JP2000352794A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material superior in surface smoothness and gloss and small in occurrence of desensitization, when it is subjected to pressure or it is bend, therefore, superior in handling, and to provide a color image forming method using it. SOLUTION: This silver halide photographic sensitive material is provided with at least 3 silver halide emulsion layers each different from each other in color sensitivity on a reflective support, and this support is coated with a water-resistant resin and at least one of the water-resistant resin layers between the support and the silver halide emulsion layer is a biaxially oriented polyolefin layer having micropores and the emulsion in this layer contains silver chloride in an amount of >=95 mol% of the total silver halides and flat silver halide grains having an average aspect ratio of >=2 and an average grain thickness of <0.3 μm occupying >=50% of the projection areas of these total silver halide grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and a method for forming a color image, and more particularly to a silver halide color photographic light-sensitive material which has excellent surface smoothness and gloss and is capable of applying pressure or bending to the light-sensitive material. The present invention relates to a color photographic light-sensitive material and a color image forming method which are less desensitized when they are used and are therefore excellent in handleability.

[0002]

2. Description of the Related Art A color photograph is an oxidized form of a developing agent formed by developing a light-sensitive material having a dye-forming coupler and a silver halide emulsion on a support with an aromatic primary amine color developing agent. And a dye-forming coupler to obtain a dye image. This simplification of the color development process is a very strong demand in the color photographic industry, with numerous improvements being made and new and faster systems are being developed every few years.

[0003] Acceleration of processing includes color development, bleach-fixing,
It is necessary to separately devise the time for each of the washing and drying steps. As a method of speeding up processing,
For example, WO 87-04534 discloses a method for rapid processing with a color photographic light-sensitive material using high silver chloride silver halide as a photographic emulsion. It has been shown that it is preferable to use Due to such efforts, a method of printing an image photographed by a color negative on a silver halide color printing paper for high silver chloride printing has been widely used as a method for easily obtaining a high-quality image.

In recent years, diversification of user needs has made it easy to obtain prints of various sizes such as a panorama size and a high-vision size. There have been demands for smoothness and glossiness not only in the print size but also in the texture of the printing material, and supports that meet such demands are being developed.

[0005] For example, European Patent EP-0507,489 discloses a printing support having excellent surface smoothness and glossiness by using a polyester as a water-resistant resin as compared with polyolefins generally used conventionally. Is obtained.

The present inventors have studied silver halide color photographic light-sensitive materials having excellent surface smoothness and gloss, particularly photographic paper for color printing. As a result, the use of polyester as the water-resistant resin can provide a printing support that has superior surface smoothness and glossiness compared to conventionally used polyolefins. It has been clarified that there is a disadvantage that desensitization occurs in a portion where the wire is added or bent.

Japanese Patent Application Laid-Open No. 6-167771 discloses a problem that, when a photosensitive material using a polyester as a support is stored for a long period of time, desensitization tends to occur when pressure is applied to the photosensitive material. It can be reduced by including a selenium, tellurium, or gold-sensitized silver halide emulsion in the emulsion layer. However, as a result of further studies by the present inventor, when pressure was applied to the photosensitive material by combining a silver halide emulsion with a blue sensitizing dye and further thinning the layer for rapid processing. It was found that the pressure desensitization caused by the above became worse, and further improvement was desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide excellent surface smoothness and glossiness, and excellent handling characteristics because pressure-sensitive materials are not subjected to pressure or desensitization when bent is small. An object of the present invention is to provide a silver halide color photographic light-sensitive material and a color image forming method.

[0009]

Means for Solving the Problems The present inventors have found that the above-mentioned objects can be effectively solved by the following means. (1) In a silver halide color photographic material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the silver halide emulsion layers is a biaxially oriented polyolefin layer having micropores, and at least one silver halide emulsion of the silver halide emulsion layer contains silver chloride. Rate 9
5 mol% or more and 50 of the projected area of all silver halide grains.
% Or more, average aspect ratio 2 or more, average thickness 0.3 μm
Silver halide color photographic light-sensitive material, characterized by having tabular grains of less than (2) In a silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the silver halide emulsion layers is a biaxially stretched polyolefin layer having micropores, wherein the polyolefin has no micropores between the polyolefin layer and the silver halide emulsion layer. And at least one silver halide emulsion in the silver halide emulsion layer has a silver chloride content of 95 mol% or more and a projected area of 50% or more of all silver halide grains.
A silver halide color photographic material comprising tabular grains having an average aspect ratio of 2 or more and an average thickness of less than 0.3 μm. (3) A silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, wherein the reflective support comprises a polyester synthesized by polycondensation from a dicarboxylic acid and a diol. A composition in which a white pigment is mixed and dispersed in a resin containing 50% by weight or more, at least on the emulsion-coated surface side,
Furthermore, at least one silver halide emulsion in the silver halide emulsion layer has a silver chloride content of 95 mol% or more, and 50% or more of the projected area of all silver halide grains has an average aspect ratio of 2 or more and an average A silver halide color photographic light-sensitive material comprising tabular grains having a thickness of less than 0.3 μm. (4) The silver halide color photographic material as described in (3) above, wherein the polyester of the reflective support is a polyester containing polyethylene terephthalate as a main component. (5) A silver halide color photographic light-sensitive material according to any one of (1) to (4), wherein the tabular grains of the silver halide color photographic light-sensitive material have {100} major surfaces. (6) A silver halide color photographic light-sensitive material according to any one of (1) to (4), wherein the tabular grains of the silver halide color photographic light-sensitive material have {111} major surfaces. (7) In an image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed by a light beam modulated based on image information and then developed, the silver halide color photographic light-sensitive material is (1) to (6). A color image forming method, characterized by being a silver halide color photographic light-sensitive material characterized by the following. (8) A color image forming method, wherein the silver halide color photographic light-sensitive material according to any one of (1) to (6) is processed in a color development processing time of 20 seconds or less.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide color photographic light-sensitive material of the present invention will be described below in more detail. One embodiment of the reflective support that can be used in the silver halide color photographic light-sensitive material according to the present invention includes the following. That is, it is a water-resistant resin-coated reflective support in which at least one of the water-resistant resin layers between the support and the silver halide emulsion layer is a biaxially stretched polyolefin layer having micropores. This will be described in detail below.

In the present invention, as a method for forming micropores in a polyolefin, a substance which serves as a nucleus having a low affinity for the polymer is added to the polyolefin and then stretched to form pores around the nucleation substance. Is preferred. The substance that becomes the core of the vacancy is called a vacancy inducer,
Although an inorganic pigment or a polymer material can be used, it is preferable to use a polymer material. The polymer material can be melt-mixed with a polymer forming a core matrix,
A polymer that can form dispersed spherical particles when the suspension is cooled is preferred, such as polybutylene terephthalate dispersed in polypropylene. The pore-inducing substance is 5 to 50% by weight based on the matrix polymer of the core.
It is preferred to use. The pore-inducing material particles remaining in the completed sheet core have a diameter of 0.1 to 10 μm and are preferably spherical. The size of the pores depends on the degree of stretching in the vertical and horizontal directions, but is approximately the cross-sectional diameter size of the pore-forming particles.

The polyolefin layer having micropores can form a polyolefin layer containing no micropores adjacent to the layer. The polyolefin layer having micropores is opaque and milky white by itself, but a white pigment such as titanium dioxide, barium sulfate, alumina, or calcium carbonate is added to the micropore-containing layer and / or the adjacent polyolefin layer to obtain a white color. The degree can be improved. In addition, known additives such as pigments, fluorescent whitening agents, and other additives for improving the properties of the polyolefin layer can also be added. In particular, when polypropylene is used, the packing density of titanium oxide or the like can be increased, which is preferable from the viewpoint of improving whiteness. The density of these one or more polyolefin layers is preferably 0.40 to 1.0 g / cc,
0.50 to 0.70 g / cc is more preferable.

In a preferred embodiment of the present invention, a unit having a sandwich structure having a polypropylene skin layer containing titanium oxide and containing no microvoids is provided on both sides of a core layer of polypropylene containing no titanium oxide and having fine pores. No. In this sandwich structure, the thickness of the core layer is preferably 5 to 150 μm, more preferably 10 to 70 μm, and the thickness of the skin layer is 1 to 50 μm, more preferably 3 to 20 μm. Further, in order to improve the adhesion between the hydrophilic photographic constituent layer and the support, microvoids are formed adjacent to the hydrophilic photographic constituent layer between the polyolefin layer containing the microvoids and the hydrophilic photographic constituent layer. It is preferable to provide a polyolefin layer having no polyolefin. The thickness of the polyolefin layer having no micropores is preferably 0.1 to 5 μm. In a particularly preferred embodiment, the polyolefin layer having micropores is preferably mainly composed of polypropylene, and the polyolefin having no micropores is preferably polyethylene. Further, it is more preferable that the polyolefin layer having no microvoids is subjected to corona discharge treatment.

It is also preferable to provide a biaxially oriented polyolefin layer on the side of the support opposite to the emulsion side, from the viewpoint of increasing the rigidity of the reflective support. In this case, the surface of the polyolefin layer on the back surface is preferably made of matte-finished polyethylene or polypropylene containing silica. Also, JP
As described in 1-65024, two or more layers of polypropylene on the back surface may be provided and printing may be performed on the first polyolefin. The thickness of the polyolefin layer on the back surface is preferably 5 to 100 μm, more preferably 10 to 7 μm.
0μ.

The support which can be preferably used in the present invention is a polymer support, a synthetic paper support, a cloth support, a woven polymer fiber support, a cellulose fiber paper support, or a laminate thereof. Particularly preferred is a photographic brand cellulose fiber paper having a base paper pH of 5 to 9 described in JP-A-6-167771. It is also preferable to adjust the thickness and rigidity so as to meet various consumer requirements. For example, for these purposes, a sheet support having a Young's modulus of 2800 MPa to 13000 MPa in the machine direction and a Young's modulus of 1400 MPa to 7000 MPa is provided on both sides of the paper support in the machine direction of 690 MPa to 5520 MPa.
Young's modulus of a and 690MPa-5520MP in the transverse direction
A laminated support having a biaxially stretched sheet having a Young's modulus of a is prepared with a thickness of about 0.18 mm to 0.28 mm
Flexural stiffness of ~ 250 millinewtons can also be achieved. The preferred embodiments of the support of the present invention described above are described in JP-A-10-333277 and JP-A-10-33327.
No. 8, JP-A-11-52513, JP-A-11-650
No. 24, EP-08880065A1, EP-0880
No. 066A1, US Pat. No. 5,888,681, US Pat. No. 5,888,714 and British Patent No. 23257.
No. 49, for example.

Another preferred embodiment of the reflective support which can be used in the silver halide color photographic light-sensitive material according to the present invention will be described below.

The reflective support of the present invention is a reflective support obtained by coating a composition comprising a resin containing 50% by weight or more of polyester with a white pigment mixed and dispersed on at least the emulsion-coated side of a substrate (preferably base paper). It is. This polyester is a polyester synthesized by polycondensation from a dicarboxylic acid and a diol. Preferred 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.

In the present invention, various polyesters obtained by polycondensation of these dicarboxylic acids alone or in combination with diols alone or in mixture can be used. Among them, at least one of the dicarboxylic acids is preferably terephthalic acid. In addition, 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 of 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 3
It is preferably from 0000 to 50,000.

It is also preferable to use a mixture of a plurality of polyesters having different compositions. Further, mixtures of these polyesters with other resins can also be preferably used. Other resins to be mixed include polyethylene, polyolefins such as polypropylene, polyethylene glycol, polyoxymethylene, polyethers such as polyoxypropylene, polyester-based polyurethane, polyether polyurethane, polycarbonate,
It can be widely selected as long as it is a resin extrudable at 270 to 350 ° C. such as polystyrene. These resins may be used alone or in combination of two or more. For example, 90% by weight of polyethylene terephthalate may be mixed with 6% by weight of polyethylene and 4% by weight of polypropylene. The mixing ratio of 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.
If the content of the polyester is less than 50% by weight, the effects of the present invention cannot be sufficiently obtained.

As the white pigment mixed and dispersed in the polyester of the reflective support of the present invention, titanium oxide, barium sulfate,
Examples include inorganic pigments such as lithopone, aluminum oxide, calcium carbonate, silicon oxide, antimony trioxide, titanium phosphate, zinc oxide, lead white, and zirconium oxide; and organic fine powders such as polystyrene and styrene-divinylbenzene copolymer. it can. Among these pigments, the use of titanium dioxide is particularly effective. Titanium dioxide may be any of rutile type and anatase type, and may be manufactured by any of a sulfate method and a chloride method. Specific product names include KA-10 and KA-20 manufactured by Titanium Industry and A-220 manufactured by Ishihara Sangyo.

The average particle size of the white pigment used is 0.1 to 0.1.
8 μm is preferred. When it is less than 0.1 μm, it is difficult to uniformly mix and disperse the resin, which is not preferable. When the thickness exceeds 0.8 μm, sufficient whiteness cannot be obtained, and projections are formed on the coated surface, which adversely affects the image quality. The mixing ratio of the white pigment to the polyester is 98/2 to 30/70 (polyester / white pigment) by weight, preferably 95/5 to 50/5.
0, particularly preferably 90/10 to 60/40. When the content of the white pigment is less than 2% by weight, the contribution to the whiteness is insufficient, and when it exceeds 70% by weight, the surface smoothness when used as a photographic paper support is insufficient, and the glossiness is excellent. Photographic paper support cannot be obtained. still,
The above-mentioned polyester and white pigment are mixed together with a dispersing agent such as a metal salt of higher fatty acid, higher fatty acid ethyl, higher fatty acid amide, higher fatty acid and the like by using a kneader such as a two-roll, three-roll, kneader, or Banbury mixer. It is kneaded in. An antioxidant can be contained in the resin layer, and the content is 50 to 1,000 ppm based on the resin.
Can be added in the range.

The thickness of the polyester / white pigment composition coated on the emulsion-coated side of the substrate of the reflective support of the present invention is 5
To 100 μm, preferably 5 to 80 μm, more preferably 10 to 50 μm. When the thickness is more than 100 μm, the problem of physical properties such as the embrittlement of the resin is emphasized to cause cracks. When the thickness is less than 5 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 to be coated on the side of the substrate other than the side on which the emulsion is coated is 5 to 1
When the thickness exceeds this range, which is preferably 00 μm, and more preferably 10 to 50 μm, there is a problem in physical properties such that the brittleness of the resin is emphasized and cracks occur. 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 are too soft, which is not preferable. Examples of a method for coating the coating layer on the emulsion-coated side and the back surface layer of the substrate include a melt extrusion lamination method.

The substrate used for the reflective support of the present invention comprises:
It is selected from materials generally used for photographic printing paper. That is, natural pulp selected from softwood, hardwood, etc.,
Using synthetic pulp as the main material, clay, talc,
Fillers such as calcium carbonate and urea resin fine particles, rosin, alkyl ketene dimer, sizing agents such as higher fatty acids, epoxidized fatty acid amides, paraffin wax, alkenyl succinic acid, etc., paper strength agents such as starch, polyamide polyamine epichlorohydrin, polyacrylamide, What added a fixing agent such as a sulfuric acid band and a cationic polymer is used. In the present invention, the base paper used for the reflective support is preferably a base paper mainly made of the natural pulp or the synthetic pulp described above. Although the type and thickness of the substrate are not particularly limited, the basis weight is 50 g / m ^{2 to} 25 g.
0 g / m ² is desirable. For the purpose of imparting smoothness and flatness, the substrate is preferably subjected to surface treatment by applying heat and pressure using a machine calender, a spar calender, or the like.

This "smoothness" is expressed using the surface roughness of the support as a scale. The surface roughness of the support of the present invention will be described. As the surface roughness, the center line average surface roughness is used as this scale. The center line average surface roughness is defined as follows. From the roughness phase, a portion of the area SM is extracted on the center plane, the orthogonal coordinate axes, the X axis, and the Y axis are set on the center line of the extracted portion, and the axis orthogonal to the center line is set as the Z axis. Is defined as the center line average surface roughness (SRa) and is expressed in μm.

[0025]

(Equation 1)

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

When the substrate is coated with the above-mentioned polyester / white pigment mixture composition, it is preferable that the surface of the substrate is preliminarily subjected to a pretreatment such as a corona discharge treatment, a flame treatment or an undercoat.

When a polyester such as polyethylene terephthalate is used, the adhesion to a photographic emulsion is weaker than that of a polyethylene. Therefore, after the polyester is melt-extruded and laminated on the substrate, the polyester surface is subjected to corona discharge treatment to coat a hydrophilic colloid layer. Is preferred. It is also preferable to apply an undercoat liquid containing a compound represented by the following general formula [U] on the surface of a thermoplastic resin containing polyester as a main component.

[0029]

Embedded image

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 content is most preferably 3 mg / m ² or more. As the content is larger, the adhesion can be strengthened, but it is disadvantageous in terms of excessive cost. Further, it is preferable to add alcohols such as methanol in order to improve the suitability of applying the undercoat liquid to 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 coating suitability, it is preferable to use various surfactants such as anionic, cationic, amphoteric, nonionic, fluorocarbon, and organic silicon-based.

It is preferable to add a water-soluble polymer such as gelatin to obtain a good undercoating surface. Considering the stability of the compound of the general formula [U], the pH of the solution is
4 to pH 11 are preferable, and pH 5 to p are more preferable.
H10. It is preferable that the surface of the thermoplastic resin is surface-treated before applying the undercoat liquid. As the surface treatment, a corona discharge treatment, a flame treatment, a plasma treatment, or the like can be used. In applying the undercoating liquid, 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, an extrusion coating method, and the like, by a generally well-known coating method. Can be applied. The drying speed of the coating is preferably 30C to 100C, more preferably 50C to 100C, and most preferably 70C to 100C. The upper limit is determined by the heat resistance of the resin, and the lower limit is determined by the production efficiency.

Next, the silver halide emulsion used in the present invention will be described. The silver halide emulsion used in the present invention includes silver chloride having a silver chloride content of 95 mol% or more, silver chlorobromide,
Silver chloroiodide or silver chloroiodobromide. Silver chloride content is 9
It is preferably from 5 to 99.9 mol%, and more preferably from 98 to 99.9 mol%.
99.9 mol%. The tabular silver halide grains used in the present invention will be described in detail. In the present invention,
The tabular grains have an aspect ratio of 1.2 or more, and the average aspect ratio means an average value of aspect ratios of all tabular grains in the emulsion. Here, the aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. The larger the aspect ratio, the thinner and flatter the particles. The thickness refers to the distance between two main planes of the tabular grains, and the average thickness means the average value of the thickness of all tabular grains. The projected diameter of a tabular grain refers to the diameter of a circle having an area equal to the projected area when the principal plane is placed parallel to the substrate surface and observed from the perpendicular direction. In the present invention, “equivalent circle diameter” or “projected area equivalent diameter” is used in the same meaning as “projected diameter”. The silver halide tabular grains of the present invention preferably have an equivalent circle diameter of 0.2 to 1.0 μm.
It is.

Hereinafter, preferred {111} in the present invention.
Tabular grains and {100} tabular grains will be described. A set of parallel planes perpendicular to the thickness direction of the tabular grains is called a main plane.
{111} tabular grains are tabular grains having a {111} plane as a main surface. In order to form particles having the {111} plane as an outer surface, a method of adding an additive (crystal phase controlling agent) at the time of particle formation is known. It is shown below.

Patent No. Crystalline phase modifier Inventor US Pat. No. 4,400,463 Azaindenes + Mascasky thioether peptizer US Pat. No. 4,783,398 2-4-Dithiazolidinone Mifune, etc. US Pat. US Pat. No. 4,983,508 Bispyridinium salt Ishiguro et al. US Pat. No. 5,185,239 Triaminopyrimidine muscasky US Pat. No. 5,178,997 7-Azaindole-based compound Mascasky US Pat. JP-A-3-212639 Aminothioether Ishiguro JP-A-4-283742 Thiourea derivative Ishiguro JP-A-4-335632 Triazolium salt Ishiguro JP-A-2-32 Bispi Dinium salt Ishiguro et al. Japanese Patent Application No. 7-146891 Monopyridinium salt Ozeki et al. Methods for using various crystal habit controlling agents as described above are disclosed. 1-42) are preferable, and crystal phase controlling agents 1-29 described in Japanese Patent Application No. 6-333780 are particularly preferable.
However, the present invention is not limited to these.

{111} tabular grains are obtained by forming two parallel twin planes. Since the formation of the twin plane depends on the temperature, the dispersion medium (gelatin), the halogen concentration, and the like, these appropriate conditions must be set. When a crystal habit controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is at least 0.01 mol / l, preferably at least 0.03 mol / l. Further, it is disclosed in JP-A-8-184931 that it is preferable not to use a crystal habit controlling agent at the time of nucleation in order to monodisperse the particles.
When the crystal habit controlling agent is not used at the time of nucleation, the gelatin concentration is 0.03% to 10%, preferably 0.05% to 1.0%.
%. Chloride concentration is 0.001 mol / l to 1
Mol / l, preferably 0.003 mol / l to 0.1 mol / l. Nucleation temperature is 2 ° C ~ 9
Although any temperature can be selected up to 0 ° C, 5 ° C to 80 ° C is preferable, and 5 ° C to 40 ° C is particularly preferable.

Although nuclei of tabular grains are formed in the first nucleation stage, immediately after nucleation, the reaction vessel contains many nuclei other than tabular grains. Therefore, after nucleation, aging is performed,
A technique for leaving only tabular grains and extinguishing others is required. When ordinary Ostwald ripening is performed, the tabular grain nuclei also dissolve and disappear, so that the tabular grain nuclei decrease and the size of the resulting tabular grains increases. In order to prevent this, a crystal habit controlling agent is added. Particularly, by using phthalated gelatin in combination, the effect of the crystal habit controlling agent can be enhanced and the dissolution of tabular grains can be prevented. The pAg during ripening is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode. Next, the formed nucleus is grown in the presence of a crystal habit controlling agent by physical ripening and addition of a silver salt and a halide. In this case, the chloride concentration is 5 mol / l or less, preferably 0.05 to 1 mol / l. The temperature at the time of grain growth can be selected from the range of 10 ° C to 90 ° C.
A range of 0 ° C. is preferred. The total amount of the crystal habit controlling agent used is preferably 6 × 10 ⁻⁵ mol or more, particularly preferably 3 × 10 ⁻⁴ mol to 6 × 10 ⁻² mol, per mol of silver halide in the finished emulsion.
The crystal habit controlling agent may be added at any time during the nucleation of silver halide grains, physical ripening, and during grain growth. The {111} plane starts forming after the addition. The crystal habit controlling agent may be added to the reaction vessel in advance, but in the case of forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel together with the growth of the grains to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to supplement the amount by addition. Preferably, 10 g / l to 100 g / l of gelatin is present for growth. As the complementary gelatin, phthalated gelatin or trimellit gelatin is preferable. The pH at the time of particle formation is arbitrary, but is preferably in a neutral to acidic range.

Next, {100} tabular grains will be described. {100} tabular grains are tabular grains having a {100} plane as a main plane. The shape of the main plane is a right-angled parallelogram or a triangular to pentagonal shape in which one corner of the right-angled parallelogram is missing (a missing shape is a side having the corner as a vertex and the corner as the corner) A right-angled triangular portion formed by the above) or the missing portion exists in two or more and four or less.
To an octagonal shape. If the right-angled parallelogram shape supplementing the missing part is a supplementary quadrilateral, the adjacent side ratio (length of the long side / length of the short side) of the right-angled parallelogram and the supplementary quadrangle is 1 to 6 , Preferably 1-4, more preferably 1-2.

As a method of forming tabular silver halide emulsion grains having {100} major planes, a silver salt aqueous solution and a halide salt aqueous solution are added to a dispersion medium such as an aqueous gelatin solution with stirring and mixed. At this time, for example, JP-A-6-301129 and JP-A-6-347929.
In JP-A-9-34045 and JP-A-9-96881, silver iodide or iodide ions or silver bromide or bromide ions are allowed to be present, and nuclei are formed due to the difference in crystal lattice size from silver chloride. There is disclosed a method of introducing a crystal defect that causes distortion and imparts anisotropic growth such as screw dislocation. When the screw dislocations are introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, so crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocations. Is done. Here, the low supersaturation condition is preferably 35% or less at the time of critical addition, and more preferably 2% or less.
Indicates 20%. Although it is not determined that the crystal defect is a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or the particles are given anisotropic growth. In order to make tabular grains thinner, it is preferable that the introduced dislocations be retained.
Nos. 122954 and 9-189977.

In Japanese Patent Application Laid-Open No. Hei 6-347928, imidazoles and 3,5-diaminotriazoles are used, and in Japanese Patent Application Laid-Open No. Hei 8-339404, polyvinyl alcohols are used. A method of forming {100} tabular grains by addition is disclosed. Further, U.S. Pat.
264,337, 5,292,632, 5,3
14,798, 5,413,904, WO94 /
It can be prepared by the method disclosed in, for example, No. 22051. However, the present invention is not limited to these.

The particles of the present invention preferably have a so-called core / shell structure comprising a core and a shell surrounding the core. It is preferable that 90 mol% or more of the core portion is silver chloride. The core portion may further include two or more portions having different halogen compositions. The shell part is preferably 50% or less of the total particle volume, and 20% or less.
% Is particularly preferable. The shell part is preferably silver iodochloride or silver iodobromochloride. The shell part preferably contains 0.5 mol% to 13 mol% of iodine, particularly preferably 1 mol% to 13 mol%. The content of silver iodide in all grains is 5 mol%
Or less, and particularly preferably 1 mol% or less.

The silver bromide content is preferably higher in the shell portion than in the core portion. The silver bromide content is preferably at most 20 mol%, particularly preferably at most 5 mol%.

The silver halide emulsion of the present invention comprises 50 to 100%, preferably 80 to 100%, more preferably 90 to 100%, further preferably 95 to 100% of the total projected area of all silver halide grains. Is a {100} plane or a {111} plane, and has an average thickness of less than 0.3 μm, preferably 0.01 to 0.30 μm, and more preferably 0.1 to 0.30 μm.
02 to 0.20 μm, more preferably 0.05 to 0.1
5 μm, and the average aspect ratio is 2.0 to 100, preferably 2.0 to 50, more preferably 4.0 to 50, and still more preferably 6.0 to 50. In particular, an average aspect ratio of 2 to 20 is preferable. The coefficient of variation of the projected diameter and thickness (standard deviation of distribution / average projected diameter or average thickness) is preferably 0 to 0.4, more preferably 0 to 0.3, and still more preferably 0.01 to 0.2. It is.

The silver halide tabular grains of the present invention can be used in any one of a silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, and a silver halide emulsion layer containing a cyan dye-forming coupler. However, it is preferable to use the silver halide emulsion layer containing a yellow dye-forming coupler and the silver halide emulsion layer containing a magenta dye-forming coupler, and it is preferable to use the silver halide emulsion layer containing a yellow dye-forming coupler. Is most preferred.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. Examples of compounds used include iron, iridium, ruthenium, osmium, rhenium, rhodium, cadmium, zinc, lead,
Salts or complex salts of metals of Group VIII of the periodic table such as copper and thallium can be used in combination. In the present invention, metal compounds having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, are particularly preferred in that they further increase the high illuminance sensitivity and also suppress the latent image sensitization. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide. These metal ions will be described in more detail, but are not limited thereto.

The iridium ion-containing compound is a trivalent or tetravalent salt or complex salt, preferably a complex salt. For example, iridium (III) chloride, iridium bromide (II)
I), iridium (II) chloride, sodium hexachloroiridate (III), hexachloroiridium (I
V) Potassium acid, hexaammine iridium (IV) salt,
Halogens such as trioxalatoiridium (III) salt and trioxalatoiridium (IV) salt, amines, and oxalato complex salts are preferred. The platinum ion-containing compound is a divalent or tetravalent salt or complex salt, preferably a complex salt. For example, platinum (IV) chloride, potassium hexachloroplatinum (IV), tetrachloroplatinum (II), tetrabromoplatinum (II), tetrakis (thiocyanato)
Sodium platinum (IV), hexaammine platinum (IV) chloride and the like are used.

The palladium ion-containing compound is usually a divalent or tetravalent salt or complex salt, and a complex salt is particularly preferred. For example, sodium tetrachloropalladium (II), sodium tetrachloropalladium (IV), potassium hexachloropalladium (IV), tetraamminepalladium (II) chloride, tetracyanopalladium (II)
Potassium acid or the like is used. As the nickel ion-containing compound, for example, nickel chloride, nickel bromide, potassium tetrachloronickelate (II), hexaamminenickel (II) chloride, sodium tetracyanonickelate (II) and the like are used.

The rhodium ion-containing compound is usually preferably a trivalent salt or complex salt. For example, potassium hexachlororhodate, sodium hexabromorhodate, ammonium hexachlororhodate and the like are used. The iron ion-containing compound is a divalent or trivalent iron ion-containing compound, preferably an iron salt or an iron complex salt having water solubility in the concentration range used. Particularly preferred is an iron complex salt which can be easily contained in silver halide grains. For example, ferrous chloride,
Ferric chloride, ferrous hydroxide, ferric hydroxide, ferrous thiocyanate, ferric thiocyanate, iron hexacyano (II)
Complex salts, hexacyanoiron (III) complex salts, ferrous thiocyanate complex salts, and ferric thiocyanate complex salts. Further, a six-coordinate metal complex having at least four cyan ligands as described in EP 336,426A is also preferably used.

The above-mentioned metal ion-providing compound is prepared by dispersing a metal ion in a gelatin aqueous solution, a halide aqueous solution, a silver salt aqueous solution or another aqueous solution, or in advance, when forming silver halide grains. The silver halide grains of the present invention can be contained in the silver halide grains of the present invention by, for example, adding silver halide grains and dissolving the grains. The metal ions used in the present invention can be contained in the particles either before, during or immediately after the formation of the particles. This can be changed depending on where the metal ions are contained in the particles.

As is generally well known, the steps of preparing a silver halide emulsion in the present invention include a step of forming silver halide grains by the reaction of a water-soluble silver salt and a water-soluble halide, a step of desalting, and a step of chemical ripening. Process.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column, are preferably used.

The silver halide emulsion used in the present invention is:
It is preferably subjected to gold sensitization known in the art. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably from 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. is there.

In the present invention, gold sensitization is carried out by other sensitization methods,
For example, it may be combined with sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The silver halide emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the emulsion or the photographic material, during storage or during photographic processing, or for stabilizing photographic performance. It can be contained. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles mercaptobenzimidazoles, mercaptothiaidiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (particularly 1-phenyl-5-mercaptotetrazole and the like), mercaptopyrimidines,
Mercaptotriazines and the like; thioketo compounds such as oxadrinethione; azaindenes such as triazaindenes and tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindene) pentaazaindene Many compounds known as antifoggants or stabilizers, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc., can be added. Particularly preferred are mercaptotetrazoles. This is preferable because it has a function of further increasing the high illuminance sensitivity in addition to preventing and stabilizing fog.

In the photographic material according to the present invention, a dye capable of being decolorized by a process described in EP-A-337,490 A2, pp. 27-76, is applied to a hydrophilic colloid layer for the purpose of improving sharpness and the like in an image. (An oxonol-based dye) so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more, or a divalent or tetravalent alcohol (for example, trimethylolethane) is added to the water-resistant resin layer of the support. ) Or the like is preferably contained in an amount of 12% by weight or more (more preferably, 14% by weight or more).

In the silver halide color photographic light-sensitive material according to the present invention, gelatin is used as a hydrophilic binder.
If necessary, other gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, and hydrophilic colloids such as synthetic hydrophilic polymer substances such as mono- or copolymers may also be used. It can be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be any of lime-processed gelatin and acid-processed gelatin, and gelatin produced from any of bovine bone, cowhide, pork skin and the like. However, lime-processed gelatin obtained from cow bone and pig skin is preferred.

In the present invention, the silver halide
Hydrophilicity farthest from the support on the side coated with the emulsion layer
Photosensitive silver halide emulsion layer up to colloid layer and insensitive
Hydrophilic binder contained in light hydrophilic colloid layer
Is 6.5 g / m2 from the viewpoint of rapid processing.^TwoLess than,
Most preferably 5.5 g / m^TwoLess than and 4.0 g / m ^Two
That is all. If the amount of hydrophilic binder is small, especially color development
It is effective for speeding up the development and washing steps.

In the present invention, [amount of hydrophilic binder / thickness of silver halide] in all silver halide emulsion layers
The ratio is preferably 1.5 or more. Hereinafter, this ratio is referred to as [B / AgX] ratio in the present invention. Here, the amount of hydrophilic binder means the amount of hydrophilic binder (g / m ² ) per 1 m ^{2 of the} silver halide emulsion layer. The amount of the hydrophilic binder is divided by the specific gravity to represent the thickness, and it is understood that the amount of the hydrophilic binder of the present invention is an amount proportional to the thickness. on the other hand,
The term "silver halide emulsion thickness" means a thickness (μm) occupied by silver halide emulsion grains in the silver halide emulsion layer in a direction perpendicular to the support. In the present invention, it is assumed that the silver halide emulsion layer is ideally coated. μm) is the thickness of the silver halide emulsion. When silver halide emulsion grains of different sizes are used in combination, the weight average of each grain is defined as the silver halide emulsion thickness.

As is clear from the following definition, the [B / AgX] ratio in the present invention indicates that as the ratio increases, the emulsion thickness in the emulsion layer relatively decreases.
In the present invention, the [B / AgX] ratio is 1.50 or more from the viewpoint of suppression of pressure fogging and reduction of color mixture during processing.
It is preferably at least 1.70, more preferably at least 1.90, and most preferably at least 6.0.

In the present invention, the silver halide emulsion layer containing a yellow coupler may be arranged at any position on the support, but the silver halide emulsion layer containing a magenta coupler or the silver halide emulsion layer containing a cyan coupler It is preferable that the coating is provided at a position more distant from the support than at least one layer. From the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers. Preferably, it is provided. Further, from the viewpoint of reduction of Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of the other silver halide emulsion layers, and from the viewpoint of reduction of photofading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055 and JP-A-9-114
No. 035, 10-246940, U.S. Pat.
As described in JP-A-76-159 and the like, it is also preferable that a coupler layer containing no silver halide emulsion is provided adjacent to the silver halide emulsion layer to form a color-forming layer.

The silver halide emulsion layer containing the yellow coupler is preferably provided farthest from the support than the silver halide emulsion layer. Is preferably 1.35 g / m ² or less, more preferably 1.25 g / m ² or less.
g / m ² or less, most preferably 1.20 g / m ² or less 0.
It is 60 g / m ² or more. Regarding the thickness of the silver halide emulsion, the side length in the case of using cubic grains is preferably 0.80 μm or less, more preferably 0.75 μm or less, most preferably 0.70 μm or less and 0.30 μm or more. When the particles are used, the side length (the side length when the volume of the cube is converted) is preferably 0.40 μm or less and 0.02 μm or more,
It is more preferably 0.30 μm or less, further preferably 0.20 μm or less, and most preferably 0.15 μm or less and 0.05 μm or more. Further, in order to control sensitivity, gradation and other photographic performance, it is preferable to use a mixture of silver halide emulsions having different sizes and shapes.

In the present invention, the coating amount of the silver halide emulsion is preferably 0.60 g / m ² or less and 0.10 g / m ² or more, more preferably 0.55 g / m ² or less and 0.20 g / m ² or less.
m ² or more, most preferably 0.50 g / m ² 0.25
g / m ² or more.

When cubic silver halide emulsion grains are used for the cyan coloring layer and the magenta coloring layer, the side length is preferably 0.50 μm or less, more preferably 0.40 μm or less and 0.10 μm or more. .

In the present invention, the film thickness of the photographic layer constitution means
It represents the thickness before processing of the photographic layer configuration above the support.
Specifically, it can be determined by any of the following methods. First, it can be obtained by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with a microscope. A second method is to calculate the film thickness from the coating amount (g / m ² ) and specific gravity of each component in the photographic layer constitution. For example, the specific gravity of typical gelatin used for photography is 1.34 g / cc, the specific gravity of silver chloride is 5.59 g / cc, and other lipophilic additives are measured before coating. Thus, the film thickness can be calculated by the second method.

In the present invention, the thickness of the photographic layer is preferably 9.0 μm or less, more preferably 8.0 μm or less, most preferably 7.0 μm or less and 3.5 μm or more.

In the present invention, the hydrophobic photographic material is
An oil-soluble component excluding the dye-forming coupler, wherein the oil-soluble component is a lipophilic component remaining in the photosensitive material after processing. Specifically, a dye-forming coupler, a high-boiling organic solvent, a color mixing inhibitor,
UV absorbers, lipophilic additives, lipophilic polymers or polymer latexes, matting agents, sliding agents, etc., which are usually added to photographic constituent layers as lipophilic fine particles. Therefore, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like do not fall under oil-soluble components. Usually, a surfactant is used when preparing the lipophilic fine particles, but the surfactant is not treated as an oil-soluble component in the present invention.

In the present invention, the total amount of the oil-soluble component is preferably 4.5 g / m ² or less, more preferably 4.0 g / m ^2.
m ² or less, most preferably 3.8 g / m ² or less 3.0 g /
m ² or more. In the present invention, the value obtained by dividing the weight (g / m ² ) of the hydrophobic photographic material contained in the layer containing the dye-forming coupler by the weight (g / m ² ) of the dye-forming coupler is 4.5 or less. And more preferably 3.
5 or less, and most preferably 3.0 or less.

In the present invention, the ratio of the oil content to the hydrophilic binder in the constitution of the photographic layer can be arbitrarily set. The preferred ratio in the photographic layer constitution other than the protective layer is 0.05 to 1.50 by weight, more preferably 0.10 to 1.4.
0, most preferably 0.20 to 1.30. By optimizing the ratio of each layer, the film strength, scratch resistance, and curl characteristics can be adjusted.

The silver halide photographic light-sensitive material of the present invention includes:
In addition, conventionally known photographic materials and additives can be used.

Further, it is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The above-mentioned reflective support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0073]

[Table 1]

[0074]

[Table 2]

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat.
No. 3,756, U.S. Pat. No. 4,225,666, JP-A-58-184142, JP-A-60-196749, and the like. And / or before desalting, during the desalting step and / or after desalting and before the start of chemical ripening, as disclosed in the specification of JP-A-58-113920 and the like. It may be added at any time during the process, just before or during the process, or before the application of the emulsion before the coating after the chemical ripening. Also, U.S. Pat.
As disclosed in the specifications such as JP-A No. 25,666 and JP-A-58-7629, the same compound may be used alone or in combination with a compound having a different structure.
Or it may be added during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening, or may be dividedly added to different steps such as before or during the chemical ripening or after the completion of the chemical ripening. The kind of the compound to be added and the combination of the compounds may be changed and added. Further, a predetermined amount may be added in a short time, or for a long time, for example, continuously in any step from the nucleation in the particle forming step to the completion of the particle formation or most of the chemical ripening step. It may be added. In such a case, the addition speed may be a constant flow rate, or the flow rate may be accelerated or decelerated. The temperature at which the sensitizing dye is added to the silver halide emulsion is not particularly limited.
To 70 ° C., and the addition temperature and the aging temperature may be changed. After adding at 45 ° C. or less, a method of raising the temperature and aging is more preferable.

The total amount of the dye used in the present invention is
Depending on the shape and size of the silver halide grains, 5.5 × 10 ^{−6 to} 1.2 × 10 per mol of silver halide.
^-2 moles can be used. For example, when the silver halide grain size is 0.2 to 2.0 μm, 4.0 × 10 ^{−7 to} 6.5 × per 1 m ² of the surface area of the silver halide grains.
An addition amount of 10 ^-6 mol is preferable, and 1.0 * 10 ^-6 to 4.
An addition amount of 2 × 10 ⁻⁶ mol is more preferred.

The cyan, magenta and yellow couplers used in combination in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Column 6th line to page 35, lower right column 11th line, European Patent No. 355,660A
No. 2, page 4, lines 15-27, page 5, lines 30-28
Couplers described in the last line of the page, lines 29 to 31 of page 45, lines 23 to 63 of page 47, line 50, JP-A-8-122984, JP-A-9-222704 and the like are also useful.
As the cyan coupler, a pyrrolotriazole coupler is preferably used.
Particularly preferred are couplers represented by the general formula (I) or (II) of the above-mentioned No. 3, couplers represented by the general formula (I) of JP-A-6-347960, and exemplified couplers described in these patents.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular redox compounds described in JP-A-5-333501, Japanese Patent Application No. 9-140.
No. 719, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, No. 10-282615, German Patent No. 1962
White couplers described in 9142A1 and the like can be used. In particular, when increasing the pH of a developer to speed up development, German Patent No. 191818686A
No. 1,980,846A1, European Patent No. 83
It is also preferable to use the redox compounds described in 9,623A1, 842,975A1, French Patent No. 2,760,460A1, and the like.

In the present invention, as an ultraviolet absorber,
It is preferable to use an ultraviolet absorber having a high molar extinction coefficient. Examples of such a compound include compounds having a triazine skeleton.
No. 55-152776, JP-A-5-1970074
Nos. 5-232630, 5-307232, 6-211813, 8-53427, and 8-23
No. 4364, No. 8-239368, No. 9-31067
No., No. 10-115598, No. 10-147577
No. 10-182621, Tokuyohei 8-501291
No. 711,804A and German Patent No. 19
Preferred are those described in US Pat.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the photosensitive material, and particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .
The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

In the case where the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) obtained by combining a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. 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) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that 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 such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the photosensitive material of the present invention depends on the scanning used.
It can be set arbitrarily according to the wavelength of the exposure light source.
Solid-state laser using semiconductor laser as excitation light source or
Is obtained by combining a semiconductor laser and a nonlinear optical crystal.
SHG light source can halve laser oscillation wavelength
Therefore, blue light and green light can be obtained. Therefore, photosensitive material
The spectral sensitivity maximum is held in the normal three wavelength ranges of blue, green and red.
It is possible to add. In such scanning exposure
The exposure time is based on the pixel density when the pixel density is 400 dpi.
If the size is defined as the exposure time, the preferred exposure
10 for time ^-FourSeconds or less, more preferably 10^-6Seconds
Below.

Preferred scanning exposure systems applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As the method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkaline agent and a developing agent, and an alkaline solution containing a developing agent incorporated in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, No. 9-152686, No. 9-152693
, Japanese Patent Application No. 7-334197, Japanese Patent Application Laid-Open No. 9-16019.
The hydrazine-type compound described in No. 3 is preferred.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and the image is amplified (intensified) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Hei 7
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-63587 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

For the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36
544 (September 1994), pages 536 to 541, and JP-A-8-234388 can be used.

In the present invention, the term "color developing time" refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called submerged time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called submerged time).
Say. In the rapid processing aimed at by the present invention, the color development time is preferably 30 seconds or less, more preferably 20 seconds or less.
Seconds or less, most preferably 15 seconds or less and 6 seconds or more. Similarly, the bleach-fix time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 15 seconds or less and 6 seconds or more. The washing or stabilization time is preferably 40 minutes.
Seconds or less, more preferably 30 seconds or less, and most preferably 2 seconds or less.
It is less than 0 seconds and more than 6 seconds.

The drying method according to the present invention may be any method known in the art for rapid drying of a color photographic light-sensitive material. It is preferable that drying can be performed within seconds, most preferably 5 seconds to 10 seconds.
As a drying method, either a contact heating method or a hot air blowing method may be used, but the combination of the contact heating method and the hot air blowing method enables quick drying compared to the case of using either method Is preferable. A further preferred embodiment of the present invention relating to the drying method is a method in which the photosensitive material is contact-heated by a heat roller and then blown and dried by warm air blown from the perforated plate or the nozzle group toward the photosensitive material. In the drying section, it is preferable that the mass velocity of the warm air blown per unit area of the heat receiving area of the photosensitive material is 1000 kg / m ² · hr or more. Further, it is preferable that the shape of the blowing outlet is a shape having a small pressure loss, and examples thereof include FIGS. 7 to 15 described in JP-A-9-33998. Since the light-sensitive material of the present invention has rapid processing properties, high sensitivity, small pressure fog, and is suitable not only for surface exposure but also especially for high-illuminance scanning exposure, a good image can be obtained in the above color development time. .

[0091]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1

Preparation of Cellulose Paper Support Pulp furnish consisting of bleached hardwood kraft 50%, bleached hardwood sulphite 25%, and bleached softwood sulphite was subjected to double disc refiner and then Jordan conical refiner. And 200 cc of Canadian Standard Freeness to make a photographic paper support. To the obtained pulp furnish, on a dry basis, 0.2% of alkyl ketene dimer, 1.0% of cationic corn starch, 0.5% of polyamide epichlorohydrin, 0.26% of anionic polyacrylamide, and 5.0% TiO ₂ was added. The paper base obtained by pressing to a Sheffield porosity of 160 Sheffield units and an apparent density of 0.70 g / cc is then 10
The surface was glued with a corn starch solution that had been hydrolyzed to give a starch loading of 3.3% by weight. The surface-glued support has an apparent density of 1.04 g / cc.
This was calendered to obtain a 145 μm thick cellulose paper support. A polymer layer having the following composition was formed on the paper support, subjected to corona discharge treatment on the emulsion side, and then subbed to prepare a reflective support. The polymer layer on the emulsion side contained 4,4'-bis (5-methylbenzoxazolyl) stilbene at 10 mg / m ² and ultramarine.

Preparation of Reflective Support A (Comparative Support) Emulsion surface side polymer composition: polyethylene layer containing titanium oxide at 20% by weight (35μ) Back surface side polymer composition: polyethylene layer (30μ)

Preparation of reflective support B (support of the present invention) Emulsion surface side polymer composition: polyethylene terephthalate layer containing 20% by weight of titanium oxide (35μ) Back surface polymer composition: polyethylene layer (30μ)

Preparation of Reflective Support C (Support of the Present Invention) Emulsion side polymer composition: polyethylene layer not containing micropores (1μ) from emulsion side, containing titanium oxide and not containing micropores Polypropylene skin layer (4μ) Polypropylene core layer containing micropores (22μ) Polypropylene skin layer containing titanium oxide and not containing micropores (4μ) Polyethylene layer containing titanium oxide and containing no micropores (4μ) Back surface polymer composition: polyethylene layer (30μ)

Preparation of reflective support D (support of the present invention) Emulsion surface polymer composition: polyethylene layer not containing micropores (3μ) from the emulsion side (polypropylene layer containing titanium oxide and containing micropores) (7μ) Polypropylene layer not containing micropores (9μ) Polypropylene layer containing titanium oxide and containing micropores (7μ) Polyethylene layer containing titanium oxide and not containing micropores (4μ) Back surface polymer composition ： Polyethylene layer (30μ)

Preparation of reflective support B2 (support of the present invention) Emulsion surface polymer composition: same as reflective support B Back surface polymer composition: polyethylene layer (28μ) silica-containing polyethylene layer (2μ) from support side

Preparation of Reflective Support C2 (Support of the Present Invention) Emulsion-side polymer composition: same as reflective support C Back-side polymer composition: polyethylene layer (9μ) polypropylene layer (24μ) silica-containing from support side Polyolefin layer (3μ)

Preparation of reflective support D2 (support of the present invention) Emulsion surface polymer composition: same as reflective support D Back surface polymer composition: polyethylene layer (6μ) polypropylene layer (27μ) silica-containing polyolefin layer (3μ) )

(Preparation of Emulsion BLA) To a 3% aqueous solution of lime-processed gelatin was added 3.5 g of sodium chloride.
-Dimethylimidazolidine-2-thione (1% aqueous solution)
Was added in an amount of 1.0 ml. An aqueous solution (Ag-1) containing 0.8 mol of silver nitrate and an aqueous solution (X-1) containing 0.8 mol of sodium chloride were added to this aqueous solution at 57 ° C. with vigorous stirring. Subsequently, an aqueous solution (Ag-2) containing 0.20 mol of silver nitrate and an aqueous solution (X-2) containing 0.20 mol of sodium chloride were added and mixed at 57 ° C. with vigorous stirring. At this time, 1 × 10 ⁻⁵ mol of yellow blood salt was added to X-2. Subsequently, the precipitate was washed by settling at 40 ° C. and desalted. 80.0 g of lime-processed gelatin was added, and the pH and pAg of the emulsion were adjusted to 6.2 and 7.0, respectively. 1.6 × 10 ^-4 mol of blue-sensitive spectral sensitizing dyes A and B were added in an amount of 1.6 × 10 ⁻⁴ mol each, and then the silver content of a silver chlorobromide fine grain emulsion (Br / Cl = 6/4) having a cube side length of 0.05 μm was adjusted. 0.4 g was added. This fine grain emulsion contained in advance 3 × 10 ⁻⁵ mol of potassium hexachloroiridate (IV) per silver amount. Sodium benzenethiosulfonate and a gold sensitizer (chloroauric acid) were added, and the mixture was optimally chemically sensitized at 60 ° C. to give 1- (5-methylureidophenyl) -5-mercaptotetrazole in an amount of 3 per silver. 0 × 10 ^-4 mol was added. From the electron micrograph, the shape of the particles was cubic, the particle size was 0.72 μm, and the coefficient of variation was 0.08. The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution used was a value obtained by dividing the standard deviation of the particle size by the average particle size. Blue-sensitive sensitizing dye

[0101]

Embedded image

(Preparation of Emulsion BLB) 1.0 g of sodium chloride was added to a 2% aqueous solution of lime-processed gelatin, and an acid was added to adjust the pH to 4.5. An aqueous solution (Ag-11) containing 0.05 mol of silver nitrate and an aqueous solution (X-11) containing 0.05 mol of sodium chloride and potassium bromide in total were added and mixed at 40 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.005 mol of potassium bromide (X-12)
, An aqueous solution containing 0.13 mol of silver nitrate (Ag-
13) and an aqueous solution containing 0.13 mol of sodium chloride (X-
13) was added. The temperature was further raised to 75 ° C and pAg
While keeping the pH 7.0, an aqueous solution (Ag-14) containing 0.9 mol of silver nitrate and an aqueous solution (X-14) containing 0.9 mol of sodium chloride were added and mixed.
Aqueous solution (Ag-15) containing 1 mol and sodium chloride
An aqueous solution (X-15) containing 1 mol was added and mixed. At this time, iodide ions equivalent to 0.4 mol% of the total silver are simultaneously added to K
I was added using an aqueous solution of I. After standing for 40 minutes, the resultant was washed by settling at 40 ° C. and desalted. Further, 100 g of lime-processed gelatin was added to adjust the pH to 6.2 and pAg to 7.0. According to the electron micrograph, the shape of the particles was
It is a tabular grain having a surface of 00 ° and a projected area equivalent diameter of 0.8.
2 μm, average thickness 0.13 μm, average aspect ratio 6,
When converted to the side length of the cube, it was 0.41 μm and the coefficient of variation was 0.20. (Iodine content: 0.4 mol%) Each of the blue-sensitive spectral sensitizing dyes A and B was 3.1 × 10 ⁻⁴ mol / mol so as to be equivalent to the dye coverage of the emulsion (BLA).
Ag, 4.6 × 10 ⁻⁴ mol / mol Ag was added. Optimal chemical sensitization at 60 ° C with sodium benzenethiosulfonate and gold sensitizer (chloroauric acid).
7.2 × 10 ⁻⁴ mol / mol Ag of (5-methylureidophenyl) -5-mercaptotetrazole was added.

(Preparation of emulsion BLC) 2.0 g of sodium chloride and 2.8 g of inert gelatin were placed in 1.2 liters of water.
Was added, and 60 cc of an aqueous silver nitrate solution (9 g of silver nitrate) and 60 cc of an aqueous sodium chloride solution (3.2 g of sodium chloride) were added to the container kept at 33 ° C. for 1 minute by a double jet method while stirring. One minute after the completion of the addition, 1 mmol of the crystal habit controlling agent 1 was added. One minute later, 3.0 g of sodium chloride was added. During the next 25 minutes, the temperature of the reaction vessel was raised to 60 ° C. After aging at 60 ° C. for 16 minutes, 290 g of a 10% aqueous solution of phthalated gelatin and 0.8 mmol of crystal habit controlling agent 1 were added. Thereafter, 754 cc (113 g) of an aqueous solution of silver nitrate and 768 of an aqueous solution of sodium chloride 768 were used.
cc (41.3 g of sodium chloride) was added at an accelerated rate over 28 minutes. During this time, 0.48 g of potassium iodide, 11 mg of yellow blood salt and 1 × 10 5 potassium potassium hexachloroiridate (IV) were taken from 21 to 28 minutes.
30c of 0.25M sodium chloride aqueous solution containing ^-8 mol
c was added.

[0104]

Embedded image

Washing was carried out at 40 ° C. for desalination. Further, 100 g of lime-processed gelatin was added, and pH6.
2, adjusted to pAg 7.0. From the electron micrograph, the shape of the particles was tabular grains having a principal plane of {111} plane, a projected area equivalent diameter of 0.82 μm, and an average thickness of 0.13.
μm, an average aspect ratio of 6, and a coefficient of variation of 0.41 μm in terms of the side length of a cube, and a coefficient of variation of 0.25. A {111} flat plate having almost the same size as the emulsion BLB was obtained. (Iodine content: 0.4 mol%) This emulsion was subjected to spectral sensitization and chemical sensitization in the same manner as for emulsion BLB to obtain emulsion BLC.

After subjecting the surface of the reflective support A to a corona discharge treatment, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided, and first to seventh photographic constituent layers are sequentially provided. Thus, a sample (110) of a silver halide color photographic light-sensitive material having the following layer constitution was prepared. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of coating solution for first layer 57 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
g of solvent (Solv-1) 21 g and ethyl acetate 80 m
1 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate.
In 0 g, the mixture was emulsified and dispersed by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion BLA were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener (hardener) for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1) was used. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{15.0mg / m 2, 60.0mg / m} 2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0109]

Embedded image

The silver chlorobromide emulsions of the green and red-sensitive emulsion layers include:
The following spectral sensitizing dyes were used respectively. Green-sensitive emulsion layer

[0111]

Embedded image

(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. ) Red-sensitive emulsion layer

[0113]

Embedded image

(Sensitizing dyes G and H were converted to silver halide 1
To the large emulsion, 8.0 × 10 ^-5 mol, and to the small emulsion, 10.7 × 10 ^-5 mol were added per mol. ) Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. )

[0115]

Embedded image

In addition, the green-sensitive emulsion layer and the red-sensitive emulsion layer
On the other hand, 1- (3-methylureidophenyl) -5-mer
Captotetrazole was added in an amount of 1 mol
3.3 × 10^-FourMol, 1.0 × 10^-3Moles and 5.
9 × 10^-FourMole was added. In addition, the second layer, the fourth layer, the
0.2 mg / m for each of the sixth and seventh layers ^Two,
0.2mg / m^Two, 0.6 mg / m^Two0.1 mg / m^Two
Was added so that In addition, a blue-sensitive emulsion layer and a green-sensitive emulsion layer
4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene is replaced by halogen
1 × 10 per mole of silver halide^-FourMole, 2 × 10^-FourMoles
Added. Also, methacrylic acid and acrylic were used in the red-sensitive emulsion layer.
Butyl acid copolymer latex (weight ratio 1: 1, average
(200,000 to 400,000)) at 0.05 g / m^Two
Was added. The second, fourth and sixth layers have catechols
-3,5-disulfonate disodium each in 6
mg / m^Two, 6mg / m^Two, 18mg / m^TwoSo that
Was added. Also, to prevent irradiation,
(The number in parentheses indicates the coating amount).

[0117]

Embedded image

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzooxazolyl) stilbene; content: 0.03% by weight), bluish dye ( Ultramarine blue)] First layer (blue-sensitive emulsion layer) Emulsion BLA 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd- 2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain side length of 0.45 μm and small-size emulsion B having an average grain side length of 0.35 μm ( The variation coefficients of the grain size distribution are 0.10 and 0.08, respectively. 0.4 mol% of silver bromide is locally applied to a part of the grain surface based on silver chloride in each size emulsion. 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd- 4) 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large-size emulsion C with an average grain side length of 0.40 μm and small-size emulsion C with a 0.30 μm size ( The variation coefficients of the grain size distributions are 0.09 and 0.11, respectively. For each size emulsion, 0.8 mol% of silver bromide is localized on a part of the surface of the silver chloride based grain. 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd) -6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) ) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd -16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05

Sixth layer (ultraviolet ray absorbing layer) Gelatin 0.46 Ultraviolet ray absorbing agent (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25 Seventh layer (protective layer) ) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

Similarly, coating sample (120) in which emulsion BLA of sample (110) was changed to emulsion BLB and BLC,
(130) was produced. Further, the coating samples (111) to (116) obtained by changing the reflective support of the sample (110) to the reflective supports B, B2, C, C2, D, and D2 are reflected by the reflective support of the sample (120). Supports B, B2, C, C
Application samples (121) to 2, D and D2, respectively
Coating samples (131) to (136) were prepared by changing the reflective support of the sample (130) to the reflective support B, B2, C, C2, D, and D2, respectively. See Table 3 for details
It was shown to.

[0134]

[Table 3]

The following experiment was conducted to examine the pressure properties of these coated samples. Experiment The sample was bent for 1 second around a 2 mm diameter stainless steel round bar at an angle of 40 °. Photometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.) for each coated sample
Was used to provide sensitometric tonal exposures. S
Low illumination (5 lux) with C-40 filter
Exposure was for 10 seconds. After the exposure, the following color development processing A was performed. The density of the unfolded portion of the processed sample at an exposure amount giving a density of 2.0 was read by microdensitometry, and the density decrease ΔD due to the bending was measured. If ΔD is a negative value, it indicates that pressure desensitization has occurred, and the greater the absolute value of the value, the greater the pressure desensitization.

The processing steps are described below. [Processing A] The photosensitive material 120 is processed into a roll having a width of 127 mm, imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then replenished to twice the capacity of the color developing tank in the following processing steps. Until this was done, continuous processing (running test) was performed. This treatment using the running liquid was designated as treatment A. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 26.g 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleaching-fixing solution] [Tank solution] [Replenishing solution] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g Ammonium sulfate 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0 6.0

[Rinse liquid] [Tank liquid] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5 or more Table 4 shows the results.

[0140]

[Table 4]

As is clear from Table 4, the sample containing the support of the present invention and the tabular grains has low pressure desensitization and has greatly improved pressure properties. Further, it was found that all of the samples of the present invention had excellent surface smoothness and gloss.

Example 2 The content examined in Example 1 was exactly the same, except that the layer structure of the coated sample was changed as follows, the coated sample was made thinner, and the same experiment was repeated. As a representative example, the sample (21
0), and Table 5 shows the content of each sample.

Preparation of Sample 210 First layer (blue-sensitive emulsion layer) Emulsion BLA 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer ( Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.60 Color mixture prevention agent (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (the same emulsion as in sample 110) 0.14 gelatin 0.73 magenta coupler (ExM) 0.15 ultraviolet absorber (UV-A) 05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 colors Image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-4) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0.06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention layer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (the same emulsion as sample 110) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) 0 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0.04 UV absorber (UV-7) 0.02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protective layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

[0149]

[Table 5]

Each of the prepared coated samples was bent with a 2 mm stainless steel rod at an angle of 40 ° in the same manner as in Experiment 1 of Example 1, and the subsequent color development was performed in accordance with the following development B. , Super fast processing.

[Processing B] The photosensitive material 220 was 127 m
After processing into a roll having a width of m and imagewise exposure, continuous processing (running test) was carried out until replenishment of twice the capacity of the color developing tank in the following processing step. The processing liquid using this running liquid was referred to as processing B. The processing is mini-lab printer processor PP12 manufactured by Fuji Photo Film Co., Ltd.
58AR was used.

Processing Step Temperature Time Replenishment amount * Color development 45.0 ° C. 12 seconds 45 ml Bleaching and fixing 40.0 ° C. 12 seconds 35 ml Rinse (1) 40.0 ° C. 4 seconds-Rinse (2) 40.0 ° C. 4 sec - rinse (3) ** 40.0 ℃ 4 seconds - rinsing (4) ** 40.0 ℃ 4 seconds 121 ml * photosensitive material 1 m ² per replenishment amount ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D Install in rinse (3), take out rinse liquid from rinse (3), and send to reverse osmosis membrane module (RC50D) by pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 10.0 g 22.0 g potassium carbonate 26. 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 75.0 g 150.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g meta-weight Potassium sulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 5.5 5.2

[Rinse solution] [Tank solution] [Replenisher] Dechlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml 1000 ml pH 6.0

Table 6 shows the results.

[0157]

[Table 6]

As is clear from Table 6, the pressure desensitization in the ultra-rapid processing in the thinned sample was remarkable, but in the sample containing the support of the present invention and the tabular grains, the pressure desensitization was low, and the pressure desensitization was low. The properties were greatly improved, and the effect was confirmed in ultra-rapid processing of thinned samples. Further, it was found that all of the samples of the present invention had excellent surface smoothness and gloss.

Example 3 Samples (110) to (116), (120) to (12)
6), (130) to (136), (210) to (21)
6), (220) to (226), (230) to (23)
An image was formed by laser scanning exposure using the method of 6). As a laser light source, a semiconductor laser GaAlA
s (oscillation wavelength: 808.5 nm) as the excitation light source
473 nm which is obtained by converting a G solid-state laser (oscillation wavelength: 946 nm) by wavelength conversion using a LiNbO ₃ SHG crystal having an inverted domain structure, and a semiconductor laser GaAs
A YVO ₄ solid-state laser (oscillation wavelength of 1064 nm) using 1As (oscillation wavelength of 808.7 nm) as an excitation light source was converted into a wavelength of 532 nm by a LiNbO ₃ SHG crystal having an inversion domain structure, and AlGaIn
P (oscillation wavelength about 680 nm: Type No.
LN9R20). The laser light of each of the three colors is moved in a direction perpendicular to the scanning direction by a polygon mirror, so that the sample can be sequentially scanned and exposed. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant.
The effective beam diameter is 80 μm and the scanning pitch is 42.
3 μm (600 dpi), and the average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. After exposure, samples (110) to (116), (120) to (126),
(130) to (136) show the color development processing A for the sample (2).
10) to (216), (220) to (226), (23)
In 0) to (236), color development processing B was performed. When the same evaluations as in Examples 1 and 2 were performed, it was found that laser scanning exposure had smaller pressure desensitization, and that the photosensitive material of the present invention became more effective as exposure to higher illuminance was performed.

[0160]

As described above, the silver halide color photographic light-sensitive material of the present invention has excellent surface smoothness and gloss.
In addition, there is little desensitization that occurs when pressure is applied to the photosensitive material or when the photosensitive material is bent, and therefore, the handleability is excellent.
Further, while maintaining this characteristic, it is possible to realize a photographic image forming system and an ultra-rapid processing system by high-illuminance short-time exposure.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 7/407 G03C 7/407

Claims (8)

[Claims] 1. A silver halide color photographic material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, wherein the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the silver halide emulsion layer and the silver halide emulsion layer has micropores.
An axis-stretched polyolefin layer, wherein at least one silver halide emulsion in the silver halide emulsion layer has a silver chloride content of 95 mol% or more and 50% or more of the projected area of all silver halide grains has an average Aspect ratio of 2 or more, average thickness
A silver halide color photographic light-sensitive material, characterized by tabular grains of less than 0.3 μm. 2. A silver halide color photographic light-sensitive material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, wherein the reflective support is a water-resistant resin-coated support, and At least one of the water-resistant resin layers between the silver halide emulsion layer and the silver halide emulsion layer has micropores.
An axially stretched polyolefin layer, wherein a polyolefin layer having no micropores is provided between the polyolefin layer and the silver halide emulsion layer, and at least one silver halide emulsion of the silver halide emulsion layer is Silver chloride content 95
At least 50% of the projected area of all silver halide grains
The above are silver halide color photographic light-sensitive materials characterized by tabular grains having an average aspect ratio of 2 or more and an average thickness of less than 0.3 μm. 3. A silver halide color photographic material having at least three silver halide emulsion layers having different photosensitivity on a reflective support, wherein the reflective support is synthesized from a dicarboxylic acid and a diol by polycondensation. A composition obtained by mixing and dispersing a white pigment in a resin containing 50% by weight or more of polyester is coated on at least the emulsion-coated side, and at least one silver halide emulsion in the silver halide emulsion layer is formed of a chloride. With a silver content of 95 mol% or more,
A silver halide color photographic light-sensitive material, wherein 50% or more of the projected area of all silver halide grains are tabular grains having an average aspect ratio of 2 or more and an average thickness of less than 0.3 µm. 4. The silver halide color photographic light-sensitive material according to claim 3, wherein the polyester of the reflection support is a polyester containing polyethylene terephthalate as a main component. 5. A silver halide color photographic light-sensitive material according to claim 1, wherein the tabular grains of the silver halide color photographic light-sensitive material have a {100} major surface. 6. A silver halide color photographic light-sensitive material according to claim 1, wherein the tabular grains of the silver halide color photographic light-sensitive material have a {111} major surface. 7. An image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed with a light beam modulated based on image information and then subjected to a development process, wherein the silver halide color photographic light-sensitive material is characterized in that: A color image forming method, which is the silver halide color photographic light-sensitive material according to any one of the above. 8. A color image forming method comprising processing the silver halide color photographic light-sensitive material according to claim 1 in a color development processing time of 20 seconds or less.