JPH0980686A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic material particularly excellent in both highlight drawing property and sharpness. SOLUTION: This photographic sensitive material has at least one silver halide emulsion layer on the coating layer side of a reflecting base having a coating layer in which an electron beam hardening resin composition having white pigment dispersed therein is hardened by electron beam emission, or a reflecting base having a coating layer consisting of a water resisting resin composition mainly containing a polyester having white pigment dispersed therein, the layer closest to the base of the silver halide emulsion layers contains two kinds or more of dyes differed in maximum absorption wavelength, and the γ of the pigment image formed by monochromic exposure of the closest layer is 1.5-2.0. Otherwise, this photographic sensitive material has a hydrophilic colloid layer containing white pigment and at least one silver halide emulsion layer on a base in this order, the layer closest to the base of the silver halide emulsion layers contains two kinds or more of dyes differed in maximum absorption wavelength, and the γ of the pigment image formed by the monochromic exposure of the closest layer is 1.5-2.0.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which is excellent in highlight descriptiveness and sharpness and has a reduced sensitivity deterioration during storage.

[0002]

2. Description of the Related Art In recent years, due to the widespread use of compact cameras, the rise of cameras with a sharp focus, the printing from half-size negatives, and the mixing of panoramic scenes, there is an increasing need to print from negatives of large and small screen sizes at the same time. There is an increasing demand to improve the sharpness and the depiction property for color light-sensitive materials for use. However, if one of the sharpness and the descriptiveness is increased, the other is deteriorated, and a technique for satisfying both qualities has not yet been found.

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 also on the reflectance and refractive index of the support.

Regarding prevention of irradiation, for example, Japanese Patent Laid-Open Nos. 50-111641 and 50-145125.
No. 52-20830, No. 61-148448,
Improvement of dyes and the like have been carried out as described in Nos. 61-151650, 62-275562, 62-283336 and the like. Further, as halation prevention, for example, JP-A-55-33172 and 59-193447.
No. 62-33448 and the like, a method of providing an antihalation layer is known. However, the improvement by these cannot satisfy the demand of the market yet, and if these are adopted, there is a problem that the sensitivity decreases with time depending on storage conditions, and further improvement is desired.

On the other hand, as a support for a color light-sensitive material for printing, a water-resistant support prepared by laminating a polyolefin resin mainly made of polyethylene on the surface of a base paper has been used in recent years for the purpose of accelerating the development processing, and the sharpness is sharp. For a white background, a white pigment such as titanium oxide is dispersed in the polyolefin layer on the photographic emulsion side. It is effective to increase the filling amount of this white pigment to improve sharpness.
-46035, 64-18144, JP-A 2-7
As described in JP-A No. 1256, if the amount of white pigment is increased in order to obtain sufficient sharpness, there are drawbacks such that the smoothness of the polyethylene layer and the adhesion between the polyethylene layer and the emulsion layer are deteriorated.

On the other hand, JP-A-58-60738
Nos. 61-9646, 61-221746, and JP-A-2-28640 propose techniques for providing a layer containing a white pigment between a support and a silver halide emulsion layer. . However, in order to obtain sufficient sharpness as well, it is necessary to increase the filling amount of the white pigment, and if the filling amount is increased, there is a problem that cracks are likely to occur on the coated surface of the photosensitive material due to bending, so that it is put to practical use. Has not reached.

Further, as a technique for improving sharpness, Japanese Patent Laid-Open Nos. 58-60738, 61-9646 and 61-
221746, JP-A-2-28640, etc.,
For a reflective support in which a composition in which a white pigment is dispersed in a water-resistant resin containing polyester as a main component is coated on at least the emulsion coating side of the substrate, and for the polyester support and the non-photosensitive layer described in JP-A-6-186673. Although a technique of adding a solid disperse dye is known, sufficient sharpness has not yet been obtained.

Further, Japanese Patent Laid-Open Nos. 61-9646 and 61-2
21746 and JP-A-2-28640, as described in
Studies have been conducted to apply a composition in which a white pigment is dispersed in an electron beam curable resin to the surface of the substrate on which the emulsion is coated, and irradiate the composition with an electron beam to cure the composition to form a coating layer to form a reflective support.
Such a reflective support is advantageous in enhancing sharpness because the smoothness does not deteriorate much even if it is filled with a large amount of white pigment, but it does not solve the problems of adhesion to the emulsion layer and cracking. , Has not been put to practical use.

Therefore, there is a demand for a technique for enhancing the sharpness without increasing the filling amount of the white pigment regardless of which reflective support is used.

On the other hand, as a technique for improving the descriptiveness, controlling the gradation of an image by mixing emulsions is disclosed in US Pat. Nos. 2,358,169 and 2,336.
JP-A-61-91 discloses a technique for enhancing the depiction property on the high density side by adding a color image different from the color image forming the main gradation to No. 260, No. 2,367,508 and the like.
Nos. 657 and 657, respectively, it is difficult to enhance the descriptive power on the highlight side, and there is no technique for improving sharpness at the same time.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a silver halide color photographic light-sensitive material (hereinafter, light-sensitive material) which is particularly excellent in both highlight descriptiveness and sharpness. It is also provided).

[0012]

The above object of the present invention is to provide an electron beam curable resin composition having a white pigment dispersed therein on the side of the coating layer on a reflection support having a coating layer cured by electron beam irradiation. Having at least one silver halide emulsion layer, and the layer closest to the support in the silver halide emulsion layer contains two or more kinds of dyes having different maximum absorption wavelengths,
And a silver halide color photographic light-sensitive material in which a dye image formed by monochromatic exposure of the closest layer has a γ of 1.5 to 2.0, and a water-resistant resin composition containing polyester in which a white pigment is dispersed as a main component. At least one silver halide emulsion layer is provided on the side of the coating layer on the reflective support having a coating layer made of a material, and the layer closest to the support in the silver halide emulsion layer has the maximum absorption wavelength. On a support containing a silver halide color photographic light-sensitive material, in which γ of a dye image formed by monochromatic exposure of the closest layer contains two or more kinds of dyes different from each other. , A hydrophilic colloid layer containing a white pigment, and at least one silver halide emulsion layer in this order, and two or more of the silver halide emulsion layers, which are closest to the support, have different maximum absorption wavelengths. Contains the dye of A silver halide color photographic light-sensitive material in which γ of a dye image formed by monochromatic exposure of adjacent layers is 1.5 to 2.0, and γ is 1.5 to 1.8,
The closest layer contains a water-soluble bromide,
Achieved by

That is, the present inventors have optimized the γ in the silver halide emulsion layer closest to the support in order to enhance the depiction of highlights, and expanded the absorption wavelength region with the intention of a stronger sharpness improving effect. By using two or more kinds of dyes together in order to improve the sharpness and descriptiveness without increasing the filling rate of the white pigment related to the support, it was found that the sensitivity during storage does not decrease. This has led to the present invention.

Hereinafter, the present invention will be described in detail.

In the present invention, the layer closest to the support contains two or more kinds of dyes having different maximum absorption wavelengths, that is, the maximum peak wavelength of the spectral absorption curve in an aqueous solution is 10
It contains at least two kinds selected from anti-irradiation dyes and anti-halation dyes that differ by not less than 20 nm, preferably not less than 20 nm.

The anti-irradiation dyes and anti-halation dyes used in the present invention include known dyes which have absorption in various wavelength ranges and flow out from the light-sensitive material in the photographic processing solution. For example, the following dyes are included. It is preferably used.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

[Chemical 6]

[0023]

[Chemical 7]

[0024]

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These dyes are described in British Patent No. 1,278,6.
No. 21, No. 1,512, 863, No. 1,579, 89
It can be synthesized with reference to the method described in No. 9.

[0026]

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[0027]

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[0028]

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[0029]

[Chemical 12]

[0030]

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[0031]

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These dyes can be synthesized by reacting a dioxopyrazolopyridine compound with an appropriate monomethine source, trimethine source, or pentamethine source compound. Specifically, Japanese Patent Publication No. 39-22069, 43
-3504, 52-38056, 54-381
29, 55-10059, JP-A-49-9962.
0, 59-16834, U.S. Pat. No. 4,181,
It can be synthesized using the method described in No. 225 or the like.

[0033]

[Chemical 15]

[0034]

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[0035]

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[0036]

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[0037]

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These dyes are disclosed in JP-A-58-143342.
No. 62-165656 and the like.

The amount of the dye is 1 to 100 mg / m ² about, preferably 3~60mg / m ^2.

As an electron beam curable resin which can be cured by electron beam irradiation and which can be used in the present invention, Japanese Patent Publication No.
Examples thereof include electron beam curable monomers and oligomers described in JP-A No. 0-17104, JP-A No. 60-126649, JP-A No. 2-157747 and the like.

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

As the acrylic and methacrylic oligomers, polyurethane acrylic ester or methacrylic ester, polyether alcohol acrylic ester or methacrylic ester, bisphenol A acrylic ester or methacrylic ester,
Mention may be made of maleic acid ester or fumaric acid ester of polyester. Further, as the polyfunctional acrylic monomer and methacrylic monomer, 1,6-hexanediol diacrylate, neopentyl diacrylate, diethylene glycol diacrylate, butadiene acrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, glycerol trimethacrylate, stearyl. Acrylate,
Polyethylene glycol diacrylate, butoxyethyl acrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, glycidyl 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 phenoxyphosphoric acid acrylate,
Neopentyl glycol diacrylate, isocyanuric acid diacrylate, isocyanuric acid triacrylate,
Trimethylolpropane triacrylate, trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane polyacrylate, glycidyl methacrylate, 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, penta Examples thereof include erythritol pentaacrylate. Examples of monofunctional acrylic and methacrylic monomers and vinyl monomers include styrene, N-vinylpyrrolidone, acrylic acid ester of polyoxyethylene phenyl alcohol, and 2-ethylhexyl acrylate.

As the white pigment dispersed in the electron beam curable resin composition, for example, titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used. Among them, titanium dioxide is used. Is preferred. The titanium dioxide may be either anatase type or rutile type, but when the whiteness is prioritized, the anatase type titanium dioxide is preferable, and when the sharpness is important, the rutile type titanium dioxide is preferable. 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 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 0.2% by weight to 2.0% by weight of an inorganic substance based on titanium dioxide,
The organic substance is preferably 0.1% by weight to 1.0% by weight. The particle size of titanium dioxide is preferably 0.1 μm to 0.4 μm.

The content of the white pigment in the electron beam curable resin may be 80% by weight or less, but 10% by weight or more is preferable, 15% by weight or more is more preferable, and 20% by weight or more is more preferable. Is. White pigment content is 10
If the content is less than 80% by weight, the photographic image obtained on the photographic paper is not sufficiently sharp, and if the content exceeds 80% by weight, the flexibility of the obtained cured resin coating layer decreases,
Membrane cracking will occur.

The electron beam curable resin layer may be a laminate of two or more layers having different white pigment contents, and in the case of the laminate of two or more layers, at least one layer is a resin layer made of an electron beam curable resin, and The layer may be a resin layer made of a resin other than the electron beam curable resin. In this case, the uppermost layer is preferably a resin layer made of an electron beam curable resin. 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 white pigments of two or more layers may be any content as long as the average content is the above content.

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, any of a roller coating method, a bar coating method, an air doctor coating method, a plate coating method, a squeeze coating method, an air 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.

There is no limitation on the electron beam irradiation apparatus used,
Generally, as such an electron beam accelerator for electron beam irradiation, a curtain beam system that is relatively inexpensive and can obtain a large output is effectively used. 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 will occur, and a large amount of energy will be required for curing, and curing will be insufficient, which is not preferable in terms of quality.

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.

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 occupying most of the main chain of polyethylene terephthalate 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 glycol (diol) having an ester bond, ethylene glycol, propylene 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. And, preferably, terephthalic acid, isophthalic acid, 4-metal sulfo-2,6 are used as the dibasic acid.
-Naphthalenedicarboxylic acid, 5-metal sulfo-isophthalic acid, 4-metal sulfo-2,6-naphthalenedicarboxylic acid, etc. are used, and ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol (number) Average molecular weight 3
00-30,000) and the like are used.

The metal ion of the metal sulfo substituent is sodium, potassium, lithium, cesium, etc., preferably sodium.

The modified portion of the modified polyester is preferably 50 mol% or less with respect to the total polyester bond, and when it exceeds 50 mol%, the physical properties as a support, such as mechanical strength, glass transition point and water resistance, are deteriorated. , 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 preferably contained in a proportion of 2 to 10 mol% with respect to the total ester bond, and has excellent adhesiveness to the emulsion layer, other resin layer and the base paper. . When the compound having an alkali metal sulfo group, for example, 5-sodium sulfo-isophthalic acid is 2 mol% or less, it is almost the same as polyethylene terephthalate, and the meaning of modification is weakened. Further, if it is 10 mol% or more, the water absorption 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 constituent components and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, “Polycondensation and Polyaddition” (Kyoritsu Shuppan, 1980).
1) pages 103 to 136, or "Synthetic Polymer V" (Asakura Shoten, 1971) pages 187 to 286.

The specific method for synthesizing the modified polyester is as follows:
U.S. Pat. No. 4,217,441, JP-A-5-2101
No. 19.

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 sufficiently high, hydrolysis may occur during melting. is there. Drying of resin chips is 10
^It is usually performed at about 150 ° C. under a vacuum of about ^-3 Torr.

The same can be said with respect to the white pigment contained in the water-resistant resin containing polyester as a main component, which coats at least the emulsion-coated surface of the present invention.

The content of the white pigment in the resin containing the polyester resin as the main component is the same as that of the electron beam curable resin system, but if the content exceeds 80% by weight, the coating properties of the obtained polyester resin are improved. Is severely deteriorated and 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 average content of white pigments contained in two or more resin layers is also the same as in the electron beam curable resin system.

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 by melt extrusion coating the molten resin on a paper support. 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.

A hydrophilic colloid layer containing the white pigment of the present invention (hereinafter also referred to as a white pigment layer), that is, a white pigment dispersed in a water-soluble binder of a hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The white pigment used for the layer formed by applying and coating is the same as that described above. The coating amount of the white pigment is about 1 to 50 g / m ² , more preferably 2 to
20 g / m ² is preferred.

Gelatin is mainly used as the water-soluble binder for the white pigment layer, and if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as proteins other than gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances can also be used together.

In the present invention, the white pigment layer is preferably provided between the support and the silver halide emulsion layer closest to the support, and a lower layer may be provided between the support and the emulsion layer if necessary. A non-photosensitive hydrophilic colloid layer such as a coating layer or an intermediate layer can be provided.

The white pigment layer preferably has a porosity of 5 to 30%, which can be determined from specific gravity, film thickness and the like. The white pigment layer also contains yellow, gray, blue or black colloidal silver,
Coloring agents such as inorganic colored pigments, organic colored pigments and dyes can also be added.

A hydrophilic colloid layer containing a colorant can be coated between the white pigment layer and the support. Examples of the colorant include yellow, gray, blue or black colloidal silver and various filter dyes. The dyes known as can be used. The colorant may be selected from those having absorption in the entire visible spectrum and those selectively absorbing only a part of the region, as required. The transmittance of such a colorant-containing hydrophilic colloid layer is preferably 50% or less, and particularly preferably 30% or less.

The support to which the white pigment layer is applied is a paper support having a paper base and resin layers on both sides, and a white pigment is applied to the resin layer on the side where the silver halide emulsion layer is applied. The paper support, the electron beam curable layer-coated support described in claim 1, and the water resistant polyester layer-coated support described in claim 2 are preferable.

The base 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.

To form the resin coating layer, a polyolefin resin or a polyethylene terephthalate resin is laminated by melt extrusion coating. The resin coating layer has a thickness of about 15 to 60 μm.

The white pigment in the resin coating layer is the same as that described so far. The content is preferably 7% by weight or more based on the resin.

In the present invention, γ of the dye image formed by monochromatic exposure is 1.5 to 2.0, preferably 1.5 to 1.
No. 8, which is a sample developed and exposed by blue exposure, green exposure, or red exposure to JIS 7612-1.
982 satisfies the geometrical condition of reflection density regulation,
In addition, the maximum transmission densities of 644 nm and 5 were used to measure the reflection densities of cyan, magenta, and yellow, respectively.
The reflection density is measured using a densitometer having an interference filter of 46 nm and 436 nm, and is calculated by the following formula.

Γ = 1.3 / log ₁₀ (E2 / E1) When the reflection density of the unexposed portion is D _min , E1 and E2 are reflection densities of D _min +0.3 and D _min +0.8, respectively. Is the amount of exposure required to give.

In the present invention, it is preferable that the silver halide emulsion layer closest to the support further contains a water-soluble bromide, because the sensitivity deterioration with time is effectively prevented.

As the water-soluble bromide, potassium bromide and sodium bromide are preferable, and the addition time may be at the start or end of the chemical ripening or at the time of adjusting the coating solution. The addition amount is 0.
About 01 to 100 mg / m ² , preferably 0.1 to 20
It is mg / m ² .

The composition of the silver halide grains used in the light-sensitive material of the present invention is arbitrary, but in view of the demand for rapid processing in recent years, chlorobromide having a silver chloride content of 95% or more and substantially no silver iodide. Silver particles are preferred.

The silver halide grains include Group 8 to 10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium and cobalt, and Group 12 transition metals such as cadmium, zinc and mercury, and It can contain heavy metal ions such as lead, rhenium, molybdenum, tungsten, chromium, among others, iron, iridium,
Platinum, ruthenium and osmium transition metal ions are preferable, and they can be added to the silver halide emulsion in the form of salt or complex salt.

The shape of the grains is arbitrary, but a preferable example is a cube having a (100) plane as a crystal surface. Further, an emulsion having a single grain shape may be used, or emulsions having various shapes may be mixed.

The grain size of the silver halide grains is not particularly limited, but is 0.1 to 0.1 depending on photographic properties such as rapid processability and sensitivity.
It is about 1.2 μ, preferably 0.2 to 1.0 μ, and this particle size can be measured by a projected area or an approximate diameter value. The particle size distribution may be polydisperse or monodisperse.

The silver halide grains can be prepared by various methods known in the art.

The silver halide emulsion used in the light-sensitive material of the present invention includes thiosulfate, allylthiocarbamidourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid, rhodanine, and sulfur sensitization with inorganic sulfur. Gold sensitization with chloroauric acid, gold sulfide, various gold complexes and the like can be performed. Antifoggants, silver halide emulsions,
A stabilizer, a water-soluble bromide, etc. can be used.

The silver halide color photographic light-sensitive material of the present invention contains a yellow dye-forming coupler, a magenta dye-forming coupler and a cyan dye-forming coupler in combination with 400
A silver halide emulsion spectrally sensitized in a specific region of a wavelength range of up to 900 nm is used. Sensitizing dyes useful for spectral sensitization include cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

Further, as a yellow dye-forming coupler,
Various acylacetanilide type couplers, magenta dye forming couplers such as 5-pyrazolone type couplers, pyrazolone benzimidazole type couplers, pyrazoloazole type couplers, open chain acylacetonitrile type couplers and the like, and cyan dye forming couplers include naphthol. A system coupler, a phenol system coupler, an imidazole system coupler, etc. can be used.

Further, in the light-sensitive material of the present invention, for the purpose of shifting the absorption wavelength of the color forming dye, JP-A-4-114154.
(D-11) and the same compound (A'-1)
Etc. may be included, and US Pat. No. 4,774,187
It is also possible to use the fluorescent dye-releasing compounds described in No.

In the silver halide color photographic light-sensitive material of the present invention, gelatin is used as a binder, and if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives,
Hydrophilic colloids such as cellulose derivatives and synthetic hydrophilic polymer substances can be used.

Gelatin may be lime-treated or acid-treated, and may be produced from any material such as cow bone, cow hide, pig skin, etc., but preferably cow bone or pig skin. Is a lime-processed gelatin.

In the light-sensitive material of the present invention, the total amount of gelatin contained from the silver halide emulsion layer closest to the support having the silver halide emulsion layer to the outermost hydrophilic colloid layer is 1 m of the light-sensitive material. ^It is preferably 10 g or less per ² . Further, a hardening agent may be used to increase the film strength of the emulsion layer or the hydrophilic colloid layer.

In addition to the above, the light-sensitive material of the present invention includes ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, etc.), development accelerators (1-aryl-3-pyrazolidone compounds, etc.), surfactants (alkylnaphthalene sulfones). Acid salt, alkyl succinic acid sulfonate, etc.), water-soluble anti-irradiation dye (azo compound, styryl compound, oxonol compound, etc.), film physical property improver (liquid paraffin, polyalkylene glycol, etc.), color turbidity prevention Agents (diffusion-resistant hydroquinone compounds, etc.), color image stabilizers (hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble fluorescent whitening agents, background color adjusting agents, competing couplers, fogging agents, development suppression Agent release coupler (so-called D
IR couplers), development inhibitor releasing compounds and the like can be added.

When coating the silver halide emulsion layer and the hydrophilic colloid layer, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are useful.

In order to form a photographic image using the silver halide color photographic light-sensitive material of the present invention, the image recorded on the negative may be optically imaged and printed, or converted into digital information. The image may be once formed on a CRT, and the image may be formed and printed on a photosensitive material, or may be exposed by scanning and exposure based on digital information, but the present invention is recorded on a negative of a small screen. It is especially useful when printing normal or magnified images from printed images.
When the area per screen is 3 to 7 cm ² , the effect of the present invention is fully exhibited.

The light-sensitive material of the present invention can be subjected to color development processing known in the art.

The pH of the color developing solution is preferably 9.5 to 13.0, and more preferably 9.5 to 12.0 from the viewpoint of rapid processing. The processing temperature for color development is 15
To about 45 ° C., preferably 20 to 45 ° C., and the color development time is usually 3 minutes and 30 seconds or less, and the rapid processing is preferably 1 minute or less.

When the light-sensitive material of the present invention is subjected to running processing while continuously replenishing the color developing solution, in order to reduce the overflow solution of the color developing solution and to reduce the environmental damage due to the waste solution, the color developing solution is used. The replenishment amount of the photosensitive material is 1 m ²
It is preferably ^{20 to} 150 ml per m ^{2, and} 20 to 60 ml per m ² of the light-sensitive material is preferable as a replenishing amount so that waste liquid due to overflow is not substantially generated.

The light-sensitive material of the present invention may be subjected to bleaching treatment and fixing treatment after color development, and the bleaching treatment may be conducted simultaneously with the fixing treatment. After the fixing process, a washing process is usually performed. Further, as a substitute for the washing treatment, a stabilizing treatment may be performed.

The development processing apparatus used for the development processing of the photosensitive material of the present invention may be an endless belt system in which the photosensitive material is sandwiched between rollers arranged in the processing tank and conveyed, but the processing tank is formed into a slit shape. Forming and supplying the processing liquid to the processing tank and conveying the photosensitive material, spraying method for spraying the processing liquid, web method by contact with a carrier impregnated with the processing liquid, method by viscous processing liquid Etc. can also be used.

[0101]

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

Example 1 << Preparation of Support >> (White base paper) 50% by weight of sulfated bleached hardwood pulp (LBKP) for photographic grade printing paper and 50% by weight of sulfated bleached softwood pulp (NBSP) 175 g /
m ² and a thickness of 180 μ were used.

(Support A) A polyethylene composition (density 0.95 g / cc, melt index (MI)) was formed on the surface of the white base paper opposite to the side coated with the silver halide emulsion.
(8.0 g / 10 min) was laminated by melt extrusion at 300 ° C. to form a back laminate layer of 30 g / m ² .

Next, a polyethylene composition (density 0.92 g / cc, MI
(5.0 g / 10 minutes) 85% by weight, and titanium oxide white pigment (anatase type) 15% by weight, after kneading, 300 ℃
Laminated by melt extrusion at 60g / m ²
To prepare a paper support having a resin coating layer on both sides.

(Support B) A polyethylene terephthalate composition (intrinsic viscosity 0.65 cc / g) was applied at 300 ° C. on the surface of the white base paper opposite to the side coated with the silver halide emulsion.
Laminated by melt extrusion at 30g / m ²
To form a back laminate layer.

Then, on the surface on which the silver halide emulsion was coated, a polyethylene terephthalate composition (intrinsic viscosity of 0.
72 cc / g) 70 wt% and titanium oxide white pigment (anatase type) 30 wt% are kneaded and then laminated by melt extrusion at 300 ° C. to coat a water resistant resin layer of 30 g / m ² on both sides. A paper support having a resin coating layer was prepared.

(Support C) A polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) 3 was applied to the surface of the white base paper opposite to the side coated with the silver halide emulsion.
30g by laminating by melt extrusion at 00 ℃
A back laminate layer of / m ² was formed.

Then, a mixture of 25% by weight of urethane acrylate oligomer, 25% by weight of diethylene glycol diacrylate and 45% by weight of anatase type titanium oxide was applied to a surface on the side on which the silver halide emulsion was coated by using a ball mill.
The composition obtained by dispersing for 0 hours has a coating amount of 2 after curing.
It was applied so as to have a concentration of 0 g / m ^2, and was irradiated with an electron beam from the back surface side of the support under the conditions of an accelerating voltage of 175 kV and an absorbed dose of 2 Mrad to cure the resin and form a white pigment-containing resin layer.

(Support D) A polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) 3 was applied to the surface of the white base paper opposite to the side coated with the silver halide emulsion.
30g by laminating by melt extrusion at 00 ℃
A back laminate layer of / m ² was formed.

Next, a polyethylene composition (density 0.92 g / cc, MI
5.0 g / 10 min) 90% by weight of anatase-type titanium oxide white pigment was added and kneaded, and a 10 g / m ² waterproof resin layer was formed by melt extrusion coating to form an inner resin layer.

A composition obtained by dispersing a mixture of 25% by weight of a urethane acrylate oligomer, 25% by weight of an acrylate monomer and 35% by weight of anatase type titanium oxide on the inner resin layer in a ball mill for 20 hours was applied. Of 20 g / m ² was applied, and an electron beam was applied from the back side of the support under the conditions of an acceleration voltage of 150 kV and an absorbed dose of 2 Mrad to cure the resin and form an intermediate resin layer.

Further, an electron beam curable composition comprising 35% by weight of polyester acrylate, 35% by weight of hexanediol diacrylate and 20% by weight of anatase type titanium oxide was prepared, and the coating amount after curing was 5 g on the intermediate resin layer. /
m ² was applied, and an electron beam was applied from the back side of the support under the conditions of an acceleration voltage of 200 kV and an absorbed dose of 2 Mrad to cure the resin and form a resin coating layer.

The white pigment-containing resin layer side of each of the supports A to D obtained was subjected to corona discharge treatment (output current value: 2 amperes), and then a gelatin subbing layer was added so that the gelatin coverage was 40 mg / m ^2. It was applied and dried.

Then, on each of the supports A to D, the following S-1
Layers and S-2 layer were sequentially applied to prepare supports E, F, G and H.

S-1 layer (white pigment layer) gelatin 1.5 g / m ² anatase type titanium dioxide 3.0 g / m ² S-2 layer (gelatin layer) gelatin 0.5 g / m ² Gelatin hard during coating The film agent H-2 was added at 20 mg / m ² .

Using the supports A to H thus obtained, from the support side, multilayer color photographic paper samples 101 to 1 having the following layer constitutions were prepared.
08 was produced. The coating solution was prepared as follows.

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.

The coating solutions for the second to seventh layers were also prepared so as to have the following coating amounts in the same manner as the coating solution for the first layer.

H-1 and H-2 were added as hardeners. As the coating aid, surfactants SU-2, SU-3
Was 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 .

First layer (blue-sensitive layer) Gelatin 1.20 g / m ² Blue-sensitive silver chlorobromide emulsion Em-B Silver amount 0.26 g / m ² Yellow coupler Y-1 0.70 g / m ² Dye image stabilizer ST-1 0.10 g / m ² Dye image stabilizer ST-2 0.10 g / m ² Stain inhibitor HQ-1 0.01 g / m ² Dye image stabilizer ST- 5 0.10 g / m ² Image stabilizer A 0.15 g / m ² DBP 0.10 g / m ² DNP 0.05 g / m ² Second layer (intermediate layer) Gelatin 1.20 g / m ² AI-3 0.01 g / m ² stain inhibitor HQ-2 0.03 g / m ² stain inhibitor HQ-3 0.03 g / m ² stain inhibitor HQ-4 0.05 g / m ² stain inhibitor ^{HQ-5 0.23 g / m 2} DIDP 0.04 g / m 2 DBP 0.02 g / m 2 fluorescent brightening agent -1 0.10 g / m ² The third layer (green-sensitive layer) Gelatin ^{1.30 g / m 2 AI-2} 0.01 g / m 2 green-sensitive silver chlorobromide emulsion Em-G as silver 0.14 g / m ² magenta coupler M-1 0.20 g / m ² dye image stabilizer ST-3 0.20 g / m ² dye image stabilizer ST-4 0.17 g / m ² DIDP 0.13 g / m ² DBP 0.13 g / m ² 4th layer (UV absorbing layer) Gelatin 0.94 g / m ² UV absorbing agent UV-1 0.28 g / m ² UV absorbing agent UV-2 0.09 g / m ² UV absorber UV-3 0.38 g / m ² AI-1 0.02 g / m ² stain inhibitor HQ-5 0.10 g / m ² Fifth layer (red sensitive layer) Gelatin 1 .30 g / m ² red-sensitive silver chlorobromide emulsion Em-R silver amount 0.21 g / m ² cyan coupler C-1 0.25 g / m ² shear Coupler ^C-2 0.08 g / m 2 dye image stabilizer ST-1 0.10 g / m ² Stain preventing agent ^{HQ-1 0.004g / m 2 DBP} 0.10 g / m 2 DOP 0.20 g / m ² 6th layer (ultraviolet absorbing layer) gelatin 0.40 g / m ² AI-1 0.01 g / m ² ultraviolet absorber UV-1 0.12 g / m ² ultraviolet absorber UV-20 .04 g / m ² UV absorber UV-3 0.16 g / m ² stain inhibitor HQ-5 0.04 g / m ² PVP 0.03 g / m ² 7th layer (protective layer) Gelatin 1. 00 g / m ² DIDP 0.002 g / m ² DBP 0.002 g / m ² Silicon dioxide 0.003 g / m ² where SU-1: sodium tri-i-propylnaphthalene sulfonate SU-2: sulfosuccinic acid Di (2-ethylhexyl) sodium salt SU-3 : Sulfosuccinate di (2,2,3,3,4,4,
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-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl ] Hydroquinone Image Stabilizer A: Pt-o Cutylphenol

[0121]

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[0122]

[Chemical 21]

[0123]

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[0124]

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[0125]

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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 is complete, 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 an aqueous solution of gelatin to obtain an average particle size of 0.71μ,
A monodisperse cubic emulsion EMP-1 having a variation coefficient of grain size distribution of 0.07 and a silver chloride content of 99.5 mol% was obtained. Next (A
Solution) and (B Solution) and the addition time of Solution (C) and Solution (D) were changed in the same manner as in EMP-1, with an average particle size of 0.64 μ and a coefficient of variation of particle size distribution of 0. 07, a monodisperse cubic emulsion EMP-1B having a silver chloride content of 99.5 mol%
I got

Each of EMP-1 and EMP-1B was optimally chemically sensitized with the following compound at 60 ° C. and then mixed at a ratio of 1: 1 in a silver amount to obtain a blue-sensitive silver halide emulsion. Em-B was obtained. Then, Em-B1 was obtained in the same manner except that the amount of sodium thiosulfate was changed to 0.9 mg / mol during the chemical sensitization of the EMP-1 emulsion. The amount of sodium thiosulfate is 0.9 mg / mol, and the amount of chloroauric acid is 0.6
Em-B2 was obtained in the same manner except that the amount was changed to mg / mol. The amount of sodium thiosulfate is 0.9 mg / mol,
Em-B3 was obtained in the same manner except that the amount of chloroauric acid was changed to 0.7 mg / mol.

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

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed in a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion Em-G. Then E
Em-G was prepared in the same manner except that the amount of sodium thiosulfate was changed to 1.6 mg / mol when chemically sensitizing the MP-2 emulsion.
1 was obtained. Em-G2 was obtained in the same manner except that the amount of sodium thiosulfate was changed to 1.6 mg / mol and the amount of chloroauric acid was changed to 1.1 mg / mol. The amount of sodium thiosulfate was 1.6 mg / mol and the amount of chloroauric acid was 1.2 mg / mol.
Em-G3 was obtained in the same manner except that the molar ratio was changed.

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 size is 0.40 μm in the same manner as EMP-1 except that the addition time of (C liquid) and the addition time of (D liquid) are changed.
A monodisperse cubic emulsion EMP-3 having a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained. The average particle size is 0.38μ,
A monodisperse cubic emulsion EMP-3B having a variation coefficient of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed 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.

[0134]

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Further, Samples 109 to 123 were prepared by changing the support and the blue-sensitive silver halide emulsion of the coating solution for the first layer and the anti-irradiation dye as follows.

Sample No. Support First Layer Silver Halide Emulsion Anti-Irradiation Dye 109 A Em-B1 I-48, I-49 110 A Em-B1 I-38, I-49 111 B Em-B1 I-38, I-49 112 C Em-B1 I-38, I-49 113 D Em-B1 I-38, I-49 114 E Em-B1 I-38, I-49 115 F Em-B1 I-38, I-49 116 G Em -B1 I-38, I-49 117 H Em-B1 I-38, I-49 118 E Em-B2 I-38, I-49 119 F Em-B2 I-38, I-49 120 G Em-B2. I-38, I-49 121 H Em-B2 I-38, I-49 122 H Em-B I-38, I-49 123 H Em-B3 I-38, I-49 Prevention of irradiation used here Dyeing The maximum wavelength of the spectral absorption of an aqueous solution of, I-38 is 535 nm, I-48
Is 434 nm and I-49 is 430 nm.

The following evaluations were performed on the obtained samples.

(Γ by monochromatic exposure) Color temperature 3300 ° K
Manufactured by Kodak Co., Ltd .: Kodak Ratten Gelatin Filter N047B for 0.5 second exposure and the following development processing, and the obtained yellow image is measured by Konica PDA84 automatic density measurement. Γ was measured using a machine.

(Sharpness) After a resolution test chart was printed on each sample with blue light and the following development processing was performed, the density of the obtained yellow image was measured with a microdensitometer PDM-5D manufactured by Konica Corporation. , "D in large area
" _{Dmax- Dmin} of dense line printed image of 3 lines / mm" (%) with respect to " _{max- Dmin} " was evaluated as a parameter of sharpness. Here, D _max is the maximum density and D _min is the minimum density. The larger the evaluation value, the better the sharpness.

(Highlight Drawability) A wedding scene was photographed using a professional 160 negative film manufactured by Konica Corporation, and after development processing, each sample was printed by a OMEGA Kronega stretcher to obtain highlight drawability. The following criteria were evaluated.

△: The fold shadow of the wedding dress is not drawn △ to ○: The fold shadow of the wedding dress is drawn to some extent ○: The fold shadow of the wedding dress is clearly seen ◎: The fold shadow of the wedding dress is detailed Process steps Process 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 30-34 ° C. 60 seconds 150 cc Dry 60-80 C. 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaminoline 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 Water is added to make the total volume 1 liter, and the tank liquid has pH. = 10.10, the replenisher has pH Adjusted to 10.60.

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriaminepentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 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 are shown below.

Sample No. Γ sharpness due to monochromatic exposure Highlight depiction Remark 101 2.10 0.57 △ Comparison 102 2.1 1 0.60 △ Comparison 103 2.09 0.60 △ Comparison 104 2.09 0.61 △ Comparison 105 2. 10 0.63 △ Comparison 106 2.10 0.62 △ Comparison 107 2.09 0.63 △ Comparison 108 2.10 0.63 △ Comparison 109 1.88 0.63 △ to ○ Comparison 110 1.88 0. 63 △ to ○ Comparison 111 1.87 0.68 ○ Present invention 112 1.89 0.67 ○ Present invention 113 1.89 0.68 ○ Present invention 114 1.89 0.70 ○ Present invention 115 1.880 .73 ○ The present invention 116 1.90 0.72 ○ The present invention 117 1.91 0.73 ○ The present invention 118 1.64 0.70 ◎ The present invention 119 1.68 0.72 ◎ The present invention 20 1.65 0.72 ◎ The present invention 121 1.68 0.73 ◎ The present invention 122 1.43 0.70 △ Comparison 123 2.05 0.72 △ Comparison As a result, the irradiation preventing dye is used as a halogen in the lowermost layer. Comparative samples 101 to 108 and 2 other than silver halide emulsion
Comparative sample 10 in which the maximum absorption wavelengths of the two dyes are substantially the same
9, Sample 110 using a support other than the present invention, Samples 122 and 123 whose γ value by monochromatic exposure is outside the present invention,
It can be seen that the samples 111 to 121 of the present invention have excellent sharpness and highlight depiction.

Example 2 Anti-irradiation dye I-38 added to the first layer,
A sample was prepared in the same manner as in Example 1 except that II-19 (maximum absorption wavelength 537 nm), II-26 (432 nm) and II-25 (435 nm) were used instead of I-48 and I-49, respectively. Then, it was found that similar results γ were obtained even when the irradiation preventing dye was changed.

Example 3 Emulsions Em-B and Em-B1 to B3 of the first layer were respectively prepared as E.
In the case of m-G and Em-G1 to G3, the emulsion of the third layer is Em-G.
To Em-B, instead of I-38, I-48 and I-49 as the anti-irradiation dye for the first layer,
III-28 (maximum absorption wavelength 645 nm), I
II-37 (533 nm), III-32 (530 nm)
nm) was used to prepare a sample in the same manner as in Example 1. Gamma measurement by monochromatic exposure is performed by green exposure (manufactured by Kodak;
When the evaluation was performed by changing to Kodak Ratten Gelatin Filter No. 61), similar tendency results were obtained.

Example 4 Konica LV400 film manufactured by Konica Corporation was used.
Negative size 8.4cm photographed ² and the person in 4.0 cm ² and the test chart, and developed by baking the samples 102,110,111, sharpness and highlights depiction of the printed image to visually following criteria Evaluated.

(Sharpness) (Highlight descriptiveness) ×: Characters are bleeding △: Face looks white △: Characters are slightly bleeding ○: Face shadows are visible ○: Characters are not bleeding ◎: Face shadows ◎: Characters are clearly visible. The results are shown below.

Sample No. Negative size 8.4cm The ² negative size 4.0 cm ² sharpness highlight depiction of sharpness highlight depiction of 102 △ △ × △ 110 △ ○ △ ○ 111 ○ ○ ◎ ◎ Thus the present invention, as the image size of the negative is small It can be seen that the effect of improving sharpness and highlight depiction is great.

Example 5 Sample 411 was prepared in the same manner as Sample 111 of Example 1 except that 10 ml of a 2% aqueous solution of potassium bromide was added to the coating solution for the first layer.

The obtained sample 411 and the samples 102 and 111 used in Example 1 were placed in a Tabai constant temperature and humidity chamber at 40 ° C.
It was stored at 80% RH for 2 weeks. The sensitivity of the stored sample and that of the sample stored in the refrigerator were determined by a conventional sensitometry, and the deterioration rates of the sensitivity were compared. The sharpness and highlight descriptiveness were also evaluated by the same method as in Example 1.

The results obtained are shown below.

Sensitivity deterioration rate Sharpness Highlight depiction property Sample 102 11% 0.60 △ Sample 111 10% 0.68 ○ Sample 411 2% 0.69 ○

[0156]

The light-sensitive material of the present invention makes it possible to obtain a printed image which is excellent in highlight depiction and sharpness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 7/20 G03C 7/20 // D21H 19/44 D21H 1/28 Z

Claims (5)

[Claims] 1. At least one silver halide emulsion layer is provided on the side of the coating layer on a reflective support having a coating layer obtained by curing an electron beam curable resin composition containing a white pigment dispersed therein by electron beam irradiation. Of the silver halide emulsion layers, the layer closest to the support contains two or more kinds of dyes having different maximum absorption wavelengths, and γ of the dye image formed by monochromatic exposure of the closest layer. Is 1.5 to 2.0. A silver halide color photographic light-sensitive material. 2. A reflective support having a coating layer made of a water-resistant resin composition containing a white pigment dispersed polyester as a main component, and having at least one silver halide emulsion layer on the coating layer side. Of the silver halide emulsion layers, the layer closest to the support contains two or more kinds of dyes having different maximum absorption wavelengths, and γ of the dye image formed by monochromatic exposure of the closest layer is 1 A silver halide color photographic light-sensitive material characterized by being 0.5 to 2.0. 3. A hydrophilic colloid layer containing a white pigment and at least one silver halide emulsion layer in this order on a support, and a layer of the silver halide emulsion layers closest to the support. Contains two or more kinds of dyes having different maximum absorption wavelengths, and γ of a dye image formed by monochromatic exposure of the closest layer is 1.5 to 2.0. Color photographic light-sensitive material. 4. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3, wherein the γ is 1.5 to 1.8. 5. The silver halide color photographic light-sensitive material according to claim 1, 2, 3 or 4, wherein the closest layer contains a water-soluble bromide.