JP2000290509A - Image forming material and photosensitive material of photograph using silver halide for thermal development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-dispersing material excellent in storage stability and giving an image forming material which improves photography performance by including inorganic particles fixed with a water soluble polymer on the surface and polymer particles. SOLUTION: Inorganic particles fixed with a water soluble polymer on the surface includes, for example, inorganic particles fixed with a water soluble polymer of a formula on colloidal silica. Further, the polymer particles includes, for example, polyethylhexyl-acrylate. The inorganic particles fixed with the water soluble polymer on the surface and the polymer particles are contained in at least one layer of hydrophilic colloidal layers of an image forming material having one or more of layers on a support. In addition, Th inorganic particles fixed with the water soluble polymer on the surface and the polymer particles are contained in a photosensitive layer containing organic acid silver, a reducing agent, a fog-preventing agent and a silver halide and the (non)photosensitive layer of a photosensitive material having a non-photosensitive layer on the support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a dispersion containing inorganic fine particles and polymer fine particles, a method for producing composite polymer fine particles, and an inorganic fine particle and polymer fine particles produced by the production method. The present invention relates to an image recording material using a dispersion and composite polymer fine particles. In particular, the present invention relates to a conventional (conventional) silver halide photographic light-sensitive material and a silver halide photographic light-sensitive material for heat development (hereinafter, may be abbreviated to a photographic light-sensitive material for heat development).

[0002]

2. Description of the Related Art In general, each constituent layer of an image recording material, for example, an undercoat layer or a hydrophilic colloid layer, has physical properties such as adhesive strength before and after development, dimensional stability before and after development, and moisture and humidity.
A certain strength is required for dimensional stability against heat, flexibility, pressure resistance, and drying property. Therefore, conventionally, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer, and a protective layer is coated on a support, a water-soluble polymer or a polymer in which various monomers are polymerized in the hydrophilic colloid layer. Various attempts have been made to incorporate latex to improve the film properties such as dimensional stability, scratch strength, flexibility, pressure resistance and drying property of the formed hydrophilic colloid film.

[0003] From such a viewpoint, Japanese Patent Application Laid-Open No. 61-690 is disclosed.
No. 61, Japanese Patent Application Laid-Open No. 61-151527 discloses the use of acrylamide derivatives in US Pat.
No. 3,32,376 discloses the use of a polymer latex of vinyl acetate in U.S. Pat.
Japanese Patent Publication No. 45-533 discloses the use of an alkyl acrylate polymer latex in the specification of Japanese Patent No. 5,286.
In Japanese Patent Publication No. 46-22506, the use of a polymer latex of n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile, etc. It can be used in JP-A-51-1302.
No. 17 proposes the use of a polymer latex of 2-acrylamido-2-methylpropanesulfonic acid or the like.

Further, in order to improve pressure fog, it has been proposed to add polymer fine particles and inorganic fine particles such as colloidal silica to the image recording material in combination, and these polymer fine particles and colloidal silica are not added. However, the compatibility with hydrophilic colloid is poor, and when added in a large amount, the applicability and abrasion resistance are deteriorated, and the image recording material is cracked in a dry atmosphere. there were. Therefore, in order to solve these problems, for example, Japanese Patent Application Laid-Open No. H08-211537 proposes to use polymer fine particles in which inorganic fine particles are combined.

[0005] However, polymer fine particle dispersions and inorganic fine particle composite polymer fine particle dispersions have poor storage stability, their particle diameters increase with time, and eventually become agglomerated. There was a problem that had to be done.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an aqueous dispersion containing inorganic fine particles and polymer fine particles having excellent storage stability, a method for producing composite polymer fine particles, and an image-forming material having improved photographic performance. And a silver halide photographic light-sensitive material for thermal development.

[0007]

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

(1) An aqueous dispersion characterized by containing inorganic fine particles whose surfaces are fixed with a water-soluble polymer, and polymer fine particles.

(2) An image-forming material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has inorganic fine particles the surface of which is fixed with a water-soluble polymer. And an image forming material comprising polymer fine particles.

(3) In a silver halide photographic light-sensitive material for thermal development having a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and a silver halide and a non-photosensitive layer on a support, A silver halide photographic light-sensitive material for heat development, characterized in that at least one layer selected from a layer and a non-photosensitive layer contains inorganic fine particles whose surfaces are fixed with a water-soluble polymer and high-molecular fine particles.

(4) After raising the temperature of the inorganic fine particle dispersion at 40 ° C. or lower to 70 ° C. or higher, an activator is added to the dispersion, and the polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C. Composite polymer fine particles obtained by the method described above.

(5) The activator solution of 40 ° C. or less is heated to 70 ° C.
After raising the temperature, an inorganic fine particle dispersion is added to the dispersion,
Composite polymer fine particles obtained by performing a polymerization reaction while maintaining the liquid temperature at 65 ° C to 90 ° C.

(6) An image recording material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers contains the fine composite polymer particles described in (4) above. Image forming material.

(7) An image recording material having at least one hydrophilic colloid layer on a support, characterized in that at least one of the hydrophilic colloid layers contains the fine composite polymer particles described in (5) above. Image recording material.

(8) In a silver halide photographic light-sensitive material for heat development, which has a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and a silver halide and a non-photosensitive layer on a support, A silver halide photographic light-sensitive material for thermal development, wherein at least one layer selected from a functional layer and the non-photosensitive layer contains the composite polymer fine particles described in 4 above.

(9) In a silver halide photographic light-sensitive material for thermal development having a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and a silver halide and a non-photosensitive layer on a support, 6. A silver halide photographic light-sensitive material for thermal development, wherein at least one layer selected from a functional layer and the non-photosensitive layer contains the composite polymer fine particles described in 5 above.

Hereinafter, the present invention will be described in detail. First, a water dispersion according to the present invention, which includes inorganic fine particles having a surface immobilized with a water-soluble polymer and polymer fine particles, will be described.

Examples of the inorganic fine particles used in the composite polymer fine particles according to the present invention include inorganic oxides, nitrides, sulfides, etc., and preferably oxides. Specifically, Si, Na, K, Ca, Ba, Al, Zn, Fe,
Cu, Sn, Ti, In, W, Y, Sb, Mn, Ga,
V, Nb, Tu, Ag, Bi, B, Mo, Ce, Cd,
Single or composite oxides such as Mg, Be, Pb, etc. are preferred, especially Si, Y, Sn, Ti, Al, V, Sb, Ib.
A single or composite oxide of n, Mn, Ce, and B is preferable from the viewpoint of miscibility with the emulsion.

These may be crystalline or amorphous, but are preferably amorphous.

The average particle size of the inorganic fine particles is 0.5 to 300.
It is about 0 nm, preferably 3 to 500 nm. The inorganic fine particles are preferably used by dispersing in water and / or a solvent soluble in water.

The addition amount of the inorganic fine particles is about 1 to 2000% by weight, preferably 30 to 1% by weight, based on the weight of the hydrophobic polymer compound.
000% by weight.

Examples of preferred oxides are shown below.

SiO ₂ , TiO ₂ , ZnO, SnO ₂ , M
nO ₂ , Fe ₂ O ₃ , ZnSiO ₄ , Al ₂ O ₃ , BeSiO
₄ , Al ₂ SiO ₅ , ZrSiO ₄ , CaWO ₄ , CaSi
O ₃ , InO ₂ , SnSbO ₂ , Sb ₂ O ₅ , Nb ₂ O ₅ , Y ₂
O ₃ , CeO ₂ , Sb ₂ O ₃ .

Particularly preferred among these are S
i, and further, colloidal silica.

As the colloidal silica, a commercially available product can be used as it is. For example, Silica Doll series (manufactured by Nissan Chemical Industries, Ltd.), Ludox series (manufactured by DuPont), Adelite AT series (manufactured by Asahi Denka Co., Ltd.), Snowtex series (manufactured by Nissan Chemical Industries, Ltd.) And the like, but are not limited thereto.

The water-soluble polymer in the present invention includes a synthetic water-soluble polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention.

Among them, synthetic water-soluble polymers include:
The molecular structure includes, for example, those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group. Examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group, and examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a phosphoric acid group or a salt thereof. And the like.

Examples of natural water-soluble polymers include those having a nonionic group, those having an anionic group, and those having a nonionic group and an anionic group in the molecular structure.

As the polymer having a hydrophilic group, a polymer having an anionic group and a polymer having a nonionic group and an anionic group can be preferably used in both cases of a synthetic water-soluble polymer and a natural water-soluble polymer. . In the present invention, the hydrophilic polymer may be dissolved in 0.05 g or more, preferably 0.1 g or more, in 100 g of water at 20 ° C.

Hereinafter, examples of the hydrophilic polymer will be described.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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Examples of natural water-soluble polymers include gelatin, lignin, starch, pullulan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, glycogen, laminaran, lichenin, nigellan, and derivatives thereof. .

Examples of the natural water-soluble polymer derivatives include sulfonated, carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylated, alkylphosphorylated, and salts thereof, and in particular, dextran, and Its derivatives are preferred. In the present invention, two or more hydrophilic polymers may be used in combination.

The polymer fine particles of the present invention are fine particles composed of a polymer compound.

The monomer forming the polymer compound constituting the polymer fine particles of the present invention is not particularly limited, and may be a hydrophilic monomer or a hydrophobic monomer. Also,
A combination of a hydrophilic monomer and a hydrophobic monomer may be used.

The hydrophobic monomers include vinyl esters, acrylic esters, methacrylic esters,
Olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, allyl compounds, vinyl ethers,
Vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, and other various unsaturated acid esters, and the like, preferably, acrylates, methacrylates and styrenes, Acrylic esters and methacrylic esters are particularly preferably those having 6 or more carbon atoms in the ester group. Furthermore, it is preferable to use at least 1.0% by weight, preferably 20 to 100% by weight, of a monomer having a glycidyl group in combination with these.

Examples of the hydrophilic monomer include carboxyl group-containing monomers such as acrylic acid and methacrylic acid, hydroxyl group-containing monomers such as hydroxyethyl acrylate, alkylene oxide-containing monomers, acrylamides and methacrylamide. , A sulfonic acid group-containing monomer, an amino group-containing monomer and the like can be preferably used, but a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amide group-containing monomer, and a sulfonic acid group-containing monomer can be preferably used. Mers are particularly preferred.

The polymer compound of the present invention may be a homopolymer or a copolymer.

Examples of the polymerization method for obtaining the polymer compound of the present invention include an emulsion polymerization method, a solution polymerization method, a suspension polymerization method and the like.

(Solution Polymerization) A monomer composition (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) of an appropriate concentration in a solvent is dissolved in the presence of an initiator at about 10 to 10% by weight. 2
At a temperature of 00 ° C, preferably 30-120 ° C, about 0.5
It is obtained by conducting the polymerization for up to 48 hours, preferably for 2 to 20 hours.

Any initiator can be used as long as it is soluble in the polymerization solvent. An organic solvent initiator such as benzoyl peroxide, azobisisobutyronitrile (AIBN) and di-tert-butyl peroxide, and ammonium persulfate ( APS), potassium peroxide, 2,2'-azobis- (2-amidinopropane)-
Water-soluble initiators such as hydrochloride,
Redox-based polymerization initiators in which a reducing agent such as a ²⁺ salt or sodium bisulfite is combined can be used.

As the solvent, any solvent can be used as long as it can dissolve the monomer composition, and examples thereof include water, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more of these. . After completion of the polymerization, the reaction mixture is poured into a solvent that does not dissolve the produced polymer compound, and the product is precipitated.
Then, by drying, the unreacted composition can be separated and removed.

(Emulsion polymerization) Using water as a dispersion medium, 1 to 50% by weight of a monomer based on water and 0.05 to
Using 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, a temperature of about 30 to 100 ° C., preferably 60 to 90 ° C.
It is obtained by polymerizing under stirring for ~ 8 hours.

Examples of the initiator include water-soluble peroxides (potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (2,2'-azobis- (2-amidinopropane) -hydrochloride, etc.), and Redox polymerization initiators in which a reducing agent such as an Fe ²⁺ salt or sodium bisulfite is combined can be used.

As the dispersant, any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants can be used. Preferably, anionic surfactants, nonionic surfactants, and nonionic surfactants are used. Agent.

(Suspension polymerization) Using water as a dispersion medium, 1 to 50% by weight of a monomer with respect to water and 0.05 to 5% by weight of the monomer.
It is obtained by polymerization under stirring at about 30 ° C. to 100 ° C. for 3 to 8 hours using 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant.

Examples of the initiator include benzoyl peroxide, lauroyl peroxide, 2,2 which are insoluble in water and soluble in monomers.
2'-azobisisobutyronitrile and the like can be mentioned.

As a dispersant, polyvinyl alcohol,
Water-soluble polymers such as carboxymethylcellulose, gelatin and starch can be mentioned.

As a dispersion method of obtaining a polymer fine particle dispersion, pulverization is carried out in a ball mill, a vibration mill, a planetary ball mill, a sand mill, a colloid mill, a jet mill or the like in the presence of a dispersant for a time necessary for mechanical pulverization. , Mesh is arranged so that it can be dispersed into fine particles, and the average particle size is 0.00
After pulverizing to about 5 to 3 μm, a dispersant such as a surfactant and a water-soluble polymer is preferably added to water to disperse the fine particles.

In the case of emulsion polymerization or suspension polymerization, the polymer fine particle dispersion may be used as it is, or may be separated by filtration or centrifugation, and then obtained by the above-mentioned dispersion method.

The means for immobilizing the water-soluble polymer on the surface of the inorganic fine particles is not particularly limited, but the water-soluble polymer and the inorganic fine particles are mixed, heated to 60 ° C. or more, cooled, and cooled. A method of adsorbing a polymer having a polymerization reactive group (for example, a double bond group) on the surface of the inorganic fine particles, and further polymerizing a polymerizable monomer based on the polymerization reactive group. Etc.

In the inorganic fine particles having the water-soluble polymer immobilized on the surface thereof and the aqueous dispersion containing the polymer fine particles, the water-soluble polymer may or may not be immobilized on the surface of the polymer fine particles. Either is fine.

Next, the composite polymer fine particles of the present invention will be described.

In the present invention, the fine composite polymer particles are a dispersion of fine composite polymer particles formed by polymerizing a composition having a monomer in the presence of inorganic fine particles.

The inorganic fine particles here are the same as those described above.

The following can be used as the monomer for forming the polymer portion of the composite polymer fine particles of the present invention, but are not limited thereto.

Examples of the hydrophobic monomer include vinyl esters such as vinyl acetate, vinyl propionate, n-vinyl valerate and vinyl pivalate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate and t-butyl. Acrylates such as acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate and glycidyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, benzyl Methacrylates such as methacrylate and glycidyl methacrylate; other styrene, vinyl chloride, vinylidene chloride , Acrylonitrile, itaconic acid ester, can be mentioned vinyl ketones.

The hydrophilic monomers include hydroxyethyl acrylate, 3-hydroxypropyl acrylate,
Acrylic esters such as butylene glycol monoacrylate and 3-sodium sulfo-2,2-dimethyl-propyl acrylate; hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, butylene glycol monomethacrylate, 3-sodium sulfo-2,2-dimethyl Methacrylic acid esters such as -propyl methacrylate; acrylamide, N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, Ni-propylacrylamide, Nn-butylacrylamide, Nt-butylacrylamide, N, N-dimethylacrylamide, N,
N-diethylacrylamide, N, Nn-dipropylacrylamide, N, Nn-dibutylacrylamide, N, Nt-dibutylacrylamide, N-morpholinoacrylamide, N-piperazinoacrylamide,
Diacetone acrylamide, 3-sodium sulfo-
Acrylamides such as 2,2-dimethylpropylacrylamide; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, Nn-propylmethacrylamide, Ni-propylmethacrylamide, N-butylmethacrylamide, N -T-butyl methacrylamide, N, N-dimethyl methacrylamide,
N, N-diethyl methacrylamide, N, Nn-dipropyl methacrylamide, N, Nn-dibutyl methacrylamide, N, Nt-butyl methacrylamide, diacetone acrylamide, 3-sodium sulfo-2,
Methacrylamides such as 2-dimethylpropyl methacrylamide; N-substituted acryloyls such as N-acryloylpyrrole, N-acryloylpyrrolidine, N-acryloylimidazole, N-acryloyltriazole, N-acryloylpiperidine, N-acryloylmorpholine; Methacryloylpyrrole, N-methacryloylpyrrolidine, N-methacryloylimidazole, N-
N-substituted methacryloyls such as methacryloyl triazole, N-methacryloyl piperidine, N-methacryloyl morpholine; p-hydroxystyrene, p-sodium sulfostyrene, p-hydroxymethylstyrene, p
And styrenes such as sulfomethylstyrene.

The polymer compound used in the composite polymer fine particles of the present invention may be a homopolymer or a copolymer of the above monomers. In the present invention, the polymer is preferably a polymer which is hydrophobic or insoluble in water or a developing solution, but a hydrophilic monomer may be copolymerized as long as such a property is maintained.

Further, a crosslinkable monomer can also be used. For example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, butylene glycol diacrylate, polyethylene glycol diacrylate, cyclohexane-1,4-dimethyl diacrylate, trimethylolpropane triacrylate, pentaerythritol Tetramethacrylate,
N, N-ethylenediaminediacrylamide, N, N-
Piperazyl dimethacrylamide and the like can be mentioned. By using a small amount of these crosslinkable monomers and copolymerizing a hydrophilic monomer and another hydrophobic monomer, a water-insoluble polymer compound having hydrophilicity can be obtained.

The method for producing the composite polymer fine particles of the present invention is as follows.
It is obtained by polymerizing the monomer in the presence of the inorganic fine particles. The polymerization method is a normal solution polymerization method,
Emulsion polymerization, radiation polymerization, suspension polymerization, bulk polymerization, and the like can be used, but emulsion polymerization is preferred.

(Emulsion Polymerization) A predetermined amount of inorganic fine particles is dispersed in water as a dispersion medium, and 1 to 50% by weight of a monomer with respect to water and 0.05 to 5% by weight with respect to a monomer. About 30 to 10 using a polymerization initiator of 0.1 to 20% by weight of a dispersant.
It is obtained by polymerizing under stirring at 0 ° C., preferably 60 to 90 ° C. for 3 to 8 hours.

Examples of the initiator for the emulsion polymerization include water-soluble peroxides (such as potassium persulfate and ammonium persulfate) and water-soluble azo compounds (2,2'-azobis- (2-amidinopropane) -hydrochloride). Redox-based polymerization initiators obtained by combining these with a reducing agent such as an Fe ²⁺ salt or sodium bisulfite can be used.

As the dispersant, any of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, and preferably, anionic surfactants, nonionic surfactants and nonionic surfactants are used. Agent.

Further, a citrate may be added to the dispersion during or after the emulsion polymerization in order to adjust the pH. Sodium citrate, potassium citrate,
Citric anhydride, citrate anhydride, or a mixture of citric acid and hydroxide are used, but sodium citrate is preferred. The amount of the citrate in the dispersion of the composite polymer fine particles is preferably about 0.4 g per 1 kg of the fine particles.

In the present invention, the timing of adding the inorganic fine particles and the activator at the time of production is specified in detail.

That is, an inorganic fine particle dispersion at 40 ° C. or lower
After the temperature is raised to 0 ° C. or higher, an activator is added to the dispersion, and a polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C.

Alternatively, an activator solution at 40 ° C. or lower
After the temperature is raised to not less than 0 ° C., an inorganic fine particle dispersion is added to the dispersion, and a polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C.

There has been a known example in the past in which an activator is added to a dispersion of inorganic fine particles to cause a polymerization reaction. For example, JP-A-8-21537, JP-A-10-239788, and JP-A-10-239788
Nos. 254081 and 10-268474. However, they did not describe strict temperature control during production.

The composite polymer fine particles produced under the above temperature conditions have not only excellent stability with time, but also the photographic performance of the image recording material even when the composite polymer fine particles are added to the hydrophilic colloid layer of the image recording material. Has the unexpected effect of improving

The composite polymer fine particles of the present invention have an average particle size of 0.00 when incorporated into a silver halide photographic material.
5-3.0 μm is good, preferably 0.01-0.8 μm
m.

Examples of the image recording material of the present invention include materials for photography, electrophotography, electrostatic photography, photothermography, migration, electrothermography, dielectric recording, and thermal dye transfer.

The case where the image recording material of the present invention is a silver halide photographic light-sensitive material will be described below.

The preferred silver halide emulsion for use in the silver halide photographic light-sensitive material of the present invention is an emulsion comprising silver chloride tabular grains having a (100) plane as a main plane, preferably (a) 30 mol of chloride. %, A step of introducing a silver salt and a halide salt into the dispersion medium to form nuclei,
(B) following nucleation, Ostwald ripening under conditions that maintain the (100) major plane of the tabular grains;
(C) It is prepared by a step of growing grains so as to have a desired grain size and silver chloride content.

As a method of reacting a silver salt and a halide salt during nucleation, it is preferable to use a double jet method.

It is preferable to use the double jet method also during grain growth, and it is preferable to use pAg in the liquid phase in which silver halide is formed.
Can be used, that is, a so-called controlled double jet method can be used.

The silver halide emulsion may be formed by supplying fine silver halide grains during part or all of the steps during grain formation. Since the particle size of the fine particles governs the supply rate of halide ions, it depends on the size and composition of the silver halide grains to be formed, but the preferred size is approximately 0.3 μm or less in terms of average sphere equivalent diameter, and more preferably 0 μm or less. .1 μm or less. In order for the fine particles to be stacked on the grown particles by recrystallization, the fine particle size is desirably smaller than the sphere equivalent diameter of the grown particles,
More preferably, it is 1/10 or less of the sphere equivalent diameter of the growth particles.

The silver halide emulsion used in the present invention may be subjected to a noodle washing method, flocculation sedimentation method, or the like in order to remove soluble salts after the growth of the silver halide grains to obtain a pAg ion concentration suitable for chemical sensitization. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or a polymer flocculant described in JP-A-2-7037 can be used. A desalting method using certain exemplified compounds G-3, G-8 and the like can be mentioned. Also, Research Disclosure (hereinafter abbreviated as RD) 102, 10208
(October 1972) and 131, 13122 (19
(May, 1975) may be used for desalting.

The silver halide emulsion may be spectrally sensitized with a cyanine dye or the like.

The silver halide photographic light-sensitive material of the present invention includes:
In the steps before and after physical ripening or chemical ripening of the silver halide emulsion, RD-17643, 18716 (November 1979)
Mon) 308119 (December 1989) and the like.

Examples of the support which can be used in the silver halide photographic light-sensitive material of the present invention include those described in the above-mentioned RD, and a plastic film or the like is suitable. May be provided with an undercoat layer, or may be subjected to corona discharge, ultraviolet irradiation, or the like.

The silver halide photographic light-sensitive material of the present invention includes:
In addition to the silver halide emulsion layer, if necessary, an ultraviolet absorbing layer, an antihalation layer, an intermediate layer, a filter layer, a protective layer and the like can be provided. In some cases, a crossover light cut layer may be provided.

The coating of the constituent layers of the silver halide photographic light-sensitive material of the present invention can be carried out by a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method or the like. Coating Produces, Coatings, pp. 27-28.
Procedures).

The processing solutions that can be used in the silver halide photographic light-sensitive material of the present invention are also described in RD-17643 and RD-17643.
08119 and the like.

Examples of the developer used for black-and-white photography include dihydroxybenzenes (such as hydroquinone), 3-pyrazolidones (1-phenyl-3-pyrazolidone), and aminophenols (N-methyl-aminophenol). In the developer, a preservative, an alkaline agent, p
An H buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone, a water softener, a dissolution aid, a viscosity-imparting agent, and the like can be added. A fixing agent such as a thiosulfate or a thiocyanate is used in the fixing solution, and a water-soluble aluminum salt (aluminum sulfate, potassium alum, etc.) as a hardening agent, a preservative, a pH adjuster, and a hardening softener are used. And the like.

The silver halide photographic light-sensitive material of the present invention was prepared by using an automatic developing machine at a dry-to-dry processing time of 2 hours.
Ultra-rapid processing such as 5 seconds or less can be performed, and processing can be performed with a low replenishment amount of a developing solution or a fixing solution such as 200 ml or less per 1 m ² of a photosensitive material.

Next, the silver halide photographic light-sensitive material for thermal development according to the present invention will be described.

The details of the photographic light-sensitive material for thermal development are described in, for example,
U.S. Pat. Nos. 3,152,904 and 3,457,0
No. 75, and D.A. Morgan (Dry Silver Photographic Materials)
Photographic Material) "and D.C.
Morgan and B.A. Shelley
y) "Heat treated silver system (The
rally Processed Silver S
systems), Imaging Processes and Materials (Imaging Processes and Materials)
and Materials) Neblette, 8th Edition, Sturge, V.A. Walworth, A .; It is disclosed in Shepp Editing, 2nd page (1969) and the like.

The photographic light-sensitive material for heat development of the present invention is preferably 80 to
It is characterized in that an image is formed by heat development at 150 ° C. and no fixing is performed. Therefore, the silver halide and the organic acid silver remaining in the unexposed areas remain in the heat-developable image forming layer without being removed, but the fog density does not increase unless heat is applied.

In the present invention, after heat development, the light transmittance of all photographic light-sensitive materials for heat development is preferably such that the optical transmission density at 400 nm is 0.2 or less, more preferably 0.02 to 0. .2 or less. If it is less than 0.02, the sensitivity may be too low to be used.

The silver halide grains in the heat-developable image forming layer according to the present invention function as an optical sensor. The average grain size of the silver halide grains is preferably as small as possible in order to keep the cloudiness of the image forming layer after image formation low and to obtain good image quality. ~ 0.1 μm, especially 0.02-0.08 μ
m is preferable. The particle size here means
When the silver halide grains are cubic or octahedral so-called normal crystals, the term refers to the length of the edge of the silver halide grains. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed. Here, the monodispersion means that the degree of monodispersion determined by the following equation is 40 or less. The particles having a monodispersity of preferably 30 or less, particularly preferably 0.1 to 20%.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The silver halide particles used in the present invention have an average particle size of 0.1.
It is more preferable that the particle size is not more than μm and that the particles are monodisperse particles, whereby the granularity of the image can be improved. The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is preferably high, and this proportion is 50% or more, more preferably 70% or more, especially 80% or more. Is preferred. The ratio of the Miller index [100] plane is determined by the T.M. Tani: J. et al. Imaging Sci. , 29
Volume, page 165 (1985).
Another preferred form of silver halide is tabular grains. The term “tabular grains” as used herein means those having an aspect ratio (AR) = r / h of 3 or more, where the square root of the projected area is r μm and the vertical thickness is h μm.

AR = average particle size (μm) / thickness (μm) Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 to 0.08 μm. These are disclosed in U.S. Patent Nos. 5,264,337 and 5,314,7.
No. 98 and 5,320,958, and the desired tabular grains can be easily obtained.
When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition of the silver halide grains is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. . The silver halide emulsion used in the present invention is a P.I. Glafkids
Author, Chimie et Physique Photo
ographique (published by Paul Montel,
1967); F. Photograph by Duffin
raphic Emulsion Chemistry
(The Focal Press, 1966),
V. L. By Zelikman et al, Makin
g and Coating Photographi
c Emulsion (The Focal Pres
s, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a silver halide forming method for reacting a soluble silver salt with a soluble halide salt may be any one of a one-side mixing method, a double-mixing method, a combination thereof and the like. May be used. When the silver halide is mixed with the heat-developable image forming layer, it is important that the silver halide is arranged close to a reducible silver source. The silver halide may be prepared by converting part or all of the silver of the organic acid silver to silver halide by a reaction between the organic acid silver and a halogen ion, or by preparing the silver halide in advance. Every
This may be added to the solution for preparing the organic acid silver, or a combination of these methods is possible,
The latter is preferred. The heat-developable image forming layer preferably contains silver halide in an amount of 0.75 to 30% by weight based on the weight of the organic acid silver.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

The following are specific examples of transition metal complex ions, but the present invention is not limited to these.

[0105] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2- 23: Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^{2 -} 27: [Ir (NS) Cl _5] ^2- these metal ions may be a metal complex or metal complex ions one type, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

The compounds providing these metals are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical ripening Although it may be added at any stage before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably. It is added at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Unexamined Patent Publication (Kokai) No. HEI 10-301, the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are used. When they are mixed simultaneously, they are added as a third aqueous solution to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method in which halogen is added. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation of silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution.

When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

In general, the formed silver halide grains are desalted of unnecessary salts by washing with water by a method known in the art such as a noodle method or a flocculation method. It may or may not be necessary.

The silver halide grains used in the photographic light-sensitive material for heat development of the present invention are preferably chemically sensitized. Chemical sensitization methods include sulfur sensitization, selenium sensitization, and tellurium sensitization as well known in the art.
Any of them can be used. In the present invention, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, iridium compound or the like can also be used. As compounds for the sulfur sensitization method, selenium sensitization method, and tellurium sensitization method, known compounds can be preferably used in the present invention, but compounds described in JP-A-7-128768 can also be used. . Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, and P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, Te heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060 and British Patent 618,06.
The compounds described in the specification of JP-A No. 1 can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Further, reduction sensitization can be performed by ripening the emulsion while keeping the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Also, reduction sensitization can be achieved by introducing a single addition portion of silver ions during grain formation.

The organic acid silver used in the present invention is one of important materials in a photographic light-sensitive material for thermal development. Organic acid silver is a reducible silver source, and silver salts of organic acids and heteroorganic acids containing a reducible silver ion source, especially long-chain (10-30, preferably 15-25) carbon fats. Group carboxylic acids and nitrogen-containing heterocycles are preferred. When the ligand is 4.0 to
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 10.0 are also useful. Examples of suitable organic acid silver salts are described in RD 17029 and 29963, and the following are useful. Organic acid silver is, for example, a salt of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid or the like; carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea , 1- (3-carboxypropyl)-
3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (eg, aldehydes formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (eg, salicylic acid, benzoic acid) , 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene, And 3-carboxymethyl-4-thiazoline-
2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole,
Complexes or salts of silver with a nitrogen acid selected from 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver of mercaptides salt. Of these, preferred organic acid silver compounds are silver behenate, silver arachidate or silver stearate.

In the present invention, the organic acid silver can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver.
A controlled double jet method or the like described in Japanese Patent No. 127463 is preferably used. For example, after adding an alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to an organic acid to produce an organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate, etc.), a controlled double jet Thus, the above-mentioned soap and silver nitrate are added to produce crystals of the organic acid silver salt. At that time, silver halide grains may be mixed.

In the present invention, the silver salt of an organic acid has an average particle size of 1
It is preferably not more than μm and monodispersed. The average particle size of the organic acid silver particles means, for example, when the particles of the organic acid silver particles are spherical, rod-shaped, or tabular, when considering a sphere equivalent to the volume of the organic acid silver particles. The average particle size is preferably from 0.01 to 0.8 μm, in particular from 0.05 to 0.
5 μm is preferred. The monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30. In the present invention, the organic acid silver is more preferably monodisperse particles having an average particle size of 1 μm or less. By setting the average particle size in this range, an image having a high density can be obtained. Further, it is preferable that tabular grains of the organic acid silver have 60% or more of the total organic acid silver. In the present invention, those having an aspect ratio of 3 or more are preferred.

In order to make the organic acid silver into these shapes,
The organic acid silver crystals can be obtained by dispersing and pulverizing the organic acid silver crystals in a binder, a surfactant, or the like using a ball mill or the like.

In order to prevent devitrification of the heat-developable image forming layer of the present invention, the total amount of silver halide and organic acid silver is preferably 0.5 to 2.2 g / m ² in terms of silver. preferable. With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is 50% by weight.
Or less, preferably 25% or less, more preferably 0.1 to
Between 15%.

The photothermographic material for heat development of the present invention contains a reducing agent. Examples of suitable reducing agents are described in US Pat.
No. 70,448, No. 3,773,512, No. 3,
No. 593,863, etc., and RD17029 and 29963, and the following are mentioned. Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); Amino reductone esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N-
Hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (E.g., hydroquinone, tert-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxamic acid);
Sulfonamidoanilines (eg, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); Tetrahydroquinoxalines (Eg, 1,2,3,4-tetrahydroquinoxaline); amideoxins; azines (eg, a combination of an arylcarboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and And / or hydrazine; hydroxanoic acids; combinations of azines and sulfonamide phenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; Phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5
-Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-
(T) butyl-5-methylphenyl) methane, bis (6
-Hydroxy-m-tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2- (t) butyl-6-methyl) phenol, an ultraviolet-sensitive ascorbic acid derivative and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0118]

Embedded image

In the formula, R is a hydrogen atom or a group having 1 carbon atom.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, te)
rt-butyl).

Specific examples of the compound represented by formula (A) are shown below. However, the present invention is not limited to the following compounds.

[0121]

Embedded image

[0122]

Embedded image

The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

As the binder suitable for the photographic light-sensitive material for thermal development of the present invention, any transparent or translucent, generally colorless, natural or synthetic polymer can be used. For example:
Gelatin, gum arabic, polyvinyl alcohol, hydroxyethyl cellulose, cellulose diacetate, cellulose acetate butyrate, polyvinyl pyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylic acid, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride Polymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, polyvinyl acetals (for example, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resin, polyvinylidene chloride, polyepoxides, polycarbonates, poly Vinyl acetate,
There are polyamides. It may be either hydrophilic or non-hydrophilic.
In order to protect the surface of the photographic light-sensitive material for heat development and prevent abrasion, a non-photosensitive layer may be provided outside the heat-developable image forming layer. The binder used for these non-photosensitive layers may be the same or different from the binder used for the photosensitive layers.

As one means for increasing the speed of thermal development of the photographic light-sensitive material for thermal development of the present invention, the binder amount of the heat-developable image forming layer is preferably 1.5 to 10 g / m ² , preferably 1.7 to 10 g / m ^2. 8 g / m ² is more preferred. This can maintain the image density by having an appropriate amount of the image forming substance in the binder.

In the present invention, it is preferable that a layer having a matting agent is provided on the side of the heat-developable image-forming layer, in order to prevent the image after heat-development from being damaged. The outermost layer preferably has a matting agent, and preferably contains 0.5 to 30% by weight of the entire binder in the heat-developable image forming layer. The material of the matting agent may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, and British Patent No. 1,173,181. The described alkaline earth metals or carbonates such as cadmium and zinc can be used as matting agents. Examples of the organic substance include starch described in U.S. Pat. No. 2,322,037, starch derivative particles described in Belgian Patent No. 625,451 and British Patent No. 981,198, and Japanese Patent Publication No. 44-3643. No. 3,079,257, polyacrylonitrile particles, US Pat. No. 3,079,257, and US Pat. No. 3,079,257. 3,022,1
Organic matting agents such as the polycarbonate particles described in the specification of JP-A No. 69 can be used. The shape of the matting agent may be either a fixed shape or an irregular shape, but is preferably a fixed shape, and a spherical shape is preferably used. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere.
The particle size of the matting agent indicates the diameter converted into a sphere. The matting agent preferably has an average particle size of 0.5 to 10 μm, more preferably 1.0 to 8.0 μm.

In the photographic light-sensitive material for thermal development of the present invention,
A photographic image is formed by heat development. The binder contains a reducible silver source (silver organic acid), a photosensitive silver halide, a reducing agent, and, if necessary, a color tone agent for suppressing the color tone of silver. Preferably, it exists in a dispersed state. The photothermographic material for heat development of the present invention is stable at room temperature, but after exposure,
For example, it is developed by heating at 80 ° C. to 150 ° C. The heat causes an oxidation-reduction reaction between the organic acid silver (functioning as an oxidizing agent) and the reducing agent to generate silver. This oxidation-reduction reaction is accelerated by a latent image generated on the silver halide by exposure as a catalyst. Silver generated by the reaction of the organic acid silver in the exposed area becomes a black image. This reaction process
The process proceeds without any supply of a processing liquid such as water from the outside.

The heat-developable photographic light-sensitive material of the present invention has at least one heat-developable image forming layer on a support,
Although only the heat-developable image forming layer may be used, it is preferable that at least one non-photosensitive layer is provided on this layer. The heat-developable photographic light-sensitive material may have a filter dye layer on the heat-developable image forming layer side, and an antihalation dye layer or a back layer on the opposite side. A pigment may be included. As the dye, any compound can be used as long as it absorbs light in a desired wavelength range. For example, JP-A-59-6481 and JP-A-59-6481.
No. 182436, U.S. Pat. No. 4,271,263
No. 4,594,312, European Patent Publication Nos. 533,008, 652,473, JP-A-2-216140 and 4-348339.
And compounds described in JP-A Nos. 7-191432 and 7-301890 are preferably used.

These non-photosensitive layers preferably contain the above-mentioned binder and matting agent, and may further contain a sliding agent such as a polysiloxane compound, wax and liquid paraffin.

The heat-developable image forming layer may have a plurality of layers.
In addition, a high sensitivity layer and a low sensitivity layer are provided for adjusting the gradation of the image,
Any layer may be on top.

It is preferable to add a toning agent to the photographic light-sensitive material for heat development of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are disclosed in RD 17029 and include the following. For example, imides such as phthalimide; succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, dione cyclic imides such as quinazoline and 2,4-thiazolidine, and pyrazolin-5-ones And quinazolinones; naphthalimides such as N-hydroxy-1,8-naphthalimide; cobalt complexes such as cobalt hexamine trifluoroacetate; mercaptans such as 3-mercapto-1,2,4-triazole; N- (aminomethyl) aryldicarboximides such as dimethylaminomethyl) phthalimide; N, N'-hexamethylene (1-carbamoyl-
3,5-dimethylpyrazole), blocked compounds such as a combination of 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole Combinations of pyrazoles and isothiuronium derivatives and certain photobleaches; 3-ethyl-5-((3-
Ethyl-2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-
Merocyanine dyes such as 2,4-oxazolidinedione; 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, or 2,3-dihydro-1,4-phthalazine Phthalazinone such as dione, phthalazinone derivatives or metal salts of these derivatives; 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone +
Combinations of phthalazinone and sulfinic acid derivatives such as sodium p-trisulfonate; phthalazine + phthalic acid combinations; phthalic acid, 4-methylphthalic acid, 4-
Phthalazine (including adducts of phthalazine) and maleic anhydride, such as in combination with at least one compound selected from nitrophthalic acid and tetrachlorophthalic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides; quinazolinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones such as 1,3-benzoxazine-2,4-dione; 2,4-
Pyrimidines such as dihydroxypyrimidine and asymmetric triazines; tetraazapentalene derivatives such as 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene And so on. Preferred toning agents are phthalazone or phthalazine.

Further, the heat-developable image-forming layer of the present invention has a function of suppressing or accelerating the heat development, controlling the development speed, improving the spectral sensitization efficiency, and further improving the preservability of the image before and after the development. For this purpose, a mercapto compound, a disulfide compound or a thione compound may be contained. In the case of a mercapto compound, a compound represented by Ar-SM ₁ or Ar-SS-Ar is preferable. In the formula, M ₁ is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole,
Naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole,
Triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine,
Purine, quinoline or quinazolinone. The heteroaromatic ring includes, for example, a halogen atom (e.g., Br and Cl), a hydroxy group, an amino group, a carboxyl group, an alkyl group (e.g., of 1-4 carbon atoms) and an alkoxy (e.g., 1-4 Carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole, −
Mercaptoquinoline, 8-mercaptopurine, 2,3
Examples include 5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole, and the like, but the invention is not limited thereto.

The photographic light-sensitive material for thermal development of the present invention contains an antifoggant. For example, US Pat. No. 4,546,075
No. 4,452,885 and JP-A-59-5959.
Antifoggants as disclosed in JP-A-57234 are preferred. Particularly preferred antifoggants, such as disclosed in U.S. Patent No. 3,874,946 No. and the second 4,756,999 compounds, -C (X ₁₎
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [00
Compounds described in [30] to [0036] are preferably used. Compounds described in paragraphs [0062] to [0063] of JP-A-9-90550. Further, antifoggants are disclosed in US Pat. No. 5,028,
No. 523 and British Patent Application Nos. 9221383.4, 9300147.7 and 9311790.1 are preferred.

The heat-developable photographic light-sensitive material of the present invention includes, for example, JP-A-63-159814 and JP-A-60-140335.
No. 63-231437, No. 63-296551
Nos. 63-304242 and 63-15245, U.S. Pat. Nos. 4,639,414 and 4,74.
No. 0,455, No. 4,741,966, No. 4,7
Sensitizing dyes described in JP-A Nos. 51,175 and 4,835,096 can be used. Useful sensitizing dyes for use in the present invention are described, for example, in RD17643 IV-A (197).
December 2008 p. 23), pp. 1831X (August 1978
Month p. 437) or in the literature cited. In particular, sensitizing dyes having spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078 and JP-A-9-54409
And compounds described in JP-A-9-80679 and the like are preferably used.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and the other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid. As these additives and the other additives described above, compounds described in RD17029 (June 9 to 19, p. 15) can be preferably used.

The support used for the silver halide photographic light-sensitive material of the present invention (including the heat-developable photographic light-sensitive material) includes polyethylene terephthalate, polyethylene naphthalate, and the like.
Polycarbonate, polyimide, nylon, cellulose triacetate, syndiotactic polystyrene and the like are preferred.

Among them, a preferable support for a heat-developable photographic light-sensitive material is a plastic (hereinafter referred to as SP) containing polyethylene terephthalate, polyethylene naphthalate and a styrene polymer having a syndiotactic structure.
S).

The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

SPS is polystyrene having steric regularity unlike ordinary polystyrene (atactic polystyrene). The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that there are more regular parts such as two, three, five or more. In the present invention, the racemo chain is 2 It is preferably 85% or more in the chain, 75% or more in the three chains, 50% or more in the five chains, and 30% or more in the further chains. The polymerization of SPS can be carried out according to the method described in JP-A-3-131843.

As the support used in the present invention, in addition to those described above, those described in RD can be mentioned. A plastic film or the like is suitable, and a subbing layer is provided on the surface of the coating layer for adhesion. Or corona discharge, ultraviolet irradiation, or the like.

For the method of forming a support and the method of producing an undercoat used in the present invention, known methods can be used. Preferably, the method described in paragraph [003] of JP-A-9-50994 is used.
0] to [0070].

In the present invention, in order to improve the antistatic properties of silver halide photographic light-sensitive materials (including heat-developable photographic light-sensitive materials), a carboxyl group-containing polymer is contained in the constituent layer. Can be used in combination. These may be contained in any layer, and may be contained in an undercoat layer, a back layer, a photosensitive layer, or the like, or a layer between these layers and the undercoat layer. You may.

[0143]

The present invention will be described below with reference to examples.
It is not limited to these.

Example 1 1. Inorganic fine particles whose surface is fixed with a water-soluble polymer,
Synthesis of Water Dispersion Containing Polymer Fine Particles (Synthesis Example 1) Synthesis of Inorganic Fine Particles whose Surfaces are Immobilized with Water-Soluble Polymer and Water Dispersion ML-1 Containing Polymer Fine Particles Colloidal silica (EId)
u Pont) was added to water in an amount to give a solid content of 15 g and an amount in which the solid content of the water-soluble polymer SP-2 was 0.5 g to a total amount of 100 g. This solution is heated at 80 ° C 4
Heated for hr and cooled. Next, polymer fine particles Lx1 having a solid content of 15.5 wt% are added to the dispersion to prepare inorganic fine particles having the surface of the present invention fixed with a water-soluble polymer, and an aqueous dispersion ML-1 containing the polymer fine particles. I got

(Synthesis Example 2) Inorganic fine particles whose surface is fixed with a water-soluble polymer, and an aqueous dispersion ML containing the polymer fine particles
Synthesis of -2 ML-2 was obtained in the same manner as in Synthesis Example 1 except that the polymer particles were changed to Lx2.

(Synthesis Example 3) Inorganic fine particles whose surfaces are immobilized with a water-soluble polymer, and an aqueous dispersion ML containing the polymer fine particles
Synthesis of -3 ML-3 was obtained in the same manner as in Synthesis Example 1 except that the polymer fine particles were changed to Lx3.

(Synthesis Example 4) Inorganic fine particles whose surfaces are fixed with a water-soluble polymer, and an aqueous dispersion ML containing the polymer fine particles
Synthesis of -4 ML-4 was obtained in the same manner as in Synthesis Example 1 except that the water-soluble polymer was changed to SP-4.

(Synthesis Example 5) An inorganic fine particle whose surface is fixed with a water-soluble polymer, and an aqueous dispersion ML containing the polymer fine particle
Synthesis of -5 ML-5 was obtained in the same manner as in Synthesis Example 1 except that the water-soluble polymer was SP-4 and the polymer particles were Lx2.

(Synthesis Example 6) Inorganic fine particles whose surfaces are fixed with a water-soluble polymer, and an aqueous dispersion ML containing polymer fine particles
Synthesis of -6 ML-6 was obtained in the same manner as in Synthesis Example 1 except that the water-soluble polymer was SP-4 and the polymer particles were Lx3.

(Synthesis Example 7) Inorganic fine particles whose surfaces are immobilized with a water-soluble polymer, and an aqueous dispersion ML containing the polymer fine particles
Synthesis of -7 ML-7 was obtained in the same manner as in Synthesis Example 1 except that the water-soluble polymer was SP-1 and the polymer particles were Lx3.

<Synthesis of Aqueous Dispersion of Inorganic Fine Particles and Polymer Fine Particles (Comparative)> Inorganic fine particles whose surfaces are immobilized with a water-soluble polymer, and water dispersions ML-1 and M
In the synthesis of L-3 and ML-5, water-dispersed HML-1 and HML-1 of inorganic fine particles and polymer fine particles were prepared in the same manner as ML-1, ML-3 and ML-5 except that each water-soluble polymer was not added.
ML-3 and HML-5 were synthesized.

(Lx1) C ₁₂ H ₂₅ OSO ₃ as a dispersant
Polyethylhexyl acrylate latex obtained by emulsion polymerization using Na (Lx2) Poly (vinyl acetate / vinyl pivalate = 1/1) latex obtained by emulsion polymerization using SP-4 (Mn20000) as a dispersant (Lx3) Poly (isononyl acrylate / cyclohexyl methacrylate / glycidyl methacrylate) obtained by emulsion polymerization using SP-4 (Mn20000) as a dispersant =
6/3/1) Latex Synthesis of Composite Polymer Fine Particles (Synthesis Example 11) Synthesis of Composite Polymer Fine Particle FL-1 A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser were attached to a 1000 ml four-necked flask, and nitrogen gas was introduced. 310 cc of distilled water and 30
wt% colloidal silica dispersion (average particle size 12nm)
270 g were added. The liquid temperature at this time was 35 ° C.
After heating until the internal temperature becomes 70 ° C, the liquid temperature becomes 65 ° C.
3.6 g of SP-4 as a dispersant was slowly added so as not to fall below 0.065 g of ammonium persulfate as a polymerization initiator, and 13.5 g of vinyl acetate was added.
A mixture of 13.5 g of vinyl pivalate was added and reacted for 4 hours. Thereafter, the mixture was cooled, and finally the pH was adjusted to 6 with sodium citrate to obtain an inorganic fine particle composite polymer fine particle dispersion FL-1 of the present invention.

(Synthesis Example 12) Composite polymer fine particles FL-2
18.0 g of vinyl pivalate and 18.
Composite polymer microparticles FL-2 were obtained in the same manner as in Synthesis Example 11 except that 240 g of a 30 wt% colloidal silica dispersion of 0 g was used.

(Synthesis Example 13) Composite polymer fine particle FL-3
Synthesis of Fine Polymer Fine Particles FL-3 was obtained in the same manner as in Synthesis Example 11 except that the monomer was 10.8 g of vinyl pivalate, 13.2 g of vinyl propionate, and the inorganic fine particles were tin oxide.

(Synthesis Example 14) Composite polymer fine particle FL-4
Synthesis of fine composite polymer particles FL-4 was obtained in the same manner as in Synthesis Example 11 except that titanium oxide was used as the inorganic fine particles.

(Synthesis Example 15) Composite polymer fine particle FL-5
A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube and a reflux condenser were attached to a 1000 ml four-necked flask, and nitrogen gas was introduced to perform deoxygenation, 310 cc of distilled water and SP-4 as a dispersant. Was added to 3.6 g. The liquid temperature at this time was 37 ° C. After heating until the internal temperature reaches 70 ° C, slowly heat the solution so that the liquid temperature does not fall below 65 ° C.
wt% colloidal silica dispersion (average particle size 12nm)
270 g were added, and 0.065 g of ammonium persulfate was added as a polymerization initiator, followed by 13.5 g of vinyl acetate,
A mixture of 13.5 g of vinyl pivalate was added and reacted for 4 hours. Thereafter, the mixture was cooled and finally adjusted to pH 6 with sodium citrate to obtain an inorganic fine particle composite polymer fine particle dispersion FL-5 of the present invention.

Composite Polymer Fine Particles HFL-1 to HFL-4
Synthesis of (Comparative) In the synthesis of the composite polymer particles FL-1 to FL-4, a colloidal silica dispersion was added, and a dispersant was added at a liquid temperature of 35 ° C., and then the internal temperature was heated to 70 ° C. Except that the composite polymer particles FL-1 to FL
-HFL-1 to HFL-1
-4 was synthesized.

<Evaluation of Chemical Stability> The aqueous dispersion of the obtained inorganic fine particles and polymer fine particles and the composite polymer fine particles were evaluated for turbidity and chemical stability as follows.

(Evaluation of turbidity) An aqueous dispersion of inorganic fine particles and polymer fine particles or a composite polymer fine particle was diluted with pure water to a solid content concentration of 1.2 wt%, and an integrating sphere turbidity meter (S
The turbidity (A) was measured by EP-PT-706D type (manufactured by Mitsubishi Kasei). In addition, an aqueous dispersion of inorganic fine particles and polymer fine particles or a composite polymer fine particle of 1.0 mol / kg
Diluted with an aqueous solution of NaCl to a solid concentration of 1.2 wt%, and then integrated sphere turbidimeter (SEP-PT-706D).
Turbidity (B) was measured by a mold (manufactured by Mitsubishi Kasei).

<Evaluation of Chemical Stability> The chemical stability was evaluated based on the difference between the turbidity (A) and the turbidity (B). Table 1 shows the obtained results.

<Evaluation of Storage Stability> The difference between the chemical stability of the aqueous dispersion of inorganic fine particles and polymer fine particles and the composite polymer fine particles at room temperature on the first day after synthesis and at 50 ° C. for 6 months after synthesis was determined. The storage stability was evaluated. Table 1 shows the obtained results.

<Evaluation of Crack Resistance> An aqueous dispersion of inorganic fine particles and polymer fine particles or a composite polymer fine particle of 13.3 wt% and gelatin of 6.100 μm on a polyethylene terephthalate support having a thickness of 100 μm previously subjected to an undercoating process. 7wt
% Of the solution was applied to a dry film thickness of 6 μm and dried to prepare a sample for crack evaluation.

Next, each sample was fixed on a glass plate, and the resistance to cracking was evaluated in the following manner while curling was suppressed.

The prepared sample was placed in a desiccator containing a silica gel desiccant, allowed to stand at 55 ° C. for 24 hours, and the degree of cracking of the sample was visually observed and evaluated according to the following criteria.

5: No cracks were observed 4: Cracks were slightly generated 3: Cracks were considerably generated 2: Cracks were significantly generated 1: Cracks were entirely generated The results are shown in Table 1.

[0166]

[Table 1]

In the present invention, an inorganic fine particle having a surface immobilized with a water-soluble polymer, and an aqueous dispersion containing polymer fine particles, M
In L-1 to ML-7, not only the aging of the turbidity did not occur but also the aging of the chemical stability did not occur.
Further, it has high crack resistance.

After raising the temperature of the inorganic fine particle dispersion of the present invention at 40 ° C. or lower to 70 ° C. or higher, an activator is added to the dispersion, and a polymerization reaction is carried out while maintaining the liquid temperature at 65 ° C. or higher and 90 or lower. After heating the obtained composite polymer fine particles FL-1 to FL-4 and the activator solution of the present invention at 40 ° C. or lower to 70 ° C. or higher, an inorganic fine particle dispersion was added to the dispersion, and the liquid temperature was lowered. 6
The composite polymer microparticles FL-5 obtained by performing the polymerization reaction while maintaining the temperature at 5 ° C. or more and 90 ° C. or less do not not only have the temporal deterioration of turbidity but also have not deteriorated the chemical stability with time. Further, it has high crack resistance.

Example 2 Conventional Silver Halide Photosensitive Material << Preparation of Emulsion Em-1 >> An emulsion Em-1 comprising tabular silver iodobromide grains was prepared as follows.

(A1 solution) Ossein gelatin 24.2 g Water 9657 ml HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5-7) ) 10% methanol solution 1.20 ml Potassium bromide 10.8 g 10% nitric acid 160 ml (B1 solution) 2.5N silver nitrate aqueous solution 2825 ml (C1 solution) Potassium bromide 841 g Water 2825 ml (D1 solution) Ossein gelatin 121 g Water 2040 ml HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5-7) 10% methanol solution 5.70 ml (E1 solution) 1.75N odor Potassium chloride aqueous solution Silver potential control amount Using a mixing stirrer described in JP-B-58-58288, the B1 solution and the C1 solution were each 475.0 at 35 ° C at 355.0 ° C.
ml was added by a double jet method in 2.0 minutes to perform nucleation. After completion of the addition of the B1 solution and the C1 solution, the A
Raise the temperature of Solution 1 to 60 ° C, add the entire amount of Solution D1, adjust the pH to 5.5 with KOH 3% aqueous solution, and again add Solution B1 and Solution C1 at an addition rate of 55.4 ml / min for 42 minutes each. did. During this time, the silver potential (saturated silver-
Measured with silver ion selective electrode using silver chloride electrode as reference electrode)
Was controlled to be +8 mV and +30 mV. After the addition was completed, the pH was adjusted to 6.0 with a 3% aqueous solution of KOH, and immediately after desalting and washing, a seed emulsion was obtained. Observation of this seed emulsion by an electron microscope revealed that 90% or more of the total projected area of the silver halide grains consisted of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains was Is 0.0
The diameter was 90 μm, and the average equivalent circle diameter was 0.510 μm.
The obtained seed emulsion was heated to 53 ° C., and spectral sensitizing dye A (5,
450 mg of 5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt), spectral sensitizing dye B (5,5'-di-
(Butoxycarbonyl) -1,1'-di-ethyl-3,
After addition of 8 mg of 3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium anhydride as a solid particulate dispersion, 4-hydroxy-6-methyl-1,3,3a, 7-tetraaza Inden (TAI) 6
0 mg, adenine 15 mg, ammonium thiocyanate 50 mg, chloroauric acid 2.5 mg, aqueous solution containing sodium thiosulfate 5.0 mg, silver iodide fine grain emulsion (average particle size 0.05 μm) equivalent to 5 mmol, triphenylphosphine selenide 6.0 mg of the dispersion was added, and aging was performed for a total of 2 hours and 30 minutes. T at the end of aging as a stabilizer
750 mg of AI was added.

The dispersion of the solid fine particles of the spectral sensitizing dye is as follows:
The dye was added to water at 27 ° C., and 3500 rpm with a high-speed stirrer (dissolver). p. m. For 30 to 120 minutes. In addition, a dispersion of triphenylphosphine selenide was prepared by mixing 120 g of triphenylphosphine selenide with 50 g of triphenylphosphine selenide.
C. in 30 kg of ethyl acetate at 30.degree. C. and stirred to completely dissolve, while 3.8 kg of gelatin was dissolved in 38 kg of pure water, and sodium dodecylbenzenesulfonate was added thereto.
93 g of a 5% by weight aqueous solution was added, and these two liquids were mixed and dispersed by a high-speed stirring type disperser having a 10 cm diameter dissolver at 50 ° C. and a dispersion blade peripheral speed of 40 m / sec for 30 minutes. Then, ethyl acetate was removed while stirring until the residual concentration of ethyl acetate became 0.3% by weight or less, and the resultant was diluted with pure water to obtain a finished product of 80 kg.

<< Preparation of Emulsion Em-2 >> Emulsion Em-2 consisting of tabular silver iodobromide grains was prepared using Emulsion Em-1 as a seed emulsion and the following solution.

(A2 solution) Ossein gelatin 19.04 g HO (CH ₂ CH ₂ O) _n [CH (CH ₃ ) CH ₂ O] ₁₇ (CH ₂ CH ₂ O) _m H (n + m = 5-7) 10 % Methanol solution 2.00 ml Potassium iodide 7.00 g Em-1 1.55 mol equivalent Make up to 2800 ml with water (Solution B2) 1493 g Potassium bromide Make up to 3585 ml with water (Solution C2) Silver nitrate 2131 g Finish up to 3585 ml with water.

(D2 solution) Fine grain emulsion (a) composed of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.028 mol Fine grain emulsion (a) contained 0.06 mol of iodine To 6.64 l of a 5.0% by weight aqueous gelatin solution containing potassium iodide, 7.06
Mol of silver nitrate and 2 l of an aqueous solution containing 7.06 mol of potassium iodide were added over 10 minutes, the pH during the formation of fine particles was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After formation, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 55 ° C., and half of each of the solutions B2 and C2 was added to 35
Over a period of minutes, the mixture was added by the simultaneous mixing method. During this time, the pH was 5.8
Kept. The pH was adjusted to 8.8 with a 1% aqueous KOH solution,
Solution 2, Solution C2 and Solution D2 were added by the simultaneous mixing method until Solution D2 disappeared. The pH was adjusted to 6.0 with a 0.3% aqueous citric acid solution, and the remaining amounts of the B2 solution and the C2 solution were added by a simultaneous mixing method over 25 minutes. During this time, the pAg was kept at 8.9. The addition rates of the B2 liquid and the C2 liquid were changed in a function according to the critical growth rate to suppress generation of small particles and polydispersion due to Ostwald ripening. After completion of addition, desalting, washing with water and redispersion were performed in the same manner as in Em-1, and after redispersion, the pH was adjusted at 40 ° C.
Was adjusted to 5.80 and pAg to 8.2. When the obtained silver halide emulsion was observed with an electron microscope, the average equivalent circle diameter was 0.91 μm, the average thickness was 0.23 μm, the average aspect ratio was about 4.0, and the width of the particle size distribution (standard particle size distribution) (E.g., deviation / average particle size) of 20.5%.

The obtained emulsion was heated to 47 ° C., and a silver iodide fine grain emulsion (average grain size: 0.05 μm) equivalent to 5 mmol,
390 mg of spectral sensitizing dye A and 4 m of spectral sensitizing dye B
g after addition as a solid particulate dispersion,
mg, an aqueous solution containing 50 mg of ammonium thiocyanate, 2.0 mg of chloroauric acid and 3.3 mg of sodium thiosulfate, 4.0 m of triphenylphosphine selenide.
g of the dispersion was added, and aging was performed for a total of 2 hours and 30 minutes.
At the end of ripening, 750 mg of TAI was added as a stabilizer.

A sample was prepared according to the following formulation using an emulsion prepared by mixing Em-1 and Em-2 in a weight ratio of 6: 4.

<< Preparation of Sample >> A cross-over light-cut layer, an emulsion layer, and a 175 μm-thick subbing layer coated with a subbing layer, which were colored blue at a concentration of 0.15, were coated on both sides with the following formulation (per side). Middle layer,
In the order of the protective layer, the amount of silver per side is 1.8 g / m ² , the amount of gelatin in the protective layer is 0.4 g / m ² , and the amount of gelatin in the intermediate layer is 0.
Sample 1 was prepared by coating and drying so that 4 g / m ² , the amount of gelatin in the emulsion layer was 1.5 g / m ² , and the amount of gelatin in the crossover light cut layer was 0.2 g / m ² .

<< First Layer, Crossover Light-Cut Layer >> Solid Fine Particle Dispersion Dye AH 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound I 5 mg / m ² Latex L 2 g / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle diameter 0.014μm) 10mg / m ² hardener A 2mg / m ² " Second Layer, Emulsion Layer >> Silver halide emulsion Silver amount 1.8 g / m ² Compound G 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl - catechol 130 mg / ^{m 2} polyvinyl pyrrolidone (average molecular weight 10000) 35mg / m ² styrene - maleic anhydride copolymer 80m / M ² of sodium polystyrenesulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl - triphenyl - phosphonium chloride 20 mg / m ² 1,3-dihydroxybenzene-4-sulfonic acid ammonium 500 mg / m 22 sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / m ² compound H 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² compound M 5 mg / m ² Compound N 5 mg / m ² Latex L 0.2 g / m ² Dextran (average molecular weight 1000) 0.2 g / m ² Compound P 0.2 g / m ² Compound Q 0.2 g / m ² << third layer, the intermediate layer "gelatin 0.4 g / m ² formaldehyde 10 mg / m ² 2, - dichloro-6-hydroxy-1,3,5-triazine Na trim salt 5 mg / m ² Bis - vinylsulfonyl methyl ether 18 mg / m ² Latex L 0.05 g / m ² Sodium polyacrylate 10 mg / m ² Compound S-1 3 mg / m ² Compound K 5 mg / m ² << 4th protective layer >> Gelatin 0.4 g / m ² Matting agent a (polymethyl methacrylate having an area average particle size of 7.0 μm) 50 mg / m ² Formaldehyde 10 mg / m ² 2 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² Bis-vinylsulfonylmethyl ether 18 mg / m ² Latex L 0.1 g / m ² Polyacrylamide (average molecular weight 10,000) 0.05 g / m ² sodium polyacrylate 20 mg / m ² polysiloxane S1 20 mg / m ² of Things I 12 mg / m ² Compound J 2 mg / m ² Compound S-1 7mg / m ² Compound K 15 mg / m ² Compound O 50 mg / m ² Compound ^{S-2 5mg / m 2 C} 9 F 19 O (CH 2 CH 2 O) ₁₁ H 3 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₃ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² C ₈ F ₁₇ SO ₂ N (C ₃ H ₃ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₂ Na 1 mg / m ² Hardener B 160 mg / m ² The pH of the protective layer coating solution was adjusted to 6.0.

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[0181]

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[0182]

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As shown in Table 2 below, an aqueous dispersion of inorganic fine particles and polymer fine particles, and composite polymer fine particles were added to Sample 1 to prepare Samples 2 to 21 of silver halide photographic materials.

For each sample, the sensitivity, transparency, and covering power were measured, and the results are shown in Table 2.

<Sensitivity> Fluorescent intensifying screen SR manufactured by Konica Corporation
Each sample was sandwiched between O-250 and irradiated with X-rays through a penetrometer type B manufactured by Konica Medical Co., Ltd.
Dry processing DRY4 at 35 ° C. using SR-DF processing solution (same as above) with automatic developing machine SRX-503
Process in 5 seconds. At this time, the reciprocal of the X-ray dose required to obtain a density of fog density +1.0 was defined as the sensitivity, and the relative sensitivity was set with the sensitivity of Sample 1 being 100.

<Covering power> Fluorescent intensifying screen SRO
-250 (manufactured by Konica Corporation) with each sample interposed therebetween and irradiated with X-rays.
Using a processing solution [the same], dry to
The processing was performed at a dry time of 45 seconds to determine the maximum density. The value obtained by dividing the obtained maximum density by the amount of silver applied is defined as the covering power.

<Transparency> The unexposed sample was treated with an automatic developing machine SR.
X-503 (manufactured by Konica Corporation) using SR-DF processing solution (same as above) at a development temperature of 35 ° C. and Dry to dry
After processing for 45 seconds, the transparency of the developed sample was visually evaluated according to the following evaluation criteria in five steps.

5: Very high transparency, clear film 4: Very slightly milky white, but not significantly reduced in transparency 3: Slightly milky white, slightly less transparent than 4: Transparency Slightly bad 1: The film is milky white and has little transparency.

[0190]

[Table 2]

Samples 2 to 9 using the inorganic fine particles having the surface immobilized with the water-soluble polymer and the aqueous dispersion containing the polymer fine particles of the present invention were excellent in sensitivity, covering power, and transparency. .

After the inorganic fine particle dispersion of the present invention having a temperature of 40 ° C. or lower is heated to 70 ° C. or higher, an activator is added to the dispersion to carry out a polymerization reaction while maintaining the liquid temperature at 65 ° C. to 90 ° C. 13 to 13 using the composite polymer fine particles obtained by
16, and after raising the activator solution of the present invention at 40 ° C. or lower to 70 ° C. or higher, an inorganic fine particle dispersion is added to the dispersion, and the polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C. or lower. 17 using the composite polymer fine particles obtained by
Was excellent in sensitivity, covering power, and transparency.

Example 3 Silver halide photographic light-sensitive material for thermal development << Preparation of silver halide emulsion A >> 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, and the temperature was 35 ° C. and the pH was 3. After adjusting to 0, silver nitrate 74
g of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) and [Ir (N
O) Cl ₅ ] ^2- salt at 1 × 10 ^-6 mole per silver mole and rhodium chloride salt at 1 × 10 ^-4 mole per silver mole, p
While maintaining Ag 7.7, it was added by a controlled double jet method. Then 4-hydroxy-6-methyl-
Add 1,3,3a, 7-tetraazaindene and add NaO
The pH is adjusted to 5 with H to give an average particle size of 0.06 μm,
The coefficient of variation of the projected diameter area with a monodispersity of 10% is 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalted, and then phenoxyethanol (0.1 g) was added thereto.
g was adjusted to 7.5 to obtain silver halide emulsion A. Further, chemical sensitization was performed with chloroauric acid and inorganic sulfur.

<< Preparation of Na Behenate Solution >> 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved in 945 ml of pure water at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

<< Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A >> 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later, 1 mole of silver nitrate solution 1
47 ml was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The prepared silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, the water was removed, washed six times with water and removed, and then dried.

<< Preparation of Photosensitive Emulsion >> 544 g of a solution of polyvinyl butyral (average molecular weight: 3000) in methyl ethyl ketone (17% by weight) and toluene 1
07g slowly added and mixed after 4000 psi
And dispersed.

Thickness 175μ colored blue with a concentration of 0.15
Sample 31 was prepared by sequentially forming the following layers on a polyethylene terephthalate film support on which an undercoat layer m had been applied. The drying was performed at 60 ° C. for 15 minutes.

Back side coating: A solution having the following composition was applied.

Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Matting agent: monodispersity 15% Average particle size 10 μm monodisperse silica 30 mg / m ² C _{9 H 17 -C 6 H 4 -SO 3} Na 10mg / m 2

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<< Coating of Photosensitive Layer Side >> Photosensitive Layer 1: A solution having the following composition was applied so that the coated silver amount was 2.1 g / m ² .

Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Fog Inhibitor-2 (10% methanol solution) 1.2 ml 2- (4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5 % Methanol solution) 17 ml Developer-1 (20% methanol solution) 29.5 ml

[0203]

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<< Coating of Surface Protective Layer >> A solution having the following composition was applied on the photosensitive layer.

Acetone 35 ml / m ² Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² 4-Methylphthalic acid 180 mg / m ² Tetrachlorophthalic acid 150 mg / m ² Tetrachlorophthale Acid anhydride 170 mg / m ² matting agent: monodispersity 10% average particle size 4 μm monodispersed silica 70 mg / m ² C ₉ H ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ² As described above, an aqueous dispersion of inorganic fine particles and polymer fine particles, and composite polymer fine particles were added to prepare silver halide photographic light-sensitive material samples 32 to 47 for thermal development.

For each sample, applicability and storage stability (increase in fog) were evaluated. The results are shown in Table 3.

<Coatability> The unexposed sample was visually evaluated on a five-point scale in terms of overall evaluation of coating unevenness and streak failure according to the following evaluation criteria.

5: Good finish without uneven coating and streaks 4: Very slight uneven coating and streaks 3: Some uneven coating and streaks 2: Uniform coating and streaks 1: The application unevenness and streaks are severely generated, and the finish is very poor.

<Storage Property> Each sample was divided into two parts, one of which was left as it was, and the other was left in an atmosphere of 40 ° C. and 80% RH for 5 days to evaluate the storage stability under high temperature and high humidity.

Each of the untreated samples and the samples subjected to the high-temperature and high-humidity treatment was exposed with an imager having a semiconductor laser of 810 nm. Thereafter, heat development was performed at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH. The fog density of the treated sample was measured by an optical densitometer (PDA-65 manufactured by Konica Corporation). The increase in fog of the sample after forced deterioration was determined for the sample immediately after coating and drying. The smaller the amount of fog increase, the better the storage stability.

[0211]

[Table 3]

The samples 32 to 37 using the inorganic fine particles having the surface immobilized with the water-soluble polymer and the aqueous dispersion containing the high-molecular fine particles of the present invention were excellent in coatability and storage stability.

After raising the temperature of the inorganic fine particle dispersion of the present invention of 40 ° C. or lower to 70 ° C. or higher, an activator is added to the dispersion to carry out polymerization while maintaining the liquid temperature at 65 ° C. to 90 ° C. 41 to 41 using the composite polymer fine particles obtained by
43 and the temperature of the activator solution of the present invention of 40 ° C. or lower is raised to 70 ° C. or higher, and then an inorganic fine particle dispersion is added to the dispersion, and a polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C. 44 using composite polymer fine particles obtained by
Had good coatability and storage stability.

[0214]

Industrial Applicability According to the present invention, an aqueous dispersion containing inorganic fine particles and polymer fine particles having excellent storage stability, a method for producing composite polymer fine particles, an image forming material having improved photographic performance, and a silver halide for thermal development are provided. A photographic light-sensitive material could be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 7/16 G03C 1/498 502 G03C 1/32 C08J 3/03 1/498 502 F term (reference) 2H023 AA00 CC02 CD08 2H123 AB00 AB03 AB23 AB28 BB00 BB15 BB20 BC11 CB00 CB03 4F070 AA03 AA18 AA29 AA37 AA45 AA66 AA72 AA74 AA77 AB13 AC13 AC19 AC20 AC22 AC23 AD06 AD07 BA07 BA08 CA14 CA16 CB12 FA042AB 002 BC BG012 BG021 BG072 BG091 BH021 BH022 BJ002 CD191 DE056 DE066 DE096 DE106 DE116 DE126 DE136 DE146 DE156 DJ016 FB266 GP03 HA06

Claims (9)

[Claims] 1. An aqueous dispersion comprising: inorganic fine particles having a surface immobilized with a water-soluble polymer; and polymer fine particles. 2. An image forming material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has inorganic fine particles the surface of which is fixed with a water-soluble polymer. An image-forming material comprising polymer fine particles. 3. A heat-developable silver halide photographic material having a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and silver halide and a non-photosensitive layer on a support. And at least one selected from non-photosensitive layers
A silver halide photographic light-sensitive material for thermal development, characterized in that a layer contains inorganic fine particles whose surface is fixed with a water-soluble polymer and high-molecular fine particles. 4. An inorganic fine particle dispersion having a temperature of 40 ° C. or less is heated to 70 ° C.
After the above temperature rise, an activator was added to the dispersion, and the liquid temperature was raised to 65.
Composite polymer fine particles obtained by performing a polymerization reaction while maintaining the temperature at not lower than 90 ° C and not higher than 90 ° C. 5. An activator solution having a temperature of 40 ° C. or lower is heated to 70 ° C. or higher, and then an inorganic fine particle dispersion is added to the dispersion, and a polymerization reaction is performed while maintaining the liquid temperature at 65 ° C. to 90 ° C. Composite polymer fine particles obtained by the method described above. 6. An image recording material having at least one hydrophilic colloid layer on a support, characterized in that at least one of the hydrophilic colloid layers contains the fine composite polymer particles according to claim 4. Image forming material. 7. An image recording material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers contains the composite polymer fine particles according to claim 5. Image recording material. 8. A heat-developable silver halide photographic material having a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and a silver halide and a non-photosensitive layer on a support. A silver halide photographic light-sensitive material for thermal development, characterized in that at least one layer selected from the group consisting of a layer and the non-photosensitive layer contains the fine composite polymer particles according to claim 4. 9. A heat-developable silver halide photographic material having a photosensitive layer containing a silver salt of an organic acid, a reducing agent, an antifoggant and silver halide and a non-photosensitive layer on a support. A silver halide photographic light-sensitive material for thermal development, characterized in that at least one layer selected from the group consisting of a layer and the non-photosensitive layer contains the fine composite polymer particles according to claim 5.