JP2000284427A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material which has high rapid processability, prevents the occurrence of magenta sensitization streaks even by processing in a mini-laboratory or the like and also suppresses curling and to provide a color image forming method using the sensitive material. SOLUTION: The silver halide color photographic sensitive material has at least three silver halide emulsion layers containing silver halide grains having >=95mol% silver chloride content and different from one another in color sensitivity on the paper substrate. The total amount of the hydrophilic binders of the photographic constituent layers of the sensitive material is <=6.5 g/m2 and the rigidity of the paper substrate in a direction perpendicular to the paper making direction is >8 to 13 g.cm. The sensitive material is processed by color development for 5 to 25 sec, bleach fixation for 5 to 25 sec, washing and/or stabilization for 5 to 45 sec and drying for 5 to 15 sec to form the objective color image.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material having excellent suitability for rapid processing and an image forming method using the same. More particularly, the present invention relates to a silver halide color photographic light-sensitive material having improved magenta streak failure during minilab processing and excellent curl characteristics, and an image forming method using the same.

[0002]

2. Description of the Related Art In recent years, in the field of photographic processing services, there has been a demand for high-quality photosensitive materials that can be processed quickly as part of improving services for users and as a means of improving productivity. At present, a light-sensitive material containing a high silver chloride emulsion is processed with a color development time of 45 seconds, and the total processing time is usually about 4 minutes (for example, Color CP-45X manufactured by Fuji Photo Film Co., Ltd.). etc).
However, other color systems (for example, an electrostatic transfer system,
Compared with the processing speed of thermal transfer method and ink jet method, the processing system of high silver chloride print material is still not satisfactory, and it is desired to further shorten the total processing time of high silver chloride color print material. ing.
As means for improving the suitability for ultra-rapid processing in color photographic light-sensitive materials, the use of highly active couplers, the use of couplers with a large molecular extinction coefficient of color-forming dyes, etc., reduce the amount of organic material applied, and reduce the amount of hydrophilic binder applied. And the use of a silver halide emulsion having a high developing speed, and the like. The silver halide emulsion layer having the largest average grain size (conventionally, a yellow coupler-containing layer in many color print materials) is provided farther from the support in the emulsion layer. Are known to be advantageous, for example, the methods described in JP-A-7-239538 and JP-A-7-239439.

As a result of intensive studies by the present inventor on the improvement of suitability for ultra-rapid processing in a color photographic light-sensitive material, it is essential to reduce the amount of a hydrophilic binder applied to a photographic constituent layer. It has been clarified that the light-sensitive material (6.5 g / m ² or less) in which the amount is reduced generates a magenta sensitizing streak when processed in a minilab and causes a problem. For example, Japanese Patent Application Laid-Open No. Hei 10-123683 describes that a photosensitive material having a high rigidity in the length direction (more than 20 g · cm) is easily subjected to pressure because of a high resistance during transportation in a minilab. However, a photosensitive material in which the amount of the hydrophilic binder applied is reduced has a low rigidity in the length direction (20 g ·
cm or less), magenta sensitizing muscles are generated. It is also known that the use of a support having a low rigidity in the longitudinal direction deteriorates the curling characteristics of the photosensitive material, which is particularly remarkable in rapid processing.

[0004]

Accordingly, the present invention provides
An object of the present invention is to provide a silver halide color photographic light-sensitive material which has high suitability for rapid processing, prevents the occurrence of magenta sensitizing streaks even in processing in a minilab, and suppresses curling. Further, the present invention provides a color image forming method capable of obtaining an excellent image with high speed in the processing of a high silver chloride color print material, having high suitability for processing by scanning exposure, and preventing the occurrence of magenta sensitized streaks. The purpose is to provide.

[0005]

In order to improve the magenta sensitizing line in a layer constitution specified with a specific hydrophilic binder amount, the present inventor has proposed that the length direction of the paper support (papermaking direction) be improved. More specifically, it has been found that it is more effective to lower the rigidity in the width direction (direction perpendicular to the papermaking direction). Further, when the rigidity in the longitudinal direction of the support is reduced as described above, curling characteristics generally decrease, but there is no practical problem by setting the rigidity in the width direction to a predetermined range at a predetermined amount of the hydrophilic binder. It has been found that a photosensitive material having curling characteristics can be obtained, and the present invention has been made based on this finding.

The above object has been achieved by the following inventions. (1) In a silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different color sensitivities containing silver halide grains having a silver chloride content of 95 mol% or more on a paper support, The total amount of the hydrophilic binder in the photographic constituent layer of the material is 6.5 g / m ² or less, and the rigidity of the paper support in the direction perpendicular to the papermaking direction is more than 8 g · cm and 13 g · cm or less. Characteristic silver halide color photographic material. (2) The thickness of the paper support exceeds 180 μm and is 235 μm
The silver halide color photographic light-sensitive material as described in the item (1), wherein: (3) The silver halide color photographic material as described in the above item (1) or (2), wherein the total amount of the hydrophilic binder in the photographic constituent layer of the photographic material is 5.5 g / m ² or less. (4) The silver halide emulsion layer farthest from the support contains a yellow coupler (1).
The silver halide color photographic light-sensitive material according to (2) or (3). (5) After imagewise exposing the silver halide color photographic light-sensitive material,
In a method for obtaining a color image through color development, bleach-fixing, washing and / or stabilization, and drying processing steps,
The silver halide color photographic light-sensitive material according to any one of the above items (1) to (4) is subjected to a color development step of 5 seconds to 25 seconds, a bleach-fixing step of 5 seconds to 25 seconds, washing with water and / or
Alternatively, a color image forming method is characterized in that the stabilization treatment is performed within 5 seconds to 45 seconds and the drying step is performed within 5 seconds to 15 seconds. (6) After imagewise exposing the silver halide color photographic light-sensitive material,
5. A method for obtaining a color image through processing steps of color development, bleach-fixing, washing and / or stabilization, and drying, wherein the silver halide color photographic light-sensitive material according to any one of claims 1 to 4 is used for image information. A color image forming method comprising: performing a scanning process with a light beam modulated on the basis of the above, followed by a developing process.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The color photographic light-sensitive material of the present invention will be described below in detail.

In the silver halide color photographic light-sensitive material of the present invention, gelatin is used as a hydrophilic binder. If necessary, another gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, and a sugar derivative may be used. ,
A hydrophilic colloid such as a cellulose derivative or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be any of lime-processed gelatin and acid-processed gelatin, and gelatin produced from any of bovine bone, cowhide, pigskin and the like. However, lime-processed gelatin obtained from cow bone and pig skin is preferred.

In the present invention, the photosensitive silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer up to the hydrophilic colloid layer farthest from the support on the side where the silver halide emulsion layer has been coated from the support. Is not more than 6.5 g / m ² , preferably 6.0 g / m ² or less.
m ² or less 3.5 g / m ² or more, most preferably 5.5 g /
m ² or less and 4.0 g / m ² or more. In particular, 5.5 g / m ² or less is preferable for rapid processing suitability. If the amount of the hydrophilic binder is larger than the range of the present invention, the effect of the present invention cannot be obtained due to impairment of the speed of color development processing, deterioration of brix discoloration, impairment of the rapid processability of the washing step, and the like. Further, when the amount of the hydrophilic binder is less than 3.5 g / m ² , there may be a case where adverse effects due to insufficient film strength are likely to occur.

In the present invention, the thickness of the support is preferably more than 180 μm and 235 μm or less. In this range, the effects of the present invention are more remarkably exhibited.

The support used in the silver halide photographic light-sensitive material of the present invention is preferably a support having paper as a base and having a coating layer of a polyolefin resin on both sides.

The base paper used for the paper support of the present invention can be selected from base papers generally used for photographic printing paper. Examples include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, and mixed pulp of softwood pulp and hardwood pulp can be widely applied. Any paper such as neutral paper and acidic paper may be used, but photographic paper grade base paper is preferably used, and particularly photographic paper grade neutral paper is preferable. Among the polyolefin resin layers coated on both sides of the paper substrate, polyethylene is preferred. Further, a paper support containing a white pigment in a resin layer (hereinafter referred to as a surface resin layer) on a side on which a silver halide emulsion layer is provided in the coating layer is preferable.

The thickness of the surface resin layer is preferably 35 μm or more, more preferably 40 μm or more, and more preferably 40 to 60 μm.
m is preferred. If it exceeds 60 μm, it is not preferable from the viewpoint of cutting properties.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silica, silica such as synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide, and more preferably titanium oxide.

The amount of the white pigment contained in the surface resin layer of the support is preferably 9% or more. In order to improve sharpness, 13% by weight or more is preferable.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above publication.

Ultraviolet, oil-soluble dyes, etc. to adjust the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer to improve the whiteness. It is preferable to add a small amount of a bluing agent or a reddish agent.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion of the support surface, (1 or 2 or more subbing layers for improving antistatic properties, dimensional stability, friction resistance, hardness, antihalation properties, friction properties and / or other properties) Good. In the present invention, the rigidity of the support is defined by a Taber-type rigidity meter according to JIS P-8125.
Means the value measured by the method described in 1. However, the rigidity of the support is a value measured after removing the coated photographic constituent layer or before coating the photographic constituent layer. In the present invention, the stiffness in the direction perpendicular to the papermaking direction (hereinafter referred to as TD) is 8
It is more than g · cm and not more than 13 g · cm. More preferably, it is 12 g · cm or less and 9 g · cm or more. TD is 1
When it exceeds 3 g · cm, magenta sensitizing streaks are generated when processed in a minilab, and when TD is 8 g · cm or less, curling occurs, which is not preferable. The rigidity in the papermaking direction (hereinafter referred to as MD) is preferably 25 g · cm or less and 14 g · cm or more. If the MD exceeds 25 g · cm, the resistance during transportation of the minilab may increase, and if the MD is smaller than 14 g · cm, curling may occur. The TD of the support is
For example, (1) selection of pulp grade, (2) selection of pulp beating conditions, (3) selection of type and amount of added chemicals (particularly paper strength enhancer), (4) adjustment of density, (5) By selecting and adjusting the orientation method of papermaking, it can be adjusted to more than 8 g · cm and not more than 13 g · cm.

In the present invention, the silver halide emulsion layer farthest from the support means that the silver halide emulsion contained in the layer is developed and can substantially contribute to dye formation by reaction with a coupler. The layer farthest from the support among the layers containing the silver halide emulsion. Therefore, a fine grain emulsion having substantially no sensitivity or a layer containing only colloidal silver and containing no coupler is not applicable.

In the present invention, the silver halide emulsion layer containing the yellow coupler is provided at a position farther from the support than at least one of the silver halide emulsion layer containing the magenta coupler and the silver halide emulsion layer containing the cyan coupler. More preferably, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers, so that color development and desilvering can be accelerated and increased. It is preferable from the viewpoint of reduction of the residual color due to the dye.

In the present invention, the ratio of the amount of hydrophilic binder / the thickness of silver halide in the silver halide emulsion layer containing the yellow coupler farthest from the support is preferably from 1.5 to 15. Hereinafter, this ratio is referred to as [B / Ag
X] ratio. Here, the amount of hydrophilic binder means the amount of hydrophilic binder (g per 1 m ^{2 of the} silver halide emulsion layer).
/ M ² ). The amount of the hydrophilic binder is divided by the specific gravity to indicate the thickness, and it is understood that the amount of the hydrophilic binder of the present invention is an amount proportional to the thickness. On the other hand, the term "silver halide emulsion thickness" means a thickness (μm) occupied by silver halide emulsion grains in the silver halide emulsion layer in a direction perpendicular to the support. In the present invention, assuming that the silver halide emulsion layer is ideally coated, the side length (μm) of the cube in the case of cubic grains, and the thickness (μm) in the direction perpendicular to the main plane in the case of tabular grains, ) Is the thickness of the silver halide emulsion. When silver halide emulsion grains of different sizes are used in combination, the weight average of each grain is defined as the silver halide emulsion thickness. For example, a silver halide emulsion grain having a side length A (μm) has a coating weight Xa (g / m ² ) and a side length B (μm).
m) when the coating weight of the silver halide emulsion grains is Xb (g / g).
m ² ) and the coating weight of silver halide emulsion grains having a side length C (μm) of Xc..., the silver halide emulsion thickness (AgX) when a mixture of these is used is given by: AgX = A · Xa / (Xa + Xb)
+ Xc + ...) + B.Xb / (Xa + Xb + Xc + ..) + C
Xc (Xa + Xb + Xc + ..) +...

As is clear from the above definition, the [B / AgX] ratio in the present invention indicates that the larger the value, the smaller the emulsion thickness in the emulsion layer. In the present invention, the [B / AgX] ratio is 1.5 or more, 15 or less, preferably 2.0 or more and 12 or less, and most preferably 5.0 in terms of suppression of pressure fogging streaks and reduction of color mixture during processing.
It is 10 or less.

In the present invention, the amount of the hydrophilic binder in the silver halide emulsion layer containing the yellow coupler farthest from the support is preferably not more than 1.35 g / m ² .
30 g / m ² or more, more preferably 1.25 g / m ²
Below, it is 0.60 g / m ² or more. When cubic grains are used, the silver halide emulsion thickness is preferably 0.8
0 μm or less, 0.10 μm or more, more preferably 0.70 μm
m or less and 0.30 μm or more, and when tabular grains are used, preferably 0.30 μm or less and 0.02 μm or more,
More preferably, it is not more than 0.15 μm and not less than 0.05 μm. The aspect ratio of the tabular grains is preferably from 2 to 12,
More preferably, it is 3-8. Further, in order to control sensitivity, gradation and other photographic performance, it is preferable to use a mixture of silver halide emulsions having different sizes and shapes. In the present invention, the silver halide emulsion layer containing the yellow coupler may be coated at any position from the support, but in order to impart ultra-rapid processing aptitude, the silver halide emulsion layer should be coated in the silver halide emulsion layer. It is preferable to apply the coating at a position farthest from the support.

The yellow coupler used in the present invention may be any of the conventionally known compounds, but an acetanilide type yellow coupler is preferred, and US Pat. No. 5,338,651
An acetanilide-type yellow coupler having a 1-alkyl-cycloalkane ring or an indoline ring described in the specification of JP-A No. 2000-284, 1989 is also preferable.

In the present invention, from the viewpoint of preventing a decrease in cyan density due to Brix fading, the silver halide emulsion layer containing a cyan coupler is preferably located between the yellow and magenta emulsion layers. From the viewpoint, it is preferable that the cyan coupler-containing silver halide emulsion layer is located closest to the support. Each of the yellow, magenta and cyan emulsion layers may be composed of two or three layers. For example, JP-A-4-75055
No., 9-114035, 10-246940,
As described in U.S. Pat. No. 5,576,159, it is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color-forming layer. One preferred embodiment of the present invention is a constitution in which a cyan coupler-containing silver halide emulsion layer composed of two layers is provided at the position closest to the support, or a cyan coupler-containing silver halide emulsion layer closest to the support and an adjacent layer. This is a configuration having a non-photosensitive cyan coupler containing layer.

The average particle diameter of the lipophilic fine particle dispersion containing a cyan coupler in the cyan coupler-containing layer of the present invention is preferably 0.05 to 0.40 μm, more preferably 0.10 to 0.35 μm, and most preferably. 0.15-
0.30 μm. If the average particle size is larger than the range of the present invention, the color development rate is poor and the maximum cyan density is lowered, and if the average particle size is smaller than the range of the present invention, it is not possible to maintain Brix discoloration at a quality having no practical problem.

[0028] The ratio of the cyan coupler coating amount of the cyan coupler-containing layer in the present invention in terms of silver coating amount of silver halide emulsion for (mol / m ²⁾ (mol ^{/ m 2) [Ag / Cp} ] is 1.0 or more 6 2.0 or less, and preferably 1.5 to 5.0.
0, and most preferably 1.8 to 4.0. [A
g / Cp] is less than the range of the present invention, it is difficult to obtain the maximum density of cyan. On the other hand, if it is larger than the above range, it is not possible to maintain Brix discoloration to a quality having no practical problem.

The silver halide emulsion used in the present invention is preferably silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide having a silver chloride content of 95 mol% or more from the viewpoint of rapid color development. It is preferable to use When tabular grains whose main plane is the (111) plane or the (100) plane are used, [B /
AgX] ratio can be increased, which is preferable in terms of speeding up color development and reducing color mixture during processing. Tabular high silver chloride emulsion grains having a (111) plane or a (100) main plane are described in JP-A-6-138609, U.S. Pat.
Nos. 99,215 and 5,061,617 and U.S. Pat. Nos. 5,320,938, 5,264,337, 5,292,632, 5,314,798, and 5, 413,904, WO94 / 22051, and the like.

In the present invention, the coating amount of the silver halide emulsion is preferably 0.60 g / m ² or less and 0.10 g / m ² or more, more preferably 0.55 g / m ² or less.
/ M ² or more, most preferably 0.50 g / m ² or less 0.2
5 g / m ² or more.

The silver halide emulsion grains used in the cyan color-forming layer and the magenta color-forming layer of the present invention may be the above-mentioned tabular grains, but are preferably cubic, and in the case of cubic grains, the side length is preferably 0.1 mm. 50μm or less 0.05μ
m or more, more preferably 0.40 μm or less 0.10 μm
m or more.

In the present invention, the oil-soluble component in the photographic constituent layer is a lipophilic component remaining in the photographic material after processing.
Specific examples include couplers, color mixing inhibitors, ultraviolet absorbers, lipophilic additives, lipophilic polymers or polymer latexes, matting agents, slip agents, etc., which are usually added to photographic constituent layers as lipophilic fine particles. It is. Accordingly, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like do not fall under oil-soluble components. Usually, a surfactant is used when preparing the lipophilic fine particles, but the surfactant is not treated as an oil-soluble component in the present invention. In the present invention, the total amount of the oil soluble component is preferably 4.5 g / m ² or less.
And at 0 g / m ² or more, preferably 4.0 g / m ² or less 2.5 g / m ² or more, and most preferably 3.8 g / m ² or less 3.0 g / m ² or more.

In the present invention, the ratio of the amount of the oil-soluble component to the amount of the hydrophilic binder in the photographic constituent layer can be arbitrarily set.
The preferred ratio in the photographic constituent layers other than the protective layer is 0.05 to 1.50 by weight, more preferably 0.10 to 1.
1.40, most preferably 0.20 to 1.30.
By optimizing the ratio of each layer, the film strength, scratch resistance and curl characteristics can be adjusted.

In the present invention, the thickness of the photographic constituent layer is preferably from 9.0 μm to 1.0 μm, more preferably 8.0 μm.
m and 2.0 μm or more, and most preferably 7.0 μm or less and 3.5 μm or more. In the present invention, the film thickness of the photographic constituent layer means the thickness of the photographic constituent layer above the support before processing. Specifically, it can be determined by any of the following methods. First, it can be obtained by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with an electron microscope. A second method is to calculate the film thickness from the coating amount (g / m ² ) of each component in the photographic constituent layer and the specific gravity. The specific gravity is 1.34 g / ml for typical gelatin used for photographic purposes, 5.59 g / ml for silver chloride particles, and can be measured for other lipophilic additives. The film thickness can be calculated.

The cyan coupler which can be preferably used in the present invention from the viewpoint of rapid processing and color reproducibility includes a cyan coupler represented by the following general formula [CI] and a cyan coupler represented by the following general formula [C-II]. And the cyan couplers represented by the formula:

Formula [C-I]

Embedded image

Wherein Y is -NHCO- or -CONH
Wherein R ₁ represents an alkyl group, an aryl group, a heterocyclic group or an amino group, X represents a hydrogen atom, a halogen atom, an alkoxy group or an acylamino group, and R ₂ represents an alkyl group, an acylamino group or X and R _{And 2} represents a non-metallic atomic group forming a 5- to 7-membered ring, and Z represents a hydrogen atom or a group capable of leaving upon coupling with an oxidized form of a developing agent.

In the general formula [C-I], R ₁ is an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 32 carbon atoms, for example, methyl, butyl, pentadecyl, cyclohexyl), aryl Groups (eg, phenyl, naphthyl), heterocyclic groups (eg, 2-pyridyl, 3-
Pyridyl, 2-furanyl, 2-oxazolyl) or an amino group, which is an alkyl group, an aryl group, an alkyl or aryloxy group (for example, methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,2
4-di-tert-amylphenoxy, 3-tert-
Butyl-4-hydroxyphenyloxy, naphthyloxy), carboxy group, alkyl or arylcarbonyl group (for example, acetyl, tetradecanoyl, benzoyl), alkyl or aryloxycarbonyl group (for example, methoxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl) ), An acyloxy group (eg, acetoxy, benzoyloxy, phenylcarbonyloxy), a sulfamoyl group (eg, N-ethylsulfamoyl, N-octadecylsulfamoyl),
Carbamoyl group (for example, N-methylcarbamoyl, N
-Methyl-dodecylcarbamoyl), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), an acylamino group (eg, acetylamino, benzamide, ethoxycarbonylamino, phenylaminocarbonylamino), an imide group (eg, succinimide, hydantoinyl) ), A sulfonyl group (eg, methanesulfonyl), a hydroxy group, a cyano group, a nitro group, and a substituent selected from a halogen atom.

In the general formula [CI], R ₂ is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl,
Represents an ethyl, butyl, pentadecyl) or acylamino group (eg, tetradecanoylamino, benzoylamino, 2- (2,4-ditert-amylphenoxy) butanamide). The alkyl group of R ₂ may be substituted with a substituent as exemplified for R ₁ . The general formula [C-
In I], X represents a hydrogen atom, a halogen atom, an alkoxy group (for example, methoxy, butoxy), or an acylamino group (for example, acetamido).

The compound represented by the general formula [C-I] includes, in addition to the above-mentioned phenolic cyan coupler, R ₂ and X
Are also preferably a condensed cyan coupler having a 5-, 6-, or 7-membered ring, and such condensed-type cyan couplers include oxindole-based and imidazol-2-one-based cyan-based couplers. Is particularly preferred.

In the general formula [CI], Z represents a hydrogen atom or a coupling-off group. Examples thereof include a halogen atom (for example, fluorine, chlorine, bromine) and an alkoxy group (for example, ethoxy, Dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy), aryloxy group (for example, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, Benzoyloxy), a sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an amide group (eg, dichloroacetylamino, heptabyrylamino, methanesulfonylamino, toluenesulfonylamino), alkoxyca Boniruokishi group (for example,
Ethoxycarbonyloxy, benzoyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), aliphatic, aromatic or heterocyclic thio groups (eg, ethylthio, phenylthio, tetrazolylthio), imide groups (eg, succinimide, Hydantoinyl), N-heterocyclic group (for example, 1
-Pyrazolyl, 1-benzotriazolyl), an aromatic azo group (for example, phenylazo) and the like. These leaving groups may include photographically useful groups.

The cyan coupler represented by the general formula [C-I] has the following general formula [I] in order to prevent Brix discoloration.
It is preferable to use together with the compound represented by I] or the general formula [III].

General formula [II]

Embedded image

General formula [III]

Embedded image

In the formula, R ₃ and R ₅ represent at least one of a halogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfoxide group, a cyano group, a nitro group and an α-position. Represents an alkyl group having two halogen atoms. R ₄ and R ₆ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group,
Represents an arylthio group or an amide group. The total number of carbon atoms of R ₃ and R ₄ and the total number of carbon atoms of R ₅ and R ₆ are each 8 or more.

In the general formulas [II] and [III], R ₃
And R ₅ are halogen atoms (specifically, F, Cl, Br,
I), an acyl group (having preferably 2 to 40 carbon atoms, for example, acetyl, benzoyl, hexadecanoyl) and a sulfonyl group (having an aliphatic or aromatic sulfonyl group having 1 to 40 carbon atoms), for example, Methanesulfonyl,
Benzenesulfonyl, 4-dodecyloxybenzenesulfonyl), alkoxycarbonyl group (preferably having 2 to 40 carbon atoms, for example, methoxycarbonyl and hexyloxycarbonyl), and aryloxycarbonyl group (preferably having 7 to 40 carbon atoms) For example, phenoxycarbonyl), carbamoyl group (preferably having 1 to 40 carbon atoms, for example, N-dodecylcarbamoyl, N, N-diphenylcarbamoyl), and sulfamoyl group (having 0 to 0 carbon atoms)
40 are preferable, for example, N, N-dipropylsulfamoyl, N-phenylsulfamoyl), a sulfoxide group (preferably having 1 to 40 carbon atoms, for example, methanesulfoxide, octanesulfoxide), a cyano group, It represents a nitro group or an alkyl group having at least one halogen atom at the α-position (preferably one having 1 to 40 carbon atoms, for example, trifluoromethyl, 1,1-dichloroethyl).

R ₄ and R ₆ are a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 40 carbon atoms, which may be linear or branched; for example, methyl, t-butyl, hexyl, t-octyl, sec-dodecyl) , Sec-eicosyl) and an aryl group (having 6 to 40 carbon atoms).
Phenyl, p-tolyl), alkoxy group (1-4 carbon atoms)
0 is preferable, for example, methoxy, hexyloxy, tetradecyloxy), an aryloxy group (having 6 to 6 carbon atoms).
40 are preferable, for example, phenoxy, p-acetamidophenoxy), an alkylthio group (having 1 to 4 carbon atoms).
0 is preferable, for example, butylthio, dodecylthio, octadecylthio), arylthio (C6-C4)
0 is preferable, for example, phenylthio) and an amide group (2 to 40 carbon atoms are preferable, for example, acetamido, benzoylamide, hexadecaneamide). These groups may be further substituted as in R ₁ . The total number of carbon atoms of R ₃ and R ₄ and the total number of carbon atoms of R ₅ and R ₆ are each 8 or more.

The compounds represented by the general formulas [II] and [III] may form bis-forms, tris-forms, oligomers and polymers. In the general formula [CI], preferred Y is -NHCO-, preferred R ₁ is an alkyl group or an aryl group, and most preferred R ₁ is an alkyl group. In the general formula [C-I], R ₂ is preferably an alkyl group having 1 to 15 carbon atoms, more preferably 1 to 4 carbon atoms. In the general formula [CI], preferred Z is a hydrogen atom or a halogen atom, and a halogen atom is particularly preferred. In the general formula [C-I], preferred X is a halogen atom, and it is also preferred that R ₂ forms a heterocyclic ring with R ₂ .

In the general formulas [II] and [III], R ₃ and R ₅ are preferably a halogen atom, an acyl group, a sulfonyl group or a carbamoyl group, more preferably a halogen atom or a sulfonyl group. Some cases are most preferred. In formulas [II] and [III], R ₄ and R ₆ are preferably a hydrogen atom, an alkyl group, an alkylthio group or an amide group, and most preferably an alkyl group. R ₃ and R ₄ in the general formula [II] and R ₅ and R ₆ in the general formula [III] are 2,5-
It is preferable that they have a substitution relationship. At least one of R ₃ and R ₄ or at least one of R ₅ and R ₆ is preferably a lipophilic (hydrophobic) group. Hereinafter, specific examples of the compounds represented by the general formulas [CI], [II] and [III] included in the present invention are shown, but the present invention is not limited thereto.

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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The synthesis method of the cyan coupler represented by the general formula [CI], the quinones and the hydroquinones represented by the general formulas [II] and [III], and the method for preparing an emulsified dispersion are described in detail. The description is given in JP-A-2-267548, ibid.
No. 144442 and the like. The compound represented by the general formula [II] and the compound represented by the general formula [III] are preferably added to a layer containing a cyan coupler. The quinones of the general formula [II] and the hydroquinones of the general formula [III] are used in an amount of 0.1 to 100 mol%, preferably 0.5 to 30 mol%, most preferably 2 to 100 mol% per 1 mol of the cyan coupler. Use up to 25 mol%.

In the silver halide photographic light-sensitive material according to the present invention, in addition to a high boiling point solvent and other water-insoluble photographically useful materials, a fine particle dispersion prepared by mixing the following polymers is used. Is preferred. Polymers preferably used include vinyl polymers, methacrylic esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers, and the like, and specific examples of each of these polymer compound groups For the polymerization method, see, for example,
No. 4442 and the like. Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited to these.

P-1) Polymethyl methacrylate P-2) Polyethyl methacrylate P-3) Polyisopropyl methacrylate P-4) Polymethyl chloroacrylate P-5) Poly (2-tert-butylphenyl acrylate) P-6) Poly (4-tert-butylphenyl acrylate) P-7) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) P-8) Methyl methacrylate-acrylonitrile copolymer (65:35) P-9) Methyl methacrylate-styrene copolymer (9
0:10) P-10) N-tert-butyl methacrylamide-methyl methacrylate-acrylic acid copolymer (60: 3)
0:10)

P-11) Methyl methacrylate-styrene-vinylsulfonamide copolymer (70: 20: 1)
0) P-12) Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50) P-13) Methyl methacrylate-acrylic acid copolymer (95: 5) P-14) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-15) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-16) Poly (N-sec-butylacrylamide) P-17) Poly (N-tert-) Butylacrylamide) P-18) Polycyclohexyl methacrylate-methyl methacrylate copolymer (60:40) P-19) n-Butyl methacrylate-methyl methacrylate-acrylamide copolymer (20: 70: 1)
0) P-20) diacetone acrylamide-methyl methacrylate copolymer (20:80)

P-21) N-tert-butylacrylamide-methyl methacrylate copolymer (40:60) P-22) Poly (Nn-butylacrylamide) P-23) Tert-butyl methacrylate-N-te
rt-butyl acrylamide copolymer (50:50) P-24) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-25) poly (N-tert-butyl methacrylamide) P-26) N -Tert-butylacrylamide-methyl methacrylate copolymer (60:40) P-27) methyl methacrylate-acrylonitrile copolymer (70:30) P-28) methyl methacrylate-styrene copolymer (75:25) P -29) Methyl methacrylate-hexyl methacrylate copolymer (70:30)

P-30) Poly (4-biphenyl acrylate) P-31) Poly (2-chlorophenyl acrylate) P-32) Poly (4-chlorophenyl acrylate) P-33) Poly (pentachlorophenyl acrylate) P-34) Poly (4-ethoxycarbonylphenyl acrylate) P-35) Poly (4-methoxycarbonylphenyl acrylate) P-36) Poly (4-cyanophenyl acrylate) P-37) Poly (4-methoxyphenyl acrylate) P-38) Poly (3,5-dimethyladamantyl acrylate) P-39) Poly (3-dimethylaminophenyl acrylate)

P-40) Poly (2-naphthyl acrylate) P-41) Poly (phenyl acrylate) P-42) Poly (N, N-dibutylacrylamide) P-43) Poly (isohexylacrylamide) P-44) Poly (isooctylacrylamide) P-45) Poly (N-methyl-N-phenylacrylamide) P-46) Poly (adamantyl methacrylate) P-47) Poly (sec-butyl methacrylate) P-48) N-tert-butyl Acrylamide-acrylic acid copolymer (97: 3) P-49) poly (2-chloroethyl methacrylate)

P-50) Poly (2-cyanoethyl methacrylate) P-51) Poly (2-cyanomethylphenyl methacrylate) P-52) Poly (4-cyanophenyl methacrylate) P-53) Poly (cyclohexyl methacrylate) P- 54) Poly (2-hydroxypropyl methacrylate) P-55) Poly (4-methoxycarbonylphenyl methacrylate) P-56) Poly (3,5-dimethyladamantyl methacrylate) P-57) Poly (phenyl methacrylate) P-58) Poly (4-butoxycarbonylphenylmethacrylamide) P-59) Poly (4-carboxyphenylmethacrylamide) P-60) Poly (4-ethoxycarbonylphenylmethacrylamide) P-61) Poly (4-methoxycarbonylphenyl) Takuriruamido) P-62) poly (cyclohexyl chloro acrylate) P-63) poly (ethyl chloro acrylate) P-64) poly (isobutyl chloro acrylate) P-65) poly (isopropyl chloro acrylate)

In the present invention, it is preferable that a copolymer having a specific acid content having a carboxylic acid group is contained in a hydrophilic binder from the viewpoint of not deteriorating Brix discoloration. Such a copolymer may be hydrophilic or polymer latex, and is more preferably polymer latex. Such a polymer latex is disclosed, for example, in JP-A-9-329.
No. 861 is preferred. In the present invention, among the above copolymers, a copolymer represented by the general formula [P] is particularly preferable.

[0076]

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In the formula, R ₇ represents a hydrogen atom or a methyl group. R ₈ represents an alkyl group having 1 to 10 carbon atoms. D represents an ethylenically unsaturated monomer. x ', y', z 'represent the weight fraction of each component, x' is 20 to 80, y 'is 80
-20 and z 'represent 0-30. Here, x '+ y' +
z ′ = 100. M represents a hydrogen atom or a cation atom.

In the general formula [P], R ₈ is preferably an unsubstituted alkyl group having 1 to 7 carbon atoms, more preferably 2 to 6 carbon atoms, a halogen or phenyl substituted alkyl group,
Represents an unsubstituted cycloalkyl group or a halogen-substituted cycloalkyl group. Accordingly, preferred examples of R ₈ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.
-Butyl, t-butyl, isobutyl, n-amyl, n-
Hexyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 3-chloropropyl, 3-bromopropyl and the like can be mentioned, among which unsubstituted linear or branched alkyl and cycloalkyl are particularly preferred. D represents a repeating unit composed of another ethylenically unsaturated monomer.

X ', y', z 'represent preferred weight percentage ratios of each component, and x' = 25-60, y '= 75-4
0, z '= 0 to 30. Where x '+ y' + z '=
100 is represented. In the polymer latex used in the present invention, the -COOH group may be neutralized as long as the latex does not dissolve in water, but from the viewpoint of the ability to prevent Brix discoloration, a lower neutralization rate is preferred. Therefore, the degree of neutralization of -COOH groups is preferably 0 to 20%, particularly preferably 0 to 10%. Here, the neutralization ratio of the carboxylic acid group is defined as the polymer latex (specifically, the general formula
It is defined as COOM (where M represents a cation) / [COOH + COOM (where M represents a cation)] in -CH ₂ -C (CH ₃ ) COOM- component of [P]. In addition, the above "does not dissolve in water"
Means the solubility of 1 g or less of polymer latex in 100 ml of water (25 ° C.).

Hereinafter, specific examples of the compound represented by the general formula [P] of the present invention will be described with respect to the copolymerization ratio (weight ratio), -COO
Examples will be given in the order of the proportion of the -COOH component in M, but the present invention is not limited to these.

P-101) Methacrylic acid / n-butyl acrylate copolymer (30/70), M = H / Na (90/10) P-102) Methacrylic acid / n-butyl acrylate copolymer (40/70) 60), M = H / Na (90/10) P-103) Methacrylic acid / n-butyl acrylate copolymer (50/50), M = H / Na (90/10) P-104) Methacrylic acid / n-butyl acrylate copolymer (55/45), M = H (100) P-105) methacrylic acid / methyl acrylate copolymer (25/75), M = H / K (90/10) P-106 Methacrylic acid / ethyl acrylate copolymer (30/70), M = H (100) P-107) Methacrylic acid / ethyl acrylate copolymer (35/65), M = H (100) P-108) Methacryl Acid / n-hexyl acrylate copolymer (45/55), M = H (100) P-109) Methacrylic acid / cyclohexyl acrylate copolymer (40/60) M = H (100) P-110) methacrylate / cyclohexyl methacrylate copolymer (40/60), M = H (100)

P-111) Methacrylic acid / methyl methacrylate copolymer (30/70), M = H / Na (80/20) P-112) Methacrylic acid / ethyl methacrylate copolymer (40/60), M = H (100) P-113) Methacrylic acid / n-propyl methacrylate copolymer (40/60), M = H (100) P-114) Methacrylic acid / sec-butyl methacrylate copolymer (40/60) M = H (100) P-115) Methacrylic acid / t-butyl methacrylate copolymer (50/50), M = H / K (90/10) P-116) Acrylic acid / ethyl acrylate copolymer ( 25/75), M = H / Na (90/10) P-117) Acrylic acid / n-butyl acrylate copolymer (35/65), M = H (100)

P-118) Acrylic acid / methyl methacrylate copolymer (30/70), M = H / Na (80/20) P-119) Acrylic acid / ethyl methacrylate copolymer (30/70), M = H / Na (95/5) P-120) Methacrylic acid / n-butyl acrylate / methyl acrylate copolymer (40/40/20), M = H (100) P-121) Acrylic acid / cyclohexyl methacrylate / 2-hydroxyethyl methacrylate copolymer (40/50/10), M = H (100) P-122) methacrylic acid / methyl methacrylate / styrene copolymer (40/30/30), M = H (100) P-123) Methacrylic acid / acrylic acid / benzyl methacrylate copolymer (20/20/60), M = H (100) P-124) Methacrylic acid / n-butyl acrylate / vinyl acetate copolymer (40/40) / 20), M = H (100) P-125) Methacrylic acid / 2-acrylic acid Do-2-methylpropane sodium sulfonic acid / ethyl methacrylate copolymer (30/5/65), M = H / Na (90/10) P-126) methacrylic acid / itaconic acid / n-butyl acrylate copolymer (30/10/60), M = H / K (95/5)

P-127) A-1 / ethyl acrylate copolymer (60/40), M = H / Na (90/10) P-128) A-3 / methyl acrylate copolymer (60/40) , M = H / Na (80/20) P-129) A-3 / acrylamide / t-butyl acrylate copolymer (40/10/50), M = H (100) P-130) A-8 / Styrene / methyl methacrylate copolymer (60/15/25), M = H (100) P-131) A-10 / 2-hydroxyethyl acrylate / n-butyl acrylate copolymer (60/10/30), M = H (100) P-132) A-17 / n-butyl methacrylate copolymer (80/20), M = H (100) P-133) A-17 / 2-acrylamide-2-methylpropanesulfone Acid soda / n-butyl methacrylate copolymer (65/5/30), M = H / Na (90/10) P-134) A-1 / methacrylic acid / n-butyl acrylate copolymer (20/25 / 55), M = H (100) P-135) A-3 / methacrylic acid / ethyl acrylate copolymer (30/20/50), M = H (100) P-136) A-5 / acrylic acid / methyl methacrylate copolymer (50/20 / 30), M = H / Na (90/10)

The particle diameter of the polymer latex is not particularly limited, but is preferably 1.0 μm or less, preferably 0.7 μm or less, particularly preferably 0.5 μm or less from the viewpoint of stability and the like. And the lower limit is preferably 0.00001 μm or more. Although excellent effects are exhibited irrespective of the molecular weight of the polymer latex, the preferred molecular weight is 5 × 1 in consideration of the diffusion to other layers during coating or treatment and the viscosity of the coating solution.
0 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 1
0 ⁶ , particularly preferably 2 × 10 ^{4 to} 3 × 10 ⁶ (in each case, weight average molecular weight). Since the obtained polymer itself is a fine particle dispersion, the polymer latex may be directly mixed with a hydrophilic colloid and applied in the form of an aqueous medium dispersion.

As the hydrophilic colloid mixed with the polymer latex, gelatin is preferably used. As the gelatin, lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used. Products and enzymatic degradation products can also be used. Also, hydrophilic colloids other than gelatin, for example, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate, dextran and starch derivatives; polyvinyl alcohol and polyvinyl alcohol Partial acetal, poly-N-
A synthetic hydrophilic polymer such as a homopolymer or a copolymer such as vinylpyrrolidone, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. The pH of the coating liquid prepared by mixing the polymer latex and the hydrophilic colloid is preferably 4.5 to 8.0.
More preferably, 5.0 to 7.0, still more preferably,
5.2 to 6.0.

The ratio between the polymer latex and the hydrophilic colloid (polymer content ratio) is not particularly limited, but the value of the polymer ratio of the following formula is preferably 0.01 to 0.30. More preferably, it is 0.02 to 0.20, and still more preferably 0.02 to 0.15. Polymer ratio = (Coating amount used for the present invention) /
(Amount of gelatin applied)

As the cyan coupler used in the present invention, in addition to the cyan coupler represented by the above general formula [C-I],
A coupler represented by the following general formula [C-II] can also be preferably used. The cyan coupler represented by the general formula [C-II] may be used in combination with the coupler represented by the general formula [C-I] in the same layer or another layer, or may be used alone.
In particular, couplers represented by the general formula [C-II] are preferably used from the viewpoints of excellent hue, and excellent brix fading even when subjected to rapid desilvering treatment by ultra-rapid processing.

[0089]

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In the general formula [C-II], R¹¹, R¹²Haso
Each independently represents an alkyl group or an aryl group,
R¹³, R¹⁴, R¹⁵Are each independently a hydrogen atom, an alkyl
Group or an aryl group, and Z 'forms a saturated ring.
Represents a group of non-metallic atoms required for ¹⁶Represents a substituent,
X 'represents a heterocyclic group, a substituted amino group or an aryl group.
And Y 'is a hydrogen atom or a group which leaves during the color development process.
Represent. In the general formula [C-II], R¹¹~ R¹⁵Represented by
The alkyl group is a linear, branched, or cyclic alkyl group having 1 to 36 carbon atoms.
Alkyl group, preferably a straight-chain having 1 to 22 carbon atoms,
A branched or cyclic alkyl group, particularly preferably having 1 carbon atom
To 8 linear or branched alkyl groups.
Chill, ethyl, n-propyl, isopropyl, t-butyl
, T-amyl, t-octyl, decyl, dodecyl,
Chill, stearyl, cyclohexyl, 2-ethylhexyl
Le. In the general formula [C-II], R¹¹~ R¹⁵
Is an aryl group having 6 to 20 carbon atoms
And preferably an aryl group having 6 to 14 carbon atoms.
And particularly preferably an aryl group having 6 to 10 carbon atoms.
For example, phenyl, 1-naphthyl, 2-naphthyl, 2
-Phenanthryl.

The group of nonmetallic atoms necessary for forming a saturated ring represented by Z ′ in the general formula [C-II] is a group of nonmetallic atoms required for forming a 5- to 8-membered ring. This ring may be substituted, may be a saturated ring or may be an unsaturated ring, non-metal atoms forming the ring include carbon atom, oxygen atom, nitrogen atom, sulfur atom, It is preferably a 6-membered saturated carbocyclic ring, and particularly preferably a cyclohexane ring substituted at the 4-position with an alkyl group having 1 to 24 carbon atoms. Examples of the substituent represented by R ¹⁶ in the general formula [C-II] include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an aliphatic group (for example, a straight or branched chain having 1 to 36 carbon atoms). Chain alkyl group, aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl,
Isopropyl, t-butyl, tridecyl, t-amyl,
t-octyl, 2-methanesulfonylethyl, 3- (3
-Pentadecylphenoxy) propyl, 3- {4-} 2
-[4- (4-hydroxyphenylsulfonyl) phenoxy] dodecanamide {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxypropyl),

Aryl groups (aryl groups having 6 to 36 carbon atoms such as phenyl, 4-t-butylphenyl,
2,4-di-t-amylphenyl, 4-tetradecanamidophenyl, 2-methoxyphenyl), a heterocyclic group (a heterocyclic group having 1 to 36 carbon atoms, for example, 2-furyl, 2-thienyl, Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkoxy group (linear, branched or cyclic alkoxy group having 1 to 36 carbon atoms, for example,
Methoxy, ethoxy, butoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-methanesulfonylethoxy), aryloxy group (aryloxy group having 6 to 36 carbon atoms, such as phenoxy, 2-methylphenoxy, 4- t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), an acylamino group (an acylamino group having 2 to 36 carbon atoms, for example, acetamido, benzamide, tetradecaneamide, 2- ( 2,
4-di-t-amylphenoxy) butanamide, 4-
(3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decaneamide), an alkylamino group (an alkylamino group having 1 to 36 carbon atoms, for example, methylamino Butylamino, dodecylamino, diethylamino, methylbutylamino), anilino group (carbon number 6)
~ 36 anilino groups such as phenylamino, 2
-Chloroanilino,

2-chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2-
(3-t-butyl-4-hydroxyphenoxy) dodecaneamide @ anilino), a ureido group (a ureido group having 2 to 36 carbon atoms, for example, phenylureide, methylureide, N, N-dibutylureide), and sulfamoyl An amino group (a sulfamoylamino group having 1 to 36 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino),
Alkylthio groups (C1-C36 alkylthio groups such as methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), and arylthio groups (An arylthio group having 6 to 36 carbon atoms such as phenylthio, 2-butoxy-5-t
-Octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), an alkoxycarbonylamino group (an alkoxycarbonylamino group having 2 to 36 carbon atoms, such as methoxycarbonylamino, Decyloxycarbonylamino), sulfonamide group (1 carbon atom)
~ 36 alkyl and aryl sulfonamide groups such as methanesulfonamide, butanesulfonamide, octanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-
5-t-butylbenzenesulfonamide), carbamoyl group (carbamoyl group having 1 to 36 carbon atoms, for example,
N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl,
N-methyl-N-dodecylcarbamoyl, N- {3-
(2,4-di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (sulfamoyl group having 1 to 36 carbon atoms, for example, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N
-Dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (alkyl and arylsulfonyl groups having 1 to 36 carbon atoms, for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (C2-C2
36 alkoxycarbonyl groups, for example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), and a heterocyclic oxy group (a heterocyclic oxy group having 1 to 36 carbon atoms, for example, 1-phenyltetrazole-5) -Oxy, 2-
Tetrahydropyranyloxy), an azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo,

2-hydroxy-4-propanoylphenylazo), an acyloxy group (an acyloxy group having 2 to 36 carbon atoms, for example, acetoxy), a carbamoyloxy group (a carbamoyloxy group having 1 to 36 carbon atoms, for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (3-36 carbon atoms)
For example, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (an aryloxycarbonylamino group having 7 to 36 carbon atoms, for example, phenoxycarbonylamino), and an imide group (4 to 36 carbon atoms) For example, N-succinimide, N-phthalimide, 3-
Octadecenylsuccinimide), a heterocyclic thio group (a heterocyclic thio group having 1 to 36 carbon atoms, for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,3)
5-triazole-6-thio, 2-pyridylthio), sulfinyl group (sulfinyl group having 1 to 36 carbon atoms, for example, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), alkyl / aryl or hetero A ring oxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenyloxycarbonyl, 2-pentadecyloxycarbonyl), an alkylaryl or heterocyclic oxycarbonylamino group (for example, methoxycarbonylamino, Decyloxycarbonylamino,
Phenoxycarbonylamino, 2,4-di-tert-butylphenoxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5) -Tert-butylbenzenesulfonamide), a carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- [3- (2,4-di-tert-amylphenoxy) propyl] carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N- Ethyl- -Dodecylsulfamoyl, N, N-diethylsulfamoyl), a phosphonyl group (eg, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), a sulfamide group (eg, dipropylsulfamoylamino), an imide group (eg, N -Succinimide, hydantoinyl, N-phthalimide, 3-octadecenylsuccinimide), azolyl group (for example, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazolyl), hydroxy group, cyano group, carboxy group, nitro group , A sulfo group, an unsubstituted amino group, and the like.

R ¹⁶ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an arylamino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. Group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, Examples include a sulfinyl group, a phosphonyl group, an acyl group, and an azolyl group. More preferred are an alkyl group and an aryl group, and more preferred is an aryl group in which at least the p-position is substituted with an alkyl group.

X 'represents a heterocyclic ring, a substituted amino group or an aryl group. The heterocyclic ring is a 5- to 8-membered ring having a nitrogen, oxygen or sulfur atom and having 1 to 36 carbon atoms. preferable. More preferably, it is a 5- or 6-membered ring linked by a nitrogen atom, of which a 6-membered ring is particularly preferred. Specific examples include imidazole, pyrazole,
Examples include triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine, pyrazolidine, thiazolidine, pyrazoline and the like, preferably morpholine and piperidine, and particularly preferably morpholine. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents represented by R ¹⁶ described above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), chloro, a hydroxyl group, a carboxyl group, May be substituted with a group. As the substituted amino group, disubstitution is preferable to monosubstitution. The aryl group has 6 to 3 carbon atoms.
6 are preferred, and a single ring is more preferred. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl,
Methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 2,4-dichlorophenyl and the like can be mentioned.

Y 'is a hydrogen atom or a compound which is eliminated in the process of color development. For example, the substituent represented by Y' is a compound which is obtained under alkaline conditions as described in JP-A-61-222844. , A group which can be separated and JP-A-56-133.
Substituents that couple off by reaction with a developing agent as described in JP-A-734 are mentioned, but Y 'is preferably a hydrogen atom. The general formula [C-
In the coupler represented by the formula [II], R ¹⁶ contains a coupler residue represented by the general formula [C-II] to form a dimer or higher multimer, or R ¹⁶ is a polymer chain. And may form a homopolymer or a copolymer. The homopolymer or copolymer having a high molecular chain is typically an addition polymer having a coupler residue represented by the general formula [C-II], a homopolymer or a copolymer of an ethylenically unsaturated compound. It is. In this case, one or more cyan coloring repeating units having a coupler residue represented by the general formula [C-II] may be contained in the polymer, and an acrylate, a methacrylate, It may be a copolymer containing one or more non-color-forming ethylene-type monomers that do not couple with the oxidation product of an aromatic primary amine developer such as maleic esters. Specific examples of the coupler used in the present invention are shown below, but the present invention is not limited thereto.

[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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The cyan coupler represented by the general formula [C-II] of the present invention can be prepared by a known method, for example, as described in JP-A-5-2553.
No. 33, No. 5-202004, No. 7-48376,
It can be synthesized by the method described in JP-A-8-110623. For the cyan coupler used in the present invention,
Conventionally used 2-acylamino-5-alkylphenol-type cyan couplers, 2,5-diacylaminophenol-type cyan couplers and 2-carbamoyl-
A 1-naphthol type cyan coupler can be used in combination. Among them, a combination with a 2-acylamino-5-alkylphenol-type cyan coupler is particularly preferable. In this case, the cyan coupler used in combination is in the range of 1 to 50 mol%, preferably 5 to 50 mol% based on the coupler used in the present invention.
It is in the range of 40 mol%, more preferably 10 to 30 mol%.

In order to improve the image fastness of the cyan coupler used in the present invention, a method of co-dispersing an organic solvent-soluble water-insoluble polymer in oil droplets is also preferably used. In this case, the polymer is preferably a styrene, acrylamide, methacrylamide, acrylate, methacrylate-based polymer or a copolymer thereof, and the number average molecular weight is preferably in the range of 20,000 to 200,000. Further, in order to improve the stability of the emulsion, an oligomer molecule having a molecular weight of about 500 to 5,000 is also preferably used.
-Methylstyrene oligomers and the like are preferred. In particular, an oligomer of styrene and α-methylstyrene is particularly preferred in terms of solubility. It is also preferable to add an amphiphilic polymer to the coating solution to promote color formation. In this case, a copolymer of acrylic acid or methacrylic acid and these esters is more preferred. Particularly, a copolymer of methacrylic acid and butyl acrylate is a particularly preferable compound having a large effect.

In the present invention, to speed up the process means to shorten the time required for developing an exposed photosensitive material and obtaining an image through a drying step. Specifically, by shortening one or more of the color developing step, desilvering step, washing and / or stabilizing step, and drying step, all the processing steps are performed for 30 to 90 seconds, preferably 50 to 90 seconds. It is a preferred embodiment of the present invention to set the time to seconds, more preferably 50 to 75 seconds. The processing time of the developing step and the processing time of the desilvering step are each 3 seconds.
It is preferably within 0 seconds, more preferably 5 to 25 seconds. At this time, the processing time (Tw) of the washing and / or stabilizing step and the processing time of the bleach-fixing step (Tb)
The ratio (Tw / Tbf) of f) is preferably 1.3 or less. In the present specification, the ultra-rapid processing refers to processing a photosensitive material containing a silver halide emulsion having a silver chloride content of 95 mol% or more in all processing steps in the above-mentioned time.

In the present invention, the term "color developing time" refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called in-solution time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (the so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time).
Say. In the ultra-rapid processing aimed at by the present invention, the color development time is preferably 30 seconds or less, more preferably 2 seconds or less.
5 seconds or less and 5 seconds or more, most preferably 15 seconds or less and 5 seconds or more. Similarly, the bleach-fixing time is preferably 30 seconds or less,
More preferably 25 seconds or less and 5 seconds or more, and most preferably 1 second or less.
5 seconds or less and 5 seconds or more. The washing and / or stabilizing time is preferably 45 seconds or less and 5 seconds or more, more preferably 30 seconds or less and 5 seconds or more, and most preferably 20 seconds or less and 10 seconds or more. The drying time is preferably 20 seconds or less,
More preferably, it is 15 seconds or less and 5 seconds or more, and most preferably 1 second or less.
0 seconds or less and 5 seconds or more.

In the silver halide photographic light-sensitive material of the present invention,
In addition, conventionally known photographic materials and additives can be used. For example, a reflective support can be used as the photographic support. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio in the case of mixing with the water-resistant resin is preferably 0.0005 to 3% by weight with respect to the resin, and more preferably 0.1 to 3% by weight.
001 to 0.5% by weight.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta or yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (stain inhibitors and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0113]

[Table 1]

[0114]

[Table 2]

The cyan, magenta and yellow couplers used in combination in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355, 660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. . Also,
The amount of calcium contained in the light-sensitive material is preferably 20
mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

In the case where the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As the method of developing the light-sensitive material of the present invention after exposure, a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkali solution containing a developing agent in the light-sensitive material and containing no developing agent, etc. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, No. 9-152686, No. 9-152693
, Japanese Patent Application No. 7-334197, Japanese Patent Application Laid-Open No. 9-16019.
The hydrazine-type compound described in No. 3 is preferred.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Hei 7
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-63587 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
-234388 can be used.

[0125]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 (Preparation of support) A support having the thickness and rigidity as shown in Table 3 was prepared by containing titanium oxide as a white pigment and laminating polyethylene on both sides.

[0126]

[Table 3]

Amount of hydrophilic binder a. 7.38 g / m ² samples (101) to (104) b. 6.41 g / m ² samples (105) to (109) c. 5.78 g / m ² sample (110) ) To (115), (121), (123) d. 4.67 g / m ² Samples (116) to (120), (122), (124)

Samples (101) to (115), (12)
1) and (123) were produced as follows. Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (ExC-1), 250 g of color image stabilizer (Cpd-1), color image stabilizer (Cpd-9) 1
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate.
6-20% aqueous solution of gelatin containing 25 g of d-20)
The resulting mixture was emulsified and dispersed in the resulting mixture to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, a 5: 5 mixture (silver molar ratio) of large-size emulsion C having an average grain size of 0.40 μm and small-size emulsion C having an average grain size of 0.40 μm. The variation coefficient of the grain size distribution is 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the grain having silver chloride as a base material). This emulsion contains the following red-sensitive sensitizing dyes G and H in an amount of 9.0 × 10 ⁻⁵ mol per mol of silver for the large-sized emulsion C and 9.0 × 10 ⁻⁵ mol for the small-sized emulsion C per mol of silver, respectively. 12.0 × 10 ^-5 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. Examples of gelatin hardeners for each layer include H-1, H-2 and H-3.
Was used. Ab-1, Ab-2, Ab-3 are formed on each layer.
And Ab-4 in a total amount of 15.0 mg / m ² and 6 respectively.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 m
g / m ² .

[0130]

Embedded image

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0132]

Embedded image

(The sensitizing dyes A and C were used in an amount of 0.42 × 1
^0-4 mol, 0.50 × each for small size emulsions
10 ^-4 mol, and sensitizing dye B per mol of silver halide is 3.4 × 10 ^-4 mol for large-size emulsion and 4.1 × 10 ^-4 mol for small-size emulsion. Was added. Green sensitive emulsion layer

[0134]

Embedded image

(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. ) Red-sensitive emulsion layer

[0136]

Embedded image

(Sensitizing dyes G and H were converted to silver halide 1
8.0 × 1 for large emulsions per mole
0 ^-5 mol, respectively 10.7 × to the small size emulsion
10 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

[0138]

Embedded image

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole,
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mole, 9 × 10^-FourMole was added. In addition, the second layer, the fourth
0.2 mg / m2 for the layer, the sixth layer and the seventh layer, respectively.
^Two 0.2 mg / m^Two, 0.6 mg / m^Two0.1 mg /
m^TwoWas added so that In addition, a blue-sensitive emulsion layer and
With respect to the green-sensitive emulsion layer, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene is converted to halo
1 × 10^-FourMole, 2 × 10^-FourMo
Was added. In addition, methacrylic acid and
Butyl acrylate copolymer latex (weight ratio 1: 1, flat
0.05 g /
m^TwoWas added. In addition, the second, fourth and sixth layers
Tecole-3,5-disulfonate disodium
6mg / m^Two, 6mg / m^Two, 18mg / m^TwoWill be
Was added. Also, to prevent irradiation,
The following dyes (in parentheses indicate the coating amount) were added.

[0140]

Embedded image

The layer structure of Samples (101) to (104) is shown below. The configuration of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content: 0.03% by weight), bluish dye ( First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, 5: 5 mixture of large-sized emulsion A having an average grain size of 0.75 μm and large-sized emulsion A of 0.55 μm ( The variation coefficients of the grain size distributions are 0.08 and 0.10, respectively. Each emulsion contains 0.3 mol% of silver bromide localized on a part of the grain surface based on silver chloride. 0.24 gelatin 1.34 yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 0.07 color image stabilizer (Cpd-2) 0.04 color image stabilizer (Cpd-3) ) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv- ) 0.21

Second layer (color mixture prevention layer) Gelatin 1.06 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and large-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively.Each size emulsion contained 0.4 mol% of silver bromide in a part of the grain surface based on silver chloride. 0.14 Gelatin 1.46 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0 11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture preventing layer) Gelatin 0.76 Color mixture inhibitor (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large emulsion C having an average grain size of 0.40 μm and large emulsion E of 0.30 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride. 0.20 gelatin 1.19 cyan coupler (ExC-1) 0.30 ultraviolet absorber (UV-A) 0.29 color image stabilizer (Cpd-1) 0.25 color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet ray absorbing layer) Gelatin 0.49 Ultraviolet ray absorbent (UV-B) 0.45 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1.08 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

The layer structure of Samples (105) to (109) is shown below. The configuration of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content: 0.03% by weight), bluish dye ( First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, 5: 5 mixture of large-sized emulsion A having an average grain size of 0.75 μm and large-sized emulsion A having a size of 0.55 μm ( The variation coefficients of the grain size distributions are 0.08 and 0.10, respectively. Each emulsion contains 0.3 mol% of silver bromide localized on a part of the grain surface based on silver chloride. 0.24 Gelatin 1.17 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) ) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv- ) 0.21

Second layer (color mixture prevention layer) Gelatin 0.92 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large emulsion B having an average grain size of 0.45 μm and large emulsion B having a diameter of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively.Each size emulsion contained 0.4 mol% of silver bromide in a part of the grain surface based on silver chloride. 0.14 Gelatin 1.26 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0 11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.66 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large-sized emulsion C having an average grain size of 0.40 μm and large-sized emulsion C of 0.30 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride. 0.20 gelatin 1.04 cyan coupler (ExC-1) 0.30 ultraviolet absorber (UV-A) 0.29 color image stabilizer (Cpd-1) 0.25 color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.43 Ultraviolet absorbing agent (UV-B) 0.45 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 0.93 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

Samples (110) to (115), (12)
The layer constitutions of 1) and (123) are shown below. The configuration of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content: 0.03% by weight), bluish dye ( First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, 5: 5 mixture of large-sized emulsion A having an average grain size of 0.75 μm and large-sized emulsion A of 0.55 μm ( The variation coefficients of the grain size distributions are 0.08 and 0.10, respectively. Each emulsion contains 0.3 mol% of silver bromide localized on a part of the grain surface based on silver chloride. 0.24 Gelatin 1.05 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) ) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv- ) 0.21

Second layer (color mixture prevention layer) Gelatin 0.83 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large emulsion B having an average grain size of 0.45 μm and large emulsion E of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively.Each size emulsion contained 0.4 mol% of silver bromide in a part of the grain surface based on silver chloride. 0.1) Gelatin 1.15 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0 11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.59 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large emulsion C having an average grain size of 0.40 μm and large emulsion C of 0.30 μm (silver mole) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride. 0.20 gelatin 0.94 cyan coupler (ExC-1) 0.30 ultraviolet absorber (UV-A) 0.29 color image stabilizer (Cpd-1) 0.25 color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.38 Ultraviolet absorbing agent (UV-B) 0.45 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 0.84 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

Samples (116) to (120), (12)
The layer configurations of 2) and (124) are shown below. First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (the same emulsion as in sample (101)) 0.24 gelatin 1.25 yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.60 Color mixture inhibitor (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (same emulsion as in sample (101)) 0.14 gelatin 0.73 magenta coupler (ExM) 0.15 ultraviolet absorber (UV-A) 0.05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.0. 03 Color image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0 .06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention agent (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (the same emulsion as sample (101)) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) ) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0 .04 UV absorber (UV-7) 0.02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protective layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

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Using the supports shown in Table 3, samples (101) to (124) shown in Table 4 were prepared, and the following evaluation tests were performed. (Evaluation Test) 1. Degree of residual color at the time of rapid processing The yellow stain of the sample treated in the process B, which will be described later, was evaluated according to the difference in density between the presence and absence of washing at 45 ° C. for 5 minutes as follows. ◎: Difference in yellow density 0.003 or less: を More than 0.003 and less than 0.005 ×: を More than 0.005 and less than 0.008 XX: 大 Greater than 0.008 (× less than a practical problem 2. Magenta sensitized muscle The sample was subjected to half-gray exposure, and the generation of magenta sensitized muscle was evaluated according to the following criteria when the sample was processed in a minilab in the step of process A described below. ◎: less than one streak generated per 10 m ○: １ one or more and less than three ×: 〃 three or more and less than ten XX: 〃 ten or more (x or less has a practical problem) 3. Curling The curling of the sample treated in the process A and dried was evaluated according to the following criteria. ◎: The plane state is maintained. ：: Curling is slightly generated, but there is no problem in practical use. ×: Curling which is a problem in practical use is observed.

[0175]

[Table 4]

As shown in Table 4, the samples having a hydrophilic binder content exceeding 6.5 g / m ² ((101) to (104))
Has a large residual color during rapid processing and is not suitable for rapid processing.
On the other hand, the samples ((105) to (124)) in which the amount of the hydrophilic binder was 6.5 g / m ² or less had a small residual color during rapid processing. Among them, the rigidity in the width direction of the support is 13 g · cm.
Samples ((105), (106), (110),
(111) and (116)) have magenta sensitized muscles. For samples having a stiffness in the width direction exceeding 13 g · cm, the occurrence of magenta sensitized muscle was not prevented even if the stiffness in the length direction was reduced ((106), (111)). On the other hand, in the sample of the present invention in which the stiffness in the width direction is more than 8 g · cm and not more than 13 g · cm, it is found that the generation of the magenta sensitizing muscle is prevented ((107) to (10).
8), (112) to (114), (117) to (11)
9)). Further, when the amount of the hydrophilic binder is 7.38 g / m ² , curling which becomes a practical problem occurs even with a stiffness of 10.3 g · cm in the width direction (sample (104)).
In the case of the sample having a hydrophilic binder amount of 5.78 g / m ² , curling characteristics having no practical problem were obtained even when the rigidity in the width direction was 8.2 g · cm (sample (114)). Also,
Samples ((117) to (119), (122), and (12)) of the present invention examples having a hydrophilic binder amount of 5.5 g / m ² or less.
In the case of 4)), the residual color is particularly small, and the effect of the present invention is remarkably exhibited also in curling and pressure compatibility.
Furthermore, from the results in Table 4, the photosensitive material of the present invention is
Although it is preferable from the viewpoint of texture and the like, even in a support having a thickness in which magenta sensitized muscle is easily generated by reducing the amount of the hydrophilic binder, generation of magenta sensitized muscle is prevented, and excellent characteristics can be obtained. I understand.

The processing method used in this embodiment will be described below. [Processing A] The above sample was processed into a roll having a width of 127 mm, and was imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. , Continuous processing (running test). This treatment using the running liquid was designated as treatment A. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml dry 70 ° C. 38 seconds * replenishment rate per photosensitive material 1 m ² ** Fuji Photo Film Co., Ltd. rinse The cleaning system RC50D is installed in the rinse (3), and the rinse liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescent brightener (Hakkol FWA-SF / Showa Kagaku) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 0.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 26 Add water 2.3ml 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml ammonium ethylenediaminetetraacetate (III) ammonium 47.0 g 94.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Refill solution] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5

[Processing B] The above sample was processed into a roll having a width of 127 mm, and after imagewise exposure, continuous processing (running test) was performed until replenishment of twice the capacity of the color developing tank in the following processing step. The processing using the running liquid was referred to as processing B. For processing, a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., which was modified so as to increase the transport speed to shorten the processing time, was used.

Processing Step Temperature Time Replenishment amount ^* Color development 45.0 ° C. 12 seconds 45 ml Bleaching and fixing 40.0 ° C. 12 seconds 35 ml Rinse (1) 40.0 ° C. 4 seconds Rinse (2) 40.0 ° C. 4 seconds − rinse (3) ** 40.0 ℃ 4 seconds - rinse (4) ** 40.0 ℃ 4 seconds 121ml drying 80 ° C. 10 seconds * photosensitive material 1 m ² per replenishment amount ** Fuji Photo Film Co., Ltd. rinse cleaning system Install RC50D in rinse (3), take out the rinse liquid from rinse (3), and send it to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescent brightener (Hakkol FWA-SF / Showa Kagaku) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 0.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 10.0 g 22.0 g Potassium carbonate 26 Add water 2.3ml 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml ammonium ethylenediaminetetraacetate (III) ammonium 75.0 g 150.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzenesulfinic acid 8.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g metabisulfite Potassium 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 5.5 5.5

[Rinse liquid] [Tank liquid] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Example 2 An evaluation test similar to that of Example 1 was performed on each of the samples (101) to (120) prepared in exactly the same manner except that the first layer and the fifth layer were replaced. As a result, as in Example 1, the sample of the present invention obtained a result in which the residual color at the time of rapid processing was small, the occurrence of magenta sensitized streaks was prevented, and the occurrence of curling which was a practical problem was not caused. .
In particular, each of the samples of this example was superior in terms of residual color during rapid processing.

Example 3 Scanning exposure (average exposure per pixel) of each sample of Examples 1 and 2 was carried out by a polygon mirror using a three-color laser light source according to the method described in JP-A-10-232476. The processing was performed at a time of 1.7 × 10 ⁻⁷ seconds. As a result, it was confirmed that each of the samples of the present invention was a silver halide color photographic light-sensitive material having ultra-rapid processing suitability. Each sample of the present invention was particularly suitable for speeding up color development.

Example 4 A sample was prepared in the same manner as in Examples 1 and 2, except that the emulsion a and the emulsion b shown below were used in place of the blue-sensitive silver halide emulsion of the sample. As a result of the evaluation test, each of the samples of the present invention, as in the case of the sample of the present invention obtained in Example 1, prevented the occurrence of residual color and magenta sensitized muscle in rapid processing and suppressed the occurrence of curling. It was confirmed that it was.

(Emulsion a. Preparation of {111} high silver chloride tabular grains) In 1.2 liters of water, 2.0 g of sodium chloride and 2.8 g of inert gelatin were added, and the mixture was stirred in a vessel kept at 33 ° C. 45 ml of silver nitrate aqueous solution (silver nitrate 18
g) and 45 ml of an aqueous sodium chloride solution (6.4 g of sodium chloride) were added in one minute by the double jet method. One minute after the completion of the addition, 0.8 mmol of the crystal habit controlling agent 1 and 560 g of a 10% aqueous solution of phthalated gelatin were added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. 60 ° C
After aging for 16 minutes, 3 g of sodium chloride and 1 × 10 ⁻⁵ mol of sodium thiosulfonate were added. After this,
295 ml of an aqueous silver nitrate solution (118 g of silver nitrate), 295 ml of an aqueous sodium chloride solution (containing 50.3 g of sodium chloride and 2 × 10 ⁻⁸ mol of iridium hexachloride) and 160 ml of an aqueous solution of a crystal phase controlling agent 1 (M / 50) were taken over 13 minutes. Added at an accelerated flow rate. Further, after 2 minutes, an aqueous silver nitrate solution (34 g of silver nitrate) and an aqueous sodium chloride solution (11.6 g of sodium chloride and 1.2 g of yellow blood salt) were added for 5 minutes.
7 mg and 0.66 g of potassium iodide). Next, 33.5 ml of a 0.1 N thiocyanic acid solution, 0.32 mmol of sensitizing dye A, and 0.48 mmol of sensitizing dye B 0.48
Mmol and 0.05 mmol of sensitizing dye C were added.
The temperature was lowered to 40 ° C., and desalting was performed by a usual flocculation method. After washing with water, 67 g of gelatin, 80 ml of phenol (5%) and 150 ml of distilled water were added. PH 6.2 with caustic soda and silver nitrate solution, pAg7.
Adjusted to 5. In the obtained particles, 90% or more of the total projected area has an average equivalent circle diameter of 0.71 μm and an average thickness of 0.13 μm.
m and tabular grains having an average equivalent sphere diameter of 0.46 μm.

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(Emulsion b; preparation of {100} silver chloroiodide grains containing 0.4 mol% of iodine based on the total silver after formation of 95% grains) 1200 ml of H ₂ O and gelatin ( 25 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g), 0.4 g of sodium chloride, and 4.5 ml of a 1N nitric acid solution (pH: 4.
5) The temperature was kept at 40 ° C. Next, an Ag-1 solution (silver nitrate 0.1.
2g / ml) and X-1 solution (0.069g of sodium chloride)
/ Ml) with vigorous stirring at 48 ml / min for 4 minutes. 15 seconds after that, an aqueous polyvinyl alcohol solution [containing 6.7 g of polyvinyl alcohol (hereinafter referred to as PVA-1) having an average degree of polymerization of vinyl acetate of 1700 and an average saponification rate of 98% or more to alcohol, and containing 1 liter of H ₂ O] Was added in an amount of 150 ml. Further, 1N nitric acid solution 12.3
ml was added to adjust the pH to 3.5. 75 ° C for 15 minutes
Temperature, add 23 ml of 1N sodium hydroxide solution and add pH
To 6.5, and 1- (5-methylureidophenyl)-
4.0 m of 5-mercaptotetrazole (0.05%)
4.0 ml of 1, N, N'-dimethylimidazolidin-2-thione (1% aqueous solution) was added. 4 g of sodium chloride was added, and the silver potential [vs.
After adjusting to 0 mV, Ag-1 solution and X-
One solution was added simultaneously for 15 minutes while keeping the silver potential at 100 mV while linearly increasing the flow rate from 40 ml / min to 42 ml / min. Further, add 12.5 ml of 1N nitric acid solution and p
H was set to 4.0. Add 28.8 g of sodium chloride,
After setting the silver potential to 60 mV, sensitizing dye A 0.38 mmol, sensitizing dye B 0.56 mmol, and sensitizing dye C0.0
After adding 6 mmol, the Ag-2 solution (silver nitrate 0.1 g / m
l) and liquid X-2 (sodium chloride 0.0345 g / m2)
l) was added at a flow rate of 40 ml / min for 7 minutes and 30 seconds. Next, 25 ml of an aqueous solution (X-4) containing 31.2 g of potassium iodide in 1 liter was added for 8 seconds. Furthermore, Ag
Solution 2 and Solution X-2 were added at a flow rate of 40 ml / min for 2 minutes and 30 seconds. Then, it was left at 75 ° C. for 10 minutes. Temperature 40
The temperature was lowered to ° C., and sedimentation washes were performed to desalinate. Gelatin 79
g, and the emulsion is redispersed to pH 6.0, pAg 7.
It was set to 3. Then, a part of the emulsion was collected, and an electron micrograph image (TEM image) of the grain replica was observed. According to the results, 90% of the projected area meter of all AgX grains is a tabular grain having a principal plane of {100} plane, the average equivalent sphere diameter is 0.47 μm, the average grain thickness is 0.10 μm, and the average aspect ratio is 7%. 0.9, and the average adjacent side ratio was 1.2.

(Chemical Sensitization) Emulsions a and b were optimally chemically treated at 60 ° C. with sodium thiosulfonate, 1- (5-methylureidophenyl) -5-mercaptotetrazole, sodium thiosulfate and chloroauric acid. I was sensitized.

[0193]

The silver halide color photographic light-sensitive material of the present invention has excellent rapid processing properties, prevents the occurrence of residual color and magenta sensitizing lines in rapid processing, and prevents curling after drying. Is suppressed. After imagewise exposing this silver halide color photographic light-sensitive material, color development is performed within a predetermined time,
According to the color image forming method of the present invention in which bleach-fixing, washing and / or stabilizing treatment and drying are performed, high silver chloride color print materials are rapidly processed to prevent generation of residual color and magenta sensitized lines. Image can be obtained, and it is possible to suitably cope with ultra-rapid processing by scanning exposure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/26 G03C 5/26 7/20 7/20

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different color sensitivity containing silver halide grains having a silver chloride content of 95 mol% or more on a paper support. The total amount of the hydrophilic binder in the photographic constituent layer of the photosensitive material is 6.5 g / m ² or less, and the rigidity of the paper support in the direction perpendicular to the papermaking direction is 8 g · c.
m and 13 g · cm or less. 2. The method according to claim 1, wherein the thickness of the paper support exceeds 180 μm.
2. The silver halide color photographic light-sensitive material according to claim 1, wherein the thickness is 35 [mu] m or less. 3. The silver halide color photographic material according to claim 1, wherein the total amount of the hydrophilic binder in the photographic constituent layer of the photographic material is 5.5 g / m ² or less. 4. A silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion layer farthest from the support contains a yellow coupler. 5. A method for obtaining a color image by subjecting a silver halide color photographic light-sensitive material to imagewise exposure, followed by color development, bleach-fixing, washing and / or stabilization, and drying processing steps. 6. The silver halide color photographic light-sensitive material according to any one of the above, wherein the color developing step is 5 seconds to 25 seconds, the bleach-fixing step is 5 seconds to 25 seconds,
Alternatively, a color image forming method is characterized in that the stabilization treatment is performed within 5 seconds to 45 seconds and the drying step is performed within 5 seconds to 15 seconds. 6. A method for obtaining a color image by subjecting a silver halide color photographic light-sensitive material to imagewise exposure, color development, bleach-fixing, washing and / or stabilization, and drying to obtain a color image. A color image forming method, comprising: subjecting the silver halide color photographic light-sensitive material according to any one of the above to scanning exposure with a light beam modulated based on image information, followed by development processing.