JPH0973148A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material having superior rapid processability, sharpness and glossiness, improved scuffing and wear remittances, improved adhesives and unevenness in drying after processing by incorporating a specified compd. SOLUTION: This silver halide photographic sensitive material contains at least one kind of compd. represented by formula I and gas 0.05-0.3g/m<2> content of a surfactant represented by formula II. In the formula I, each of R2 -R5 and R8 -R11 is H, alkyl or aryl, each of R6 and R12 is alkyl, aryl or -(R7 )p -A, R7 is a divalent combining group, A is aryl, epoxy, a fluorine modified group or cyano, each of (1), (m) and (n) is an integer of 0-200 and (p) is 0 or 1. In the formula II, R is alkyl, alkenyl, etc., L is a divalent combining group, (n) is 0 or an integer of 1-10 and M<+> is H<+> or a cation.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly, it has excellent suitability for rapid processing, sharpness and glossiness, improved scratch resistance, adhesiveness and dryness after processing. The present invention relates to a silver halide photographic light-sensitive material having improved unevenness (hereinafter also abbreviated as photographic light-sensitive material or light-sensitive material).

[0002]

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

Irradiation and halation are generally known as factors affecting sharpness. The former is brought about by the scattering of incident light by oil droplets such as silver halide grains and couplers dispersed in a gelatin film, and its degree mainly depends on the gelatin amount, silver halide amount, and oil droplet amount. The latter depends on the degree of light reflection from the support, and on the reflectance and refractive index of the support.

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

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

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

Improvements to the support have also been investigated. In recent years, as a support for color print photosensitive materials, a water-resistant support prepared by laminating a polyolefin resin mainly made of polyethylene on the surface of a base paper has been used for speeding up development processing. A white pigment such as titanium oxide is dispersed in the polyolefin layer on the emulsion side. To improve the sharpness, JP-A-54-6035 is used.
No. 64-18144, JP-A No. 2-71256 and the like, combining the technique of using a paper support in which a polyethylene resin layer on the side coated with a photographic emulsion is filled with a large amount of white pigment. However, it is difficult to use as a support of a silver halide color photographic light-sensitive material because it has drawbacks such as deterioration of smoothness of the polyethylene layer and deterioration of adhesion between the polyethylene layer and the emulsion layer.

Further, as a technique capable of improving the sharpness, Japanese Patent Laid-Open Nos. 6-167768, 6-186673 and 6-
No. 202276, No. 6-289532, etc., a reflective support obtained by coating at least the emulsion coating side surface of a substrate with a composition in which a white pigment is mixed and dispersed in a water resistant resin containing polyester as a main component. Body and special public Sho 60
-17104, Japanese Patent Publication No. 1-23773, 1-23
No. 774, JP-A-63-198049, etc., the composition in which the reflective support is prepared by mixing and dispersing a white pigment in an electron beam curable resin is coated on at least the surface of the substrate on which the emulsion is coated. Studies have been conducted using a reflective support obtained by irradiating an electron beam for curing and coating. Unlike the polyethylene resin, these reflective supports were effective in increasing the sharpness because even if they were filled with a large amount of white pigment, the deterioration of smoothness was small. However, it has been found that when these reflective supports are used, scratch resistance is likely to be deteriorated, adhesiveness after treatment is poor, and drying unevenness is noticeable.

By the way, in the photographic light-sensitive material, various devices, machines, etc. are exposed to light when handling such as winding, rewinding or conveying in the manufacturing process such as coating, drying, processing, etc. Scratches and scratches are likely to occur due to contact friction between the parts that come into contact with the material or the adhesion with dust, fiber scraps, and the like. These scratches are directly seen by the customer in the printed photosensitive material, which is a serious problem. In addition, recently, due to the expansion of use and processing methods for photosensitive materials such as high-speed coating and rapid processing, the photosensitive materials are subject to more severe handling than ever before, causing scratches and deterioration of drivability. It is becoming more likely to happen. Therefore, there is a demand for a light-sensitive material having a highly symmetrical surface quality that can sufficiently withstand even under such severe conditions.

Conventionally, a method of providing a surface layer containing a lubricant has been used as a means for improving the scratch resistance of a light-sensitive material. As the slip agent, for example, dimethylpolysiloxane disclosed in Japanese Patent Publication No. 508657, higher fatty acid amides disclosed in US Pat. No. 4,275,146, Japanese Patent Publication No. 58-33541, British Patent 92
Higher fatty acid esters disclosed in 7,446 and the like,
Higher fatty acid metal salts and the like as disclosed in US Pat. No. 3,933,516 are known.

By adding such a slip agent to the surface layer, the scratch resistance of the photographic light-sensitive material is improved, but a composition prepared by mixing and dispersing a white pigment in a water-resistant resin containing polyester as a main component is used as a base material. A reflective support formed by coating at least the silver halide emulsion coating side surface or a composition in which a white pigment is mixed and dispersed in an electron beam curing resin is coated on at least the silver halide emulsion coating side surface of the substrate and then exposed to an electron beam. In a photographic light-sensitive material using a reflection support which is cured and coated by irradiation, addition of these slip agents is not enough to improve scratch resistance, and conversely, the adhesiveness and drying unevenness after processing are further increased. There is a problem that makes it worse.

In recent years, there has been a strong demand for reduction of processing waste liquid from the viewpoint of environmental protection in the processing of silver halide light-sensitive materials. Therefore, the replenishment of the processing liquid is being promoted. If the replenishment amount of the processing solution is reduced, the retention time of the processing solution in the processing bath becomes long, and the processing solution is easily affected by air oxidation and the like, which has various adverse effects on the silver halide photographic light-sensitive material.

For example, the unnecessary processing composition is poorly washed out, and the adhesiveness of the light-sensitive material is deteriorated.

Further, due to the demand for speeding up, short-time processing is being advanced. While it is desired to shorten the drying process,
Since water droplets attached to the surface of the emulsion surface after processing are prevented from drying uniformly in the drying process, uneven drying occurs, and there is a problem that the emulsion surface flickers, which impedes speeding up.

Therefore, it is strongly desired to improve the adhesiveness and eliminate drying unevenness.

By the way, the method of silver halide color photographic light-sensitive material allows the photographer to easily photograph due to the characteristics of the silver halide photographic light-sensitive material, and also print halogen through the image recorded on the color negative film. In the so-called negative-positive method in which a silver halide photographic light-sensitive material is exposed and developed, color misregistration can be corrected to some extent during printing, so that a high-quality printed image can be stably provided and the print yield is good. , Very often used. Currently using a negative film of 135 format (1 area per screen 8.4 cm ^2), but the mainstream to burn the E plate size (screen area 98.4cm ^2), the diversification of user needs, panorama size, Various sizes of prints with high magnification such as high-definition size are made.

For the photographer, there has been a great demand for further convenience in photography, and a typical example thereof was a 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 cause a large enlargement ratio from the negative film to the print, so that the image quality of the print image is deteriorated and sharpened. It is also necessary to improve the properties and graininess.

Therefore, in order to improve the image quality of the negative film,
Techniques such as DIR couplers have been known so far, and these can improve the image quality to some extent.

In order to further improve the sharpness, it is necessary to improve the sharpness of the photosensitive material for printing.

Further, the reduction in sharpness and graininess due to the downsizing of the negative film is noticeable when the glossiness of the photosensitive material for printing is poor, and further deteriorates when gloss deterioration or scratches due to uneven drying occurs. Is emphasized.

Therefore, in a panorama 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 glossiness and which is free from uneven drying and scratches is obtained. Was wanted.

[0023]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a halogen having excellent rapid processing suitability, sharpness and gloss, improved scratch resistance, and improved adhesion and drying unevenness after processing. It is to provide a silver halide photographic light-sensitive material.

[0024]

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

(1). A silver halide having at least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride on one side of a reflection support having a resin coating layer on both sides of a base paper. In the photographic light-sensitive material, the reflective support is a composition in which a white pigment is mixed and dispersed in a water resistant resin containing polyester as a main component,
A reflective support comprising a substrate and at least a silver halide emulsion coating side surface thereof, wherein the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [P-I], and The content of the surfactant represented by the following general formula [SI] is such that the silver halide photographic light-sensitive material 1
A silver halide photographic light-sensitive material characterized in that it is from 0.05 g to 0.3 g per m ² .

[0026]

Embedded image

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₈ ,
R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group or an aryl group. R ₆ and R ₁₂ are each an alkyl group, an aryl group, or - represents an (R _{7) p} -A. R ₇ represents a divalent linking group. A represents an aryl group, an epoxy group, a fluorine-modified group or a cyano group. l, m and n each represent an integer of 0 to 200, and p represents an integer of 0 or 1. ]

[0028]

Embedded image

[In the formula, R represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group, and the total number of carbon atoms contained in R is 8 to 36. L represents a divalent linking group, and n is 0 or an integer of 1 to 10. M ⁺ represents a hydrogen cation or a cation. (2). A silver halide having at least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride on one side of a reflection support having a resin coating layer on both sides of a base paper. In a photographic light-sensitive material, the reflective support is coated with a composition prepared by mixing and dispersing a white pigment in an electron beam curable resin on at least a surface of a substrate on which a silver halide emulsion is coated, and then irradiating with an electron beam for curing and coating. A reflective support, wherein the silver halide photographic light-sensitive material contains at least one compound represented by the general formula [P-I] and contains a surfactant represented by the general formula [S-I]. The content is 1 m ^{2 of the} silver halide photographic light-sensitive material.
The silver halide photographic light-sensitive material is characterized in that it is 0.05 g or more and 0.3 g or less.

(3). The silver halide photographic light-sensitive material described in (1), wherein the silver halide photographic light-sensitive material contains at least one betaine surfactant.

(4). The silver halide photographic light-sensitive material according to (2), wherein the silver halide photographic light-sensitive material contains at least one betaine-based surfactant.

The present invention will be described in detail below.

The halogen composition of the silver halide grains according to the present invention is based on silver chlorobromide containing 95% or more of all silver halides constituting the silver halide grains and containing substantially no silver iodide. Need to be The preferred halogen composition of the silver halide grains is 97 mol% or more, more preferably 98 to 99.99, of the total silver halide constituting the silver halide.
Mol% is silver chloride.

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

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

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

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

In order to contain a heavy metal ion in the silver halide emulsion according to the present invention, the heavy metal compound is added to the physical layer before the formation of silver halide grains, during the formation of silver halide grains and after the formation of silver halide grains. It may be added at any place during each step during aging. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, a heavy metal compound can be dissolved together with a halide salt and continuously added during the whole or part of the grain forming process.

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

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756 and 4,225,666;
JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39.
(1973), etc., particles having an octahedral, tetradecahedral, dodecahedral shape or the like can be prepared and used. Further, particles having a twin plane may be used.

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

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

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

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

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

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

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

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

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

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

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

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

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

As the gold sensitizer according to the present invention, 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, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide.
It is preferably molar. More preferably, 1 × 10 ⁻⁵
Mol to 1 × 10 ⁻⁸ mol.

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

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

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

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

Further, the support may be blended with additives such as sizing agents, fixing agents, tension enhancers, densities, antistatic agents, dyes and antifoggants, which are generally used in papermaking, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

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

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

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

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

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

Preferred dibasic acids are terephthalic acid, isophthalic acid, 4-metal sulfo-2,6-naphthalenedicarboxylic acid, 5-metal sulfo-isophthalic acid and 4-dicarboxylic acid.
Metal sulfo-2,6-naphthalenedicarboxylic acid or the like is used, and as glycols, ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol,
Polyethylene glycol (number average molecular weight 300 to 30,
000) and the like are used.

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

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

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

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

The modified polyester resin useful in the present invention can be synthesized by a conventionally known polyester production method. For example, in the esterification reaction, either a method of directly esterifying an acid component with a glycol component or a method of esterifying an acid component as a dimethyl ester with glycol by a transesterification method can be used. At this time, if necessary, a polyester can be polymerized and synthesized by using a transesterification reaction catalyst for the esterification and a polymerization reaction catalyst such as antimony oxide in the polymerization reaction.
Regarding the polyester components and the synthetic method described above, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pages 103 to 136, or "Synthetic Polymer V" (Asakura Shoten) , 1971) No. 187-
The description on page 286 can be referred to.

The specific method for synthesizing the modified polyester is as follows:
U.S. Pat. No. 4,217,441, JP-A-5-21011
The modified polyesters described in No. 9 and useful in the present invention can be synthesized by these methods.

Polyesters (including modified polyesters) useful in the present invention should have sufficiently high molecular weights. Generally, the molecular weight of a polymer compound such as polyester is expressed as an intrinsic viscosity (for example, edited by the Chemical Society of Japan,
Standard Chemistry Dictionary, page 24, 1991, published by Maruzen)
The intrinsic viscosity of the polyester used in the present invention is 0.50.
The above is necessary, preferably 0.53 or more, particularly preferably 0.55 or more. When the intrinsic viscosity of the polyester is less than the above, the resin becomes white and becomes brittle after melt extrusion. Also, if melt extrusion is performed with water contained, the intrinsic viscosity will drop extremely, so special care must be taken when drying before melting, and even if the intrinsic viscosity is sufficiently high, hydrolysis may occur during melting. is there. Drying of resin chips is 10
^It is usually performed under a vacuum of about ^-3 Torr at about 150 ° C.

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

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

The titanium dioxide may be either anatase type or rutile type, but 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 used in one layer of the multilayer resin coating layer and the other layer. Rutile type titanium dioxide may be used for this.

The titanium dioxide to be used is generally surface-treated with an inorganic substance such as aluminum oxide 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 resin containing the polyester resin as a main component may be from 0 to 60% by weight, but 10% by weight or more is preferable, preferably 15% by weight, more preferably 20% by weight. % By weight. When the content of the white pigment is less than 10% by weight, the sharpness of the obtained photographic image on the photographic paper is not sufficient, and the content is 6%.
When it exceeds 0% by weight, the coating property of the obtained polyester resin is severely deteriorated and it cannot be put to practical use.

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

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

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

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

The water-resistant resin containing polyester as a main component according to the present invention contains a trace amount of a bluing agent such as ultramarine blue, an oil-soluble dye or red to adjust the spectral reflection density balance of a white background and improve whiteness. It is preferable to add a seasoning agent.

In the present invention, the electron beam curable resin is a resin curable by electron beam irradiation.

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. In the present invention, compounds that can be cured by electron beam irradiation that can be used include, for example, JP-B-60-17104 and JP-A-60-1.
The electron beam-curable compounds described in JP-A No. 26649 or JP-A No. 2-157747 and the like include electron beam-curable monomers and oligomers.

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 1 is used as a monomer used by diluting the above curable monomer.
An unsaturated compound having at least a carbon-carbon double bond in the molecule (for example, a monofunctional acrylic monomer, a methacrylic monomer, a vinyl monomer, etc.) is used. Examples of the acrylic and methacrylic oligomers include polyurethane acrylate ester or methacrylic acid ester, polyether alcohol acrylate ester or methacrylic acid ester, bisphenol A acrylate ester or methacrylic acid ester, polyester maleate ester or Examples thereof include fumaric acid ester. Further, as the polyfunctional acrylic monomer and the methacrylic monomer, 1,6-hexanediol diacrylate, neopentyl diacrylate,
Diethylene glycol diacrylate, butadiene acrylate, diethylene glycol dimethacrylate, etraethylene glycol diacrylate, glycerol trimethacrylate, stearyl acrylate, polyethylene glycol diacrylate, butoxyethyl acrylate, 1,4-butanediol diacrylate, 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, trimethylolpropane triacrylate, trimethylolpropane triacrylate, propylene oxide modified trimethylolpropane Examples thereof include polyacrylate, glycyl methacrylate, 1,3-bis (N, N-diepoxypropylaminomethyl) cyclohexane, trimethylolpropane triacrylate, pentaerythritol pentaacrylate and the like. Examples of monofunctional acrylic and methacrylic monomers and vinyl monomers include styrene, N-vinylpyrrolidone, acrylic acid esters of polyoxyethylene phenyl alcohol, and 2-ethylhexyl acrylate.

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

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

The titanium dioxide used is generally surface-treated with an inorganic substance such as aluminum oxide hydroxide or silicon oxide 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 is
Any amount of 0 to 70% by weight may be used, but 10% by weight or more is preferable, 15% by weight is more preferable, and 2 is more preferable.
0% by weight. The content of the white pigment is less than 10% by weight, the sharpness of the photographic image on the photographic paper obtained is not sufficient, and when the content exceeds 70% by weight, the flexibility of the cured resin coating layer obtained is Property is deteriorated and film cracking occurs.

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

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 or the like can be used. .

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

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

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

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

To the electron beam curable resin relating to the present invention, a slight amount of a bluing agent or a reddishing agent such as ultramarine or an oil-soluble dye is added in order to adjust the spectral reflection density balance of a white background and improve the whiteness. Preferably.

The compound represented by the general formula [P-I] according to the present invention will be described.

[0099]

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[In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₈ and
R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group or an aryl group. R ₆ and R ₁₂ are each an alkyl group, an aryl group, or - represents an (R _{7) p} -A.
R ₇ represents a divalent linking group. A represents an aryl group, an epoxy group, a fluorine-modified group or a cyano group. l, m and n each represent an integer of 0 to 200, and p is 0 or 1.
Represents the integer. ] In the general formula [P-I], R ₁ , R ₂ , R ₃ , R ₄ ,
Examples of the alkyl group represented by R ₅ , R ₈ , R ₉ , R ₁₀ and R ₁₁ include a methyl group and an ethyl group.
Examples of the aryl group include a phenyl group.

The alkyl group represented by R ₆ and R ₁₂ is, for example, a methyl group, an ethyl group or the like, the aryl group is, for example, a phenyl group or the like, and-(R ₇ ) _p —A is, for example, R ₇ The divalent linking group represented is preferably an alkylene group (eg, monomethylene group, dimethylene group, trimethylene group, etc.), an arylene group (eg, phenylene group, etc.), and more preferably carbon. An alkylene group having 2 to 4 atoms is preferable.

Examples of the aryl group represented by A include a phenyl group. Examples of the epoxy group include ethylene oxide group (epoxyethyl group), trimethylene oxide group (1,3-epoxypropyl group),
Examples thereof include a methylethylene oxide group (1,2-epoxypropyl group), and a particularly preferable epoxy group is an ethylene oxide group (epoxyethyl group). Examples of the fluorine-modified group include a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group and the like, and a particularly preferable fluorine-modified group is a trifluoromethyl group.

L, m, and n are integers of 0 to 200, and p is an integer of 0 or 1.

The typical examples of the compounds represented by formula (P-I) according to the present invention are shown below, but the present invention is not limited thereto.

[0105]

[Chemical 6]

[0106]

[Chemical 7]

[0107]

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[0108]

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[0109]

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[0110]

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[0111]

[Chemical 12]

The process for producing the compound represented by the general formula [P-I] according to the present invention is described in, for example, EG Loco (E.G.
Rochou) “Chemistry of the Silicone (Chapman & Hall 1951 Edition)”
Pages 66-70, "Processing and Application of Silicones" (Kansai Plastics Research Group, 1954), page 26, F.G.
A. Stone and F.A. Graham (W.A. Graha)
m) by "Inorganic Polymers" (Academic Press 1962), pages 230-231, 288-29.
In addition to being described on page 5, etc., Japanese Examined Patent Publication No. 35-10771
No. 43-28694, No. 45-14898, etc., or a method by addition reaction of olefins to siloxane containing SiH by a metal catalyst as described in JP-B-36-22361. It can be synthesized by applying such a method by cohydrolysis of each component organofluorosilane. In addition, a part of the compound represented by the general formula [P-I] according to the present invention can be obtained by using Petrarch Systems.
ns) as well as domestic products such as Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Silicone Co., Ltd., and Toshiba Silicone Co., Ltd., and can be easily obtained.

The viscosity of the compound represented by the general formula [P-I] according to the present invention is preferably such that the viscosity measured at 25 ° C. by a rotational viscometer is about 10 to 100,000 centimeter stroke.

In order to incorporate the compound represented by the general formula [P-I] according to the present invention into the photographic constituent layers, the method of adding it to the coating solution in advance and the compound represented by the general formula [P-I] There is a method such as overcoating or permeating with, but the former is preferable in terms of manufacturing cost. The method of adding to the coating solution is to disperse in water or a hydrophilic colloid solution represented by the general formula [P-I] in the presence of a dispersant, for example, a gelatin solution, and further add a desired photograph. There are a method of adding to a coating solution for coating, a method of dispersing in a gelatin solution for photography in the presence of a dispersant, and coating as it is.

As the dispersant, a surfactant usually used for photography can be used. For example, it is appropriately selected from anionic surfactants, nonionic surfactants or cationic surfactants. Any thing can be used.

As a dispersion method, an ultrasonic homogenizer or a valve homogenizer can be used.

At the time of dispersion, a low boiling point solvent such as ethyl acetate, methanol or acetone, or tricresyl phosphate or the like is often used in order to facilitate the dispersion and control the dispersed particle size. A high boiling point solvent may be used.

The preferable particle size of the compound represented by the general formula [P-I] according to the present invention in a dispersed state is 0.1 to 0.1.
Used with a particle size of 10 μm. If the particle size is too small, the effects of the present invention, in particular, the effect on the slip property and scratch resistance, cannot be seen.

The refractive index of the compound represented by the general formula [P-I] according to the present invention is not particularly limited, but it is usually suitable that the measured value at 25 ° C. is about 1.320 to 1.685. Yes, preferably 1.35 measured at 25 ° C
Those in the range of 0 or more and 1.540 or less are effective.
If the refractive index is smaller than 1.320 or larger than 1.685, the transparency of the applied photographic light-sensitive material, especially the dried photographic light-sensitive material after photographic processing, is affected. May be affected.

The amount of the compound represented by the general formula [P-I] according to the present invention is preferably 0.001 g or more and 0.050 g or less, and 0.003 g or more per 1 m ^{2 of the} silver halide photographic light-sensitive material. It is more preferably 0.020 g or less. When it is 0.001 g or less, the effect of the present invention is slightly reduced, and when it is 0.050 g or more, it becomes disadvantageous in terms of cost.

In the present invention, the photographic constituent layers constituting the silver halide photographic light-sensitive material include a silver halide emulsion layer and non-photosensitive layers such as a protective layer, an intermediate layer, an antihalation layer and a back coat layer. Say.

The compound represented by the general formula [P-I] according to the present invention may be used in any of the photographic constitutional layers, but in particular, it is the outermost protective layer or the backside outermost layer. The effect of the present invention is remarkable when it is used for the coat layer, which is preferable.

The surfactant represented by the general formula [SI] according to the present invention will be described.

[0124]

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[In the formula, R represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group, and the total number of carbon atoms contained in R is 8 to 36. L represents a divalent linking group, and n is 0 or an integer of 1 to 10. M ⁺ represents a hydrogen cation or a cation. In the formula [S-I], L is a divalent or trivalent linking group, but n is an integer of 0 or 1 to 10, L is _{- (OCH 2 CH 2) m} -, - (OCH ₂ CH (CH ₃ )) _{m
-, - (O (CH 3} ) CH 2) m - when n = m in, m is 1
It is preferably 10 to 10, and particularly preferably m is 1 to 5. In the case of n = 1, L is ^{-O -, - (R 1)} p H
_{^{C = CH (R 2) q}} -, - OOCCH 2 CH (-) COO
^{-, - CONR 3 (R 4} ) r -, - SO 2 NR 5 (R 6) s -
Etc. are preferred, -OOCCH ₂ CH (-) COO-
The linking group of is preferred. In this case, p, q, r and s are 0 or 1, and R ¹ , R ² , R ⁴ and R ⁵ have 2 to 1 carbon atoms.
A linear or branched alkylene group having 2 carbon atoms and R ³ is preferably an alkyl group having 1 to 12 carbon atoms.

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

Specific examples of the surfactant represented by the general formula [SI] are shown below, but the invention is not limited thereto.

[0128]

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[0129]

[Chemical 15]

The surface active agent represented by the general formula [SI] has a coating amount of 0.3 g or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material, but preferably 0.05 to 0.25 g / m ^2.
It is in the range of m ² .

If the amount of the surfactant represented by the general formula [SI] exceeds 0.3 g / m ² in the light-sensitive material, the sharpness and gloss will be deteriorated, and no improvement in adhesiveness will be observed. 0
If it is less than 5 g / m ² , applicability is significantly deteriorated, oil-soluble components such as couplers and high-boiling organic solvents are likely to precipitate, sharpness is deteriorated, and drying unevenness is a serious problem. Comes out.

The surfactant represented by the general formula [SI] according to the present invention is a dispersant when an oil-soluble photographically useful substance such as a coupler is dispersedly added to a silver halide emulsion layer or a non-photosensitive layer. Or as a coating aid in the case of coating on a support.

A method for reducing the content of the surfactant represented by the general formula [SI] according to the present invention is described in JP-B-52-129136 and JP-A-29-3537. As described in JP-A-57-53227 and JP-A-57-78038, or by using the phase inversion method.
The surfactant in the hydrophilic colloid layer can be reduced by an improved rolling method for increasing the dispersion efficiency as disclosed in Nos. 3227 and 57-94746. In addition, there is also a method of combining a method of removing excess surfactant after emulsification and dispersion.

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

[0135]

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[0136]

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[0137]

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

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

The silver halide photographic light-sensitive material of the present invention is preferably used as a printing material. In a print material using the silver halide photographic light-sensitive material of the present invention,
The effect of the present invention is great in printing when printing is performed at a magnification of 20 or more in terms of area ratio from a negative film, and a clear difference from the silver halide photographic light-sensitive material other than the present invention can be obtained.

A printing light-sensitive material using the silver halide photographic light-sensitive material of the present invention is disclosed in JP-A-4-62543.
When the color negative film having the transparent magnetic recording layer described in JP-A No. 1993-242242 is used, the effect of the present invention is great, and a clear difference from the silver halide photographic light-sensitive material outside the present invention can be obtained.

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

The amount of these dyes added is 680 nm for an untreated sample of a light-sensitive material for the purpose of improving sharpness.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

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

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

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

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

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

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

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

As magenta couplers which can be preferably used in the silver halide photographic light-sensitive material of the present invention, the general formulas (MI) and (M-I) described in the upper right column of page 4 of JP-A-4-114154 are disclosed. The coupler represented by II) can be mentioned. Specific compounds are described in the same specification on page 4, lower left column to page 5, upper right column MC-1 to MC-.
Those listed as 11 can be mentioned.
More preferable among the above-mentioned magenta couplers are couplers represented by the general formula (M-I) described in the upper right column of page 4 of the specification of the same publication, and among them, the above-mentioned general formula (M-
A coupler in which RM of I) is a tertiary alkyl group is particularly preferable because it has excellent light resistance. MC-8 to MC-11 described in the upper column on page 5 of the publication are excellent in reproducing colors from blue to purple and red, and are also excellent in detail delineation power, and thus are preferable.

A yellow coupler which can be preferably used in the silver halide photographic light-sensitive material of the present invention is represented by the general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. A coupler can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column of page 3 of the same publication. Among them, a coupler in which RY1 of the general formula [Y-1] in the specification of the publication is an alkoxy group or a coupler represented by the general formula [I] described in the specification of JP-A-6-67388 can reproduce a preferable yellow color tone. preferable. Of these, particularly preferred examples of compounds are described in JP-A-4-114154, page 4, lower left column, YC-8, YC-9, and JP-A-6-67388, pages 13-14. N
o. Compounds represented by (1) to (47) can be mentioned. The most preferable compound is JP-A-4-818.
A compound represented by the general formula [Y-1] described on page 1 of Japanese Patent Publication No. 47 and page 11 to 17 of the same Japanese Patent Publication.

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

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

Preferred compounds as the surfactant used for dispersing the photographic additives and adjusting the surface tension at the time of coating include the surfactant represented by the above general formula [S-1] and the alkyl group. A surfactant in which a fluorine atom is substituted is included.

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 general formulas I and II described on page 3 of JP-A-2-66541 and general formula IIIB described in JP-A-3-174150.
A phenolic compound represented by JP-A 64-9044
Amine compounds represented by the general formula A described in JP-A No. 5-5, and general formulas XII and XII described in JP-A-62-182741.
The metal complexes represented by I, XIV and XV are particularly preferable for the magenta dye. Further, the compound represented by the general formula I ′ described in JP-A-1-196049 and JP-A-5-114
The compound represented by the general formula II described in JP-A No. 17 is particularly preferable for yellow and cyan dyes.

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

In the silver halide light-sensitive material of the present invention, a compound which reacts with an oxidized product of a developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer. It is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkylhydroquinone such as 2,5-di-t-octylhydroquinone. A particularly preferable compound is the compound represented by the general formula II described in JP-A No. 4-133056, and the specifications 13 to 1 of the same publication.
Compounds II-1 to II-14 described on page 4 and compound 1 described on page 17 can be mentioned.

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

In the silver halide photographic light-sensitive material of the present invention,
It is advantageous to use gelatin as the binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, homopolymers or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used.

As the hardener for these binders, it is preferable to use a vinyl sulfone type hardener, a chlorotriazine type hardener or a carboxy-active type hardener alone or in combination. JP-A-61-249054 and 61-245
It is preferable to use the compound described in JP-A-153-153. Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria which adversely affect photographic performance and image storability. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the surface of the photosensitive material or the processed sample.

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

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

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

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

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

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

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

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is preferably 40 seconds or less, more preferably 25 seconds or less.

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

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

[0172]

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

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

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

Next, a polyethylene composition (density 0.92 g / cc, MI
(5.0 g / 10 min) 85 wt% and titanium oxide white pigment (anatase type) 15 wt% after kneading
Was coated with a water-resistant resin layer of 30 g / m ² by melt-extrusion lamination to prepare a paper support having a resin coating layer on both sides.

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

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

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

Next, on the surface on which the silver halide emulsion was coated, a polyethylene terephthalate composition (with an intrinsic viscosity of 0.
72 wt% of 72 cc / g) and 28 wt% of titanium oxide white pigment (anatase type) are kneaded, and then melt extruded at 300 ° C. and laminated with a water-resistant resin layer of 30 g / m ² by resin coating on both sides. A paper support with layers was made.

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

Next, the following modified polyester resin was prepared.

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

75% by weight of this modified polyester, oxidized
Knead 25% by weight of titanium white pigment (anatase type)
30g by melt extrusion lamination after heating
/ M ²Of water resistant resin layer, and resin coating layer on both sides
Was prepared.

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

Next, the following resin layers were coated on the side coated with the silver halide emulsion.

90% by weight of the polyethylene terephthalate composition (intrinsic viscosity 0.72 cc / g) as the inner resin layer,
1% by kneading 10% by weight of titanium oxide white pigment (anatase type) and then melt extrusion laminating at 300 ° C.
A water-resistant resin layer of 5 g / m ² was coated on the surface of the white base paper on which the silver halide emulsion was coated.

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

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

Next, each of the following various photographic constituent layers was coated on Support A having a gelatin subbing layer to prepare a multilayer color photographic paper sample 101 having the following layer structure. The coating solution was prepared as follows.

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

Coating solution for first layer 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), 3.34 of (ST-2)
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 (DN)
60 ml of ethyl acetate was added to 1.67 g of P) to dissolve it, and this solution was dissolved in the surfactant S-3 represented by the general formula [SI].
Was dispersed in 220 ml of 10% aqueous gelatin solution containing 7 ml of 20% aqueous solution of E. coli using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

Each of the coating liquids for the second to seventh layers was 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.

In Sample 101, the surfactants S-3 and S-9 represented by the general formula [SI] as the emulsifying dispersant for the coating aid and the oil-soluble substance such as the coupler are contained in the first layer to the first layer. It was appropriately used for the seventh layer, and the total amount was added as shown in Table 3.

Further, as a hardener (H-1), (H-2)
Was added. The total amount of F-1 in each layer is 0.04 g / m
^It was added to be ² .

[0195]

[Table 1]

[0196]

[Table 2]

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-tetradecyl Hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone Image stabilizer A: P -T-octylphenol

[0198]

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[0199]

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[0200]

[Chemical 21]

[0201]

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[0202]

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

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

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

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stable Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing dye BS-1 4 × 10 ^-4 mol / mol AgX sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion) Preparation) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, average particle size 0.5
A monodisperse cubic emulsion EMP-2B having a thickness of 0 μm, a coefficient of variation 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 (Preparation of red-sensitive silver halide emulsion) (Solution A) and (Solution B)
The average particle diameter was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

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

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

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[0212]

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Next, for the sample 101, the type of support is shown in Table 3,
4, the type of surfactant represented by the general formula [SI] used as an emulsifying dispersant for oil-soluble substances such as coating aids and couplers, and total addition of the first to seventh layers. The amount was added as shown in Tables 3 and 4, and dimethylpolysiloxane P-a (comparative compound) shown below as an oil-soluble compound or a compound represented by the general formula [SI] was added to the seventh layer. An emulsified dispersion of the compound according to the invention (the emulsified dispersion is shown below) was added as shown in Tables 3 and 4 so that the amount added as an oil-soluble compound would be 15 mg / m ^2, and further added to the present invention. Sample 10 except that the betaine-based surfactant was added to the seventh layer of the sample at 20 mg / m ² as shown in Tables 3 and 4.
Samples 102 to 120 were prepared in the same manner as 1.

[0214]

[Chemical formula 26]

<< Emulsion Dispersion Method of Dimethylpolysiloxane S-a or Compound Represented by General Formula [P-I] >> (Liquid A) Dimethylpolysiloxane S-a or General Formula [P-I] Compound 100 g Ethyl acetate 200 ml (solution B) Gelatin 50 g Di (2-ethylhexyl) sulphosuccinate-sodium salt (1% aqueous solution) 300 ml Water 300 ml (solution A) and (solution B) under incubation at 40 ° C. After dissolution, (B solution) was added to (A solution) and mixed and stirred, and then emulsified and dispersed by an ultrasonic homogenizer to adjust the particle size of the emulsified dispersed particles to 0.2 μm. The method of measuring the emulsified and dispersed particles here can be easily measured by a method well known in the art. After the completion of the emulsification and dispersion, water was added to the emulsified dispersion to make up to 1000 ml. At this time, before finishing by adding water, a means for completely evaporating the ethyl acetate in the emulsified dispersion may be used, or it may be used separately.

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

<< Evaluation of Sharpness >> A resolution test chart was printed on each sample with red light, and the following development processing steps were carried out. Then, the obtained cyan image was recorded on a microdensitometer PDM-5D (Konica Corp.). Manufactured)
The value shown by the following formula was defined as the sharpness.

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

<< Surface Gloss >> The sample exposed to white light was subjected to the following development processing, and the surface of the obtained black sample was visually evaluated.

⊚: Very good gloss ○: Good gloss and acceptable as a product Δ: Gloss looks slightly inferior, but acceptable as a product ×: Poor gloss, unfavorable as a product XX: Unsatisfactory as a product because of extremely poor gloss << Evaluation of scratch resistance >>
After conditioning the humidity at 55 ° C. and 55% RH for 2 hours, the sample was set on a Haydon scratch strength tester type 18 (manufactured by Shinto Scientific Co., Ltd.), and a 0.1 mmR diamond needle was placed vertically on the emulsion side of the sample. A continuous load of 0 to 100 g was applied, and the load (g) applied when scratches began to occur on the sample surface was measured by a specified method to evaluate scratch resistance. The larger the value, the better the scratch resistance.

<< Adhesion Test of Sample Surface >> A sample exposed to white light was subjected to the following development processing steps, and the obtained black sample was conditioned at a temperature of 25 ° C. and a humidity of 55% RH for 2 hours, and then,
The sample is cut into 3.5 cm × 12 cm and the emulsion surfaces are superposed and the samples are bundled. After fixing it with cellophane tape, it was left under conditions of a temperature of 40 ° C. and a humidity of 80% RH for 24 hours, and then peeled off, and the degree of adhesion on the emulsion side was evaluated in the following four stages.

A: No adhesion has occurred B: Adhesion area is 1 to 10%, no resistance to peeling between samples C: Adhesion area is 10 to 20%, peeling occurs when peeling between samples There is sound and resistance to peeling D ... Adhesion area is 20 to 50%, image surface is damaged when peeling between samples E ... Adhesion area is 50% or more, peeling between samples The image forming layer is destroyed and the image surface is significantly impaired. << Dry unevenness >> A sample exposed to white light is subjected to the same development processing step except that the drying processing temperature in the following development processing step is set to 50 to 55 ° C. The obtained black background sample was visually observed, and the degree of unevenness in drying was evaluated according to the following four grades from the flicker of the glossy surface and the degree of deterioration.

⊚: No drying unevenness was observed at all ◯: Drying unevenness was slightly seen, but acceptable as a product Δ: Drying unevenness was observed, which is not preferable as a product ×: Irregular drying unevenness was observed, and not acceptable as a product << Development processing step> Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 cc Bleach fixing 35.0 ± 0.5 ° C. 45 seconds 120 cc Stabilization 30 to 34 ° C. 60 seconds 150 cc Dry 60 to 80 ° C., 30 seconds The composition of the development processing solution is shown below.

Color developer tank solution and replenisher tank solution replenisher pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine penta Sodium acetate salt 2.0 g 2.0 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to bring the total volume to 1 liter, and the tank liquid had pH. = 10.10, the replenisher has pH = 10.60.

Bleach-fixing solution tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 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 obtained results are shown in Tables 3 and 4.

[0228]

[Table 3]

[0229]

[Table 4]

From Tables 3 and 4, the samples according to the present invention have rapid processability, are excellent in sharpness and gloss, have improved scratch resistance, and have no problem in adhesion and drying unevenness after processing. I understand.

Particularly, it can be seen that the samples using the betaine activator according to the present invention have improved adhesiveness and drying unevenness after the treatment without any problem, and the effect of the present invention is remarkably large.

Example 2 A color negative film (F-1) having a transparent magnetic recording layer described in JP-A-4-62543 and having a support composed of polyethylene terephthalate and polyethylene-2,6-naphthalate. A color negative film (F-
The same multi-group scene was photographed using 2), and using the frames of this scene, the photosensitive material prepared in Example 1 was print-baked using an automatic printer and the printed sample was visually inspected after development. Observation and evaluation was performed. as a result,
It was found that when the color negative film (F-1) was used, the print quality using the sample of the present invention was particularly good.

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

Example 3 135 format (area per screen 8.4 cm ² ).
Of the same multi-person scene using the color negative film (F-3) of No. ^{2 and} the color negative film (F-4) having an area of 4 cm ² per screen, and using the frames of this scene, Example 1 The E plate print was printed on the light-sensitive material prepared in 1. using an automatic printer, and after development, the print sample was visually observed and evaluated.

As a result, in the prints using the samples other than those of the present invention, when F-4 was used for the negative film, the sharpness was conspicuously deteriorated, and the deterioration of the graininess was recognized. The print using is sufficiently sharp even if F-4, which has a small negative film size, is used.
The gloss was outstanding and the graininess was good.

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

Example 4 << Preparation of Support >> White base paper (50 g of basis weight: 175 g / gram)
m ² and thickness 180 μm), a polyethylene composition (density 0.95 g / cc, MI 8.0 g / 10 min) was extrusion-coated on one surface to form a back laminate layer of 25 g / m ² , and a sheet-like substrate was formed. Manufactured.

Next, a white pigment-containing resin layer made of water resistant titanium oxide having the following composition was provided on the surface not back-laminated to obtain supports F, G, H, I and J.

<Support F> Polyethylene composition (density 0.92 g / cc, melt index (MI) 5.0)
g / 10 minutes) and 18% by weight of anatase type titanium oxide were added, and after kneading, a 30 g / m ² water resistant resin layer was applied on the surface of the sheet-like substrate by melt extrusion coating. The surface of the cooling roller used for cooling the molten polyethylene was smooth.

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

Dipentaerythritol hexaacrylate 65% by weight Titanium oxide (rutile type) 35% by weight A mixture of the above components was dispersed in a ball mill for 20 hours.

The composition thus obtained was applied onto the surface of the sheet-like substrate so that the coating amount after curing would be 10 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate at an accelerating voltage of 175 KV and an absorbed dose of 2 Mrad to cure the resin and form a surface resin coating layer.

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

Urethane acrylate oligomer 25% by weight Diethylene glycol diacrylate 25% by weight Anatase type titanium oxide 50% by weight A mixture of the above components was dispersed by a ball mill for 20 hours.

The composition thus obtained was applied onto the surface of the sheet-like substrate so that the coating amount after curing would be 25 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate at an accelerating voltage of 175 KV and an absorbed dose of 2 Mrad to cure the resin and form a surface resin coating layer.

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

Polyester acrylate 20% by weight Hexanediol diacrylate 20% by weight Trimethylolpropane triacrylate 15% by weight Anatase type titanium oxide 45% by weight A mixture of the above components was dispersed by a ball mill for 20 hours.

The composition thus obtained was applied onto the surface of the sheet-like substrate so that the coating amount after curing was 25 g / m ² . Next, an electron beam was irradiated from the back surface of the sheet-shaped substrate at an accelerating voltage of 175 KV and an absorbed dose of 2 Mrad to cure the resin and form a surface resin coating layer.

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

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

Urethane acrylate oligomer 25% by weight Acrylate monomer 25% by weight Anatase type titanium oxide 50% by weight A mixture of the above components was dispersed in a ball mill for 20 hours.

The composition thus obtained was coated on the inner resin layer so that the coating amount after curing was 25 g / m ² . Then, from the back surface of the sheet-like substrate, acceleration voltage: 15
An intermediate resin layer was formed by irradiating an electron beam at 0 KV under the condition of absorbed dose: 2 Mrad to cure the resin.

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

Dipentaerythritol hexaacrylate 80% by weight Anatase type titanium oxide 20% by weight The composition thus obtained was used as an outer resin layer on the surface of the middle resin layer, and the coating amount after curing was 5 g / m 2. ^It was applied so as to be ² . Next, an electron beam was irradiated from the back surface of the sheet-like substrate at an accelerating voltage of 200 KV and an absorbed dose of 2 Mrad to cure the resin and form a resin coating layer.

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

Then, various photographic constituent layers were coated on the support F provided with the gelatin subbing layer in the same manner as in Example 1 to prepare a multilayer color photographic paper 401. The coating liquid was prepared in the same manner as in Example 1.

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

Next, with respect to the sample 401, as shown in Tables 5 and 6, the support species, the surfactant species represented by the general formula [SI] and the amount of the surfactant added were changed, and In the seventh layer, the dimethylpolysiloxane P- as an oil-soluble compound
a or an emulsified dispersion of the compound represented by the general formula [P-I] (the emulsified dispersion is as described above) is shown in Tables 5 and 6 so that the added amount as an oil-soluble compound is 15 mg / m ^2. And the betaine-based surfactant according to the present invention was added to the seventh layer of the sample at 20 mg /
Samples 402 to 420 were prepared by adding m ² .

Each sample thus prepared was evaluated in the same manner as in Example 1.

The obtained results are shown in Tables 5 and 6.

[0261]

[Table 5]

[0262]

[Table 6]

From Tables 5 and 6, the samples according to the present invention have rapid processability, are excellent in sharpness and gloss, have improved scratch resistance, and have no problem in adhesion and drying unevenness after processing. I understand.

Especially, it can be seen that the samples using the betaine activator according to the present invention are improved in adhesion and drying unevenness after the treatment without any problem, and the effect of the present invention is remarkably large.

Example 5 A color negative film (F-1) having a transparent magnetic recording layer described in JP-A-4-62543 and having a support composed of polyethylene terephthalate and polyethylene-2,6-naphthalate, A color negative film (F-
2) is used to photograph the same group scene of a large number of people, and using the frames of this scene, the photosensitive material prepared in Example 4 is printed with an automatic printer, and the printed sample is visually inspected after development. Observation and evaluation was performed. as a result,
It was found that when the color negative film (F-1) was used, the print quality using the sample of the present invention was particularly good.

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

Example 6 135 format (area per screen 8.4 cm ² ).
Of the same group of people using the color negative film (F-3) of No. 4 and the color negative film (F-4) having an area of 4 cm ² per screen, and using the frames of this scene, Example 4 The E plate print was printed on the light-sensitive material prepared in 1. using an automatic printer, and after development, the print sample was visually observed and evaluated.

As a result, in the prints using the samples other than those of the present invention, when F-4 was used as the negative film, the sharpness was conspicuously deteriorated and the deterioration of the graininess was recognized, whereas the samples of the present invention were observed. The print using is sufficiently sharp even if F-4, which has a small negative film size, is used.
The gloss was outstanding and the graininess was good.

Therefore, when the negative film having a small screen size is used for the sample of the present invention, a print having a high quality image can be provided and the effect of the present invention can be more effectively exhibited. Example 7 The processes changed as follows in Examples 1 and 4 were performed.

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

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

Bleach-fixing solution Tank solution and replenishing solution Tank solution Replenishing solution Diethylenetriamine pentaacetic acid Ammonium dihydrate 100 g 50 g Diethylenetriamine pentaacetic acid 3 g 3 g Ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto- 1,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml 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 solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was carried out in the same manner as in Examples 1 and 4, and it was confirmed that the effects of the present invention were effectively obtained.

Example 8 In Example 7, as an automatic processor, N manufactured by Konica Corporation was used.
PS-868J, ECOJET-P as processing chemical
Was used according to the process name CPK-2-J1. Evaluations were made in the same manner as in Examples 1 and 4, and it was confirmed that the effects of the present invention were obtained.

[0276]

According to the present invention, the silver halide has good rapid processability, is excellent in glossiness and sharpness, has improved scratch resistance, and has no problem of adhesion after processing and uneven drying. A photographic light-sensitive material is obtained.

Claims (4)

[Claims] 1. At least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride on one side of a reflective support having a resin coating layer on both sides of a base paper. In a silver halide photographic light-sensitive material having, the reflective support is coated with a composition in which a white pigment is mixed and dispersed in a water-resistant resin containing polyester as a main component, and at least the surface of the substrate on which the silver halide emulsion is coated is coated. A reflective support, wherein the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [P-I] and is a surfactant represented by the following general formula [SI]. A silver halide photographic light-sensitive material having a content of 0.05 g or more and 0.3 g or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. Embedded image [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₈ , R ₉ , R ₁₀ and R ₁₁ each represent a hydrogen atom, an alkyl group or an aryl group. R ₆ and R ₁₂ are each an alkyl group,
Aryl group, or - represents an (R _{7) p} -A. R ₇ represents a divalent linking group. A represents an aryl group, an epoxy group, a fluorine-modified group or a cyano group. l, m and n each represent an integer of 0 to 200, and p represents an integer of 0 or 1. ] [Chemical 2] [In the formula, R represents an alkyl group, an aryl group, an aralkyl group or an alkenyl group, and the total number of carbon atoms contained in R is 8 to 36. L represents a divalent linking group, and n is 0 or an integer of 1 to 10. M ⁺ represents a hydrogen cation or a cation. ] 2. At least one silver halide emulsion layer containing a silver halide emulsion containing at least 95 mol% of silver chloride on one side of a reflection support having resin coating layers on both sides of a base paper. In a silver halide photographic light-sensitive material having a composition, the reflective support is coated with a composition in which a white pigment is mixed and dispersed in an electron beam curable resin, and the composition is coated on at least the surface of the substrate on which the silver halide emulsion is coated and then irradiated with an electron beam. It is a reflection support which is hardened and coated, wherein the silver halide photographic light-sensitive material contains at least one compound represented by the general formula [P-I] and is represented by the general formula [SI]. The silver halide photographic light-sensitive material is characterized in that the content of the surface active agent is 0.05 g or more and 0.3 g or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains at least one betaine-based surfactant. 4. The silver halide photographic light-sensitive material according to claim 2, wherein the silver halide photographic light-sensitive material contains at least one betaine-based surfactant.