JP2002351023A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material having enhanced color reproducibility on the basis of excellent spectral absorption characteristics of a yellow developing dye and an excellent white background and to further provide a silver halide color photographic sensitive material giving a dye image and a white background having high stability to light and heat. SOLUTION: Each of the silver halide color photographic sensitive materials has at least one yellow developing photosensitive silver halide emulsion layer, at least one magenta developing photosensitive silver halide emulsion layer, at least one cyan developing photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloidal layer developing no color on a reflective substrate, reflection density A (λ) at wavelength λ nm in unexposed regions after color development is <=0.08 at 450 nm, <=0.10 at 550 nm and <=0.08 at 650 nm, and the standardized spectral distribution curve of a yellow developing dye has a density of 0.9-1.0 at 450 nm and a density of 0.1-0.3 at 520 nm.

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 light-sensitive material, and
The present invention relates to a silver halide color photographic material having improved color reproducibility.

[0002]

2. Description of the Related Art Silver halide color photographic light-sensitive materials are widely used as materials for providing inexpensive and high-quality images and because of their stable quality and excellent productivity.
Photosensitive materials for color printing, especially color paper, are currently widely used, but higher quality is required. The quality required for color paper includes production stability, storage stability for unexposed products, and performance stability during development processing, and color reproducibility for color prints completed after development processing. It is required that the whiteness and sharpness be excellent, and that the dye image be robust to light, heat and humidity and not fade. Further, to improve the productivity, the speed of the processing and the quality of the photosensitive material which can be adapted to the rapid processing are required.

In order to obtain a color print having excellent color reproducibility, it is necessary to form a coloring dye having excellent absorption characteristics, that is, yellow, magenta and cyan dyes having no unnecessary absorption components. Dyes are generally prepared by oxidizing aromatic primary
It is obtained by reacting a secondary amine developing agent with a coupler to form a dye such as azomethine.

[0004] Of the couplers, a pivaloyl type yellow coupler has conventionally been used for forming a yellow dye image.
Benzoyl-type yellow couplers have been commonly used. With regard to couplers for color paper, the hue and fastness of the resulting dye are emphasized, and pivaloyl-type yellow couplers are mainly used. In order to improve the color reproducibility of color prints, pivaloylacetoanilide couplers having an alkoxy group at the ortho position of the anilide ring are known. Although this coupler is certainly improved to some extent in terms of color reproducibility, European Patent EP
No. 0,447,969 A1, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure, EP
No. 5,482,552 A1, a malondianilide type yellow coupler having a cyclic structure described in U.S. Pat.
No. 18,599, an acylacetanilide type yellow coupler having a dioxane structure has been proposed. However, the above-mentioned conventional yellow couplers have not been sufficiently improved in color reproducibility, or have poor image fastness even with excellent color reproducibility, and are expensive. It wasn't good.

[0005] On the other hand, since the color reproducibility is affected by the fluorescent whitening of the white background and the spectral absorption characteristics of the support itself, it is also important that the whiteness of the white background is excellent. Causes of fouling the white background include fog, staining by dye and sensitization, and staining during processing by the coloring component of the processing solution. As means for improving these, fog inhibitors, removal that promotes elution of dyes and sensitizing dyes There is known a technique in which an accelerator, a whitening agent, a surfactant and the like are used for a photosensitive material or a processing agent. Further, for the purpose of improving a white background, improvement of a support has been conventionally studied. The method of adding a white pigment such as titanium dioxide to the resin layer, the method of adjusting the tint of a white background by tinting such as ultramarine blue, and the method of adding a fluorescent whitening agent to the resin layer depend on the support. Used as an improvement. However, although the whiteness of a white background has been further improved by the above-mentioned conventional technology in recent years, it is not always sufficient, and there still remains a problem that the color of the white background changes over time.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to solve the above-mentioned conventional problems and achieve the following objects. That is, the present invention provides a silver halide photographic light-sensitive material having excellent color reproduction, and more specifically, a silver halide color photographic material having an excellent spectral absorption characteristic of a yellow coloring dye and an improved color reproduction based on an excellent white background. It is another object of the present invention to provide a light-sensitive material, and further provide a silver halide color photographic light-sensitive material in which the obtained dye image and white background have high stability to light and heat.

[0007]

As a result of intensive studies, the present inventors have found that the object of the present invention can be achieved by the following silver halide photographic material and an image forming method using the same.

<1> On a reflective support, at least one layer each of a yellow color-forming light-sensitive silver halide emulsion layer, a magenta color-forming light-sensitive silver halide emulsion layer, and a cyan color-forming light-sensitive silver halide emulsion layer is provided. In a silver halide color photographic light-sensitive material having at least one non-photosensitive, non-color-forming hydrophilic colloid layer, a reflection density A (λ) at a wavelength of λ nm in an unexposed portion after color development processing
Is 0.08 or less at 450 nm and 0.10 at 550 nm.
Below, and 0.08 or less at 650 nm, and further, the normalized spectral distribution curve of the yellow coloring dye has a density of 0.9 to 1.0 at 450 nm and 0.1 to 0.3 at 520 nm. And a silver halide color photographic light-sensitive material.

<2> The reflection density A (λ) at the wavelength λ nm of the unexposed portion after the color development processing is 450 n
0.07 or less at m, 0.09 or less at 550 nm, and 6
The silver halide color photographic light-sensitive material according to <1>, wherein the light-sensitive material has a value of 0.07 or less at 50 nm.

<3> The reflection density A (λ) at the wavelength λ nm of the unexposed portion after the color development processing is 0.06 or less at 450 nm, 0.07 or less at 550 nm, and 650.
The silver halide color photographic light-sensitive material according to <1>, wherein the light-sensitive material has a nm of 0.05 or less.

<4> The density ratio of the reflection density A (λ) at the wavelength λ nm in the unexposed portion after the color development processing is as follows:
From the above <1> to <1 which satisfies the following conditional expressions (I) and (II):
3> The silver halide color photographic light-sensitive material described in any one of the above. (I) 1.0 ≦ A (550) / A (450) ≦ 1.4 (II) 0.6 ≦ A (650) / A (450) ≦ 1.2

<5> On a reflective support, at least one layer of each of a yellow-sensitive photosensitive silver halide emulsion layer, a magenta-sensitive photosensitive silver halide emulsion layer, and a cyan-sensitive photosensitive silver halide emulsion layer is provided. In a silver halide color photographic light-sensitive material containing at least one non-photosensitive and non-color-forming hydrophilic colloid layer, the chromaticity of the unexposed portion after the color development process satisfies the following condition [A]; The normalized spectral distribution curve of the yellow coloring dye is 450 n
A silver halide color photographic light-sensitive material having a density of 0.9 to 1.0 at m and 0.1 to 0.3 at 520 nm. Condition [A] 91 ≦ L ^* ≦ 96, 0 ≦ a ^* ≦ 2.0, −9.0 ≦ b ^* ≦
-3.0

<6> The silver halide color photographic material as described in <5>, wherein the chromaticity of the unexposed portion after the color development processing satisfies the following condition [B]. Condition [B] 91 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b
^* ≦ −4.8

<7> The silver halide color photographic material as described in <5>, wherein the chromaticity of the unexposed portion after the color development processing satisfies the following condition [C]. Condition [C] 93 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b
^* ≦ −4.8

<8> The normalized spectral distribution curve of the yellow coloring dye is 0.95 to 1.0 at 450 nm,
The silver halide color photographic light-sensitive material according to any one of the above items <1> to <7>, which has a density of 0.20 to 0.28 at 520 nm.

<9> The above-mentioned <containing at least one of yellow couplers represented by the following general formula (I):
A silver halide color photographic material according to any one of <1> to <8>.

[0017]

Embedded image

In the general formula (I), Q is -C
Represents a group represented by ^{- (-R 11) = C (} -R 12) -SO 2. R ¹¹ and R ¹² are mutually bonded to form a 5- to 7-membered ring together with —C ＝ C—, or each independently represents a hydrogen atom or a substituent. R ¹ represents a substituent. R ³ represents a substituent. R ⁴ represents a substituent. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R ⁴ may be the same or different, and may combine with each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developing agent.

<10> The silver halide color photographic light-sensitive material as described in any one of <1> to <8> above, which comprises at least one of yellow couplers represented by the following general formula (II): .

[0020]

Embedded image

In the general formula (II), R ¹ represents a substituent. R ² represents a substituent. l represents an integer of 0 or more and 4 or less. When 1 is 2 or more, a plurality of R ² may be the same or different, and may combine with each other to form a ring. R ³ represents a substituent. R ⁴ represents a substituent. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R ⁴ may be the same or different, and may combine with each other to form a ring. Y represents a group capable of leaving by a coupling reaction with an oxidized developing agent.

<11> At least one of the layers constituting the light-sensitive material contains a pigment in the above-mentioned <1> to <10>.
> The silver halide color photographic light-sensitive material described in any one of <1> to <3>.

<12> The pigment is at least one selected from the group consisting of indanthrone pigments, indigo pigments, triarylcarbonium pigments, azo pigments, quinacridone pigments, dioxazine pigments, and diketopyrrolopyrrole pigments. <11> The silver halide color photographic light-sensitive material described in <11>. [Detailed description of the invention]

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide color photographic light-sensitive material of the present invention will be described in detail below. The silver halide color photographic light-sensitive material of the present invention comprises, on a reflective support, layers of a yellow color-forming light-sensitive silver halide emulsion layer, a magenta color-forming light-sensitive silver halide emulsion layer, and a cyan color-forming light-sensitive silver halide emulsion layer. And at least one non-photosensitive non-color-forming hydrophilic colloid layer, and a reflection density A (λ) at a wavelength λ nm in an unexposed portion after the color development processing is: 0.08 at 450 nm
Hereinafter, 0.10 or less at 550 nm, and 0.08 or less at 650 nm, and further, the normalized spectral distribution curve of the yellow coloring dye is 0.9 to 1.0 at 450 nm,
And having a concentration of 0.1 to 0.3 at 520 nm. In the silver halide photographic light-sensitive material of the present invention, the chromaticity of the unexposed portion after the color development processing satisfies the following condition [A], and the standardized spectral distribution curve of the yellow colorant is 0.4 at 450 nm. It has a concentration of 9 or more and 1.0 or less, and 0.1 to 0.3 at 520 nm. Condition [A]: 91 ≦ L ^* ≦ 96, 0 ≦ a ^* ≦ 2.0, −
9.0 ≦ b ^* ≦ −3.0

In the present invention, the chromaticity of the unexposed portion (white background) after the color development processing is CIE1976L ^*.
It is preferable that the following conditions be satisfied in a ^* b ^* color space (hereinafter, may be referred to as “CIELAB color space”). L ^* is 91 or more and 96 or less, more preferably 92 or more and 96 or less, and still more preferably 93 or more and 96 or less.
a ^* is preferably 0 or more and 2.0 or less, more preferably 0.3 or more and 1.6 or less, and still more preferably 0.5 or more and 1 or less.
3 or less. b ^* is preferably from -9.0 to -3.0, more preferably from -8.0 to -4.8, even more preferably from -8.0 to -4.0. Therefore, in the silver halide color photographic light-sensitive material of the present invention, the chromaticity of the unexposed portion (white background) after the color development processing preferably satisfies the following conditional expression [A] on the CIELAB color space, It is more preferable that the following conditional expression [B] is satisfied, and it is more preferable that the following conditional expression [C] is satisfied. Condition [A]: 91 ≦ L ^* ≦ 96, 0 ≦ a ^* ≦ 2.0, −9.0 ≦ b ^* ≦ −3.0 Condition [B]: 91 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b ^* ≦ −4.8 Condition [C]: 93 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b ^* ≦ − 4.8

The details of the CIE1976L ^* a ^* b ^* color space are described in “Fine Imaging and Color Hard Copy”, edited by the Photographic Society of Japan and the Imaging Society of Japan, page 354 (1999).
Year, published by Corona). The three-color stimulus values when using this color space are X,
JIS Z8, which defines a method for measuring tristimulus values of Y and Z coordinates
717 is a value obtained according to the method described in FIG. CIE
The chromaticity in the 1976L ^* a ^* b ^* color space (hereinafter abbreviated as CIELAB color space) is measured by placing the reference white chromaticity in CIED65 (6504K), which is the international standard for standard daylight. Therefore, the above conditional expression [A],
The measurement for verifying that [B] and [C] are satisfied is C
Any chromaticity measuring device capable of measuring chromaticity in the IE1976L ^* a ^* b ^* color space can be used. For example,
It can be measured using a C-2000 color analyzer manufactured by Hitachi, Ltd. and CIED65 (6504K) as a reference light source.

In the present invention, the reflection density A (λ) at a wavelength of λ nm in the unexposed portion after the color development processing preferably satisfies the following condition. 450nm
At the reflection density A [hereinafter, abbreviated as A (450). ] Is preferably 0.08 or less, and more preferably 0.08 or less.
07, most preferably 0.06 or less. 550
Reflection density A in nm [hereinafter abbreviated as A (550). ] Is preferably 0.10 or less, more preferably 0.09 or less, and most preferably 0.07 or less. The reflection density A at 650 nm [hereinafter, A (65
0). ] Is preferably 0.08 or less, more preferably 0.07 or less, and most preferably 0.05 or less. The A value is preferably as small as possible, but when a paper support coated with a white pigment-containing polyethylene resin is used, substantially A (450), A (550) and A (550) are used.
Both (650) are 0.01 or more. Furthermore, since the tendency to look sensual “white” in consideration of human preference changes depending on the color balance, favorable conditions also exist for the density ratio of the reflection density A (λ), preferably 1.0 ≦ A (5
50) / A (450) ≦ 1.4 and 0.6 ≦ A (65
0) / A (450) ≦ 1.2, more preferably 1.1 ≦ A (550) / A (450) ≦ 1.3, and 0.6 ≦ A (650) / A (450) ≦ 1.2,
More preferably, 1.1 ≦ A (550) / A (450) ≦
1.2 and 0.8 ≦ A (650) / A (450) ≦
1.1. The reflection density A at the wavelength λ nm
Details of (λ) are defined as follows. 25 ° C 60% RH
Under the conditions, the opening ratio of the integrating sphere is 2%, the slit width is 5 nm, and the reflection absorbance excluding the specular light is defined. As a typical example of the reflection absorbance measuring device, U-manufactured by Hitachi, Ltd.
3410 type spectrophotometer.

In the present invention, the method for adjusting the white background within the above-mentioned preferred range is roughly classified into two methods: a method of adjusting the whiteness of the support and a method of adjusting the hydrophilic colloid layer forming the photographic constituent layer. can do. The reflection support preferably used in the present invention will be described in detail. In the reflective support of the present invention, it is preferable that a white pigment is contained in the water-resistant resin coating layer on the photosensitive layer coating side of the reflective support. Examples of white pigments mixed and dispersed in the water-resistant resin include inorganic pigments such as titanium dioxide, barium sulfate, lithopone, aluminum oxide, calcium carbonate, silicon oxide, antimony trioxide, titanium phosphate, zinc oxide, lead white, zirconium oxide, and polystyrene. And organic fine powder such as styrene-divinylbenzene copolymer. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be either a rutile type or an anatase type, but anatase type is preferred when whiteness is prioritized, and rutile type is preferred when sharpness is prioritized. Anatase type and rutile type may be blended and used in consideration of both whiteness and sharpness. Further, when the water-resistant resin layer is composed of multiple layers, some layers have anatase type,
A method using a rutile type for other layers is also preferable. Further, these titanium dioxides may be produced by any of a sulfate method and a chloride method.

The water-resistant resin of the reflective support used in the present invention is defined as having a water absorption (% by mass) of 0.5 or less, preferably 0.1% or less.
No more than 1 resin, for example, polyolefins such as polyethylene, polypropylene, and polyethylene polymers, vinyl polymers and copolymers thereof (polystyrene, polyacrylate and copolymers thereof), and polyesters (polyethylene terephthalate, polyethylene isophthalate, etc.)
And its copolymers. Particularly preferred are polyethylene and polyester. As the polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and a blend of these polyethylenes can be used.

As the polyester, a polyester synthesized by condensation polymerization from a dicarboxylic acid and a diol is preferable, and a preferable dicarboxylic acid is
Examples include terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Preferred diols include ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, butanediol, hexylene glycol, bisphenol A ethylene oxide adduct (2,2-bis (4- (2-hydroxyethyloxy) phenyl) propane ), 1,4-dihydroxymethylcyclohexane and the like. Various polyesters obtained by condensation polymerization of these dicarboxylic acids alone or in mixtures with diols alone or in mixtures can be used. Among them, at least one of the dicarboxylic acids is preferably terephthalic acid.

The mixing ratio of the water-resistant resin and the white pigment is from 98/2 to 30/70 by mass (water-resistant resin /
White pigment), preferably 95/5 to 50/50, particularly preferably 90/10 to 60/40. These water-resistant resin layers are preferably coated on the substrate with a thickness of 2 to 200 µm, more preferably 5 to 80 µm. The thickness of the resin or resin composition coated on the surface of the substrate other than the photosensitive layer application surface is preferably 5 to 100 μm, more preferably 10 to 50 μm.

In the reflective support used in the present invention, the water-resistant resin coating layer on the photosensitive layer coating side may be a reflective support comprising two or more water-resistant resin coating layers having different white pigment contents. It may be more preferable from the viewpoints of cost, suitability for production of the support, and the like. In this case, among the water-resistant resin coating layers having different contents of the white pigment, the content of the white pigment of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above the layer. It is preferably lower than the content of the white pigment.

The content of the white pigment in each layer in the multilayer water-resistant resin layer is from 0% by mass to 70% by mass, preferably from 0% by mass to 50% by mass, more preferably from 0% by mass to 40% by mass.
% By mass. The content of the layer having the highest white pigment content in the multilayer water-resistant resin layer was 9% by mass.
The content is preferably from 70 to 70% by mass, preferably from 15 to 50% by mass, and more preferably from 20 to 40% by mass.

The water-resistant resin layer may contain a bluing agent so as to be adjusted within the range of the white background of the present invention. As the bluing agent, generally known ultramarine blue, cobalt blue, cobalt oxide phosphate, quinacridone pigments and the like and a mixture thereof are used. The particle size of the bluing agent is not particularly limited, but the particle size of a commercially available bluing agent is usually about 0.3 μm to 10 μm. When the water-resistant resin layer of the reflective support used in the present invention has a multilayer structure, the content of the bluing agent in the water-resistant resin layer, the content in the water-resistant resin layer of the uppermost layer, the content of the lower layer It is preferable to make the above. The preferable content of the bluing agent is 0.2 to 0.5% by mass in the uppermost layer, and 0 to 0.45% by mass in the lower layer.

The substrate used for the reflective support of the present invention comprises:
Natural pulp paper made from natural pulp as a main raw material, mixed paper made from natural pulp and synthetic fiber, synthetic fiber paper containing synthetic fiber as a main component, so-called synthetic paper made from synthetic resin films such as polystyrene and polypropylene Polyester films such as polyethylene terephthalate and polybutylene terephthalate, and polyolefin films such as cellulose triacetate film, polystyrene film, and polypropylene film may be used. Paper (hereinafter simply referred to as base paper) is particularly preferably and advantageously used. If necessary, a white background can be adjusted to the range of the present invention by adding a dye or a fluorescent dye.

The thickness of the base paper of the support used in the present invention is not particularly limited.
0g / m ² ~250g / m ² is, the thickness, 50 [mu] m
２５０250 μm is preferred.

As a more preferred reflection support in the present invention, a support having a polyolefin layer having micropores on a paper substrate on which a silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer, preferably on the side of the silver halide emulsion layer, has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of these multilayers or polyolefin layers located between the paper substrate and the photographic component layer is between 0.40 and 0.40.
1.0 g / ml, preferably 0.50 to 0.1 g / ml.
70 g / ml is more preferred. The thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably from 10 to 100 μm, more preferably from 15 to 70 μm. The thickness ratio between the polyolefin layer and the paper substrate is 0.05 to 0.5.
2 is preferable, and 0.1 to 0.15 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back surface) of the paper substrate from the photographic component layer, from the viewpoint of increasing the rigidity of the reflection support. In this case, the polyolefin layer on the back surface has a matte surface. Polyethylene or polypropylene is preferred, and polypropylene is more preferred. 5-50 μm for the back polyolefin layer
Is preferably 10 to 30 μm, and more preferably the density is 0.7 to 1.1 g / ml. In the reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in
-333277, 10-333278, 11-
Nos. 52513, 11-65024, EP0
Examples described in the specifications of JP 880065 and EP 088066 are described.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. Further, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, benzoxazole-based, coumarin-based, and pyrazoline-based fluorescent whitening agents can be preferably used, and benzoxazolylnaphthalene-based and benzooxazolylstilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 m
g / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass, based on the resin.

The reflective support may be a transmissive support or the above-described reflective support provided with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The method of adjusting the white background within the scope of the present invention with a hydrophilic colloid layer forming a photographic constituent layer coated on a support will be described in detail. Factors that deteriorate the white background due to the photographic constituent layers include fog of silver halide emulsion,
Examples include the residual color of the sensitizing dye and the adsorption of stains on the processing solution. By reducing these deterioration factors, the whiteness of the support itself can be approximated. Further, by adding a dye or a pigment which is not decolored by the processing to color, or by adding a fluorescent whitening agent to the processed light-sensitive material, the white background can be adjusted to a preferable range of the present invention.

The pigment preferably used in the present invention for coloring the hydrophilic colloid layer of the photographic constituent layer will be described. The silver halide photographic light-sensitive material of the present invention has at least one pigment dispersed in at least one of a light-sensitive silver halide emulsion layer and a non-light-sensitive layer coated on a reflective support (ie, , Dispersed pigments) are preferred. In the present invention, the layer containing the pigment may be a photosensitive layer containing a silver halide emulsion, or an intermediate layer located between the silver halide emulsion layers or an ultraviolet absorbing layer located above the silver halide emulsion layer. Or a non-photosensitive layer such as a gelatin undercoat layer. Since the coating flow rate of the silver halide emulsion layer is usually changed to adjust the characteristic curve, it is often preferable to introduce a pigment into the non-photosensitive layer in order to keep the tinting constant.

Usually, in order to overcome the yellow stain, a blue tint is applied. As this coloring, we usually antagonize yellow stain and make it neutral color,
The pigment is added in an amount sufficient to make it white to the human eye. Further, by using two or more types of pigments and changing the usage ratio of those pigments, it is possible to perform yellow stain correction in a wide range. In general, a combination of a blue pigment that changes the hue in the cyan direction and a red or violet pigment that changes the hue in the magenta direction is used. This allows a wide range of color adjustments. The pigment used in the present invention may be any pigment as long as it is water-insoluble, but is preferably a pigment which has a strong affinity for an organic solvent and is easily dispersed in the organic solvent. Generally, the particle size of the pigment is 0.01 μm to 5 μm.
m is good for coloring efficiently. Preferably, 0.
01 μm to 3 μm.

In the present invention, the pigment is most preferably introduced as follows. That is, similarly to emulsifying and dispersing a photographically useful substance such as a usual dye-forming coupler (also referred to as a coupler in the present specification) and incorporating the same into a light-sensitive material as a dispersion, the pigment used in the present invention is treated with a high boiling organic compound. In addition to the solvent, a uniform spontaneous dispersion composed of the fine particle pigment is generated. In a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a surfactant dispersant, ultrasonic, colloid mill, homogenizer, Mentongorin, emulsified and dispersed in fine particles by a known device such as high-speed dissolver,
Obtain a dispersion. The high boiling organic solvent used in the present invention,
There is no particular limitation, and ordinary ones are used. For example, US Pat. No. 2,322,027,
JP-A-152129. In addition, an auxiliary solvent can be used together with a high-boiling organic solvent. Examples of auxiliary solvents include ethyl acetate, acetate of lower alcohols such as butyl acetate, ethyl propionate,
Secondary butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, cyclohexanone and the like can be mentioned. The pigment used in the present invention is most preferably prepared by coexisting in an organic solvent that dissolves a useful photographic compound such as a coupler used in the light-sensitive material of the present invention and co-emulsifying to prepare an emulsion. .

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples unless otherwise specified. In the present invention, any kind of pigment can be used without limitation as long as the required color tone can be adjusted and remains in the photosensitive material without being changed during the development processing. Hereinafter, preferred pigments will be described with reference to specific examples, and the blue pigment used in the present invention is referred to as a “color index”.
(The Society of Dyers and
colourists), C.I. I. Pigme
Refers to pigments classified as nt Blue. Similarly, the red pigment used in the present invention is C.I. I. Pigm
ent Red, The purple pigment used in the present invention is:
C. I. Pigment Violet.

The blue pigment which can be used in the present invention includes, for example, azo pigments (for example, CI Pigmen).
t Blue 25), phthalocyanine pigments (for example,
C. I. Pigment Blue 15: 1, 1
5: 3, 15: 6, 16 and 75), indanthrone pigments (for example, CI Pigment Blue)
60, 64 and 21), triarylcarbonium-based basic dye lake pigments (for example, CI Pigm
ent Blue 1, 2, 9, 10, 14,
62), and also a triarylcarbonium-based acid dye lake pigment (for example, CI Pigment Bl).
ue 18, 19, 24: 1, 24: x, 5
6, 61), indigo pigments (for example, CI Pig
organic pigments such as MentBlue 63 and 66). Among these, indanthrone pigments, triarylcarbonium-based basic dye lake pigments, acid dye lake pigments, and indigo pigments are preferable in terms of hue, and indanthrone pigments are most preferable in terms of fastness. As the blue pigment in the present invention, ultramarine blue and cobalt blue, which are inorganic pigments, can also be preferably used.
As the indanthrone pigment used in the present invention, those having a high affinity for an organic solvent are particularly preferable, and these can be selected from commercially available products. For example, Ciba Specia
BlueA3R-KP (trade name), BlueA3R-K (trade name), etc., manufactured by lighty Chemicals (Ciba Specialty Chemicals) can be used.

In the present invention, in order to adjust the hue, it is preferable to use a red or purple pigment in combination.
As preferred red pigments, azo pigments (for example, CIP
imagment Red 2, 3, 5, 12, 12
3, same 48: 2, same 48: 3, same 52: 1, same 53:
1, 57: 1, 63: 2, 112, 144, 146, 150, 151, 166, 175, 176, 184, 187, 220, 221 and 245 ), Quinacridone pigments (for example, CI Pig
ment Red 122, 192, 202, 2
06, 207 and 209), diketopyrrolopyrrole pigments (for example, CI Pigment Red 254, 255, 264 and 272), and perylene pigments (for example, CI Pigment Red 123 and 149).
178, 179, 190, and 224), perinone pigments (for example, CI Pigment Red 19)
4), anthraquinone pigments (for example, CI Pigm
ent Red 83: 1, 89, 168, 17
7), benzimidazolone pigments (for example, CI Pi
gment Red 171, 175, 176, 185, and 208) and triarylcarbonium-based basic dye lake pigments (for example, CI Pigment).
Red 81: 1, 169), thioindigo pigments (for example, CI Pigment Red 88, 181), pyranthrone pigments (for example, CI Pig)
Ment Red 216 and 226), pyrazoloquinazolone pigments (for example, CI Pigment Red)
251 and 252), isoindoline pigments (for example,
C. I. Pigment Red 260). Among them, azo pigments, quinacridone pigments, diketopyrrolopyrrole pigments, and perylene pigments are more preferred, and azo pigments and diketopyrrolopyrrole pigments are particularly preferred.

Preferred violet pigments include azo pigments (for example, CI Pigment Violet 13, 2).
5, 44 and 50), dioxazine pigments (for example, C.I.
I. Pigment Violet 23, 37),
Quinacridone pigments (for example, CI Pigment V
iolet 19, 42), triarylcarbonium-based basic dye lake pigments (for example, CI Pig
ment Violet 1, 2, 3, 27, 39), anthraquinone pigments (for example, CI Pig
ment Violet 5: 1 and 33), perylene pigments (for example, CI Pigment Violet)
29), isoviolanthrone pigments (for example, CIP
Pigment Violet 31), benzimidazolone pigments (for example, CI Pigment Viol)
et 32) and the like. Among them, azo pigments, dioxazine pigments, quinacridone pigments are preferred,
Dioxazine pigments are particularly preferred. As the dioxazine pigment used in the present invention, those having a high affinity for an organic solvent are particularly preferred, which can be selected from commercial products,
For example, Ciba Specialty Chemical
Violet BK (trade name), V
iolet B-KP (trade name) or the like can be used.

In the present invention, in addition to the above-mentioned pigments, other pigments (CI Pigment) may be used for adjusting the color tone.
Yellow, C.I. I. Pigment Orange
e, C.I. I. Pigment Brown, C.I. I. P
pigments classified by CI.I.Green Green) can be used in combination. For specific compounds, see “Color Index” (The Society of D).
yers and colors), W.S. He
rbst, K .; Hunger co-authored "Industria
l Organic pigments ", (VCH
Verlagsgesellschsft mbH19
1993).

The pigment which can be used in the present invention may be the above-mentioned naked pigment or a pigment which has been subjected to a surface treatment. Surface treatment methods include a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, or a polyisocyanate) to the pigment surface,
A method using a pigment derivative (synergist) can be considered, for example, “Properties and Applications of Metallic Soap” (Koshobo), “Printing Ink Technology” (CMC Publishing, 1984), “Latest Pigment Application Technology” (CMC Publishing, 1986) )). Among them, commercially available easily dispersible pigments in which the pigment surface is coated in advance with a resin or wax, so-called instant pigments (for example, Ciba Specialist)
y Microlith pigment manufactured by Chemicals)
Is particularly preferable because it does not need to be dispersed when introduced into a photosensitive material and can be satisfactorily dispersed in a high-boiling organic solvent. In this case, the high-boiling organic solvent in which the pigment is dispersed can be further dispersed in a hydrophilic colloid such as gelatin.

In the present invention, as described above, the pigment may be dispersed in a high-boiling organic solvent and then dispersed in a hydrophilic colloid such as gelatin, but the pigment may be directly dispersed in the hydrophilic colloid. It may be dispersed. The dispersant used at this time can be various ones according to the binder and the pigment used, for example, a surfactant type low molecular dispersant or a polymer type dispersant, but from the viewpoint of dispersion stability. It is more preferable to use a polymer type dispersant. Examples of dispersants include JP-A-3-69949 and EP 549486.
And the like can be mentioned. As the particle size of the pigment that can be used in the present invention, after dispersion, 0.01
Preferably in the range of 0.02 to 10 μm.
More preferably, it is μm. As a method for dispersing the pigment in the binder, a known dispersion technique used in the production of ink or toner can be used. Examples of the dispersing machine include a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill, and a pressure kneader. The details are described in "Latest Pigment Application Technology" (CMC Publishing, published in 1986).

The total amount of the pigment used in the present invention is preferred.
A good range is 0.1 mg / m ^Two-10mg / m^Twoso
Yes, more preferably 0.3 mg / m^Two~ 5mg / m^Two
It is. In addition, a blue pigment and a pigment of a different hue
It is preferred to use The pigment is used as the parent for forming the photographic constituent layer.
The method of adding the pigment to the aqueous colloid layer is as follows.
For the method of adding into the olefin coating resin, the same
Significantly reduce the amount of pigment required to adjust the color
Therefore, there is a merit in terms of cost, which is preferable. Departure
In the light, the blue pigment, the red pigment and / or purple face
When used together, the same or different hydrophilic colloid
It can be used by dispersing it in layers.
There is no.

In the present invention, it is also preferable to adjust the white background by using an oil-soluble dye in the photographic constituent layer of the light-sensitive material.
Representative examples of oil-soluble dyes are described in JP-A-2-842.
And Compounds 1 to 27 described on pages (8) and (9) of JP-A No. 6-1980.

In the present invention, the white background can be adjusted by incorporating a fluorescent whitening agent in the hydrophilic colloid layer of the light-sensitive material and leaving the fluorescent whitening agent in the light-sensitive material after processing. Further, a polymer that captures a fluorescent whitening agent such as polyvinylpyrrolidone can be added to the photosensitive material.

Preferred embodiments of the yellow dye image, magenta dye image and cyan dye image in the present invention will be described. The spectral characteristics of each color are represented by a normalized spectral distribution curve obtained from the relationship between the visible region wavelength defined at a density of 1.0 at the maximum wavelength of the spectrum and the reflection density. Here, the wavelength characteristic of the reflection density includes a component belonging to a dye, a component belonging to a reflective support, and a component belonging to other photosensitive material components. Measurement method is 25 ° C
Using a U-3410 type spectrophotometer manufactured by Hitachi, Ltd. under the conditions of 60% RH, the measurement is performed by removing the specular light with an aperture ratio of the integrating sphere of 2%, the slit width of 5 nm.

In the present invention, the spectral characteristic is 400
Yellow is defined as having an absorption maximum at 500 to 600 nm, magenta is defined as having an absorption maximum at 500 to 600 nm, and cyan is defined as having an absorption maximum at 600 to 700 nm. Further, in the present invention, the normalized spectral distribution curve refers to a spectral distribution curve normalized such that the density at the wavelength giving the maximum density is 1.0. In the present invention, the normalized spectral distribution curves of the magenta and cyan dye images are not particularly limited for the purpose of the present invention, but the normalized spectral distribution curves of the magenta dye image are 0.6 nm at 520 nm. ~ 1.0 and 540
0.9 to 1.0 at nm and 0.85 at 560 nm
It preferably has a density of 1.0 and the normalized spectral distribution curve of the cyan dye image is 0.7-1.
0, and 0.8 to 1.0 at 610 nm, and 650 nm
Is preferably 0.9 to 1.0.

The normalized spectral distribution curve of the yellow dye image in the present invention is defined when the yellow coupler-containing layer is exposed to color development and the magenta and cyan color development layers are not exposed. In the present invention, the normalized spectral distribution curve of the yellow coloring dye is 0.9 to 0.9 at 450 nm.
1.0, and preferably has a concentration of 0.1 to 0.3 at 520 nm, more preferably 0.95 to 1.0 at 450 nm, and more preferably 0.15 to 0.30 at 520 nm. It is particularly preferred to have a concentration of 0.95 to 1.0 at 450 nm and 0.20 to 0.28 at 520 nm. According to the preferred range of the normalized spectral distribution curve of the yellow coloring matter of the present invention, the reason why the effect of the present invention is obtained is not clear, but by matching with the whiteness of the preferred white background of the present invention, a higher saturation than before is obtained. Image is expected to be achieved in the yellow region. Moreover, the configuration of the present invention also suppresses temporal discoloration (change in chromaticity point) of the yellow dye coloring portion under light irradiation and suppresses temporal discoloration of white background under light irradiation of whiteness. preferable.

The yellow coupler used in the present invention is not particularly limited as long as it satisfies the conditions of the above-mentioned normalized spectral distribution curve, but is preferably represented by the following general formula (I):
To (V), more preferably a yellow coupler represented by the general formula (I) or (II), and most preferably a yellow coupler represented by the general formula (II). . The following formulas (I) and (II)
The yellow coupler represented by is described.

[0059]

Embedded image

In the general formula (I), R ¹ represents a substituent other than a hydrogen atom. As this substituent, for example,
A halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group,
Aryl group, heterocyclic group, cyano group, hydroxyl group,
Nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy, amino group (including alkylamino group and anilino group) An acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkyl and arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, Sulfo group,
Alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups,
Examples include a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

The above-mentioned substituent may be further substituted with a substituent, and examples of the substituent include the above-mentioned groups.

Hereinafter, examples of the substituent of R ¹ will be further described.
As these substituents, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) Yes, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-
Octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, 3- (2,4-di-t-
Amylphenoxy) propyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl,
4-n-dodecylcyclohexyl; a polycycloalkyl group, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] And polycyclic groups such as heptane-2-yl, bicyclo [2,2,2] octan-3-yl) and tricycloalkyl groups. Preferred are a monocyclic cycloalkyl group and a bicycloalkyl group, and a monocyclic cycloalkyl group is particularly preferred. ),

An alkenyl group [a linear or branched substituted or unsubstituted alkenyl group, preferably having 2 to 30 carbon atoms;
Alkenyl groups such as vinyl, allyl, prenyl, geranyl and oleyl), cycloalkenyl groups (preferably substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms, for example, 2-cyclopentene-1-
Yl, 2-cyclohexen-1-yl), and a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo [2, 2,
1] Hept-2-en-1-yl, bicyclo [2,2,
2] oct-2-en-4-yl)], a tricycloalkenyl group and a bicycloalkenyl group, and a monocyclic cycloalkenyl group is particularly preferred. ) Alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl,
p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or A condensed heterocyclic group, more preferably a heterocyclic ring in which the ring-constituting atoms are selected from a carbon atom, a nitrogen atom and a sulfur atom, and have at least one heteroatom of nitrogen, oxygen and sulfur And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-
Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

An alkoxy group (preferably having 1 to 3 carbon atoms)
0 substituted or unsubstituted alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy, n
-Octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy,
-Methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms) And, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and a heterocyclic portion is the aforementioned heterocyclic group. The described heterocyclic moieties are preferred, for example 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy group Acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethyl Carbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, For example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably having 7 to 3 carbon atoms)
0 substituted or unsubstituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

Amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a heterocyclic group having 0 to 30 carbon atoms) An amino group such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-
1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, having 1 to 3 carbon atoms)
A substituted or unsubstituted alkylcarbonylamino group of 0 or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino,
Benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N , N-dimethylaminocarbonylamino,
N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonyl Amino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxy Carbonylamino), a sulfamoylamino group (preferably having 0 carbon atoms)
30 to 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably A substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms,
For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group,

An alkylthio group (preferably having a carbon number of 1 to
30 substituted or unsubstituted alkylthio groups, for example, methylthio, ethylthio, n-hexadecylthio), and arylthio groups (preferably substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms, for example, phenylthio,
p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic portion is the heterocyclic group described above for the heterocyclic group. A ring portion is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfoyl). Famoyl, N- (3-
Dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl,
N-benzoylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), a sulfo group,

Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms, such as methylsulfinyl,
Ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms) Yes, for example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substitution of 7 to 30 carbon atoms) Or an unsubstituted arylcarbonyl group such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), and an aryloxycarbonyl group (preferably having 7 to 3 carbon atoms).
0 substituted or unsubstituted aryloxycarbonyl groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p
-T-butylphenoxycarbonyl),

An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably having 6 to 3 carbon atoms)
0 substituted or unsubstituted arylazo group, having 3 to 3 carbon atoms
30 substituted or unsubstituted heterocyclic azo groups (the heterocyclic portion is preferably the heterocyclic portion described for the aforementioned heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4 -Thiadiazole-2
-Ylazo), an imide group (preferably having 2 to 30 carbon atoms)
A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, Methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl An amino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms such as dimethoxyphosphinylamino and dimethylaminophosphinylamino), a silyl group (preferably having 3 to 30 carbon atoms); 30 substituted or unsubstituted silyl groups, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above-mentioned functional groups, those having a hydrogen atom may be removed and further substituted with the above-mentioned groups. Examples of such functional groups include alkylcarbonylaminosulfonyl, arylcarbonylaminosulfonyl, alkylsulfonylaminocarbonyl,
An arylsulfonylaminocarbonyl group is exemplified, and specific examples thereof include a methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl group.

As R ¹ , a substituted or unsubstituted alkyl group is preferable, and a substituted alkyl group is more preferable.
Examples of the substituent of the substituted alkyl group include the examples described above as the substituent of R ¹ . The total carbon number of R ¹ is preferably 1 or more and 60 or less, more preferably 6 or more and 50 or less, further preferably 11 or more and 40 or less, and 16
It is most preferably at least 30 and at most 30.

R ¹ is preferably an alkyl group substituted at the 2-, 3- or 4-position with an alkoxy group or an aryloxy group, more preferably an alkyl group substituted at the 3-position with an alkoxy group or an aryloxy group. A 3- (2,4-di-t-amylphenoxy) propyl group is most preferred.

In the general formula (I), Q represents -C (-
R ¹¹ ) = C (-R ¹² ) -SO _2- .
R ¹¹ and R ¹² are bonded to each other and together with —C ＝ C—
A group forming a 7-membered ring, or each independently represents a hydrogen atom or a substituent; The formed 5- to 7-membered ring is a saturated ring or an unsaturated ring, and the ring may be an alicyclic ring, an aromatic ring, or a hetero ring, for example, a benzene ring, a furan ring, a thiophene ring, Examples include a pentane ring and a cyclohexane ring. Examples of the substituent include those described above as the substituent of R ¹ .

The ring formed by combining each of these substituents or a plurality of substituents may be further substituted with a substituent (for example, the groups exemplified as the substituent for R ¹ described above).

In the general formula (I), R ³ represents a substituent other than a hydrogen atom. Examples of the substituent include those described above as examples of the substituent of R ¹ . R ³
As a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (eg, methyl, isopropyl), an alkoxy group (eg, methoxy, isopropyloxy), an aryloxy group (eg, phenoxy), an amino group (eg, dimethylamino) , Morpholino), an acylamino group (eg, acetamido), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), more preferably a halogen atom, an alkoxy group, an aryloxy group, or an alkyl group, and most preferably a chlorine atom. And an alkoxy group is preferred.

In the general formula (I), R ⁴ represents a substituent. Examples of the substituent include those described above as examples of the substituent of R ¹ . R ⁴ is preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, an alkyl or an arylsulfonylamino group. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R ⁴ may be the same or different, and may combine with each other to form a ring.

In the general formula (I), X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developing agent. Examples of the case where X is a group which can be separated by a coupling reaction with an oxidized developing agent include a group which is separated by a nitrogen atom, a group which is separated by an oxygen atom, a group which is separated by a sulfur atom, a halogen atom (for example, chlorine Atom, bromine atom). Examples of the group capable of leaving at the nitrogen atom include a heterocyclic group (preferably 5 to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic (4n +
A non-aromatic, monocyclic or condensed ring heterocyclic group, more preferably a ring-constituting atom is selected from a carbon atom, a nitrogen atom and a sulfur atom; 5 having at least one hetero atom of any of a nitrogen atom, an oxygen atom and a sulfur atom
And 6-membered heterocyclic groups such as succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole,
2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2-one, benzimidazoline-2-one, benzoxazoline -2-one, benzothiazolin-2-one, 2-pyrrolin-5-
On, 2-imidazolin-5-one, indoline-2,
3-dione, 2,6-dioxypurineparabanic acid, 1,
2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone,
2-pyrazone, 2-amino-1,3,4-thiazolidine-4-one), carbonamide group (eg, acetamide, trifluoroacetamide), sulfonamide group (eg, methanesulfonamide, benzenesulfonamide), arylazo group ( For example, phenylazo, naphthylazo), carbamoylamino group (for example, N-methylcarbamoylazo) and the like can be mentioned.

Of the above-mentioned groups which are split off by a nitrogen atom, preferred are heterocyclic groups, and more preferred are aromatic heterocyclic groups having 1, 2, 3 or 4 nitrogen atoms as ring-constituting atoms, or It is a heterocyclic group represented by the following general formula (L), and particularly preferably a heterocyclic group represented by the following general formula (L).

[0082]

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In the general formula (L), L is -NC
(= O)-represents a residue that forms a 5- to 6-membered nitrogen-containing heterocycle. Examples of these are given in the description of the above heterocyclic group, and these are more preferred. Above all, L
Is preferably a residue forming a 5-membered nitrogen-containing heterocycle.

Examples of the group capable of leaving by an oxygen atom include an aryloxy group (for example, phenoxy and 1-naphthoxy),
A heterocyclic oxy group (eg, pyridyloxy, pyrazolyloxy), an acyloxy group (eg, acetoxy, benzoyloxy), an alkoxy group (eg, methoxy, dodecyloxy), a carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, morpholinocarbamoyloxy), Aryloxycarbonyloxy group (eg, phenoxycarbonyloxy), alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy), alkylsulfonyloxy group (eg, methanesulfonyloxy), arylsulfonyloxy group (eg, benzenesulfonyloxy, toluenesulfonyl) Oxy) and the like. Among the groups which are separated by the oxygen atom, an aryloxy group, an acyloxy group and a heterocyclic oxy group are preferred.

Examples of the group leaving with the sulfur atom include an arylthio group (eg, phenylthio, naphthylthio),
Heterocyclic thio groups (eg, tetrazolylthio, 1,3,4
-Thiadiazolylthio, 1,3,4-oxazolylthio, benzimidazolylthio), alkylthio groups (eg, methylthio, octylthio, hexadecylthio), alkylsulfinyl groups (eg, methanesulfinyl),
An arylsulfinyl group (eg, benzenesulfinyl), an arylsulfonyl group (eg, benzenesulfonyl), an alkylsulfonyl group (eg, methanesulfonyl), and the like can be given. Among the groups which are eliminated by the sulfur atom, preferred are an arylthio group and a heterocyclic thio group, and a heterocyclic thio group is more preferred.

In the general formula (I), X may be substituted by a substituent, and examples of the substituent that substitutes X include those described above as examples of the substituent of R ^1. . X is preferably a group capable of leaving at a nitrogen atom, a group capable of leaving at an oxygen atom, or a group capable of leaving at a sulfur atom;
More preferred are groups which can be eliminated with a nitrogen atom, and further preferred are those in the order of the preferred groups described for the group which can be eliminated with a nitrogen atom. The preferred group for X is further described below. An aromatic heterocyclic group having 1, 2, 3 or 4 nitrogen atoms as a ring-constituting atom, or a heterocyclic group represented by the general formula (L) (particularly preferably A heterocyclic group represented by the general formula (L), a group capable of leaving with an oxygen atom (particularly preferably an aryloxy group, an acyloxy group or a heterocyclic oxy group), a group capable of leaving with a sulfur atom (preferably an arylthio group, A cyclic thio group, particularly preferably a heterocyclic thio group)
It is.

Further, X may be a photographically useful group.
As the photographically useful group, a development inhibitor, a desilvering accelerator,
Redox compounds, dyes, couplers, and the like, and precursors thereof are exemplified. More preferably, X is a development inhibitor and a precursor thereof.
JP-A No. 00-17195 discloses a development inhibitor and a precursor thereof, and preferable examples thereof are also the same as those described as preferable.

In order to immobilize the coupler in the light-sensitive material, at least one of Q, R ¹ , X, R ^{3 and} R ⁴ has a total carbon number including a substituent of 8 or more and 50 or less. It is more preferable that the total number of carbon atoms is 10 or more and 40 or less.

Next, the compound represented by formula (II) of the present invention (which may be referred to as “dye-forming coupler” in the present application) will be described in detail.

[0090]

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In the general formula (II), R ¹ , R ³ , R
⁴ represents a substituent, which is the same as that described in the formula (I), and the preferable range is also the same.

In the general formula (II), R ² represents a substituent. Examples of the substituent include those described above as examples of the substituent of R ¹ . l represents an integer of 0 or more and 4 or less. When 1 is 2 or more, a plurality of R ² may be the same or different, and may combine with each other to form a ring.

In the general formula (II), Y represents a group capable of leaving by a coupling reaction with an oxidized developing agent. Examples of Y include those exemplified when X is a group capable of leaving by a coupling reaction with an oxidized developing agent, and preferred examples are also the same.

In the present invention, among the couplers represented by formula (I) or (II), preferred specific examples [exemplified compounds (1) to (40)] are shown below. Is not limited to these. It should be noted that the present invention also includes a tautomer in which a hydrogen atom at the coupling position is transferred onto the nitrogen at the C = N portion bonded to the coupling position.

[0095]

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[0096]

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[0097]

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[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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In the following description, when the above-mentioned exemplified compounds are referred to, they are indicated as “coupler (x)” using the parenthesized number (x) attached to each exemplified compound. It shall be.

Hereinafter, specific examples of the synthesis of the compound represented by formula (I) will be described. <Synthesis Example 1: Synthesis of Coupler (1)> Coupler (1)
Was synthesized by the following route.

[0105]

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To a solution of 38.8 g of a 40% aqueous solution of methylamine and 200 ml of acetonitrile, 44.3 g of orthonitrobenzenesulfonyl chloride was added little by little under ice-cooling. The temperature of the system was raised to room temperature, and the mixture was further stirred for 1 hour. Ethyl acetate and water were added, and the mixture was separated.
The organic layer was washed with diluted hydrochloric acid and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 28.6 g of compound (A-1).

44.8 g of reduced iron, ammonium chloride 4.
5 g was dispersed in 270 ml of isopropanol and 45 ml of water, and heated under reflux for 1 hour. Compound (A-1) 2
5.9 g were added little by little with stirring. After further heating and refluxing for 1 hour, suction filtration was performed through Celite. Ethyl acetate and water were added to the filtrate, and the mixture was separated, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain an oily compound 2 of compound (A-2).
1.5 g were obtained.

A solution of 18.9 g of the compound (A-2), 39.1 g of the hydrochloride of the imino ether (A-0) and 200 ml of ethyl alcohol was stirred with heating under reflux for one day. Further, 19.2 g of hydrochloride of imino ether was added, and the mixture was further stirred for 1 day under reflux. Ethyl acetate and water were added, and the mixture was separated. The organic layer was washed with diluted hydrochloric acid and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 21.0 g of a compound (A-3).

5.6 g of compound (A-3), 7.2 g of 2-methoxy-5-tetradecyloxycarbonylaniline
g, a solution of 20 ml of m-dichlorobenzene was stirred for 6 hours while heating under reflux. 7. After cooling, hexane was added for crystallization.
8 g of compound (A-4) was obtained.

To a solution of 5.4 g of the compound (A-4) in 110 ml of methylene chloride was added dropwise 10 ml of a solution of 0.45 ml of bromine in methylene chloride under ice-cooling. After stirring at room temperature for 30 minutes, methylene chloride and water were added to separate the layers, and the organic layer was washed with saturated saline. After drying over anhydrous magnesium sulfate,
The solvent was distilled off under reduced pressure to obtain a crude compound (A-5).

5,5-dimethyloxazolidine-2,4
-3.5 g of dione, 3.8 ml of triethylamine in N,
It was dissolved in 110 ml of N-dimethylacetamide, and at room temperature, a solution of the crude compound (A-5) synthesized above in 25 ml of acetonitrile was added dropwise over 10 minutes, followed by stirring at room temperature for 2 hours. Ethyl acetate and water were added and the mixture was separated, and the organic layer was washed with a 0.1 N aqueous potassium hydroxide solution, diluted hydrochloric acid, and saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of acetone and hexane as an eluent.
Crystallized from hexane mixed solvent, 4.7 g of coupler (1)
I got

<Synthesis Example 2: Synthesis of Coupler (3)> Coupler (3) was synthesized by the following route.

[0113]

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438 g of 3- (2,4-di-t-amylphenoxy) propylamine, triethylamine 210
333 g of ortho-nitrobenzenesulfonyl chloride were added to a solution of 1 ml of acetonitrile under stirring with ice while stirring little by little. The temperature of the system was raised to room temperature, and the mixture was further stirred for 1 hour. Ethyl acetate and water were added, and the mixture was separated.
The organic layer was washed with diluted hydrochloric acid and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl acetate and hexane to obtain 588 g of compound (B-1).

84.0 g of reduced iron;
4 g was dispersed in 540 ml of isopropanol and 90 ml of water, and the mixture was heated under reflux for 1 hour. Compound (B-1) 11
9 g were added little by little with stirring. After further heating and refluxing for 2 hours, the mixture was suction-filtered through Celite. Ethyl acetate and water were added to the filtrate, and the mixture was separated, and the organic layer was washed with saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 111 g of an oily compound (B-2).

111 g of compound (B-2), 68.4 g of hydrochloride of iminoether (A-0), ethyl alcohol 1
50 ml of the solution was stirred under reflux for 1 hour. Further, 4.9 g of hydrochloride of imino ether was added, and the mixture was further heated under reflux for 3 more hours.
Stirred for 0 minutes. After cooling, the mixture was filtered by suction, 100 ml of p-xylene was added to the filtrate, and the mixture was refluxed for 4 hours while distilling off ethanol. The reaction solution was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent, and crystallized from methanol to give 93.1 g.
(B-3) was obtained.

A solution of 40.7 g of the compound (B-3), 18.5 g of 2-methoxyaniline and 10 ml of p-xylene was stirred for 6 hours while heating under reflux. Ethyl acetate and water were added, and the mixture was separated. The organic layer was washed with diluted hydrochloric acid and saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of ethyl acetate and hexane as an eluent,
37.7 g of an oily compound (B-4) was obtained.

To a solution of 24.8 g of the compound (B-4) in 400 ml of methylene chloride was added dropwise 35 ml of a methylene chloride solution of 2.1 ml of bromine under ice cooling. After stirring for 30 minutes under ice-cooling, methylene chloride and water were added to carry out liquid separation, and the organic layer was washed with saturated saline. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product of compound (B-5).

5,5-dimethyloxazolidine-2,4
-Dione (15.5 g) and triethylamine (16.8 ml) were dissolved in N, N-dimethylacetamide (200 ml). At room temperature, a crude product of the compound (B-5) previously synthesized was dissolved in acetonitrile (40 ml). Then, the mixture was heated to 40 ° C. and stirred for 30 minutes. Ethyl acetate and water were added and the mixture was separated, and the organic layer was washed with a 0.1 N aqueous potassium hydroxide solution, diluted hydrochloric acid, and saturated saline. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography using a mixed solvent of acetone and hexane as an eluent, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 23.4 g of coupler (3).

Next, the yellow couplers represented by formulas (III) to (V) will be described.

[0121]

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[0122]

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[0123]

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In the above formula (III), X represents an organic residue necessary for forming a nitrogen-containing heterocyclic ring together with a nitrogen atom, Y represents an aromatic group or a heterocyclic group,
¹ represents a group which is released when the coupler represented by the general formula (III) reacts with an oxidized developing agent. In the general formula (IV), R ² represents a monovalent group excluding a hydrogen atom, and Q ¹ is a carbon atom and a 3- to 5-membered hydrocarbon ring or at least one selected from N, O, S, and P Represents a group of non-metallic atoms necessary for forming a 3- to 6-membered heterocyclic ring having one hetero atom in the ring. However, R ² may combine with Q ¹ to form a polycyclo ring having a bicyclo ring or more. Z ²
Has the same meaning as Z ¹ in formula (III). Y
² has the same meaning as Y ^{1 in} formula (III). In the general formula (V), D represents a tertiary alkyl group, and V ¹
Represents a fluorine atom, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group, an arylthio group or an alkyl group. Z ³ has the same meaning as Z ^{1 in} formula (III). W ¹ represents a group that can be substituted on the benzene ring, and t represents an integer of 0 to 4.

Among the yellow couplers represented by the general formula (III), preferred couplers are those represented by the following general formula (III)
-A).

[0126]

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In the general formula (III-A), Y ¹ and Z ¹ have the same meanings as those described in the general formula (III), and X ¹ represents> C (R ²³ ) (R ²⁴ ),> N - represents an organic residue required to form a nitrogen-containing heterocyclic ring together with, R ²³
And R ²⁴ each represent a hydrogen atom or a substituent. Among the couplers represented by the general formula (III-A), more preferred couplers are represented by the general formula (III-B).
In the general formula (III-B), R ²⁵ represents a hydrogen atom or a substituent, and R ²⁶ , R ²⁷ , and R ²⁸ represent a substituent.
Z ¹ has the same meaning as that described in the formula (III). m and n1 each represent an integer of 0-4. When m and n1 each represent an integer of 2 or more, R ²⁶ and R ²⁸ may be the same or different, or may combine with each other to form a condensed ring.

In the general formula (III-B), R ²⁵ ,
When R ²⁶ represents a substituent, examples of the substituent are the same as those in the general formula (III) when the group represented by A ¹ has a substituent. Preferred examples of R ²⁵ include a hydrogen atom, an alkyl group and an aryl group, and preferred examples of R ²⁶ include a halogen atom, an alkoxy group, an acylamino group, a carbamoyl group, an alkyl group, a sulfonamide group, a cyano group and a nitro group. Groups. m is preferably an integer of 0 to 2.

In the general formula (III-B), R ²⁷ ,
When R ²⁸ represents a substituent, examples of the substituent are the same as the substituent when the group represented by A ¹ in the general formula (III) has a substituent. Preferred examples of R ²⁷ are a halogen atom, an alkoxy group, an aryloxy group or an alkyl group, and preferred examples of R ²⁸ are the same as the preferred examples of the substituent represented by the general formula Y ¹ . n1 is preferably an integer of 0 to 2.

The yellow coupler represented by the general formula (IV) of the present invention is preferably represented by the following general formula (IV-A).

[0131]

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In the general formula (IV-A), R^TwoIs water
Q represents a monovalent substituent excluding an element atom,¹Is 3 with carbon
A 5-membered hydrocarbon ring or at least one N, S, O,
A 3- to 6-membered heterocyclic ring containing a heteroatom selected from P
Represents a group of nonmetallic atoms necessary to form a ring,²⁹Is
Hydrogen atom, halogen atom, alkoxy group, aryloxy
Group, alkylthio group, arylthio group, alkyl group or
Represents an amino group; ³⁰Can be substituted on the benzene ring
Z represents a group^TwoThe coupler reacts with the oxidized developer
Represents a group that leaves when R³⁰Examples of halogen
Atom, alkyl group, aryl group, alkoxy group, aryl
Ruoxy group, alkoxycarbonyl group, aryloxy
Carbonyl group, carbonamide group, sulfonamide group,
Carbamoyl group, sulfamoyl group, alkylsulfoni
Group, ureido group, sulfamoylamino group, alkoxy
Cicarbonylamino group, aryloxysulfonyl group,
Acyloxy, nitro, heterocyclic, cyano, acyl
Group, acyloxy group, alkylsulfonyloxy group,
Arylsulfonyloxy groups.

In the general formula (V), W ¹ represents a group that can be substituted on the benzene ring, and specifically means the same group as R ³⁰ in the general formula (IV-A). t is 1
Represents an integer of 4, and when t is 2 or more, a plurality of W ¹ may be the same or different. In the general formula (V), D is preferably a tertiary alkyl group having 4 to 8 carbon atoms, and particularly preferably a tert-butyl group. V
¹ is preferably an alkoxy group having 1 to 24 carbon atoms or an aryloxy group having 1 to 30 carbon atoms. The above alkoxy group and aryloxy group may have a suitable substituent, and preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, and a sulfonyl. Examples include an amino group and a sulfamoyl group. Particularly preferred are an alkoxy group and an aryloxy group substituted with a branched or linear alkyl group, an alkoxy group, an alkoxycarbonyl group, and an alkylsulfonyl group.
The couplers represented by formulas (III) to (V) may form a dimer or a multimer thereof. Specific examples of the compounds represented by formulas (III) to (V) of the present invention include compound examples of yellow couplers described in JP-A-7-159953.

Here, the silver halide color photographic light-sensitive material of the present invention will be described. In the present invention, a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a "light-sensitive material") comprises a support, a silver halide emulsion layer containing a yellow dye-forming coupler, and a magenta dye-forming coupler. And a silver halide emulsion layer containing at least one silver halide emulsion layer containing a cyan dye-forming coupler. In the present invention, the silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow color-forming layer, the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta color-forming layer, and containing the cyan dye-forming coupler. The silver halide emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow, magenta and cyan coloring layers, respectively, are sensitive to light in different wavelength ranges (for example, blue, green and red). It is preferable to have

The light-sensitive material of the present invention may have, if desired, a hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer in addition to the yellow, magenta, and cyan coloring layers. Good.

The silver halide light-sensitive material preferably used in the present invention will be described in detail below. The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded apexes and higher order faces). Octahedral crystal grains, or tabular grains having an aspect ratio of 2 or more in which at least 50% of the total projected area is composed of {100} planes or {111} planes.
The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, cubic or tabular grains having a {100} plane as a principal plane or tabular grains having a {111} plane as a principal plane are preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like are used. A silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a content of 90 mol% or more is preferable.
A silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a mol% or more is preferable. Among such silver halide emulsions, 0.01 to 0.50 mol%, more preferably 0.05 to 0.5 mol%, per mol of total silver is added to the shell portion of silver halide grains.
Those having a silver iodochloride phase of from .about.0.40 mol% are also preferred because they provide high sensitivity and are excellent in high illuminance exposure suitability. Alternatively, those having a silver bromide localized phase of 0.2 to 5 mol%, more preferably 0.5 to 3 mol%, based on the total silver mole on the surface of silver halide grains can provide high sensitivity, and It is particularly preferable because photographic performance can be stabilized.

The emulsion of the present invention preferably contains silver iodide. For the introduction of iodide ions, an iodide salt solution may be added alone, or an iodide salt solution may be added together with the addition of a silver salt solution and a high chloride salt solution. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt, such as an alkali or alkaline earth iodide salt. Alternatively, iodide can be introduced by cleaving iodide ions from organic molecules described in US Pat. No. 5,389,508. Further, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be performed intensively at one time of grain formation, or may be performed over a certain period of time. The position at which iodide ions are introduced into a high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fogging. As the iodide ion is introduced into the emulsion grains, the increase in sensitivity is smaller. Therefore, the addition of the iodide salt solution is preferably effected from outside 50% of the particle volume, more preferably from outside 70%, most preferably from outside 80%. Also, the addition of the iodide salt solution is preferably terminated within 98% of the particle volume, most preferably within 96% of the particle volume. When the addition of the iodide salt solution is finished slightly inside the grain surface, an emulsion with higher sensitivity and lower fogging can be obtained.

The distribution of iodide ion concentration in the depth direction in the grain is determined by etching / TOF-SIMS (Timeo
f Flight (Secondary Ion
Mass spectrometry) method, for example, TRIFII type TOF-SI manufactured by Phi Evans.
It can be measured using MS. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Book” edited by the Surface Science Society of Japan.
Secondary ion mass spectrometry "published by Maruzen Co., Ltd. (issued in 1999). Etching / TOF-SIMS
When the emulsion grains are analyzed by the method, even if the addition of the iodide salt solution is completed inside the grains, it can be analyzed that the iodide ions are seeping out toward the grain surface. When the emulsion of the present invention contains silver iodide, analysis by etching / TOF-SIMS shows that the iodide ion has a maximum concentration on the grain surface and the iodide ion concentration is attenuated inward. Is preferred.

The emulsion in the light-sensitive material of the present invention preferably has a silver bromide localized layer. When the emulsion of the present invention contains a silver bromide localized phase, it is preferable to form a silver bromide localized phase having a silver bromide content of at least 10 mol% or more on the grain surface by epitaxial growth. Further, it is preferable to have an outermost shell portion having a silver bromide content of 1 mol% or more near the surface layer. The silver bromide content of the silver bromide localized phase is preferably in the range of 1 to 80 mol%, and most preferably in the range of 5 to 70 mol%. The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 30 mol% of the total silver constituting the silver halide grains in the invention, and is preferably composed of silver in an amount of 0.3 to 20 mol%. More preferably, it is constituted. The silver bromide localized phase preferably contains a group VIII metal complex ion such as iridium ion. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

In the present invention, it is preferable to add a transition metal ion in the process of forming and / or growing the silver halide grains, and to incorporate the metal ions inside and / or on the surface of the silver halide grains. Transition metal ions are preferred as the metal ions used, and among them, iron, ruthenium, iridium, osmium, lead, cadmium, or
Preferably it is zinc. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When using an inorganic compound as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion Nitrosyl ions are preferably used, and the above iron, ruthenium, iridium, osmium,
It is also preferable to coordinate with any metal ion of lead, cadmium or zinc, and it is also preferable to use plural kinds of ligands in one complex molecule.

Among them, the silver halide emulsion of the present invention includes:
It is particularly preferable to have an iridium ion having at least one organic ligand for the purpose of improving high-illuminance reciprocity failure. When an organic compound is used as a ligand, the same applies to the case of other transition metals, but preferred organic compounds include a chain compound having 5 or less carbon atoms in a main chain, and / or 5
And a 6-membered or 6-membered heterocyclic compound. Further preferred organic compounds include a nitrogen atom in the molecule,
A compound having a phosphorus atom, an oxygen atom, or a sulfur atom as a coordinating atom to a metal, most preferably furan,
Thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, pyrazine. preferable. Among them, preferred ligands for iridium ions include 5-thiazole ligands.
Methylthiazole is particularly preferably used.

The combination of a metal ion and a ligand is preferably a combination of an iron ion or ruthenium ion and a cyanide ion. In these compounds, the cyanide ion preferably occupies the majority of the coordination number to the central metal iron or ruthenium,
Preferably, the remaining coordination sites are occupied by thiocyan, ammonia, water, nitrosyl ions, dimethyl sulfoxide, pyridine, pyrazine, or 4,4 (-bipyridine. Most preferably, the six coordination sites of the central metal are All of them are occupied by cyanide ions to form hexacyanoiron complex or hexacyanoruthenium complex.The complex having these cyanide ions as ligands is 1 × 10 ⁻⁸ mol per mol of silver during grain formation. 1 × 10
It is preferable to add ^-2 mol, from 1 × 10 ^-6 mol to 5
It is most preferable to add × 10 ^-4 mol. Further, as the iridium ion, not only an organic ligand but also a fluoride ion, a chloride ion, a bromide ion, and an iodide ion, particularly, a chloride ion or a bromide ion is preferably used. As the iridium complex, the following specific compounds can be used other than those having the above-mentioned organic ligand. That is, [IrCl ₆ ] ³⁻ , [IrCl ₆ ] ²⁻ , [Ir
Cl ₅ (H ₂ O)] ²⁻ , [IrCl ₅ (H ₂ O)] ⁻ , [I
rCl ₄ (H ₂ O) ₂ ] ⁻ , [IrCl ₄ (H ₂ O) ₂ ] ⁰ ,
[IrCl ₃ (H ₂ O) ₃ ] ³ , [IrCl ₃ (H
₂ O) ₃ ] ⁺ , [IrBr ₆ ] ³⁻ , [IrBr ₆ ] ²⁻ , [I
rBr ₅ (H ₂ O)] ²⁻ , [IrBr ₅ (H ₂ O)] ⁻ ,
[IrBr ₄ (H ₂ O) ₂ ] ⁻ , [IrBr ₄ (H
^{_{2 O) 2] 0, [}} IrBr 3 (H 2 O) 3] 0, and [IRB
r ₃ (H ₂ O) ₃ ] ⁺ . These iridium complexes are
1 × 10 ⁻¹⁰ mol to 1 × per mol of silver during grain formation
It is preferably added in an amount of 10 ^-3 mol, and most preferably 1 × 10 ^-8 mol to 1 × 10 ^-5 mol. When ruthenium and osmium are used as the central metal, it is also preferable to use a nitrosyl ion, a thionitrosyl ion, or a water molecule and a chloride ion together as a ligand. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes, 1 × 10 from 1 × 10 ^-10 mol per mol of silver in the grain formation ^- preferably added ⁶ mol, more preferably 1 × 10 ^-9 mol from 1 × 1
0 ^-6 mole that is added.

In the present invention, the above-mentioned complex is directly added to a reaction solution at the time of forming silver halide grains, or is added to an aqueous halide solution for forming silver halide grains, or to another solution. It is preferable to incorporate into silver halide grains by adding it to a grain forming reaction solution. Further, it is also preferable to incorporate these methods into silver halide grains in combination.

When these complexes are incorporated into silver halide grains, it is preferable that they are uniformly present in the grains. However, JP-A-4-208936 and JP-A-2-12524.
No. 5 and JP-A-3-18837, it is also preferable that the complex be present only in the particle surface layer, and that the complex be present only inside the particle and a layer containing no complex be added to the particle surface. It is also preferable to do so. Further, as disclosed in U.S. Patent Nos. 5,252,451 and 5,256,530, it is also possible to physically ripen the complex with fine particles having the particles incorporated therein to modify the surface phase of the particles. preferable. Further, these methods may be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the complex is contained, and a silver chloride layer, a silver chlorobromide layer,
It is also preferred that any of the silver bromide, silver iodochloride and silver iodobromide layers contain a complex.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 0.01 μm to 2 μm is preferred. The particle size distribution is represented by a coefficient of variation (standard deviation of particle size distribution divided by average particle size) 2.
0% or less, preferably 15% or less, more preferably 10% or less.
% Or less, so-called monodispersed one. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide emulsion used in the present invention may contain various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
What is described on page 39-page 72 of 15272 is preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

In the present invention, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-327 are disclosed in JP-A-11-109576 in order to enhance the storage stability of the silver halide emulsion.
No. 094, a cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group (particularly those represented by the general formula (S1); 0071 can be incorporated in the specification of the present application.) And sulfo-substituted catechols and hydroquinones (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,2) described in JP-A-11-143011. 5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5
-Dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof),
General formula (I) described in JP-A-11-102045
The water-soluble reducing agents represented by-(III) are also preferably used in the present invention.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of the spectral sensitizing dye used for spectral sensitization in the red region include F.I. M. Heterocycl by Harmer
ic compounds-Cyanine dyes
and related compounds (J
ohn Wiley & Sons [New Yor
k, London], published in 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A-Hei 3
The spectral sensitizing dyes described in JP-A-123340 are very preferable from the viewpoint of stability, strength of adsorption, temperature dependency of exposure, and the like.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215272, No. 1
Those described in the lower right column of page 8 to the upper right column of page 22 are preferably used. Among them, it is particularly preferable that the metal is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed using a laser beam or the like can be further reduced.

To perform gold sensitization on the silver halide emulsion used in the present invention, various inorganic gold compounds, gold (I) complexes having an inorganic ligand, and gold (I) compounds having an organic ligand can be used. Can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and examples of the gold (I) complex having an inorganic ligand include a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and a gold (I) 3 dithiosulfate. It is preferable to use a compound such as sodium dithiosulfate compound such as sodium.

Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoion heterocycles described in JP-A-4-267249, for example, gold (I) bis (1,4) borate tetrafluoroborate 4,5-trimethyl-1,2,4-triazolium-3-thiolate), JP-A-11-218
No. 870, for example, potassium bis (1- [3- (2-sulfonatobenzamido) phenyl] -5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, Kaihei 4-2
A gold (I) compound coordinated with a nitrogen compound anion described in Japanese Patent No. 68550, for example, bis (1-methylhydantoinato) gold (I) sodium salt tetrahydrate can be used. Also, gold (I) thiolate compounds described in U.S. Pat. Nos. 3,503,749 and described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554. Nos. 5,620,841, 5,9121,112 and 562
Compounds described in the specifications of JP0841, JP5939245, and JP5912111 can also be used. The addition amount of these compounds may vary widely depending on the case, but may be from 5 × 10 ^{−7 to} 5 × 10 ⁻⁷ per mol of silver halide.
× 10 ^-3 mol, preferably 5 × 10 ^-6 ~5 × 10 ^-4 mol.

It is also possible to use colloidal gold sulfide, and its production method is described in Research Disclosure, 3715.
4), Solid State Ionics (Solid)
State Ionics) Vol. 79, pp. 60-66,
1995, Compt. Rend. Hebt. Se
ances Acad. Sci. Sect. B-263
Vol., Page 1328, published in 1966. Various sizes of colloidal gold sulfide can be used, and those having a particle size of 50 nm or less can also be used. Although the addition amount can vary widely depending on the case, it is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol as gold atom per mol of silver halide. is there. In the present invention, gold sensitization may be further combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound.

The light-sensitive material of the present invention contains a hydrophilic colloid layer in order to prevent irradiation or halation or to improve safelight safety and the like.
337490A2, pages 27-76,
Dyes that can be decolorized by treatment (including oxonol dyes,
It is preferable to add a cyanine dye). Furthermore, dyes described in European Patent EP 0819977 are preferably added to the present invention. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Dyes that can be used without deteriorating color separation are described in JP-A-5-127324 and JP-A-5-12773.
Water-soluble dyes described in JP-A Nos. 25 and 5-216185 are preferred.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by a treatment in combination with a water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below (on the side of the support) the emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is within the wavelength range used for exposure (400 nm in normal printer exposure).
The optical density value at the wavelength having the highest optical density in the visible light region of 700 to 700 nm, or the wavelength of the scanning exposure light source used in the case of scanning exposure) is preferably 0.2 or more and 3.0 or less. It is more preferably from 5 to 2.5, particularly preferably from 0.8 to 2.0.

In order to form the colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244
As disclosed in Japanese Unexamined Patent Publication No. 3-7931, JP-A-3-7931, the dyes described in the upper right column of page 3 to the lower right column of page 11 are hydrophilic in the state of solid fine particle dispersion. A method in which the dye is contained in a colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, a method in which the dye is adsorbed on fine particles such as silver halide and fixed in the layer,
No. 9544, which uses colloidal silver. As a method of dispersing the fine powder of the dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in No. 2-308244, pages 4-13. Also, for example, a method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. The preparation of colloidal silver as a light absorber is described in US Pat.
No. 8,601 and 3,459,563. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

The color photographic light-sensitive material of the present invention may have at least one yellow color-forming silver halide emulsion layer, at least one magenta color-forming silver halide emulsion layer, and at least one cyan color-forming silver halide emulsion layer. Preferably, these silver halide emulsion layers are generally a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer in the order of distance from the support.

However, a different layer configuration may be adopted. The yellow-coupler-containing silver halide emulsion layer may be arranged at any position on the support. However, when the yellow coupler-containing layer contains silver halide tabular grains, the silver halide emulsion layer containing a magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. Further, from the viewpoint of reduction of Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of the other silver halide emulsion layers, and from the viewpoint of reduction of photofading, the cyan coupler-containing silver halide emulsion layer is preferred. Is preferably the lowermost layer. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, Japanese Patent Application Laid-Open No. 4-75055, 9
Nos. 114035 and 10-246940,
As described in U.S. Pat. No. 5,576,159, a coupler layer containing no silver halide emulsion is preferably provided adjacent to the silver halide emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangements, etc.) used in the present invention, and the processing methods and processing additions applied for processing this light-sensitive material As the agent, JP-A-62-21
No. 5,272, JP-A-2-33144 and those described in European Patent EP 0,355,660 A2, particularly those described in European Patent EP 0,355,660 A2 are preferably used. Can be Further, JP-A-5-34889 and JP-A-4-359249,
4-313375, 4-270344, 5-
No. 66527, No. 4-34548, No. 4-14543
No. 3, 2-854, 1-158431, 2-
No. 90145, No. 3-194439, No. 2-9364
Preferred are silver halide color photographic light-sensitive materials described in JP-A No. 1-20, European Patent Publication No. 0520457A2, and the like, and a processing method therefor.

In particular, in the present invention, the above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of silver halide emulsion or antifoggant , Chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (stain inhibitors and anti-fading agents), Regarding the dye (colored layer), the kind of gelatin, the layer structure of the photosensitive material, the coating pH of the photosensitive material, and the like, those described in each part of the patent shown in the following table can be particularly preferably applied.

[0163]

[Table 1]

The cyan, magenta and yellow couplers used in the present invention are described in
No.-215272, page 91, upper right column, lines 4 to 121
Line 6 in the upper left column of the page, line 14 in the upper right column of page 3 to line 18 in the upper left column of page 18, and line 6 in the upper right column of page 30 to line 11 in the lower right column of JP-A-2-33144. EP0355,660
From page 15, lines 15 to 27, page 5, line 30 to page 28, page 45, lines 29 to 31, page 47, line 23 to page 63, page 50 of the specification of A2 The couplers described are also useful. Further, the present invention relates to the compounds of the general formulas (II) and (III) described in WO-98 / 33760, and JP-A-10-221825.
It is preferable to add a compound represented by the general formula (D) described in Japanese Unexamined Patent Publication (Kokai) No. H10-205163.

As the cyan dye-forming coupler (hereinafter sometimes simply referred to as "cyan coupler") usable in the present invention, a pyrrolotriazole coupler is preferably used. A coupler represented by I) or (II);
The couplers represented by the general formula (I) in JP-A-347960 and the couplers exemplified in these patents are particularly preferred. Phenolic and naphthol cyan couplers are also preferable.
A cyan coupler represented by the general formula (ADF) described in JP-A-3297 is preferred. Other cyan couplers include those described in European Patent EP 0 488 248 and EP
Pyrroazole type cyan couplers described in JP-A-0491197 A1, 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, U.S. Pat. Nos. 4,873,183 and 4,916, 051
Pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in JP-A No.
Nos. 71185, 8-31360, 8-3390
Also preferred are pyrazoloazole-type cyan couplers having a carbamoyl group at the 6-position described in JP-A-60-160.

In addition to the diphenylimidazole-based cyan couplers described in JP-A-2-33144, 3-hydroxypyridine-based cyan couplers described in European Patent No. EP 0333185A2 (including couplers listed as specific examples) (42) 4-equivalent coupler obtained by giving a chlorine leaving group to a 2-equivalent coupler, and couplers (6) and (9) are particularly preferred) and JP-A-64-322.
No. 60, the cyclic active methylene cyan coupler (among others, coupler examples 3, which are listed as specific examples,
8, 34 are particularly preferred), EP 0 422 622
A pyrrolopyrazole-type cyan coupler described in 6A1 and a pyrroleimidazole-type cyan coupler described in European Patent EP 0484909 can also be used.

Of these cyan couplers, pyrroloazole-based cyan couplers represented by the general formula (I) described in JP-A-11-282138 are particularly preferred. Is applied to the present application as it is, including the exemplified cyan couplers (1) to (47), and is preferably incorporated as a part of the specification of the present application.

Examples of the magenta dye-forming coupler (hereinafter sometimes simply referred to as "magenta coupler") used in the present invention include 5-pyrazolone-based magenta couplers and pyramids described in the publicly known documents in the above table. Zoloazole-based magenta couplers are used. Among them, a secondary or tertiary alkyl group such as described in JP-A-61-65245 has a pyrazolotriazole ring as described in JP-A-61-65245. Pyrazolotriazole couplers directly linked to the 3- or 6-position, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group as described in JP-A No. 262,086 and an alkoxy group at the 6-position as described in European Patent Nos. 226,849A and 294,785A. It is preferable to use a pyrazoloazole coupler having an aryloxy group. Particularly, a magenta coupler is disclosed in
Pyrazoloazole couplers represented by the general formula (MI) described in JP-A-1222984 are preferred, and paragraphs 0009 to 0026 of the patent are applied to the present application as they are,
Incorporated as part of the description of the present application. In addition, pyrazoloazole couplers having a sterically hindered group at both the 3-position and the 6-position described in the specifications of European Patent Nos. 854384 and 844640 are also preferably used.

As the yellow dye-forming coupler (hereinafter sometimes simply referred to as “yellow coupler”), in addition to the compounds described in the above table, the couplers described in European Patent EP 0 474 969 A1 can be used. Acylacetamide-type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group, malondianilide-type yellow couplers having a cyclic structure described in EP 0 482 552 A1, European Patent No. 953870 A1,
Pyrrole-2 described in the respective specifications of Nos. 953831A1, 955872A1, 953873A1, 953874A1 and 953875A1.
Or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide-based couplers, US Pat.
Acylacetamide type yellow couplers having a dioxane structure described in JP-A-8,599 are preferably used. Among them, it is particularly preferable to use an acylacetamide-type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide-type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention can be prepared by loading a loadable latex polymer (for example, US Pat. No. 4,20
3,716) or dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, column 7 to column 7.
Homopolymers or copolymers described in column 15 and pages 12 to 30 of WO 88/00723 can be mentioned. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferred from the viewpoint of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular-weight redox compounds described in JP-A-5-333501, WO98 /
No. 33760, U.S. Pat. No. 4,923,787, etc., phenidone and hydrazine compounds described in
-249637, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, when increasing the pH of the developer to speed up the development, German Patent No. 191878686A1 and European Patent No. 8396 can be used.
No. 23A1, EP 842975 A1, German Patent 198 06 846 A1 and French Patent No. 2760460.
It is also preferable to use the redox compounds described in the specifications of A1.

In the present invention, as the ultraviolet absorber,
It is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient. For example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer or / and the non-photosensitive. For example, JP
Nos. -3335 and 55-152776, JP-A-5-1
97074, 5-232630, 5-3072
No. 32, No. 6-211813, No. 8-53427,
8-234364, 8-239368, 9-
No. 31067, No. 10-1159898, No. 10-14
Nos. 7577 and 10-182621, German Patent No. 19739797A, and European Patent No. 711804A.
And the compounds described in the specifications of Japanese Patent Application Laid-Open No. H8-501291 and the like.

As a binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. As a preferred gelatin, heavy metals contained as impurities such as iron, copper, zinc, and manganese are preferably 5 ppm.
Or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive 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.

In the present invention, in order to prevent various fungi and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / antifungal agent as described in JP-A-63-271247 is used. It is preferably added. Further, the coating pH of the photosensitive material is preferably from 4.0 to 7.0, and more preferably from 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material in terms of improving the coating stability of the light-sensitive material, preventing generation of static electricity, adjusting the amount of charge, and the like. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. As the surfactant used in the present invention, a fluorine atom-containing surfactant is preferable. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants to be added to the photosensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. It is 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The photosensitive material of the present invention can form an image by an exposure step of irradiating light in accordance with image information and a developing step of developing the illuminated photosensitive material. The light-sensitive material of the present invention can be used for a cathode ray (CR) besides being used in a printing system using a normal negative printer.
It is also suitable for a scanning exposure method using T). 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. For the cathode ray tube used for image exposure, various luminous bodies that emit light in a spectral region are used as necessary. 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.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray is exposed. A plurality of color image signals may be input to the tube to emit light from the tube surface. 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 improving image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic emission light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined.
A digital scanning exposure method using monochromatic high-density light is preferably used. 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.

In the case of using such a scanning exposure light source,
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 to be 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.

The silver halide color photographic light-sensitive material of the present invention can be preferably used in combination with an exposure and development system described in the following known materials. The developing system includes an automatic printing and developing system described in JP-A-10-333253,
JP-A-10-20206, a photosensitive material conveying apparatus, a recording system including an image reading apparatus described in JP-A-11-215312, a color system described in JP-A-11-88619 and JP-A-10-202950. Exposure system using image recording method, Japanese Patent Application Laid-Open No. H10-210206
A digital photo print system including a remote diagnosis system described in Japanese Patent Application Laid-Open Publication No. 10-159187, and a photo print system including an image recording device described in Japanese Patent Application No. 10-159187.

The preferred scanning exposure method applicable to the present invention is described in detail in the patents listed in the above table.

When the photosensitive material of the present invention is exposed to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. In the present invention, European Patent EP 0789270A
As described in the specifications of JP-A No. 1 and EP 0 789 480 A1, a yellow microdot pattern may be pre-exposed beforehand and image copy control may be performed before image information is added.

The processing of the light-sensitive material of the present invention is described in
No. 207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column, line 17 to page 18, lower right column, line 20 The processing materials and processing methods described above are preferably applicable. As the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

Typically, a minilab “PP350” manufactured by Fuji Photo Film Co., Ltd. and CP48S Chemical as a processing agent are used for color development processing for defining the hue and white background in the present invention. There is a method in which imagewise exposure is performed from a film, and processing is performed using a processing solution that has been subjected to continuous processing until the volume of the color developing replenisher becomes twice the capacity of the color developing tank.

As the chemicals of the treating agent, CP45X and CP47L manufactured by Fuji Photo Film Co., Ltd., RA-100 and RA-4 manufactured by Eastman Kodak Co., Ltd. can be applied.

A known or commercially available diaminostilbene-based fluorescent whitening agent can be used in the color developing solution. As the known bistriazinyl diaminostilbene disulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625 or JP-A-10-104809 are preferable. Commercially available compounds are described, for example, in "Dyeing Note", 19th edition (Shirosensha), p. 165-P.
168, and among the products described herein, Blankophor UWliq, Bla
nkophor REU or Hakkol BRK is preferred. The following compounds can also be preferably used.

In the present invention, in particular, Br
It is preferable to contain a halide ion such as I or I from the viewpoint of preventing image unevenness occurring when entering the bleach-fixing solution from the developing solution, and having excellent fixing ability and preventing contamination of uncolored areas with silver sulfide on a white background. . In the bleach-fixing solution of the present invention, the bromide ion concentration is preferably from 0 to 1.0 mol / L, more preferably from 0.01 to 0.3 mol, for the purpose of preventing coloring contamination by residual silver and achieving the object of the present invention. / L is preferable. For the same purpose, it may contain an iodide ion concentration, and a preferable iodide ion concentration is 0 to 0.1 mol / mol.
L, more preferably 0.001 to 0.01 mol /
L.

The present invention is preferably applied to light-sensitive materials having suitability for rapid processing. When rapid processing is performed, the color development time is preferably 60 seconds or less, more preferably 50 seconds or less, 6 seconds or more, and still more preferably 30 seconds or less.
Seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less, and 6 seconds or more.
More preferably, it is 30 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less and 6 seconds or more. The color development 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 submerged time) and the time when the photosensitive material leaves the color developing solution and bleach in the next processing step The sum of the time during which the paper is conveyed through the air toward the fixing bath (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 in-solution time).

As a method for developing the photosensitive material of the present invention after exposure, a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkaline solution containing a developing agent in the photosensitive material and containing no developing agent is used. In addition to a wet method such as a method of developing with an activator liquid, a thermal developing method without using a processing liquid can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because the developing agent is not contained in the processing solution, so that the processing solution can be easily managed and handled, and the load at the time of processing the waste solution is small. 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
And hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193 are preferable.

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 Laid-Open
An image forming method using an activator liquid containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, desilvering processing is usually performed.However, in an image amplification processing method using a low-silver amount photosensitive material, desilvering processing is omitted, and simple processing such as washing or stabilization processing is performed. Method can be performed. In the method of reading image information from a photosensitive material with a scanner or the like, even when a photosensitive material having a high silver amount such as a photosensitive material for photography is used,
A processing mode that does not require desilvering processing can be adopted.

The activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention may be any of known materials and processing methods. Preferably, Research Disclosure Item 3654
4 (September 1994), pages 536 to 541, and JP-A-8-234388 can be used.

The effects of the present invention can be obtained in a color light-sensitive material for digital direct color proof using a silver halide color light-sensitive material (hereinafter referred to as a light-sensitive material for proof), a digital direct color proof system, and an image forming method thereof. Applicable. The proofing light-sensitive material is generally a silver halide color light-sensitive material having a silver halide light-sensitive layer that forms at least a yellow dye, a magenta dye, and a cyan dye on a support. Based on the halftone image information, exposure is performed using three or more light source units of different wavelengths to form an area-modulated image. A fourth photosensitive layer may be provided for the purpose of achieving compatibility between black (chromaticity and Dmax) and solid monochrome (chromaticity and Dmax) (improvement of color reproducibility) and discrimination of black plate. In this case, three or four light sources having different wavelengths are used as exposure light sources. The exposure light source often has a plurality (preferably eight or more) of light source units of each color, and it is possible to use an LED, LD, or other device. The exposure light source is blue,
It is possible to use a light source of any wavelength in the visible and infrared regions such as green and red, and any combination of these is also possible.

The system automatically takes out the photosensitive material from the magazine, cuts it into a sheet, winds it around the outer drum for exposure, rotates it, and converts the halftone image information into three or more light sources of different wavelengths. 8 units each
After recording a halftone dot image of area gradation with dots of 2,000 dpi or more by performing scanning exposure using an array light source for exposure combined with more than one, the exposed color photosensitive material is automatically processed by an automatic developing machine. Development processing,
A direct digital color proof system and an image forming method for outputting a halftone color proof image of A3 size or more (a B1 size system is also possible if necessary) are preferable, but the present invention is applied to color proof. This is not limited to the proofing photosensitive material, system and image forming described above. 2400
A resolution of not less than dpi, an exposure beam diameter of one dot being 0.5 μm or more and 50 μm in half width of light intensity, and an exposure time of at least one exposure light source exposing one dot is 10 ⁻⁸ seconds or more and 10 ^{−. 2} seconds or less, the rotation speed of the outer drum is 100 rpm or more and 4000 rpm or less, and the wavelength of at least one exposure light source is 700
nm or more, the exposure amount of at least one exposure light source is two or more steps, the exposure energy of the longest exposure light source is 1.1 times or more of other exposure energy, Is peeled off from the outer drum and transported so that the exposed surface faces downward, and transported so that the emulsion surface turns downward in the color developing solution, bleach-fixing solution and washing bath of the automatic developing machine. That the time from the end of exposure of the photosensitive material to the tip of the color developing solution is 20 seconds or more and 3 minutes or less, and from the end of the exposure, the top of the exposed photosensitive material in the transport direction is changed to the color developing solution. The difference between the time required to enter the color developing solution and the time required to enter the color developing solution at the rear end in the transport direction is 1 minute or more and within 10 minutes.
Not more than 100 seconds and the difference in processing time is not more than 30 seconds; the capacity of the processing tank for the color developing solution and the bleach-fixing solution is not less than 8 L and not more than 20 L; 5 tanks or less, supplied by an integrated kit with color development and bleach-fix solution,
And replenishment rate of the color color development per photosensitive material 1 m ^2,
In 50ml least 300ml or less, and bleach replenishment rate of the fixing solution is not more than the photosensitive material 1 m ² per 30ml or 250 ml, and the replenishing amount of washing water is more than 50ml the entire washing water 1
2,000 ml or less, and automatically replenished by automatically detecting the area of the photosensitive material to be processed, having an automatic developing machine having a mechanism for automatically washing at least one aerial turn transport roller with water, At least one guide plate that is in contact with the emulsion surface uses Teflon (registered trademark) material. Write a specific image during proof printing or another output print, and measure the image density or chromaticity. Or, a calibration function for compensating for a change in sensitivity due to a lot-to-lot difference of a photosensitive material, a change over time, a change in a temperature and a humidity processing liquid at the time of exposure by visually comparing with a target image, and a Dmax of the photosensitive material.
Having a function of performing calibration with a continuous tone image having a lower density than that of the above, and having a capability of performing calibration by visual judgment or density measurement or color difference colorimetry of a flat screen image of 20% to 80%. When the photosensitive material of the same size is supplied in the magazine and the photosensitive material of one magazine runs out, the photosensitive material of the other magazine is automatically supplied. It is supplied at the same time and automatically switches the size. The winding length of one photosensitive material is 30m or more and 100m or less. It takes 10 seconds or more to draw out the photosensitive material from the magazine and start exposure after the drawing is completed. Within 100 seconds, the black plate image is formed from yellow, magenta, and cyan. The difference in dot gain for each color to be formed is 5
%, The total thickness of the support used for the photosensitive material is 50 μm to 150 μm, and the thickness of the surface laminate of the support used for the photosensitive material is 10 μm to 5 μm.
0 μm, the thickness of the backing laminate of the support used for the photosensitive material is 10 μm or more and 50 μm, and 0.1 μm is applied to the surface of the photosensitive material opposite to the surface on which the photosensitive layer is provided.
Having a back layer of 1 μm or more and 30 μm or less, and a total thickness of the photosensitive material-containing surface of the photosensitive material of 3 μm
Not less than 30 μm, and the difference between the total film thickness of the surface having photosensitive silver halide and the total film thickness of the back surface of the photosensitive material is 1
0 μm or less, the photosensitive silver halide used in the photosensitive material has a silver chloride content of 90% or more, and the photosensitive material is processed into a roll with the emulsion surface facing outward. Used, the peak wavelength of at least one layer of the maximum spectral sensitivity is 700 nm or more, and cut (cut) into a sheet by a squeeze roller.
A direct digital color proof system, an image forming method, and a proofing light-sensitive material having one or more characteristics selected from the characteristics of automatically winding the obtained light-sensitive material around a drum can also be applied to the effects of the present invention. Is possible.

The spot shape is circular, elliptical,
Any of rectangular shapes may be used. The light amount distribution of one spot may be a Gaussian distribution, or may be a trapezoid with a relatively constant intensity. In particular, one light source may be used, but an array in which a plurality of light sources are arranged is preferable.

Regarding an exposure method and an image forming method using a laser, an LED, or an array thereof as a light source,
JP-A-10-142752, JP-A-11-24231
5, JP-A-2000-147723, JP-A-2000-147723
246958, JP-A-2000-354174, JP-A-2000-206654, European Patent EP-1
It is described in detail in, for example, Japanese Patent No. 048976A and can be preferably used in the present invention.

More specifically, it is as follows. A preferred embodiment of the exposure light source is described in JP-A-2000-147.
No. 723, JP-A-2000-20
No. 6,654, paragraphs 0053, 0059-006.
1, 0064 to 0067, and are preferably applied to the present invention. The shape of the beam of the exposure light source and a preferable mode of the array of the exposure light source are described in JP-A-2000-147.
No. 723, paragraphs 0022 to 0023 and JP-A-20
Nos. 00-206654, Paragraph Nos. 0025-003
0, and is preferably applied to the present invention. In order to improve the productivity at the time of exposure, a method of winding a photosensitive material around a drum and performing scanning exposure is excellent. A preferred embodiment of the light source is an LED array described in JP-A-2000-246958, and the image recording apparatus described in JP-A-2000-246958 having the LED array is preferably applied according to the present invention. Regarding a method of winding around a drum, see JP-A-2000-206654.
No. 0057-0058, 0062-00
63, and is also preferably applied to the present invention. It is also preferable to perform calibration by the method described in European Patent EP 1048976A to stably form an image, and the present invention is applied to the present invention. Japanese Patent Application Laid-Open No. 2000-35 discloses a method of converting digital image data into image data for exposure and an exposure processing method, which are preferably employed when producing a color proof in the present invention.
Nos. 4174 and JP-A-2000-147723 can be used as they are. More specifically, FIG. 1 described in JP-A-2000-354174.
1. The color proof production apparatus of FIG.
4, FIG. 4, paragraph numbers 0011 to 0021, the first sentence of paragraph number 0022, and paragraph numbers 0034 to 005.
The description portion 7 is preferably incorporated as a part of the specification of the present invention.

[0197]

The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 <Preparation of Emulsion A for Blue Sensitive Layer of the Present Invention> 46.3 ml of a 10% solution of NaCl was added to 1.06 liter of deionized distilled water containing 5.7% by mass of deionized gelatin. In addition, H ₂
46.4 ml of SO ₄ (1N) was added, and 0.012 g of the compound represented by (X) was further added. After the solution temperature was adjusted to 60 ° C., 0.1 mol of silver nitrate was immediately added with high-speed stirring. 0.1 mol of NaCl was added into the reaction vessel over 10 minutes. Subsequently, a 1.5 mol silver nitrate and NaCl solution were added by a flow rate acceleration method over 60 minutes so that the final addition rate was four times the initial addition rate. Next, a 0.2 mol% silver nitrate and NaCl solution was added at a constant addition rate over 6 minutes. At this time, Na
To the Cl solution, K ₃ IrCl ₅ (H ₂ O) was added in an amount of 5 × 10 ⁻⁷ mol based on the total silver amount, and iridium aquoide was doped into the grains. Further, 0.2 mol of silver nitrate, 0.18 mol of NaCl and 0.02 mol of KBr solution were added over 6 minutes. At this time, K ₄ corresponding to 0.5 × 10 ⁻⁵ mol with respect to the total silver amount was contained in the aqueous halogen solution.
Ru (CN) ₆ and K ₄ Fe (CN) ₆ were each dissolved and added to silver halide grains. During the final grain growth, the KI corresponding to 0.001 mol with respect to the total silver was measured.
The aqueous solution was added to the reaction vessel over 1 minute. The start of the addition was started when 93% of the total grain formation was completed. Thereafter, at 40 ° C., a compound (Y) precipitant was added,
The pH was adjusted to around 3.5 and desalting and washing were performed.

[0199]

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Deionized gelatin, an aqueous solution of NaCl, and an aqueous solution of NaOH were added to the emulsion after washing with demineralized water.
And adjusted to pAg 7.6 and pH 5.6. In this way, a halogen composition comprising 98.9 mol of silver chloride, 1 mol% of silver bromide, and 0.1 mol% of silver iodide, having an average side length of 0.70 μm and a variation coefficient of side length of 8%. Gelatin containing silver cubic particles was obtained.

While maintaining the above emulsion grains at 60 ° C., each of spectral sensitizing dyes 1 and 2 was added in an amount of 2.5 × 10 ⁻⁴ mol / Ag
Mole and 2.0 × 10 ^-4 mole / Ag mole. Furthermore, thiosulfonic acid compound-1 was added at 1 × 10 ⁻⁵ mol / A.
g of mol, and a fine grain emulsion doped with iridium hexachloride at 90 mol% of silver bromide and 10 mol% of silver chloride having an average grain diameter of 0.05 μm was added, followed by ripening for 10 minutes. Further, fine grains of 40 mol% of silver bromide having an average particle diameter of 0.05 μm and 60 mol% of silver chloride were added and ripened for 10 minutes. The fine particles dissolve, whereby the silver bromide content of the host cubic particles is:
Increased to 1.3 moles. In addition, iridium hexachloride is 1 ×
10 ^-7 mol / Ag mol was doped.

Subsequently, 1 × 10 ⁻⁵ sodium thiosulfate
Mol / Ag mol and 2 × 10 ^-5 mol of gold sensitizer-1 were added. Immediately, the temperature was raised to 60 ° C., aged for 40 minutes, and then lowered to 50 ° C. Immediately after cooling,
Each of mercapto compound-1 and 6 × 10 ^-4 mol /
It was added so as to be Ag mole. After aging for 10 minutes, an aqueous KBr solution was added to the silver in an amount of 0.008 mol, and after aging for 10 minutes, the temperature was lowered and stored. Thus, a high-sensitivity side emulsion A-1 for a blue-sensitive layer was prepared. Except for the above emulsion preparation method and the temperature during grain formation, the average side length was 0.55 μm and the side length variation coefficient was 9
% Cubic particles were formed. The temperature during particle formation is 55
° C. Spectral sensitization and chemical sensitization are corrected to adjust the specific surface area (side length ratio 0.7 / 0.55 = 1.27 times)
Was carried out in the same amount as described above to prepare a low-sensitivity emulsion A-2 for a blue-sensitive layer.

[0203]

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<Preparation of Emulsion B for Comparative Blue Sensitive Layer> Emulsion A-1
In the emulsion preparation conditions described above, the temperature at the time of grain formation was set at 68 ° C., so that the grain size was 0.85 μm in average side length. The variation coefficient of the side length is 12%. Further, the introduction of iodine ions at the final stage of particle formation was stopped and replaced with Cl ions. Therefore, the halogen composition at the end of the grain formation is 99 mol% of silver chloride and 1 mol% of silver bromide. The addition amount of the spectral sensitizing dye-1 and the spectral sensitizing dye-2 was 1.25 times that of the emulsion A-1. Thiosulfonate compound-1 was used in an equal amount.
The chemical sensitization was changed as follows. A fine grain emulsion doped with 90 mol% of silver bromide and 10 mol% of silver chloride having an average grain size of 0.05 μm and doped with iridium hexachloride was added to give 1
Aged for 0 minutes. Further, fine grains of 40 mol% of silver bromide having an average particle diameter of 0.05 μm and 60 mol% of silver chloride were added and ripened for 10 minutes. The fine particles dissolved, thereby increasing the silver bromide content of the host cubic particles to 2.0 mol%. Further, iridium hexachloride was doped at 2 × 10 ⁻⁷ mol / Ag mol. Subsequently, 1 × 10 ⁻⁵ mol / Ag mol of sodium thiosulfate was added. Immediately, the temperature was raised to 55 ° C., aged for 70 minutes, and then lowered to 50 ° C. No gold sensitizer was added. Immediately after cooling, 4 × 10 ^-4 mol / Ag of mercapto compounds-1 and 2 were added.
It was added in molar amounts. Thereafter, after aging for 10 minutes, an aqueous KBr solution was added to the silver in an amount of 0.010 mol, and after aging for 10 minutes, the temperature was lowered and stored.
Thus, a high-sensitivity emulsion B-1 for a comparative blue-sensitive layer was prepared. Grains having an average side length of 0.68 μm and a side length variation coefficient of 12% were formed in the same manner as in Emulsion B-1, except that the temperature during grain formation was lowered. The spectral sensitizer and the chemical sensitizer were added to the emulsion B-1 in an amount of 1.2 in consideration of the surface area ratio.
The ratio was 5 times, and a low-sensitive emulsion B-2 for a comparative blue-sensitive layer was prepared.

<Preparation of Emulsion C for Green Sensitive Layer of the Present Invention> The emulsion E-1 of the present invention was prepared in the same manner as the emulsion A-1 of the present invention except that the temperature during grain formation was lowered and the type of sensitizing dye was changed as follows. A
In the same manner as in the preparation conditions of -1 and 2, a high-sensitivity side emulsion C-1 for a green-sensitive layer and a low-sensitivity side emulsion C-2 for a green-sensitive layer were prepared.

[0206]

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The grain size of the emulsion on the sensitive side was 0.4 mm on average side length.
0 μm, the low-sensitivity side emulsion had an average side length of 0.30 μm,
The coefficients of variation were all 8%. Sensitizing dye D
2. For large-size emulsions per mole of silver halide.
0x10 ^-Four3.6 × 10 for mol, small size emulsion
^-FourMoles of sensitizing dye E per mole of silver halide,
4.0 × 10 for large emulsions^-FiveMol, small size
7.0 × 10 for the emulsion^-FiveMole was added.

<Preparation of Emulsion D for Comparative Green Sensitive Layer> Comparative Emulsion B
-1, the temperature at the time of grain formation was lowered and a sensitizing dye was used.
Of emulsions B-1 and B-2, except that the type of
In the same manner as in the preparation conditions, the high sensitivity side emulsion D-
Nos. 1 and 2 were prepared. grain
The size of the emulsion was 0.50 μm on the average side length of the emulsion on the high sensitivity side,
The side emulsion had an average side length of 0.40 μm, and
The numbers are all 10%. Halogenating sensitizing dye D
4.0 × 10 for large emulsions per mole of silver ^-Four
4.5 × 10 for mol, small size emulsion^-FourMole, ma
In addition, sensitizing dye E was added to large-sized milk per mole of silver halide.
5.0 × 10 for the agent^-FiveMole, for small size emulsions
8.8 × 10^-FiveMole was added.

<Preparation of Emulsion E for Red Sensitive Layer of the Present Invention> An emulsion was prepared in the same manner as the emulsion A-1 of the present invention except that the temperature during grain formation was lowered and the type of sensitizing dye was changed as follows. A
Emulsion E for red-sensitive layer in the same manner as in the preparation conditions of E-1 and E-2
-1 and a low-sensitive emulsion E-2 for a red-sensitive layer.

[0210]

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The grain size of the emulsion on the high sensitivity side was 0.1 mm.
38 μm, the emulsion on the low sensitivity side had an average side length of 0.32 μm, and the coefficient of variation of the side length was 9% and 10%, respectively. The sensitizing dyes G and H were used, respectively, per mole of silver halide.
8.0 × 10 ^-5 mol was added to the large size emulsion, and 10.7 × 10 ^-5 mol was added to the small size emulsion. 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.

[0212]

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<Preparation of Emulsion F for Comparative Red-Sensitive Layer> Comparative Emulsion B
Higher sensitivity emulsion for comparative red-sensitive layer F-1 except that the temperature at the time of grain formation was lowered and the type of sensitizing dye was changed as follows, except that the type of sensitizing dye was changed as described below. And a low sensitivity side emulsion F-2 for a comparative red sensitive layer. The grain size of the high-sensitivity side emulsion was 0.57 μm, and that of the low-sensitivity side emulsion was 0.43 μm. The variation coefficient of the side length was 9%.
And 10%. The sensitizing dyes G and H were used in an amount of 1.0 × 1 for the large size emulsion per mole of silver halide.
^0-4 mol and 1.34 × 10 ^-4 mol were added to the small size emulsion. Further, the compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide.

<Preparation of First to Seventh Layer Coating Solutions> Yellow coupler (ExY) 57 g, color image stabilizer (Cpd-1)
7 g, 4 g of color image stabilizer (Cpd-2), and color image stabilizer (C
7 g of pd-3) and 2 g of a color image stabilizer (Cpd-8) are dissolved in 21 g of a solvent (Solv-1) and 80 ml of ethyl acetate. It was emulsified and dispersed in 220 g of the aqueous solution by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsions A-1 and A-2 were mixed and dissolved to prepare a first 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 second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. The total amount of Ab-1, Ab-2, Ab-3, and Ab-4 was 15.0 mg / m ² , 6 in each layer.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m ²
m ² .

[0216]

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[0219]

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Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the second, fourth, sixth and seventh layers in an amount of 0.2 mg / m ² ,
0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg / m ²
Was added so that Further, 4-hydroxy-6-methyl-1,3,3 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
3a, 7-tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide. Further, 0.05 g / m ^{2 of a} copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000 to 400,000) was added to the red-sensitive emulsion layer. Also, catechol-in the second, fourth and sixth layers
Each of disodium 3,5-disulfonate at 6 mg /
m ² , 6 mg / m ² , and 18 mg / m ² . To prevent irradiation, the following dyes were added (in parentheses, the coating amount is shown).

[0219]

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<Layer Structure> The structure of each layer in the photosensitive material 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 mass, ZnO; content 4% by mass), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content 0.03% by mass), bluish dye ( Ultramarine blue, content 0.33 mass%). The amount of the polyethylene resin is 29.2 g / m ² ]

-First layer (blue-sensitive emulsion layer)-Silver chloride emulsion A (gold-sulfur sensitized cube, 3: 7 mixture of large size emulsion A-1 and small size emulsion A-2 (silver mole Ratio).) 0.24 Gelatin 1.25 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-1) 0.21

—Second Layer (Color Mixing Prevention Layer) —Gelatin 1.15 Color Mixture Prevention Agent (Cpd-4) 0.10 Color Image Stabilizer (Cpd-5) 0.018 Color Image Stabilizer (Cpd-6) 0 .13 Color image stabilizer (Cpd-7) 0.07 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.12 Solvent (Solv-5) 0.11

-Third Layer (Green-Sensitive Emulsion Layer)-Silver chlorobromide emulsion C (gold-sulfur sensitized cube, 1: 3 mixture of large size emulsion C-1 and small size emulsion C-2 (silver 0.14 Gelatin 1.21 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.003 Color image stabilizer (Cpd- 4) 0.002 color image stabilizer (Cpd-6) 0.09 color image stabilizer (Cpd-8) 0.02 color image stabilizer (Cpd-9) 0.01 color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.09 Solvent (Solv-4) 0.18 Solvent (Solv-5) 0.17

—Fourth layer (color mixture prevention layer) —Gelatin 0.68 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.011 Color image stabilizer (Cpd-6) 0 0.08 Color image stabilizer (Cpd-7) 0.04 Solvent (Solv-1) 0.02 Solvent (Solv-2) 0.07 Solvent (Solv-5) 0.065

-Fifth layer (red-sensitive emulsion layer)-Silver chlorobromide emulsion E (gold-sulfur sensitized cube, 5: 5 mixture of large size emulsion E-1 and small size emulsion E-2 (silver) 0.16 Gelatin 0.95 Cyan coupler (ExC-1) 0.023 Cyan coupler (ExC-2) 0.05 Cyan coupler (ExC-3) 0.17 Ultraviolet absorber (UV-A) 0.055 Color image stabilizer (Cpd-1) 0.22 Color image stabilizer (Cpd-7) 0.003 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-12) 01 Solvent (Solv-8) 0.05

—Sixth layer (ultraviolet ray absorbing layer) —Gelatin 0.46 Ultraviolet ray absorbent (UV-B) 0.35 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.18

—Seventh Layer (Protective Layer) —Gelatin 1.00 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.4 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.02

Hereinafter, couplers, color image stabilizers, solvents, color mixing inhibitors, ultraviolet absorbers, and the like used in Examples of the present invention will be described.
1 shows a structural formula of a surfactant and the like.

[0230]

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[0231]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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The processing method used in this embodiment will be described below. <Development processing A> The above-mentioned photosensitive material sample was processed into a 127 mm wide roll, and the photosensitive material sample was subjected to imagewise exposure from a negative film having an average density using a mini-lab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. Continuous processing (running test) was performed until the volume of the color developing replenisher used in the following processing step was twice the capacity of the color developing tank. The treatment using the running treatment liquid was designated as treatment A.

Processing Step Temperature Time Replenishment Amount of 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 338.0 ° C. 20 seconds - mounted rinsed 4 38.0 ° C. 20 seconds 121mL dried 80 ° C. to Note * per photosensitive material 1 m ² replenishing amount ** manufactured by Fuji Photo Film Co., Ltd. rinse cleaning system RC50D the rinse (3), Rinse (3)
The rinsing liquid is taken out from the tank and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid 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 performed in a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Fluorescent whitening agent (FL-1) 2.2 g 5.1 g Fluorescent whitening agent (FL-2) 0.35 g 1.75 g Triisopropanolamine 8 8.8 g 8.8 g Polyethylene glycol average molecular weight 300 10.0 g 10.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10 g 0.20 g Potassium chloride 10.0 g-4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 14.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) Aniline 3/2 sulfate monohydrate 4.8 g 14.0 g potassium carbonate Total amount 1000mL 1000mL pH (25 ℃, adjusted with sulfuric acid and KOH) was added to arm 26.3 g 26.3 g Water 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL 8.3 g of m-carboxybenzenesulfinic acid 8.3 g 16.5 g Ammonium iron (III) ethylenediaminetetraacetate 47. 0 g 94.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium sulfite 16.0 g 32.0 g potassium metabisulfite 23.1 g 46.2 g water And a total amount of 1000 mL 1000 mL pH (adjusted with nitric acid and ammonia water) at 6.5 6.5

[Rinse liquid] [Tank liquid] [Refill liquid] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5

[0246]

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With respect to the sample 101 prepared as described above,
Samples with the following changes were prepared. <Preparation of Sample 201> Sample 201 was prepared in exactly the same manner as Sample 101, except that the silver halide emulsions of the first layer, the third layer, and the fifth layer were changed as follows. .・ Silver halide emulsion for the first layer Silver chloride emulsion B (cube, large size emulsion B sensitized with sulfur)
1: 7 mixture of small size emulsion B-2 (silver molar ratio). -Silver halide emulsion for third layer Silver chlorobromide emulsion D (gold-sulfur sensitized cube, 1: 3 mixture of large size emulsion D-1 and small size emulsion D-2 (silver molar ratio). Silver halide emulsion for fifth layer Silver chlorobromide emulsion F (gold-sulfur sensitized cube, 5: 5 mixture of large-size emulsion F-1 and small-size emulsion F-2 (silver molar ratio). )

<Preparation of Sample 301> Sample 301 was prepared in exactly the same manner as in Sample 101, except that the amount of ultramarine blue in the polyethylene resin on the emulsion layer side of the support was reduced to 70%. did.

<Preparation of Sample 401> Sample 401 was prepared in exactly the same manner as in Sample 101, except that the amount of ultramarine blue in the polyethylene resin on the emulsion layer side of the support was reduced to 50%. did.

<Preparation of Other Samples> Each of the samples 101 to 401 prepared above was prepared by changing the composition of the first layer as follows. Sample 102: The yellow coupler in the first layer of Sample 101 was changed to an equimolar amount of ExY-1. Sample 103: Exemplified compound (3) of general formula (II) in an amount equivalent to 70 mol% of the yellow coupler in the first layer of Sample 101
And the silver halide emulsion in the first layer was changed to 70 mol%. Sample 202: The yellow coupler in the first layer of Sample 201 was changed to an equimolar amount of ExY-1. Sample 203: The yellow coupler of the first layer of Sample 201 was added in an amount of 70 mol% equivalent to the exemplified compound (3) of the general formula (II).
And the silver halide emulsion in the first layer was changed to 70 mol%. Sample 302: The yellow coupler in the first layer of Sample 301 was changed to an equimolar amount of ExY-1. Sample 303: The yellow coupler in the first layer of Sample 301 was changed to an equimolar amount of ExY-2. Sample 304: Exemplified compound (3) of general formula (II) in an amount equivalent to 70 mol% of the yellow coupler in the first layer of Sample 301
And the silver halide emulsion in the first layer was changed to 70 mol%. Sample 305: The yellow coupler of the first layer of Sample 301 was converted to an equivalent compound of the general formula (II) (1
1) The silver halide emulsion in the first layer was changed to 70
Changed to mol%. Sample 306: The yellow coupler in the first layer of Sample 301 was converted to a compound represented by the general formula (II) (2) in an amount of 70 mol%.
1) The silver halide emulsion in the first layer was changed to 70
Mol%. Sample 402: The yellow coupler in the first layer of Sample 401 was changed to an equimolar amount of ExY-1. Sample 403: The yellow coupler of the first layer of Sample 401 was added in an amount of 70 mol% equivalent to the exemplified compound (3) of the general formula (II).
And the silver halide emulsion in the first layer was changed to 70 mol%.

The prepared sample was applied at 25 ° C. and 55% RH.
After storage for 10 days, exposure and development were performed.
After a running process was performed using the sample 101 according to the method of the development process A shown below, each of the samples was also exposed and developed to obtain a color print from each sample. The obtained samples were evaluated for characteristic values according to the following methods.

<Measurement of Reflection Density of Unexposed Area> Wavelength λ nm
Of the reflection density A (λ) at
25 ° C. using a -3410 type spectrophotometer
Under the condition of 60% RH, the opening ratio of the integrating sphere is 2%, and the slit width is 5n.
The absorbance at each wavelength of 450 nm, 550 nm, and 650 nm was determined by measuring the unexposed portion except for m and specular light. From the ratio of the values at this time, A
(550) / A (450) and A (650) / A
The value of (450) was determined.

<Measurement of Normalized Spectral Distribution Characteristics of Yellow Dye Image> A color-developed sample in which only the yellow coupler-containing layer was subjected to gradation exposure was subjected to 25
Under the condition of 60 ° C. and 60% RH, the opening ratio of the integrating sphere is 2% and the slit width is 5
The spectra were measured with the exception of nm and specular light. The yellow density at the wavelength giving the maximum absorbance was normalized to 1.0, and the absorbance at each wavelength of 450 nm and 520 nm was determined. The characteristic values determined for each sample as described above are shown below.

[0254]

[Table 2]

<Evaluation of Whiteness of Unexposed Area> A sensory evaluation of a white background sample (30 cm × 30 cm) of an unexposed area was performed on 50 persons based on the following criteria, and an average value was obtained. 5 points: Excellent in whiteness. 4 points: Excellent in whiteness. 3 points: Normally white. 2 points: Slightly colored. 1 point: Tint. 0 point: not white.

<Temperature Test of Unexposed Area> A white sample was irradiated with light using a xenon lamp for 100,000 lux for 7 days, and the distance Δ in the color space was determined from the values of L ^* a ^* b ^* before and after the irradiation.
L ^* a ^* b ^* was determined. ^{ΔL * a * b * = {} (L 1 * -L 2 *) 2 + (a 1 * -a 2 *) 2 +
The smaller the value of (b ₁ ^* −b ₂ ^* ) ² ｝ ^1/2 ΔL ^* a ^* b ^* , the smaller the change in color over time. Further, the sample was stored at 50 ° C. and 70% for 7 days.
L ^* a ^* b ^* was determined.

<Evaluation of Color Reproducibility> The density of the yellow colored portion of the sample was measured at intervals of 0.1 using a C-2000 color analyzer manufactured by Hitachi, Ltd. and a xenon common light source, and color reproducibility was possible using D65 as a white point. L ^* a ^* b ^* chromaticity space volume V was calculated. The above results are shown in Table 3 below.

[0258]

[Table 3]

From the results shown in Table 3, it was confirmed that the sample of the present invention was excellent in whiteness on a white background, and that the change in color with the lapse of time due to irradiation with light or storage with heat was small. Further, the light-sensitive material of the present invention showed better color reproducibility than the conventional one in the structure for forming a yellow dye image having a specific hue according to the present invention.

(Example 2) The following samples were prepared in the same manner as in Example 1. <Preparation of Sample 501> A sample 501 was prepared in exactly the same manner as the sample 101 except that the coating amount of the sixth layer was reduced to 70%.

<Preparation of Sample 601> A support was prepared from Sample 101 by removing ultramarine blue from the polyethylene resin on the emulsion layer side of the support. A pigment (Ciba Specialty Chemical) together with a yellow coupler, a color image stabilizer, a solvent and an auxiliary solvent in the first layer coating solution.
Blue A3R-K and Violet B
-K), and the mixture was made uniform, and then dispersed and emulsified.
A sample 601 was prepared by applying the same composition as that of Sample 101 on the support from which the ultramarine blue had been removed, except for using. The coating amount of Blue A3R-K is 0.0018 g.
/ M ² , the coating amount of Violet BK is 0.0012
g / m ² . Next, with respect to the samples 501 and 601 prepared above, each sample was prepared by changing the composition of the first layer as follows.

<Preparation of Other Samples> Sample 502: The yellow coupler in the first layer of Sample 501 was changed to an equimolar amount of ExY-1. Sample 503: Exemplified compound (3) of general formula (II) in an amount equivalent to 70 mol% of the yellow coupler in the first layer of Sample 501
And the silver halide emulsion in the first layer was changed to 70 mol%. Sample 602: The yellow coupler in the first layer of Sample 601 was changed to an equimolar amount of ExY-1. Sample 603: Exemplified compound (3) of general formula (II) in an amount equivalent to 70 mol% of the yellow coupler in the first layer of Sample 601
And the silver halide emulsion in the first layer was changed to 70 mol%.

With respect to the above sample and the sample of Example 1,
The L ^* a ^* b ^* value of the unexposed portion of the developed sample was measured. The measurement was performed using a C-2000 color analyzer manufactured by Hitachi, Ltd. and a xenon common light source, and the colorimetric value in the L ^* a ^* b ^* chromaticity space was determined using D65 as a white point. The normalized spectral distribution characteristics of the yellow dye image were measured in the same manner as in Example 1, and the yellow dye image A (450) was measured.
And A (520) were determined. The measurement results are shown in Table 4 below.

[0264]

[Table 4]

The same evaluation as in Example 1 was performed for the above samples, and the results are shown in Table 5 below.

[0266]

[Table 5]

From the results shown in Tables 4 and 5, it was confirmed that the light-sensitive material of the present invention was excellent in whiteness on a white background, and that the color change due to light irradiation or heat storage with time was small. Further, the light-sensitive material of the present invention showed better color reproducibility than the conventional one in the structure for forming a yellow dye image having a specific hue according to the present invention.

Example 3 Samples 701 to 70 shown below
3 was manufactured and evaluated by the same method as in Example 1. As a result, the same effect of the present invention as in Example 1 was obtained also in the sample of this example.

<Preparation of Samples 701 to 703> Sample 101
A sample 701 was prepared in the same manner except that the fifth layer was changed to the following fifth layer (2).

—Fifth Layer (2) — Silver chlorobromide emulsion E (gold-sulfur sensitized cube, 5: 5 mixture of large size emulsion E-1 and small size emulsion E-2 (silver molar ratio) ).) 0.10 Gelatin 1.11 Cyan coupler (ExC-1) 0.02 Cyan coupler (ExC-3) 0.01 Cyan coupler (ExC-4) 0.11 Cyan coupler (ExC-5) 0.01 Color image stabilizer (Cpd-1) 0.01 Color image stabilizer (Cpd-6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image Stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.01 Color image stabilizer (Cpd-17) 0.01 Color image stabilizer (Cpd-18) 0.07 Color image Jozai (Cpd-20) 0.01 UV absorber (UV-7) 0.01 solvent (Solv-5) 0.15

Sample 702: The yellow coupler in the first layer of Sample 701 was changed to an equimolar amount of ExY-1. Sample 703: Exemplified compound (3) of general formula (II) in an amount equivalent to 70 mol% of the yellow coupler in the first layer of Sample 701
And the silver halide emulsion in the first layer was changed to 70 mol%.

Example 4 A color print sample was prepared in the same manner as in Example 1 except that the sample used in Example 1 was used, and the developing method was changed from developing processing A to developing processing B shown below. I got As a result of the same evaluation as in Example 1, the effect of the present invention was obtained in the light-sensitive material of the present invention.

<Development processing B>
The photosensitive material sample was processed from a negative film of average density to a 7 mm width roll using an experimental processing apparatus modified from a mini photo printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. so that the processing time and processing temperature could be changed. Exposure was performed, and continuous processing (running test) was performed until the volume of the color developing replenisher used in the following processing step was twice the capacity of the color developing tank. The processing using this running processing liquid was referred to as processing B.

Processing Step Temperature Time Replenishment Amount of color development 45.0 ° C. 20 seconds 45 mL Bleaching and fixing 40.0 ° C. 20 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds-Rinse 2 40.0 ° C. 8 seconds-Rinse 3 40.0 8 ° C.-Rinse 4 38.0 ° C. 8 seconds 121 mL Drying 80 ° C. 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} photographic material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attached, the rinse liquid is taken out of the rinse (3), and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). Permeate volume to reverse osmosis module is 50-300mL
/ Min was maintained, and the temperature was circulated for 10 hours a day. Rinsing was performed in a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Fluorescent whitening agent (FL-3) 4.0 g 8.0 g Residual color reducing agent (SR-1) 3.0 g 5.5 g Triisopropanolamine 8 8.8 g 8.8 g Sodium p-toluenesulfonate 10.0 g 10.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10 g 0.10 g Potassium chloride 10.0 g-4,5-dihydroxybenzene-1,3 -Sodium disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5 g 14.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamide Ethyl) aniline 3/2 sulfate monohydrate 7.0 g 19.0 g potassium carbonate 26. 3g 26.3g Water is added and the total amount is 1000mL 1000mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.25 12.6

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 214 mL Succinic acid 29.5 g 59.0 g Ammonium iron (III) ethylenediaminetetraacetate 47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5 g 35.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water was added and the whole amount was added. 1000 mL 1000 mL pH (adjusted at 25 ° C. with nitric acid and aqueous ammonia) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5

[0278]

According to the present invention, the whiteness of a white background in an unexposed area is improved, the deterioration of the whiteness due to light irradiation or storage over time at high humidity and high temperature is improved, and a yellow dye excellent in hue is further improved. It is possible to provide a silver halide color photographic light-sensitive material which can provide extremely excellent color reproducibility by forming an image.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiroyuki Yoneyama 210 Nakamura, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H016 AB00 AB03 BD03 BE03 BF00

Claims (12)

[Claims] 1. A reflective support having at least one layer each of a yellow color-forming photosensitive silver halide emulsion layer, a magenta color-forming photosensitive silver halide emulsion layer, and a cyan color-forming photosensitive silver halide emulsion layer, In a silver halide color photographic material having at least one non-photosensitive, non-color-forming hydrophilic colloid layer, a reflection density A (λ) at a wavelength of λ nm in an unexposed portion after color development processing is 450 nm. 0.08 or less, 550
0.10 or less at 650 nm, and 0.08 or less at 650 nm.
A silver halide color photographic material having a density of 0.1 or more and 0.3 or less in m. 2. A reflection density A (λ) at a wavelength λ nm of an unexposed portion after the color development processing is 0.07 or less at 450 nm, 0.09 or less at 550 nm, and 650.
2. The silver halide color photographic light-sensitive material according to claim 1, which has a value of 0.07 or less in nm. 3. The reflection density A (λ) at a wavelength of λ nm in an unexposed portion after color development processing is 0.04 at 450 nm.
2. The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic material is 0.07 or less at 550 nm and 0.05 or less at 650 nm. 4. The method according to claim 1, wherein a density ratio of a reflection density A (λ) at a wavelength of λ nm in an unexposed portion after the color development processing satisfies the following conditional expressions (I) and (II). The silver halide color photographic light-sensitive material described in the above item. (I) 1.0 ≦ A (550) / A (450) ≦ 1.4 (II) 0.6 ≦ A (650) / A (450) ≦ 1.2 5. A reflective support having at least one layer each of a yellow-sensitive photosensitive silver halide emulsion layer, a magenta-sensitive photosensitive silver halide emulsion layer, and a cyan-sensitive photosensitive silver halide emulsion layer, In a silver halide color photographic light-sensitive material containing at least one non-photosensitive, non-color-forming hydrophilic colloid layer, the chromaticity of the unexposed portion after color development processing satisfies the following condition [A], and furthermore, A silver halide color photographic light-sensitive material, characterized in that a standardized spectral distribution curve of a coloring dye has a density of 0.9 to 1.0 at 450 nm and a density of 0.1 to 0.3 at 520 nm. Condition [A] 91 ≦ L ^* ≦ 96, 0 ≦ a ^* ≦ 2.0, −9.0 ≦ b ^* ≦
-3.0 6. The silver halide color photographic material according to claim 5, wherein the chromaticity of the unexposed portion after the color development processing satisfies the following condition [B]. Condition [B] 91 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b
^* ≦ −4.8 7. The silver halide color photographic material according to claim 5, wherein the chromaticity of the unexposed portion after the color development processing satisfies the following condition [C]. Condition [C] 93 ≦ L ^* ≦ 96, 0.3 ≦ a ^* ≦ 1.6, −8.0 ≦ b
^* ≦ −4.8 8. A standardized spectral distribution curve of the yellow coloring dye at 450 nm is from 0.95 to 1.0 and from 5 to 5.
The silver halide color photographic light-sensitive material according to any one of claims 1 to 7, which has a density of 0.20 or more and 0.28 or less at 20 nm. 9. The silver halide color photographic light-sensitive material according to claim 1, comprising at least one of yellow couplers represented by the following general formula (I). Embedded image In the general formula (I), Q represents -C (-R ¹¹ ) = C
Represents a group represented by (—R ¹² ) —SO ₂ —. R ¹¹ , R ¹²
Represents a group bonded to each other to form a 5- to 7-membered ring together with -C = C-, or each independently represents a hydrogen atom or a substituent. R ¹ represents a substituent. R ³ represents a substituent. R
⁴ represents a substituent. m represents an integer of 0 or more and 4 or less. When m is 2 or more, a plurality of R ⁴ may be the same or different, and may combine with each other to form a ring. X represents a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized developing agent. 10. The silver halide color photographic light-sensitive material according to claim 1, which comprises at least one of yellow couplers represented by the following general formula (II). Embedded image In the general formula (II), R ¹ represents a substituent. R ²
Represents a substituent. l represents an integer of 0 or more and 4 or less.
When 1 is 2 or more, a plurality of R ² may be the same or different, and may combine with each other to form a ring.
R ³ represents a substituent. R ⁴ represents a substituent. m is 0
Represents an integer of 4 or more and 4 or less. When m is 2 or more, a plurality of R
⁴ may be the same or different, and may combine with each other to form a ring. Y represents a group capable of leaving by a coupling reaction with an oxidized developing agent. 11. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one of the layers constituting the light-sensitive material contains a pigment. 12. The pigment according to claim 12, wherein the pigment is at least one selected from the group consisting of an indanthrone pigment, an indigo pigment, a triarylcarbonium pigment, an azo pigment, a quinacridone pigment, a dioxazine pigment, and a diketopyrrolopyrrole pigment. 12. The silver halide color photographic light-sensitive material according to item 11.