JPH095924A - Silver halide photographic sensitive material and color image forming method - Google Patents

Abstract

PURPOSE: To provide a halide photographic sensitive material prevented from the occurrence of fog or the like even when pressure is applied in the case of a reflective type photosensitive material high in sharpness and sensitivity in the photosensitive material high in silver chloride content and capable of providing a photograph by rapid processing. CONSTITUTION: The silver halide photographic sensitive material has at least one photosensitive layer containing silver halide emulsion grains on a reflective support, and a waterresistant resin film on the side of the reflective support coated with the photosensitive layer contains a white pigment in an amount of >=2g/m<2> , and the silver halide grains contained in the photosensitive silver halide emulsion layer are silver chloride or silver chlorobromide having a silver chloride content of >=95mol% and having been ripened in the presence of at least one kind of nonunstable Se compound and a nucleophilic agent for promoting decomposition of this Se compound.

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 to a silver halide photographic light-sensitive material having excellent sharpness and suppressing fog caused when pressure is applied to the light-sensitive material. This is a color image forming method.

[0002]

2. Description of the Related Art With the advent of the multimedia age, various types of systems for making hard copies of electronic images have been developed. A popular method is a method using a non-photosensitive recording material such as an ink jet method, and an image obtained by these methods is apparently inexpensive per sheet. However, this cannot be said to be the case when comparing images using photographic light-sensitive materials and image quality (for example, per recording capacity). Therefore, the use of silver halide photographic light-sensitive materials as not only photographic print materials but also hard copy materials for electronic images has come into consideration. Under these circumstances, in order to further highlight the characteristics of silver halide photographic light-sensitive materials, sharpness and color reproducibility are improved to achieve higher image quality, and the processing time and processing method are improved to simplify processing. Researches such as imparting swiftness are being actively conducted. With regard to simple and rapid processing, advances in simple and rapid development processing represented by a minilab system have made it possible to supply printed images of extremely high image quality relatively easily in a short time and at low cost. Further, by using a silver halide emulsion having a high silver chloride content, the processing time has been greatly shortened and the processing fluctuation has been improved.

Various methods are conventionally known as means for improving the sharpness of a silver halide photographic light-sensitive material having a reflective support. As the method, 1) prevention of irradiation by using a water-soluble raw material. 2) Prevention of halation by colloidal silver, mordant dye, solid fine particle dye, etc. 3) Increasing the filling rate of the white pigment in the paper support laminate resin, or newly coating the support with a white pigment as a gelatin dispersion to prevent the penetration of light into the support.

It has been disclosed in JP-A-3-156452 that the sharpness is greatly improved by increasing the content of the white pigment in the water-resistant resin coating layer on the photosensitive layer coating side on the reflective support. There is. Further, JP-A-4-256948 and the like disclose a reflective support having two or more polyolefin layers having different white pigment contents. However, when pressure such as scratching is applied to a photosensitive material using a support in which the content ratio of the white pigment in the water-resistant resin coating layer is further increased, a new problem that fogging is likely to occur at a position where the pressure is applied There has occurred. Moreover, it has been found that this problem is greater in silver halide emulsion grains having a very high silver chloride content.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity silver chloride photographic material capable of rapid processing even when pressure is applied to a reflective type photographic material which has excellent sharpness and high sensitivity. It is an object to provide a photographic light-sensitive material that does not cause fogging at a low price, and to provide a color image forming method that uses the photographic light-sensitive material to quickly provide a high-quality photograph.

The above objects of the present invention have been achieved by the following silver halide photographic light-sensitive material and color image forming method. (1) In a silver halide photographic light-sensitive material having at least one layer containing a photosensitive silver halide emulsion grain on a reflective support, in the water-resistant resin coating on the side of the reflective support where the photosensitive layer is coated, The white pigment is contained in an amount of ² g / m ² or more, and the silver halide emulsion grains contained in the photosensitive silver halide emulsion layer have silver chloride or chlorobromide having an average silver chloride content of 95 mol% or more. A silver halide photographic light-sensitive material, which is silver and is aged in the presence of at least one non-unstable Se compound and a nucleophile that promotes decomposition of the non-unstable Se compound. (2) A silver halide color obtained by coating a photographic constituent layer containing at least three kinds of silver halide emulsion layers having different color sensitivities each containing a coupler capable of coloring yellow, magenta or cyan on a reflective support. In the photographic light-sensitive material, the water-resistant resin coating on the light-sensitive layer coating side of the reflective support contains a white pigment in an amount of 2 g / m ² or more, and is contained in at least one of the silver halide emulsion layers. The silver halide emulsion grains have an average silver chloride content of 95 mol%.
The above halogenated silver chloride or silver chlorobromide, which is aged in the presence of at least one non-unstable Se compound and a nucleophile that promotes the decomposition of the non-unstable Se compound. Silver photographic light-sensitive material. (3) The silver halide photographic light-sensitive material according to item (1) or (2), wherein the nucleophile is represented by the following general formula (I).

[0007]

Embedded image

In the formula, R ¹ is a hydrogen atom or an alkyl group, m is 0 or 1, Z is a condensed benzene ring when m is 1 and R ² is bonded to this, and m is 0 ² is bonded to the 4- or 5-position of the thiazolium ring, R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, or an electron-withdrawing group, and n is 2
In the above case, plural R ² may be the same or different,
In addition, R ^2's may be linked to each other to form a condensation space. R
³ is a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, X ⁻ is an anion, n is 0 or 1 to 3, and is represented by the general formula (I)
A compound in which the thiazolium ring is opened may be as follows.

[0009]

Embedded image

(4) The silver halide emulsion grains are grains having a silver bromide localized phase on the surface (1)
The silver halide photographic light-sensitive material according to any one of the above-mentioned items. (5) A color image forming method, which comprises exposing the silver halide photographic light-sensitive material according to any one of items (1) to (4) by a scanning exposure method, and then performing color development processing. (6) The silver halide photographic light-sensitive material described in any one of (1) to (4) is color-developed in 25 seconds or less, and the total processing time from the color-developing processing to the drying is 12
A color image forming method, characterized in that processing is performed in 0 second or less. (7) The silver halide photographic light-sensitive material is color-developed in 25 seconds or less, and the total processing time from color development to drying is 120 seconds or less. Color image forming method.

Hereinafter, the present invention will be described in detail. The reflective support of the present invention is required to contain a white pigment in an amount of 2 g / m ² or more in the water resistant resin coating layer on the photosensitive layer coating side of the reflective support. If this content is less than 2 g / m ² , sharpness is greatly deteriorated and the object of the present invention cannot be achieved. The content of the white pigment is more preferably 3.0 g / m ² or more, still more preferably 4.0 g / m ² or more. The upper limit is not particularly limited, but 30 g / m ² or less is preferable from the viewpoint of cost.

The white pigment mixed and dispersed in the water resistant resin includes inorganic materials such as titanium dioxide, barium sulfate, lithopone, aluminum oxide, calcium carbonate, silicon oxide, antimony trioxide, titanium phosphate, zinc oxide, lead white, zirconium oxide and the like. Examples thereof include pigments, polystyrene, and organic fine powders such as styrene-divinylbenzene copolymer. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be either rutile type or anatase type, but anatase type is preferred when whiteness is prioritized, and rutile type is preferred when sharpness is prioritized. Anatase type and rutile type may be blended and used in consideration of both whiteness and sharpness. Furthermore, when the waterproof resin layer is composed of multiple layers, an anatase type is used for a certain layer,
A method of using a rutile type for the other layers is also preferable. Further, these titanium dioxides may be produced by either the sulfate method or the chloride method.
Specific product names include titanium industry KA-10 and KA-
20, Ishihara Sangyo A-220 and the like.

The titanium dioxide used generally has a surface-treated surface with an inorganic substance such as aluminum hydroxide or silicon hydroxide, a polyhydric alcohol or a polyamine in order to suppress the activity of the titanium dioxide and prevent yellowing. It is preferable to use those which have been surface-treated with an organic substance such as metal soap, alkyl titanate and polysiloxane, and those which have been surface-treated in combination with an inorganic / organic treating agent. When used, the amount of the surface-treating substance is 0.2 wt% to 2.0 wt% for the inorganic substance and 0.1 wt% for the organic substance, based on titanium dioxide.
~ 1.0% by weight is preferred. The average particle size of titanium dioxide used is preferably 0.1 to 0.8 μm. 0.1 μm
If it is less than the above range, it is difficult to uniformly mix and disperse in the resin, which is not preferable. If it exceeds 0.8 μm, sufficient whiteness cannot be obtained, and projections are formed on the coated surface, which adversely affects the image quality.

In the present invention, it is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of the particles, and the size of the distribution is the occupation area ratio of the fine particles projected on a unit area. (%) (Ri) can be measured and obtained. The coefficient of variation of the occupied area ratio (%) is
Ratio s / of standard deviation s of Ri to average value (R) of Ri
It can be calculated by R. In the present invention, the variation coefficient of the occupied area ratio (%) of the fine particles of the white pigment is 0.1.
It is preferably 5 or less, more preferably 0.12 or less. Especially 0.08
The following is preferred.

The water-resistant resin of the reflective support used in the present invention has a water absorption rate (% by weight) of 0.5 or less, preferably 0.
Resins of 1 or less, for example, polyolefins such as polyethylene, polypropylene, polyethylene-based polymers, vinyl polymers and their copolymers (polystyrene, polyacrylates and their copolymers), polyesters (polyethylene terephthalate, polyethylene isophthalate, etc.)
And its copolymers. Particularly preferred are polyethylene and polyester. As the polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and a blend of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) of these polyethylene resins before processing is shown in Table 1 of JISK 7210.
The value measured under the condition 4 of 1.2 g / 10 min to 12 g /
A range of 10 minutes is preferred. The MFR of the polyolefin resin before processing refers to the MFR of the resin before kneading a bluing agent and a white pigment.

The polyester is preferably a polyester synthesized by condensation polymerization from a dicarboxylic acid and a diol, and preferable dicarboxylic acids include terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Preferred diols include ethylene glycol, butylene glycol, neopentyl glycol, triethylene glycol, butanediol, hexylene glycol, bisphenol A ethylene oxide adduct (2,2-bis (4- (2-hydroxyethyloxy)
Phenyl) propane), 1,4-dihydroxymethylcyclohexane and the like. Various polyesters obtained by condensation polymerization of these dicarboxylic acids alone or in mixtures with diols alone or in mixtures can be used. Among them, at least one of the dicarboxylic acids is preferably terephthalic acid. A mixture of terephthalic acid and isophthalic acid (molar ratio 9: 1 to 2: 8) or a mixture of terephthalic acid and naphthalenedicarboxylic acid (molar ratio 9: 1 to 2: 8) is also preferably used. As the diol, it is preferable to use ethylene glycol or a mixed diol containing ethylene glycol. The molecular weight of these polymers is preferably from 30,000 to 50,000.

It is also preferable to use a mixture of a plurality of these polyesters having different compositions. Further, mixtures of these polyesters with other resins can also be preferably used. As other resins to be mixed, polyethylene, polyolefins such as polypropylene, polyethylene glycol, polyoxymethylene, polyethers such as polyoxypropylene, polyester-based polyurethane, polyether polyurethane, polycarbonate,
Any resin that can be extruded at 270 to 350 ° C., such as polystyrene, can be widely selected. These resins may be used alone or in combination of two or more. For example, 6% by weight of polyethylene and 4% by weight of polypropylene can be mixed with 90% by weight of polyethylene terephthalate. The mixing ratio between polyester and other resin varies depending on the type of resin to be mixed, but for polyolefins, the weight ratio of polyester / other resin = 1.
00/0 to 80/20 is appropriate. If it exceeds this range, the physical properties of the mixed resin are sharply reduced. In the case of resin other than polyolefin, polyester / other resin = 1 by weight ratio
It can be mixed in the range of 00/0 to 50/50.

The weight ratio of the water resistant resin to the white pigment is 98/2 to 30/70 (water resistant resin / white pigment), preferably 95/5 to 50/50, particularly preferably 90/10. It is 60/40. 2% by weight of white pigment
If it is less than 70%, the contribution to the whiteness is insufficient. If it exceeds 70% by weight, the surface smoothness of the photographic support is insufficient, and a photographic support having excellent gloss is obtained. Can not. These water-resistant resin layers are 2 to 200
It is preferably coated on the substrate with a thickness of μm, more preferably 5 to 80 μm. If the thickness is more than 200 μm, the brittleness of the resin will be emphasized, causing problems such as cracking. If the thickness is less than 2 μm, the waterproofness, which is the original purpose of the coating, is impaired, and the whiteness and the surface smoothness cannot be simultaneously satisfied, and the physical properties become too soft, which is not preferable. The thickness of the resin or resin composition coated on the surface of the substrate other than the photosensitive layer application surface is 5 to 100.
μm is preferable, and more preferably 10 to 50 μm. If the thickness exceeds this range, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. If the ratio is less than the above range, the waterproof property, which is the original purpose of the coating, is impaired and the physical properties become too soft, which is not preferable.

In the reflective support of the present invention, the water-resistant resin coating layer on the side coated with the photosensitive layer is a reflective support comprising two or more water-resistant resin coating layers having different white pigment contents. In some cases, it is more preferable from the viewpoints of cost, suitability for producing the support, and the like. In this case, among the water-resistant resin coating layers having different white pigment contents, the content of the white pigment of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above the layer. It is preferably lower than the content of the white pigment. In a further preferred embodiment,
Among the water resistant resin coating layers having different white pigment contents, the reflective support having the highest white pigment content in the water resistant resin coating layer closest to the photosensitive layer, or the water resistant resin having at least three reflective support layers Reflection with the highest content of white pigment in any layer between the water-resistant resin coating layer closest to the photosensitive layer and the water-resistant resin coating layer closest to the substrate. A support is mentioned.

The content of the white pigment in each layer of the multilayer waterproof resin layer is 0% by weight to 70% by weight, preferably 0% by weight.
-50% by weight, more preferably 0-40% by weight. The content of the layer having the highest white pigment content in the multilayer water-resistant resin layer is 9% by weight to 70% by weight, preferably 15% by weight to 50% by weight, more preferably 20% by weight to 40% by weight. It is. When the content of the white pigment in the layer having the highest content of the white pigment is less than 9% by weight, the sharpness of the image is low, and when it exceeds 70% by weight, the melt-extruded film is cracked. Further, the thickness of each layer of the multilayer waterproof resin layer is preferably 0.5 μm to 50 μm. For example, 2
In the case of a multilayer waterproof resin layer having a layer structure, the thickness of each layer is 0.5.
μm to 50 μm is preferable, and the combined total film thickness is preferably within the above range (2 to 200 μm).
In the case of a three-layer structure, the thickness of the uppermost layer is 0.5 μm to 10 μm
m, the thickness of the intermediate layer is preferably 5 μm to 50 μm, and the thickness of the lower layer (the layer closest to the substrate) is preferably 0.5 to 10 μm. When the film thickness of the uppermost layer and the lowermost layer is 0.5 μm or less, die lip streaks are likely to occur due to the action of the highly filled white pigment in the intermediate layer. On the other hand, when the thickness of the uppermost layer and the lowermost layer, particularly the uppermost layer, is 10 μm or more, the sharpness is likely to decrease.

The water-resistant resin and the white pigment are mixed with each other by adding a metal salt of higher fatty acid, higher fatty acid ethyl ester, higher fatty acid amide,
A higher fatty acid or the like is used as a dispersion aid and kneaded into the resin with a kneader such as a two-roll, three-roll, kneader or Banbury mixer. The dispersion aid is generally about 0.5 to 10% by weight with respect to the white pigment. An antioxidant may be contained in the resin layer, and the content is preferably 50 to 1000 ppm with respect to the resin.

Further, it is preferable that the waterproof resin layer contains a bluing agent. As the bluing agent, generally known ultramarine blue, cobalt blue, cobalt oxide phosphate, quinacridone pigments and the like and mixtures thereof are used.
The particle size of the bluing agent is not particularly limited, but the particle size of a commercially available bluing agent is usually about 0.3 μm to 10 μm, and if the particle size is within this range, there is no particular problem in use.
When the water-resistant resin layer of the reflective support used in the present invention has a multilayer structure, the content of the bluing agent in the water-resistant resin layer, the content in the uppermost water-resistant resin layer, the content of the lower layer The above is preferable. The content of the preferable bluing agent is 0.2% by weight to 0.5% by weight in the uppermost layer and 0 to 0.45% by weight in the lower layer. The bluing agent is kneaded into the waterproof resin with a kneading machine such as a two-roll, three-roll, kneader, Banbury mixer. At this time, a white pigment can be kneaded together,
In order to help disperse the bluing agent, a low molecular weight water resistant resin, a metal salt of a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid or the like can be used as a dispersing aid.

The method for forming the water-resistant resin layer in the present invention includes paper as a running substrate, base paper such as synthetic paper, polyester film such as polyethylene terephthalate and polybutylene terephthalate, cellulose triacetate film, polystyrene film, polypropylene film. Pellets containing the above-mentioned white pigment and / or bluing agent, which have been melted by heating, are melted on a polyolefin film, such as Polyolefin film, etc., and if necessary, diluted with a heat resistant resin and melted, and a sequential laminating method is used. Or a foot block type, a multi-manifold type, or a multi-layer extrusion die of multi-slot type. The shape of the multilayer extrusion die is generally a T die, a coat hanger die or the like, and is not particularly limited. The outlet temperature of the water-resistant resin during heat-melt extrusion is usually 270 ° C.
-350 degreeC, Especially preferably, it is 300-330 degreeC. Further, it is preferable to perform activation treatment such as corona discharge treatment, flame treatment and glow discharge treatment on the substrate before coating the substrate with the resin.

The uppermost surface of the water-resistant resin layer on the side on which the emulsion is coated can be imprinted with a glossy surface, or a fine surface, a matte surface or a silk surface as described in JP-A-55-26507. The back surface can be applied with a matte surface. The surface of the water resistant resin is preferably subjected to activation treatment such as corona discharge treatment, flame treatment and plasma treatment. After the activation treatment, a subbing treatment as described in JP-A-61-84643 is performed. Preferably. It is also preferable to apply an undercoat liquid containing the compound represented by the general formula [U] on the surface of the water resistant resin.

[0025]

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The coating amount of the compound represented by the general formula [U] is preferably 0.1 mg / m ² or more, more preferably 1 mg / m ^2.
As described above, the most preferable amount is 3 mg / m ² or more, and the larger the amount is, the stronger the adhesion can be strengthened, but excessive use is disadvantageous in cost. Further, it is preferable to add alcohols such as methanol in order to improve the suitability for coating the undercoat liquid on the resin surface. In this case, the proportion of alcohols is preferably 20% by weight or more, more preferably 40% by weight or more, and most preferably 60% by weight or more. Further, in order to further improve the coating suitability, anionic, cationic, amphoteric, nonionic, fluorocarbon based,
It is preferable to use various surfactants such as organic silicon type.

Further, it is preferable to add a water-soluble polymer such as gelatin in order to obtain a good surface condition of the undercoat. Considering the stability of the compound of general formula [U], the pH of the liquid is
4 to pH 11 is preferable, and more preferably pH 5 to p.
It is H10. Before applying the undercoating liquid, it is more preferable to subject the surface of the water resistant resin to the surface activation treatment as described above. In applying the undercoat liquid, a generally well-known coating method such as a gravure coater, a bar coater, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a doctor coating method or an extrusion coating method is used. It can be applied. The coating drying rate is preferably 30 ° C to 100 ° C, more preferably 50 ° C to 100 ° C, and most preferably 70 ° C to 100 ° C. The upper limit is determined from the heat resistance of the resin, and the lower limit is determined from the productivity efficiency.

The substrate used for the reflective support of the present invention is
Natural pulp paper mainly made of natural pulp, mixed paper made of natural pulp and synthetic fiber, synthetic fiber paper mainly made of synthetic fiber, so-called synthetic paper made by synthesizing synthetic resin film such as polystyrene and polypropylene Polyester film such as polyethylene terephthalate or polybutylene terephthalate, plastic film such as cellulose triacetate film, polystyrene film, polyolefin film such as polypropylene film, etc. may be used, but natural pulp paper is used as the base of the waterproof resin for photography. (Hereinafter simply referred to as base paper) is particularly preferably and advantageously used. Chemicals to be added to the base paper include clay, talc, calcium carbonate, fillers such as urea resin fine particles, rosin, alkyl ketene dimer, higher fatty acid, epoxidized fatty acid amide, paraffin wax, alkenyl succinic acid and the like size, starch, polyamide Those to which a paper strengthening agent such as polyamine epichlorohydrin and polyacrylamide, a sulfuric acid band, a fixing agent such as a cationic polymer and the like are added are used. In addition, if necessary, a dye, a fluorescent dye, a slime control agent, an antifoaming agent, and the like are added.
Moreover, the following softening agents can be added as needed.

Regarding the softening agent, for example, New Paper Processing Handbook (edited by Shiyaku Times Co .; 1980), pages 554 to 5
There is a description on page 55. Particularly, those having a molecular weight of 200 or more are preferable. That is, having a hydrophobic group having 10 or more carbon atoms,
It also has an amine salt or quaternary ammonium salt that self-fixes with cellulose. Specifically, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine, a reaction product of a higher fatty acid and a polyalkylene polyamine, a reaction product of a urethane alcohol and an alkylating agent, a quaternary ammonium salt of a higher fatty acid, etc. However, a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine and a reaction product of a urethane alcohol and an alkylating agent are particularly preferable.

The pulp surface can be surface-sized with a film-forming polymer such as gelatin, starch, carboxymethyl cellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol. In this case, examples of the modified polyvinyl alcohol include a modified carboxyl group, a modified silanol, and a copolymer with acrylamide. The coating amount of the film-forming polymer in the case of surface sizing treatment with a film-forming ^{polymer, 0.1g / m 2 ~5.0g / m} 2, is preferably 0.5g / m ² ~2.0g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, a defoaming agent, etc. can be added to the film-forming polymer at this time, if necessary.

The base paper is prepared by making a pulp slurry containing the above-mentioned pulp and optionally added fillers, sizing agents, paper-strengthening agents, fixing agents, etc., with a paper machine such as a Fourdrinier paper machine and drying it. Manufactured by winding. Either before or after this drying, the surface sizing is performed,
Further, it is preferable that calendering is performed after drying and before winding. When the surface sizing treatment is performed after drying, this calendering treatment can be carried out either before or after the surface sizing treatment, but it is preferable to carry out the calendering treatment in the final finishing step after various treatments have been carried out. . In the calendering process, known metal rolls and elastic rolls used for ordinary paper production are used.

The thickness of the base paper of the support used in the present invention is not particularly limited, but the basis weight is 50 g.
/ M ^{2 to} 250 g / m ² as the thickness is 50 μm to 25
0 μm is desirable. The backing layer used in the present invention may be coated with various back coat layers for the purpose of preventing electrification and curling. Also, the back coat layer is Japanese Patent Publication No.
18020, Japanese Patent Publication No. 57-9059, Japanese Patent Publication No. 57-
53940, JP-B-58-56859, JP-A-59.
-214849, JP-A-58-184144 and the like, or examples of inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments,
Surfactants and the like can be contained in appropriate combination.

As the photographic support, one having excellent smoothness on the surface coated with the photosensitive layer is preferable. This "smoothness" is
The surface roughness of the support is expressed as a scale. The surface roughness of the support of the present invention will be described. The center line average surface roughness is used as the surface roughness. The centerline average surface roughness is defined as follows. From the roughness curved surface, a portion having an area SM is extracted on the center plane, the orthogonal coordinate axes, the X axis, and the Y axis are placed on the center line of the extracted portion, and the axis orthogonal to the center line is placed on the Z axis. The value given by the formula is defined as the center line average surface roughness (SRa),
It is expressed in μm.

[0034]

[Equation 1]

The value of the average surface roughness of the center line and the height of the protrusion from the center line is, for example, using a three-dimensional surface roughness measuring device (SE-30H) manufactured by Kosaka Laboratory Ltd. It can be determined by measuring an area of 5 mm ² with a cutoff value of 0.8 mm, a horizontal magnification of 20 times, and a height magnification of 2000 times with a needle. Further, the feeding speed of the measuring needle at this time is preferably about 0.5 mm / sec. A support having a value obtained by this measurement of 0.15 μm or less is preferable, and 0.10 μm or less is more preferable. By using a support having such surface roughness (smoothness),
A print having a surface with excellent smoothness can be obtained.

The constitution of the light-sensitive material of the present invention can be applied to various silver halide photographic light-sensitive materials using a reflective support. For example, the color light-sensitive material using the present invention,
At least one yellow coloring silver halide emulsion layer, at least one magenta coloring silver halide emulsion layer, and at least one cyan coloring silver halide emulsion layer can be coated on the reflective support. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the above-mentioned color forming layers, and the above-mentioned order on the reflective support. Can be applied by coating. In the case of reversal color paper, the silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color forming layers described above, and the red-sensitive layer and the green-sensitive layer are formed on the support. The layers are formed by coating in this order, the blue-sensitive layer. However, the order may be different.
In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used. Further, each of these photosensitive layers may be provided in plural layers. Further, between the photosensitive layer of these photosensitive materials and the support, or between the photosensitive layers and the upper layer of the photosensitive layer (the layer farthest from the support), color mixing prevention, irradiation / halation prevention, an optical filter, A non-photosensitive layer is provided for various purposes such as protection of the photosensitive layer. In the case of black-and-white photographic printing paper, at least one silver halide emulsion layer spectrally sensitized or not spectrally sensitized in the panchromatic or ortho region is coated on the support.

In the silver halide photographic light-sensitive material of the present invention, silver chloride or silver chlorobromide containing 95 mol% or more of silver chloride is used as the silver halide grains. Especially,
In order to shorten the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any portion of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition in the inside or the surface of the particle (in the case of being on the surface of the particle, the edge of the particle, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content, and more preferably more than 20 mol%. The silver bromide content of the silver bromide localized phase is analyzed using an X-ray diffraction method (for example, described in “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) and the like. can do. And these localized phases are inside the particle, at the edge of the particle surface,
Although it can be on a corner or on a plane, one preferred example is one that is epitaxially grown at the corner of a grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, a substantially pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in photographic emulsions is regular (regu- lar) such as cubic, tetradecahedral or octahedral.
It is possible to use those having a lar) crystal form, those having an irregular crystal form such as spheres and plates, or those having a composite form thereof. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected areas exceed 50% of all grains can be preferably used.

The silver salt (bromide) bromide emulsion used in the present invention is P.Gl.
afkides, Chimie et Phisique Photographique (Paul
Montel, 1967), Photographi by GFDuffin
c Emulsion Chemistry (Focal Press, 1966
Year), Making and Coating Phot by VLZelikman et al
It can be prepared using a method described in, for example, ographic Emulsion (Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains different metal ions or complex ions thereof. Preferred metals are selected from metal ions or metal complexes belonging to Groups VIII and IIb of the periodic table, lead ions and thallium ions. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. In particular, the iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
The silver halide grains of the present invention may be dissolved in an aqueous halide solution, an aqueous silver salt solution or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. Include in the localized phase and / or other particle parts (substrates). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

Ripening of silver halide emulsion grains used in the present invention is carried out by adding a non-unstable Se compound and a nucleophile to the silver halide emulsion, and preferably at 40 ° C. to 60 ° C. (30 to 90 minutes) by stirring. The non-labile Se compound and the nucleophile are preferably added separately, but may be added simultaneously and / or in advance as a mixture. The non-unstable Se compound is preferably added after the emulsion has been washed with water, desalted, and redispersed in an aqueous gelatin solution. The nucleophile is preferably added after the non-unstable Se compound is added. Examples of the non-labile selenium compound used in the present invention include JP-B-46-4553 and JP-B-52.
The compounds described in JP-A-34492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound include selenious acid; selenocyanates such as potassium selenocyanate and sodium selenocyanate; heterocycles such as selenazoles and selenadiazoles; quaternary salts of selenazoles; diaryl selenide; Examples thereof include selenoethers such as diaryl diselenide, dialkyl selenide and dialkyl diselenide, diselenides; 2-selenazolidinedione, 2-selenooxazolidinethione and derivatives thereof. Among these, potassium selenocyanate is particularly preferable.

The amount of the non-labile selenium compound used depends on the type of the non-labile selenium compound used, silver halide grains (halogen type and content, grain size, crystal form, etc.),
Although it varies depending on the chemical ripening conditions and the like, it is generally 10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to 10 mol per mol of silver halide.
^-4 mol.

As the nucleophile used in the present invention, Nuc
leophilicity (JM Harrise
t al, Advances in Chemistr
y series (1987)), Introducti
on to Organic Chemistry
(A. Streetwieser et al, Mac
-Millan, New York (1976)),
J. Am. Chem. Soc. , 90 , 319, (19
Known compounds described in 68) and the like are used. Examples of the nucleophile used in the present invention include sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, and sodium hydrogen sulfite; mercaptos such as thiosalicylic acid, thioglycolic acid, cysteine, thiolactic acid, and 2-mercaptobenzothiazole. Triphenylphosphine,
Phosphines such as tributylphosphine; 3-methylbenzothiazolium iodide, 3-allylthiazolium bromide, 2-hydroxymethyl-3-ethylbenzothiazolium iodide, 2-hydroxymethyl-3-
Thiazolium salts showing nucleophilicity by ring opening such as methylbenzothiazolium iodide, 3- (2-propenyl) benzothiazolium bromide, and 3- (2-propargyl) benzothiazolium bromide; ethanesulfinic acid Sulfinic acids such as sodium and sodium benzenesulfinate; Thiosulfonic acids such as methanethiosulfonic acid and benzenethiosulfonic acid; Hydrazines such as methylhydrazine and phenylhydrazine; Ethanolamine,
Amines such as ethylenediamine; Hydroxamic acids; N
And hydroxylamines such as methylhydroxylamine. Among these, thiazolium salts and mercaptos are preferable, and thiazolium salts represented by the above general formula (I) are particularly preferable.

The compound of the general formula (I) is described in detail below. The groups represented by R ^{1 to} R ³ in formula (I) may each further have a substituent. Where:
The alkyl group represented by R ¹ preferably has 1 to 6 carbon atoms.
(The above-mentioned substituents are not included in this carbon number), and examples thereof include a methyl group and a propyl group. Where:
The alkyl group, alkenyl group, alkynyl group and alkoxy group represented by R ² also preferably have 1 to 6 carbon atoms (the carbon number does not include the above substituents).
For example, methyl group, ethyl group, hexyl group, allyl group,
Examples include propargyl group and methoxy group. Examples of the group capable of substituting for R ¹ and R ² include a hydroxyl group, a carboxyl group, an amino group, a carbamoyl group, a sulfamoyl group and a halogen atom.

In the formula, the electron-withdrawing group represented by R ² is a halogen atom (for example, Cl), a carboxyl group, a trifluoromethyl group, a cyano group, a nitro group, or -S.
O ₂ R ⁴ sulfonyl group, —SO ₂ NHR ⁴ aminosulfonyl group, —CONHR ⁴ aminocarbonyl group, and —
There is an acyl group of COR ⁴ (R ⁴ represents a hydrogen atom, a lower alkyl (preferably having a carbon number of 1 to 4) or a phenyl group). When a plurality of R ^2's are linked to each other to form a condensed ring, for example, the general formula (I) is naphthothiazonium.

Examples of the alkyl group, alkenyl group, alkylnyl group and aralkyl group represented by R ³ include, for example,
Examples thereof include methyl group, propyl group, butyl group, hexyl group, allyl group, bropargyl group and benzyl group. These groups may further have a substituent. Examples of the group substituting these, sulfonic group, hydroxyl group, optionally substituted amino group, a halogen atom, -SO ₂ R ^4, -
_{^{SO 2 NHR 4, -NHSO 2 R}} 4, -CONHR 4,
^{-NHCOR 4, -COR 4, -COOR 4} (R 4 is as defined above), or a Hajime Tamaki (e.g., a pyrimidine group, a pyridine group, etc. furan), and the like. Examples of the anion represented by X ⁻ include a halide ion, a nitrate ion, a phosphate ion, a chlorate ion, or an anion derived from an organic acid, such as a formate (formate) ion, an acetate (acetic acid) ion or p. -Toluene sulfonate (PTS) ions. However, when R ^{1 to} R ³ have an anionic group, X
^- is not required. The thiazolium ring of the compound of the general formula (I) can be opened, and the ring-opened form may be used. In the compound of general formula (I), R ¹ is preferably a hydrogen atom. More preferably, m is 1
And R ¹ is a hydrogen atom. The following compounds may be mentioned as specific examples of the general formula (I).

[0049]

[Chemical 6]

[0050]

[Chemical 7]

[0051]

Embedded image

[0052]

Embedded image

The amount of the compound of the general formula (I) added may be appropriately adjusted according to the silver halide used and the timing of addition, but generally 10 ^-6 to 10 ^-10 mol per mol of silver halide.
^-1 mol, preferably 5 × 10 ^{-6 to} 5 × 10 ^-2 mol may be used. As an addition method, it can be dissolved in water or an organic solvent miscible with water (for example, methanol), or can be added to the emulsion in the form of being finely dispersed in a gelatin solution or the like.

In the silver halide emulsion used in the present invention, in addition to ripening with a non-labile Se compound and a nucleophile, chemical sensitization using other chalcogen sensitizers (specifically, unstable sulfur is used). Sulfur sensitization typified by the addition of a compound, selenium sensitization by the Se compound, tellurium sensitization by the Te compound can be mentioned.), Noble metal sensitization typified by gold sensitization, or reduction sensitization, alone or in combination. You may use together. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is preferably a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

The silver halide emulsion used in the present invention is usually spectrally sensitized. Spectral sensitization is performed for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include those described by FM Harmer in Heterocyclic comp.
ounds-Cyanine dyes andrelated compounds (John Wile
y & Sons [New York, London] 1964). Specific examples of compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-215.
Those described in the right upper column of page 22 to page 38 of Japanese Patent No. 272 are preferably used. In particular, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, spectral sensitizing dyes described in JP-A-3-123340 are useful in terms of stability, adsorption strength, and exposure temperature. It is very preferable from the viewpoint of dependence and the like.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, EP-0,420,011
No. 4, page 21 line to page 6, line 54, EP-0,420,012
No. 4, page 12, line 10 to page 33, EP-0,443,46
The sensitizing dyes described in US Pat. No. 6, US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089 and the like, an acid or a base is allowed to coexist to prepare an aqueous solution, and as described in U.S. Pat. No. 3,822,135 and U.S. Pat. It may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having spectral sensitization sensitivity from the red region to the infrared region is used, the compounds described in JP-A-2-157747, page 13, lower right column to page 22, lower right column may be used in combination. preferable. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of from 0.5 × 10 ^-5 mol to 5.0 per mol of silver halide.
× 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 5.0.
An amount of × 10 ^-3 mol is used, and is 0.1 to 10,000 times, preferably 0.5 to 500 times per mol of the sensitizing dye.
There is an advantageous amount used in the range of 0 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser and a nonlinear optical crystal. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the laser oscillation wavelength, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable, and compact, at least two layers preferably have a spectral sensitivity maximum at 670 nm or more. This is because the currently available, inexpensive and stable III-V semiconductor laser has an emission wavelength range only from the red to the infrared region. However, at the laboratory level, oscillations of II-VI group semiconductor lasers in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated. In such a case, it is less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. The exposure time is preferably defined as ^10-4 seconds or less, and more preferably ^10-6 seconds or less, when the pixel density is defined as 400 dpi and the pixel size is defined as the exposure time.

In the light-sensitive material according to the present invention, it is preferable to color the hydrophilic colloid layer for the purpose of preventing irradiation or halation and improving safety of safelight. European patent EP as water-soluble dye that can be used
There are dyes which can be decolorized by treatment (among others, oxonol dyes and cyanine dyes) described on pages 27 to 76 of the specification of 0337490A2. Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. Examples of dyes that can be used without deteriorating color separation include water-soluble dyes described in European Patents EP0539978A1, JP-A-5-127325 and JP-A-5-127324, and it may be preferable to use them in combination. . In such coloring, the coloring substance diffuses regardless of the position of the addition layer of the coloring substance and spreads over the entire photosensitive material constituting layer. This coloring density is 0.2 or more, preferably 0.3 or more, and more preferably 0.5 or more at the maximum light amount wavelength of the light source to be exposed.

In the present invention, instead of the above water-soluble dye or in combination with the water-soluble dye, a colored layer which can be decolorized by treatment is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below the emulsion layer (on the side of the support) that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. It is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection densities of these colored layers are in the wavelength range used for exposure (4 for ordinary printer exposure).
The optical density value at a wavelength having the highest optical density in the visible light region of 00 nm to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure) is preferably 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Application Laid-Open No. 2-282244-3
Dyes described from the upper right column of the page to page 8 and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing on fine particles such as silver and fixing in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing a fine powder of a dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pp. 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. The preparation method of colloidal silver as a light absorber is described in U.S. Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Also, Japanese Patent Application Laid-Open No. 5-134
It is also preferable to use thin tabular colloidal silver particles having a thickness of up to 20 nm described in JP-A-358. Among these methods, a method of incorporating a fine powder dye, a method of using colloidal silver, and the like are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 ppm
It is preferable to use low calcium gelatin of 200 ppm or less, more preferably below. In order to prevent various fungi and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add a fungicide as described in JP-A-63-271247.

When exposing the light-sensitive material of the present invention to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to a conventional color developing treatment, but in the case of the color light-sensitive material of the present invention, it is preferable to carry out bleach-fixing treatment after color development for the purpose of rapid processing. Especially when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fixing solution is about 6.
It is preferably 5 or less, more preferably about 6 or less.

Silver halide emulsions and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material according to the present invention, and a processing method applied for processing the light-sensitive material. As the treatment additives, those described in the following patent publications, particularly European Patent EP0,355,660A2 (JP-A-2-139544) are preferably used.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

Cyan, magenta, or yellow couplers are impregnated into rollable latex polymers (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the table above. It is preferable that the water-insoluble and organic solvent-soluble polymer is very dissolved and emulsified and dispersed in the hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 007.
Homopolymers or copolymers described on pages 12 to 30 of the specification of JP-A No. 23 are mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, particularly acrylamide-based polymer, from the viewpoint of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
A compound chemically bonded to the compound in the above-mentioned patent specification which produces a substantially colorless compound and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment It is possible to use the compounds in the above-mentioned patent specification, which form an inactive and substantially colorless compound, simultaneously or alone, for example, the reaction of the coupler with the residual color developing agent in the film or its oxidant and the coupler during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of the coloring pigment.

Further, as a cyan coupler, there is disclosed in JP-A-2-
In addition to the diphenylimidazole-based cyan coupler described in Japanese Patent No. 33144, European Patent EP 0333185A2.
3-hydroxypyridine type cyan couplers described in the above specification (in particular, the couplers listed as specific examples (4
(2) 4-equivalent couplers having a chlorine-releasing group to make them 2-equivalent, and couplers (6) and (9) are particularly preferable)
And cyclic active methylene cyan couplers described in JP-A-64-32260 (particularly, coupler examples 3, 8, and 34 listed as specific examples), and pyrrolo described in EP 0456226A1. Pyrazole type cyan coupler, European Patent EP044890
Pyrroylimidazole type cyan couplers described in No. 9, European Patent Nos. EP0488248 and EP04911.
Preference is given to using the pyrrolotriazole type cyan couplers described in 97A1. Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta coupler used in the present invention, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the above-mentioned publicly known documents are used. Among them, hue, image stability,
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly bonded to the 2, 3 or 6 position of a pyrazolotriazole ring as described in JP-A-61-65245 in terms of color developability, etc. -65246, a pyrazoloazole coupler containing a sulfonamide group in the molecule, a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described in JP-A-61-147254, and Europe. Patent No. 226,849
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. A and No. 294,785A.

The processing method of the color light-sensitive material of the present invention is as follows:
Other than the methods described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column, lines 17 to 18 The processing material and processing method described in the lower right column, line 20 are preferred.

Example 1 (Preparation of Support) Titanium dioxide was added to low density polyethylene having MFR = 3 at a ratio shown in Table 6, and zinc stearate was added in an amount of 3.0% by weight based on the amount of titanium dioxide. A masterbatch was formed by mixing in a ratio, kneading with ultramarine blue (Daiichi Kasei Kogyo DV-1) in a Banbury mixer, and then forming into pellets. Titanium dioxide is 0.15μm ~
A coating of 0.35 μm and a hydrated aluminum oxide content of 0.75% by weight based on titanium dioxide was used in the form of aluminum oxide. 10 kV on a paper substrate with a basis weight of 170 g / m ^2.
After the corona discharge treatment of A, melt extrusion was performed at 320 ° C. using a multi-layer extrusion coating die to provide a polyethylene laminate layer having a film thickness shown in Table 6. The surface of this polyethylene layer was subjected to glow discharge treatment.

[0082]

[Table 6]

(Preparation of Silver Halide Emulsion) 32 g of lime-processed gelatin was added to 800 cc of distilled water and dissolved at 40 ° C., then 5.8 g of sodium chloride and N, N′-dimethylimidazolidine-2-thione (1 % Aqueous solution) 1.9c
c was added and the temperature was raised to 72 ° C. Subsequently, a solution obtained by dissolving 80 g of silver nitrate in 480 cc of distilled water and a solution obtained by dissolving 27.6 g of sodium chloride in 480 cc of distilled water were mixed with each other.
While maintaining the temperature at 2 ° C., the above liquid was added and mixed for 60 minutes. Next, a solution prepared by dissolving 80 g of silver nitrate in 300 cc of distilled water, 24.3 g of sodium chloride and hexacyanoiron (I
A solution prepared by dissolving 4 mg of I) potassium acid trihydrate in 300 cc of distilled water was added and mixed over 20 minutes while maintaining the temperature at 72 ° C. After desalting and washing with water at 40 ° C., 90 g of lime-processed gelatin was added, and pAg was adjusted to 7.4 and pH was adjusted to 6.4 with sodium chloride and sodium hydroxide. After heating to 58 ° C., 1 × 10 ⁻⁵ mol of triethylthiourea was added per 1 mol of silver halide for optimum sulfur sensitization. Further, the blue sensitizing dye shown below was added in an amount of 1.4 × 10 ⁻⁴ mol per mol of silver halide for spectral sensitization. The silver chloride emulsion thus obtained was designated as emulsion α.

An emulsion β was prepared which was different from the emulsion α only in that it was subjected to gold-sulfur sensitization by adding tetrachloroauric (III) acid tetrahydrate after the addition of triethylthiourea. An emulsion γ was prepared which was different from the emulsion α only in that it was ripened with potassium selenocyanate and 3-methylbenzothiazolium iodide in place of sulfur sensitization with triethylthiourea. An emulsion γ ′ was prepared which was different from the emulsion α only in that it was sensitized with potassium selenocyanate and thiosalicylic acid instead of sulfur sensitization with triethylthiourea. An emulsion γ ″ was prepared which was different from the emulsion α only in that it was sensitized with potassium selenocyanate and cysteine instead of sulfur sensitization with triethylthiourea. The emulsion α was prepared before the addition of triethylthiourea. An ultrafine silver bromide emulsion (grain size: 0.05 μm) was added in an amount to give a silver bromide content of 0.4 mol% with respect to silver chloride to form a silver bromide localized phase on the silver chloride grain surface. Emulsion δ was prepared by the addition of triethylthiourea tetrahydrate and tetrachloroauric (III) acid tetrahydrate, and emulsion ε different from that of emulsion δ. An emulsion ζ was prepared which was different from the emulsion δ only in that it was subjected to aging with potassium selenocyanate and 3-methylbenzothiazolium iodide instead of sulfur sensitization with triethylthiourea. Prepared an emulsion ζ ', which was different from the sulfur sensitization with triethylthiourea only in that it was aged with potassium selenocyanate and thiosalicylic acid. , An emulsion ζ ″ was prepared which differs only in the ripening with potassium selenocyanate and cysteine.

The grain shape, grain size, and grain size distribution of the 10 kinds of emulsions thus prepared from α to ζ ″ were determined from electron micrographs. The average grain size was equivalent to the projected area of grains. The average value of the diameters of the circles was used, and the grain size distribution was obtained by dividing the standard deviation of the grain size by the average grain size. The ten kinds of emulsions from α to ζ ″ all had grain sizes of 0.8 μm. It was a cubic particle with sharp corners and a particle size distribution of 0.08. Further, the X-ray diffraction of the emulsions δ, ε, ζ, ζ ′ and ζ ″ showed weak diffraction in the portion corresponding to the silver bromide content of 10 mol% to 40 mol%. ζ
It can be said that, in the case of ζ ”, a localized phase having a silver bromide content of 10 mol% to 40 mol% is epitaxially grown in the corner portion of the cubic silver chloride grain.

(Preparation of Photosensitive Material 100) Various photographic constituent layers were coated on the above reflective support (A) to prepare a multilayer color photographic paper (100) having the following layer structure. The coating solution was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, a color image stabilizer (Cpd-3) 16.0 g, a color image stabilizer (Cpd-5) 2.0 g, a solvent (Solv-
1) 25 g, a solvent (Solv-2) 25 g, and ethyl acetate 180 cc, and this solution was dissolved in 10% sodium dodecylbenzenesulfonate 60 cc and citric acid 10 g.
After adding to 1000 g of 10% gelatin aqueous solution containing
It was emulsified and dispersed with an ultrasonic homogenizer. The obtained dispersion was mixed and dissolved with the above-mentioned silver chloride emulsion α to prepare a coating solution for the first layer. .

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-12 and C are added to each layer.
pd-13, Cpd-14 and Cpd-15 the total amount each ^{15.0mg / m 2, 60.0mg / m} 2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue photosensitive emulsion layer

[0090]

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(1.4 × 10 ^-4 mol per mol of silver halide was used with respect to emulsion α) Green light-sensitive emulsion layer

[0092]

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(The green light-sensitive sensitizing dyes D, E, and F are 3.0 × 10 ⁻⁴ mol and 4.0 × 10 ⁻⁵ mol, respectively, per mol of silver halide for a large-sized emulsion. , 2.0
^{X10 -4} mol was added, and for small-sized emulsions, 3.6 x 10 ^-4 mol per mol of silver halide,
7.0 × 10 ⁻⁵ mol and 2.8 × 10 ⁻⁴ mol were added. ) Red photosensitive emulsion layer

[0094]

[Chemical 12]

(The red light-sensitive sensitizing dye G was 4.0 × 10 ⁻⁵ mol per mol of silver halide for a large size emulsion and 5.0 × 10 ⁻ for a small size emulsion. ⁵ moles, per mol of the silver halide red-sensitive sensitizing dye H, with respect to the to the large size emulsion, 5.0 × 10 ^-5 mol to the small size emulsion, 6.0 × 10 ^{- The} following compounds were further added to the red light-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0096]

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Further, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, at 8.5 × per mol of silver halide. 10 ^-4 mol, 3.0 x 10 ^-3
Mol, 2.5 × 10 ^-4 mol. Further, 4-hydroxy-6-methyl-1,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ^-4 mol and 2 ×, respectively, per mol of silver halide. 10 ⁻⁴ mol was added. The following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

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[0099]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support (A) The resin layer on the first layer side contains a bluish dye (ultramarine).

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion α 0.27 Gelatin 1.22 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer ( Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.01 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 0.90 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B-1 (Cubic, 1: 3 Mixture of Large Size Emulsion with Average Grain Size 0.55 μm and Small Size Emulsion with 0.39 μm (Silver) Molar ratio). The coefficient of variation of the grain size distribution is 0.08 and 0.06, respectively. For each size emulsion, 0.8 mol% of silver bromide is localized on a part of the grain surface based on silver chloride. Further, 0.1 mg of potassium hexachloroiridium (IV) ate was added per 1 mol of silver and 1 mg of potassium ferrocyanide was added together to the inside of the grain and the localized phase of silver bromide. 13 Gelatin 1.45 Magenta coupler (ExM) 0.16 Ultraviolet absorber (UV-2) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image Stabilizer (Cpd-6) 0.01 Color image stability Agent (Cpd-7) 0.08 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-10) 0.02 Solvent (Solv-3) 0.13 Solvent (Solv-4) 0. 39 Solvent (Solv-6) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.68 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-8) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 (cubic, 1: 4 mixture of large size emulsion with average grain size 0.50 μm and small size emulsion with 0.41 μm (silver Molar ratio). The coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively. For each size emulsion, 0.8 mol% of silver bromide is localized on a part of the grain surface based on silver chloride. Further, 0.3 mg of potassium hexachloroiridium (IV) was added per mol of silver and 1.5 mg of potassium ferrocyanide was added inside the grain and to the silver bromide localized phase.) 0.18 Gelatin 0.80 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-6) 0.01 Color image Constant (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.02 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-7) 0 .22

Sixth Layer (UV Absorbing Layer) Gelatin 0.48 UV Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.01 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-9) 0.05

Seventh Layer (Protective Layer) Gelatin 0.90 Acrylic Modified Copolymer of Polyvinyl Alcohol (Degree of Modification 17%) 0.05 Liquid Paraffin 0.02 Color Image Stabilizer (Cpd-11) 0.01

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

[Chemical 21]

[0114]

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Samples 101 to 159 "similar to sample 100 were prepared, except that the kind of support and the blue-sensitive emulsion were changed as shown in Table 7 for sample 100 prepared as described above.

[0116]

[Table 7]

The prepared photosensitive material was subjected to a scratch test shown below in order to examine the degree of pressure fog using a sample for which the film hardening reaction was completed. (Scratch test method) A nylon scrubber piece (1 cm x 3 cm) is stretched on an acrylic plate and a 200 g load is applied to fix it. Scissor the sensitive material cut into 3 cm x 15 cm to this acrylic plate (sandwich the coated surface of the photosensitive layer so that it touches the nylon scrubber), and pull it in the direction perpendicular to the weight at a constant speed in a dark room with the nylon scrubber. Give a scratch. This scratching experiment was conducted in a room under constant conditions of 25 ° C. and 55% RH.

The scratched sample was developed using the processing steps shown below. The degree of yellow fog caused by this scratching was visually evaluated on the obtained sample. [Evaluation criteria are ◯; scratches are scarcely seen. Δ: Slight scratching is observed. ×: Scratch is observed.
XX: Scratch is observed on the entire surface and cannot be put to practical use. ]
The obtained results are shown in Tables 8 and 9.

[0119]

[Table 8]

[0120]

[Table 9]

Further, for the purpose of evaluating the effect of the support on the sharpness of the light-sensitive material, for the light-sensitive materials 100 to 109,
The resolution of yellow color is obtained by exposing the optical material having rectangular patterns of various frequencies in close contact with the photosensitive material using light passing through the vapor deposition interference filter 470 nm as the light source of the sensitometer (Fuji Photo Film Co., Ltd.). It was As an index of resolution, the CTF value (frequency 0, that is, the rectangular pattern does not repeat, and the difference in density between the high-density portion and the low-density portion when continuous exposure is performed over a very large area of the high-light area and the low-light area ΔD _O and frequency C of rectangular pattern
Ratio of similar density difference ΔD _C in (line / mm): ΔD _C /
The frequency C (lines / mm) at which ΔD _O ) was 0.5 was determined.
The obtained results are shown in Table 8 and Table 9 at the same time. (This C
The larger the value of, the higher the resolution. )
When the value of C is about 10 or more, a photosensitive material having high sharpness can be provided.

Treatment process Temperature Time Replenisher * Tank capacity Color development 35 ℃ 45 seconds 161m 10 liters Bleach fixing 30-35 ℃ 45 seconds 215 10 liters Rinse 30-35 ℃ 20 seconds −5 liters Rinse 30-35 ℃ 20 seconds −5 liters Rinse 30-35 ℃ 20 seconds 350 5 liters Dry 70-80 ℃ 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse is a 3-tank countercurrent method to →)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5g 2.0g Potassium bromide 0.015g-Triethanolamine 8.0g 12.0g Sodium chloride 1.4g-Potassium carbonate 25 g 25.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0 g 5.0 g N, N -Di (sulfoethyl) hydroxylamine 1Na 4.0g 5.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g Add water 1000ml 1000ml pH (25 ℃) 10.05 10.45

Bleach-fix solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0

Rinse solution (tank solution and replenisher are the same) Ion-exchanged water (3 pp each for calcium and magnesium)
m or less)

The following can be understood from the obtained results. Samples 100, 110, 1 having supports A and E having a water resistant resin coating layer in which the amount of titanium oxide used is less than 2.0 g / m ^2.
30 and 140 and samples 104, 114, 134, and 144 do not cause the problem of scratching without using the compound of the present invention, but have a problem of low sharpness. By using a support having a water resistant resin coating layer containing titanium oxide of 2.0 g / m ² or more, a light-sensitive material having excellent sharpness can be provided, but at the same time, scratching is increased. (Samples 102, 112, 132, 142, etc.). It can also be seen that the degree of this covering becomes worse as the amount of titanium oxide used increases (Samples 103 and 11).
3, 133, 143). On the other hand, it can be seen that the sample of the present invention can provide a light-sensitive material that suppresses this scratching, has excellent sharpness, and has improved scratching (samples 121, 121 ', 121 ", 151, 151', 15).
1 ").

Example 2 The same evaluation as in Example 1 was carried out except that the photosensitive material produced in Example 1 was subjected to scanning exposure with the following laser exposure apparatus. The results obtained were the same as in Example 1. (Laser exposure device and scanning exposure) The semiconductor laser GaAlAs (oscillation wavelength, 8
YAG solid-state laser (oscillation wavelength, 946 nm) having a wavelength of 08.5 nm as an excitation light source was converted to wavelength 473 nm by an SHG crystal of KNbO ₃ and extracted 473 nm, and semiconductor laser GaAlAs (oscillation wavelength, 808.7 nm) was used as an excitation light source for YVO ₄ solid-state laser (oscillation wavelength, 1064n
m) Wavelength converted by a KTP SHG crystal and extracted 532 nm, AlGaInP (oscillation wavelength, about 670 n
m: Toshiba type No. TOLD9211). Each laser beam is irradiated by a polygon mirror onto a photosensitive material that moves in the direction perpendicular to the scanning direction, and the photosensitive material is sequentially scanned and exposed. The amount of each laser beam can be modulated using an external modulator. In addition, the temperature of the semiconductor laser is kept constant by a Peltier element in order to suppress the fluctuation of the light quantity due to the temperature change. Using the blue light of this device as a light source, various rectangular patterns were generated by light intensity modulation using an external modulator, and scanning exposure was performed on the photosensitive material.
This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The obtained exposed light-sensitive material was processed in the same manner as in Example 1 to determine the resolution of yellow color development.

Example 3 The light-sensitive material produced in Example 1 was evaluated in the same manner as in Example 1 except that the following processing was carried out. The results obtained were the same as in Example 1. Processing time Temperature Time Tank capacity Color development 40 ° C 15 seconds 2 liters Bleach fixing 40 ° C 15 seconds 2 liters rinse 40 ° C 3 seconds 1 liter rinse 40 ° C 3 seconds 1 liter rinse 40 ° C 3 seconds 1 liter rinse 40 ° C 3 seconds 1 liter rinse 40 ℃ 6 seconds 1 liter dry 70-80 ℃ 15 seconds

The rinse water was pumped to the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not permeate the reverse osmosis membrane was returned to the rinse for use. In addition, in order to shorten the crossover time between the rinses, a blade was installed between the tanks and the blades were passed between them. The composition of each processing solution is as follows.

Color developer tank solution replenisher water 700 ml 700 ml ethylenediaminetetraacetic acid 1.5 g 3.75 g 1,2-dihydroxybenzene-4,6 disulfonic acid disodium salt 0.25 g 0.7 g triethanolamine 5.8 g 14 0.5 g potassium chloride 10.0 g-potassium bromide 0.03 g-potassium carbonate 18.0 g 24.0 g optical brightener (UVX) 1.5 g 4.5 g sodium sulfite 0.1 g 0.1 g disodium-N, N -Bis (sulfonatoethyl) hydroxylamine 14.8 g 29.6 g 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline.2-p-toluenesulfonic acid 9.8 g 29.3 g water 1000 ml 1000 ml pH (25 ° C) 10.05 11.6 0

Bleach-fixing solution (a replenishing solution was prepared by separating the components into two solutions) [First replenishing solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite monohydrate 190 g Ethylenediaminetetraacetic acid 7.5 g Bromide Ammonium 30g Ammonium thiosulfate (700g / l) 340ml Acetic acid (50%) 250ml Add water 1000ml pH [25 ° C] 4.8 [Second replenisher] Water 140ml Ethylenediaminetetraacetic acid 11.0g Ethylenediaminetetraacetic acid iron (III) Ammonium 715 g Acetic acid (50%) 100 ml Water added 1000 ml pH (25 ° C) 2.0 Bleach-fix solution tank solution 1st replenisher 300 ml 2nd replenisher 200 ml Water added 1000 ml pH (25 ° C) 5.0 the replenishing amount of bleach-fixing solution (total 35ml per 1 m ² in the following weight) first replenisher 1ml second replenisher 14ml rinse solution (tank solution and replenisher are the same) Ion-exchanged water (calcium, magnesium each 3ppm or less)

[0132]

By containing the emulsion of the present invention in the photographic constituent layers, pressure fog can be effectively suppressed even when a reflective support which gives high sharpness is used.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 7/00 520 G03C 7/00 520 7/407 7/407

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material having at least one layer containing a photosensitive silver halide emulsion grain on a reflective support, wherein the water-resistant resin coating on the side of the reflective support on which the photosensitive layer is coated. Contains 2 g / m ² or more of a white pigment, and the silver halide emulsion grains contained in the light-sensitive silver halide emulsion layer have a silver chloride or salt odor having an average silver chloride content of 95 mol% or more. A silver halide photographic light-sensitive material, which is a silver halide and has been aged in the presence of at least one non-unstable Se compound and a nucleophile that promotes decomposition of the non-unstable Se compound. 2. A halogenation obtained by coating a photographic constituent layer containing at least three kinds of silver halide emulsion layers having different color sensitivities each containing a coupler capable of coloring yellow, magenta or cyan on a reflective support. In the silver color photographic light-sensitive material, the water-resistant resin coating on the light-sensitive layer coating side of the reflective support contains a white pigment in an amount of 2 g / m ² or more, and at least one of the silver halide emulsion layers is The silver halide emulsion grains contained are silver chloride or silver chlorobromide having an average content of silver chloride of 95 mol% or more, and promote the decomposition of at least one non-unstable Se compound and the non-unstable Se compound. A silver halide photographic light-sensitive material characterized by being aged in the presence of a nucleophile. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the nucleophile is represented by the following general formula (I). Embedded image In the formula, R ¹ is a hydrogen atom or an alkyl group, m is 0 or 1, and when m is 1, Z is a condensed benzene ring and R ²
Is bonded to this, when m is 0, R ² is bonded to the 4- or 5-position of the thiazolium ring, R ² is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an alkoxy group, or an electron-withdrawing group. And when n is 2 or more, a plurality of R ^{2 s} may be the same or different, and R ^{2 s} may be linked to each other to form a condensed ring. R ³ is a hydrogen atom or an alkyl group, an alkenyl group, an alkynyl group or an aralkyl group, X ⁻ is an anion, n is 0 or 1 to 3, and a thiazolium ring represented by the general formula (I) is The compound may be a ring-opened compound. Embedded image 4. The silver halide emulsion grain is a grain having a silver bromide localized phase on the surface thereof.
3. The silver halide photographic light-sensitive material described in 3. 5. A color image forming method, which comprises exposing the silver halide photographic light-sensitive material according to any one of claims 1 to 4 by a scanning exposure method, and then performing color development processing. 6. The silver halide photographic light-sensitive material according to claim 1 is subjected to color development processing in 25 seconds or less, and a total processing time from color development processing to drying is 120 seconds. A color image forming method comprising the following processing. 7. A silver halide photographic light-sensitive material is color-developed in 25 seconds or less, and the total processing time from color development to drying is 120 seconds or less. Color image forming method.