JP2000305218A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material superior in sharpness and rapid processing aptitude and color reproducibility and enhanced in resistance to pressures from the side of emulsion layers and from the reverse side of a reflective support and excellent in cutting aptitude. SOLUTION: This photographic sensitive material is provided with a reflective support having resin layers on both sides and at least, one silver halide emulsion layer on the support and the resin layer on the side of the emulsion layer includes a 10-30 μm thick biaxially stretched polymer sheet containing a white pigment in an amount of at least 10 weight %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent sharpness, rapid processing suitability, and glossiness, and having a pressure resistance from the emulsion side and a pressure resistance from the back side of the reflective support. The present invention relates to a silver halide photographic light-sensitive material having improved and better cutting suitability.

[0002]

2. Description of the Related Art In recent years, with the spread of color photographic light-sensitive materials, color development processing has been increasingly simplified and speeded up.
It is desired that rapid processing be possible and that processing be stable.

[0003] In color photographic paper, researches on shortening, speeding up, increasing sensitivity, processing stability, color reproducibility, tone reproducibility, sharpness improvement, glossiness, etc. of a printing process and a developing process have been conventionally performed. It has been widely practiced.

[0004] From the viewpoint of shortening the development processing time, silver bromide, silver chlorobromide and silver chloride containing substantially no silver iodide are used as silver halide emulsions applied to color photographic paper. Have been. It is known that silver halide emulsions having a higher silver chloride content have higher developability and are advantageous for rapid processing.

[0005] In addition, the silver developing agent can be developed by reducing the amount of silver applied to the light-sensitive material by using a means such as speeding up silver development or increasing the color-forming efficiency, or by reducing the amount of binder to reduce the emulsion film thickness. There are ways to increase sex.

[0006] As a result, the ratio of the time required for the drying step to the entire processing step is increasing as the time required for the color development processing is accelerated, and there is also a demand for rapid drying after the development processing. Gelatin is used as a binder for each photographic constituent layer of the photographic light-sensitive material.However, if the amount of gelatin contained in the photographic light-sensitive material is large, the amount of moisture in the light-sensitive material brought into the drying step increases, There are problems such as a long drying time and poor drying under high humidity conditions such as during the rainy season, and a reduction in the amount of gelatin is desired.

However, the use of a silver halide emulsion having a high silver chloride content, a reduction in the amount of silver, a reduction in the amount of gelatin applied, and the like, to increase the development processing efficiency and drying efficiency mean that silver halide color photographic light-sensitive. A phenomenon called pressure fogging in which unexposed silver halide grains are developed when the material is subjected to pressure such as claw breaks or being scratched by protrusions, or when printing is performed strongly from the back of the support. Turned out to be easier.

When pressure (hereinafter referred to as surface pressure) is applied from the emulsion side of a silver halide photographic light-sensitive material, it is often due to the effect of solid matter attached to a transport line such as a printer or a roller of a developing machine. There is
Frequent work such as removing solid matter adhering to the transfer line is required, and care must be taken to avoid applying pressure, resulting in reduced productivity. turn into. In particular, in the case of the developing solution, the reduction in the replenishment amount of the processing solution per processing area of the photosensitive material with the speeding up of processing is caused by the precipitation of components dissolved in the processing solution, etc. Therefore, it can be said that the importance of the pressure resistance of the photosensitive material tends to increase as the processing speeds up.

In recent years, an integrated minilab system of a very small and inexpensive color negative film automatic developing machine and a printer / paper automatic developing machine has been developed and introduced into a camera shop and a photo shop. It has become possible to bring in a film taken in the store and finish a color print only a few tens of minutes later. For this reason, the shorter the time required from the development of the color film to the completion of the color print, the better, and the tendency is increasing.In addition, when performing exposure processing with a minilab system, data such as the exposure conditions from the negative are printed on the back of the color paper. The number of mini-lab devices that print on printers is increasing. With minilab equipment,
Due to the printing pressure on the back side of the color paper, desensitization and fogging occur on the color paper emulsion side (hereinafter referred to as back printing pressure), which causes a great problem in image quality, so there is no back printing pressure There is a need for photosensitive materials.

On the other hand, silver halide color photographic materials are desired to be excellent in image quality such as color reproducibility and tone reproducibility.

With respect to the color reproducibility, the absorption characteristics of the obtained dye image are very important. Therefore, recently, couplers having good absorption characteristics have been actively studied.

In a photosensitive material for printing, as a so-called dye-forming coupler which forms yellow, magenta and cyan dyes, an active methylene or a compound having a methylene position in the molecule is commonly used. Pivaloyl acetanilides, 5-pyrazolones or pyrazolotriazoles as magenta couplers, and phenols or naphthols as cyan couplers can be mentioned.

The pivaloylacetoanilides used in the yellow coupler generally have a slightly longer wavelength light absorption profile in the blue light region and are broad. For this reason, the obtained hue has an orange color, and has a disadvantage that color reproduction using a yellow dye cannot be sufficiently obtained.

As yellow couplers for improving this disadvantage, JP-A-63-123047 and JP-A-4-9051 are known.
And pivaloyl acetanilide yellow couplers having an alkoxy group in the anilide moiety described in JP-A Nos. 4-124661 and the like, pivaloyl acetanilide yellow couplers having a cycloalkyl group in the acyl moiety described in JP-A-4-21842, and Asymmetric malondianilide-based yellow couplers described in JP-A-4-174428, JP-A-4-184434 and JP-A-5-114416 have been proposed. These couplers have sharp absorption of a coloring dye and color reproduction. The performance is improved.

However, in the light-sensitive material using the yellow coupler, there is a problem that the backing pressure is deteriorated.

As a coupler for forming a cyan dye image, a phenol or naphthol cyan coupler is generally used. However, since the cyan dyes formed by these couplers have unfavorable absorptions in the green light region and the blue light region, there is a serious problem that the color reproducibility of green and blue is remarkably deteriorated. ing. Therefore, it is strongly desired to solve this.

As cyan couplers for improving this disadvantage, JP-A-64-552, JP-A-64-553, and JP-A-64-553 are known.
Pyrazoloazole-based cyan couplers described in JP-A-554, JP-A-64-555, JP-A-64-556, JP-A-64-557 and JP-A-1-144052;
174429, 4-230746, 5-165
No. 172, No. 5-204107, No. 5-313324
And cyano couplers described in JP-A-5-313325 and JP-A-4-133505
And cyan couplers described in JP-A-5-232648 and the like. These cyan coupler coloring dyes are excellent in that a cyan coloring image having a sharp light absorption profile and little side absorption can be obtained. However, these cyan couplers have a high coupling reaction activity with the oxidized form of the developing agent, and furthermore, because of the high extinction coefficient of the formed dye, the cyan color density per developed silver is higher than that of the conventional coupler. Therefore, the photosensitive material using the cyan coupler has a defect that the occurrence of fogging (hereinafter referred to as surface pressure) when the pressure is applied to the photosensitive material before exposure from the uppermost layer side of the emulsion becomes noticeable. Therefore, the deterioration of the pressure resistance is a serious problem in practical use.

Meanwhile, improvement of the support has been studied for speeding up. In recent years, as a support for a color print photosensitive material, a water-resistant support in which a polyethylene resin is laminated on both sides of a base paper has been used for rapid development processing, and a photographic emulsion side has been used for sharpness and white background. A white pigment such as titanium oxide is dispersed in the polyethylene layer.
In order to improve the sharpness, as described in JP-A-54-46035, JP-A-64-18144 and JP-A-2-71256, a white pigment is added to the polyethylene resin layer on the side to which a photographic emulsion is applied. It is effective to combine techniques using a paper support filled with a large amount of. However, in these laminated paper supports, the above-mentioned surface pressure and back surface pressure tend to be poor, and if the white pigment content of the polyolefin layer on the photographic emulsion side is further increased in order to improve sharpness, the surface pressure or the back surface The disadvantages to pressure are exacerbated.

In the case of photographic printing paper, it is printed from a negative in a developing laboratory and then developed to produce a print having a positive image, which is then cut into a prescribed size by a cutter or the like. In addition, some types of minilabs can be cut into a prescribed size by a cutter or the like before printing, and then printed and developed to obtain a print material. Generally, photographic printing paper and prints obtained from photographic printing paper are subjected to a shearing force between the upper and lower blades of a cutter during cutting.

At this time, in the case of a photographic printing paper using a paper support in which the above-mentioned polyethylene resin is melt-extruded and laminated on both sides of the base paper, when a cutter having poor cutting properties is used,
At the time of cutting, the polyethylene resin coating layer does not show a sharp cut surface, and the polyethylene resin coating layer often has an elongated shape. A photographic paper or print having such a cut surface has a poor appearance, so that its commercial value naturally declines.

Further, the polyethylene resin layer is too thick,
No. 167768, No. 6-167772, No. 10-3
No. 33277, No. 10-333278, and the like, a paper support using a resin other than the polyethylene resin requires a large force at the time of cutting, so that pressure fogging may occur at the cut portion. In other cases, the product value may be reduced due to poor appearance.

[0022]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to sharpness, rapid processing suitability,
It is another object of the present invention to provide a silver halide photographic light-sensitive material having excellent color reproducibility, improved pressure resistance from the emulsion side and pressure resistance from the back side of the reflective support, and further having good cutting suitability. It is.

[0023]

Means for Solving the Problems The present inventors have found that the above objects of the present invention can be achieved by the following silver halide photographic materials.

1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having a resin layer on both sides of a base paper, The resin layer on the side on which the emulsion layer is provided comprises a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the biaxially stretched polymer sheet has a thickness of 10 to 30 μm, and the biaxially stretched polymer sheet has a thickness of 10 to 30 μm. A silver halide photographic material, wherein the sheet contains at least 10% by weight of a white pigment.

2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having a resin layer on both sides of a base paper, The resin layer on the side on which the emulsion layer is provided comprises a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the biaxially stretched polymer sheet has a thickness of 10 to 30 μm, and the silver halide emulsion A silver halide photographic material characterized in that the total amount of gelatin contained in the layer and the non-photosensitive hydrophilic colloid layer is 6.5 g / m ² or less.

3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having a resin layer on both sides of a base paper, The resin layer on the side on which the emulsion layer is provided comprises a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the biaxially stretched polymer sheet has a thickness of 10 to 30 μm, and the silver halide emulsion At least one of the layers has the following general formula [Y-I], [Y
-II] or a silver halide photographic material comprising at least one yellow coupler represented by [Y-III].

[0027]

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[In the formula, R ₁ represents an alkyl group, a cycloalkyl group or an allyl group, R ₂ represents an alkyl group, a cycloalkyl group or an aryl group, and R ₃ represents a hydrogen atom, a halogen atom or an acylamino group. . X ₁ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. ]

[0029]

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[In the formula, R ₁₁ represents a monovalent substituent excluding a hydrogen atom, and Q forms a 3- to 5-membered hydrocarbon ring with C, or is selected from N, S, O and P. Represents a group of non-metallic atoms necessary for forming a 3- to 5-membered heterocyclic ring containing at least one hetero atom in the ring. R ₁₂ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group or an amino group, and R ₁₃ represents a group that can be substituted on a benzene ring. X ₂ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. ]

[0031]

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[Wherein, R ₂₁ and R ₂₂ each represent an alkyl group, an aryl group or a heterocyclic group, and R ₂₃ represents an aryl group or a heterocyclic group. X ₃ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. R ₂₁ and R ₂₂ may be bonded to each other to form a nitrogen-containing heterocyclic ring together with N. ] 4. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having a resin layer on both sides of a base paper, The resin layer on the side on which the emulsion layer is to be applied is composed of a resin layer containing a biaxially oriented polymer sheet containing a white pigment, and the biaxially oriented polymer sheet has a thickness of 1%.
0 to 30 μm, and at least one of the silver halide emulsion layers has the following general formulas [CI], [C-II], [C
-III] or a silver halide photographic material containing at least one cyan coupler represented by [C-IV].

[0033]

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[In the formula, R ₄₁ represents a hydrogen atom or a substituent, and R ₄₂ represents a substituent. m represents the number of substituents R _42.
When m is 0, R ₄₁ has a Hammett's substituent constant σp of 0.2
Represents an electron-withdrawing group of 0 or more, and when m is 1 or 2 or more,
At least one of R ₄₁ and R ₄₂ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Z ₁ represents a nonmetallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

R ₄₃ represents a hydrogen atom or a substituent; Z ₂ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring by condensing with —NH— with a pyrazole ring; The membered heterocyclic ring may have a substituent and may form a condensed ring with a benzene ring or the like in addition to the pyrazole ring.

R ₄₄ and R ₄₅ are Hammett's substituent constant σp
Represents an electron-withdrawing group of 0.20 or more. Provided that the sum of σp values of R ₄₄ and R ₄₅ is 0.65 or more. Z ₃ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring,
The 5-membered heterocyclic ring may have a substituent.

R ₄₆ and R ₄₇ each represent a hydrogen atom or a substituent; Z ₄ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; and the 6-membered heterocyclic ring has a substituent. It may be.

X ₃₁ , X ₃₂ , X ₃₃ and X ₃₄ each represent a group or an atom which is released by a coupling reaction with an oxidized color developing agent. Hereinafter, the details of the present invention will be described.

The support used in the present invention is a biaxially stretched polymer which is based on paper, has a resin layer on both sides of a base paper, and contains a white pigment on the side on which the silver halide emulsion layer is coated. A paper support having a resin layer containing a sheet (hereinafter referred to as a front resin layer), wherein a resin layer opposite to a side on which a silver halide emulsion layer is provided (hereinafter referred to as a back resin layer) is biaxial. A resin layer containing a stretched polymer resin sheet may be used.

The base paper used in the paper support of the present invention can be selected from raw materials generally used for photographic paper. Examples include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, and mixed pulp of softwood pulp and hardwood pulp can be widely used. Neutral paper, acidic paper, and any other paper may be used, but photographic paper grade base paper is preferably used, and photographic grade neutral paper is particularly preferable. The thickness of the paper is preferably from 40 μm to 250 μm.

Further, the support may contain additives generally used in papermaking, such as a sizing agent, a fixing agent, a tension enhancer, a filler, an antistatic agent, a dye and an antifoggant. Further, a surface sizing agent, a surface tension agent, an antistatic agent or the like may be appropriately applied to the surface.

The biaxially stretched polymer resin sheet containing a white pigment in the surface resin layer is prepared by melt-extruding a thermoplastic polymer containing a white pigment suitable for biaxial stretching at 190 ° C. to 350 ° C. by melt extrusion. After forming a stretched film, a sheet can be prepared by performing a biaxial stretching process.

Examples of thermoplastic polymers suitable for biaxial stretching include polyolefins, polyesters, polyamides, polycarbonates, cellulose esters, polystyrene, polyvinyl resins, polyethers, polysulfonamides, polyethers, and polyimides. And thermoplastic polymers such as polyurethanes, polyvinylidenes and polyacetals. Polyolefins such as polypropylene, polyesters such as polyethylene terephthalate, and polystyrene are preferred.

The biaxial stretching method includes a tubular method,
A flat film method of sequential biaxial stretching, a flat film method of simultaneous biaxial stretching, and an octobas method are known,
By using these methods, the biaxially stretched polymer sheet of the present invention can be prepared.

As the white pigment contained in the biaxially stretched polymer sheet in the surface resin layer, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like are used. Of these, titanium dioxide is particularly preferred for various reasons.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when whiteness is prioritized, and rutile type titanium dioxide is preferred when sharpness is emphasized. Taking both whiteness and sharpness into account, anatase-type titanium dioxide and rutile-type titanium dioxide may be blended and used.

The titanium dioxide used is generally one whose surface is surface-treated with an inorganic substance such as hydrous aluminum hydroxide or hydrous silicon oxide in order to suppress the activity of titanium dioxide and prevent yellowing, polyhydric alcohols, polyhydric alcohols and the like. Amines, metal soaps,
Those whose surface is treated with an organic substance such as alkyl titanate or polysiloxane, and those whose surface is treated with an inorganic or organic treating agent in combination can be used. The surface treatment amount is 0.2% by weight to 2.0% by weight of an inorganic substance with respect to titanium dioxide,
0.1% to 1.0% by weight of organic material is preferred. The particle size of titanium dioxide is preferably from 0.1 μm to 0.4 μm.

The content of the white pigment contained in the biaxially stretched polymer sheet in the surface resin layer is 5% by weight or more, preferably 10% by weight or more, from the viewpoint of sharpness of the print. It is difficult to set the upper limit to 30% by weight or more from the viewpoint of production suitability.

In order to disperse and mix the white pigment in the polymer resin, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a Cowles dissolver, a homomixer, a sand grinder, an ultrasonic disperser and the like are used. be able to.

The thickness of the stretched polymer sheet containing the white pigment in the surface resin layer should be 10
To 30 μm, preferably 10 to 20 μm.

The biaxially stretched polymer sheet containing the white pigment in the surface resin layer is adhered to the base paper via the adhesive layer.
As the bonding method using the bonding layer, polyolefins,
Polyesters, polyamides, polycarbonates,
Melts thermoplastic polymers such as cellulose esters, polystyrene, polyvinyl resins, polyethers, polysulfonamides, polyethers, polyimides, polyurethanes, polyvinylidenes, polyacetals, etc. to form a biaxially oriented polymer sheet and base. A method of applying between papers and nipping and bonding, a method of applying an ultraviolet curable resin monomer between a biaxially stretched polymer sheet and a base paper, and then irradiating ultraviolet rays to cure and bond the ultraviolet curable resin, an electron beam There is a method in which a cured resin monomer is applied between a biaxially stretched polymer sheet and a base paper and then irradiated with an electron beam to cure and bond the electron beam cured resin.

A new resin layer may be provided between the biaxially oriented polymer sheet containing a white pigment in the surface resin layer and the emulsion layer. As these resin layers, polyethylene, polyolefins such as polypropylene, polyesters, polyamides, polycarbonates, cellulose esters, polystyrene, polyvinyl resin, polyethers,
A method of laminating thermoplastic polymers such as polysulfonamides, polyethers, polyimides, polyurethanes, polyvinylidenes, polyacetals, etc. on a biaxially stretched polymer sheet containing a white pigment by a melt extrusion method. A method of applying an ultraviolet curable resin monomer onto a biaxially stretched polymer sheet containing the same and then irradiating ultraviolet rays to cure the ultraviolet curable resin, and applying an electron beam curable resin monomer onto a biaxially stretched polymer sheet containing a white pigment. A method of irradiating an electron beam later to cure the electron beam-curable resin may be used.

The resin layer between the biaxially oriented polymer sheet containing the white pigment and the emulsion layer may not contain the white pigment, but preferably contains the white pigment.

A biaxially stretched polymer sheet containing a white pigment in the surface resin layer and a resin layer between the sheet and the emulsion layer may have a slight bluish tint such as ultramarine blue or an oil-soluble dye to improve whiteness. Agents and reddish additives may be added.

The silver halide photographic light-sensitive material of the present invention may be subjected to corona discharge, ultraviolet irradiation, flame treatment, plasma treatment or the like on the surface of the surface resin layer of the paper support of the present invention, if necessary, and then directly or downwardly. Coating layer (one or more layers for improving adhesion, antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional properties and / or other properties of the support surface) (Undercoat layer).

As the back resin layer of the paper support of the present invention, polyolefins such as polyethylene and polypropylene used for the conventional paper support are used. In addition, a resin layer containing a biaxially stretched polymer sheet is used. No problem.

These polyolefins such as polyethylene and polypropylene are laminated on a base paper by a melt extrusion method. There is no particular limitation on the thickness, but 15 to 50 μm
m is preferred.

In the resin layer in which the backside resin layer contains a biaxially stretched polymer sheet, the biaxially stretched polymer sheet is formed by the same method as the above-described biaxially stretched polymer sheet of the front resin layer. The base paper can be adhered by the same method. The polymer resin of the biaxially oriented polymer sheet of the back resin layer may be different from the polymer resin of the biaxially oriented polymer sheet of the front resin layer, but the same resin is preferred. The thickness of the biaxially stretched polymer sheet backside resin layer in the backside resin layer is not particularly limited,
10 to 30 μm is preferred.

The hydrophilic colloid contained in the silver halide photographic light-sensitive material of the present invention is mainly gelatin. The total amount of gelatin contained in the silver halide photographic light-sensitive material of the present invention is preferably small from the viewpoint of speeding up the processing step and the drying step, and the silver halide photograph using the paper support of the present invention is preferred. In the light-sensitive material, the effect of the present invention is preferably such that the total amount of gelatin is smaller than the total amount of gelatin contained in the silver halide photographic light-sensitive material of the present invention from the viewpoint of speeding up the processing step and drying step. In the silver halide photographic material using the paper support of the present invention, the effect of the present invention is particularly remarkable when the total amount of gelatin is 6.5 g / m ² or less.

The lower limit of the total amount of gelatin contained in the silver halide photographic light-sensitive material is not particularly limited, but is generally 4.0 g / g in terms of physical characteristics or photographic performance.
It is preferably at least m ² . The amount of gelatin can be determined by the method of measuring water described in the Pagui's method, in terms of the weight of gelatin containing 11.0% of water.

The gelatin used in the present invention has a jelly strength (based on the Pagi method) of preferably at least 250 g, particularly preferably at least 270 g.

The calcium content of the gelatin used in the present invention (according to the Pagii method) is preferably 1000 pp
m or less. In order to reduce the amount of calcium in gelatin, generally, treatment with an ion exchange resin column is preferably used.

The molecular weight of the gelatin used in the present invention is not particularly limited, but is preferably 10,000 to 10,000.
200,000.

The gelatin used in the silver halide photographic light-sensitive material of the present invention may be a lime-processed gelatin or an acid-processed gelatin. Although it may be manufactured gelatin,
Preferred is lime-processed gelatin made from bovine bone and pork skin.

Next, the yellow coupler of the present invention will be described. The yellow coupler used in the invention of claim 3 of the present invention is at least one of the compounds represented by the above general formulas [Y-I], [Y-II] or [Y-III].

The yellow coupler represented by the general formula [Y-I] will be described in detail.

Examples of the alkyl group represented by R ₁ include a linear or branched alkyl group such as methyl, ethyl, i-propyl, t-butyl, dodecyl, 1-hexylnonyl and the like. Examples of the cycloalkyl group represented by R ₁ include groups such as cyclopropyl, cyclohexyl, and adamantyl. Examples of the allyl group represented by R ₁ include groups such as phenyl which may have a substituent.

The alkyl group and cycloalkyl group represented by R ₁ may further have a substituent. As the substituent, a halogen atom (chlorine, bromine, etc.), a cyano group, a nitro group, an aryl group (phenyl, pt-octylphenyl, 2,4-di-t-amylphenyl, etc.), hydroxyl group, alkoxy group (methoxy, 2-ethoxyethoxy, etc.), aryloxy group (phenoxy, 2,4-di-
t-amylphenoxy, 4- (4-hydroxyphenylsulfonyl) phenoxy and the like), heterocyclic oxy group (4-pyridyloxy, 2-hexahydropyranyloxy and the like),
Carbonyloxy groups (alkylcarbonyloxy groups such as acetyloxy and pivaloyloxy, aryloxy groups such as benzoyloxy, etc.), sulfonyloxy groups (alkylsulfonyloxy groups such as methanesulfonyloxy, trifluoromethanesulfonyloxy, dodecanesulfonyloxy, and benzenesulfonyl) Oxy, arylsulfonyloxy groups such as p-toluenesulfonyloxy),
Carbonyl group (alkylcarbonyl groups such as acetyl and pivaloyl, benzoyl, 3,5-di-t-butyl-4-
Arylcarbonyl group such as hydroxybenzoyl),
An oxycarbonyl group (an alkoxycarbonyl group such as methoxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, etc .; an aryloxycarbonyl group such as 2,4-di-t-amylphenoxycarbonyl);
A heterocyclic oxycarbonyl group such as -pyridyloxycarbonyl, 1-phenylpyrazolyl-5-oxycarbonyl, etc.), a carbamoyl group (dimethylcarbamoyl,
Alkylcarbamoyl groups such as (2,4-di-t-amylphenoxy) butylaminocarbonyl, arylcarbamoyl groups such as phenylcarbamoyl and 1-naphthylcarbamoyl), sulfonyl groups (alkylsulfonyl groups such as methanesulfonyl and trifluoromethanesulfonyl); p
An arylsulfonyl group such as toluenesulfonyl), a sulfamoyl group (dimethylsulfamoyl, 4- (2,
4-di-t-amylphenoxy) alkylsulfamoyl groups such as butylaminosulfonyl, arylsulfamoyl groups such as phenylsulfamoyl and acylsulfamoyl groups such as acetylsulfamoyl and ethylcarbonylaminosulfonyl), Amino group (alkylamino group such as dimethylamino, cyclohexylamino, dodecylamino, arylamino group such as anilino, pt-octylanilino, etc.), sulfonamide group (methanesulfonamide, heptafluoropropanesulfonamide, hexadecyl) Alkyl sulfonamide groups such as sulfonamide,
arylsulfonamide groups such as p-toluenesulfonamide and pentafluorobenzenesulfonamide; acylamino groups (alkylcarbonylamino groups such as acetylamino and myristoylamino; arylcarbonylamino groups such as benzoylamino); alkylthio groups (methylthio, t -Octylthio, etc.), an arylthio group (phenylthio, p-tolylthio, etc.) and a heterocyclic thio group (1-phenyltetrazol-5-thio, 5-methyl-1,3,
4-oxadiazole-2-thio, etc.).

R ₁ is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

Examples of the alkyl group and cycloalkyl group represented by R ₂ include the same groups as the alkyl group and cycloalkyl group represented by R ₁ .
Examples of the aryl group represented by R ₂ include a phenyl group and a 1-naphthyl group. Alkyl groups represented by these R _2, cycloalkyl group and aryl group may also have a substituent, examples of the substituent include an alkyl group and cycloalkyl group as defined group and R ₁ represented by R ₁ And the groups having the same meanings as those described above as the substituents of the alkyl group and the cycloalkyl group.

Examples of the group or atom capable of leaving by reaction with the oxidized form of the developing agent represented by X ₁ include a nitrogen-containing heterocyclic group, an aryloxy group, and a nitrogen atom bonded to the coupling position.
Arylthio group, heterocyclic oxy group, heterocyclic thio group, acyloxy group, carbamoyloxy group, alkylthio group,
Examples include a hydrogen atom or a halogen atom.

When X ₁ represents a nitrogen-containing heterocyclic group bonded to the coupling position via a nitrogen atom, this nitrogen-containing heterocyclic group has 1 to 15, preferably 1 to 10 carbon atoms. It is preferably a 5- or 6-membered substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group. The hetero atom may include an oxygen atom or a sulfur atom in addition to the nitrogen atom. Preferred specific examples of the heterocyclic group include 1-pyrazolyl, 1-imidazolyl, pyrrino,
1,2,3-triazol-2-yl, 1,2,3-triazol-1-yl, benzotriazolyl, benzimidazolyl, imidazolidine-2,4-dione-3-yl, oxazolidine-2,4 -Dion-3-yl, 1,
2,4-triazolidine-3,5-dione-4-yl,
Imidazolidine-2,4,5-trion-3-yl, 2
-Imidazolinone-1-yl, 3,5-dioxomorpholino or 1-indazolyl. When these heterocyclic groups have a substituent, the substituent is not particularly limited. Preferred examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, and an aryloxycarbonyl group. , An alkylthio group, an acylamino group, a sulfonamide group, an aryl group,
A nitro group, a carbamoyl group, a cyano group or a sulfonyl group.

When X ₁ represents an aryloxy group, it is preferably a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenoxy group. When the aryloxy group has a substituent, a preferred substituent is a case where at least one substituent is an electron-withdrawing group, and examples thereof include a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, Examples include a carbamoyl group, a nitro group, a cyano group, and an acyl group.

When X ₁ represents an arylthio group, it is preferably a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms. Particularly preferred is a substituted or unsubstituted phenylthio group. When having a substituent, preferred substituents include
At least one substituent is an alkyl group, an alkoxy group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a halogen atom, a carbamoyl group or a nitro group.

When X ₁ represents a heterocyclic oxy group, the part of the heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and at least a nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group of 3 to 12, preferably 5 to 6 membered rings containing one or more. Examples of heterocyclic oxy groups include pyridyloxy, pyrazolyloxy or furyloxy groups. When the heterocyclic oxy group has a substituent, preferred substituents include one substituent such as an alkyl group, an aryl group, a carboxyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group,
An aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group or a sulfonyl group.

When X ₁ represents a heterocyclic thio group, the part of the heterocyclic group has from 1 to 20, preferably from 1 to 10 carbon atoms and has at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a substituted or unsubstituted, saturated or unsaturated, monocyclic or condensed heterocyclic group of 3 to 12, preferably 5 to 6 membered rings containing one or more. Examples of heterocyclic thio groups include tetrazolylthio, 1,3,4
-Thiadiazolylthio, 1,3,4-oxadiazolylthio, 1,3,4-triazolylthio, benzimidazolylthio, benzothiazolylthio or 2-pyridylthio groups. When the heterocyclic thio group has a substituent, preferred substituents are those in which at least one of the substituents is an alkyl group, an aryl group, a carboxyl group, an alkoxy group,
A halogen atom, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acylamino group, a sulfonamide group, a nitro group, a carbamoyl group, a heterocyclic group or a sulfonyl group.

When X ₁ represents an acyloxy group, this acyloxy group preferably has 6 to 10 carbon atoms and is a monocyclic or condensed ring. A substituted or unsubstituted aromatic acyloxy group or a group having 2 to 30, preferably 2 carbon atoms
And a substituted or unsubstituted aliphatic acyloxy group of -20. These may further have a substituent.

When X ₁ represents a carbamoyloxy group, this carbamoyloxy group is an aliphatic, aromatic, heterocyclic, substituted or unsubstituted carbamoyloxy group having 1 to 30, preferably 1 to 20 carbon atoms. is there. For example, N, N-
Diethylcarbamoyloxy, N-phenylcarbamoyloxy, 1-imidazolylcarbonyloxy or 1-
And a pyrrolocarbonyloxy group.

When X ₁ represents an alkylthio group, this alkylthio group is a linear, branched, saturated or unsaturated, substituted or unsubstituted alkylthio group having 1 to 30, preferably 1 to 20 carbon atoms. These may further have a substituent.

Among X ₁ , groups represented by the following formulas (I), (II) and (III) are preferred.

Formula (I) -OR ₄ Formula (II) -OCOR ₄

[0082]

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In the above general formulas (I) and (II), R
₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, cycloalkyl group and aryl group represented by R ₄ include groups having the same meaning as the alkyl group, cycloalkyl group and aryl group represented by R ₂ in the general formula [Y-I]. be able to. Examples of the heterocyclic group represented by R ₄ include groups such as 4-pyridyl and 2-hexahydropyranyl. The alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₄ may have a substituent, and examples of the substituent include alkyl represented by R ₂ in the general formula [Y-I]. Examples of the group include the same as the groups described as the substituents of the group, the cycloalkyl group, and the aryl group.

Among the alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R ₄ , an aryl group is preferable. Examples of the substituent of R ₄ include an electron-withdrawing group (oxycarbonyl group such as carboxyl, methoxycarbonyl or i-propyloxycarbonyl, acyl group such as acetyl or benzoyl, trifluoromethanesulfonyl group, 4-hydroxyphenylsulfonyl and the like). A sulfonyl group, a nitro group, a cyano group, a halogen atom, a sulfamoyl group such as dimethylsulfamoyl, an acylamino group such as acetylamino or pentafluorobenzoylamino, and a sulfonamide group such as methanesulfonamide.

In the general formula (III), Z ₁₁ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring together with a nitrogen atom. Here, the atom group necessary for forming the non-metal atom group includes, for example, methylene, methine, substituted methine, —CO—, —N (R ₅ ) — (R ₅ is a hydrogen atom, an alkyl group, an aryl group or Represents a heterocyclic group), -N =,
-O- and -S (O) _u - _(u represents an integer of 0 to 2)
And the like.

X ₁ is particularly preferably represented by the following general formula (I
V).

[0087]

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In the above general formula (IV), Y ₁ is -N
(R ₆₎ - (R ₆ represents a group as defined for groups represented by R ₅ in the general formula (III)), - O- and -S (O) _r -
(R represents an integer of 0 to 2) and the like;
Or _{-CO -, - C (R 7} ) (R 8) - (R 7 and R _8,
A hydrogen atom or a group having the same meaning as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R ₄ in formula (I)) and —C (R ₉ ) —
(R ₉ is a hydrogen atom or R _{2 in the} above general formula [Y-I]
Represents a group having the same meaning as the groups exemplified as the substituents of the alkyl group, cycloalkyl group and aryl group represented by.

Z ₁₂ represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered ring in cooperation with -Y ₁ -N-CO-. Examples of the atomic group necessary for forming a non-metallic atomic group can be, for example, the general formula (III) in Z ₁₁ atomic group as defined group of atoms represented by.

The substituent represented by R ₃ represents a hydrogen atom, a halogen atom or an acylamino group. The acylamino group is preferably an unsubstituted acylamino group having 11 to 21 carbon atoms, and is preferably a linear acylamino group. Is more preferred.

The 2-equivalent yellow coupler represented by the general formula [Y-I] may be bonded at any substituent to form a bis-form, tris-form, tetrakis-form or polymer-form.

The yellow coupler represented by the general formula [Y-I] can be prepared by using a commercially available compound as a starting material and a conventionally known method, for example, a method described in JP-A-63-1230.
No. 47, JP-A-4-9051, JP-A-4-124661, and the like, and can be easily synthesized.

Specific examples of the yellow coupler represented by [Y-I] are shown below, but the yellow coupler of the present invention is not limited thereto.

[0094]

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[0095]

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[0096]

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Next, the yellow coupler of the formula [Y-II] will be described.

In the general formula [Y-II], R ₁₁ is preferably a halogen atom, a cyano group or a monovalent aliphatic group having a total of 1 to 30 carbon atoms which may be substituted (such as an alkyl group or an alkoxy group). ) Or a monovalent aromatic group having 6 to 30 carbon atoms (aryl group, aryloxy group, etc.), and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group, an acylamino group. Group, sulfonamide group, acyl group and the like.

Q is preferably a 3- to 5-membered, optionally substituted, C3-C30 hydrocarbon ring or at least one heteroatom selected from N, S, O, P together with C. A non-metallic atomic group necessary for forming a heterocyclic ring having 2 to 30 carbon atoms contained in the ring. The ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include cyclopropane, cyclobutane, cyclopentane, cyclopropene, cyclobutene, cyclopentene, oxetane, oxolan, 1,3-dioxolan, thiethane, thiolan, and pyrrolidine.
Examples of the substituent that may be present include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group, and an arylthio group.

R ₁₂ is preferably a halogen atom, an optionally substituted alkoxy group having 1 to 30 carbon atoms, and a carbon atom having 6 to 3 carbon atoms.
0 represents an aryloxy group, an alkyl group having 1 to 30 carbon atoms or an amino group having 0 to 30 carbon atoms, and examples of the substituent include a halogen atom, an alkyl group, an alkoxy group,
Aryloxy groups.

R ₁₃ is preferably a halogen atom, an alkyl group having 1 to 30 carbon atoms which may be substituted, or a carbon atom having 6 to 30 carbon atoms.
Aryl group, an alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 2 to 30 carbon atoms, an aryloxycarbonyl group having 7 to 30 carbon atoms, an acylamino group having 1 to 30 carbon atoms, and a sulfone having 1 to 30 carbon atoms Amide group, carbamoyl group having 1 to 30 carbon atoms, sulfamoyl group having 0 to 30 carbon atoms, alkylsulfonyl group having 1 to 30 carbon atoms, arylsulfonyl group having 6 to 30 carbon atoms, 1 to 30 carbon atoms
A ureido group, a sulfamoylamino group having 0 to 30 carbon atoms, an alkoxycarbonylamino group having 2 to 30 carbon atoms,
A heterocyclic group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkylsulfonyloxy group having 1 to 30 carbon atoms, and an arylsulfonyloxy group having 6 to 30 carbon atoms. Halogen atom, alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acylamino group, sulfonamide group, carbamoyl group , A sulfamoyl group, an alkoxycarbonylamino group, a sulfamoylamino group, a ureido group, a cyano group, a nitro group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, and an arylsulfonyloxy group.

In the general formula [Y-II], the substitution position of R ₁₃ is as follows in the benzene ring of the anilide.

[0103]

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The meta position or the para position is preferred.

X ₂ represents the same group as X ₁ in the general formula [Y-I].

Next, particularly preferred substituents in the formula [Y-II] will be described.

R ₁₁ is particularly preferably a halogen atom or an alkyl group, most preferably a methyl group.

Q is particularly preferably a group of non-metallic atoms forming a 3- to 5-membered hydrocarbon ring together with C.

[0109]

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Is as follows.

Here, R represents a hydrogen atom, a halogen atom or an alkyl group. However, a plurality of Rs may be the same or different.

Most preferably, Q forms a three-membered ring together with C to be bonded.

[0113]

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Is as follows.

R ₁₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms (methyl, trifluoromethyl, ethyl, i-propyl, t-butyl, etc.),
An alkoxy group having 1 to 8 carbon atoms (methoxy, ethoxy, methoxyethoxy, butoxy, etc.) or an aryloxy group having 6 to 24 carbon atoms (phenoxy, p-tolyloxy, p-
Methoxyphenoxy), and most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

R ₁₃ is particularly preferably a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, most preferably an alkoxy group, an alkoxycarbonyl group, It is an acylamino group or a sulfonamide group.

X ₂ is particularly preferably a group represented by the general formula (IV) described in the general formula [Y-I].

The yellow coupler represented by the general formula [Y-II] can be prepared by using a commercially available compound as a starting material and a conventionally known method, for example, a method disclosed in JP-A-4-21804.
It can be easily synthesized according to the method described in No. 2, etc.

Specific examples of the yellow coupler represented by the general formula [Y-II] are shown below, but the yellow coupler of the present invention is not limited to these.

[0120]

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[0121]

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[0122]

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[0123]

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Next, the coupler represented by formula [Y-III] will be described in detail.

When R ₂₁ and R _{22 in the} formula [Y-III] represent an alkyl group, they have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Is a linear, branched, cyclic, saturated, unsaturated, substituted or unsubstituted alkyl group. Examples of alkyl groups include methyl, ethyl, propyl, butyl, cyclopropyl, allyl, t
-Octyl, i-butyl, dodecyl, 2-hexyldecyl and the like.

When R ₂₁ and R ₂₂ represent a heterocyclic group, this heterocyclic group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and has at least a nitrogen atom, oxygen atom or sulfur atom as a hetero atom. It is a 3- to 12-membered, preferably 5- to 6-membered, saturated or unsaturated, substituted or unsubstituted, monocyclic or condensed heterocyclic group containing one or more rings. Examples of heterocyclic groups include 3-pyrrolidinyl, 1,
2,4-triazol-3-yl, 2-pyridyl, 4-
Pyrimidinyl, 3-pyrazolyl, 2-pyrrolyl, 2,4
-Dioxo-1,3-imidazolidin-5-yl or pyranyl.

When R ₂₁ and R ₂₂ represent an aryl group, they represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Examples of aryl groups include phenyl,
Naphthyl is a typical example.

The nitrogen-containing heterocyclic group which may be formed together with N by combining R ₂₁ and R ₂₂ has 1 to 20 carbon atoms, preferably 1 to 2 carbon atoms.
To 15 and, in addition to a nitrogen atom as a hetero atom, which may contain, for example, an oxygen atom or a sulfur atom, a 3- to 12-membered ring, preferably a 5- to 6-membered ring, substituted or unsubstituted, saturated or unsaturated, and It is a monocyclic or condensed-ring heterocyclic group. Examples of this heterocyclic group include pyrrolidino, piperidino, morpholino, 1-piperazinyl, 1-indolinyl, 1,2,3,4-tetrahydroquinoline-1-
Yl, 1-imidazolidinyl, 1-pyrazolyl, 1-pyrrolinyl, 1-pyrazolidinyl, 2,3-dihydro-1
-Indazolyl, 2-isoindolinyl, 1-indolyl, 1-pyrrolyl, 4-thiazine-S, S-dioxo-
4-yl or benzoxazin-4-yl.

When R ₂₁ and R ₂₂ each represent an alkyl group having the substituent, the same aryl group or the same heterocyclic group,
_{When 21} and R ₂₂ are bonded to each other and the nitrogen-containing heterocyclic group formed with N has a substituent, examples of the substituent include the following.

A halogen atom (such as fluorine and chlorine) and an alkoxycarbonyl group (having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms)
Methoxycarbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, etc.), acylamino group (acetamido having 2 to 30, preferably 2 to 20 carbon atoms, tetradecaneamide, 2- (2,4-di-t-amylphenoxy) butanamide) , Benzamide, etc.), a sulfonamide group (such as methanesulfonamide having 1 to 30, preferably 1 to 20 carbon atoms, dodecanesulfonamide, hexadecanesulfonamide, benzenesulfonamide), a carbamoyl group (having 1 to 30 carbon atoms, preferably N from 1 to 20
-Butylcarbamoyl, N, N-diethylcarbamoyl), N-sulfonylcarbamoyl group (1 to 3 carbon atoms)
0, preferably 1-20 N-mesylcarbamoyl, N
-Dodecylsulfonylcarbamoyl, etc.), sulfamoyl group (N-butylsulfamoyl having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, N-dodecylsulfamoyl, N-
Hexadecylsulfamoyl, N-3- (2,4-di-
t-amylphenoxy) butylsulfamoyl, N, N
-Diethylsulfamoyl), an alkoxy group (1 carbon atom)
-30, preferably 1-20 methoxy, hexadecyloxy, i-propoxy, etc.) and aryloxy groups (6-20, preferably 6-10 phenoxy, 4-methoxyphenoxy, 3-t-butyl- 4-hydroxyphenoxy, naphthoxy), aryloxycarbonyl group (phenoxycarbonyl having 7 to 21, preferably 7 to 11 carbon atoms), N-acylsulfamoyl group (2 carbon atoms)
-30, preferably 2-20, for example, N-propanoylsulfamoyl, N-tetradecanoylsulfamoyl and the like, a sulfonyl group (1-30 carbon atoms, preferably 1-20 carbon atoms).
20 methanesulfonyl, octanesulfonyl, 4-hydroxyphenylsulfonyl, dodecanesulfonyl, etc.), alkoxycarbonylamino group (1 to 3 carbon atoms)
0, preferably 1 to 20 ethoxycarbonylamino), a cyano group, a nitro group, a carboxyl group, a hydroxyl group, a sulfo group, an alkylthio group (having 1 to 30 carbon atoms)
Preferably 1-20 methylthio, dodecylthio, dodecylcarbamoylmethylthio, etc.), ureido group (1-30 carbon atoms, preferably 1-20 N-phenylureido, N-hexadecylureide, etc.), aryl group (6 carbon atoms). -20, preferably 6-10 phenyl, naphthyl, 4-methoxyphenyl, etc.)
20, preferably 1 to 10, containing at least one or more of nitrogen, oxygen or sulfur as a heteroatom;
12-membered, preferably 5- to 6-membered, monocyclic or condensed ring 2-pyridyl, 3-pyrazolyl, 1-pyrrolyl,
2,4-dioxo-1,3-imidazolidin-1-yl, 2-benzoxazolyl, morpholino, indolyl and the like, an alkyl group (1 to 30, preferably 1 to 2 carbon atoms)
0, linear, branched or cyclic, and saturated or unsaturated alkyl, such as methyl, ethyl, i-propyl,
Cyclopropyl, t-pentyl, t-octyl, cyclopentyl, t-butyl, sec-butyl, dodecyl, 2
-Hexyldecyl, etc.), an acyl group (C 1-30, preferably 2-20 acetyl, benzoyl, etc.), an acyloxy group (C 2-30, preferably 2-20 propanoyloxy, tetradecanoyloxy An arylthio group (C6-20, preferably C6-10 phenylthio, naphthylthio, etc.), a sulfamoylamino group (C0-30, preferably 0-20 N-butylsulfamoylamino, N-dodecylsulfamoylamino, N-phenylsulfamoylamino, etc.) or N-sulfonylsulfamoyl group (N-mesylsulfamoyl having 1 to 30, preferably 1 to 20 carbon atoms, N-ethanesulfonylsulfur) Famoyl, N-dodecanesulfonylsulfamoyl, N-hexadecanesulfonylsulfamoyl, etc.).

The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

Among the above preferred substituents, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a nitro group, an alkyl group or an aryl group Is mentioned.

In the general formula [Y-III], the aryl group represented by R ₂₃ has 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
0 is a substituted or unsubstituted aryl group. For example, a phenyl group and a naphthyl group are typical examples.

The heterocyclic group represented by R ₂₃ includes the aforementioned R ₂₁
Or, it has the same meaning as described when R ₂₂ represents a heterocyclic group.

When R ₂₃ represents a substituted aryl group or a substituted heterocyclic group, examples of the substituent include the substituents listed as examples when R ₂₁ has a substituent. R
Preferred examples of the substituent of ₂₃ include one of the substituents
Is a halogen atom, alkoxycarbonyl group, sulfamoyl group, carbamoyl group, sulfonyl group, N-sulfonylsulfamoyl group, N-acylsulfamoyl group, alkoxy group, acylamino group, N-sulfonylcarbamoyl group, sulfonamide group Or an alkyl group.

R ₂₃ is particularly preferably at least 1
Are phenyl groups in the ortho position.

Examples of the group represented by X ₃ in the general formula [Y-III] include the same groups as those of X _{1 in the} general formula [Y-I], and are particularly preferably represented by the general formula (IV). Group.

Next, a particularly preferred range of the coupler represented by the general formula [Y-III] will be described below.

The group represented by R ₂₁ is preferably an alkyl group. Particularly preferred is an alkyl group having 1 to 10 carbon atoms.

The group represented by R ₂₃ is preferably an aromatic group. Particularly preferred is a phenyl group having at least one substituent at the ortho position. Examples of the substituent include those described above as the substituent which R ₂₃ may have when R ₂₃ is an aryl group. The same applies to examples of preferred substituents.

The group represented by X ₃ is preferably a nitrogen-containing heterocyclic group, an aryloxy group, a 5- or 6-membered heterocyclic oxy group or a 5- to 6-membered heterocyclic oxy group which is bonded to the coupling position by a 5- or 6-membered nitrogen atom. Membered heterocyclic thio groups.

Among the couplers represented by the general formula [Y-III], particularly preferred couplers are those represented by the following general formula [Y-III]
a], [Y-IIIb] or [Y-IIIc].

[0143]

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In the formula, X ₃ is the same as X ₃ in the general formula [Y-III].
_As defined for ₃ , R ₂₄ represents an alkyl group, R ₂₅ represents an alkyl group or an aromatic group, Ar represents a phenyl group having at least one substituent at the ortho position, and Z ₁₃ represents —C
(R ₂₆₎ (R ₂₇₎ represents an organic residue forming a -N nitrogen-containing Hajime Tamaki together with <(monocyclic or condensed), Z ₁₄ is -C (R
₂₈₎ = C (R ₂₉₎ represents an organic residue forming a -N nitrogen-containing Hajime Tamaki together with <(monocyclic or condensed _{ring), R 26, R 27,} R
₂₈ and R ₂₉ each represent a hydrogen atom or a substituent.

For the detailed description and the preferred range of the groups represented by R _{24 to} R ₂₉ , Z ₁₃ , Z ₁₄ and Ar, refer to the description of the corresponding groups in the description of the general formula [Y-III]. It has the same meaning as the description. When R _{26 to} R ₂₉ represent a substituent, those exemplified as the substituent which the above-mentioned R ₂₁ and R ₂₂ may combine to form a nitrogen-containing heterocyclic group formed together with N may be mentioned as examples.

Particularly preferred couplers among the general formulas [Y-IIIa] to [Y-IIIc] are those represented by the general formulas [Y-IIIb] or [Y-IIIc].

The coupler represented by the general formula [Y-III] has two groups represented by R ₂₁ , R ₂₂ , R ₂₃ and X _3.
Dimers or higher multimers (e.g., telomers or polymers) may be formed that are linked to each other via valency or higher groups. In this case, the number of carbon atoms may be out of the specified range for each substituent.

The coupler represented by the general formula [Y-III] is preferably a diffusion-resistant coupler. The diffusion-resistant coupler is a coupler having a group (diffusion-resistant group) for sufficiently increasing the molecular weight in the molecule in order to immobilize the molecule in the added layer. As the diffusion-resistant group, an alkyl group having a total of 8 to 30, preferably 10 to 20, or an aryl group having a substituent having a total of 4 to 20 carbon atoms is generally used. These diffusion-resistant groups may be substituted at any position in the molecule, and may have a plurality of groups.

The yellow coupler represented by the general formula [Y-III] is prepared by using a commercially available compound as a starting material, and by a conventionally known method, for example, a method disclosed in JP-A-4-1744.
Compounds can be easily synthesized according to the methods described in Nos. 28, 4-184434, 5-111416 and the like.

Specific examples of the yellow coupler represented by the general formula [Y-III] are shown below, but the present invention is not limited thereto.

[0151]

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[0152]

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[0153]

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[0154]

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Among the yellow couplers represented by formulas [Y-I] to [Y-III] of the present invention, the yellow couplers represented by formula [Y-I] are most preferred.

The general formulas [Y-I] to [Y-III] of the present invention
The yellow coupler represented by formula (1) can be used in the range of 1.0 to 1.0 × 10 ⁻³ mol per mol of silver halide. Preferably 5.0 × 10 ^{-1 to} 5.0 × 10 ^-2
Mol, more preferably 4.0 × 10 ^{−1 to} 2.0 ×
It is in the range of 10 ^-2 mol. The addition amount of the yellow coupler is preferably 0.70 g / m ² or less, and 0.65 g / m ² or less.
g / m ² or less is particularly preferred.

Next, the cyan coupler of the present invention will be described. The cyan coupler used in the invention according to claim 4 of the present invention has the general formulas [CI], [C-II], and [C-
III] or at least one compound represented by [C-IV].

The cyan coupler represented by the general formula [CI] will be described in detail.

The substituent having a substituent constant σp defined by Hammett according to the present invention of +0.20 or more is specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, Carboxyl,
Examples include groups such as cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, and halogen-substituted arylsulfonyl; and sulfinyl groups include alkylsulfinyl and arylsulfinyl; and sulfonyloxy groups include alkylsulfonyloxy and arylsulfonyloxy. Sulfamoyl groups include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-N-arylsulfamoyl, and the like; phosphoryl groups include alkoxyphosphoryl, aryloxyphosphoryl, alkyl Phosphoryl, arylphosphoryl and the like; carbamoyl groups include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-
N-arylcarbamoyl and the like; acyl groups as alkylcarbonyl, arylcarbonyl and the like; acyloxy groups as alkylcarbonyloxy and the like; oxycarbonyl groups as alkoxycarbonyl and aryloxycarbonyl and the like; halogen-substituted alkoxy groups as α -Halogen-substituted alkoxy and the like; halogen-substituted aryloxy groups include tetrafluoroaryloxy and pentafluoroaryloxy; pyrrolyl groups include 1-pyrrolyl and the like; tetrazolyl groups include 1-tetrazolyl and the like.

In addition to the above substituents, trifluoromethyl, heptafluoroisopropyl, nonylfluoro-
A t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

In the general formula [CI], R ₄₁ or R ₄₂
Among the substituents represented by, the substituents other than the electron-withdrawing group include, but are not particularly limited to, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, and arylthio. ,
Alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide,
Ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto, spiro compound residue, bridged hydrocarbon compound residue, etc. Is mentioned.

The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. As the aryl group, a phenyl group is preferable.

As the acylamino group, an alkylcarbonylamino group or an arylcarbonylamino group; as the sulfonamide group, an alkylsulfonylamino group or an arylsulfonylamino group; Groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially
To 7 are preferable, and the alkenyl group may be linear or branched. A cycloalkenyl group having 3 to 12 carbon atoms;
Particularly, those having 5 to 7 are preferable.

As the ureido group, an alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3 , 5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group;
3-heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residues such as spiro [3.3] heptane-1-yl; and bridged hydrocarbon compound residues as bicyclo [2.2. 1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

These groups may further contain a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

[0168] In general formula [C-I], the group or atom capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _31, for example a hydrogen atom, a halogen atom (hydrochloric, bromine, fluorine, etc.) and Alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, N
Examples include nitrogen-containing heterocycles bonded with atoms, alkoxycarbonylamino, aryloxycarbonylamino, carboxyl, and the like, and among these, a hydrogen atom and alkoxy, aryloxy, alkylthio, arylthio groups, N A nitrogen-containing heterocyclic group bonded by an atom.

In the general formula [CI], examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₁ include pyrazole, imidazole, benzimidazole, triazole and tetrazole. m is preferably from 0 to 5.

More specifically, the compound represented by the general formula [CI] is represented by the following general formulas [I] -1 to [I] -7.

[0171]

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In the above general formula, R _{41 in} [I] -1
And at least one of R _51, [I] at least one of R ₄₁ and R ₅₂ in -2, [I] in the -3 R _41, R
₅₃ and at least one of the at least one, [I] R ₄₁ in -4, R ₅₅ and R ₅₆ of the R _54, [I] -5
At least one of R ₄₁ and R ₅₇ in, [I] R ₄₁ in -6, at least one of (I) in -7 R ₄₁ and R ₅₈ are σp of 0.20 or more It is an electron-withdrawing group.

X ₃₁ has the same meaning as X ₃₁ in formula [CI], and p represents an integer of 0 to 4.

In the general formulas [I] -1 to [I] -7, among R ₄₁ and R _{51 to} R ₅₈ , those in which σp is not an electron-withdrawing group having 0.20 or more are a hydrogen atom or a substituted atom. Represents a group,
Among R ₅₈ , those which are not electron-withdrawing groups are not particularly limited as substituents. Specifically, in the general formula [C-I],
When R ₄₁ or R ₄₂ is other than an electron-withdrawing group, those described as the substituent represented by R ₄₁ or R ₄₂ can be mentioned.

The cyan coupler having an electron-withdrawing group according to the present invention is disclosed in JP-A-64-554 and JP-A-64-555.
, And can be easily synthesized according to the methods described in JP-A Nos. 64-557 and JP-A-1-105251.

Next, the cyan coupler represented by the general formula [C-II] will be described.

The cyan coupler of the general formula [C-II] has a structure in which a heterocyclic ring is formed by condensing with a pyrazole ring, and the substituent represented by R ₄₃ is not particularly limited.
Representative groups include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and the like.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, Phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfonic acid, etc. And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R ₄₃ preferably has 1 to 32 carbon atoms, may be linear or branched, and the aryl group is preferably a phenyl group.

The acylamino group represented by R ₄₃ includes:
Alkylcarbonylamino group, arylcarbonylamino group, etc .; sulfonamide groups include alkylsulfonylamino group, arylsulfonylamino group, etc .; the alkyl component and the aryl component in the alkylthio group and the arylthio group are the alkyl group and aryl represented by R ₄₃ above. Groups.

The alkenyl group represented by R ₄₃ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
~ 12, particularly preferably 5 ~ 7, and the alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R ₄₃ include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; and examples of the phosphonyl group include an alkylphosphonyl group, an alkoxyphosphonyl group and an arylphosphonyl group. An oxyphosphonyl group, an arylphosphonyl group, etc .; an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .; a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .; a sulfamoyl group, an alkylsulfamoyl group, arylsulfa Moyl group and the like; acyloxy group as alkylcarbonyloxy group and arylcarbonyloxy group and the like; carbamoyloxy group as alkylcarbamoyloxy group and arylcarbamoyloxy group and the like; As an id group, an alkylureido group, an arylureido group, etc .; as a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as a heterocyclic group, a 5- to 7-membered group is preferable. Typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
-Pyrrolyl group, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyl As a heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, and a 2,4-diphenoxy-1,3. , 5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutar Imido group and the like; spiro compound residue as spiro [3.3]
Heptane-1-yl and the like; as bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7
-Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like. Each of these groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

[0182] X ₃₁ as the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _32, the general formula [C-I]
And the same groups as described above.

In formula [C-II], the nitrogen-containing 6-membered ring formed by Z ₂ is preferably a 6π electron system or 8π
Electronic, containing at least one -NH-
At least one carbonyl group containing four nitrogen atoms and contained in the 6-membered ring represents a group such as> C = O or> C = S. Further, the at least one sulfonyl group the 6-membered ring contains -SO ₂ - represents a group.

Preferred examples of the cyan coupler of the present invention include compounds represented by the following general formulas [II] -1 to [II] -6.

[0185]

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In the formula, R ₄₃ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R
₆₅ , R ₆₆ , R ₆₇ and R ₆₈ have the same meanings as R ₄₁ in the general formula [CI], and X ₃₂ represents X in the general formula [CI].
And has the same meaning as _{31. In} the general formula [II] -5, n is 0 to
Represents an integer of 4, and when n is 2 or more, a plurality of R ₆₆ may be the same or different.

R ₆₄ , R ₆₅ , R ₆₇ and R ₆₈ in the general formulas [II] -4 and [II] -6 have the same meaning as R ₄₁ in the general formula [CI], but R ₆₄ and R ₆₇ Is not a hydroxyl group.

In the general formula [C-III], R ₄₄ and R
₄₅ represents an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more, and these electron-withdrawing groups are the same as those of R ₄₁ and R ₄₂ in the general formula [C-I]. And the group of Where σp of R ₄₄ and R ₄₅
The sum of the values is 0.65 or more.

Examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₃ include rings such as pyrazole, imidazole and tetrazole. These 5-membered nitrogen-containing heterocycles may have a substituent.

The compounds represented by the general formula [C-III] are more specifically described by the following general formulas [III] -1 to [III]-
8.

[0191]

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In the formula, R ₄₄ , R ₄₅ and X ₃₃ are represented by the general formula [C
-III]. R ₇₁ represents a hydrogen atom or a substituent, and R ₇₂ is a Hammett's substituent constant σp
Represents an electron-withdrawing group of 0.20 or more.

The substituent represented by R ₇₁ is represented by the general formula [C-
The same groups as those for R _{43 in} II] can be mentioned. As the electron-withdrawing group represented by R ₇₂ , R ₄₁ in the general formula [CI]
And include the same groups as the electron-withdrawing groups R _42.

The cyan coupler represented by the general formula [C-III] can be a cyan coupler represented by the general formula [III] -1, [III] -2 or [III]
The cyan coupler represented by -3 is preferable, and the cyan coupler represented by the general formula [III] -2 is particularly preferable.

In the general formula [C-IV], R ₄₆ and R ₄₇
Represents a hydrogen atom or a substituent, and examples of these substituents include the same groups as R _{43 in} formula [C-II].

Z ₄ in the general formula [C-IV] represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring.
However, the heterocyclic ring has at least one dissociating group.
Examples of four divalent linking groups for forming a nitrogen-containing 6-membered heterocyclic ring include -NH-, -N (R)-, -N =,-
CH (R)-, -CH =, -C (R) =, -CO-,-
S -, - SO -, - SO 2 - and the like (R is a substituent group, include substituents exemplified in R ₇₁ and examples thereof).

As the dissociating group, for example, -NH-, -CH
Examples thereof include those having an acidic proton such as (R)-, and preferably have a pKa in water of 3 to 12.

Of the couplers represented by the general formula [C-IV], preferred specific examples are the following general formulas [IV] -1 to
The compound represented by [IV] -6 is exemplified.

[0199]

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In the formula, R ₄₆ , R ₄₇ and X ₃₄ are represented by the general formula [C
-IV]. R ₈₁ and R ₈₂ each represent a hydrogen atom or a substituent, and R ₈₃ represents an electro-attractive group having a Hammett's substituent constant σp value of 0.20 or more.

Specific examples of the substituents of R ₈₁ and R ₈₂ are the same as those of R _{43 in} the general formula [C-II]. Specific examples of the electron-withdrawing group represented by R ₈₃ are those of the general formula [C-I] R ₄₁ and R ₄₂
And the same as the electron-withdrawing group.

[0202] X ₃₁ as the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _34, the general formula [C-I]
And the same groups as described above.

Hereinafter, specific examples of the cyan couplers represented by the general formulas [CI] to [C-IV] (hereinafter, referred to as the cyan coupler of the present invention) will be given, but the invention is not limited thereto. .

[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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The cyan coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide.
It can be used in the range of × 10 ^-2 to 8 × 10 ^-1 mol. Further, the coupler of the present invention can be used in combination with another type of cyan coupler.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferred. Quick processing,
From the viewpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 100 mol% of silver chloride is preferred.

For obtaining the silver halide emulsion according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing a high concentration of silver bromide may be epitaxy-bonded to silver halide emulsion grains, a so-called core-shell emulsion, or may be formed only partially without forming a complete layer. May simply have regions with different compositions. Further, the composition may change continuously or discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

In order to obtain the silver halide emulsion according to the present invention, it is advantageous to include a heavy metal ion. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples include Group 8 to 10 metals such as osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferred.

These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl ion. , Ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order for the silver halide emulsion according to the present invention to contain heavy metal ions, the heavy metal compound is physically added before, during, and after the formation of silver halide grains. What is necessary is just to add in arbitrary places of each process during ripening. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound can be dissolved together with a halide salt and added continuously over the whole or a part of the grain forming step.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
Mol or more and 1 × 10 ^-2 mol or less, particularly 1 mol
It is preferably at least 10 ^-8 mol and not more than 5 10 ^-5 mol.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-B-55-42
No. 737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm in consideration of other photographic properties such as rapid processing and sensitivity.
m, more preferably in the range of 0.2 to 1.0 μm.

The particle diameter can be measured by using the projected area of the particle or an approximate value of the diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains of the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably a coefficient of variation of 0 or less. .15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (where, S is the standard deviation of the particle size distribution, and R is the average particle size.) The particle size here is the diameter of a spherical silver halide particle. In the case of a particle having a shape other than a cube or a sphere, it represents a diameter when the projected image is converted into a circular image having the same area.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Also, JP-A-57-92523, JP-A-57-92523
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt and a water-soluble solution described in German Patent Publication No. 292,164. Apparatus for continuously changing the concentration of an aqueous halide salt solution, JP-B-56-50
The reaction mother liquor was taken out of the reactor described in No. 1776, etc.
An apparatus that forms grains while keeping the distance between silver halide grains constant by concentrating by ultrafiltration may be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion according to the present invention can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but a sulfur sensitizer is preferable. Thiosulfates as sulfur sensitizers,
Allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, inorganic sulfur and the like can be mentioned.

The addition amount of the sulfur sensitizer according to the present invention is preferably changed depending on the kind of the silver halide emulsion to be applied and the size of the expected effect, but 5 × 10 5 per mol of silver halide. ^In the range of ^{-10 to} 5 × 10 ^-5 mol,
Preferably, it is in the range of 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol.

As the gold sensitizer according to the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide.
Preferably it is molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

The chemical sensitization of the silver halide emulsion according to the present invention may be a reduction sensitization.

The silver halide emulsion according to the present invention is intended to prevent fogging during the preparation process of the silver halide photographic material, reduce performance fluctuation during storage, and prevent fogging during development. And known antifoggants and stabilizers can be used. Examples of preferred compounds that can be used for such purposes include JP-A-2-146.
No. 036, page 7 of the specification, compounds represented by the general formula (II) described below, and more preferred specific compounds are (IIa-1) described on page 8 of the same publication. )-(IIa-8), (IIb-1)-(II
b-7) or 1- (3-methoxyphenyl)-
Compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds may be used, depending on the purpose, in a step of preparing silver halide emulsion grains, a step of chemical sensitization,
At the end of the chemical sensitization step, it is added in a step such as a coating liquid preparation step. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 ×
It is preferably used in an amount of about 10 ^-4 mol. When added at the end of chemical sensitization, 1 × per mole of silver halide
An amount of about 10 ⁻⁶ mol to 1 × 10 ⁻² mol is preferable, and 1 ×
The amount is more preferably from 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. In the step of preparing a coating solution, when added to the silver halide emulsion layer, 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of silver halide is used.
An amount of about ^-1 mol is preferred, and 1 × 10 ^-5 mol to 1 × 10
^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ^-9 mol to 1 × 10 ^-3 mol per 1 m ² .

In the silver halide photographic light-sensitive material of the present invention,
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compounds can be used. In particular, dyes having absorption in the visible region include AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used. Examples of the infrared-absorbing dye include general formulas (I) and (I) described in the lower left column of page 2 of JP-A-1-280750. The compounds represented by II) and (III) have preferable spectral characteristics, do not affect the photographic characteristics of the silver halide photographic emulsion, and are preferable without contamination by residual color. Specific examples of preferred compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column of the same publication.

In order to improve the sharpness, the amount of these dyes added was 680 nm for an unprocessed sample of a light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

In the silver halide photographic light-sensitive material of the present invention,
It is preferable to add a fluorescent whitening agent because the whiteness can be improved.
Compounds preferably used are described in JP-A-2-232.
No. 652, compounds represented by the general formula II.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, a halogen spectrally sensitized to a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. It has a layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye for use in the silver halide emulsion according to the present invention, any known compounds can be used.
BS-1 to 8 described on page 28 of JP-A-251840 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Nos. S-1 to S-17 described on pages 15 to 17
Are preferably used in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

The sensitizing dye may be added by dissolving it in a water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, or dimethylformamide or water, or adding it as a solid dispersion. It may be added.

The couplers used in the silver halide photographic light-sensitive material of the present invention include, in addition to the above-mentioned yellow coupler and cyan coupler, a spectral reaction in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent. Any compound capable of forming a coupling product having a maximum wavelength can be used, and typical examples thereof include yellow dye-forming couplers other than those having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, Wavelength range 5
Representative examples include magenta dye-forming couplers having a spectral absorption maximum wavelength in the range of 00 to 600 nm, and other cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

The magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include those represented by formulas (MI) and (M-II) described in the upper right column on page 4 of JP-A-4-114154. And a coupler represented by the following formula: Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the publication. Among the above magenta couplers, a coupler represented by the general formula (MI) described in the upper right column on page 4 of the same publication is preferable, and among them, the RM of the general formula (MI) is tertiary. Couplers that are alkyl groups are particularly preferred because of their excellent light resistance. MC-8 to MC-1 described in the upper column of page 5 of the gazette
No. 1 is preferable because it is excellent in reproducing colors from blue to purple and red, and is also excellent in detail description.

When an oil-in-water emulsion dispersion method is used to add the couplers and other organic compounds used in the silver halide photographic light-sensitive material of the present invention, the boiling point is usually 15 points.
It is dissolved in a water-insoluble high-boiling organic solvent at 0 ° C. or higher, if necessary, in combination with a low-boiling and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. . As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer,
An ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low boiling organic solvent may be added. Examples of high boiling organic solvents that can be used to dissolve and disperse the coupler include dioctyl phthalate, diisodecyl phthalate, phthalic acid esters such as dibutyl phthalate, tricresyl phosphate, and phosphoric acid esters such as trioctyl phosphate; Is preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means.
Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

As a compound preferable as a surfactant used for dispersing a photographic additive or adjusting a surface tension at the time of coating, a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule are preferable. Containing. Specifically, A- described in JP-A-64-26854 is described.
1 to A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are preferably as short as 10 hours each. Preferably within 3 hours, more preferably within 20 minutes.

It is preferable to use an anti-fading agent in combination with the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541 and phenolic compounds represented by general formula IIIB described in JP-A-3-174150. Amine compounds represented by the general formula A described in Japanese Patent Application Laid-Open No. 64-90445;
The metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP 182741 are particularly preferred for magenta dyes. Further, compounds represented by the general formula I 'described in JP-A-1-19649 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, the compound (d-11) described in the lower left column of page 9 of JP-A-4-114154 and the compound described in the lower left column of page 10 of the same specification are disclosed. Compounds such as (A'-1) can be used. In addition, U.S. Pat.
No. 74,187 can also be used.

In the silver halide light-sensitive material of the present invention, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula II described in JP-A-4-133056, and include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17 of the same publication. .

It is preferable to add an ultraviolet absorber to the silver halide light-sensitive material of the present invention to prevent static fog or to improve the light fastness of a dye image. Preferable ultraviolet absorbers include benzotriazoles. Particularly preferred compounds are compounds represented by the general formula III-3 described in JP-A-1-250944,
No. 66646, compounds represented by the general formula III,
UV-1L to U described in JP-A-63-187240
V-27L, general formula I described in JP-A-4-1633
And the compounds represented by formulas (I) and (II) described in JP-A-5-165144.

In the silver halide photographic light-sensitive material of the present invention,
It is advantageous to use the above-mentioned gelatin as a binder, but if necessary, other gelatin, a gelatin derivative,
A graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, or a hydrophilic colloid such as a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. JP-A-61-24
It is preferable to use the compounds described in JP-A Nos. 9054 and 61-245153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the photosensitive material or the surface of the processed sample.

In coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. Extrusion coating and curtain coating, in which two or more layers can be applied simultaneously, are particularly useful as a coating method.

In order to form a photographic image using the silver halide photographic light-sensitive material of the present invention, an image recorded on a negative is optically formed on a silver halide photographic light-sensitive material to be printed. The image may be converted into digital information, then formed into an image on a CRT (cathode ray tube), and the image may be formed on a silver halide photographic material to be printed. The printing may be performed, or the printing may be performed by changing the intensity of the laser beam based on the digital information and scanning.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material which directly forms an image for viewing. For example, color paper, color reversal paper, a photosensitive material for forming a positive image, a photosensitive material for a display, and a photosensitive material for a color proof can be used. It is particularly preferable to apply the invention to a photosensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-Amino-3-methyl-N-ethyl-N
-([Beta]-(methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9 ) 4-Amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.3.
0, more preferably pH 9.8-
Used in the range of 12.0.

The processing temperature of color development according to the present invention is 35
The temperature is preferably from 70 ° C to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

Conventionally, the color development time is generally about 3 minutes and 30 seconds, but in the present invention, it is preferably within 40 seconds, and more preferably within 25 seconds.

In the color developer, in addition to the above-described color developing agent, a known developer component compound can be added. Usually, alkaline agents having a pH buffering action, chloride ions, development inhibitors such as benzotriazoles, preservatives,
A chelating agent or the like is used.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a water washing process is performed. Further, as an alternative to the water washing treatment, a stabilization treatment may be performed. The developing apparatus used for developing the silver halide photographic light-sensitive material of the present invention may be a roller transport type in which the light-sensitive material is conveyed across rollers arranged in a processing tank.
An endless belt type in which the photosensitive material is fixed to the belt and transported may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported or a processing liquid is transported. A spray method of spraying, a web method by contact with a carrier impregnated with a treatment liquid, a method using a viscous treatment liquid, and the like can also be used. When processing in large quantities, it is normal to run using an automatic processor, but in this case, the smaller the replenishment amount of the replenisher, the more preferable, and the most preferable processing form from environmental suitability is
The replenishment method is to add a processing agent in the form of a tablet, and the method described in Publication Technique 94-16935 is most preferred.

[0264]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <White base paper> 170 g / basis of 50% by weight of sulfated bleached hardwood pulp (LBKP) and 50% by weight of sulfated bleached softwood pulp (NBSP) for photographic paper for photographic grade
A white base paper having an m ² and a thickness of 175 μm was prepared.

<Preparation of Paper Supports A to C> As the back resin layer of the white base paper, polyethylene was melt-extruded and laminated at 300 ° C. to cover a back laminate layer of 27 g / m ² .

Next, as a surface resin layer, 95% by weight of polyethylene and 5% by weight of anatase type titanium oxide were kneaded, and then a water-resistant resin layer of 30 g / m ² was coated by melt extrusion lamination at 300 ° C. Paper support A having a coating layer was prepared.

Paper supports B and C were prepared in the same manner as paper support A except that the composition of titanium oxide in the surface resin layer was changed from paper support A as shown in Table 1.

[0269]

[Table 1]

<Paper Supports D to I> As a back resin layer of the white base paper, polyethylene was melt-extruded and laminated at 300 ° C. to cover a 25 g / m ² back laminate layer.

After kneading 95% by weight of polypropylene and 5% by weight of anatase-type titanium oxide, the mixture was melt-extruded at 300 ° C., and a biaxially oriented polypropylene resin sheet having a thickness of 20 μm was formed using a flat film sequential biaxial stretching apparatus. After the production, the polyethylene extruded at a thickness of 5 μm is laminated between the opposite side of the white base paper provided with the backing resin layer and the sheet, and then nipped to form a laminated surface resin layer,
Paper support D was prepared.

The support E to I were the same as the support D except that the thickness of the biaxially stretched polypropylene resin sheet of the surface resin layer and the content of titanium oxide were changed as shown in Table 2 from the paper support D. Was prepared.

[0273]

[Table 2]

<Paper Supports J to N> After the clear polypropylene was melt-extruded at 300 ° C., a biaxially oriented polypropylene resin sheet having a thickness of 15 μm was prepared using a flat film sequential biaxial stretching apparatus, and then 5 μm thick. Was laminated between the white base paper and the sheet, and then nipped to form a laminated back resin layer.

Subsequently, 95% by weight of polypropylene and 5% by weight of anatase-type titanium oxide were kneaded and then melt-extruded at 300 ° C., and then a biaxially oriented polypropylene resin having a thickness of 15 μm was obtained using a flat film sequential biaxial stretching apparatus. After the sheet is produced, polyethylene extruded at a thickness of 5 μm is laminated between the opposite side of the white base paper on which the back resin layer is provided and the sheet, and then nipped to form a laminated surface resin layer. Support J was prepared.

The support K was the same as the support K except that the thickness of the biaxially oriented polypropylene resin sheet of the surface resin layer and the content of titanium oxide were changed as shown in Table 3 from the paper support J.
To N were prepared.

[0277]

[Table 3]

<Paper Support O> Polyethylene was melt-extruded and laminated at 300 ° C. as a back resin layer of the white base paper to cover a 25 g / m ² back laminate layer.

After kneading 89% by weight of polystyrene and 11% by weight of anatase type titanium oxide, the mixture was melt-extruded at 330 ° C., and a biaxially oriented styrene resin sheet having a thickness of 20 μm was formed using a flat film sequential biaxial stretching apparatus. After being produced, polyethylene extruded with a thickness of 5 μm is laminated between the opposite side of the white base paper on which the back resin layer is provided and the sheet, and then nip is formed to form a laminated surface resin layer. O was produced.

<Paper Support P> Polyethylene was melt-extruded and laminated at 300 ° C. as a back resin layer of the white base paper to cover a 25 g / m ² back laminate layer.

89% by weight of polyethylene terephthalate,
After kneading 11% by weight of anatase type titanium oxide,
After melt-extrusion at 0 ° C., a biaxially stretched polyethylene terephthalate resin sheet having a thickness of 20 μm was prepared using a flat film method sequential biaxial stretching apparatus. After laminating between the opposite surface on which the back resin layer was provided and the sheet, the sheet was nipped to form a laminated surface resin layer, thereby producing a paper support P.

After subjecting the surface resin layer side of each of the supports A to P to a corona discharge treatment (output current value: 2 amps), a gelatin undercoat layer was coated and dried so that the gelatin coverage was 40 mg / m ^2. Provided.

Next, Supports A to P provided with a gelatin undercoat layer
Were coated with the photographic constituent layers shown in Tables 4 and 5 below to produce multilayer color photographic paper samples 101 to 116 shown in Table 6. The coating solution was prepared as follows.

In the order of layers, the layer closest to the support is the first layer, and the layer farthest from the support is the seventh layer.

Coating solution for the first layer 23.4 g of yellow coupler (YA-1), 3.34 g of dye image stabilizer (ST-1), dye image stabilizer (ST-
2) 3.34 g, dye image stabilizer (ST-5) 3.34
g, 0.34 g of stain inhibitor (HQ-1), 5.0 g of image stabilizer A, 5.0 g of high-boiling organic solvent (DBP) and 1.67 g of high-boiling organic solvent (DNP), and ethyl acetate 6
Add 0 ml and dissolve, 10% surfactant (SU-1)
Emulsified and dispersed in 320 ml of a 7% aqueous gelatin solution containing 5 ml using an ultrasonic homogenizer to prepare 500 ml of a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 4 and 5.

Further, (H-1), (H-2)
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount became 0.04 g / m ² .

[0288]

[Table 4]

[0289]

[Table 5]

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Di (2-ethylhexyl) sodium sulfosuccinate SU-3: Di (2,2,3,3,4, sulfosuccinate) 4,
5,5-octafluoropentyl) sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-Dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2.5 -Di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] Hydroquinone Image stabilizer A: pt-octylfe Nord

[0291]

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[0292]

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[0293]

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[0294]

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(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
The following (solution A) and (solution B) were added in 1 liter of a 2% aqueous gelatin solution kept at a temperature of pAg = 7.3 and pH = 3.0.
And simultaneously added over 30 minutes.
Solution) and (Solution D) were added simultaneously over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg
Was controlled by the method described in JP-A-59-45437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was again mixed with an aqueous gelatin solution to give an average particle diameter of 0.71.
μm, variation coefficient of particle size distribution 0.07, silver chloride content 9
A 9.5 mol% monodispersed cubic emulsion EMP-1 was obtained.

Next, EMP was performed except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
In the same manner as -1, a monodispersed cubic emulsion EMP-1B having an average particle size of 0.64 μm, a coefficient of variation of 0.07, and a silver chloride content of 99.5 mol% was obtained.

The above-mentioned EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver amount of 1: 1 to obtain a blue-sensitive silver halide emulsion Em-B.

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%.

Next, similarly to EMP-2, the average particle size is 0.50 μm, the coefficient of variation is 0.08, and the silver chloride content is 99.
A 5% monodisperse cubic emulsion EMP-2B was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion Em-G.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation of 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5% were obtained. A monodispersed cubic emulsion EMP-3B having an average particle size of 0.38 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained in the same manner as in EMP-3.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver amount of 1: 1 to obtain a red-sensitive silver halide emulsion Em-R.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole 2.0 × 10 ^-3 mol of SS-1 was added per mol of silver halide.

[0305]

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[0306]

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The samples 101 to 116 produced in this manner
Was evaluated as follows.

<Evaluation of Sharpness> After a resolving power test chart was printed on each sample with red light and subjected to the following developing process, the obtained cyan image was subjected to microdensitometer PDM-5D (manufactured by Konica Corporation). ) Was measured, and the value represented by the following equation was defined as sharpness.

Sharpness (%) = (Dmax−Dmin of dense line print image of 5 lines / mm) / (Dma in large area portion)
x-Dmin) Here, Dmax: maximum density Dmin: minimum density The larger this value is, the better the sharpness is.
It is preferably at least 0%.

<Emulsion Surface Pressure Resistance> Unexposed samples were measured using a scratch meter (manufactured by Shinto Kagaku Co., Ltd.) at 10 g, 15 g, 20 g, 25 g, 30 g, 35 g,
After scratching using a diamond needle having a diameter of 0.1 mm to which a load of 40 g, 45 g, and 50 g was applied, development was performed according to the following development processing step A, and the load at which pressure fogging of cyan was generated was examined.

[0311] The higher the load, the less the occurrence of pressure fog, and the better the resistance against pressure failure.

[0312] In practice, the amount of 20 g or less is a problem, and 30 g or less is a problem.
It is preferable that it is above.

<Backside pressure resistance> A ball point needle having a ball diameter of 0.3 mm was placed on the sample, which had been subjected to uniform exposure so that the developed color density of yellow after development processing was 0.1 to 0.3, from the back side at 1 cm / cm. At the same time, a load of 0 to 400 g is continuously changed and applied to the ball point needle while being translated by 10 cm at a speed of seconds. After the color development in the liquid of the above-mentioned processing composition and the development processing step, the load at the ball point when the yellow density increases due to the pressure from the back surface of the sample on the emulsion surface of the sample is recorded. It is evaluated that the larger the value of the load, the more excellent the back pressure resistance.

Practically, 200 g or less is a problem.
It is preferably 0 g or more.

<Evaluation of Cut Surface> Each sample was cut with a guillotine cutter, and on the cut surface, the state where the front and back resin layers were stretched and deformed was observed, and the results were evaluated in the following four grades.

A: The cut surface is extremely smooth and no deformation is observed in the front and back resin layers. B: The front and back resin layers are partially stretched and deformed partially on the cut surface. The layer is stretched and deformed. D: The front and back resin layers are greatly stretched and greatly deformed over the entire cut surface. <Press fog at the cutting section> Each sample is cut with a guillotine cutter, and the degree of fog due to the pressure at the time of cutting is determined in three stages. evaluated. If a large force is required at the time of cutting, fogging becomes easy.

A: Fog is scarcely recognized at the cut portion. B: Fog is recognized at the cut portion, but there is no practical problem. C: Fog at the cut portion is apparent and poses a practical problem.

[Development Processing Step A] Processing Step Processing Temperature Time Replenishment Color Development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 Second 150ml Drying 60-80 ° C 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N-β methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriaminepentaacetic acid Penta sodium salt 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make a total volume of 1 liter. 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution tank solution and replenisher diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 0.0g ammonium sulfite (40% aqueous solution) 27.5ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g Polyvinylpyrrolidone 1.0 g Ammonia water (25% aqueous ammonium hydroxide solution) 2.5 g Nitrilotriacetic acid disodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[0322]

[Table 6]

From Table 6, it can be seen that the sample of the present invention has excellent sharpness, excellent pressure resistance from the emulsion side and from the back side, and further has excellent cutting properties.

Example 2 Only the gelatin was reduced on average from each layer of the photographic constituent layer of Sample 102 of Example 1, and the total amount of gelatin was 6.8 g / g.
samples were produced 201 and m ^2.

Next, from Sample 201, the support was changed as shown in Table 7 and only gelatin was reduced on average from each layer of the photographic constituent layers, and the total amount of gelatin was changed as shown in Table 7 except for the above. Samples 202 to 213 which were the same as the sample 201 were produced.

Next, the samples 201 to 213 were evaluated for suitability for rapid processing as described below. Further, as in Example 1, <Emulsion surface pressure resistance>, <Back pressure resistance>, <Evaluation of cut surface>, <Cutting surface evaluation> Pressure fog> was evaluated.

The results obtained are shown in Table 7.

<Evaluation of aptitude for rapid processing> After exposure to wedges with white light according to a conventional method, the development processing step A of Example 1 was carried out.
And the following development processing step B. The obtained sample was subjected to reflection density measurement using a PDA-65 densitometer manufactured by Konica Corporation with blue light, and each gradation (two points of density 0.80 and 1.80 of the characteristic curve were connected to each other to form a straight line). Slope (γ)).

The rapid processability was determined by the following equation.

Rapid processing property = γ _B (gradation in processing in development processing step B) / γ _A (gradation in processing in development processing step A) The closer this value is to 1, the more excellent the rapid processing property, and 0 .95 or more is preferred.

[Development Step B] Evaluation was conducted in the same manner as in Example 1, and it was confirmed that the effects of the present invention could be effectively obtained.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 25 seconds 81 ml Bleaching and fixing 35.0 ± 0.5 ° C. 25 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Drying 60-80 30 ° C. The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3. 5 g 6.0 g Triethanolamine 10.0 g 10.0 g Sodium salt of diethylenetriaminepentaacetic acid 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter, PH = 1
Adjust the replenisher to pH = 10.60 to 0.10.

Bleach-fix solution tank solution and replenisher tank solution Replenisher diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to make the tank solution pH = 7.0, and make up the replenisher solution pH = 6.
Adjust to 5.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

[0336]

[Table 7]

From Table 7, it can be seen from Table 7 that the samples other than the present invention had an adverse effect on the pressure resistance from the emulsion side and the back side when the amount of gelatin was reduced for the purpose of improving the suitability for rapid processing. It can be seen that even when the amount of the emulsion is reduced, the emulsion surface side and the back side have excellent performance with respect to pressure resistance.

Example 3 From the sample 102 of Example 1, the yellow coupler (YA-1) of the first layer was used in order to improve the color reproduction of a yellow image.
Was changed to the yellow coupler of the present invention shown in Table 8 in the same molar amount, and the same procedure as in Sample 102 was carried out.
1 was produced.

Next, the support was changed from Sample 301 as shown in Table 8, and the yellow coupler of the first layer of the present invention was changed to that shown in Table 8.
Samples 302 to 317, which were all the same as Sample 301, except that the Y coupler was changed to the Y coupler shown in FIG.

Next, the samples 301 to 317 were evaluated in the same manner as in Example 1 for <back surface pressure resistance>, <cut surface evaluation>, and <cut portion pressure fog>.

Table 8 shows the obtained results.

[0342]

[Table 8]

As can be seen from Table 8, when the yellow coupler of the present invention was used for the purpose of improving the color reproduction of a yellow image, the backing pressure resistance of the samples other than the present invention was significantly deteriorated. It turns out that it has excellent backing pressure resistance.

Example 4 From the sample 102 of Example 1, in order to improve the color reproduction of a cyan image, the cyan couplers (CA-1 and CA-1) of the fifth layer were used.
Sample 401 was prepared in the same manner as Sample 101, except that -2) was changed to the cyan coupler of the present invention shown in Table 9 in the same molar amount.

Next, the same as Sample 401 except that the support was changed from Sample 401 as shown in Table 9 and the cyan coupler of the present invention in the first layer was changed to the cyan coupler of the present invention shown in Table 9. Samples 402 to 416 were prepared.

Next, the samples 401 to 416 were evaluated in the same manner as in Example 1 for <emulsion surface pressure resistance>, <cut surface evaluation>, and <cut portion pressure fog>.

Table 9 shows the obtained results.

[0348]

[Table 9]

As can be seen from Table 9, when the cyan coupler of the present invention was used for the purpose of improving the color reproduction of the cyan image, the backing pressure resistance of the samples other than the present invention was significantly deteriorated. It can be seen that the emulsion has excellent emulsion surface pressure resistance.

[0350]

According to the present invention, a halogenated halide having excellent sharpness and rapid processing suitability, improved pressure resistance from the emulsion surface side and pressure resistance from the back surface of the reflective support, and further excellent cutting suitability. A silver photographic light-sensitive material can be obtained.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having resin layers on both sides of a base paper, The resin layer of the reflective support on the side on which the emulsion layer is to be provided is composed of a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the thickness of the biaxially stretched polymer sheet is 10 to 30 μm, and A silver halide photographic material, wherein the biaxially stretched polymer sheet contains at least 10% by weight of a white pigment. 2. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having resin layers on both sides of a base paper, The resin layer of the reflective support on the side on which the emulsion layer is to be provided is composed of a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the thickness of the biaxially stretched polymer sheet is 10 to 30 μm, and A silver halide photographic material, wherein the total amount of gelatin contained in the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer is 6.5 g / m ² or less. 3. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having resin layers on both sides of a base paper, The resin layer on the side of the reflective support on which the emulsion layer is provided is composed of a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the thickness of the biaxially stretched polymer sheet is 10 to 30 μm, and At least one of the silver halide emulsion layers has the following general formula [Y-I], [Y-
A silver halide photographic material comprising at least one yellow coupler represented by formula [II] or [Y-III]. Embedded image [Wherein, R ₁ represents an alkyl group, a cycloalkyl group or an allyl group, R ₂ represents an alkyl group, a cycloalkyl group or an aryl group, and R ₃ represents a hydrogen atom, a halogen atom or an acylamino group. X ₁ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. [Chemical formula 2] [Wherein, R ₁₁ represents a monovalent substituent excluding a hydrogen atom;
Is necessary for forming a 3- to 5-membered hydrocarbon ring together with C, or a 3- to 5-membered heterocyclic ring containing at least one heteroatom selected from N, S, O and P in the ring. Represents a non-metallic atomic group. R ₁₂ is a hydrogen atom, a halogen atom,
Represents an alkyl group, an alkoxy group, an aryloxy group or an amino group, and R ₁₃ represents a group capable of being substituted on a benzene ring.
X ₂ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. [Chemical formula 3] [Wherein, R ₂₁ and R ₂₂ each represent an alkyl group, an aryl group, or a heterocyclic group, and R ₂₃ represents an aryl group or a heterocyclic group. X ₃ represents a group or an atom which is released by a reaction with an oxidized form of the color developing agent. Further, R ₂₁ and R ₂₂ are bonded to each other, and N
May form a nitrogen-containing heterocyclic ring together. ] 4. A silver halide photographic material having at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a reflective support having resin layers on both sides of a base paper, The resin layer of the reflective support on the side on which the emulsion layer is to be provided is composed of a resin layer containing a biaxially stretched polymer sheet containing a white pigment, the thickness of the biaxially stretched polymer sheet is 10 to 30 μm, and At least one of the silver halide emulsion layers has the following general formula [C-I], [C-
A silver halide photographic material comprising at least one of the cyan couplers represented by [II], [C-III] and [C-IV]. Embedded image [In the formula, R ₄₁ represents a hydrogen atom or a substituent, and R ₄₂ represents a substituent. m represents the number of substituents R _42. When m is 0, R
₄₁ Hammett's substituent constant σp represents 0.20 or more electron-withdrawing group, when m is 1 or 2 or more, at least one of R ₄₁ and R ₄₂ Hammett's substituent constant σp of 0.20
It represents the above electron-withdrawing group. Z ₁ represents a nonmetallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like. R ₄₃ represents a hydrogen atom or a substituent; Z ₂ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring by condensing together with —NH— with a pyrazole ring; May have a substituent, and may form a condensed ring with a benzene ring or the like other than the pyrazole ring. R
₄₄ and R ₄₅ represent an electron-withdrawing group having a Hammett's substituent constant σp of 0.20 or more. Provided that the sum of σp values of R ₄₄ and R ₄₅ is 0.65 or more. Z ₃ represents a group of nonmetal atoms necessary to form a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered heterocyclic ring may have a substituent. R ₄₆ and R ₄₇ each represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; Is also good. X ₃₁ , X ₃₂ , X ₃₃ and X ₃₄ each represent a group or an atom which is released by a coupling reaction with an oxidized color developing agent. ]