JPH07319114A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the color photosensitive material superior in sharpness and gloss and small in uneven density and low in tendency to deteriorate in sharpness and gloss after storage for a long period by regulating a titanium oxide content in the resin of a photographic support and the central face average roughness on the surface of the resin layer on the side coated with a silver halide emulsion layer. CONSTITUTION:The support of the color photosensitive material contains the titanium oxide in an am<cunt o$>=9g/m<2> and has the central face average roughness (SRa) of <=0.08mum on the resin surface on the side coated with the silver halide photosensitive layer and the roughness (SRa) is represented by the equation in which Lx is the length of a measured face area in the direction of the X-axis; Ly is its length in the direction of the Y-axis; SA is the area of the measured face (LxXLy). At that time, Lx=7.5mm and Ly is 21mm, f(x, y) represents the roughened face of the surface, and each of x and y is the the coordinates of the measured position.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color print photographic light-sensitive material excellent in sharpness and gloss and having improved density unevenness in an image.

[0002]

2. Description of the Related Art With the widespread use of color photographic paper photographic light-sensitive materials, the demand for high-quality images is increasing. Under such circumstances, studies on color reproducibility, tone reproducibility, sharpness improvement, density unevenness improvement, and the like have been widely conducted in color print photosensitive materials.

Irradiation and halation are generally known as factors affecting sharpness. The former is caused by scattering of incident light by oil droplets such as silver halide grains and couplers dispersed in a gelatin film, and its degree depends mainly on the gelatin amount, silver halide amount, and oil droplet amount. On the other hand, in the latter case, sharpness is deteriorated by harmful reflected light on the interface between the emulsion layer and the support or on the back surface of the support, and it depends on the degree of light reflection from the support and the reflectance of the support or It is known to depend on the refractive index.

Dye improvements have been made to prevent irradiation. For example, Japanese Patent Publication No. 50-145125
52-20830, 50-111641, 61-148448,
No. 61-151650, No. 62-275262, No. 62-283336, Research Disclosure RD-17643 (December 22, 1979, p. 22) and RD-18716 (November, 647).
Page) etc. for the improvement of dyes. As the antihalation method, a method of providing an antihalation layer on a light-sensitive material is known. For example, JP-A-55-33172 and 59-33
-193447 and 62-33448.

However, in these methods, the sharpness is improved and the sensitivity is remarkably lowered, and it is difficult to improve the sharpness while maintaining the practically sufficient sensitivity only by such means. Further, when a large amount of antihalation dye is used, the gradation is softened, and the used dye remains after the treatment, which is one of the reasons why a high reflection density cannot be practically provided. In the method of providing the antihalation layer, a new layer is added to the conventional layer structure, which increases manufacturing difficulty and is not preferable.

[0006] On the other hand, improvement of the support for these has also been investigated. In recent years, as a support for a color print photosensitive material, a water-resistant support in which polyethylene is laminated on the surface of a raw paper has been used for the purpose of speeding up development processing. A white pigment such as titanium oxide is dispersed and used in the polyethylene layer for a white background of a color print. The amount of titanium oxide in the resin layer of the polyethylene support is increased to improve the sharpness, but the smoothness of the polyethylene layer deteriorates, the glossiness decreases, and the adhesion between the polyethylene layer and the sewing seat phase is reduced. It became difficult to increase the filling rate of the white pigment in the polyethylene layer. It is also known that in a silver halide color photographic light-sensitive material using a polyethylene layer support, unevenness in density tends to occur in an image portion after development processing due to unevenness of the polyethylene layer surface.

Further, in a coating layer such as an emulsion layer or a non-emulsion layer such as an intermediate layer (hereinafter referred to as a light-sensitive layer), as a coating aid for improving coatability and for improving dispersibility of a coupler. A surfactant is used as a dispersion aid of a dye and a solid dispersion aid of a dye.However, when the photosensitive material is exposed to adverse conditions, a sweating phenomenon occurs or the surfactant desorbs from the dispersion. In some cases, it became easy, or the active agent moved from the dispersed oil droplets to other parts and diffused to cause a bleeding phenomenon, resulting in a decrease in sharpness. Furthermore, when the silver halide color photographic light-sensitive material is stored for a long period of time, the sharpness and glossiness of the material are likely to deteriorate, and improvements in these materials have been desired.

[0008]

A silver halide color photographic light-sensitive material, particularly a silver halide color photographic light-sensitive material for color prints, is excellent in sharpness, glossiness and density unevenness of color prints for various reasons as mentioned above. The present invention intends to improve all of these properties in combination, because the sharpness and the gloss are deteriorated by long-term storage.

That is, a first object of the present invention is to provide a silver halide color photographic light-sensitive material having excellent image sharpness, and a second object is to have excellent gloss on the printed surface and image. A third object of the present invention is to provide a silver halide color photographic light-sensitive material having less uneven density. Further, a third object is to provide a silver halide color photographic material which is not easily deteriorated in sharpness and glossiness even after long-term storage. To provide a light-sensitive material.

[0010]

The present inventor has made an improvement and regulation of the surface roughness on the photographic screen side of a photographic support of a silver halide color photographic light-sensitive material as described below. By specifying the amount of titanium oxide white pigment per unit area of the white resin layer of the body and the type and concentration of the surfactant in the photosensitive layer such as a silver halide emulsion layer, the above-mentioned various purposes are effective. I have found that it will be achieved.

1. A silver halide color photographic light-sensitive material comprising at least one silver halide photographic light-sensitive layer provided on a photographic support having at least one resin layer containing titanium oxide on a paper support. The titanium oxide content of the photographic support is 9 g / m ² or more, and the center surface average roughness of the resin surface of the photographic support on the side coated with the silver halide photosensitive layer is represented by the following mathematical formula. Sa (SR _a )
A silver halide color photographic light-sensitive material characterized by being 0.08 μm or less,

[0012]

[Equation 2]

Here, SR _a represents the center plane average roughness, Lx represents the length of the measurement surface area in the X-axis direction, and Ly represents the length of the measurement surface area in the Y-axis direction. S _A represents the area of the measurement surface area, and S _A = Lx × Ly, where Lx = 7.5 mm,
Ly = 21 mm, f (x, y) represents the surface irregularity surface, x, y
Represents the position coordinates of the measurement point in the x direction and the y direction, respectively.

2. The content of the surfactant represented by the general formula (I) is 0.3 per 1 m ^{2 of} silver halide color photographic light-sensitive material.
The silver halide color photographic material as claimed paragraph 1, wherein the g or less, the general formula _{(I) R- (L) n} -SO 3 - M + ( where in the formula, R is an alkyl Represents a group, an aryl group or an aralkyl group, and the total number of carbon atoms contained in R is between 8 and 36. L represents a divalent or trivalent linking group, and n is 0 or an integer of 1 to 10. . M represents a cation).

The present invention will be described in detail below.

<Paper Support> The paper support (also referred to as base paper) used for the photographic support of the silver halide color photographic light-sensitive material of the present invention is a photographic printing paper grade. In addition, as raw materials for raw paper, natural pulp, synthetic pulp,
In addition to a mixture of natural pulp and synthetic pulp, various raw materials for paper making can be mentioned. As the natural pulp, softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, and the like are used. There are neutral paper, acid paper, etc. produced by the manufacturing method, but it does not depend on the type of the base paper according to the manufacturing method, and any other neutral paper, acid paper, etc. may be used. It is preferable to use a grade base paper. Particularly, photographic printing paper grade neutral paper is preferable. The paper thickness is preferably 40 to 250 μm.

The above paper support may contain additives such as a sizing agent, a fixing agent, a tension enhancer, a denaturant, an antistatic agent, a dye and an antifoggant, which are generally used in papermaking. Alternatively, a surface sizing agent, a surface tension agent, an antistatic agent or the like may be appropriately applied to the surface.

<Resin Layer and Photographic Support> In recent years, a water-resistant polyethylene-coated photographic support (hereinafter also referred to as a polyethylene photographic support or a polyethylene-laminated photographic support) has replaced the variator-processed photographic paper support. ) Has become popular and most of the photographic supports are used except for some.

In recent years, in place of the polyethylene laminated photographic support technology, a photographic support obtained by coating an electron beam-curable resin on a paper support and irradiating it with an electron beam to cure the photographic support has been disclosed, for example, in Japanese Patent Application Laid-Open No. 57-57. -27257, 57-49946, 61-262
Nos. 738 and 62-61049, and a method of laminating a polyester resin in the same manner as a polyethylene laminated photographic support is disclosed in, for example, JP-A-5-127309.
No. 5, Doihira 5-127310, Dodaira 5-127311, Doihei 5-204091
No. 5, Dohei 5-265133, No. 5-323495, No. 6-3767,
It is described in Dohei 6-3768 and Dohei 6-3769.

A photographic paper photographic support such as a polyethylene laminated photographic support is one in which a resin layer is provided on both sides of a paper support to make it hydrophobic.

The resin applied to both sides of the paper support includes
Polyolefin resin such as polyethylene and polypropylene, polyester resin such as polyethylene terephthalate and modified polyester, polyether resin such as polyethylene glycol, polyoxymethylene and polyoxypropylene, urethane resin such as polyester urethane and polyether urethane, polycarbonate resin, Examples thereof include polystyrene resins, electron beam curable resins, cellulose nitrate, and cellulose derivative resins such as cellulose triacetate, which may be used alone or in combination. Preferred resins include polyethylene resins, polyethylene terephthalate resins, modified polyester resins, electron beam curable resins, etc., which may be used alone in the resin layer, and these are the main components and mixed with any of the other resins mentioned above. It can also be used.

Providing a paper support with the above resin layer on a photographic support is commonly used in the art for laminating or laminating. It is described in the Standard Chemistry Dictionary (Maruzen, edited by The Chemical Society of Japan) that polymer materials are laminated or that polymer materials and different materials are laminated by adhesion or pressure bonding. In the present invention, the term "laminating" is used for the provision of the resin on the paper support or the provision of the resin.

The polyethylene resins useful in the present invention include low density polyethylene and high density polyethylene, both of which are preferably used, and these may be used alone or in combination.

Polyester resins useful in the present invention include polyethylene terephthalate and modified polyesters having polyethylene terephthalate as a main structure (hereinafter referred to as modified polyesters). The modified polyester has polyethylene terephthalate as the main chain and comprises a polyester part and a modified part. The main chain constituent molecules of the modified part are terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 2,7-naphthalene as dibasic acid of ester bond. Dicarboxylic acid, p-xylidene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, 5-alkali metal sulfo-isophthalic acid, 4-alkali metal sulfo-2,6-naphthalenedicarboxylic acid, etc. , Ethylene glycol, propylene glycol, 1,4-butanediol, 1,4-hexylenediol as ester-bonded glycol (diol),
1,4-benzenediol (hydroquinone), 1,4-cyclohexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, (number average molecular weight 300 to 30,000), polypropylene glycol (number average molecular weight 300 to 30,000), Etc. Preferably, the dibasic acid is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,4-
Cyclohexanedicarboxylic acid, 5-metal sulfo-isophthalic acid, 4-metal sulfo-2,6-naphthalenedicarboxylic acid and the like are used, and ethylene glycol, propylene glycol, 1,4-cyclohexane dimethanol as a glycol,
Polyethylene glycol (number average molecular weight 300-30,000)
Etc. are used. The metal ion of the metal sulfo substituent is sodium, potassium, lithium, cesium, etc., preferably sodium.

The modified portion of the modified polyester useful in the present invention is 50 mol% or less based on the total polyester bonds, and when it exceeds 50 mol%, the physical properties as a support, such as mechanical strength, glass transition point, and water resistance. The properties are deteriorated and it becomes difficult to use as a support. It is preferably 40 mol% and particularly preferably 30 mol% or less.

The compound having an alkali metal sulfo group in the modified portion of the modified polyester has a total ester bond of 2
It is preferably contained in a proportion of from 10 to 10 mol%, and the adhesiveness between the emulsion layer and the photographic support is excellent. When this compound having an alkali metal sulfo group, such as 5-sodium sulfo-isophthalic acid, is 2 mol% or less, it is almost the same as polyethylene terephthalate, and the meaning of modification is weakened. Further, if it is 10 mol% or more, the water absorption rate becomes large, the adhesiveness between the paper support and the resin deteriorates, and there is a risk of peeling during the photographic processing. The problem comes out as a support. It is preferably 2 to 7 mol%, and particularly preferably 3 to 6 mol%.

In the modified portion of the modified polyester, it is also preferable to use polyethylene glycol and / or a saturated aliphatic dicarboxylic acid such as adipic acid together with the sulfo compound.

The modified polyester resin useful in the present invention can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, either an acid component can be directly esterified with a glycol component, or an acid component can be used as a dimethyl ester with glycol by a transesterification method. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for esterification and a polymerization reaction catalyst such as antimony oxide in the polymerization reaction. Regarding the polyester constituent components and the synthetic method described above, for example, Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) Nos. 103-136
Page or "Synthetic Polymer V" (Asakura Shoten, 1971) No. 1
It can be performed with reference to the description on pages 87 to 286.

The specific method for synthesizing the modified polyester is described in US Pat. No. 4,217,441 and JP-A-5-210199, and the modified polyester useful in the present invention can be synthesized by these methods.

Polyesters (including modified polyesters) useful in the present invention should have sufficiently high molecular weights. Generally, the molecular weight of a high molecular compound such as polyester is expressed as an intrinsic viscosity (for example, edited by The Chemical Society of Japan, Dictionary of Standard Chemistry, 224 pages, 1991, published by Maruzen), but the intrinsic viscosity of the polyester used in the present invention is 0.50 or more. And is preferably 0.53 or more, and particularly preferably 0.55 or more. When the intrinsic viscosity of the polyester is less than the above, the resin becomes white and brittle after melt extrusion. Further, when melt-extruding while containing water, the intrinsic viscosity is extremely lowered, so that special attention must be paid to drying before melting, and even if the intrinsic viscosity is sufficiently high, hydrolysis may occur during melting. The resin chips are usually dried at about 150 ° C under a vacuum of about 10 ^-3 Torr.

The polyolefin resin or polyester resin is formed into a layer by melt-extruding and coating the molten resin on a paper support. This melt extrusion coating method is
The resin composition is melted at a predetermined temperature in an extruder and melt-coated on a running paper support (supported by a roll on the back side of the paper support at the coating position) from a die slit. However, the resin composition layer to be melt-coated may be a single layer coated from a single slit, or may be a plurality of layers formed from a plurality of slits. Since the melt extrusion temperature is carried out at 200 ~ 350 ℃, the resin,
For example, if a resin such as a polyolefin resin, a polyester resin, a polyether resin, a polyamide resin, a polyimide resin, or a polycarbonate resin that is melted in this temperature range is mixed and melted, a layer can be formed.

As the electron beam-curable compound of the electron beam-curable resin useful in the present invention, any compound that can be cured by electron beam irradiation can be used. Examples of the compound curable by electron beam irradiation that can be used in the present invention include electron beam curable compounds described in JP-B-60-17104, JP-A-60-126649, or JP-A-2-157747. This is the case with electron beam curable monomers or oligomers.

The curable monomers or oligomers used in the electron beam curable photographic support useful in the present invention include unsaturated compounds containing two or more carbon-carbon double bonds in one molecule (for example, Acrylic or methacrylic oligomer, polyfunctional acrylic or methacrylic monomer), and at least one carbon-carbon double bond in one molecule as a monomer when the curable monomer is diluted and used. An unsaturated compound containing (for example, a monofunctional acrylic monomer, a methacrylic monomer, a vinyl monomer, etc.) is used.

Monomers having two or more of these unsaturated double bonds are radically polymerized by electron beam irradiation to form intermolecular,
A cross-linking bond is formed by a cross-linking reaction and cured to produce a cured resin. Examples thereof include acrylic acid or methacrylic acid ester of polyurethane, acrylic acid or methacrylic acid ester of polyether alcohol, bisphenol A or acrylic acid or methacrylic acid ester of bisphenol A or its epoxy condensate, 1,6-hexanediacrylate. Or methacrylate, neopentyl diacrylate or dimethacrylate, diethylene glycol diacrylate or dimethacrylate, butadiene acrylate or diacrylate, tetraethylene glycol diacrylate or dimethacrylate, glycerol triacrylate or trimethacrylate, polyethylene glycol (repeating unit n = 4 to 300) ) Diacrylate or dimethacrylate, 1,4-butanediol diacrylate Or dimethacrylate, neopentyl glycol diacrylate or dimethacrylate, isocyanuric acid diacrylate or dimethacrylate, isocyanuric acid triacrylate or trimethacrylate, trimethylolpropane triacrylate or trimethacrylate, propylene oxide modified trimethylolpropane polyacrylate, 1 2,3-Bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, polyester maleic or fumaric acid ester, divalent or polyvalent organic acid such as adipic acid Condensation of dihydric or polyhydric alcohol such as ethylene glycol with poly or oligoester or polyester di- Mention may be made of polyacrylate or methacrylate.

When it is necessary to adjust the viscosity of the composition liquid containing the crosslinkable monomer or oligomer, the unsaturated double bond which can be incorporated into the crosslinked polymer is 1
It is possible to use a diluting monomer having each, and as the diluting monomer, glycyl acrylate or methacrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
(N or iso) -propyl acrylate or methacrylate, butyl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl acrylate or methacrylate, phenoxyethyl acrylate or methacrylate, cyclohexyl acrylate or methacrylate, benzyl acrylate or methacrylate,
N, N-dimethylaminoethyl acrylate or methacrylate, N, N-diethylaminoethyl acrylate or methacrylate, ethylene oxide-modified phenoxyphosphoric acid acrylate, styrene, polyoxyethylene phenyl alcohol acrylic ester, 2-ethylhexyl acrylate, etc. be able to.

In the electron beam curable composition useful in the present invention, an organic solvent may be used as a diluent, if necessary. In that case, these solvents are evaporated after coating and remain in the coating layer. It is preferable to irradiate with an electron beam after drying so as not to cause it. Examples of these are acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane,
Benzene, toluene, xylene, etc. can be used.

The method for applying the prepared coating solution onto the paper support includes roll coating, bar coating, air doctor coating, plate coating, squeeze coating,
Any of an air knife method, a reverse roll coating method, a transfer coating method and the like may be used. Also,
A fountain coater or slit orifice coater system can also be used.

As the electron beam accelerator for curing the electron beam curable resin composition applied to the paper support, a van de Graaff type scanning system, a double scanning system, a curtain beam system or the like is used. As electron beam characteristics, pressurization voltage is 100-1000KV, absorbed dose is 0.5-20
It is Megarad. The electron beam irradiation device used for the photographic support of the present invention is not particularly limited, and generally, as such an electron beam accelerator for electron beam irradiation, a curtain beam system which can obtain a large output at a relatively low cost. Are effectively used. Accelerating voltage during electron beam irradiation is 100 to 3
00kV is preferable, and the absorbed dose is 0.5-10M
It is preferably rad.

Titanium oxide is used as a white pigment in the resin layer composition on the side of the photographic support to which the silver halide photosensitive layer of the photographic support of the present invention is applied. White pigments such as zinc oxide, barium oxide and neodymium oxide are used. A pigment can also be used as a mixture with titanium oxide. There are two types of titanium oxide, anatase type and rutile type. The anatase type is preferably used, but the rutile type is also used. Further, these titanium oxides may be mixed and used.

Further, tinting dyes or pigments such as cobalt blue, ultramarine blue, organic dyes (for example, phthalocyanine dyes) may be contained together with these white pigments, and the content thereof is preferably 0.0001 to 0.05% by weight. .

The titanium oxide may be untreated titanium oxide which is not surface-treated, but it may be hydrous aluminum oxide,
Surface treated titanium oxide with various inorganic compounds such as silicon dioxide, zirconium oxide and magnesium hydroxide, or titanium oxide treated with various organic compounds such as various alcohols, surfactants, siloxanes and silane coupling agents.
Further, titanium oxide or the like which has been subjected to both the inorganic surface treatment and the organic surface treatment can be used.

As a method for mixing the white pigment, in the polyethylene resin composition and the polyester resin composition, the resin chips obtained by heating the resin under high vacuum and drying are directly sprinkled with the white pigment to a predetermined concentration. And then put it in an extruder, melt and mix the resin at a predetermined temperature within the range of 200 to 350 ° C, and apply it on the paper support, and melt the resin chips and white pigment beforehand with a kneader such as a kneader. There is a method in which mixed chips are taken out as colored chips, dried in vacuum, and then colored chips having a predetermined concentration are mixed as they are or with colorless chips so as to have a predetermined concentration and then melted (mixed) by an extruder. Either method is suitable for the photographic support resin composition of the present invention.

Further, in the case of the electron beam curable resin composition, a homomixer, or a homomixer, is used to prepare a coating solution containing a white pigment.
It is desirable to use a Cowles dissolver, an ultrasonic disperser, a roll mill, a ball mill or the like according to the properties of the coating liquid. In order to uniformly disperse the white pigment in the liquid, it is preferable to use a white pigment, particularly titanium oxide whose surface is previously treated with a metal oxide such as aluminum hydroxide. The electron beam curable resin composition is preferably applied by coating with a curable monomer or oligomer liquid containing a white pigment as it is, but when the viscosity is high, a diluting monomer may be additionally applied for coating. Depending on the case, the viscosity may be adjusted by mixing an ordinary diluent (solvent) not related to curing. For ease of coating, the concentration of the effective component of the coating liquid and the viscosity of the coating liquid may be set in consideration of the finished film thickness and the like.

When the coating amount of the titanium oxide white pigment contained in the resin composition layer (after coating or after curing) on the side on which the silver halide photosensitive layer of the present invention is coated is 9 g / m ² or more, Surface roughness SR of the side coated with the silver halide photosensitive layer
_{When a} is in the range of 0.08 μm or less, the sharpness and gloss of the present invention are excellent, and these properties are not satisfied unless both the coating amount and the roughness are satisfied. More preferably, the coating amount of titanium oxide is 10 g / m ² or more, and the surface roughness SR _a is 0.0.
It is preferably 7 μm or less.

In order to obtain the coating amount and the surface roughness within the claims of the present invention, the concentration of the titanium oxide white pigment in the resin composition is in the range of 4 to 70%, and the coating amount of the resin composition layer is Ten
Any range within the range of up to 150 g / m ² may be selected. For example, the polyethylene resin composition has a titanium oxide content of 6 to
The coating amount is 30 to 30% by weight, the coating amount is 60 to 130 g / m ² , the titanium oxide content is 4 to 40% by weight in the polyester resin composition, and the coating amount is 40 to 140 g / m ² , the electron beam curing resin composition (electron beam The amount after curing is 4 to 70% by weight, and the coating amount is 20 to 100 g / m ²
Is preferred. In all cases, if the amount is out of this range, the smaller amount is inferior in surface property, and the larger amount is economically disadvantageous. If the coating amount of the electron beam curable resin composition deviates from the above range, coating unevenness may occur, or if it is too large, a large amount of energy may be required for curing, or curing may be insufficient and sticky. You will not be able to obtain quality products. Therefore, the coating amount of the electron beam curable resin composition is particularly 20 to 60 g / m ²
Is preferred.

The photographic support of the present invention is provided with the above-mentioned resin layer containing a white pigment on the surface on which the silver halide photosensitive layer is coated. The resin layer coated on the side opposite to the photosensitive layer is a photosensitive layer. Although it may be the same as or different from the resin on the layer side,
It is preferable to use a polyolefin resin. Inorganic particles may be mixed into the resin composition of the back layer in order to improve the writability and the ink receptivity, and also to provide the antistatic property. A back coat layer may be provided. The thickness of the resin layer of the back layer may be determined depending on the balance with the thickness of the resin layer on the photosensitive layer side. At this time, the surface of the back resin layer may be subjected to activation treatment such as corona discharge treatment or flame treatment.

The center surface average surface roughness (S of the photographic support of the present invention on the side coated with the silver halide photosensitive layer)
R _a) is for example manufactured by Kosaka Kenkyusho surface roughness analyzer SE
It can be measured using -3AK.

<Undercoating and Undercoating Layer> In order to strengthen the adhesion of the light-sensitive layer as the silver halide color photographic light-sensitive material of the present invention to the photographic support, surface treatment or coating of an undercoating layer, etc. Is generally done. This surface treatment and provision of a so-called undercoat layer are collectively referred to as an undercoat treatment. The method of each support for the subbing treatment will be described below.

For the surface of the polyethylene laminate photographic support useful in the present invention on the side where the silver halide photosensitive layer is coated, corona discharge treatment, flame treatment, glow discharge treatment, ultraviolet irradiation treatment, high frequency treatment, activation Plasma treatment,
Activation treatment such as laser treatment is applied, and this alone is sufficient for adhering the photosensitive layer, but the adhesion may be insufficient depending on the formulation of the photosensitive layer.In such a case, after the corona discharge treatment, A hydrophilic colloid solution such as gelatin may be applied. In the case of an electron beam curable resin, the undercoating treatment can be performed by applying the above corona discharge treatment and the gelatin undercoating solution.

The undercoating treatment of the photographic support laminated with the polyester resin useful in the present invention can be performed in the same manner as the former two. Further, the hydrophilic resins cited below (for example, maleic anhydride to
A solvent (for example, acetone) coating solution containing a vinyl acetate copolymer) can be coated on any surface with or without treatment such as corona discharge. Further, the same method as the subbing treatment of a usual stretched polyethylene terephthalate support can be used. That is, a quaternary copolymer latex composed of n-butyl methacrylate: t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate according to the method described in JP-A-55-67745, JP-A-59-19941 and the like, interface Activator,
The undercoating treatment is completed by applying a water-based undercoating liquid consisting of a curing agent, drying, and then again subjecting it to corona discharge treatment, etc. Can be used for various subbing processes. In addition, after applying the same treatment or an undercoat layer as the above to the antistatic layer on the back surface,
A desired photographic light-sensitive material can be finished by directly applying the antistatic composition or a binder for the antistatic layer such as cellulose diacetate and then applying the antistatic composition as an organic solvent-based liquid. The modified polyester support of the present invention can be subbed in the same manner.

<Silver Halide Photosensitive Layer> The composition of silver halide grains used in the silver halide color photographic light-sensitive material of the present invention is such that 90 mol% or more of all silver halide constituting the silver halide grains is silver chloride. It is preferable that it is composed of silver chlorobromide containing substantially no silver iodide. The preferred silver halide composition of the silver halide grains is 95 mol% or more, more preferably 98 mol% or more of the total silver halide constituting the silver halide.
~ 99.99 mol% is silver chloride. This so-called high silver chloride emulsion having a high silver chloride content is suitable for speeding up development processing.

Here, the halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the grains having a uniform structure having the same composition in any part of the silver halide grains, the core inside the silver halide grains and the shell surrounding them ( Laminated structure particles with different halogen compositions with one or more layers of shells, or structures with non-layered parts with different halogen compositions inside or on the surface (edges, corners or surfaces of particles when on the particle surface) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is
It may be a clear boundary, an unclear boundary by forming a mixed crystal due to a difference in composition, or may be one which positively has a continuous structural change.

In the high silver chloride emulsion such as the silver halide color photographic light-sensitive material of the present invention, the silver bromide localized phase is formed in the silver halide grain inside and / or in the layered or non-layered form as described above. A structure having a surface is preferable. These localized phases can be on the edges, corners or planes, but one preferred example is that epitaxially grown on the corners of the grains.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. In addition, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737 and The Journal of Photographic Science (J.
Photo. Sci. ) Volume 21, page 39 (1973) and the like, and the like, particles having an octahedral shape, a tetradecahedral shape, a dodecahedron shape and the like can be prepared and used. Further, grains having twin planes may be used.

The silver halide grains used in the present invention are
Particles having a single shape may be used, or particles having various shapes may be mixed.

The grain size of the silver halide grains used in the present invention is not particularly limited, but in view of other photographic performance such as rapid processing property and sensitivity, it is preferably 0.1 to 1.2 μm.
m, more preferably 0.2 to 1.0 μm. In addition,
The above particle size can be measured by various methods generally used in the art. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122).
Page (1955)) or "Theory of Photographic Processes, Third Edition"
(Mies and James Co., Chapter 2, published by Macmillan, (1966)).

This particle size can be measured using the projected area of the particle or an approximate diameter. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area.

The grain size distribution of the silver halide grains used in the present invention may be polydisperse or monodisperse.

Heavy metal ions can be incorporated into the silver halide emulsion used in the present invention. Examples of the heavy metal ions used include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, and cobalt; Group 12 transition metals such as cadmium, zinc, and mercury; and lead, Rhenium, molybdenum,
Each of the ions of tungsten and chromium can be mentioned. Of these, transition metal ions of iron, iridium, platinum, ruthenium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of salt or complex salt.

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

The silver halide emulsion used in the present invention is
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The method of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, etc., but a method obtained by the simultaneous mixing method. Is preferred. As one form of the simultaneous mixing method, the pAg controlled double jet method described in JP-A-54-48521 may be used.

Further, if necessary, a silver halide solvent such as thioether or a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye is used at the time of forming silver halide grains or at the end of grain formation. You may add and use it later.

The silver halide emulsion used in the present invention is
A sensitization method using a sulfur compound, a sensitization method using a gold compound,
Then, it is possible to perform sensitization by using a sensitizing method in which sulfur and a gold compound are used in combination. Examples of the sulfur sensitizer applied to the silver halide emulsion used in the present invention include thiosulfate, allylthiocarbamidourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid, rhodanine, and inorganic sulfur. .

As the gold sensitizer applied to the silver halide emulsion used in the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above gold compounds can be preferably used.

The silver halide emulsion used in the present invention can prevent fog occurring during the process of preparing a silver halide color photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog occurring during development. Known antifoggants and stabilizers can be used for the purpose. As an example of a compound that can be used for such a purpose, JP-A 2-14
Examples thereof include compounds represented by the general formula (II) described in the lower column of page 6036 of the publication, and specific compounds thereof include ( _IIa- 1) to ( _IIa- 1) described on page 8 of the publication. (II _a-
8), compounds of (II _b -1) to (II _b -7), compounds of 1- (3-methoxyphenyl) -5-mercaptotetrazole, 1- (4-ethoxyphenyl) -5-mercaptotetrazole, etc. Can be mentioned. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

The silver halide color photographic light-sensitive material of the present invention is spectrally sensitized to a specific region in the wavelength range of 400 to 900 nm by combining it with a yellow coupler, a magenta coupler and a cyan coupler and by using respective spectral sensitizing dyes. There are a number of layers containing a silver halide emulsion. One sensitizing dye or a combination of two or more sensitizing dyes may be used in one silver halide emulsion.

Sensitizing dyes useful in the silver halide color photographic light-sensitive material of the present invention include cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

The couplers used in the silver halide color photographic light-sensitive material of the present invention include aromatic primary amine developers such as p-phenylenediamine derivatives and aminophenol derivatives as color developing agents in color development processing. Any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength range longer than 340 nm can be used by a coupling reaction with an oxidant of the above-mentioned compound. However,
Typical examples include a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a cyan coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm. Can be used as a thing.

These dye-forming couplers preferably have a group called a ballast group having a carbon number of 8 or more, which makes the coupler non-diffusible, in the molecule. Also, these dye-forming couplers, even though they are 4-equivalent, require 4 molecules of silver ion to be reduced in order to form 1 molecule of dye.
It may be either of two equivalents which only needs to reduce the silver ion of the molecule.

In the silver halide color photographic light-sensitive material of the present invention, various acylacetanilide type couplers are preferably used as the yellow dye forming coupler. Of these, benzoylacetanilide type and pivaloylacetanilide type couplers are advantageously used. As the magenta dye-forming coupler, 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers, pyrazolotriazole type couplers and open chain acylacetonitrile type couplers are advantageously used. Further, as the cyan dye forming coupler, a naphthol type coupler, a phenol type coupler, an imidazole type coupler and the like can be used.

The yellow couplers preferably used in the silver halide color photographic light-sensitive material of the present invention include the general formula (YI) described on page 8 of JP-A-4-114154.
A coupler represented by Specific compounds are
It is described as YC-1 to YC-9 on pages 9 to 11 of the same specification, and these can be used. Among them, YC-8 and YC-9 described on page 11 of the same specification can reproduce the desirable yellow color and can be preferably used.

As the magenta coupler preferably used in the silver halide color photographic light-sensitive material of the present invention, a general formula (MI) described on page 12 of JP-A-4-114154 can be used.
Examples thereof include couplers represented by (M-II). Specific compounds are described as MC-1 to MC-11 on pages 13 to 16 of the same specification, and these can be used. Among them, the coupler represented by formula (M-II) is particularly preferable for enhancing the effect of the present invention, and specific compounds thereof are described in
MC-8 to MC-11 described on page can be preferably used. Cyan couplers that can be preferably used in the silver halide color photographic light-sensitive material of the present invention include the general formula (CI) described on page 17 of JP-A-4-114154.
The coupler represented by (C-II) may be mentioned.
Specific compounds are described on pages 18 to 21 of the specification in CC-1 to CC.
Those described as -14 can be preferably used.
Any coupler is useful in the present invention without limitation. Further, for the purpose of shifting the absorption wavelength of the dye to be colored, the compound (d-11) described on page 33 of JP-A-4-114154 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Other than this, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

As the method for adding the coupler used in the silver halide color photographic light-sensitive material of the present invention to the silver halide emulsion, there are an oil-in-water type emulsion dispersion method and a method not using a high boiling point organic solvent. In the case of, the coupler is usually dissolved in a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C or higher,
If necessary, a low boiling point and / or water-soluble organic solvent may be used in combination, and the solution may be dissolved. A method of emulsifying and dispersing this solution in a hydrophilic binder such as an aqueous gelatin solution using a surfactant is used. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like is used. After the dispersion, or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be performed. High boiling organic solvents for dissolving and dispersing couplers include dibutyl phthalate, dinonyl phthalate, dioctyl phthalate, di-iso-decyl phthalate and other phthalates, triphenyl phosphate, diphenyl biphenyl phosphate and other phosphate esters. It is preferably used. In the latter, there is a method of emulsifying and dispersing a coupler and a water-insoluble and organic solvent-soluble polymer compound in a hydrophilic binder such as an aqueous gelatin solution using a surfactant, and this method can also be used. In this case, it may be dissolved in a low boiling point and / or water-soluble organic solvent, if necessary, and then similarly dispersed. As a polymer which is insoluble in water and soluble in an organic solvent, poly (Nt-butylacrylamide) can be typically mentioned. For the dispersion of this method, various means similar to the above can be used.

The high-boiling organic solvent is preferably a compound having a dielectric constant (at 30 ° C.) of 6.5 or less. For example, esters such as phthalic acid ester and phosphoric acid ester having a dielectric constant of 6.5 or less, organic acid amides, ketones, Hydrocarbon compounds and the like. More preferably, a high boiling point organic solvent having a dielectric constant of 6.5 or less and 1.9 or more and a vapor pressure at 100 ° C. of 0.5 mmHg or less,
Among these, phthalic acid esters or phosphoric acid esters are more preferably used, and most preferably dialkyl phthalate having an alkyl group having 9 or more carbon atoms. The high boiling point organic solvent may be used as a mixture of two or more kinds. These high boiling point organic solvents are generally used in a proportion of 0 to 400% by weight based on the coupler.
It is preferably 10 to 100% by weight based on the coupler.

In order to disperse the coupler in the silver halide emulsion layer as described above, a surfactant is used as a dispersant. At this time, a large amount of a surfactant is required in order to sufficiently disperse the coupler as fine particles in the emulsion, but the sharpness is lowered, and the above-mentioned deterioration occurs during storage of the light-sensitive material. Therefore, it is necessary to reduce the amount of surfactant used. Further, a surfactant is also required to facilitate the coating of a hydrophilic colloid layer such as a silver halide emulsion layer, and the amount of the surfactant contained in such a total hydrophilic colloid layer becomes considerably large. The quality of photographs will be more and more affected.

Therefore, as a method for reducing the content of the surfactant, an improved dispersing device as described in Japanese Patent Publication No. 52-129136, Japanese Patent Publication No. 29-3537, etc. may be used, or a special dispersing device may be used. As described in the specifications of Kaisha 57-53227, 57-78038, etc., the phase inversion method can be used, or JP-A-57-53227 can be used.
No. 57-94746, etc., the surfactant in the hydrophilic colloid layer can be reduced by an improved addition method for increasing the dispersion state as disclosed in the specification. In addition, it is possible to further reduce the amount by combining a method of removing excess surfactant after the coupler is emulsified and dispersed. For example, as a method for removing the surfactant from the emulsified dispersion, various methods are described in U.S. Pat.No. 3,396,027, JP-A-55-151634, JP-A-60-158437, etc. It can be used in the invention. Also, a method of mixing an emulsion with an ion exchange resin to reduce the amount can be used.

[0078] Surfactants used in the silver halide color photographic light-sensitive material of the present invention have the general formula _{(I) R- (L) n} SO 3 - M + in detail it will be described.

In the formula, L is a divalent or trivalent linking group,
n is 0 or an integer of 1 to 10, but L is-(OCH ₂ C
H ₂ ) _m −, − (OCH ₂ CH (CH ₃ )) _m −, − (O (CH ₃ ) CH ₂ ) _m −
= M, m is preferably 1-10, and particularly preferably 1-5. When n = 1, L is -O-,
− (R ¹ ) _p HC = CH (R ² ) _q −, −OOCCH ₂ CH (−) COO−, −CONR ³
(R ⁴ ) _r −, −SO ₂ NR ⁵ (R ⁶ ) _s − and the like are preferable, and especially −OOCCH ₂
A CH (−) COO— linking group is preferred. In this case, p, q,
r and s are 0 or 1, R ¹ , R ² , R ⁴ and R ⁵ are linear or branched alkylene groups having 2 to 12 carbon atoms, and R ³ is an alkyl group having 1 to 12 carbon atoms. preferable.

R has a total carbon number of 8 to 36, but is preferably a straight chain, branched chain or alicyclic alkyl group having 2 to 24 carbon atoms, and a straight chain, branched chain or fatty group having 1 to 24 carbon atoms. A phenyl group or a naphthyl group having a substituent such as a cyclic alkyl group, a hydroxyl group, a carboxyl group, an amino group, a cyano group, a halogen group and an alkoxycarbonyl group is preferable. Particularly, an alkyl group-substituted phenyl group and a naphthyl group are preferable. The alkyl portion of R may be a fluorinated hydrocarbon having 2 to 36 fluorine atoms. Further, in the carbon chain of the alkyl part of R, —O—, —S—, —COO—, —CONR ⁶ —, —SO ₂ —, —SO ₂
NR ⁷ −, −NR ⁸ CO−, −NR ⁹ SO ₂ − can be included. R
⁶ , R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom, an alkyl group or an aryl group. M ⁺ is a cation, preferably Na ⁺ , K ⁺ and NH ₄ ⁺ , particularly preferably Na ⁺ .

Specific examples of the surfactant represented by the general formula (I) are shown below, but the surfactant is not limited thereto.

[0082]

[Chemical 1]

[0083]

[Chemical 2]

The surface active agent of the above-mentioned general formula (I) has a coating amount of 0.3 g or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, preferably 0.05 to 0.25 g / m ² .
When the amount of the surfactant exceeds 0.3 g / m ² in the light-sensitive material, the amount of titanium oxide in the resin layer on the side coated with the silver halide light-sensitive layer of the present invention is set to 9 g / m ² or more, and SR _{a of the} surface is increased. To 0.08
By this, even if the sharpness is improved, uneven density, deterioration of the white background or deterioration of the sharpness occurs over time, and the effect is diminished. On the other hand, if the coating amount is less than 0.05 g / m ² , the coating properties will be poor, and oil-soluble components such as couplers and high-boiling organic solvents will be prone to deposit, resulting in poor sharpness.

In the emulsion layer of the silver halide color photographic light-sensitive material of the present invention, in addition to the above-mentioned compounds, various other photographic additives such as an ultraviolet absorber (for example, a benzophenone compound, a benzotriazole compound). Compound etc.), development accelerator (eg 1-aryl-3-pyrazolidone compound etc.), water-soluble anti-irradiation dye (eg azo compound, styryl compound, oxonol compound etc.), film physical property improver ( For example, liquid paraffin, polyalkylene glycol, etc.), color turbidity preventing agent (eg, diffusion resistant hydroquinone compound etc.), color image stabilizer (eg, hydroquinone derivative, gallic acid derivative etc.), others, water-soluble or oil-soluble The fluorescent whitening agents, background color adjusting agents, etc. can be used.

In addition to this, if necessary, a competitive coupler,
Fog agent, development inhibitor releasing coupler (so-called DIR
A coupler), a development inhibitor releasing compound and the like can be added.

The binder used in the silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention or in the non-light-sensitive layer such as the intermediate layer and the protective layer is mostly gelatin because of its excellent properties. ,If necessary,
Gelatin derivatives such as phthalated gelatin, gelatin graft polymers in which other polymers such as acrylic polymers are bound and dispersed with gelatin, proteins other than gelatin such as casein, sugar derivatives such as polysaccharides, and cellulose such as hydroxyethyl cellulose. Derivatives, vinylpyrrolidone, acrylic acid and its salts, methacrylic acid and its salts, vinylsulfonic acid and its salts, sulfopropyl acrylate and its salts, diethylaminoethyl methacrylate hydrochloride, etc. A hydrophilic colloid such as a molecular substance can be used in combination with gelatin.

Even if the gelatin used in the silver halide color photographic light-sensitive material of the present invention is lime-processed gelatin,
Acid-processed gelatin may be used, or gelatin produced from any of cow bone, cowhide, pig skin, etc. may be used, but lime-treated or acid-processed gelatin made from cow bone or pig skin is preferable. .

Gelatin molecules mainly constituting the binders of the photographic emulsion layer and the non-photosensitive layer of the silver halide color photographic light-sensitive material of the present invention are cross-linked by a hardening agent to form a solution in a processing solution such as a color developing solution. Swelling is controlled, and various properties necessary for a silver halide color photographic light-sensitive material such as development speed, spread of developed silver, film strength when wet, and drying speed are controlled. The degree of swelling is generally determined by the amount ratio of gelatin and hardener.

In the silver halide color photographic light-sensitive material of the present invention, when a hydrophilic colloid layer such as a silver halide emulsion layer and a gelatin layer is coated on a photographic support, a coating solution having a relatively low viscosity is coated. A thickener may be added to improve the properties and used to control the viscosity.
As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are useful.

To form a photographic image on the silver halide color photographic light-sensitive material of the present invention, an image recorded on a negative or positive is printed on the light-sensitive surface of the light-sensitive material so-called optical negative-positive or positive. -Positive print method,
After converting the image into digital information, CRT the image.
There are a method of forming an image on a (cathode ray tube) and printing this image on the photosensitive surface, and a method of printing by scanning a laser beam based on digital information. Any method can be used.

The silver halide color photographic light-sensitive material of the present invention is a color photographic paper light-sensitive material, and an image can be formed by performing color development processing known in the art.

<Color development processing of silver halide color photographic light-sensitive material> As the aromatic primary amine developing agent used in the color development processing of the silver halide color photographic light-sensitive material of the present invention, known compounds can be used. . The following compounds may 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-Amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline CD-5) 2-Methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) Aniline CD-6) 4-amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfone Amide 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 Silver halide of the present invention Color developing agent to be used in development of the over photographic material, typically a color developing solution 1 used in liters per 1 × 10 ^-2 ~2 × 10 ^-1 mol per mol of silver, the color developing solution in view of rapid processing 1.5 × 10 ^-2 ~ per liter
It is preferably used in the range of 2 × 10 ^-1 mol. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developing solution used in the silver halide color photographic light-sensitive material of the present invention may contain the following color developing solution components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicate or the like can be used alone or in combination, It can be used in combination within the range where no precipitation occurs and the pH stabilizing effect is maintained. In addition, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, borate, etc. may be prepared for the purpose of preparation or for increasing the ionic strength. It can be used in a color developer. Inorganic and organic antifoggants can be added as required. Further, a halide salt is often added to the color developing solution for the purpose of suppressing development, but in order to complete development in a very short time, mainly chloride such as potassium chloride or sodium chloride is used. Is preferred. The amount of these chlorides added is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^{-2 to} 5.0 × 10 ^-1 mol, per liter of the color developing solution. Bromide can be used within a range that does not impair the effects of the present invention, but bromide tends to suppress development, and is about 1.0 per liter of color developing solution.
It can be used if it is not more than × 10 ^-3 mol, preferably not more than 5.0 × 10 ^-4 . Furthermore, if necessary, a development accelerator can be added to the color developing solution. Examples of the development accelerator include U.S. Pat. Nos. 2,648,604, 3,671,247 and JP-B-44-9.
Various pyridinium compounds typified by the compounds described in No. 503, other cationic compounds,
Cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, US Patents 2,533,990, 2,531,832
No. 2, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No.
Polyethylene glycol and its derivatives, nonionic compounds such as polythioethers described in each specification.
Organic solvents and organic amines described in 44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also, US Patent 2,
In addition to phenethyl alcohol described in the specification of 304,925, acetylene glycol, methyl ethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like can be mentioned.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and other Japanese Patent Publication Nos. 47-33378 and 44-9509 are described. The compound can be used as an organic solvent for increasing the solubility of the color developing agent.

Further, an auxiliary developing agent may be used together with the color developing agent. As these auxiliary developers, for example, N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride,
N, N, N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of color developing solution.

Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a small container prepared in advance in a solid state into water and stirring. You can also

In processing the silver halide color photographic light-sensitive material of the present invention, the color developer can be used in any pH range, but it is preferably pH 9.6 to 13.0.

The color development processing temperature of the silver halide color photographic light-sensitive material of the present invention is preferably 15 ° C. or higher and 45 ° C. or lower, and particularly preferably 20 ° C. or higher and 45 ° C. or lower.
The color development time is conventionally about 3 minutes and 30 seconds, but the color development time of the rapid development in the present invention is preferably 45 seconds or less.

When the silver halide color photographic light-sensitive material of the present invention is subjected to running processing (processing is continued while continuously replenishing color developing solution), color development is carried out in order to reduce environmental pollution due to waste liquid disposal. The amount of overflow solution is reduced, and the replenishment amount of the color developing solution is 20 to 1 m ²
It is preferably 150 ml. Further, it is more preferable that the amount of replenishment is such that waste liquid is not generated even if the liquid is substantially overflowed. As a concrete amount of replenishment, 20 to 60 ml per 1 m ² of the light-sensitive material is suitable and more preferable. Under such conditions, the performance of the silver halide color photographic light-sensitive material is generally liable to change, but the silver halide color photographic light-sensitive material of the present invention does not change in performance under such conditions and is particularly advantageous. Can be used for.

The silver halide color photographic light-sensitive material of the present invention can be subjected to usual bleaching treatment and fixing treatment after color development, but the bleaching treatment may be conducted simultaneously with the fixing treatment. After the fixing process, a washing process is usually performed, but a stabilizing process may be performed as an alternative to the washing process.

The development processing apparatus used for the silver halide color photographic light-sensitive material of the present invention is a roller transport type in which the light-sensitive material is sandwiched between the rollers arranged in the processing tank, and the light-sensitive material is loaded on the belt. An endless belt method of fixing and conveying may be used. Further, the processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the contact with the carrier impregnated with the processing solution. It is also possible to use a web method according to the above method or a method using a viscous treatment liquid.

[0104]

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) <Preparation of photographic support> White PE resin layer / paper support / PE resin layer laminate Photographic support: sulphate method bleached hardwood pulp (LBKP) for photographic grade photographic paper Basis weight of 175 g / m ² and thickness 1 consisting of 50% by weight and 50% by weight of sulfated bleached softwood pulp (NBSP)
Prepare a paper support of 80 μm, and apply a polyethylene (abbreviation: PE) resin layer on the surface of the paper support opposite to the photosensitive layer and the surface on which the silver halide photosensitive layer is applied as follows. did.
First, a PE resin [density 0.95 g / cc, melt index (abbreviation: MI) 8.0 g / min] composition chip for the back layer is dried and put into an extruder, melted at 300 ° C., and the paper is passed through a die slit. A molten PE resin composition was extrusion-coated on the surface of the support opposite to the photosensitive layer, and a PE back layer was provided so as to have a predetermined thickness (see Table 1). Next, PE resin containing titanium oxide white pigment (see Table 1) [density 0.92 g / cc, MI5.
0 g / min] The composition chip is dried and then put into an extruder, kneaded and melted at 300 ° C., and the surface on the side to which the silver halide photosensitive layer is applied through the die slit has a predetermined thickness on the paper support. (See Table 1) to obtain water-resistant photographic supports A to H having a white resin layer. After the corona discharge treatment with an output current value of 2 amps was applied to the surface of the photosensitive layer side (white resin layer side) of each photographic support, the gelatin subbing layer of the following composition liquid was adjusted to 40 mg / m ^2. It was provided by coating and drying, and provided for coating of the following photosensitive layer. In addition, white P
Table 1 shows the values of the surface roughness SR _a of the E polyethylene resin layer on the side coated with the silver halide photosensitive layer.

[0106]

[Table 1]

<< Gelatin Subbing Layer Composition >> Gelatin (4.5
g), sodium (2-ethylhexyl) sulfonate (10
mg) and H-1 (30 mg) were mixed and dissolved in 100 cc of water. <Production of silver halide color photographic light-sensitive material><< First layer coating solution >> 23.4 g of yellow coupler (Y-1),
Dye image stabilizer (ST-1) 3.34 g, dye image stabilizer (ST-2) 3.34 g, dye image stabilizer (ST-5)
3.34 g, stain inhibitor (HQ-1) 0.33 g, compound A
5.0 g and 5.0 g of high boiling organic solvent (DBP) with ethyl acetate
Add 60 cc and dissolve, and emulsify and disperse in 220 cc of 10% gelatin aqueous solution containing 7 cc of 20% aqueous solution of at least one surfactant S-1 to 14 described in Chemical formula 8 or 9 using an ultrasonic homogenizer, and yellow. A coupler dispersion was prepared. This dispersion was mixed with a blue-sensitive silver halide emulsion (Em-B) prepared under the following conditions to prepare a coating solution for the first layer. The ingredients and coating amount are shown below.

<< Second Layer to Seventh Layer Coating Liquid >> The components and coating amounts are shown below as in the case of the above first layer coating liquid. Each coating liquid was prepared to have such coating amount.

As a coating aid, at least one of the surfactants S-1 to S-14 shown in Chemical formula 8 or 9 was added and adjusted. Table 1 shows the types of surfactants and the amounts added.

The total amount of the antifungal agent (F-1) was 0.04 in each layer.
It was added so as to be g / m ² .

<< Photosensitive layer composition >> The components and the coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared according to the following respective manufacturing methods.

First layer (blue-sensitive layer) Gelatin 1.50 Blue-sensitive silver chlorobromide emulsion (Em-B) 0.26 Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST -2) 0.10 Dye image stabilizer (ST-5) 0.10 Anti-staining agent (HQ-1) 0.01 Compound A 0.15 DBP 0.15 Second layer (intermediate layer) Gelatin 1.20 AI-3 0.01 Anti-staining agent (HQ-2) 0.03 Anti-staining agent (HQ-3) 0.03 Anti-staining agent (HQ-4) 0.05 Anti-staining agent (HQ-5) 0.23 DIDP 0.06 Optical brightening agent (W-1) 0.10 Third layer (green sensitive layer) Gelatin 1.30 AI -1 0.01 Green-sensitive silver chlorobromide emulsion (Em-G) 0.14 Magenta coupler (M-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17 DIDP 0.13 DBP 0.13 Fourth Layer (UV absorption layer) Gelatin 1.10 Purple Line absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 AI-2 0.02 Anti-staining agent (HQ-3) 0.10 Fifth layer (red sensitive layer) Gelatin 1.30 Red-sensitive silver chlorobromide emulsion (Em-R) 0.21 Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.08 Dye image stabilizer (ST-1) 0.10 Anti-staining agent (HQ-1) 0.004 DOP 0.34 6th layer (UV absorbing layer) Gelatin 0.50 AI-2 0.01 UV absorbing agent (UV-1) 0.12 UV absorbing agent (UV-2) 0.04 UV absorbing agent (UV-3) 0.16 Stain inhibitor (HQ-5) 0.04 PVP 0.03 7th layer (protective layer) Gelatin 1.00 DIDP 0.005 Silicon dioxide 0.003 Hardener H-1 0.596 Hardener H-2 0.229 The above abbreviations are shown below as compound names or structural formulas.

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 Compound A: pt-octylphenol

[0114]

[Chemical 3]

[0115]

[Chemical 4]

[0116]

[Chemical 5]

[0117]

[Chemical 6]

[0118]

[Chemical 7]

[0119]

[Chemical 8]

<< Preparation of Blue-Sensitive Silver Halide Emulsion >> In a liter of a 2% gelatin aqueous solution kept at 40 ° C., the following (A
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over a period of time, and further add the following (C liquid) and (D liquid)
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX << Preparation of green-sensitive silver halide emulsion >> (Solution A) and (Solution B)
A monodisperse cubic emulsion E having an average grain size of 0.43 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (C liquid) are changed.
MP-2 was obtained.

The following compounds were used for EMP-2.
Optimal chemical sensitization was carried out at 55 ° C. 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 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mole AgX << Preparation of red-sensitive silver halide emulsion >> (solution A) and (solution B)
A monodisperse cubic emulsion E having an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C solution) and the addition time of (C solution) are changed.
MP-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. 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 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 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 Here, the above abbreviations are shown below by compound order or structural formula.

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0129]

[Chemical 9]

<< Coating of Photosensitive Layer and the Like >> The above-prepared photographic support is connected, and the above coating solution is coated thereon so that the photosensitive layer and the non-photosensitive layer are in the order of all seven layers. As shown in Table 1, the samples were Nos. 1 to 23.

<< Preparation of test sample >> Each coated silver halide color photographic material was slit into rolls of a predetermined width for each sample number so that it could be processed by an automatic processor, and then subjected to the following test. I served. The results are shown in Table 2.

<Testing / Evaluation Method><< Evaluation of Sharpness >> A resolution test chart is printed on a sample to be written with red light and the following development processing is carried out.
The concentration was measured by (manufactured by Konica Corporation), and the value represented by the following formula was defined as the sharpness.

Sharpness (%) = (Dmax-Dmin of a dense line print image of 3 lines / mm) / (Dmax-Dmin in large area) Here, Dmax is the maximum density and Dmin is the minimum density.
The larger this value, the better the sharpness.

<< Gloss Test and Evaluation >> A sample subjected to solid exposure with white light (overall exposure) was subjected to development processing, and the surface glossiness of the obtained black exposed and developed sample was measured by Nippon Denshoku Industries VG.
It was measured with a D-type gloss meter at an incident angle of 60 ° and an acceptance angle of 60 °.

<< Test and Evaluation of Density Unevenness >> After processing, a sample which was uniformly exposed with a light amount corresponding to a gray color was subjected to development processing, and the density unevenness of the obtained gray sample was visually evaluated according to the following criteria. ⊚: No density unevenness is observed.

O: A slight density unevenness is observed, but it is acceptable as a product.

Δ: Uneven density is observed, which is not preferable as a product.

X: Density unevenness is considerably observed and it is not possible as a product.

<< Evaluation with Time >> The samples for the evaluation of sharpness and the sample for evaluation of gloss were stored under high temperature and high humidity at a temperature of 75 ° C. and a relative humidity of 60% RH for 10 days. And the glossiness over time were evaluated.

<Processing such as development> Processing was performed under the following conditions using an automatic developing machine for color printing.

<Development processing step> Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ° C 45 seconds 120cc Stabilization 30 to 34 ° C 60 seconds 150cc Dry 60 to 80 C. 30 seconds The composition of the developing solution is shown below.

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

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc Add water to make the total volume 1 liter, and adjust to pH = 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid 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 Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1.0 g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g Nitrilotriacetic acid / trisodium salt 1.5 g Add water to bring the total volume to 1 liter, and adjust to pH = 7.5 with sulfuric acid or aqueous ammonia.

<< Results and Evaluation >>

[0146]

[Table 2]

As can be seen from Table 2, the center surface average roughness of the surface of the polyethylene resin layer on the side of the photographic support on which the silver halide photosensitive layer is coated and the content of the titanium oxide white pigment in the resin layer are determined. It can be seen that by setting the content within the range of the present invention, the sample of the present invention has excellent sharpness and glossiness, and the uneven density is improved. By setting the surfactant contained in the photosensitive layer and the like within the range of the present invention,
It can be seen that the samples of the present invention stored under high temperature and high humidity show very little deterioration in sharpness. When the type of the surfactant of the present invention was changed to another test, similar results were obtained.

(Example 2) << Synthesis of modified polyester resin >> Modified polyester resin having terephthalic acid / 5-sodium sulfo-isophthalic acid / ethylene glycol / polyethylene glycol as a constitutional unit (abbreviation: TSEP resin) dimethyl terephthalate 100% by weight Part, ethylene glycol 6
4 parts by weight and 0.1 part by weight of calcium acetate hydrate as a transesterification catalyst were added, and the transesterification reaction was carried out by a conventional method.

The obtained product was added to sodium- (β-hydroxyethyl) isophthalic acid-5-sulfonate (abbreviation: S
28 parts by weight of IP) in ethylene glycol solution (concentration 35% by weight), and polyethylene glycol (abbreviation: PEG)
(Number average molecular weight: 3000) 8.1 parts by weight was added, and then
Antimony oxide 0.05 part by weight, phosphoric acid trimethyl ester
0.13 parts by weight, Irganox 1010 (CI
0.2 parts by weight of BA-GEIGY) and 0.02 parts by weight of sodium hydroxide were added. Then gradually raise the temperature and reduce the pressure to 280 ° C and 0.5
Polymerization was carried out under the condition of mmHg, and after completion of the polymerization, the polymer was taken out from the bottom of the reaction vessel into a noodle through a nozzle having a diameter of about 2 to 4 mm, immediately cooled in a water bath and pulled up to a length of about 5 to 7
A chip was obtained by cutting into mm to obtain a TSEP resin having an intrinsic viscosity of 0.55.

Modified polyester resin having terephthalic acid / 5-sodium sulfo-isophthalic acid / adipic acid / ethylene glycol as a constitutional unit (abbreviation: TSAE resin) It can be synthesized (copolymerized) in the same manner as the above TSEP resin.

<< Preparation of Photographic Support >> 2-1. White TSEP resin layer / paper support / TSEP resin layer laminate Photographic support: Using the uncoated paper support of Example 1, the above modified polyester TSE
P resin was applied to both sides. Chip-shaped TSAE resin 15
After vacuum-drying at 0 ° C., it was introduced into an extruder, melt-extruded at 285 ° C., and applied at a predetermined thickness (see Table 3) from the die slit to the non-photosensitive layer side of the paper support. Subsequently, TSEP resin chips and titanium oxide powder were put in a predetermined amount (see Table 3) in a rotary vacuum dryer and dried while sprinkling at 150 ° C.,
Introduced into an extruder, melt-kneaded at 285 ° C, extruded, and applied to the surface on the side where the silver halide photosensitive layer is applied from the die slit to a predetermined thickness (see Table 3), which has a white resin layer and is water resistant. Photosensitive supports I to L were prepared and used to prepare silver halide color photographic light-sensitive materials.

2-2. White TSAE / PET resin mixed layer / paper support / TSAE / PET mixed resin layer laminate Photographic support: Using the uncoated paper support of Example 1, the modified polyester TSAE resin (Resin 1) And polyethylene terephthalate resin (abbreviation: PET resin)
A polyester resin laminated photographic support having a resin layer mixed with (Resin 2) on both sides was prepared. Mix a predetermined amount of TSAE resin chips and PET resin chips (see Table 3)
Except for this, Example 2-1. Mixed polyester resin laminate photographic support M
P was obtained and similarly used for preparing a silver halide color photographic light-sensitive material.

2-3. White TSEP / PE mixed resin layer /
Paper support / PE resin layer laminated photographic support: For photographic use in which a white modified polyester resin layer is provided on the silver halide photosensitive layer side of the paper support having a PE layer only on the non-photosensitive layer side of Example 1. The support was prepared as follows. TSEP resin chip (resin 1), PE resin chip (resin 2) and titanium oxide were put into a rotary vacuum dryer in a predetermined amount, mixed and dried at 150 ° C, then introduced into an extruder, melt-kneaded at 295 ° C, A white resin layer is provided on the surface of the support on the side of the photosensitive layer through a die slit to provide a white resin layer with a predetermined thickness (see Table 3) to obtain photographic supports Q to V. Similarly, a silver halide color photograph is prepared. It was used to prepare a light-sensitive material.

Table 3 shows the values of the surface roughness SR _a of these white resin layers on the side coated with the silver halide photosensitive layer.

<Preparation of Photosensitive Material><< Undercoating Layer and Antistatic Layer >> Corrosion discharge of 8 W / (m ² · min) was applied to both surfaces of the above-mentioned photographic supports I to U, and undercoating was applied to the photosensitive layer coated side. Coating solution B-1 is coated to a dry film thickness of 0.8 μm to form an undercoat layer B-1, and the other surface of the support is coated with the following undercoating solution B-2 to a dry film thickness of 0.8 μm. To form an undercoat layer B-2.

<< Undercoating Liquid B-1 >> Copolymerized latex liquid (solid content 30%) 270 g Butyl acrylate 30 wt% t-Butyl acrylate 20 wt% Styrene 25 wt% 2-Hydroxyethyl acrylate 20 wt% Compound ( UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml << Subbing coating solution B-2 >> Copolymer latex solution (solid content 30%) 270g Butyl acrylate 40% by weight Styrene 20% by weight Glycidyl acrylate 40% by weight Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml Furthermore, undercoat layer B-1 and undercoat layer B-2 On top of 8W / (m ²
-Min) corona discharge is applied, and on the undercoat layer B-1,
The undercoating layer B-3 was formed by applying the following coating solution B-3 to a dry film thickness of 0.1 μm.

<< Undercoating Coating Solution B-3 >> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Water Finished with 1000 ml The above UL-1, UL-2, and UL-3 are shown below.

[0158]

[Chemical 10]

<< Coating of photosensitive layer-Evaluation >> Photographic support I-
A corona discharge of 25 W / (m ² · min) was applied on B-3 of U, and the photosensitive layers used in Example 1 were multilayer-coated in the same manner as in Example 1 to prepare Sample Nos. 24 to 36. did.

[0160]

[Table 3]

[0161]

[Table 4]

Further, test sample preparation, development processing, and test / evaluation were conducted in the same manner as in Example 1. The results are shown in Table 5.

<< Results and Evaluation >>

[0164]

[Table 5]

As can be seen from Table 5, the center of the resin layer surface of the modified polyester resin photographic support and the modified polyester resin and polyethylene terephthalate resin or polyethylene resin mixed photographic support on the side where the silver halide photosensitive layer is coated. By adjusting the surface average roughness and the content of the titanium oxide white pigment in the resin layer within the range of the present invention, the samples of the present invention (Sample No. 26, 27, 28, 29, 30, 32, 3
It can be seen that 3, 34) have excellent sharpness and glossiness and have improved density unevenness. Further, it can be seen that when the surfactant contained in the photosensitive layer is within the range of the present invention, the sample of the present invention stored under high temperature and high humidity shows very little deterioration in sharpness.

(Example 3) PE on the side opposite to the photosensitive layer in Example 1
The following electron beam curable resin composition was applied to the silver halide photosensitive layer side of the paper support provided with a resin layer to prepare a photographic support.

<< Preparation of Electron Beam-Curable Resin Composition Coating Liquid Containing White Pigment >> 3-1. Urethane acrylate oligomer (Beamset 550B manufactured by Arakawa Chemical Industries) 25 parts by weight Diethylene glycol diacrylate 25 parts by weight Titanium oxide (anatase type average particle size 0.2 μm) 50 parts by weight 3-2. Pentaerythritol oligomer (Beamset 700 manufactured by Arakawa Chemical Industry Co., Ltd.) 65 parts by weight Titanium oxide (rutile type average particle size 0.2 μm) 35 parts by weight Each composition described above was dispersed in a ball mill for 20 hours to prepare a coating solution.

<< White electron beam curable resin layer / paper support / P
Preparation of E-layer Laminated Photographic Support >> Each coating solution is applied by a roll coating method to the surface of the paper support having a PE layer already provided on the back side on which the silver halide photosensitive layer is applied, and vice versa. Acceleration voltage: 175KV, absorbed dose:
An electron beam is irradiated under the condition of 2 Mrad to cure the resin, and a white electron beam curable resin layer (abbreviation:
Photographic supports ah having EBC) were obtained. The surface of each photographic support on the photosensitive layer side (white resin side) was subjected to corona discharge treatment at an output current value of 2 amps, and then a gelatin subbing layer was provided in the same manner as in Example 1. Table 6 shows SR _a of the surface on the side coated with the silver halide photosensitive layer.

[0169]

[Table 6]

<< Coating-Evaluation of Photosensitive Layer >> A total of 7 layers of the above-prepared photographic support were coated in the same manner as in Example 1 to obtain sample Nos. 37 to 44 as shown in Table 6. As in Example 1, the test sample was prepared, developed, and tested and evaluated. The results and evaluation are shown in Table 7.

<< Results and Evaluation >>

[0172]

[Table 7]

As can be seen from Table 7, the center surface average roughness of the surface of the resin layer on the side of the electron beam curable resin photographic support coated with the silver halide photosensitive layer and the titanium oxide white pigment in the resin layer. By setting the content of the above in the range of the present invention, the samples of the present invention (Sample Nos. 39, 40, 43, 44) have excellent sharpness and glossiness, and the uneven density is improved. I understand. Further, it can be seen that when the surfactant contained in the photosensitive layer is within the range of the present invention, the sample of the present invention stored under high temperature and high humidity shows very little deterioration in sharpness.

[0174]

EFFECTS OF THE INVENTION According to the present invention, it has excellent sharpness and glossiness, less uneven density, and little deterioration in sharpness and glossiness even when stored under high humidity and high temperature conditions for a long time. It is also possible to obtain a silver halide color photographic light-sensitive material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/95 7/00 520

Claims (5)

[Claims] 1. A silver halide color photographic light-sensitive material in which at least one silver halide photographic light-sensitive layer is provided on a photographic support having at least one resin layer containing titanium oxide on a paper support. A material having a titanium oxide content of 9 g / m ² or more with respect to the resin of the photographic support and having a silver halide photosensitive layer coated side of the photographic support represented by the following mathematical formula 1. A silver halide color photographic light-sensitive material characterized in that the center surface average roughness (SR _a ) of the surface of the resin layer is 0.08 μm or less. [Equation 1] Here, in the formula, SR _a represents the central surface average roughness, Lx represents the length of the measurement surface area in the X-axis direction, Ly represents the length of the measurement surface area in the Y-axis direction, and S _A is It represents the area of the measurement area, and S _A = Lx × Ly, where Lx = 7.5 mm and Ly = 21 mm
Where f (x, y) represents the surface uneven surface, and x and y represent the position coordinates of the measurement point in the x direction and the y direction, respectively. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the content of titanium oxide in the resin of the photographic support is 10 g / m ² or more. 3. The center average roughness (SR _a ) of the surface of the resin layer on the side of the photographic support on which the silver halide photosensitive layer is coated.
Is less than 0.07 μm. 3.
The described silver halide color photographic light-sensitive material. 4. The content of the surfactant represented by the general formula (I) is 0.3 g per 1 m ^{2 of} silver halide color photographic light-sensitive material.
The silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein: General formula _{(I) R- (L) n} -SO 3 - M + ( where in the formula, R is an alkyl group, an aryl group, an aralkyl group, while the total number of carbon atoms contained in R is from 8 36 L is a divalent or trivalent linking group, n is 0 or an integer from 1 to 10, and M is a cation). 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the content of the surfactant is 0.05 to 0.25 g per 1 m ^{2 of the} silver halide color photographic light-sensitive material.