JPH0973151A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having satisfactory rapid processability, excellent in sharpness and having improved curl and unevenness in density and superior whiteness of a background. SOLUTION: In this silver halide photographic sensitive material with at least one silver halide emulsion layer on one side of the reflective substrate formed by disposing resin coating layers on both sides of base paper, the reflective substrate is a reflective substrate formed by coating at least the surface of a base on the emulsion coated side with a compsn. prepd. by mixing and dispersing a white pigment in a water resistant resin based on polyester. This sensitive material has a hydrophilic colloidal layer contg. a white pigment on the substrate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it has excellent rapid processing suitability and sharpness, and has improved density unevenness, color unevenness and curl after color development.
The present invention relates to a silver halide photographic light-sensitive material having a good white background.

[0002]

2. Description of the Related Art With the spread of color 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 brought about by the scattering of incident light by oil droplets such as silver halide grains and couplers dispersed in a gelatin film, and its degree mainly depends on the gelatin amount, silver halide amount, and oil droplet amount. The latter depends on the degree of light reflection from the support, and on the reflectance and refractive index of the support.

Dye improvements have been made to prevent irradiation. For example, JP-A-50-1451
No. 25, No. 52-20830, No. 50-111641.
No. 61, No. 61-148448, No. 61-151650.
No. 62-275562, No. 62-283336 and the like.

As a method for preventing halation, a method of providing an antihalation layer is known. For example, JP-A-55-33172, JP-A-59-193447 and JP-A-62.
The improvement is described in, for example, No. 33,448.

However, in these methods, the sharpness is remarkably lowered together with the improvement of the sharpness, and it is difficult to improve the sharpness while maintaining the practically sufficient sensitivity only by such means.

Improvements in the support have also been investigated. In recent years, as a support for color print photosensitive materials, a water-resistant support prepared by laminating a polyolefin resin mainly made of polyethylene on the surface of a base paper has been used for speeding up development processing. A white pigment such as titanium oxide is dispersed in the polyolefin layer on the emulsion side. To improve the sharpness, JP-A-54-4603 is used.
No. 5, No. 64-18144, JP-A No. 2-71256, and the like, a technique of using a paper support in which a polyethylene resin layer on the side coated with a photographic emulsion is filled with a large amount of white pigment is combined. However, it is difficult to use it as a support for silver halide color photographic light-sensitive materials because it has drawbacks such as deterioration of smoothness of polyethylene layer and deterioration of adhesion between polyethylene layer and emulsion layer. .

Due to these difficulties, Japanese Patent Laid-Open Nos. 58-60738 and 61-96 disclose techniques capable of improving sharpness.
46, 61-221746, JP-A-2-2864.
As described in No. 0 etc., a technique of providing a layer containing a white pigment between a support and a silver halide emulsion layer has been considered. However, in recent years, a hydrophilic colloid layer containing a white pigment is provided on one surface of a reflection support which is provided with resin coating layers on both sides of a base paper which has been mainly used in recent years, and a silver halide emulsion layer is applied thereon. The above-described silver halide color photographic light-sensitive material has a problem that the curl becomes large, and when it is bent, cracks easily occur on the coated surface. If the curl is large, it tends to stick to one of the rollers when it is pinched by the rollers when it is fed by an automatic processor, etc.
Even when it is necessary to pass through a narrow slit at the time of exposure, it is difficult to pass through this, and jams often occur. Further, a silver halide color photographic light-sensitive material having a hydrophilic colloid layer containing a white pigment provided on one surface of a reflective support and a silver halide emulsion layer coated on the hydrophilic colloid layer is used. It was found that is likely to occur.

By the way, in recent years, the color developing process has become simpler and faster, and the process can be performed quickly.
Moreover, it is desired that the treatment is stable.

From the viewpoint of accelerating the development processing time, silver bromide, silver chlorobromide and silver chloride containing substantially no silver iodide are used as silver halide emulsions applied to color photographic paper. Came. It is known that a silver halide emulsion having a higher silver chloride content has a higher developability and is advantageous for rapid processing.

However, since rapid processing accelerates the defects of density unevenness and color unevenness, a hydrophilic colloid layer containing a white pigment is provided on one surface of the reflective support, and a silver halide emulsion layer is provided thereon. The coated silver halide color photographic light-sensitive material was unsuitable for rapid processing.

Further, as a technique capable of improving the sharpness, Japanese Patent Laid-Open Nos. 6-167768, 6-186673 and 6-
No. 202276, No. 6-289532, etc., a reflective support obtained by coating at least the emulsion coating side surface of a substrate with a composition in which a white pigment is mixed and dispersed in a water resistant resin containing polyester as a main component. Body and special public Sho 60
-17104, Tokuhei 1-23773, Tokuhei 1-
No. 23774, JP-A No. 63-198049, etc., the composition in which the reflection support is prepared by mixing and dispersing a white pigment in an electron beam curable resin is coated on at least the surface of the substrate on which the emulsion is coated. Studies have been conducted using a reflective support obtained by irradiating an electron beam for curing and coating. Unlike the polyethylene resin, these reflective supports were effective in increasing the sharpness because even if they were filled with a large amount of white pigment, the deterioration of smoothness was small. However, in the print photosensitive material using these reflective supports, when the developed print photosensitive material is observed under a fluorescent lamp, it can be seen that interference fringes can be seen on a white background or a low density portion, which is a fatal defect in the print photosensitive material. turn into.

[0012]

Therefore, the first aspect of the present invention
The purpose of is to provide a silver halide photographic light-sensitive material capable of rapid processing and excellent in sharpness.

A second object of the present invention is to provide a silver halide photographic light-sensitive material in which curl, uneven density and uneven color are improved.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which does not show interference fringes and has an excellent white background.

[0015]

The above object of the present invention has been achieved by the following constitution.

(1) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a reflective support having resin coating layers on both sides of a base paper.
The reflective support is a reflective support obtained by coating a composition in which a white pigment is mixed and dispersed in a water resistant resin containing polyester as a main component on at least the emulsion coating side surface of a substrate,
A silver halide photographic light-sensitive material characterized in that the light-sensitive material has a hydrophilic colloid layer containing a white pigment on a support.

(2) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a reflection support having resin coating layers on both sides of a base paper.
The reflective support is a reflective support obtained by coating a composition prepared by mixing and dispersing a white pigment in an electron beam curable resin on at least the surface of the substrate on which the emulsion is coated, and then irradiating with an electron beam for curing and coating. A silver halide photographic light-sensitive material characterized in that the light-sensitive material has a hydrophilic colloid layer containing a white pigment on a support.

(3) The halide according to (1), wherein the silver halide emulsion layer is a silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride. Silver color photographic light-sensitive material.

(4) The halide according to (2), wherein the silver halide emulsion layer is a silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride. Silver color photographic light-sensitive material.

(5) The silver halide color photographic light-sensitive material described in (3) or (4), wherein the silver halide color photographic light-sensitive material contains at least one betaine surfactant.

The present invention will be described in detail below.

The white pigment used in the hydrophilic colloid layer (hereinafter referred to as the white pigment layer) containing the white pigment according to the present invention is, for example, rutile titanium dioxide, anatase titanium dioxide, barium sulfate, barium stearate,
Although silica, alumina, zirconium oxide, kaolin and the like can be used, titanium dioxide is preferable among them for various reasons. The white pigment is dispersed in a water-soluble binder of hydrophilic colloid such as gelatin so that the treatment liquid can permeate, and applied as a white pigment layer. The coating amount of the white pigment is preferably 1 g / m ² to 50 g / m ^2.
Range, more preferably 2 g / m ² to 20 g
The range is / m ² .

As the water-soluble binder used in the white pigment layer, gelatin is mainly used, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives,
A hydrophilic colloid such as a cellulose derivative or a synthetic hydrophilic polymer such as a single or copolymer can also be used in combination with gelatin.

The white pigment layer according to the present invention comprises a support,
It can be provided between the support and the closest silver halide emulsion layer. Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment layer, an undercoat layer may be provided on the support, or a non-photosensitive hydrophilic layer such as an intermediate layer may be provided at any position. A colloidal layer can be provided.

The white pigment layer according to the present invention preferably has a porosity of 5 to 30% by weight based on the hydrophilic colloid layer. The porosity is obtained from the specific gravity, the film thickness and the like.

In addition to the white pigment, colorants such as yellow, gray, blue, and black colloidal silver, inorganic colored pigments, organic colored pigments, and dyes can be added to the white pigment layer according to the present invention.

A hydrophilic colloid layer containing a colorant can be coated between the white pigment layer according to the present invention and the support. As the colorant, various known filter dyes can be used in addition to yellow, gray, blue, and black colloidal silver. As such a light-absorbing substance, it is possible to use a substance that absorbs only light in the entire visible spectrum region, or a substance that selectively absorbs light in a certain part of the region as necessary. You can choose. The transmittance of the colorant-containing hydrophilic colloid layer is preferably 50% or less, and particularly preferably 30% or less.

The support used in the present invention is a paper support having a resin layer on both sides, based on paper, and the resin layer on the side coated with the silver halide emulsion layer (hereinafter referred to as the front resin layer). ) Is a laminate of two or more layers and is a paper support containing a white pigment.

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

Further, the support may be blended with 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, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

Regarding the method of applying the resin coating layer (hereinafter referred to as the back resin layer) on the side opposite to the side coated with the silver halide emulsion layer in the support used in the present invention, a polyolefin resin or polyethylene terephthalate resin is laminated. There are known methods for doing so.

In general, a resin laminate can be formed by melt-extruding a resin composition on a support and coating it. In order to carry out this melt extrusion coating method, usually, a resin composition is melt extrusion coated in a form of a single layer or a plurality of layers from a slit die of an extruder on a running support. Usually, the melt extrusion temperature is preferably 200 to 350 ° C. The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

Next, the water resistant resin containing polyester as a main component according to the present invention will be described.

Examples of the polyester resin useful in the present invention include polyethylene terephthalate and modified polyester having polyethylene terephthalate as a main structure (hereinafter referred to as modified polyester). The modified polyester is composed of a polyester part in which polyethylene terephthalate occupies most of the main chain and a modified part. The main chain constituent molecule of the modified portion is terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, as an ester bond dibasic acid,
1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-
Xylidene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, 5-alkali metal sulfoisophthalic acid, 4-alkali metal sulfo-2,6
-Naphthalenedicarboxylic acid and the like.

As the ester-bonded glycol (diol), ethylene glycol, propion glycol, 1,4-butanediol, 1,4-hexylenediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (number average molecular weight 300 ~ 30,000), polypropylene glycol (number average molecular weight 300 to 30,000)
And the like.

Preferably, the dibasic acid is terephthalic acid, isophthalic acid, 4-metalsulfo-2,6-naphthalenedicarboxylic acid, 5-metalsulfo-isophthalic acid, 4-metalsulfo-2,6-naphthalenedicarboxylic acid. Acid or the like is used, ethylene glycol is used as glycol,
Propylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol (number average molecular weight 300
~ 30,000) is 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% or less, and particularly preferably 30 mol% or less.

The compound having an alkali metal sulfo group in the modified portion of the modified polyester is 2 for all ester bonds.
It is preferably contained in a proportion of from 10 to 10 mol%, and has excellent adhesiveness to the emulsion layer, the resin layer and the base paper. This compound having an alkali metal sulfo group, for example, 5-sodium sulfo-
When 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 becomes large, the adhesiveness between the paper support and the resin deteriorates, and there is a risk of peeling during the photographic processing. Also, the water resistance of the photographic support becomes poor and the photographic support is also used. Problems arise as a support. It is preferably 2 to 7 mol%, and particularly preferably 3 to 6 mol%.

For 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, both a method of directly esterifying an acid component with a glycol component and a method of esterifying an acid component as a dimethyl ester with glycol by a transesterification method can be used. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for the esterification and a polymerization reaction catalyst such as antimony oxide in the polymerization reaction. Regarding the polyester components and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1
980), pp. 103-136, or "Synthetic Polymer V" (Asakura Shoten, 1971), pp. 187-286, can be referred to.

The specific method for synthesizing the modified polyester is as follows:
U.S. Pat. No. 4,217,441, JP-A-5-21011
The modified polyesters described in No. 9 and 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 polymer compound such as polyester is expressed as an intrinsic viscosity (for example, edited by the Chemical Society of Japan,
Standard Chemistry Dictionary, page 24, 1991, published by Maruzen)
The intrinsic viscosity of the polyester used in the present invention is 0.50.
The above is necessary, preferably 0.53 or more, particularly preferably 0.55 or more. When the intrinsic viscosity of the polyester is less than the above, the resin becomes white and becomes brittle after melt extrusion. Also, if melt extrusion is performed with water contained, the intrinsic viscosity will drop extremely, so special care must be taken when drying before melting, and even if the intrinsic viscosity is high, hydrolysis may occur during melting. There is. Drying of resin chips is 10
^It is usually performed under a vacuum of about ^-3 Torr at about 150 ° C.

A white pigment is contained in the water-resistant resin containing polyester as a main component, which coats at least the emulsion-coated surface of the substrate according to the present invention.

As the white pigment used, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used. Titanium dioxide is preferred.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when the whiteness is prioritized, and rutile type titanium dioxide is preferred when the sharpness is important. Anatase type titanium dioxide and rutile type titanium dioxide may be blended and used in consideration of both whiteness and sharpness, or anatase type titanium dioxide may be added to another layer in a layer having a resin coating layer composed of multiple layers. Rutile titanium dioxide may be used.

The titanium dioxide to be used is generally one whose surface is treated with an inorganic substance such as hydrous aluminum oxide or hydrous silicon oxide, a polyhydric alcohol or a polyhydric alcohol in order to suppress the activity of the titanium dioxide and prevent yellowing. Amine, metal soap,
It is possible to use those whose surface is treated with an organic substance such as alkyl titanate or polysiloxane, and those whose surface is treated with an inorganic or organic treating agent in combination. The amount of surface treatment is preferably 0.2 to 2.0% by weight for inorganic substances and 0.1 to 1.0% by weight for organic substances with respect to titanium dioxide. The particle size of titanium dioxide is preferably 0.1 to 0.4 μm.

The content of the white pigment in the resin containing the polyester resin as the main component may be from 0 to 60% by weight, but is preferably 10% by weight or more, preferably 15% by weight, more preferably 20% by weight. % By weight. When the content of the white pigment is less than 10% by weight, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and the content is 6%.
When it exceeds 0% by weight, the coating property of the obtained polyester resin is severely deteriorated and it cannot be put to practical use.

The polyester resin layer may be a laminate of two or more layers having different white pigment contents. The content of the white pigment in the resin layer is preferably such that the average content of the white pigment contained in the two or more resin layers is 10% by weight or more, preferably 15% by weight or more, and 20% by weight or more. More preferable. The content of each of the two or more layers of the white pigment may be any content as long as the average content is the above.

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

The polyester resin is layered on a paper support by melt extrusion coating these molten resins. In this melt extrusion coating method, the resin composition is melted to a predetermined temperature in an extruder and melted from a die slit on a running paper support (supported by a roll at the coating position on the back side of the paper support). Although it is applied, the resin composition layer to be melt-applied may be a single layer in which it is applied from a single slit, or may be a plurality of layers from a plurality of slits. Usually, the melt extrusion temperature is 20
It is preferably 0 to 350 ° C.

If necessary, after coating or curing, the surface may be smoothed by a mirror surface roll or surface matted by a mat roll such as a silk roll.

The electron beam curable resin according to the present invention is a resin curable by electron beam irradiation. As the electron beam curing compound of the electron beam curing resin useful in the present invention, any compound that can be cured by electron beam irradiation can be used. In the present invention, examples of the compound curable by electron beam irradiation that can be used include, for example, Japanese Patent Publication No. 60-1710
4, electron beam curable compounds described in JP-A-60-126649, JP-A-2-157747 and the like,
An electron beam curable monomer or oligomer corresponds to this.

The electron beam-curable monomers or oligomers useful in the present invention include unsaturated compounds containing two or more carbon-carbon double bonds in one molecule (eg, acrylic compounds,
Or, a methacrylic oligomer, a polyfunctional acrylic or methacrylic monomer is used, and an unsaturated compound containing at least a carbon-carbon double bond in one molecule as a monomer to be used by diluting the above curable monomer (for example, , Monofunctional acrylic monomers, methacrylic monomers, vinyl monomers, etc.) are used.

The acrylic and methacrylic oligomers include polyurethane acrylic acid esters or methacrylic acid esters, polyether alcohol acrylic acid esters or methacrylic acid esters, bisphenol A acrylic acid esters or methacrylic acid esters,
Mention may be made of maleic acid ester or fumaric acid ester of polyester. Further, as the polyfunctional acrylic monomer and the methacrylic monomer, 1,6-
Hexanediol diacrylate, neopentyl diacrylate, diethylene glycol diacrylate, butadiene acrylate, diethylene glycol dimethacrylate, etraethylene glycol diacrylate, glycerol trimethacrylate, stearyl acrylate, polyethylene glycol diacrylate, butoxyethyl acrylate, 1,4-butanediol diacrylate Acrylate, ethylene glycol dimethacrylate, glycyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, benzyl acrylate, N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate,
Ethylene oxide modified phenoxy phosphate acrylate, neopentyl glycol diacrylate, isocyanuric acid diacrylate, isocyanuric acid triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane polyacrylate, glycyl methacrylate, Examples thereof include 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, pentaerythritol pentaacrylate, and the like. In addition, monofunctional acrylic monomers and methacrylic monomers,
Examples of vinyl monomers include styrene, N-vinylpyrrolidone, polyoxyethylene phenyl alcohol acrylic acid ester, and 2-ethylhexyl acrylate.

The coating solution of the present invention contains a pigment, usually a white inorganic pigment, which is uniformly mixed with the electron beam-curable organic compound. The white pigment used may be, for example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin, etc., but for various reasons, titanium dioxide is particularly preferable. preferable.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when whiteness is prioritized, and rutile type titanium dioxide is preferred when sharpness is emphasized. Anatase type titanium dioxide and rutile type titanium dioxide may be blended and used in consideration of both whiteness and sharpness, or anatase type titanium dioxide may be added to another layer in a layer having a resin coating layer composed of multiple layers. Rutile titanium dioxide may be used.

The titanium dioxide to be used is generally surface-treated with an inorganic substance such as aluminum hydroxide and silicon hydroxide in order to suppress the activity of titanium dioxide and prevent yellowing, polyhydric alcohol, polyhydric alcohol. Amine, metal soap,
It is possible to use those whose surface is treated with an organic substance such as alkyl titanate or polysiloxane, and those whose surface is treated with an inorganic or organic treating agent in combination. The amount of surface treatment is preferably 0.2 to 2.0% by weight for inorganic substances and 0.1 to 1.0% by weight for organic substances with respect to titanium dioxide. The particle size of titanium dioxide is preferably 0.1 to 0.4 μm.

The content of the white pigment in the electron beam effect resin is
Any amount of 0 to 70% by weight may be used, but 10% by weight or more is preferable, 15% by weight is preferable, and 20 is more preferable.
% By weight. If the content of the white pigment is less than 10% by weight, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and if the content exceeds 70% by weight,
The flexibility of the obtained cured resin coating layer decreases, and film cracking occurs.

The electron beam effect resin layer may be a laminate of two or more layers having different white pigment contents. The content of the white pigment in the resin layer is preferably such that the average content of the white pigment contained in the two or more resin layers is 10% by weight or more, preferably 15% by weight or more, and 20% by weight or more. More preferable. The content of each of the two or more layers of the white pigment may be any content as long as the average content is the above.

In order to disperse the white inorganic pigment in the electron beam-curable unsaturated organic compound, three roll mill (three roll mill), two roll mill (two roll mill), cowles dissolver, homomixer, sand grinder,
Also, an ultrasonic disperser or the like can be used.

As the organic solvent, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene, ethylene chloride, carbon tetrachloride, chloroform, dichlorobenzene and the like can be used. .

As a coating method, a roller coating method may be used, or alternatively, a general method used for coating a sheet, for example, a bar coating method, an air doctor coating method, a plate coating method, a squeeze coating method, or an air coating method. Any of a knife method, a reverse roll coating method, a transfer coating method and the like may be used. A fountain coater or slit orifice coater system can also be used.

The electron beam irradiation apparatus used in the present invention is not particularly limited, and generally, as such an electron beam accelerator for electron beam irradiation, a curtain beam type which is relatively inexpensive and can obtain a large output. Is used effectively. The acceleration voltage at the time of electron beam irradiation is preferably 100 to 300 kV, and the absorbed dose is preferably 0.5 to 10 Mrad.

The thickness of the coating layer is 3 to 100 μ, preferably 5 to 50 μ. If it deviates from this range, coating unevenness occurs, a large amount of energy is required for curing, and curing becomes insufficient, which is not preferable in terms of quality.

If necessary, after coating or curing, the surface may be smoothed by a mirror-finished roll or surface-matted by a matte roll such as a silk roll.

The betaine-based surfactants of the present invention include carboxybetaine type, sulfobetaine type, imidazolium betaine type and the like. Some specific examples of the betaine-based surfactant used in the present invention are shown below, but the present invention is not limited thereto.

[0068]

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[0069]

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[0070]

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In the present invention, the amount of betaine surfactant used is 0.0001 to 1.0 g / m ² , preferably 0.0005 to 0.5 g / m ² , and more preferably 0.001. Is about 0.2 g / m ² .

In the present invention, the betaine surfactant is
It may be added to either the silver halide emulsion layer or the non-photosensitive hydrophilic colloid layer constituting the light-sensitive material of the present invention. Is preferably added to the layer closest to the substrate and / or the layer farthest from the support.

The composition of the silver halide photographic emulsion according to the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. Quick processing,
From the viewpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, and more preferably 98 to 99.9 mol% silver chloride is preferable.

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

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

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

When the above-mentioned heavy metal ions form a complex, their ligands or ions are cyanide ions,
Thiocyanate ion, cyanate ion, chloride ion,
Examples thereof include bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, cyanate ion,
Chloride ions, bromide ions and the like are preferred.

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

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

The shape of the silver halide grains according to the present invention can be arbitrary. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,6
66, JP-A-55-26589, JP-B-55-42
737 and The Journal of Photographic Science (J. Photogr. Sci.) 2
1, 39 (1973), etc., particles having an octahedral, tetradecahedral, dodecahedral or the like shape can be prepared and used. Further, particles having a twin plane may be used.

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

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

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 of the present invention is preferably monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and a coefficient of variation of 0 is particularly preferred. It is to add two or more kinds of monodisperse emulsions of 0.15 or less to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

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

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

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

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

Further, JP-A-57-92523 and 57-57.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
For example, an apparatus described in No. 501776, which takes out the reaction mother liquor from the reactor and concentrates it by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant, may be used.

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

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

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

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

The gold sensitizer according to the present invention may be added as various gold complexes other than chloroauric acid, gold sulfide and the like. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

A reduction sensitization method may be used as the chemical sensitization method for the silver halide emulsion according to the present invention.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuation during storage, and preventing fog that occurs during development. Antifoggant known in
Stabilizers can be used. As examples of preferred compounds that can be used for such purposes, JP-A-2-14
The compound represented by the general formula (II) described in the lower column of the specification of page 6036 can be mentioned, and more preferable specific compounds include (IIa-1 )-(IIa-8), (IIb-1)-(IIb
-7) or 1- (3-methoxyphenyl) -5
Compounds such as -mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds, depending on their purpose,
It is added in the steps of preparing the silver halide emulsion grains, the chemical sensitization step, the completion of the chemical sensitization step, and the coating liquid preparation step. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, 1 × 10 ^-6 to 1 mol per mol of silver halide
An amount of about 1 × 10 ⁻² mol is preferable, and 1 × 10 ⁻⁵ mol or more.
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating liquid preparation step, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. More preferably 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × 10 ⁻⁹ to 1 × 1 per 1 m ^2.
The amount is preferably about 0 ^-3 mol.

The silver halide photographic light-sensitive material of the present invention comprises
Dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. Particularly, as a dye having absorption in the visible region, AI-1 described in JP-A-3-251840, page 308.
To 11 and the dyes described in JP-A-6-3770 are preferably used, and as the infrared absorbing dye,
The compounds represented by the general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A No. 1-280750 have preferable spectral characteristics and are suitable for the photographic characteristics of silver halide photographic emulsions. It is preferable because there is no influence of the above and there is no contamination due to residual color. As specific examples of preferred compounds, exemplified compounds (1) to (3) on the lower left column of page 3 to the lower left column of page 5 of the same publication
(45) can be mentioned.

The amount of these dyes added is 680 nm for an untreated sample of a light-sensitive material for the purpose of improving sharpness.
Is more preferably 0.7 or more, and even more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material of the present invention because the whiteness can be improved. Examples of compounds preferably used include compounds represented by the general formula described in JP-A-2-232652.

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

As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used, but as the blue-sensitive sensitizing dye, JP-A-3-2 is used.
BS-1 to 8 described in page 28 of JP 51840 can be preferably used alone or in combination. Examples of the green photosensitive sensitizing dye include G
S-1 to S-5 are preferably used. RS-1 to 8 described on page 29 of the same publication are preferably used as red-sensitive sensitizing dyes. In the case of performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye. The dyes of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. These infrared, red, green, and blue photosensitive sensitizing dyes may be added to supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pp. 8-9, and JP-A-5-66515. Issue 1
It is preferable to use the compounds S-1 to S-17 described on pages 5 to 17 in combination.

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

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

The coupler used in the silver halide photographic light-sensitive material of the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Any compound to be obtained can be used. Particularly, as a typical example, a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 6 is used.
A magenta dye-forming coupler having a spectral absorption maximum wavelength at 00 nm and a cyan dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm are typical.

Cyan couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention include general formulas (CI) and (CI) described in JP-A-4-114154, page 5, lower left column. The coupler represented by II) can be mentioned. Specific compounds are described in the same specification at page 5, lower right column to page 6, lower left column, CC-1 to CC-9.
Can be mentioned.

As magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention, the general formulas (M-I) and (M-I) described in JP-A-4-114154, page 4, upper right column, can be used. The coupler represented by II) can be mentioned. Specific compounds are described in the same specification on page 4, lower left column to page 5, upper right column MC-1 to MC-.
Those listed as 11 can be mentioned.
Among the above-mentioned magenta couplers, more preferable are the couplers represented by the general formula (M-I) described in the upper right column of page 4 of the same publication, among which the above-mentioned general formula (M-I).
Are particularly preferred because of their high light resistance. MC-8 to MC-11 described in the upper column of page 5 of the publication are preferable because they are excellent in the reproduction of colors ranging from blue to purple and red, and are also excellent in the depiction of details.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. A coupler can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Among them, a coupler in which RY1 in the general formula [Y-1] in the specification of the publication is an alkoxy group or a coupler represented by the general formula [I] in the specification of JP-A-6-67388 can reproduce a preferable yellow color tone. preferable. Of these, particularly preferred examples of compounds include YC-8, YC-9 and JP-A-6-6 described in the lower left column of page 4 of JP-A-4-114154.
No. 7388, Nos.
Compounds represented by (1) to (47) can be mentioned. The most preferred compounds are disclosed in JP-A-4-81847, page 1 and page 11, page 1 to 1.
It is a compound represented by the general formula [Y-1] on page 7.

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

Further, instead of the method using a high-boiling point organic solvent, or in combination with a high-boiling point organic solvent, a water-insoluble and organic solvent-soluble polymer compound is optionally added to a low-boiling point and / or water-soluble organic solvent. It is also possible to employ a method in which the surfactant is dissolved in a hydrophilic binder such as an aqueous gelatin solution and the resulting mixture is emulsified by various dispersing means using a surfactant. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof in one molecule. The thing contained is mentioned. Specifically, A-1 described in JP-A-64-26854 is described.
To A-11. Also, a surfactant in which a fluorine atom is substituted for an alkyl group is preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is preferable that the time from dispersion to addition to the coating solution and the time from addition to the coating solution and coating are short, respectively.
It is preferably within the time, more preferably within 3 hours and within 20 minutes.

An anti-fading agent is preferably used in combination with each of the above couplers in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas I and II described on page 3 of JP-A-2-66541,
A phenolic compound represented by the general formula IIIB described in JP-A-3-174150, an amine-based compound represented by the general formula A described in JP-A-64-90445, and a general formula described in JP-A-62-182741. XII, XIII, XI
Metal complexes represented by V and XV are particularly preferred for magenta dyes. Further, the compound represented by the general formula I ′ described in JP-A-1-196049 and the compound represented by the general formula II described in JP-A-5-11417 are particularly yellow,
Preferred for cyan dyes.

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described in JP-A-4-114154, page 9, lower left column, the compound described in the same specification, page 10, lower left column. Compounds such as (A'-1) can be used. In addition to this, US Pat.
The fluorescent dye-releasing compounds described in No. 74,187 can also be used.

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

It is preferable to add an ultraviolet absorber to the light-sensitive material of the present invention to prevent static fog and improve the light resistance of the dye image. Benzotriazoles are mentioned as preferable ultraviolet absorbers, and particularly preferable compounds are those represented by the general formula described in JP-A-1-250944.
Compounds represented by formula III-3, compounds represented by formula III described in JP-A-64-66646, JP-A-63-
UV-1L to UV-27L described in Japanese Patent No. 187240,
Examples thereof include compounds represented by the general formula I described in JP-A-4-1633 and compounds represented by general formulas (I) and (II) described in JP-A-5-165144.

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

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener, a chlorotriazine type hardener or a carboxy-active type hardener alone or in combination. JP-A-61-249054 and 61-2451
It is preferable to use the compound described in Japanese Patent No. 53. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of mold and bacteria which adversely affect the photographic performance and image storability. Further, in order to improve the physical properties of the surface of the light-sensitive material or the sample after processing, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer.

In the silver halide photographic light-sensitive material of the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of support surface, electrostatic charge). It may be applied via one or more undercoat layers) for improving anti-preventive property, dimensional stability, abrasion resistance, hardness, antihalation property, frictional property and / or other property). .

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

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

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

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds 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- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β
-Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N-ethyl-N
-(Β- (Methanesulfonamido) ethyl) aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4 -Amino-3-methyl-N-ethyl-N
-Methoxyethylaniline CD-10) 4-Amino-3-methyl-N-ethyl-
N- (β-ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-
N- (γ-hydroxypropyl) aniline In the present invention, the above color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is 9.5 to 13.0.
And more preferably pH 9.8-1.
It is used in the range of 2.0.

In the present invention, the processing temperature for color development is
It is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the processing time is possible, which is preferable. However, from the viewpoint of the stability of the processing solution, the higher the temperature, the more preferable.

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

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

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

[0127]

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

Example 1 << White Base Paper >> A basis weight of 175 g / containing 50% by weight of sulfated bleached hardwood pulp (LBKP) and 50% by weight of sulfated bleached softwood pulp (NBSP) for photographic grade photographic paper.
A white base paper with m ² and a thickness of 180 μm was prepared.

<Support A> A polyethylene composition (density 0.95 g / cc, melt index (abbreviation: M) is provided on the side of the white base paper opposite to the side coated with the silver halide emulsion.
I) 8.0 g / 10 min) was melt-extruded and laminated at 300 ° C. to cover a back laminate layer of 30 g / m ² .

Next, a polyethylene composition (density 0.92 g / cc, MI) was formed on the surface on which the silver halide emulsion was coated.
300 g after kneading 90% by weight of 5.0 g / 10 minutes) and 10% by weight of titanium oxide white pigment (anatase type)
Was coated with a water-resistant resin layer of 30 g / m ² by melt-extrusion lamination to prepare a paper support having a resin coating layer on both sides.

<Support B> 300 parts of a polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) was applied to the side of the white base paper opposite to the side coated with the silver halide emulsion.
Melt extrusion lamination was performed at 0 ° C. to cover a back laminate layer of 30 g / m ² .

Next, on the surface on which the silver halide emulsion was coated, a polyethylene terephthalate composition (intrinsic viscosity of 0.
72 cc / g) and 75% by weight of titanium oxide white pigment (anatase type) are kneaded, and then melt-extruded at 300 ° C. and laminated with a water-resistant resin layer of 30 g / m ² by resin coating on both sides. A paper support with layers was made.

<Support C> A polyethylene terephthalate composition (intrinsic viscosity 0.65 cc / g) was melt-extruded and laminated at 300 ° C. on the surface of the white base paper opposite to the side on which the silver halide emulsion was coated to give 30 g. / M ² of back laminate layer was coated.

Next, on the surface on which the silver halide emulsion was coated, a polyethylene terephthalate composition (with an intrinsic viscosity of 0.
72 cc / g) and 30% by weight of titanium oxide white pigment (anatase type) are kneaded, and then melt extruded at 300 ° C. and laminated with a water-resistant resin layer of 30 g / m ² by resin coating on both sides. A paper support with layers was made.

<Support D> A polyethylene terephthalate composition (intrinsic viscosity 0.65 cc / g) was melt-extruded and laminated at 300 ° C. on the surface of the white base paper opposite to the side on which the silver halide emulsion was coated to give 30 g. / M ² of back laminate layer was coated.

Next, on the surface on which the silver halide emulsion was coated, a polyethylene terephthalate composition (with an intrinsic viscosity of 0.
72 cc / g) and 20% by weight of titanium oxide white pigment (anatase type) are kneaded and then melt-extruded at 300 ° C. and laminated with a water-resistant resin layer of 30 g / m ² by resin coating on both sides. A paper support with layers was made.

<Support E> The polyethylene terephthalate composition (intrinsic viscosity 0.65 cc / g) was melt-extruded and laminated at 30 ° C. on the surface of the white base paper opposite to the side on which the silver halide emulsion was coated, to give 30 g. / M ² of back laminate layer was coated.

Next, the following modified polyester resin was prepared.

100 parts by weight of dimethyl terephthalate, 14 parts by weight of naphthalene-2,6-dicarboxylic acid dimethyl ester and 80 parts by weight of ethylene glycol were added, and transesterification was carried out by a conventional method. 0.05 parts by weight of antimony trioxide was added to the obtained product, and the temperature was gradually raised and the pressure was reduced to carry out polymerization under the conditions of 280 ° C. and 0.5 mmHg, and terephthalic acid / naphthalenedicarboxylic acid = 9
A modified polyester of 0/10 (molar ratio) was obtained. The intrinsic viscosity of the obtained modified polyester was 0.7 cc / g.

70% by weight of this modified polyester and 30% by weight of a titanium oxide white pigment (anatase type) were kneaded and then melt-extruded at 300 ° C. to obtain 30 g by lamination.
A paper support having a resin coating layer on both sides was prepared by coating with a water resistant resin layer of / m ² .

<Support F> A polyethylene terephthalate composition (intrinsic viscosity 0.65 cc / g) was melt-extruded and laminated at 300 ° C. on the surface of the white base paper opposite to the side on which the silver halide emulsion was coated. / M ² of back laminate layer was coated.

Next, the following modified polyester resin was prepared.

100 parts by weight of dimethyl terephthalate, 126 parts by weight of naphthalene-2,6-dicarboxylic acid dimethyl ester, and 80 parts by weight of ethylene glycol were added, and transesterification reaction was carried out by a conventional method. 0.05 parts by weight of antimony trioxide was added to the obtained product, and the temperature was gradually raised and the pressure was reduced to carry out polymerization under the conditions of 280 ° C. and 0.5 mmHg, and terephthalic acid / naphthalenedicarboxylic acid =
A modified polyester of 50/50 (molar ratio) was obtained.
The obtained modified polyester has an intrinsic viscosity of 0.68 cc /
g.

75% by weight of this modified polyester and 25% by weight of a titanium oxide white pigment (anatase type) were kneaded and then melt-extruded at 300 ° C. and laminated to give 15 g.
A paper support having a resin coating layer on both sides was prepared by coating with a water resistant resin layer of / m ² . << Support G >> A polyethylene terephthalate composition having an intrinsic viscosity of 0.65 cc /
g) is melt-extruded at 300 ° C and laminated for 3
A back laminate layer of 0 g / m ² was coated.

Next, the following resin layer was coated on the side on which the silver halide emulsion was coated.

85% by weight of the polyethylene terephthalate composition (intrinsic viscosity 0.72 cc / g) as the inner resin layer,
1% by kneading 15% by weight of titanium oxide white pigment (anatase type) and then melt extrusion laminating at 300 ° C.
A water-resistant resin layer of 5 g / m ² was coated on the surface of the white base paper on which the silver halide emulsion was coated.

70% by weight of the polyethylene terephthalate composition (intrinsic viscosity 0.72 cc / g) as the outer resin layer,
1% by kneading 30% by weight of titanium oxide white pigment (anatase type) and then melt-extruding and laminating at 300 ° C.
A water-resistant resin layer of 5 g / m ² was coated on the surface of the inner resin layer to prepare a paper support having a resin coating layer on both sides.

Corona discharge treatment (output current value: 2 amps) was applied to the surface resin layer side of the supports A to G having a white pigment, and then a gelatin subbing layer was applied with a gelatin coating amount of 40 mg /
It was provided by coating and drying so as to be m ² .

Next, supports A to G provided with a gelatin subbing layer
Various photographic constituent layers were respectively coated on the above to prepare a multilayer color photographic paper having the following layer constitution. The coating solution was prepared as follows.

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

First layer coating solution Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34.
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 0.34 g, 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and high-boiling organic solvent (DNP)
To 1.67 g, 60 ml of ethyl acetate was added and dissolved.
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 ml of 0% gelatin aqueous solution using an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

Each of the coating solutions for the second to seventh layers was prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2.

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

[0154]

[Table 1]

[0155]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate sodium salt SU-3: Di (sulfo2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) -sodium salt DBP: dibutylphthalate DNP: dinonylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-
Sodium triazine HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di (1,1-dimethyl-4-hexyloxycarbonyl) butyl hydroquinone Image stabilizer A: Pt-octylphenol

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[Chemical 6]

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[Chemical 7]

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(Preparation of blue-sensitive silver halide emulsion) 40 ° C.
In 1 liter of a 2% gelatin aqueous solution kept at
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 ml (solution D) Silver nitrate 300 g Water added 600 ml After addition, Kao Atlas Desalination was performed using a 5% aqueous solution of DEMOL N and a 20% aqueous solution of magnesium sulfate, and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.71μ.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, except that the addition time of the (A liquid) and the (B liquid) and the addition time of the (C) liquid and the (D) liquid were changed, the average particle diameter was 0.64 μm in the same manner as EMP-1. Monodisperse cubic emulsion EMP- with a coefficient of variation of 0.07 and a silver chloride content of 99.5 mol%
1B was obtained.

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

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (green-sensitive silver halide emulsion) Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a particle size of .mu.m, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

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

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

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

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole In the red-sensitive emulsion, SS-1 was used per mole of silver halide. 2.0 × 10 ^{-3 was} added.

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The samples thus obtained are referred to as Samples 101 to 10
7 was set.

Then, in the same manner as in Samples 101 to 107, S-1 having the following structure was provided between the support and the first layer.
Layers and S-2 layer were applied to prepare Samples 108 to 114.

S-2 Layer (Layer between White Pigment Layer and First Layer) Gelatin 0.5 g / m ² S-1 Layer (White Pigment Layer, Support Adjacent Layer) Gelatin 1.5 g / m ² Anatase Type Titanium dioxide 3.0 g / m ² 20 mg / m ² of (H-2) was added to the S-2 layer as a gelatin hardener.

Samples 108 to 11 except that the betaine surfactant shown in Table 3 was added to the 7th layer in an amount of 10 mg / m ^2.
Samples 115 to 121 were prepared in the same manner as in No. 4.

A sample 122 was prepared in the same manner as the sample 103 except that the betaine surfactant shown in Table 3 was added to the sample 103 in an amount of 10 mg / m ² .

The following evaluations were performed on each of the samples thus prepared.

<< Evaluation of Sharpness >> A resolution test chart was printed on each sample with red light, and the following development processing was performed. Then, the obtained cyan image was used as a microdensitometer PDM-5D (Konica Corp.). (Made in) to measure the concentration,
The value shown by the following formula was defined as the sharpness.

Sharpness (%) = [D _max of a dense line print image of 3 lines / mm −D _min ] / [D _max at large area −
D _min ] Here, D _max : maximum density D _min : minimum density The larger this value, the better the sharpness.

<< Evaluation of Curl >> An undeveloped sample of 10 cm × 10 cm was allowed to stand under the conditions of 30 ° C. and 20% RH for 24 hours, and the curl degree was determined by the reciprocal of the radius of curvature.

Curl = 1 / Radius of curvature (m) When it exceeds 20, the handling becomes very poor and it becomes a level that cannot be practically used.

<< Evaluation of Density Unevenness >> A sample subjected to uniform exposure was subjected to the following development processing steps, and the obtained gray sample was subjected to density measurement with a PDA-65 densitometer manufactured by Konica Corporation. The density unevenness was evaluated by the density difference between the highest density and the lowest density.

The gray sample was also visually evaluated.

⊚: No density unevenness observed at all ◯: Density unevenness slightly observed, but acceptable as a product Δ: Density unevenness is observed, which is not preferable as a product ×: Density unevenness is considerably observed Not as a product.

<< Evaluation of white background interference fringes >> After the following development processing steps were carried out with each sample left unexposed, a fluorescent lamp type FL2 was used.
The degree of occurrence of interference fringes was observed under a 0S.EX-D fluorescent lamp.

⊚: No interference fringes observed, no problem ◯: Interference fringes slightly observed, but practically no problem Δ: Interference fringes slightly observed, practically concerned ×: Interference fringes clearly observed, It's a problem. Not practical.

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

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0g 2.0g Optical brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to make the total volume 1 liter. = 10.10, the replenisher has pH Adjusted to 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 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Add water to make the total volume 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Nitrilotriacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

The results obtained are shown in Table 3.

[0192]

[Table 3]

From Table 3, samples 109 to 1 according to the present invention are shown.
14 and 116 to 121 have excellent sharpness, curl and uneven density are improved, and there is no problem with white background interference fringes.

In particular, Samples 116 to 121 using the betaine activator according to the present invention can improve the density unevenness, which was a big problem when a hydrophilic colloid layer containing a white pigment was provided, to the point where it could not be seen at all. It can be seen that the effect is great.

Example 2 Samples 109 to 114 and 116 according to the present invention of Example 1
~ 121, S-1 layer, S-2 shown in Example 1
The layers 1 to 7 were all samples 109 to 114 and 11 except that the layers S-1 and S-2 shown below were changed.
Samples were prepared in the same manner as 6 to 121. When the same evaluation as in Example 1 was performed, the same effect as in Example 1 was obtained.

S-2 Layer (Layer between White Pigment Layer and First Layer) Gelatin 0.5 g / m ² S-1 Layer (White Pigment Layer, Support Adjacent Layer) Gelatin 1.5 g / m ² Anatase Type Titanium dioxide 3.0 g / m ² Black colloidal silver 1.0 g / m ² 20 mg / m ² of (H-2) was added as a gelatin hardener to the S-2 layer.

Example 3 Samples 109 to 114 and 116 according to the present invention of Example 1
~ 121, S-1 layer, S-2 shown in Example 1
The layers 1 to 7 were all samples 109 to 11 except that the layers were changed to the S-0 layer, S-1 layer, and S-2 layer shown below.
Samples were prepared in the same manner as 4, 116 to 121. When the same evaluation as in Example 1 was performed, the same effect as in Example 1 was obtained.

S-2 layer (layer between white pigment layer and first layer) gelatin 0.5 g / m ² S-1 layer (white pigment layer) gelatin 2.0 g / m ² anatase type titanium dioxide 4.0 g / M ² S-0 layer (colored layer, support-adjacent layer) Gelatin 0.8 g / m ² Black colloidal silver 1.2 g / m ² Furthermore, 30 mg of (H-2) as a gelatin hardener in the S-2 layer. / M ^{2 was} added.

Example 4 A color negative film (F-1) having a transparent magnetic recording layer described in JP-A-4-62543 and having a support made of polyethylene terephthalate and polyethylene-2,6-naphthalate, A color negative film (F-
2) and were used to shoot the same multi-group scene, and the frames of this scene were used to print print on the photosensitive materials prepared in Examples 1, 2 and 3 using an automatic printer, and to develop them. The post-print sample was visually observed and evaluated. As a result, it was found that when the color negative film (F-1) was used, the print quality using the sample of the present invention looked particularly good.

Therefore, it has a transparent magnetic recording layer, and the support is polyethylene terephthalate and polyethylene-2,6.
-In a system in combination with a color negative film consisting of naphthalate, the samples of the invention can provide particularly high quality images.

Example 5 135 format (area per screen 8.4 cm ² ).
Of the same group of many people using the color negative film (F-3) of No. 3 and the color negative film (F-4) having an area of 4 cm ² per screen, and using the frames of this scene, The photosensitive materials prepared in 1, 2, and 3 were print-baked using an automatic printer, and after development, the printed samples were visually observed and evaluated.

As a result, in the prints using the samples other than the present invention, the sharpness was greatly decreased when F-4 was used as the negative film, whereas the prints using the samples of the present invention were negative. It was found that even if F-4 having a small screen size of 1 was used, it had sufficient sharpness.

Therefore, in the sample of the present invention, when a negative film having a small screen size is used, a print having a high quality image can be provided and the effect of the present invention can be more effectively exhibited.

Example 6 <Preparation of support> White base paper (50 g by weight: 175 g / gram basis weight) of LBKP (sulfate bleached hardwood pulp) 50% by weight and NBSP (sulfate bleached softwood pulp) 50% by weight for photographic printing paper
m ² and thickness 180 μm), a polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) was extrusion-coated on one surface to form a back laminate layer of 25 g / m ² , and a sheet-like substrate was formed. Manufactured.

Next, a white pigment-containing resin layer made of water-resistant titanium oxide having the following composition was provided on the surface not back-laminated, and the supports H, I, J, K, L, and
M and N were obtained.

<Support H> Polyethylene composition (density 0.92 g / cc, melt index (MI) 5.0)
(g / 10 minutes) and 85% by weight of anatase type titanium oxide were added, and after kneading, a water-resistant resin layer of 30 g / m ² was applied on the surface of the sheet-like substrate by melt extrusion coating. The surface of the cooling roller used for cooling the molten polyethylene was smooth.

<Support I> An electron beam curable organic compound-white pigment composition having the following composition was prepared.

Dipentaerythritol hexaacrylate 60% by weight Titanium oxide (rutile type) 40% by weight A mixture of the above components was dispersed in a ball mill for 20 hours. The composition thus obtained was applied to the surface of the sheet-like substrate so that the coating amount after curing was 10 g / m ² . Then, from the back surface of the sheet substrate, accelerating voltage: 175
The surface resin coating layer was formed by irradiating an electron beam with KV under the condition of absorbed dose: 2 Mrad to cure the resin.

<Support J> An electron beam curable organic compound-white pigment composition having the following composition was prepared.

Urethane acrylate oligomer 25% by weight Diethylene glycol diacrylate 25% by weight Anatase type titanium oxide 50% by weight A mixture of the above components was dispersed in a ball mill for 20 hours. The composition thus obtained was applied to the surface of the sheet-like substrate so that the coating amount after curing was 25 g / m ² . Then, from the back surface of the sheet substrate, accelerating voltage: 175
The surface resin coating layer was formed by irradiating an electron beam with KV under the condition of absorbed dose: 2 Mrad to cure the resin.

<Support K> An electron beam curable organic compound-white pigment composition having the following composition was prepared.

Polyester acrylate 25% by weight Hexanediol diacrylate 25% by weight Trimethylolpropane triacrylate 15% by weight Anatase type titanium oxide 35% by weight A mixture of the above components was dispersed by a ball mill for 20 hours. The composition thus obtained was applied to the surface of the sheet-like substrate so that the coating amount after curing was 25 g / m ² . Then, from the back surface of the sheet substrate, accelerating voltage: 175
The surface resin coating layer was formed by irradiating an electron beam with KV under the condition of absorbed dose: 2 Mrad to cure the resin.

<Support L> An electron beam curable organic compound-white pigment composition having the following composition was prepared.

Urethane acrylate oligomer 20% by weight Acrylate monomer 20% by weight Anatase type titanium oxide 60% by weight A mixture of the above components was dispersed by a ball mill for 20 hours. The composition thus obtained was applied to the surface of the sheet-like substrate so that the coating amount after curing was 25 g / m ² . Then, from the back surface of the sheet substrate, accelerating voltage: 175
The surface resin coating layer was formed by irradiating an electron beam with KV under the condition of absorbed dose: 2 Mrad to cure the resin.

<Support M> An electron beam curable organic compound having the following composition was prepared.

Urethane acrylate oligomer 30% by weight Acrylate monomer 30% by weight Anatase type titanium oxide 40% by weight This composition was treated with 50% by weight of LBKP (sulfate method bleached hardwood pulp) for photographic printing paper and NBSP (sulfate method bleaching). Softwood pulp) 50% by weight white base paper (grammage 175 g / m ² ,
Thickness of 180 μm), the amount of coating after curing is 25
After coating so as to g / m ^2, the acceleration voltage from the back:
At 175 KV, an electron beam was irradiated under the condition of absorbed dose: 2 Mrad to cure the resin and produce a sheet-like substrate having a back coat resin coating layer.

Subsequently, an electron beam curable organic compound-white pigment composition having the following composition was prepared.

Dipentaerythritol hexaacrylate 75% by weight Anatase type titanium oxide 25% by weight A mixture of the above components was dispersed by a ball mill for 20 hours. The composition thus obtained was applied to the surface of the sheet-like substrate so that the coating amount after curing was 10 g / m ² . Then, from the back surface of the sheet substrate, accelerating voltage: 175
The surface resin coating layer was formed by irradiating an electron beam with KV under the condition of absorbed dose: 2 Mrad to cure the resin.

<Support N> As a resin layer inside, 90% by weight of polyethylene composition (density 0.92 g / cc, melt index (MI) 5.0 g / 10 min), 10% of anatase type titanium oxide white pigment %, And after kneading, a water-resistant resin layer of 15 g / m ² was applied on the surface of the sheet-shaped substrate by melt extrusion coating.

An electron beam curable organic compound-white pigment composition having the following composition was prepared.

Urethane acrylate oligomer 25% by weight Acrylate monomer 25% by weight Anatase type titanium oxide 50% by weight A mixture of the above components was dispersed by a ball mill for 20 hours. The composition thus obtained was applied onto the inner resin layer so that the applied amount after curing was 25 g / m ² . Then, an electron beam was irradiated from the back surface of the sheet-shaped substrate at an accelerating voltage of 150 KV and an absorbed dose of 2 Mrad to cure the resin and form a middle resin layer.

Next, an electron beam curable organic compound having the following composition was prepared.

Dipentaerythritol hexaacrylate 70% by weight Anatase type titanium oxide 30% by weight The composition thus obtained was used as the outer resin layer on the surface of the middle resin layer, and the coating amount after curing was 5 g / m 2. ^It was applied so as to be ² . Next, an electron beam was irradiated from the back surface of the sheet-like substrate at an accelerating voltage of 200 KV and an absorbed dose of 2 Mrad to cure the resin and form a resin coating layer.

Corona discharge treatment (output current value: 2 amps) was applied to the surface resin layer side of the above supports H to N having a white pigment, and then a gelatin subbing layer was applied with a gelatin coating amount of 40 mg /
It was provided by coating and drying so as to be m ² .

Next, supports H to N provided with a gelatin subbing layer were prepared.
Further, various photographic constituent layers were coated in the same manner as in Example 1 to prepare a multilayer color photographic paper. The coating liquid was prepared in the same manner as in Example 1.

In the order of layers, the layer closest to the support is the first layer and the layer farthest from the support is the seventh layer, as in Example 1.

Samples 601 to 60 thus obtained
7 was set.

Then, in the same manner as in Samples 601 to 607, S-1 having the following structure was provided between the support and the first layer.
Layers and S-2 layer were applied to prepare samples 608 to 614.

S-2 Layer (Layer between White Pigment Layer and First Layer) Gelatin 0.5 g / m ² S-1 Layer (White Pigment Layer, Support Adjacent Layer) Gelatin 1.5 g / m ² Anatase Type Titanium dioxide 3.0 g / m ² 20 mg / m ² of (H-2) was added to the S-2 layer as a gelatin hardener.

Further, as shown in Table 4, sample 608 was prepared except that a betaine type surfactant was added in an amount of 10 mg / m ^2.
Samples 615 to 621 were prepared in the same manner as described above.

A sample 622 was prepared in the same manner as the sample 607 except that the betaine type surfactant was added to the seventh layer in an amount of 10 mg / m ² as shown in Table 3.

The samples thus prepared were evaluated in the same manner as in Example 1.

The results obtained are shown in Table 4.

[0234]

[Table 4]

As is clear from Table 4, Samples 609 to 614 and 616 to 621 according to the present invention have excellent sharpness, curl and density unevenness are improved, and there is no problem with white background interference fringes. .

In particular, in the samples 616 to 621 using the betaine activator according to the present invention, it was possible to improve the density unevenness, which was a big problem when the hydrophilic colloid layer containing the white pigment was provided, to the extent that it could not be seen at all. It can be seen that the effect is great.

Example 7 Samples 609 to 614 and 616 of Example 1 according to the present invention.
~ 621, S-1 layer, S-2 shown in Example 1
The layers 1 to 7 were all samples 609 to 614, 61 except that the layers were changed to the S-1 layer and the S-2 layer shown below.
Samples were prepared in the same manner as 6 to 621. When evaluated in the same manner as in Example 6, the same effect as in Example 6 was obtained.

S-2 Layer (Layer between White Pigment Layer and First Layer) Gelatin 0.5 g / m ² S-1 Layer (White Pigment Layer, Support Adjacent Layer) Gelatin 1.5 g / m ² Anatase Type Titanium dioxide 3.0 g / m ² Black colloidal silver 1.0 g / m ² 20 mg / m ² of (H-2) was added as a gelatin hardener to the S-2 layer.

Example 8 Samples 609 to 614 and 616 according to the present invention of Example 1
~ 621, S-1 layer, S-2 shown in Example 1
The layers 1 to 7 were all samples 609 to 61 except that the layers were changed to the S-0 layer, S-1 layer, and S-2 layer shown below.
Samples were prepared in the same manner as 4, 616 to 621. When evaluated in the same manner as in Example 6, the same effect as in Example 6 was obtained.

S-2 layer (layer between white pigment layer and first layer) Gelatin 0.5 g / m ² S-1 layer (white pigment layer) Gelatin 2.0 g / m ² anatase type titanium dioxide 4.0 g / M ² S-0 layer (colored layer, support-adjacent layer) Gelatin 0.8 g / m ² Black colloidal silver 1.2 g / m ² Furthermore, 30 mg of (H-2) as a gelatin hardener in the S-2 layer. / M ^{2 was} added.

Example 9 A color negative film (F-1) having a transparent magnetic recording layer described in JP-A-4-62543 and having a support composed of polyethylene terephthalate and polyethylene-2,6-naphthalate. A color negative film (F-
The same multi-group scene was photographed using 2), and using the frames of this scene, the photosensitive materials prepared in Examples 6, 7, and 8 were printed and printed using an automatic printer, and after development. The printed sample was visually observed and evaluated. As a result, when using the color negative film (F-1),
It has been found that prints using the samples of the invention look particularly good in image quality.

Therefore, it has a transparent magnetic recording layer, and the support has polyethylene terephthalate and polyethylene-2,6.
-In a system in combination with a color negative film consisting of naphthalate, the samples of the invention can provide particularly high quality images.

Example 10 135 format (area per screen 8.4 cm ² ).
Of the same group of multiple people using the color negative film (F-3) of No. 4 and the color negative film (F-4) having an area of 4 cm ² per screen, and using the frames of this scene, Example 6 The photosensitive materials prepared in Nos. 7, 7 and 8 were print-baked using an automatic printer, and after development, the print samples were visually observed and evaluated.

As a result, in the prints using the samples other than the present invention, the sharpness was greatly reduced when F-4 was used as the negative film, whereas the prints using the samples of the present invention were It was found that the F-4, which has a small screen size, had sufficient sharpness.

Therefore, when the negative film having a small screen size is used for the sample of the present invention, a print having a high quality image can be provided, and the effect of the present invention can be more effectively exhibited.

Example 11 The following modified treatments were carried out in Examples 1, 2, 3, 6, 7 and 8.

Treatment Process Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleach-fix 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Dry 60 The composition of the developing treatment solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3. 5g 6.0g Triethanolamine 10.0g 10.0g Diethylenetriamine pentaacetic acid sodium salt 2.0g 2.0g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter and The pH of the liquid concentrate is adjusted to 10.10 and the replenisher is adjusted to pH 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriamine pentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriamine pentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 , 3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to bring the total volume to 1 liter, and use potassium carbonate or glacial acetic acid to adjust the pH of the tank solution to 7.0 and replenish the solution. Adjust to pH = 6.5.

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 PVP 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was carried out in the same manner as in Examples 1, 2, 3, 6, 7 and 8 and it was confirmed that the effects of the present invention were effectively obtained.

Example 12 In Example 11, NPS-868J manufactured by Konica Co., Ltd. as an automatic processor and ECOJET- as a processing chemical.
P was used for running according to the process name CPK-2-J1. It was confirmed in the same manner as in Examples 1, 2, 3, 6, 7 and 8 that the effects of the present invention were obtained.

[0253]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having good rapid processability, excellent sharpness, improved curl and uneven density, and excellent whiteness. did it.

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Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a reflection support comprising resin coating layers on both sides of a base paper, the reflection support being mainly polyester. A hydrophilic support in which a composition in which a white pigment is mixed and dispersed in a water-resistant resin as a component is coated on at least an emulsion-coated surface of a substrate, and the photosensitive material contains a white pigment on the substrate. A silver halide photographic light-sensitive material having an organic colloid layer. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a reflective support having resin coating layers on both sides of a base paper, wherein the reflective support is electron beam cured. A reflective support obtained by coating a composition in which a white pigment is mixed and dispersed in a resin on at least the surface of the substrate on which the emulsion is applied, and then curing and coating by irradiating with an electron beam, and the light-sensitive material is white on the support. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a pigment. 3. The silver halide emulsion layer is at least 9
2. A silver halide emulsion layer containing a silver halide emulsion containing 5 mol% or more of silver chloride.
A silver halide color photographic light-sensitive material described in 1. 4. The silver halide emulsion layer is at least 9
3. A silver halide emulsion layer containing a silver halide emulsion containing 5 mol% or more of silver chloride.
A silver halide color photographic light-sensitive material described in 1. 5. The silver halide color photographic light-sensitive material according to claim 3, wherein the silver halide color photographic light-sensitive material contains at least one betaine-based surfactant.