bromide content of the entire grain was 2 mol%, and ΔBr was 38 mol%. Emulsion F was obtained by lowering the temperature of the solution to 56° C. and changing the addition times of the A g N O s aqueous solution and the NaCI2 aqueous solution in the formulation of Emulsion E. Emulsion F has an average grain size of 0.45 by Coulter Counter.
The profile was similar to that of Emulsion E except for the μm. In the formulation of emulsion E, by removing the step of adding KBr aqueous solution after adding A g N O * aqueous solution, emulsion G
I got it. Emulsion G had the same profile as Emulsion E, except that it had pure silver chloride grains. In the formulation of emulsion F,
Emulsion H was obtained by removing the step of adding the KBr aqueous solution after adding the A g N O s aqueous solution. Emulsion H had a similar profile to Emulsion F, except that it had pure silver chloride grains. In the preparation of the above emulsions A-H, IXIO-'
K in the alkali halide aqueous solution so as to be mol%
*Contains IrCβ6. Table 1 summarizes the profiles of emulsions A-H. (Dye C) (Dye D) Next, a method for solid dispersion of dyes will be described.

Dye made into fine particles by sand mill! -11.5g was dissolved in 5cc of a 5% aqueous solution of the following surfactant, and further,
25c of 10% gelatin aqueous solution dissolved in 1g of citric acid
After dispersion in c, the used sand was removed using a glass filter. Wash off the dye adsorbed on the sand on the glass filter using hot water and add 100 c of 7% gelatin solution.
c (solid fine particle dispersion of dye) was obtained. Dispersion A
Suppose that In the dispersion method for dispersion A, 1.5 g of dye 111-3 was used instead of 1.5 g of dye x-i to obtain a solid fine particle dispersion of the same dye as dispersion A. This is the loser B
shall be.

Next, water-soluble dyes for comparison are shown.

For dispersion A, dye C was used, and for dispersion B, dye D was used. Example 1 A multilayer color print material having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene.

The coating solution was prepared as follows. Second layer coating solution preparation Yellow coupler (ExY) 19.1g, color image stabilizer (Cpd-1) 4.4g and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-1) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylbenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, the following blue-sensitive sensitizing dye was added to a silver chlorobromide emulsion (emulsion E) at a rate of 2.0% per mole of silver. A sample containing 10-' mol of OX was prepared. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a second coating solution having the composition shown below. Coating solutions for layers other than those mentioned above were prepared in the same manner as the second layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (per mole of silver halide, for large size emulsions 4
．． OX 10-' moles, 5.6X for small size emulsions
10-' moles) and (2.0XlO-' moles per mole of silver halide) (7.0
X10-' moles, and for small size emulsions l. OX
10-' mole) red-sensitive emulsion layer (per mole of silver halide, 0 for large emulsions)
．． 9 x 10-' moles, or 1.0 for small size emulsions.
To the red-sensitive emulsion layer, the following compound was added in an amount of 2.6XIO-'' mole per 1 mole of silver halide.

In addition, for the noble-sensitive emulsion layer, the green-sensitive emulsion layer, and the red-sensitive emulsion layer, 1-(5-methylureidofenifre)-5-mercaptotetrazole was added at 8.5×10 −' mol and 7 mol per mol of silver halide, respectively. .7XIO-' moles, 2.
5X 10-'Mo71, added.

In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added per mole of silver halide, respectively, to lX10-'
mol and 2X10-' mol were added.

The following dyes were added to the emulsion layer to prevent irradiation. and (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/durability). Silver halide emulsions represent coating amounts in terms of silver. Support polyethylene laminate paper [No.-M side (7) White content (TL
O*) Containing bluish dye (ulmarine blue) 1 First layer (hydrophilic colloid layer) Gelatin 0.50 Second layer (blue sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin l. 86 Yellow Cabler (ExY) 0. 82 color image stabilizer (Cpd-1) 0. 19
Solvent (Solv-1)'
0.35 color image stabilizer (Cpd-7)
0. 06 Third layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0. 08
Solvent (Solv-1) 0.
16 solvent (Solv-4)
O. OR fourth layer (green-sensitive layer) Silver chlorobromide emulsion c-cube, 1=3 mixture (Ag molar ratio) of one with an average grain size of 0.55 μm and one with an average grain size of 0.39 μm. The coefficient of variation of particle size distribution is 0. lO and 0.0
8. Each emulsion was AgBrO. (111 mol% was locally contained on the particle surface) 0.12 Gelatin 1.24 Magenta Cobra (ExM) 0. 20 color image stabilizer (Cpd-2) 0. 03 color image stabilizer (Cpd-3) 0.
15 color image stabilizer (Cpd-4)
o. oz color image stabilizer (Cpd-9)
0. 02 solvent (Solv-2)
0. 40 Fifth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0. 0
5 Solvent (Solv-5) 0
．． 24 Sixth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture (Ag molar ratio) of one with an average grain size of 0.58 μm and one with an average grain size of 0.45 μm. Coefficient of variation of grain size distribution are 0.09 and 0.1
1. Each emulsion contains AgBrO. (6 mol% was locally contained on a part of the particle surface) 0. 23 gelatin
1.34 cyan coupler (
ExC) 0. 32 color image stabilizer (
Cpd-6) 0. 17 color image stabilizer (Cpd-7) 0. 40
Color image stabilizer (Cpd-8) 0.
04 Solvent (Solv-6)
0. 15 Seventh layer (ultraviolet absorbing layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0. 16 Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Eighth layer (protective layer) Gelatin polyvinyl alcohol scum (denaturation degree 17%) Liquid paraffin 0.02 0.08 1.33 Lyle modified copolymer 0 ,17 0.03 (ExY) 1=1 mixture (molar ratio) with yellow coupler (ExC) Cyan coupler - 2:4:4 mixture of R-CJs and CaH9 and 0H by weight (Cpd-1) Color image Stabilizer (E state) L:1 mixture of magenta coupler (molar ratio) (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture Inhibitor 0H (Cpd-6) 2:4=4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer-{CIh-Cll}=-1 (Cpd-8) Color image stabilizer (Solv-1) solution (Solv-2) solution 2: l mixture (volume ratio) (Solv-4) solution (Cpd-9) color image stabilizer (υV-1) ultraviolet absorber 4: 2: 4 Mixture (weight ratio) (Solv-5) Solvent COO(:III?1 (CIlg)*1 COOCIII1? (Solv-6) Solvent Sample 101 was obtained in the above manner.

Hereinafter, according to sample 101, the first layer and second layer (blue-sensitive layer)
Test samples 102 to 112 were prepared by changing the following values as shown in Table 2. Table 2 (Note) l. The average particle size of the fine powder dye is approximately 0.2 μm. In order to investigate the photographic properties of these samples, the following experiments were conducted. First, each sample was subjected to sensitometric WItl exposure through blue, green, and red filters using a sensitometer (Fuji Photo Film Co., Ltd. model fliFWH, light source color temperature 3200''K). The exposure was carried out at an exposure time of 1710 seconds and an exposure amount of 250 CMS.After the exposure, the sample was sent through a paper processing machine and color development was carried out in the next processing step. 35℃ 45 seconds 161ag l?
1 Bleach-fixing 30-35℃ 45 seconds 215atl!
1? j! Rinse■ 30-35℃ 20 seconds
10 1 rinse■ 30-35℃ 20 seconds
■ 10 1 Rinse ■ 30-35℃ 20 seconds 3
50ml! 10 j! Drying 70-80℃
The replenishment amount for 60 seconds was per 1 rn'' of photosensitive material (3 tank countercurrent method was used from rinse ■ to ■.) The composition of each processing solution was as follows.

Color developer tank liquid Shosan Aoisui
1100 d 800
-Ethylenediamine-N, N. N. N-tetramethylenephosphonic acid Potassium bromide Triethanolamine Sodium chloride Potassium carbonate N-ethyl-N-(β-methanesulfone Tmidoethyl)-3-methyl-4- aminotenyline sulfate N,N-bis(carboxymethyl)hydrazine 'it optical brightener (WHITBX 4B, ?.5 g
2.0 g Q. OL5 g ■ 8.0 g 12.0 g 1.4 g 25 g 25 g 5.0 g 7.0 g 5.5 g 'log g Add water p}l (25℃) 1000ml! 1000ml! 10.05 10.45 Bleach-fix solution (tank solution and replenisher are the same) water
400! lLl! Ammonium thiosulfate (70%) 100 ml
! Sodium sulfite 17 g Iron(II!) ethylenediaminetetraacetate Ammonium 55 g Disodium ethylenediaminetetraacetate 5g Add water
1000 dPN (25℃)6.
0. Rinse solution (tank solution and refill solution are the same), ion exchange water (
Calcium and magnesium concentrations were measured for Samples 101 to 112 treated in this manner using red light, green light, or blue light to determine the relative sensitivity of each layer. In addition, to measure resolution, a rectangular wave pattern for CTF measurement was brought into close contact with each sample surface, and exposed using the sensitometer described above. The exposed sample was subjected to the color development process described above, and the density was measured using a microdensitometer using red light, green light, or blue light, and the relative resolution (calculated from the spatial frequency at 50% CTF value) was determined. .

Table 3 shows the relative sensitivity and relative resolution of each sample. Table 3 Example 2 The following Nti multilayer color photographic paper was prepared on a support that was laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (S01v-1) to 0.7 g, and dissolve this solution in 10% sodium dodecylbenzenesulfonate. c.
It was emulsified and dispersed in 185 cc of a 10% gelatin aqueous solution containing c. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.
A 3:7 mixture of 88- and 0.70-1 (i
molar ratio). The coefficient of variation of particle size distribution is 0.08 and 0.08.
10. Each emulsion contains 0.2 mol % of silver bromide locally on the grain surface) and the blue-sensitive sensitizing dye shown below per 1 mol of silver for the large emulsion. Add 10-' moles of OX, and for small size emulsions, 2.5X each
A sulfur sensitized product was prepared after adding 10-' mole of the sample. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below. The coating liquids for the second to seventh layers are also applied in the same manner as the first layer coating liquid.
JI! L. As the gelatin hardening agent for each layer, 1-.oxy-3.5-dichloros-}riazine sodium salt was used. The following spectral sensitizing dyes were used in each layer. Blue-sensitive emulsion layer Green-sensitive emulsion layer (per mole of halide, 4.OX10-' mole for large size emulsions, 5.OX10-' mole for small size emulsions)
6×10°4 mol) and (2.OX10-' mol each for large-sized emulsions and 2.5×10-' mol each for small-sized emulsions per mole of silver halide) (1! halogenide). per mole, ?.OXIG-' mole for large size emulsions and l.OX10 mol for small size emulsions) Red-sensitive emulsion layer (.0.9XIO-' mole per mole of silver halide) B.I. per mole of ionized II. 5X10-'Monore? ．． 7
X10-'mol, 2.5X10-'mol were added. In addition, for the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1.3.3a,7-tetrazaindene was added per mole of silver halide, IXIO-' mol and 2X10-' mol, respectively. Added. The following dyes were added to the emulsion layer to prevent irradiation. For the red-sensitive emulsion layer, 2.6 x 1 G-'' mole of the following compound was added per mole of silver halide. Also for the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, 1-( 5-Methyureidophenyl)-5-merkabutotetrazole (layer structure) The composition of each layer is shown below.The numbers are coating amounts (g/rrf)
represents. The silver halide emulsion represents the coating weight of jl conversion'X.
Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TlOz) and a bluish dye (ulmarine blue)] First layer (Seidaku 1) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (1!xY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35
Color image stabilizer (Cpd-7) 0.
06 Second N (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6 solvent (Solv-4) 0
．． 08 Third layer (green-sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture of one with an average grain size of 0.55μ and one with an average grain size of 0.39tsa (Ag molar ratio). Coefficient of variation of grain size distribution are 0.10 and 0.0
8. Each emulsion contained AgBfO. (8 mol% was locally contained on the particle surface) 0. 12 gelatin
1.24 magenta coupler (
ExM) 0.20 color image stabilizer (Cp
d-2) o. oa color image stabilizer (
Cpd-3) 0. 15 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.0
2 solvent (Solv-2) 0
．． 40 Fourth FJ (ultraviolet absorbing layer) Gelatin l. 58 Ultraviolet absorber (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.0
5 Solvent (Solv-5) 0
．． 24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (emulsion F) Gelatin cyan coupler (ExC) Color image stabilizer (Cpd-6) Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-1 ) Color mixing inhibitor (Cp'd-5) Solvent (So1v-5) Seventh layer (protective FM') Gelatin polyvinyl alcohol scum (denaturation degree 17%) Liquid paraffin 23 34 32 l 7 0.53 0.16 0 .02 0.08 1.33 Lyle modified copolymer 0.17 0.03 (ExY) 1:1 mixture (molar ratio) with yellow coupler (ExM) 1:1 mixture (molar ratio) of magenta coupler (Cpd -2> Color image stabilizer (Cpd-3> Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-5) Color mixture prevention agent 0H (ExC) Cyan coupler R-C.I1. and CaHq and 0M Mixture of 2:4:4 by weight of each color image stabilizer (Cpd-1) Color image stabilizer (Cpd-6) 2:4:4 mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer → CL -CI1}-r-・1 CONHCaHw(t) Average molecule 1ft 60.000 (Cpd-8) Color image stabilizer 0H (Cpd-9) Color image stabilizer (Solv-1) t volume (Solv-2) Solution (UV-1) 2:1 mixture (volume ratio) of ultraviolet absorber (Solv-4) 4:2:4 mixture (weight ratio) (SOIV-5) solvent Sample 201 was obtained in the above manner. .

COOCJI? 1 (Clh)s 1 COOCaLt below, According to sample 201, Fourth layer (ultraviolet absorption convergence) and the fifth layer (red sensitive layer) Change as shown in Table 4. Samples 202-212 were prepared.

(Solv-6) Solvent Table 4 An experiment similar to Example 1 was conducted to investigate the photographic properties of these samples. The results are shown in Table 5.

Table 5 As is clear from the results in Tables 3 and 5, the photosensitive material of the present invention in which high silver chloride tabular grains and a colored layer containing a solid fine powder dispersion were combined was different from that of other comparative materials. It can be seen that this effect is unexpectedly remarkable compared to the resolution improvement effect of photosensitive materials.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention has excellent processing speed and sharpness, and is particularly suitable as a print material having a white reflective support.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a reflective support, an average of at least 50% of the total projected area of silver halide grains is present in at least one of the silver halide emulsion layers. The silver halide grains contain tabular grains having an aspect ratio of 5 or more, and the silver halide grains are high silver chloride grains with a silver chloride content of 80 mol% or more, and the reflective support and the tabular silver halide emulsion described above A silver halide color characterized by having at least one hydrophilic colloid layer between the layers containing a finely powdered dye that is substantially water-insoluble at least at a pH of 6 or below but is substantially water-soluble at least at a pH of 8 or above. Photographic material.