JP2001201822A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve sharpness, brightness and light resistance and to represent depth. SOLUTION: For the silver halide photographic sensitive material with at least one photosensitive silver halide emulsion layer on the base, resin coated paper with a resin layer is used as the base and a pearlescent pigment is contained in the resin layer on the silver halide emulsion layer side of the base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material containing a pearlescent pigment.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials have hitherto been used, but the demands on the light-sensitive materials are becoming increasingly severe.

An object of the present invention is to provide a silver halide photographic material in which sharpness (resolution) and brightness (brightness) are improved, an image having a sense of depth can be formed, and light resistance is improved. And

[0004]

The present invention is as follows. <1> A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material, wherein a resin-coated paper having a resin layer is used as the support, and a pearlescent pigment is contained in the resin layer of the support on the side of the photosensitive silver halide emulsion layer. <2> The silver halide photographic material as described in <1>, wherein the resin layer contains a polyolefin resin. <3> The resin layer contains an electron beam cured product of an unsaturated organic compound curable by electron beam irradiation.
1> The silver halide photographic light-sensitive material as described above. <4> The method according to <1>, wherein the resin layer is a laminate including a layer made of a polyolefin resin and a layer made of an electron beam cured product of an unsaturated organic compound curable by electron beam irradiation. Silver halide photographic material. <5> A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support,
A silver halide photographic material comprising a layer containing gelatin and a pearlescent pigment provided between the support and the photosensitive silver halide emulsion layer. <6> The silver halide photographic light-sensitive material according to any one of <1> to <5>, wherein the pearlescent pigment is a flat mica whose surface is coated with titanium dioxide fine particles.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, paper, synthetic paper, polymer film, resin-coated paper having a resin layer and the like can be used as the support, but it is preferable to use resin-coated paper.

[0006] Paper substrates used for resin-coated paper include:
Natural pulp paper containing natural pulp as a main component, mixed paper made of natural pulp and synthetic fibers, synthetic fiber paper containing synthetic fibers as a main component, and synthetic resin films made of polystyrene, polyethylene terephthalate, polypropylene, etc. However, natural pulp paper (hereinafter simply referred to as base paper) is particularly preferably used.
The base paper may be neutral paper (pH 5 to 9) or acidic paper, but neutral paper is preferred.

[0007] Base paper includes fillers such as alkyl ketene dimer, clay, talc, calcium carbonate and urea resin fine particles, sizing agents such as rosin, higher fatty acid salts, paraffin wax and alkenyl succinic acid, and paper strength enhancement such as polyacrylamide. And a fixing agent such as a sulfuric acid band can be added. In addition, a dye, a pigment, a slime control agent, an antifoaming agent and the like are added as required. Further, a softening agent can be added as needed. Regarding the softening agent, see, for example, New Paper Processing Handbook (edited by Kayaku Time Co., Ltd.) 5
Although it is described on pages 54 to 555 (issued in 1980), those having a molecular weight of 200 or more are particularly preferable. This softener has a hydrophobic group having 10 or more carbon atoms and is an amine salt or a quaternary ammonium salt which self-fixes to cellulose. Specific examples of the softener include a reaction product of a maleic anhydride copolymer and a polyalkylene polyamine,
Reaction products of higher fatty acids with polyalkylene polyamines, reaction products of urethane alcohols with alkylating agents, quaternary ammonium salts of higher fatty acids, and the like, and especially maleic anhydride copolymers and polyalkylene polyamines Reaction products, reaction products of urethane alcohols and alkylating agents are preferred.

[0008] The base paper is prepared by making a pulp slurry containing the above-mentioned pulp and additives such as fillers, sizing agents, paper-strengthening agents, fixing agents and the like added as required by a paper machine such as a fourdrinier paper machine. It is manufactured by drying, drying and winding. A surface sizing treatment can be performed before or after the drying. For the surface sizing treatment, a film-forming polymer such as gelatin, starch, carboxymethylcellulose, polyacrylamide, polyvinyl alcohol, or a modified product of polyvinyl alcohol is used. Examples of the modified polyvinyl alcohol include carboxyl group-modified products, silanol-modified products, and copolymers with acrylamide. The coating amount of the film-forming polymer is usually 0.1.
It is adjusted to ¹ to 5.0 g / m ² , preferably 0.5 to 2.0 g / m ² . Further, an antistatic agent, a fluorescent whitening agent, a pigment, an antifoaming agent, and the like can be added to the film-forming polymer as needed.

[0009] After the drying and during the winding, a calendering treatment can be performed. In the case where the surface sizing treatment is performed after drying, the calendering treatment can be performed before or after the surface sizing treatment. However, it is preferable to perform the calendering treatment in the final finishing step in which various treatments are performed. As the metal roll and the elastic roll used in the calendering process, known rolls used in the production of ordinary paper are used. The base paper is finally adjusted to a film thickness of 50 to 250 μm by the above-described calendering process.
The density of the base paper is usually 0.8 to 1.3 g / m ³ , preferably 1.0 to 1.2 g / m ³ .

A resin layer is provided on at least one surface of the paper substrate as described above. Before coating the resin on the paper substrate, it is preferable to perform an activation process such as a corona transfer process, a flame process, a glow discharge process, and a plasma process on the paper substrate.

Examples of the resin constituting the resin layer include polyolefins and electron beam cured products of unsaturated organic compounds which can be cured by electron beam irradiation. The resin layer may be a single layer or a multilayer. In the case of a multilayer, a combination of a polyolefin layer, a combination of an electron beam cured product layer, and a combination of a polyolefin layer and an electron beam cured product layer can be used.

[0012] Among the polyolefins, polyethylene is particularly preferred, but polyester is also effective. As the polyester, 2,6-naphthalenedicarboxylic acid (NDC
Polyesters of A) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid and EG, and polyethylene terephthalate are preferred.

The unsaturated organic compounds curable by an electron beam include (1) aliphatic, alicyclic, and aromatic
(2) acrylate compounds of aliphatic, alicyclic, and aromatic alcohols to which alkylene oxide is added, and (3) poly (alkylene glycol) and acrylate compounds of polyalkylene glycol. Acryloyl alkyl phosphates, (4) reaction product of carboxylic acid, polyol and acrylic acid, (5)
Reaction products of isocyanate, polyol and acrylic acid, (6) reaction product of epoxy compound and acrylic acid, (7) reaction product of epoxy compound, polyol and acrylic acid, etc.

Specifically, polyoxyethylene epichlorohydrin-modified bisphenol A diacrylate, dicyclohexyl acrylate, epichlorohydrin-modified polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, hydroxybivalic acid ester neopentyl glycol diacrylate, nonylphenoxy Polyethylene glycol acrylate, ethylene oxide-modified phenoxylated phosphoric acid acrylate, ethylene oxide-modified phthalic acid acrylate, polybutadiene acrylate, caprolactam-modified tetrahydrofurfuryl acrylate, tris (acryloxyethyl) isocyanurate, trimethylolpropane triacrylate, pentaerythritol triacrylate,
Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, polyethylene glycol diacrylate, 1,4-butadienediol diacrylate, neopentyl glycol diacrylate,
And neopentyl glycol-modified trimethylolpropane diacrylate. In the present invention, these compounds can be used alone or in combination of two or more.

A pearlescent pigment can be added to the resin layer on the side where the photosensitive silver halide emulsion layer described later is provided. When the resin layer on the side on which the photosensitive silver halide emulsion layer is provided is a multilayer, a pearlescent pigment may be added to at least one layer. Although there are various pearlescent pigments, the pearlescent pigment used in the present invention is required to have no adverse effect on the photographic emulsion. Specifically, there are guanine crystals extracted from fish scales, bismuth oxychloride and natural mica coated with anatase-type titanium oxide and rutile-type titanium oxide. From the viewpoints of price, light fastness, stability, photographic emulsion properties, etc., a type in which titanium oxide fine particles are coated on a flat mica is preferably used.
Such pearlescent pigments are sold under the registered trade name Iriodin by E. Merck of West Germany, and include various types such as those having a particle size, a coverage of titanium oxide, and a coating of iron oxide. It is sold as a silver type, an iris type, a coloring type and the like, and a white type can be used in the present invention. The method for producing pearlescent pigments is described in JP-A-5-61153.

The thickness of the pearlescent pigment preferably used in the present invention is preferably 0.1 to 0.5 μm, and the average particle size (planar size) is preferably 3 to 150 μm, more preferably 5 to 150 μm. １００100 μm.
For diffusion control, the thinner the better, the better, and the planar size is better as long as the smoothness and transparency of the coated surface are not deteriorated. When the plane size is smaller than 3 μm, the effect of improving sharpness and brightness is low.
If it is larger than 50 μm, the smoothness of the resin layer containing the pearlescent pigment is inferior. The aspect ratio of the pearlescent pigment is preferably 6 or more, more preferably 10 or more, and particularly preferably 15 or more.

The content of the pearlescent pigment in the resin layer is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight. Less than 0.5% by weight has less effect,
If it is more than 70% by weight, the dispersibility is insufficient, and the production stability is poor.

A white pigment can be added to the resin layer. Examples of the white pigment to be added include titanium dioxide, barium sulfate, barium carbonate, calcium carbonate, lithopone, alumina white, zinc oxide, silica antimony trioxide, titanium phosphate and the like. These can be used alone or as a mixture. Among these, titanium dioxide and zinc oxide are particularly preferred from the viewpoint of whiteness, dispersibility and stability. The filling amount of the white pigment in the resin varies depending on the type of the white pigment, the type of the resin and the thickness of the resin layer, but is usually selected to be between 5 and 20% by weight.

Further, known additives such as a fluorescent whitening agent, an antioxidant and a bluing agent can be added to the resin layer. Examples of titanium dioxide, a fluorescent brightening agent and a bluing agent include those described in JP-A-9-204001.

The polyolefin resin layer may include two rolls of a pearlescent pigment, a dispersing aid, and a white pigment, if necessary.
Kneading into the resin with a kneader such as a three-roll, kneader, Banbury mixer, continuous kneader, etc. to form pellets,
This pellet is diluted with a polyolefin resin as necessary, melted, and then, on a paper substrate, is usually used for laminating, sequential laminating, or single-layer or multilayer extrusion such as a foot block type, a multi-manifold type, and a multi-slot type. It is formed by lamination by any one of lamination methods using a die. The shape of the die is not particularly limited, but generally a T die, a coat hanger die and the like are preferably used.

In order to improve the adhesion between the paper substrate and the resin layer, rosin derivative resin, terpene resin (for example, high-molecular β-pinene), cumarone / indene resin, petroleum hydrocarbon resin, etc. A selectable tackifier resin can be used. These may be used alone or as a mixture of two or more.

Specific examples of the petroleum hydrocarbon resin include aliphatic petroleum resin, aromatic petroleum resin, dicyclopentadiene petroleum resin, copolymer petroleum resin, hydrogenated petroleum resin, and alicyclic petroleum resin. And petroleum resins. The aliphatic petroleum resin preferably has 5 carbon atoms, and the aromatic petroleum resin particularly preferably has 9 carbon atoms. The compounding amount of such a tackifier resin is in the range of 0.5 to 60% by weight based on the polyolefin, and preferably 10 to 60% by weight.
３５35% by weight. If the compounding amount of the tackifier resin is less than 0.5% by weight, poor adhesion will result. If it exceeds 60% by weight, thickness unevenness in the width direction of the coating will occur at the time of production, and especially the end portion of the support will become thick. Adversely affect the efficiency of the system. Further, an adhesive resin that can be thermally fused to the polyolefin may be used. Examples of such an adhesive resin include an ionomer, an ethylene-vinyl acetate copolymer (EVA), an ethylene-acrylic acid copolymer, and a metal salt thereof. The amount of the adhesive resin is in the range of 20 to 500% by weight, preferably 50 to 200% by weight, based on the polyolefin.
Incidentally, a tackifier resin and an adhesive resin may be used in combination.

In the case of a layer composed of an electron beam-curable unsaturated organic compound, a pearlescent pigment may be dispersed in the electron beam-curable unsaturated organic compound, if necessary, and the resultant is coated on a paper substrate. Apply. To disperse the pearlescent pigment in the electron beam-curable unsaturated organic compound, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a cowles dissolver, a homomixer, a sand grinder, a planetary mixer, and An ultrasonic disperser or the like can be used.

The method for applying the electron beam-curable unsaturated organic compound composition includes, for example, bar coating, blade coating, squeeze coating, air knife coating, roll coating, gravure coating, and transfer coating. Either may be used. Further, for this purpose, a fountain coater or a slit die coater method can be used. In particular, when the surface of a metal drum is used as a molding surface, a roll coating method using a rubber roll or an offset gravure coating method is used to prevent scratches on the molding surface, and a non-contact type fountain is used. A coater or a slit die coater method is advantageously used.

In the present invention, various types of back coat layers can be applied to the support to prevent static charge and curl. The back coat layer is made of Japanese Patent Publication No. 52-20020.
No., JP-B-57-9059, JP-B-57-53940
No., JP-B-58-56859, JP-A-59-2148.
No. 49, an inorganic antistatic agent, an organic antistatic agent, a hydrophilic binder, a latex, a curing agent, a pigment, a surfactant and the like described or exemplified in each publication such as JP-A-58-184144. Can be contained.

The outermost layer surface of the resin layer on the emulsion coating side is provided with a glossy surface, a fine surface, a matte surface or a silk surface as described in JP-A-55-26507, and the back surface is provided with a matte surface. You may do. The surface after molding can be subjected to an activation treatment such as a corona discharge treatment or a flame treatment, and after the activation treatment, a subbing treatment as described in JP-A-61-846443 can be performed. .

In the present invention, a layer containing gelatin and a pearlescent pigment can be provided on a support. This layer can be used as a subbing layer. As the pearlescent pigment, those described above can be used.

As gelatin, phthalated gelatin, lime-processed gelatin and the like can be used. Also, PAG
Gelatin having a viscosity of 10 mP to 30 mP according to Method I and a jelly strength of 15 g to 70 g according to the PAGI method can also be suitably used. If the viscosity of the PAGI method is less than 10 mP,
The decrease in the viscosity of the coating liquid increases, and the dispersion state of the pearlescent pigment in the coating liquid deteriorates, while the viscosity of the PAGI method is 30 m.
If it is larger than P, the viscosity of the coating liquid increases, and coating failure is likely to occur. The jelly strength of the PAGI method was 15
If it is smaller than g, the strength of the coating film decreases and the adhesive strength to the support decreases. On the other hand, if the jelly strength of the PAGI method is greater than 70 g, the curl of the coating film increases due to environmental changes.

Here, the viscosity of the PAGI method and the jelly strength of the PAGI method are measured based on the test by the Pagui's Method: Photographic Gelatin Test Method, 7th edition (1992 edition), issued by the Joint Review Committee for Photographic Gelatin Test Method. it can. This gelatin can be obtained by reducing the molecular weight of known gelatin (ordinary gelatin) produced by a usual method. The term "normal gelatin" used herein means, for example, "river and gelatin (edited by Abiko Yoshihiro, published by Nippon Nippon, Gelatin Industry Association, 1987), and used as a raw material for lime, such as beef bone, cow skin, and pig skin. It is manufactured by treating with an acid or the like, and has much higher viscosity and jelly strength than the above gelatin.

[0030] Ordinary gelatin is characterized by conditions such as raw materials, processing method (for example, lime treatment or acid treatment) and extraction conditions (temperature and number of extractions). Any gelatin may be used to reduce the molecular weight, but those having a low extraction temperature and a small number of extractions are preferred because both low viscosity and jelly strength can be achieved. As a method for reducing the molecular weight of gelatin, there is a method using an enzyme, heat, or the like. Of these, a method using an enzyme is preferable. As the enzyme, for example, papain is preferable. Lowering the molecular weight by heat is disadvantageous because when the viscosity is reduced to a preferable value, the jelly strength decreases.

The low-molecular-weight gelatin may be cross-linked by using a hardening agent, if necessary. As the hardener, a known hardener used as a hardener for gelatin can be used. Specific examples of the hardener include a vinyl sulfone compound, an active halogen compound, an isocyanate compound, and an epoxy compound. Among them, the epoxy compound is particularly preferable. Examples of the epoxy compound include the following.

[0032]

Embedded image

The coated amount of gelatin is 0.05 to 10 g /
m ² is desirable. Further, the addition amount of the pearlescent pigment in gelatin is preferably from 1 to 90% by weight, more preferably from 30 to 70% by weight. Less than 1% by weight has little effect,
If the amount is more than 0% by weight, the dispersibility is insufficient.

A photosensitive silver halide emulsion layer is formed on the resin layer containing the pearlescent pigment or the layer containing the pearlescent pigment and gelatin on the support. In forming the light-sensitive silver halide emulsion layer and the non-light-sensitive layer, it is preferable to use a hydrophilic colloid, specifically, gelatin as a binder.
Each layer contains compounds necessary for image formation, such as a silver halide emulsion, a color former emulsion and a color mixing inhibitor emulsion.

The silver halide photographic light-sensitive material of the present invention is preferably provided with at least one yellow-color-forming silver halide emulsion layer, one magenta-color-forming silver halide emulsion layer, and one cyan-color-forming silver halide emulsion layer on a support. It can be formed by coating. In a general color photographic paper, the color reproduction by the subtractive color method can be performed by including a color coupler that forms a dye having a complementary color with the light to which the silver halide emulsion is exposed. In general color photographic paper, silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive, and red-sensitive spectral sensitizing dyes in the order of the above-described color-forming layers, respectively, and on a support in the order described above. It can be formed by coating. However, the order may be different. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

In the present invention, the silver halide grains may be 9
It is preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide grains in which 5 mol% or more is silver chloride. In particular, in the present invention, silver bromochloride or silver chloride substantially free of silver iodide can be preferably used in order to speed up the development processing time. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, 0.01 to 3 mol% of the emulsion surface described in JP-A-3-84545 is used for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the stability over time of the photosensitive material. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (shell)
[Single or plural layers] grains having a so-called laminated structure having different halogen compositions from each other or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grains. Particles having a structure in which portions having different compositions are joined together) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided.

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

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grains, and the number average thereof) is 0.1. 1μ to 2μ is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion has a regular (regular) shape such as cubic, tetrahedral or octahedral.
One having an lar) crystal form, one having an irregular (for example, spherical or plate-like) crystal form, or one having a complex form thereof can be used. Further, it may be composed of a mixture of those having various crystal forms. In the present invention, among these, the particles having the above-mentioned regular crystal form are contained in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more. In addition to these, emulsions in which tabular grains having an average aspect ratio (diameter / circle diameter in circle) of 5 or more, preferably 8 or more, as projected areas exceed 50% of all grains can be preferably used. As the tabular grains, both tabular grains having a (111) plane and tabular grains having a (100) plane can be preferably used.

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

It is preferred that the localized phase of silver halide grains or its substrate contains a foreign metal ion or its complex ion. Preferred metal is VI of the periodic table
Metal ions or metal complexes belonging to Group II, Group IIb,
And lead ions and thallium ions. The effect of the constitution of the light-sensitive material of the present invention is more remarkable when a gold-sensitized high silver chloride emulsion is used. The photosensitive material of the present invention may be used in a printing system using a normal negative printer, a gas laser, a light-emitting diode, a semiconductor laser, a solid-state laser using a semiconductor laser as an excitation light source, and a nonlinear optical crystal. It is preferably used for digital scanning exposure using monochromatic high-density light such as a combined second harmonic generation light source (SHG). In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) combining a solid-state laser and a nonlinear optical crystal. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

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

As the cyan coupler, JP-A-2-33
No. 144, a diphenylimidazole cyan coupler, a 3-hydroxypyridine cyan coupler described in EP 0 333 185 A2, a cyclic active methylene cyan coupler described in JP-A 64-32260, and a European patent. EP0456226A1
The pyrrolopyrazole type cyan coupler described in the specification,
Preference is given to using pyrroleimidazole cyan couplers described in EP 0 484 909 and pyrrolotriazole cyan couplers described in EP 0 488 248 and EP 0 411 197 A1.
Among them, use of a pyrrolotriazole type cyan coupler is particularly preferred.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler can be used. Among them, JP-A-61-65245 discloses a colorant in terms of hue, image stability, and coloring.
Pyrazolotriazole couplers having a secondary or tertiary alkyl group directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring as described in JP-A-61-65246. Pyrazoloazole couplers containing a sulfonamide group, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and EP 226,849A and EP 294,785A It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in (1).

As the yellow coupler, an acylacetamide-type yellow coupler having a 3- to 5-membered cyclic structure in an acyl group described in European Patent No. EP0447969A1 and a cyclic structure described in European Patent No. EP0482552A1 can be used. A malondianilide type yellow coupler and an acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 are preferably used. Among them, it is particularly preferable to use an acylacetamide-type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide-type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

The silver halide emulsion and other materials (additives, etc.) applied to the silver halide photographic light-sensitive material of the present invention.
And as a photographic constituent layer (layer arrangement etc.), in addition to the above,
The following patent publications, in particular European Patent EP 0,355,660
A2 (JP-A-2-139544) is preferably used.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

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 Adjustment of Support A wood pulp composed of 100 parts by weight of LBKP was subjected to Canadian Freeness 300 using a double disc refiner.
beaten to 0.5 ml, epoxidized behenamide 0.5 part by weight, anionic polyacrylamide 1.0 part by weight, polyamide polyamine epichlorohydrin 0.1 part by weight, and cationic polyacrylamide 0.5 part by weight to absolute pulp weight ratio. And weighed by a Fourdrinier paper machine 150 g / m
² of the base paper and papermaking, surface size polyvinyl alcohol 1.0 g / m ² bone dry weight, and adjusted to a density 1.0 by calendering.

After performing a corona discharge treatment on the wire surface (back surface) of the base paper, high-density polyethylene was coated to a resin thickness of 35 μm by a melt extruder to form a back surface resin layer composed of a mat surface.

After a corona discharge treatment was applied to the felt surface (front surface) of the base paper, low-density polyethylene containing 10 parts by weight of anatase type titanium oxide and a small amount of ultramarine blue was melted by a hot melt extruder to a resin thickness of 30 μm. To form a surface resin layer having a glossy surface. 60 parts by weight of water was added to 40 parts by weight of an enzymatically decomposed gelatin (average molecular weight 10,000, PAGI viscosity 15 mP, PAGI jelly strength 20 g) of the undercoat layer, and the mixture was stirred at 40 ° C. to dissolve the gelatin.

Pearlescent pigment (Irio, manufactured by MERCK, Inc.)
40 parts by weight of din # 123, particle size of 5 to 25 μm, titanium oxide coverage 39%) and 60 parts by weight of water were mixed and stirred, and then added to the above gelatin solution to prepare an undercoat liquid. Before further coating, the following epoxy-based gelatin hardener 7
Parts by weight were added to the undercoat solution.

[0054]

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After the surface resin layer of the support was subjected to corona discharge treatment, the undercoat liquid was applied after drying so that the coating amount was 2.0 g / m ² . Formation of a photographic constituent layer On the undercoat layer, a photographic constituent layer was formed in the same manner as the photographic materials 101A to 101G of Example 1 of JP-A-9-204001 to obtain a silver halide photographic light-sensitive material. (Example 2) Adjustment of support Wood pulp composed of 100 parts by weight of LBKP was subjected to Canadian Freeness 300 by a double disc refiner.
beaten to 0.5 ml, epoxidized behenamide 0.5 part by weight, anionic polyacrylamide 1.0 part by weight, polyamide polyamine epichlorohydrin 0.1 part by weight, and cationic polyacrylamide 0.5 part by weight to absolute pulp weight ratio. And weighed by a Fourdrinier paper machine 150 g / m
² of the base paper and papermaking, surface size polyvinyl alcohol 1.0 g / m ² bone dry weight, and adjusted to a density 1.0 by calendering.

After the corona discharge treatment was performed on the wire surface (back surface) of the base paper, high-density polyethylene was coated to a resin thickness of 35 μm by a melt extruder to form a back surface resin layer composed of a mat surface.

After performing corona discharge treatment on the felt surface (front surface) side of the base paper, 5 parts by weight of pearlescent pigment (Iriodin # 123, manufactured by MERCK, particle size 5 to 25 μm, titanium oxide coverage 39%), Low-density polyethylene containing 10 parts by weight of anatase type titanium oxide and a trace amount of ultramarine blue was coated with a hot melt extruder so that the resin thickness became 30 μm, to form a surface resin layer having a glossy surface. 60 parts by weight of water was added to 40 parts by weight of an enzyme-decomposed gelatin (average molecular weight 10,000, PAGI viscosity 15 mP, PAGI jelly strength 20 g) of the undercoat layer, and the mixture was stirred at 40 ° C. to dissolve the gelatin and prepare an undercoat liquid. .

After the surface resin layer of the support was subjected to corona discharge treatment, the undercoat liquid was dried and applied so that the coating amount was 0.1 g / m ² . Formation of photographic constituent layer The photographic constituent layer in Example 1 was formed on the undercoat layer,
A silver halide photographic light-sensitive material was obtained. Example 3 Adjustment of Support Material Wood pulp consisting of 100 parts by weight of LBKP was subjected to Canadian Freeness 300 using a double disc refiner.
beaten to 0.5 ml, epoxidized behenamide 0.5 part by weight, anionic polyacrylamide 1.0 part by weight, polyamide polyamine epichlorohydrin 0.1 part by weight, and cationic polyacrylamide 0.5 part by weight to absolute pulp weight ratio. And weighed by a Fourdrinier paper machine 150 g / m
² of the base paper and papermaking, surface size polyvinyl alcohol 1.0 g / m ² bone dry weight, and adjusted to a density 1.0 by calendering.

After performing a corona discharge treatment on the wire surface (back surface) of the base paper, high-density polyethylene was coated by a melt extruder so as to have a resin thickness of 35 μm, thereby forming a back surface resin layer composed of a mat surface.

Further, after a corona discharge treatment was performed on the felt surface (front surface) side of the base paper, an electron beam-curable resin layer was applied as described below. <Electron beam curable resin composition for outermost layer> 80 parts by weight of dipentaerythritol hexaacrylate 10 parts by weight of titanium dioxide 10 parts by weight of pearlescent pigment (manufactured by MERCK, Iriodin # 123) 10 parts by weight of a mixture of the above components for 1 hour with a paint conditioner The mixture was mixed to prepare an electron beam curing resin composition for the outermost layer.

The composition was applied to the surface of a chromium-plated metal plate used as a molding surface using a wire bar so that the applied amount after curing was 5 g / m ² .
An acceleration voltage of 175 kV and an absorbed dose of 2 Mra
An electron beam was irradiated under the condition of d, and was cured to form an outermost layer. <Electron Beam Curable Resin Composition for Inner Layer> Bifunctional urethane acrylate oligomer 36 parts by weight Bifunctional acrylate monomer 24 parts by weight Titanium dioxide 30 parts by weight Pearlescent pigment (Merck, Iriodin # 123) 10 parts by weight The mixture was mixed for 1 hour with a paint conditioner to prepare an electron beam-curable resin composition for the inner layer.

This composition was applied on an undercoat layer on a support using a wire bar so that the applied amount after curing was 25 g / m ^2, and the applied liquid layer was applied onto the above-mentioned metal plate molding surface. Was irradiated with an electron beam from the base paper side under the conditions of an acceleration voltage of 175 kV and an absorbed dose of 2 Mrad, and this was cured and adhered. Next, the resin-coated paper obtained in the above process was peeled off from the metal plate molding surface,
A support was obtained. 60 parts by weight of water was added to 40 parts by weight of an enzyme-decomposed gelatin (average molecular weight 10,000, PAGI viscosity 15 mP, PAGI jelly strength 20 g) of the undercoat layer, and the mixture was stirred at 40 ° C. to dissolve the gelatin and prepare an undercoat liquid. .

After the surface resin layer of the support was subjected to a corona discharge treatment, the undercoating liquid was dried and applied so that the coating amount was 0.1 g / m ² . Formation of photographic constituent layer The photographic constituent layer in Example 1 was formed on the undercoat layer,
A silver halide photographic light-sensitive material was obtained. (Comparative Example 1) A silver halide photographic light-sensitive material was prepared in the same manner as in Example 1 except that the undercoat layer used in Example 2 (coating amount after drying was 0.1 g / m ² ) was provided in place of the undercoat layer in Example 1. Made the material. Comparative Example 2 A silver halide photographic material was prepared in the same manner as in Example 2 except that the resin layer on the felt side of the support used in Example 2 did not contain a pearlescent pigment. Comparative Example 3 A silver halide photographic material was prepared in the same manner as in Example 3 except that the resin layer of the support used in Example 3 did not contain a pearlescent pigment.

The following evaluations were made on these silver halide photographic materials. (1) Sharpness The resolution chart is closely attached to the silver halide photographic material,
Exposure with green light and color image processing. The densities of the image portion and the background portion of the processed silver halide photographic light-sensitive material were measured with a microdensitometer, calculated by a personal computer according to a conventional method, and calculated for the CTF (C
ontrast Transfer Function
n: contrast transfer function, value at 10 lines / mm) was determined as the image sharpness.

The larger the value of CTF, the higher the sharpness of the image. (2) Brightness The obtained silver halide photographic light-sensitive material was exposed from a color negative film, baked, and subjected to color development to obtain a color print.

By visual comparison of the printed images, evaluations of 感, △, Δ, and × were made from those having a brilliant feeling. (3) Image lightfastness A strip schart having magenta, yellow, and cyan density gradations was printed on a silver halide photographic light-sensitive material and subjected to color development processing to obtain a density gradation strip splint.

[0067] This print is
rCI65 (Atlas Electric Device)
e co. Irradiation at 0.9 W / m ² for 4 weeks.

The reflection density of the magenta component before the irradiation treatment is measured in advance, and the reflection densities after the irradiation test, which are approximately at the reflection density of about 1.0, are measured. , And expressed as a percentage.

The higher the number, the better the image light fastness.

[0070]

[Table 5] It can be seen that the silver halide photographic light-sensitive materials of the examples are superior to those of the comparative examples in sharpness, shine and image light fastness. In particular, when a photograph such as a night view, a wedding ceremony, or a portrait was visually compared with the color print of the comparative example, a brilliant image with a shining feeling was obtained.

[0071]

According to the present invention, sharpness and brightness are improved by using a pearlescent pigment, whereby an image having a sense of depth can be formed and light resistance can be improved.

Claims (6)

[Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein a resin-coated paper having a resin layer is used as the support. A silver halide photographic material comprising a pearlescent pigment in a resin layer on the side of a silver halide emulsion layer. 2. The silver halide photographic light-sensitive material according to claim 1, wherein said resin layer contains a polyolefin resin. 3. The silver halide photographic material according to claim 1, wherein said resin layer contains an electron beam cured product of an unsaturated organic compound which can be cured by irradiation with an electron beam. 4. The resin layer according to claim 1, wherein said resin layer is a laminate comprising a layer made of a polyolefin resin and a layer made of an electron beam cured product of an unsaturated organic compound curable by electron beam irradiation. The silver halide photographic light-sensitive material as described above. 5. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein gelatin and a pearlescent pigment are provided between the support and the photosensitive silver halide emulsion layer. A silver halide photographic material comprising a layer containing 6. The silver halide photographic light-sensitive material according to claim 1, wherein the pearlescent pigment is a flat mica whose surface is coated with titanium dioxide fine particles.