JPH0980689A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in sharpness, gloss, minimized in density unevenness near a cut surface, and excellent in crude storing property near the cut surface. SOLUTION: In a silver halide photographic sensitive material having a photosensitive silver halide emulsion layer and a non-photosensitive layer on at least one side of a paper base having resin coating layers applied to both surfaces of a base paper, the resin coating layer on the silver halide emulsion layer applied side of the paper base is formed of one layer or more of an electron beam hardened resin or polyester resin containing white pigment, and the swelling ratio on the side having the photosensitive silver halide emulsion layer is 60-200%. In a preferred embodiment, the swelling ratio is 110-150%, and the base paper water content of the paper base is 3-12%.

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 is excellent in sharpness and gloss, has little unevenness in density near the cut surface, and is excellent in raw storability near the cut surface. The present invention relates to a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, a water-resistant polyolefin coated support has become widespread in place of a baryter-printed photographic paper support, and at present, except for a part thereof, this photographic support is almost used.

However, although a silver halide photographic light-sensitive material (hereinafter also simply referred to as "light-sensitive material") using a polyolefin laminate photographic support has excellent water resistance, it is insufficient in terms of gloss and sharpness. there were.

In order to improve these drawbacks, in recent years, a method of laminating a polyester resin in the same manner as a polyethylene laminated photographic support in place of the technique of a polyolefin laminated photographic support is disclosed in, for example, Japanese Patent Laid-Open Publication No. Hei 5 (1999) -53187.
-127309, 5-127310, 5-12
No. 7311, No. 5-204091, No. 5-26513.
No. 3, No. 5-323495, No. 6-3767, No. 6
-3768, 6-3769, EP-050748.
Proposed in No. 9 etc. Further, a photographic paper support coated with an electron beam curing resin is disclosed in JP-A-2-176648 and JP-A-4-176648.
-2044643. Photosensitive materials using these photographic supports certainly have high gloss and high sharpness, but when cut, density unevenness occurs near the cut surface, and raw storage fog near the cut surface (raw sample It has been found that there is a drawback that the fog on a white background obtained by processing after storage for a long period under the condition is high.

By the way, the current color light-sensitive material system allows the photographer to easily photograph because of its characteristics, and also exposes and develops the print light-sensitive material through the image recorded on the color negative film. In the so-called negative / positive method, color misregistration can be corrected to some extent during printing, a high-quality printed image can be stably provided, and the printing yield is good, so that it is used in large quantities. Currently, it is the mainstream to use a negative film of 135 format (area per screen 8.4 cm ² ) and print it on E plate size (screen area 98.4 cm ² ), but due to diversifying user needs, panorama size,
Various sizes of prints with high magnification such as high-definition size are made.

[0006] Further, there has been a great demand from the photographer for convenience in photography, and a typical example thereof was the proposal of a photography kit with improved portability as seen in a one-shot camera. Further miniaturization of the camera is considered to further improve portability, but it is necessary to reduce the area of one screen of the negative film. This is also effective for downsizing a normal lens shutter camera or a single-lens reflex camera, and downsizing of a negative film is desired.

However, the use of the panoramic print and the reduction of the area of one screen of the negative film naturally increase the enlargement ratio from the negative film to the print, so that the image quality of the print image deteriorates and the sharpness is increased. It is also necessary to improve the graininess.

Techniques such as DIR couplers have been conventionally known for improving the image quality of a negative film, and it is possible to improve the image quality to some extent by using these, but in order to further improve the sharpness, a photosensitive material for printing is used. It is also necessary to improve the sharpness of the material. Further, the decrease in sharpness and graininess due to downsizing of the negative film becomes more noticeable when the glossiness of the photosensitive material for printing is poor.

Therefore, in a panoramic print or a print with a large enlargement ratio such as when a small negative film is used, a photosensitive material for printing which is particularly excellent in sharpness and gloss has been desired.

[0010]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in sharpness and gloss, has less unevenness in density near the cutting surface, and is excellent in raw storability near the cutting surface. To provide.

[0011]

The above object of the present invention is attained by the following constitutions.

(1) A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive layer on at least one side of a paper support coated with a resin coating layer on both sides of a base paper. The resin coating layer on the silver halide emulsion layer-coated side of the paper support is made of an electron beam curable resin containing one or more white pigments, and has a swelling ratio of 60 to 60 on the side having the photosensitive silver halide emulsion layer. 200% silver halide photographic light-sensitive material.

(2) The silver halide photographic light-sensitive material according to (1), which has a swelling ratio of 110 to 150%.

(3) The water content of the base paper of the paper support is 3 to 12%.
The silver halide photographic light-sensitive material as described in (2) above.

(4) A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive layer on at least one side of a paper support coated with resin coating layers on both sides of a base paper. The resin coating layer of the paper support on the side coated with the silver halide emulsion layer is made of a polyester resin containing one or more white pigments, and the swelling ratio on the side having the photosensitive silver halide emulsion layer is 60 to 200. % Silver halide photographic light-sensitive material.

(5) The silver halide photographic light-sensitive material according to (4), which has a swelling ratio of 110 to 150%.

(6) The water content of the base paper of the paper support is 3 to 12%.
(5) The silver halide photographic light-sensitive material as described in (5) above.

Hereinafter, the present invention will be described in detail.

As the electron beam-curable compound of the electron beam-curable resin useful in the present invention, any compound that can be cured by electron beam irradiation can be used. Examples of the compound usable in the present invention include JP-B-60-17104, JP-A-60-126649, and JP-A-2-157.
There are electron beam-curable compounds described in JP No. 747, etc., which correspond to electron beam-curable monomers or oligomers.

As the electron beam curable monomer or oligomer, an unsaturated compound containing two or more carbon-carbon double bonds in one molecule (for example, an acrylic or methacrylic oligomer, a polyfunctional acrylic or methacrylic compound) is used. Monomer) is used, and in addition, as a monomer to be used after diluting the curable monomer, at least carbon-
An unsaturated compound containing a carbon double bond (eg, monofunctional acrylic monomer, methacrylic monomer, vinyl monomer, etc.) is used.

The acrylic and methacrylic oligomers include acrylic acid esters or methacrylic acid esters of polyurethane, acrylic acid esters or methacrylic acid esters of polyether alcohols, acrylic acid esters or methacrylic acid esters of bisphenol A, and maleic acid of polyesters. Examples thereof include esters and fumaric acid esters. Further, as the polyfunctional acrylic monomer and 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, 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 phenoxyphosphoric acid acrylate, neopentyl glycol diacrylate, isocyanuric acid diacrylate, isocyanuric Acid triacrylate, trimethylolpropa Triacrylate, trimethylolpropane triacrylate, propylene oxide-modified trimethylolpropane polyacrylate, glycyl methacrylate, 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, pentaerythritol penta An acrylate etc. can be mentioned. Further, as the monofunctional acrylic monomer, methacrylic monomer, and vinyl monomer, styrene, N-vinylpyrrolidone,
Examples thereof include acrylic acid esters of polyoxyethylene phenyl alcohol, 2-ethylhexyl acrylate and the like.

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 is, for example, titanium dioxide, barium sulfate, barium stearate, silica,
Alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable among them for various reasons.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when whiteness is prioritized, and rutile type titanium dioxide is preferred when sharpness is important. Anatase type titanium dioxide and rutile type titanium dioxide may be blended in consideration of both whiteness and sharpness, or anatase type titanium dioxide may be used in one layer of a multilayer resin coating layer while other layers are used. Rutile type titanium dioxide may be used for this.

The titanium dioxide used is generally surface-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. It is possible to use those whose surface is treated with an organic substance such as amine, metal soap, alkyl titanate, and polysiloxane, and those whose surface is treated in combination with an inorganic or organic treating agent. 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 curing resin is
The amount may be 0 to 80% by weight, 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. White pigment content is 10% by weight
If it is less, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and if the content exceeds 80% by weight,
The flexibility of the obtained cured resin coating layer decreases, and film cracking occurs.

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 composed of an electron beam curable resin, The other 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 such that the average content of the white pigment contained in the two or more resin layers is 10 to 10.
80% by weight is preferable, 15% by weight or more is preferable, and 20% by weight or more is 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.

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 and super mill are used. A sonic 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, torque converter, 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 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, an air knife method,
Either a reverse roll coating method or a transfer coating method may be used. A fountain coater or slit orifice coater system can also be used.

There is no particular limitation on the electron beam irradiation apparatus used, and in general, as the electron beam accelerator for such electron beam irradiation, a curtain beam type, which is relatively inexpensive and can obtain a large output, is effectively used. To be The accelerating 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 resin coating layer is 3 to 100 μm.
m, preferably 5 to 50 μm. If the amount is out of 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 surface roll or matted by a matte roll such as a silk roll.

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

Examples of useful polyester resins include polyethylene terephthalate and modified polyesters having polyethylene terephthalate as a main structure (hereinafter referred to as modified polyesters). 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, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,7-naphthalene as dibasic acid of ester bond. Dicarboxylic acid, p-xylidene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Examples thereof include 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, propylene glycol,
1,4-butanediol, 1,4-hexylenediol, diethylene glycol, triethylene glycol,
Examples thereof include tetraethylene glycol, polyethylene glycol (number average molecular weight 300 to 30,000), polypropylene glycol (number average molecular weight 300 to 30,000).

Preferred dibasic acids are terephthalic acid, isophthalic acid, 4-metalsulfo-2,6-naphthalenedicarboxylic acid, 5-metalsulfoisophthalic acid, 4-metalsulfo-2,6-naphthalenedicarboxylic acid and the like. Used as glycols are ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol, polyethylene glycol (number average molecular weight 300 to 30,0).
00) 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 0 to 50 mol% based on the total polyester bond, and 50 mol%
If it exceeds the above range, the physical properties of the support, such as mechanical strength, glass transition point, water resistance, etc., deteriorate, and it becomes difficult to use it 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 ratio of 2 to 10 mol% with respect to the total ester bond, and has excellent adhesiveness to the emulsion layer, other resin layer, and base paper. ing.
A compound having this alkali metal sulfo group, for example, 5-
When sodium sulfoisophthalic acid is 2 mol% or less, it is almost the same as polyethylene terephthalate, and the meaning of modification is weakened. On the other hand, 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, and the water resistance of the photographic support deteriorates. This is a problem as a support for piercing photographs. It is preferably 2 to 7 mol%, 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 above-mentioned sulfo compound.

The modified polyester resin can be synthesized by a conventionally known method for producing polyester. For example, in the esterification reaction, either direct esterification of an acid component and a glycol component or esterification by a transesterification method with a dimethyl ester as an acid component 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 for the polymerization reaction. Regarding the polyester constituent components and the synthesis method described above, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) 103-136.
Page or "Synthetic Polymer V" (Asakura Shoten, 1971) 1
The description on pages 87 to 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
No. 9, and the modified polyester used in the present invention can be synthesized by these methods.

Polyester (including modified polyester)
It is necessary to use a polymer having a sufficiently high molecular weight. 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; Dictionary of Standard Chemistry, page 24, 1991, published by Maruzen), but the intrinsic viscosity of the polyester used in the present invention is 0. .50 or more is necessary, preferably 0.53 or more, particularly preferably 0.55.
That is all. When the intrinsic viscosity is less than the above, the resin becomes white and brittle after melt extrusion. In addition, when melt-extruding while containing water, the intrinsic viscosity decreases 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. The resin chips are dried at about 150 ° C under a vacuum of about 10 ^-3 Torr.
It is usually done in.

A white pigment is contained in the water-resistant resin whose main component is polyester, which coats at least the emulsion-coated surface of the paper support of the present invention.

As the white pigment to be used, for example, titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is preferable among them for various reasons.

The titanium dioxide may be either anatase type or rutile type, but anatase type titanium dioxide is preferred when whiteness is prioritized, and rutile type titanium dioxide is preferred when sharpness is important. Considering both whiteness and sharpness, anatase type titanium dioxide, may be used by blending rutile type titanium dioxide, anatase type titanium dioxide in a certain layer of the resin coating layer consisting of multiple layers,
Rutile titanium dioxide may be used for the other layer.

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,
Those whose surface is treated with an organic substance such as alkyl titanate or polysiloxane, and those whose surface is treated with an inorganic or organic treating agent in combination can be used. The 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 0 to 80% by weight.
The amount is preferably 10% by weight or more, preferably 15% by weight or more, and more preferably 20% by weight or more. 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 of the white pigment is 80%.
When the content is more than 5% by weight, the coating property of the obtained polyester resin is significantly 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. As for the content of the white pigment in the resin layer, the average content of the white pigment contained in the two or more resin layers is preferably 10 to 80% by weight, preferably 15% by weight or more, and preferably 20% by weight or more. Is 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.

To disperse and mix the white pigment in the polyester resin, three roll mills (three roll mills), two roll mills are used.
The present roll mill (two-roll mill), cowles dissolver, homomixer, sand grinder, ultrasonic disperser and the like can be used.

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 on the back side of the paper support at the coating position). Although applied, the melt-applied resin composition layer 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 200 to 3
It is preferably 50 ° 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 raw paper used for 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 paper making. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any paper other than neutral paper and acid paper may be used, but it is preferable to use a photographic printing paper grade base paper, and particularly photographic grade neutral paper. The thickness of the paper is preferably 40 to 250 μm.

In the above-mentioned support, a sizing agent, a fixing agent, a tension enhancer, a binder, an antistatic agent, which are generally used in papermaking,
Additives such as dyes and antifoggants may be blended, or a surface sizing agent, a surface tension agent, an antistatic agent, etc. may be appropriately applied to the surface.

The light-sensitive material of the present invention has a swelling ratio of 60 to 200.
%, But preferably 110 to 150%,
More preferably, it is 110 to 135%.

The swelling ratio here is defined as follows. That is, a raw sample of a light-sensitive material was immersed in a color developing solution whose temperature was adjusted to 35 ° C. for 45 seconds, and the swelling ratio of the paper at that time was determined by the weight ratio of the raw sample before swelling and the swollen sample after swelling. Is.

Swelling rate (%) = {(weight of swollen sample after swelling-weight of support) / (weight of raw sample before swelling-weight of support)} × 100 Paper support of the light-sensitive material of the present invention Body base paper moisture content 3-12%
It is preferred that The water content of the base paper here is the ratio of the weight of water to the weight of the base paper.

The light-sensitive material of the present invention is preferably used as a printing material. When it is used as a printing light-sensitive material, the effect of the present invention is great in printing when it is printed at an enlargement magnification of 20 or more in terms of area ratio from a negative film.
A clear difference can be obtained from the light-sensitive material other than the present invention. In this case, the area per screen of the negative film is preferably 3
~ 7 cm ² is preferred.

In the print light-sensitive material using the light-sensitive material of the present invention, when the color negative film having the transparent magnetic recording layer described in JP-A-4-62543 is used, the effect of the present invention is large, and A clear difference can be obtained from the silver halide photographic light-sensitive material outside the invention.

The composition of the silver halide photographic emulsion used in the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. Although it may be contained, silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide is preferable. From the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

In order to obtain the above silver halide emulsion, a silver halide emulsion having a portion containing silver bromide in a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change 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.

To obtain such a silver halide emulsion,
It is advantageous to include heavy metal ions. Heavy metal ions that can be used for such purposes include iron,
Iridium, platinum, palladium, nickel, rhodium,
Examples thereof include Group 8-10 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, chromium, and the like. 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 salt or complex salt.

When the heavy metal ion forms a complex,
Examples of the ligand or ion include cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl, and ammonia. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion,
Chloride ions, bromide ions and the like are preferred.

In order to contain a heavy metal ion in the silver halide emulsion, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, a heavy metal compound may be dissolved together with a halide salt and continuously added over the whole or part of the grain forming process.

The amount of heavy metal ions added to the silver halide emulsion is 1 × 10 ⁻⁹ to 1 × 1 per mol of silver halide.
It is preferably from 0 to ² mol, and particularly preferably from 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol.

The silver halide grains may have any shape. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737,
The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1
973) and other methods described in the literature to produce particles having a shape such as an octahedron, a tetradecahedron, a dodecahedron,
It can also be used. Further, particles having a twin plane may be used.

As the silver halide grains, 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 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, more preferably 0.2 to It is in the range of 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately represented as a diameter or projected area.

The grain size distribution of the silver halide grains is preferably monodisperse silver halide grains having a coefficient of variation of 0.05 to 0.22, more preferably 0.05 to 0.15,
Particularly preferably, two or more monodispersed emulsions of 0.05 to 0.15 are added to the same layer. Where the coefficient of variation is
This is a coefficient indicating the width of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R (S is the standard deviation of the grain size distribution, R is the average grain size.) The grain size referred to here is the diameter of spherical silver halide grains, or In the case of a cube or a particle having a shape other than 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 a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at a time, or may be grown after seed particles have been produced. The method for producing the seed particles and the method for growing the seed particles may be the same or different.

The method of reacting the soluble silver salt with the soluble halide may be any of a forward mixing method, a back mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. . Further, as one form of the simultaneous mixing method, pA described in JP-A-54-48521 and the like are described.
g The controlled double jet method can also be used.

Further, JP-A-57-92523 and 57-57
No. 92524, etc., a device for supplying a water-soluble silver salt and a water-soluble halide aqueous solution from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in DE 2,921,164. And an apparatus for continuously adding an aqueous solution of a water-soluble halide while changing its concentration, Japanese Patent Publication No. 56-5017.
No. 76, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

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 and used during the formation of silver halide grains or after the completion of grain formation.

The silver halide emulsion 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, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, but the sulfur sensitizer is preferable.

Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and inorganic sulfur.

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

As the gold sensitizer, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. Is preferably
More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization method for silver halide emulsions is as follows:
A reduction sensitization method may be used.

The silver halide emulsion contains a known antifoggant for the purpose of preventing fog during the process of preparing a light-sensitive material, reducing performance fluctuation during storage, and preventing fog during development. Agents can be used. Preferred examples of the compound used for such purpose include a compound represented by the general formula [II] described in the lower column on page 7 of JP-A-2-14636, and more preferred specific compounds include II described on page 8 of the publication
a-1 to IIa-8, IIb-1 to IIb-7, 1
Compounds such as-(3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added in the steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution, depending on the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ^-2 mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution 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 × 10 ^{−. 2} mol is more preferred.
Further, when added to a layer other than the silver halide emulsion layer,
The amount in the coating film is 1 × 10 ⁻⁹ to 1 × 10 ⁻³ per m ^2.
Amounts on the order of moles are preferred.

Dyes having absorption in various wavelength regions can be used in the light-sensitive material for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used. Particularly, as the dye having absorption in the visible region, the dyes of AI-1 to 11 described in JP-A-3-251840, p. The dyes described in No. 3770 are preferably used, and as the infrared absorbing dye, the compounds represented by the general formulas (I), (II) and (III) described in JP-A 1-280750, page 2, lower left column are preferable. It is preferable because it has a spectral characteristic, has no influence on the photographic characteristics of the photographic emulsion, and has no stain due to residual color. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the lower left column of page 3 to the lower left column of page 5 of the same publication. For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of an unprocessed sample of the light-sensitive material is 0.7 to 3.0, and more preferably 0.8 to 3.0. More preferably, it is 3.0.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because the whiteness can be improved. The compound preferably used is a compound represented by the general formula [I] described in JP-A-2-232652.
I].

When the light-sensitive material of the present invention is used as a color light-sensitive material, it is used in combination with a yellow coupler, a magenta coupler, and a cyan coupler to obtain 400 to 900 nm.
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of 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 present invention, any of known compounds can be used. As the blue-sensitive sensitizing dye, BS-1 to BS-1 described in JP-A-3-251840, page 28 can be used. BS-8 can be preferably used alone or in combination. Green photosensitive sensitizing dyes include:
GS-1 to GS-5 described on page 28 of the publication are preferable,
Further, as the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared-sensitive sensitizing dye,
As the infrared-sensitive sensitizing dye, JP-A-4-285950
The dyes IRS-1 to IRS-11 described on pages 6 to 8 are preferably used. Further, for these infrared, red, green and blue photosensitive sensitizing dyes, the supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-665.
It is preferable to use a combination of compounds S-1 to S-17 described in No. 15, pages 15 to 17.

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.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized product of a color developing agent. Although a typical coupler can also be used, a yellow dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm,
Examples include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in a wavelength range of 600 to 750 nm.

Examples of cyan couplers that can be preferably used include couplers represented by the general formulas [CI] and [C-II] described in JP-A-4-114154, page 5, lower left column, As a specific compound, the same publication 5
There can be mentioned those described as CC-1 to CC-9 in the lower right column of page 6 to the lower left column of page 6.

Examples of magenta couplers that can be preferably used include couplers represented by the general formulas [MI] and [M-II] described in JP-A-4-114154, page 4, upper right column, Specific compounds include those described as MC-1 to MC-11 in the same publication, page 4, lower left column to page 5, upper right column. Among the above magenta couplers, more preferred are those represented by the general formula [MI]
A coupler represented by the general formula [M-
The coupler of the formula (I) wherein R _M is a tertiary alkyl group is particularly preferred because of its excellent light resistance. M described in the upper column of page 5 of the same publication
C-8 to MC-11 are preferable because they are excellent in reproduction of colors ranging from blue to purple and red, and are also excellent in detail description.

Examples of yellow couplers that can be preferably used include couplers represented by the general formula [Y-I] described in JP-A-4-114154, page 3, upper right column, and specific compounds are the same as those disclosed in the publication. YC on page 3, lower left column
-1 to YC-9. Among them, a coupler in which R _{Y1 of} the general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce a preferable yellow color. Of these, particularly preferable examples of compounds include YC-8, YC-9 and JP-A-6-67388 described in JP-A-4-114154, page 4, upper left column.
Compounds represented by Nos. (1) to (47) on pages 3 to 14 can be exemplified. The most preferred compound is a compound represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

When the oil-in-water type emulsion dispersion method is used to add the coupler or other organic compound used in the light-sensitive material, it is usually added to a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher, if necessary. A low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill,
A flow jet mixer, an ultrasonic disperser or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be included.

As the high-boiling organic solvent which can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl phosphate can be used. And the like are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination. .

In place of the method using a high-boiling organic solvent, or in combination with a high-boiling organic solvent, a water-insoluble and organic-solvent-soluble polymer compound is added, if necessary, to a low-boiling 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 various emulsion means are used for emulsion dispersion. 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 to A-1 described in JP-A-64-26854.
1 is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are
Usually, it is added to a coating solution containing a silver halide emulsion, but it is better that the time until the addition to the coating solution after dispersion and the time from the addition to the coating solution to the coating are shorter, each being preferably within 10 hours. 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 formulas [I] and [II] described in JP-A-2-66541, page 3, and phenol represented by formula [IIIB] described in JP-A-3-174150. Compounds, amine compounds represented by the general formula [A] described in JP-A No. 64-90445, JP-A No. 62-
General formulas (XII), (XIII) and (XI) described in No. 182741
V] and metal complexes represented by [XV] are particularly preferred for magenta dyes. Also, a compound represented by the general formula [I] described in JP-A-1-19649 and JP-A-5-1141.
The compound represented by the general formula [II] described in No. 7 is particularly preferable for yellow and cyan dyes.

For the purpose of shifting the absorption wavelength of the coloring dye, compounds d-11 described in JP-A-4-114154, page 9, lower left column, and compound A'-1, described in page 10, upper left column are used. be able to. In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, 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 to a silver halide emulsion layer to fog. Is preferably improved. The compound for this purpose is preferably a hydroquinone derivative, more preferably 2,
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are those represented by the general formula [II] described in JP-A-4-133056, and the compounds II-1 to II-14 described on pages 13 to 14 of the same publication.
Compounds-1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or improve the light resistance of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by the general formula [III-] described in JP-A-1-250944.
3], a compound represented by the general formula [III] described in JP-A-64-66646, and a compound represented by JP-A-63-18
No. 7240, UV-1L to UV-27L;
Examples thereof include compounds represented by the general formula [I] described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is advantageous to use gelatin as a binder in the light-sensitive material of the present invention, but if necessary, a gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, Hydrophilic colloids such as synthetic hydrophilic polymeric substances such as homopolymers or copolymers 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 carboxyl group active type hardener alone or in combination. JP-A-61-249054, 61-
It is preferable to use the compounds described in US Pat. Further, in order to prevent the growth of molds and bacteria which adversely affect the photographic performance and image storability, JP-A-3-15764 is incorporated in the colloid layer.
It is preferable to add a preservative and an antifungal agent as described in No. 6. In order to improve the physical properties of the surface of the light-sensitive material or the processed sample, 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.

The photosensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or undercoat (adhesiveness, antistatic property, dimensional stability of the support surface). , One or more undercoating layers for improving abrasion resistance, hardness, antihalation property, frictional properties and / or other properties).

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

In order to form a photographic image using the photosensitive material of the present invention, an image recorded on a negative may be optically formed on a photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

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

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

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-lauryl) aminotoluene CD-4: 4- (N-ethyl-N-β-hydroxyethyl) aminoaniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamido) ethylaniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline 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) ethylaniline 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.

The processing temperature for color development in the present invention is 3
5-70 ° C is preferred. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

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

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ion and benzotriazole, a preservative, a chelating agent and the like are used.

After the color development, the photosensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a water washing process is usually performed. Further, as a substitute for the washing treatment, a stabilizing treatment may be performed.

The developing apparatus used for processing the photosensitive material of the present invention is a roller transport type in which the photosensitive material is conveyed by sandwiching the photosensitive material between rollers disposed in a processing tank. An endless belt system for conveying may be used, but a processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and a photosensitive material is conveyed and a spray method for spraying the processing liquid,
A web method by contact with a carrier impregnated with the processing solution,
A method using a viscous treatment liquid can also be used. When processing in large quantities, it is normal to run using an automatic developing machine, but in this case, the replenishment amount of the replenisher is preferably as small as possible. And the method described in JP-A-94-16935 is most preferable.

[0115]

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

As the supports used in the examples, AK prepared as follows were used. These also include the support of the present invention.

(Preparation of Support) LBKP for Photographic Paper
(Sulfuric acid method bleached hardwood pulp) 50% by weight and NBSP (Sulfite method bleached softwood pulp) 50% by weight of white base paper (grammage 17
Extrusion coating of a polyethylene composition (density 0.95 g / cc, melt index (MI) 8.0 g / 10 min) was performed on one surface of 5 g / m ² and a thickness of 180 μm to obtain 3
A back laminate layer of 0 g / m ² was formed to produce a sheet substrate.

Next, a resin layer having the following composition was provided on the surface opposite to the surface on which the back laminate layer was placed to obtain supports A to Z.

(Support A) Polyethylene composition (density 0.92 g / cc, MI 5.0 g / 10 min) 90% by weight
And a titanium oxide white pigment (anatase type) 10% by weight are kneaded and then melt-extrusion coated to 30 g / m ^2.
The water resistant resin layer of was coated on the surface of the sheet substrate.

(Support B) Polyethylene terephthalate (PET) composition (intrinsic viscosity 0.72 cc / g) 75% by weight and titanium oxide white pigment (anatase type) 25% by weight
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 lamination at 300 ° C.

(Supports C to E) Support B has the same kind of resin and the same amount of resin layer (the total amount of resin and white pigment), and the content of white pigment is changed as shown in Table 4. Supports C to E were prepared in the same manner as the support B, except that (resin content = 100 wt% -white pigment wt%).

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

Polyester acrylate 25 wt% Hexanediol diacrylate 25 wt% Trimethylolpropane triacrylate 15 wt% Titanium oxide (anatase type) 40 wt% A composition obtained by dispersing the above mixture in a ball mill for 20 hours is The coating was applied onto the surface of the sheet-shaped substrate so that the coating amount after curing was 30 g / m ² . Then, from the back surface of the sheet-shaped substrate, an acceleration voltage of 200 KV and an absorbed dose of 2 Mrad
The resin coating layer was formed by irradiating with an electron beam under the conditions described above to cure the resin.

(Support G) The support F has the same kind of resin and the same amount of resin layer (the total amount of resin and white pigment), and the content of the white pigment is changed as shown in Table 3. A support G was prepared in the same manner as the support F except for the above.

As a resin layer in (Support H), 75% by weight of a PET composition (intrinsic viscosity 0.72 cc / g) and 25% by weight of a titanium oxide white pigment (anatase type) were kneaded, and then 3
A water-resistant resin layer of 15 g / m ² was applied to the surface of the sheet-like substrate by melt extrusion lamination at 00 ° C.

Next, after kneading 85% by weight of a PET composition (intrinsic viscosity 0.72 cc / g) and 15% by weight of titanium oxide white pigment (anatase type) as an outer resin layer, the mixture was heated to 300 ° C.
Then, a water-resistant resin layer of 15 g / m ² was applied on the surface of the inner resin layer by melt extrusion lamination.

(Supports I to K) Supports H have the same kind of resin in the inner resin layer and outer resin layer and the same amount of resin layer (the total amount of resin and white pigment), and are shown in Table 4. Like the support H, except that the content of the white pigment is changed as described above.
Supports I-K were made.

(Support L) 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 Titanium oxide (anatase type) 50% by weight The above mixture was dispersed in a ball mill for 20 hours.

The composition thus obtained was applied as an inner resin layer onto the surface of the sheet-like substrate so that the coating amount after curing was 20 g / m ² . Then, from the back surface of the sheet-shaped substrate, an acceleration voltage of 200 KV and an absorbed dose of 2 Mrad
The resin coating layer was formed by irradiating with an electron beam under the conditions described above to cure the resin.

Next, a polyethylene composition (density 0.92 g / c) was formed as an outer resin layer on the resin-cured inner coating layer.
c, MI 5.0 g / 10 min) 99.5 wt% and titanium oxide white pigment (anatase type) 0.5 wt% were kneaded, and then a 10 g / m ² waterproof resin layer was applied by melt extrusion coating. .

(Support M to O) The support L has the same kind of resin in the inner resin layer and the outer resin layer, and the same amount of the resin layer (the amount of the resin and the white pigment combined) as shown in Table 3. As in the case of the support L, except that the content of the white pigment is changed as described above.
Supports M to O were prepared.

(Support P) 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 Titanium oxide (anatase type) 50% by weight A composition obtained by dispersing the above mixture in a ball mill for 20 hours is used as an inner resin layer of the sheet-like substrate. The surface was coated so that the coating amount after curing was 20 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate 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.

Next, as an outer resin layer, 80% by weight of a PET composition (intrinsic viscosity 0.72 cc / g) and 20% by weight of a titanium oxide white pigment (anatase type) were kneaded, and then 300
A water-resistant resin layer of 10 g / m ² was coated on the surface of the inner resin layer by melt extrusion lamination at ℃.

(Support Q) 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 10% by weight Titanium oxide (anatase type) 40% by weight A composition obtained by dispersing the above mixture in a ball mill for 20 hours was used. The resin layer was applied onto the water resistant resin layer so that the coating amount after curing was 15 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate 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 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 mixed, and transesterification was carried out by a conventional method. 0.05 parts by weight of antimony trioxide was added to the obtained product, 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 this modified polyester was 0.7 cc / g.

This modified polyester 9 was used as the outer resin layer.
After 0% by weight and 10% by weight of titanium oxide white pigment (anatase type) were kneaded, a water-resistant resin layer of 15 g / m ² was applied on the surface of the inner resin layer by melt extrusion lamination at 300 ° C.

As the resin layer in the (support R), a polyethylene composition (density 0.92 g / cc, MI 5.0 g / 10
Min) 85 wt% and titanium oxide white pigment (anatase type)
After kneading 15% by weight, a 20 g / m ² waterproof resin layer was applied on the surface of the sheet-like substrate by melt extrusion coating.

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

Polyester acrylate 35 wt% Hexanediol diacrylate 35 wt% Trimethylolpropane triacrylate 15 wt% Titanium oxide (anatase type) 15 wt% The composition obtained by dispersing the above mixture in a ball mill for 20 hours was removed. As a resin layer, it was applied on the water resistant resin layer so that the applied amount after curing was 10 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate under the conditions of an acceleration voltage of 200 KV and an absorbed dose of 2 Mrad to cure the resin and form an outer resin layer.

(Support S) As for the support R, the resin species of the inner resin layer and the outer resin layer and the resin layer coating amount (the total amount of the resin and the white pigment) are the same, and as shown in Table 3, white A support S was prepared in the same manner as the support R except that the pigment content was changed.

As the resin layer in the (support T), a polyethylene composition (density 0.92 g / cc, MI 5.0 g / 10
Min) 80% by weight and titanium oxide white pigment (anatase type)
After kneading 20% by weight, a water-resistant resin layer of 15 g / m ² was applied on the surface of the sheet-like substrate by melt extrusion coating.

The mixture of the above components was dispersed by a ball mill for 20 hours.

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

Dipentaerythritol hexaacrylate 70% by weight Titanium oxide (rutile type) 30% by weight The composition obtained by dispersing the above mixture in a ball mill for 20 hours is cured as an outer resin layer on the water resistant resin layer. The subsequent coating amount was 15 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate under the conditions of an acceleration voltage of 200 KV and an absorbed dose of 2 Mrad to cure the resin and form an outer resin layer.

(Support U) PET composition (intrinsic viscosity of 0.
72 cc / g) and 30% by weight of titanium oxide white pigment (anatase type) were kneaded and then melt-extruded and laminated at 300 ° C. to form a waterproof resin layer of 15 g / m ^{2 on} the surface of the sheet substrate. It was painted.

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

Polyester acrylate 30% by weight Hexanediol diacrylate 30% by weight Trimethylolpropane triacrylate 25% by weight Titanium oxide (anatase type) 15% by weight A composition obtained by dispersing the above mixture in a ball mill for 20 hours is The coating amount after curing is 15 g / m ² on the resin layer.
Was applied. Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate under the conditions of an acceleration voltage of 200 KV and an absorbed dose of 2 Mrad to cure the resin and form an outer resin layer.

(Support V) As a resin layer inside, a polyethylene composition (density 0.92 g / cc, MI 5.0 g / 10
Min) 90% by weight and titanium oxide white pigment (anatase type)
After kneading 10% by weight, a water-resistant resin layer of 10 g / m ² was applied on the surface of the sheet-like 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 Titanium oxide (anatase type) 50% by weight A composition obtained by dispersing the mixture of the above components in a ball mill for 20 hours is applied onto the inner resin layer and after curing. Application amount of 15g
It was applied so as to be / m ² . Then, an electron beam was irradiated from the back surface of the sheet-shaped substrate under the conditions of an acceleration 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.

Polyester acrylate 35% by weight Hexanediol diacrylate 35% by weight Trimethylolpropane triacrylate 30% by weight The composition thus obtained is used as the outer resin layer on the surface of the middle resin layer, and the coating amount after curing is set. Of 5 g / m ² was applied. Then, from the back surface of the sheet-like substrate, the acceleration voltage 2
An electron beam was irradiated under the conditions of 00 KV and an absorbed dose of 2 Mrad to cure the resin and form a resin coating layer.

(Support W) The inner resin layer and the intermediate resin layer were the same as those of the support V.

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

Polyester acrylate 30 wt% Hexanediol diacrylate 30 wt% Trimethylolpropane triacrylate 25 wt% Titanium oxide (anatase type) 15 wt% A composition obtained by dispersing a mixture of the above components in a ball mill for 20 hours. The outer resin layer was coated on the surface of the middle resin layer so that the coating amount after curing was 5 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate 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.

(Support X) The inner resin layer and the intermediate resin layer were the same as those of the support V.

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

Polyester acrylate 27 wt% Hexanediol diacrylate 27 wt% Trimethylolpropane triacrylate 20 wt% Titanium oxide (anatase type) 26 wt% The composition obtained by dispersing the above mixture in a ball mill for 20 hours was removed. A resin layer was applied on the surface of the intermediate resin layer so that the applied amount after curing was 5 g / m ² . Next, from the back surface of the sheet-shaped substrate, acceleration voltage 200 KV, absorbed dose 2 Mr
An electron beam was irradiated under the condition of ad to cure the resin and form a surface resin coating layer.

As the resin layer in the (support Y), a polyethylene composition (density 0.92 g / cc, MI 5.0 g / 10
Min) 85 wt% and titanium oxide white pigment (anatase type)
After kneading 10% by weight, a water-resistant resin layer of 10 g / m ² was applied on the surface of the sheet-like substrate by melt extrusion coating.

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

Polyester acrylate 25 wt% Hexanediol diacrylate 25 wt% Trimethylolpropane triacrylate 10 wt% Titanium oxide (anatase type) 40 wt% A composition obtained by dispersing the above mixture in a ball mill for 20 hours is used. It was coated on the resin layer so that the coating amount after curing was 15 g / m ² . Then, an electron beam was irradiated from the back surface of the sheet-shaped substrate under the conditions of an acceleration 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
A white pigment composition was prepared.

Dipentaerythritol hexaacrylate 80% by weight Titanium oxide (anatase type) 20% by weight The composition obtained by dispersing the above mixture in a ball mill for 20 hours is used as an outer resin layer after curing on the surface of the middle resin layer. The coating amount was 5 g / m ² . Next, from the back surface of the sheet-shaped substrate, acceleration voltage 200 KV, absorbed dose 2 Mr
An electron beam was irradiated under the condition of ad to cure the resin and form a resin coating layer.

(Support Z) The inner resin layer and the intermediate resin layer were the same as those of the support V.

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

Polyester acrylate 35 wt% Hexanediol diacrylate 35 wt% Trimethylolpropane triacrylate 20 wt% Titanium oxide (anatase type) 10 wt% The composition obtained by dispersing the above mixture in a ball mill for 20 hours was used. An outer resin layer was applied on the surface of the middle resin layer so that the applied amount after curing was 5 g / m ² . Next, from the back surface of the sheet-shaped substrate, acceleration voltage 200 KV, absorbed dose 2 Mr
An electron beam was irradiated under the condition of ad to cure the resin and form a resin coating layer.

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

Example 1 A support A having a gelatin subbing layer was coated with each layer having the following constitution to prepare a color light-sensitive material sample. The coating liquid was prepared as follows.

First Layer Coating Liquid 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 cc of ethyl acetate was added and dissolved, and this solution was added with 7 cc of 20% surfactant (SU-1) 1
A yellow coupler dispersion was prepared by emulsifying and dispersing 220 cc 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 liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardening agent (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 .

[0176]

[Table 1]

[0177]

[Table 2]

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

[0179]

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[0181]

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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 cc (Solution B) Silver nitrate 10 g Water was added to 200 cc (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 cc (solution D) Silver nitrate 300 g Water added 600 cc After the 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, EMP was performed except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
As in the case of -1, the average particle diameter is 0.64 μm, and the coefficient of variation is 0.1.
07, a monodispersed cubic emulsion EMP-1B having a silver chloride content of 99.5 mol% 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%.

Then, a monodisperse cubic emulsion EMP-2B having an average grain size of 0.50 μm, a variation coefficient of 0.08 and a silver chloride content of 99.5% was obtained.

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

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 added per mol of silver halide. 2.0 × 10 ⁻³ mol was added.

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[0194]

[Chemical 6]

Samples 102 to 122 were prepared in the same manner except that the sample thus obtained was 101 and the support shown in Table 3 was used.

The following performance evaluation was performed on each sample.
The swelling ratios of these samples were adjusted to the values shown in Table 3 by adjusting the amount of the hardener added and the standing environment of the sample after coating.

<Gloss> A sample exposed to white light was subjected to the following development processing step A, and the glossiness of the surface of the obtained black background sample was measured with a VG-ID type gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. The incident angle was 60 ° and the light receiving angle was 60 °.

<Sharpness> A resolution test chart was printed on each sample with red light, and the following development processing step A was carried out. Then, the obtained cyan image was analyzed by a microdensitometer P.
The concentration was measured with DM-5D (manufactured by Konica), and the value represented by the following formula was taken as the immediate sharpness.

Immediate sharpness (%) = ( _{Dmax- Dmin of} 3 lines / mm dense line print image) / ( _Dmax-in large area _portion-
D _min ) Here, D _max indicates the maximum density and D _min indicates the minimum density.

<Density unevenness> Each sample exposed to white light was
The following development processing step A was performed, and the density unevenness near the cut surface of the obtained black sample was visually evaluated in the following four steps.

⊚: Very good density unevenness is not seen even at a distance of 10 cm. ◯: Visible at a distance of 10 cm, but not visible at a further distance. Δ: Seen at a distance. The density unevenness is slightly visible x: Extremely uneven density is conspicuous even when viewed from a distance. <Fog on raw storage> Samples and freezers stored for 3 weeks in an atmosphere of 40 ° C and 40% RH. The sample stored for 3 weeks therein was processed in the following processing step A without exposure. X-rit at 5 mm from the cut surface of the processed sample
The Y concentration was measured using an e310 densitometer (manufactured by X-rite), and the concentration difference between the sample stored for 3 weeks in an atmosphere of 40 ° C. and 40% RH and the sample stored for 3 weeks in the freezer was defined as ΔD. . The larger this value is, the poorer the raw storability is.

Treatment Step A Treatment Temperature Temperature Replenishment Amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach-fix 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30-34 ° C. 60 seconds 150 cc Dry Dry 60-80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developing solution tank solution and replenishing solution tank solution replenishing solution pure water 800 cc 800 cc 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 penta Sodium acetate salt 2.0 g 2.0 g Fluorescent brightener (4,4′-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank liquid had pH = At 10.10, the replenisher has a pH of 1 Adjusted to .60.

Bleach-fixing solution tank solution and replenishing solution Diethylenetriamine pentaacetic acid ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2 0.0 g Ammonium sulfite (40% aqueous solution) 27.5 cc 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 summarized in Table 3.

[0207]

[Table 3]

Example 2 The same treatment as in Example 1 was carried out with the following modifications.

Treatment Step B Treatment Temperature Time Replenishment Amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 cc Bleach fixing 35.0 ± 0.5 ° C. 22 seconds 54 cc Stabilization 30-34 ° C. 25 seconds 150 cc Dry Dry 60-80 ° C. 30 seconds The composition of the development processing solution is shown below.

Color developing solution tank solution and replenishing solution tank solution replenishing solution pure water 800 cc 800 cc 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 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 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 Liquor to pH = 10.10, replenishing solution is adjusted to pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution tank solution replenishing solution diethylenetriaminepentaacetic acid ammonium ferric acid dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 cc 100 cc 2-amino-5-mercapto-1 , 3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 cc 25 cc Water was added to bring the total volume to 1 liter, and the tank solution was adjusted to pH = 7.0 with potassium carbonate or glacial acetic acid. 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 cc Water is added to make the total volume 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 Example 1, and it was confirmed that the effects of the present invention were effectively obtained.

Example 3 In Example 2, NPS manufactured by Konica Corporation was used as an automatic processor.
-868J, ECOJET-P was used as a treatment chemical, and a running treatment was performed according to the process CPK-2-J1. Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effects of the present invention were obtained.

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 PET and PEN, and a support having no magnetic recording layer. Was photographed with a color negative film (F-2) consisting of triacetyl cellulose (TAC), and the same scene was photographed by a large number of people. Was used for print baking, and visual observation and evaluation of the print sample after development were performed.

As a result, the color negative film (F-1)
In the case of using, the print using the sample of the present invention was particularly excellent in sharpness and glossiness, and was also excellent in graininess.

That is, in a system having a transparent magnetic recording layer and a support in combination with a color negative film composed of PET and PEN, the sample of the present invention can provide particularly high quality images.

Example 5 135 format (area per screen 8.4c
m ² ) color negative film (F-3) and color negative film (F-4) with an area of 4 cm ² per screen were used to shoot the same group of large number of people. The photosensitive material prepared in Example 4 was printed with an E plate print using an automatic printer, and the printed sample after development was visually observed and evaluated.

As a result, in the prints using the samples other than the present invention, when F-4 was used for the negative film, the sharpness was conspicuously deteriorated and the graininess was deteriorated. The print using the sample had sufficient sharpness, remarkably good gloss, and good graininess even when F-4 having a small negative film size was used.

That is, the sample of the present invention can provide a print having a high quality image even if a negative film having a small screen size is used.

Example 6 Samples 201 to 215 were prepared in the same manner as in Example 1 except that the support was changed as shown in Table 4, and the same treatment and evaluation as in Example 1 were carried out.

The results are shown in Table 4.

[0223]

[Table 4]

Example 7 In Example 6, the same treatment and evaluation as in Example 2 were carried out, and it was confirmed that the effects of the present invention were effectively obtained.

Example 8 In Example 6, the same treatment and evaluation as in Example 3 were carried out, and it was confirmed that the effects of the present invention were effectively obtained.

Example 9 Using the sample produced in Example 6, the same treatment and evaluation as in Example 4 were carried out, and it was confirmed that the sample of the present invention can provide particularly high quality images.

Example 10 Using the sample prepared in Example 6, the same treatment and evaluation as in Example 5 were carried out, and it was confirmed that the sample of the present invention can provide a particularly high quality image.

[0228]

With the constitution of the present invention, a silver halide photographic light-sensitive material having excellent gloss and sharpness, less density unevenness near the cut surface, and excellent raw storability near the cut surface can be obtained.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive layer on at least one side of a paper support coated with a resin coating layer on both sides of a base paper. The resin coating layer on the silver halide emulsion layer-coated side of the support is composed of an electron beam curable resin containing one or more white pigments, and the swelling ratio on the side having the photosensitive silver halide emulsion layer is 60 to 200. %, A silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, which has a swelling ratio of 110 to 150%. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the water content of the base paper of the paper support is 3 to 12%. 4. A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and a non-light-sensitive layer on at least one side of a paper support coated with a resin coating layer on both sides of a base paper. The resin coating layer on the side coated with the silver halide emulsion layer of the support is made of a polyester resin containing one or more white pigments, and the swelling rate on the side having the photosensitive silver halide emulsion layer is 60 to 200%. And a silver halide photographic light-sensitive material. 5. The silver halide photographic light-sensitive material according to claim 4, which has a swelling ratio of 110 to 150%. 6. The silver halide photographic light-sensitive material according to claim 5, wherein the water content of the base paper of the paper support is 3 to 12%.