JPH10228076A - Heat developable photosensitive recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve image color tones and to improve the color tone stability at the time of preservation by incorporating polymer particulates contg. dyes and/or microcapsules contg. the dyes into at least one layer of the constitution layers disposed on a base. SOLUTION: The polymer particulates contg. the dyes and/or the microcapsules contg. the dyes are incorporated into at least one layer of the constitution layers of the heat developable photosensitive recording material having the base and binder. The dyes are added into the photosensitive material in the form of incorporating the dyes into the polymer particulates and/or microcapsules, by which the image color tones are improved. The recording material which is free from color fading of the image color tones by photoirradiation and has excellent fastness to light. Such effect is enhanced when the polymer particulates contg. the dyes and/or the microcapsules contg. the dyes are incorporated into at least one layer of the photosensitive layers contg. photosensitive silver halide among the constitution layers in particular.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material having excellent color tone stability during storage.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3,457,075 and D.C. Morgan
And B. `` Thermally Processed Silver System '' by Shely,
Imaging Processes and Materials
(Imaging Processes and Materials), 8th edition, Sturge, V.E. Walworth, A .; Shepp, page 2, 1969).

Such a photothermographic material generally comprises a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent. It is contained in a dispersed state in the organic binder matrix. Although the photothermographic material is stable at room temperature, it can be reduced by a redox reaction between a silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature (for example, 80 ° C. or higher) after exposure. Produces silver. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

In recent years, in the medical field, technology has been advanced with the keywords of simplification and speeding up of processing and gentleness to the earth. For example, a medical image recording system which is exposed by a laser and thermally developed has begun to be developed. Dry systems that do not waste liquid have begun to spread. Under these circumstances, the laser output has been improved in recent years, the range of choice of lasers has been widened, and the demand for visible light lasers has also increased.

Conventionally, in such a photographic light-sensitive material, a method of adjusting the color tone by adding a dye to the light-sensitive material in order to make the color tone of the entire image appear blacker, for example, Japanese Patent Application Laid-Open No. 60-24365.
4, a method of using an oil-soluble dye in a silver halide photographic light-sensitive material, a method of using a specific anthraquinone dye emulsified and dispersed in JP-A-1-139607,
There is known a method described in JP-A-289227 and JP-A-5-341441, in which a colored dye is emulsified and dispersed together with a polymer and introduced into an emulsion layer.

However, when a dye is contained in an emulsion layer of a photothermographic material by a conventional method, fog due to development is increased or sensitivity is reduced more than necessary, which may adversely affect photographic properties. .

Further, the coexistence of a polyhalogen compound which is important as an antifoggant for heat development sometimes causes bleaching of the dye during storage, resulting in deterioration of image color tone or discoloration.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-developable photosensitive recording material having good image color tone and excellent color tone stability during storage.

[0009]

The above objects have been achieved by the present invention described below as a result of earnest studies. (1) In a photothermographic recording material having a support and a binder, at least one of the constituent layers thereof is
A heat-developable photosensitive recording material comprising dye-containing polymer fine particles and / or dye-containing microcapsules. (2) The photothermographic recording material according to (1), wherein at least one of the constituent layers contains a photosensitive silver halide and a reducing agent. (3) The photothermographic recording material according to the above (1) or (2), wherein at least one of the constituent layers contains a non-photosensitive organic silver salt and a color tone agent. (4) The photothermographic material according to any one of (1) to (3), wherein at least one of the constituent layers contains a polyhalogen compound. (5) A photosensitive layer containing photosensitive silver halide and a binder is provided as a constituent layer on a transparent support, and at least one of the photosensitive layers contains polymer fine particles containing a dye and / or a dye. The heat-developable photosensitive recording material according to any one of the above (1) to (4), comprising a microcapsule and a polyhalogen compound. (6) Polymer fine particles containing a dye having at least one absorption maximum at 500 to 700 nm and / or 500 to 7
The photothermographic recording material according to any one of the above (1) to (5), comprising microcapsules containing a dye having at least one absorption maximum at 00 nm. (7) The photothermographic recording material according to any one of the above (1) to (6), wherein an aqueous latex is used as a binder.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The heat-developable photosensitive recording material of the present invention contains at least one of the constituent layers provided on the support containing polymer fine particles containing a dye and / or microcapsules containing a dye.

By adding the dye to the photographic material in the form of polymer particles or microcapsules, the image tone is improved, and the image tone is not discolored by light irradiation and has excellent light fastness. It will be. There is no adverse effect on photographic properties.

[0012] Such an effect is achieved by at least one of the constituent layers.
When a polyhalogen compound is contained as an antifoggant in the layer, in particular, at least one of the photosensitive layers containing photosensitive silver halide among the constituent layers contains fine particles of a polymer containing a dye and / or a microparticle containing a dye. Increases when capsules are included.

On the other hand, if the dye is added as it is, the light stability of the image color tone is not sufficient. Particularly, in the presence of a polyhalogen compound, bleaching of the dye occurs due to light irradiation and the discoloration becomes remarkable. I will.

The dye used in the photosensitive recording material of the present invention may be any dye. For example, pyrazoloazole dye, anthraquinone dye, azo dye, azomethine dye, oxonol dye, carbocyanine dye, styryl dye, triphenylmethane dye , Indoaniline dye,
Examples include indophenol dyes and squalilium dyes. Preferred dyes used in the present invention include anthraquinone dyes (for example, compound 1 described in JP-A-5-341441).
To 9, compounds 3-6 to 18 and 3-23 described in JP-A-5-165147
Azomethine dyes (e.g., compounds 17 to 47 described in JP-A-5-341441), indoaniline dyes (e.g., JP-A-5-341441).
Compounds 11 to 19 described in 289227, Compound 47 described in JP-A-5-341441, Compounds 2-10 to 11 described in JP-A-5-165147) and azo dyes (Compound 10 described in JP-A-5-341441) ~
16). The amount of these dyes used is determined by the desired absorption, but generally 1 m ²
It is preferable to use in a range of 1 μg or more and 1 g or less.

The dye used in the present invention preferably has a maximum absorption in a desired wavelength range of 0.1 or more and 2 or less. The dye used in the present invention has an antihalation or irradiation preventing function, and the layer containing the dye may be an antihalation layer or an irradiation preventing layer.

When a dye is used for the purpose of preventing halation or irradiation in the present invention, such a dye has a desired absorption in a wavelength range, and a preferable absorbance spectrum shape of the antihalation layer or the anti-irradiation layer. Any compound may be used as long as is obtained. For example, the following are disclosed, but the present invention is not limited thereto. As a single dye,
No. 59-56458, JP-A-2-216140, 7-13295, 7-114
No. 32, U.S. Pat.No. 5,380,635, JP-A-2-68539
Page 13, lower left column, line 1 to page 14, lower left column, line 9, 3-24539
There are compounds described in JP-A-52-139136 from page 14, lower left column to page 16, lower right column of the same as the dyes which can be decolorized by the treatment.
No. 53-132334, No. 56-501480, No. 57-16060, No.
Nos. 57-68831, 57-101835, 59-182436, JP-A-7-
36145, 7-199409, JP-B-48-33692, 50-1664
No. 8, Japanese Patent Publication No. 2-41734, U.S. Pat.Nos. 4,088,497, 4,2
83,487, 4,548,896 and 5,187,049.

The dye used in the present invention preferably has at least one maximum absorption in the wavelength region of 500 to 700 nm, whereby the effect of preventing halation and irradiation can be obtained.

Specific examples of useful dyes used in the present invention are shown below, but the present invention is not limited thereto.

[0019]

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[0020]

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[0021]

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In the present invention, the polymer used for the dye-containing polymer fine particles is preferably a water-insoluble and organic solvent-soluble polymer.

The following are preferred as the water-insoluble and organic solvent-soluble polymer used in the present invention.
The present invention is not limited to these.

In the present invention, a vinyl polymer obtained from the following monomers is preferably used. Examples of the monomer forming such a vinyl polymer include acrylic esters: specifically, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, cyclohexyl acrylate, and the like; methacrylic esters: Is methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc .; vinyl esters: specific examples thereof are vinyl acetate, vinyl benzoate, etc .; acrylamides: such as tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, etc .; methacrylamides : For example, methoxyethyl methacrylamide and the like; Olefin: for example, propylene, vinyl chloride, vinylidene chloride, butadiene, 2,3-dimethylbutane Diene, etc .; styrenes; for example, styrene, vinyl benzoic acid methyl ester, etc .; vinyl ethers: for example, methoxyethyl vinyl ether; and others, butyl crotonate, dimethyl itaconate, dimethyl maleate, phenyl vinyl ketone, glycidyl acrylate, glycidyl Examples thereof include methacrylate, N-vinylpyrrolidone, acrylonitrile, and methacrylonitrile.

As the monomers (for example, the above-mentioned monomers) used in the polymer of the present invention, two or more kinds of monomers are used as comonomers for various purposes (for example, for improving the solubility). Also, for solubility control, etc.
As long as the copolymer does not become water-soluble, monomers having an acid group as exemplified below are also used as comonomers. Acrylic acid; methacrylic acid; itaconic acid;
Maleic acid; monoalkyl itaconate, such as monomethyl itaconate; monoalkyl maleate, such as monomethyl maleate; citraconic acid; styrene sulfonic acid, etc .; these acids are alkali metals (eg, Na, K, etc.) or It may be a salt of ammonium ion.

Among the above-mentioned vinyl monomers and other vinyl monomers used in the present invention, hydrophilic monomers (here, those which become water-soluble when homopolymerized) are used as comonomers. If used,
As long as the copolymer does not become water-soluble, the ratio of the hydrophilic monomer in the copolymer is not particularly limited, but is usually preferably 40 mol% or less, more preferably 20 mol% or less, and further preferably, 10 mol% or less. When the hydrophilic comonomer to be copolymerized with the monomer of the present invention has an acid group, the proportion of the comonomer having an acid group in the copolymer is usually 20 mol% or less, preferably 10 mol% or less. And most preferably when such a comonomer is not contained.

The monomers of the invention in the polymer are preferably of the methacrylate, acrylamide and methacrylamide type. Particularly preferred are acrylamide and methacrylamide.

Two or more of the above-mentioned polymers of the present invention may be used in combination. The water-insoluble polymer in the present invention is a polymer having a solubility of 3 g or less, preferably 1 g or less in 100 g of distilled water. The oil-soluble polymer used in the present invention preferably contains 30 to 70% by weight of a component having a molecular weight of 40,000 or less.

Some specific examples of the polymer used in the present invention are described below, but the present invention is not limited to these. The numerical values in parentheses are% by weight.

Specific examples Polymer type P-1) Polyvinyl acetate P-2) Polymethyl methacrylate P-3) Polyethyl methacrylate P-4) Vinyl acetate-vinyl alcohol copolymer (95: 5) P-5) Polybutyl Acrylate P-6) Polybutyl methacrylate P-7) Butyl acrylate-acrylamide copolymer (95: 5) P-8) Methyl methacrylate-vinyl chloride copolymer (70:30) P-9) Methyl methacrylate-styrene copolymer Polymer (90:10) P-10) Vinyl acetate-acrylamide copolymer (85:15) P-11) Vinyl chloride-vinyl acetate copolymer (65:35) P-12) Methyl methacrylate-acrylonitrile copolymer Polymer (65:35) P-13) Diacetone acrylamide-methyl methacrylate copolymer (50:50) P-14) Methyl methacrylate-cyclohexyl methacrylate copolymer (50:50) P -15) Methyl methacrylate-styrene-vinylsulfonamide copolymer (70:20:10) P-16) Butyl acrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:38:24) P -17) Methyl methacrylate-butyl methacrylate-isobutyl methacrylate-acrylic acid polymer (37: 29: 25: 9) P-18) Butyl methacrylate-acrylic acid (95: 5) P-19) Methyl methacrylate-acrylic acid Polymer (95: 5) P-20) Benzyl methacrylate-acrylic acid copolymer (90:10) P-21) Butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-22) Butyl Methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P-23) Butyl methacrylate-styrene copolymer (90:10) P-24) Methyl methacrylate-N Vinyl-2-pyrrolidone copolymer (90:10) P-25) Butyl methacrylate-vinyl chloride copolymer (90:19) P-26) Butyl methacrylate-styrene copolymer (70:30) P-27 ) Poly (N-tert-butylacrylamide) P-28) Diacetone acrylamide-methyl methacrylate copolymer (62:38) P-29) Tert-butyl acrylamide-methyl methacrylate copolymer (60:40) P- 30) Methyl methacrylate-acrylonitrile copolymer (70:30) P-31) Poly (tert-butyl acrylate) P-32) Poly (4-chlorophenyl acrylate) P-33) Poly (hexadecyl acrylate) P- 34) Polyvinyl-tert-butylate P-35) Poly (benzyl methacrylate) P-36) Poly (α-pyrrolidone) P-37) Poly (ε-caprolactam) P-38) Poly (vinyl acetal)

These compounds can be produced by known methods, for example, the methods described in US Pat. No. 3,392,022 and Japanese Patent Publication No. 49-17367.

The method of incorporating the dye of the present invention into the polymer fine particles comprises dissolving the dye and the polymer in a low boiling organic solvent insoluble in water (having a solubility of 30% or less in water),
A method in which the aqueous phase is emulsified and dispersed (an emulsifying aid such as a surfactant and gelatin may be used if necessary). After the dye is contained in the polymer fine particles, it is preferable from the viewpoint of storage stability to remove an unnecessary organic solvent.

The dispersion of polymer fine particles containing the dye of the present invention is prepared as follows. After completely dissolving the dye and polymer together in a low boiling organic solvent, disperse the solution in water, preferably in an aqueous hydrophilic colloid solution, more preferably in an aqueous gelatin solution, if necessary, a dispersing aid such as a surfactant. And dispersed in fine particles by ultrasonic waves, a colloid mill, a dissolver, or the like, and contained in the coating solution. Removing the low boiling organic solvent from the prepared dispersion is effective for the stability of the dispersion, particularly for preventing the precipitation of the dye during storage. Examples of the method for removing the low-boiling organic solvent include distillation under reduced pressure with heating, distillation under normal pressure with heating in a gas atmosphere such as nitrogen or argon, washing with noodles, or ultrafiltration. Here, the low-boiling organic solvent is an organic solvent useful at the time of emulsification and dispersion, a drying step at the time of coating, and finally from the photosensitive material substantially by the above-described method and the like,
Organic solvent with a low boiling point, or
A solvent that has some solubility in water and can be removed by washing with water. Ethyl acetate, as a low boiling point organic solvent,
Butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β
-Ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone and the like. Further, if necessary, an organic solvent which is completely mixed with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran or the like can be partially used. These organic solvents can be used in combination of two or more. The pH of the emulsion is the chemical stability of the compound itself, when gelatin is used for the dispersion, which is preferably neutral to acidic in view of the stability of the dispersion, when the gelatin has an isoelectric point of 0.3 or more, preferably 0.5 or more, more preferably It is preferable to adjust the value to a high value of 0.5 or more and 5 or less, since it is possible to prevent the generation of so-called syneresis water which naturally separates and contracts the liquid when the gel is left. To adjust the pH, organic acids such as citric acid, oxalic acid, acetic acid, tartaric acid,
Succinic acid, malic acid, etc.) and alkalis (eg KOH, NaOH
Etc.) should be used.

In the present invention, when the dye is contained in the polymer latex particles as described above, it is extremely preferable to use a melting point depressant. The melting point depressant used in the present invention means a substantially water-insoluble organic compound that has a function of lowering the melting point when mixed with a dye that is substantially diffusion-resistant and oil-soluble. I do.

The average particle size of the particles in the emulsion thus obtained is preferably from 0.02 μm to 2 μm, more preferably from 0.04 μm to 0.4 μm. In the emulsion,
The particle size of the particles can be measured, for example, with a measuring device such as a Nanosizer manufactured by Coulter, USA. The polymer fine particles in the emulsion of the present invention can contain various photographic hydrophobic substances as long as the dye can sufficiently fulfill its purpose of use. Examples of photographic hydrophobic substances include high boiling organic solvents, colored couplers, colorless couplers, developers, developer precursors, development inhibitors, development inhibitor precursors, ultraviolet absorbers, development accelerators, hydroquinones, and the like. , A dye, a dye releasing agent, an antioxidant, an optical brightener, a fog inhibitor, and the like. Further, these hydrophobic substances may be used in combination with each other. The dyes may be used alone or in combination of two or more.

In the present invention, the above-mentioned melting point depressant is preferably used in an amount of usually from 10 to 200% by weight, especially from 20 to 100% by weight, based on the dye. In the present invention, the polymer is
Usually, it is preferably used in the range of 10 to 400% by weight, particularly 20 to 300% by weight based on the dye.

For the production of the microphone capsule containing the dye used in the present invention, any of an interfacial polymerization method, an internal polymerization method and an external polymerization method can be employed. In particular, the dye is dissolved or dissolved in an organic solvent. It is preferable to employ an interfacial polymerization method in which the dispersed core material is emulsified in an aqueous solution in which a water-soluble polymer is dissolved, and then a polymer wall is formed around the oil droplet.

Examples of the organic solvent include carboxylic esters such as ethyl acetate and butyl acetate, toluene, xylene, and the like.
The boiling point of the phosphate ester or the like is 150 ° C. or less, preferably 6 ° C.
It is preferable to use a non-aqueous solvent having a temperature of 0 ° C to 150 ° C. The reactant forming the polymeric substance is added inside the oil droplet and / or outside the oil droplet.

Specific examples of the polymer substance include polyurethane, polyurea, polyamide, polyester, polycarbonate, urea-formaldehyde resin, melamine-formaldehyde resin, polyamic acid, polystyrene,
Styrene-methacrylate copolymer, styrene-acrylate copolymer and the like can be mentioned. Preferred polymer substances are polyurethane, polyurea, polyamide, polyester, and polycarbonate, and polyurethane and polyurea are particularly preferred. Two or more polymer substances can be used in combination.

On the other hand, specific examples of the water-soluble polymer include gelatin, polyvinylpyrrolidone, and polyvinyl alcohol.

For example, when polyurea or polyurethane is used as the capsule wall material, a polyvalent isocyanate such as diisocyanate, triisocyanate, tetraisocyanate or polyisocyanate prepolymer and a diamine, triamine, tetramine or the like are used. The microcapsule wall can be easily formed by reacting a polyamine, a prepolymer containing two or more amino groups, piperazine or a derivative thereof, a polyhydric alcohol or the like, or water with an interfacial polymerization method in an aqueous solvent. it can. Microcapsules in this case are particularly preferred because the walls are dense.

The composite wall composed of polyurea and polyamide or the composite wall composed of polyurethane and polyamide is added, for example, by adjusting the pH of an emulsifying medium to be a reaction solution using polyisocyanate and acid chloride or polyamine and polyhydric alcohol. It can be prepared by heating. For details of the method for producing a composite wall composed of these polyurea and polyamide, see JP-A-58-669.
No. 48 publication. The capsule made of polyamic acid is formed, for example, by an interfacial reaction between a polystyrene-maleic anhydride copolymer and a polyvalent amine.

The particle size of the microcapsules containing the dye is in the range from 0.3 to 5 μm. The amount of the polymer used as a wall for the dye is 30 to 99% by weight, especially 50 to 99% by weight.
It is preferably wt%.

According to the above-mentioned production method, microcapsules containing an emulsion of a dye can be obtained. However, in a heat-developable photosensitive recording material, the organic solvent in the emulsion of the dye is dried in the coating film after application to form a coating. Hardly survive.

In the present invention, an organic halide is used as an antifoggant, for example, JP-A-50-119624 and JP-A-50-119624.
-120328, 51-121332, 54-
58022, 56-70543, 56-993
No. 35, No. 59-90842, No. 61-129642
No. 62-129845, JP-A-6-208191
No., No. 7-5621, No. 7-2781, No. 8-15
No. 809, U.S. Pat. Nos. 5,340,712 and 53,690.
Nos. 00 and 5464737; U.S. Pat.
6, No. 4,756,999, No. 5,340,712, European Patent No. 605981A1, No. 622666A1, No. 631176A1, Japanese Patent Publication No. 54-165, Japanese Unexamined Patent Publication No.
And compounds described in U.S. Pat. Nos. 4,108,665 and 4,442,202.

Further, a polyhalogen compound represented by the following general formula (I) is also preferably used.

[0047]

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In the general formula (I), Q represents an alkyl group, an aryl group or a heterocyclic group, and X ₁ and X ₂ each represent a halogen atom. Z represents a hydrogen atom or an electron-withdrawing group. Y is -C (= O) -, - SO- or -SO ₂ -
Represents n represents 0 or 1.

The aryl group represented by Q may be monocyclic or condensed, and is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms (eg, phenyl, naphthyl, etc.)
And more preferably a phenyl group and a naphthyl group, and further preferably a phenyl group.

The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one atom of N, O or S, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring.

The heterocyclic group is preferably a 5- or 6-membered unsaturated heterocyclic group optionally having a condensed ring, and more preferably a 5- or 6-membered aromatic group optionally having a condensed ring. Group heterocyclic group. More preferably, it is a 5- or 6-membered aromatic heterocyclic group which may have a condensed ring containing a nitrogen atom, particularly preferably a condensed ring which may have a condensed ring containing 1 to 4 nitrogen atoms. And a 6-membered aromatic heterocyclic group. As the heterocycle in such a heterocyclic group, preferably, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole, indolenine, tetrazaindene Yes, more preferably imidazole, pyridine, pyrimidine, pyrazine, pyridazine, triazole, triazine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, benzimidazole, benzoxazole, benz Thiazole and tetrazaindene, more preferably imidazole and pyridene. Down, pyrimidine, pyrazine,
Pyridazine, triazole, triazine, thiadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, benzimidazole and benzthiazole, particularly preferably pyridine, thiadiazole, quinoline and benzthiazole.

The aryl group and heterocyclic group represented by Q may have a substituent in addition to-(Y) _n -CZ (X ₁ ) (X ₂ ), and the substituent is preferably an alkyl group. ,
Alkenyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group,
Aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, ureido group, phosphoric acid amide group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, heterocyclic group, and more preferably Are alkyl, aryl, alkoxy, aryloxy, acyl, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, ureido, phosphoric amide, halogen Atom, cyano group, nitro group, heterocyclic group, more preferably alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, acylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, halogen atom, Anomoto, nitro group, a heterocyclic group, particularly preferably an alkyl group, an aryl group, a halogen atom.

The alkyl group represented by Q may be linear, branched or cyclic, and preferably has 1 to 30 carbon atoms, more preferably has 1 to 15 carbon atoms. Examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a tertiary octyl group.

The alkyl group represented by Q is-(Y) _n -C
It may have a substituent other than Z (X ₁ ) (X ₂ ),
Examples of the substituent include those similar to the substituents that can be used when Q is a heterocyclic group or an aryl group. As the substituent, preferably, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, a ureido group, and phosphorus Acid amide group, hydroxy group, halogen atom, heterocyclic group, more preferably aryl group, alkoxy group, aryloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, ureido group, A phosphoric amide group, a halogen atom, more preferably an aryl group, an alkoxy group,
An aryloxy group, an acylamino group, a sulfonylamino group, a ureido group, and a phosphoric amide group.

Y is -C (= O)-, -SO- or -S
O ₂ —, preferably —C (＝ O) —, —SO ₂
—, And more preferably —SO ₂ —.

N represents 0 or 1, but is preferably 1.

X ₁ and X ₂ represent a halogen atom.
_The halogen atoms represented by ₁ and X ₂ may be the same or different from each other and are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom, more preferably a chlorine atom. And a bromine atom, particularly preferably a bromine atom.

Z represents a hydrogen atom or an electron-withdrawing group, and the electron-withdrawing group represented by Z is preferably σp
It is a substituent having a value of 0.01 or more, and more preferably 0.1.
One or more substituents. Regarding Hammett's substituent constant, see Journal of Medicinal Chemistry, 1973, Vol.
6, No. 11, 1207-1216 etc. can be referred to.

Z is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl. Group, carbamoyl group, sulfamoyl group,
Particularly preferred is a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

Of the above polyhalogen compounds, the compounds represented by the general formula (Ia) are more preferably used.

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In the general formula (Ia), Q, X ₁ , X ₂ , Z
Has the same meaning as in formula (I), and the preferred range is also the same.

The following are specific examples of the polyhalogen compound used in the present invention, but are not limited thereto.

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[0065]

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In the present invention, the polyhalogen compound is used in an amount of 10 mg / m ^{2 to 3} g / m ² , which is represented by a coating amount per m ² of the recording material.
² and more preferably 50 mg / m ^{2 to 1} g / m ² .

In the present invention, the polyhalogen compound may be added by any method such as a solution, a powder and a dispersion of solid fine particles, and it is particularly preferable that the solid fine particles are dispersed in the photosensitive layer. Dispersion of solid fine particles can be performed by a known micronizing means (for example, ball mill, vibrating ball mill, sand mill,
Colloid mill, jet mill, roller mill, etc.). At the time of dispersion, a dispersion aid may be used. Further, it may be added as a solution mixed with other additives such as a sensitizing dye, a reducing agent and a color tone agent.

The heat-developable photosensitive recording material of the present invention preferably contains a photosensitive silver halide.

The photosensitive silver halide used in the present invention is:
It can be used in the range of 1 to 50 mol%, preferably 3 to 20 mol% of the organic silver salt.

The silver halide may be any photosensitive silver halide such as silver bromide, silver iodide, silver chloride, silver bromoiodide, silver chlorobromoiodide, silver chlorobromide and the like. The silver halide is photosensitive and may have any shape including a cubic shape, an orthorhombic shape, a plate shape, a tetrahedral shape, and the like, but is not limited thereto. May grow. The amount of silver halide used is preferably from 0.1 mol% to 50 mol%, more preferably from 0.5 mol% to 20 mol% of the non-photosensitive silver salt.

The silver halide used in the present invention is
Can be used without modification. However,
Chemically sensitized by chemical sensitizers such as compounds containing sulfur, selenium, tellurium, etc., compounds containing gold, platinum, palladium, rhodium or iridium, reducing agents such as tin halides or a combination thereof Can be done. For more information on these procedures, see
James' Theory of the Photographic Process, 4th Edition, Chapter 5, 149-169
Page.

The silver halide can be added to the emulsion layer in any manner that places the non-photosensitive silver salt in catalytic proximity. The silver halide and organic silver salt, separately formed or "preformed" in the binder, can be mixed before use to prepare a coating solution, but both are mixed in a ball mill for an extended period of time. Is also effective. Further, it is also effective to use a method comprising converting a part of the silver of the non-photosensitive silver salt into silver halide in addition to the non-photosensitive silver salt prepared with the halogen-containing compound. Methods of preparing these silver halides and organic silver salts and methods of mixing them are known in the art and are described in Research Disclosure, June 1978, Item No. 17029 and U.S. Pat. No. 3,700. No. 458.

The preformed silver halide emulsion of the present invention may not be washed, or may be washed to remove soluble salts. In the latter case, for example, U.S. Pat.
No. 618,556, No. 2,614,928, No. 2,5
65,418, 3,241,969, and 2,489,341,
The soluble salts may be removed by cooling coagulation and leaching, or the emulsion may be coagulated and washed.

The silver halide grains may be of any crystalline form, including, but not limited to, cubic, tetrahedral, orthorhombic, plate, layer, plate, and the like.

The content of silver halide is represented by the coating amount per 1 m ² of the recording material, and is preferably 1 g / m ² or less and 0.03 g / m ² or more, and 0.5 g / m ² or less and 0.1 g / m ² or more. Particularly preferred.

In the present invention, it is preferable to use a non-photosensitive organic silver salt.

The non-photosensitive organic silver salt which can be used in the present invention is relatively stable to light, but can be used in the presence of an exposed photocatalyst (such as a photographic silver salt) and a reducing agent.
It is a silver salt that forms a silver image when heated to or above ° C. Such a silver salt may be any organic material containing a source capable of reducing silver ions. As the silver salt of an organic acid, in particular, a compound having 10 to 30 carbon atoms, preferably 15 to 30 carbon atoms.
28) Long chain fatty carboxylic acids are preferred. Also preferred are organic or inorganic silver salt complexes wherein the ligand has a total stability constant in the range of 4.0 to 10.0. The non-photosensitive silver salt is preferably contained in the recording material in an amount of about 5 to 30% by weight of the image forming layer. Preferred organic silver salts are silver salts of organic compounds having a carboxyl group, and include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver aliphatic carboxylate include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate,
Silver maleate, silver fumarate, silver tartrate, silver linoleate,
Silver butyrate and silver camphorate, and mixtures thereof. The coating amount of the non-photosensitive silver salt is preferably 0.1 g or more and 5 g or less per 1 m ² of the recording material, and
It is more preferably at least 3 g.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. As is well known in photosensitive silver halide light-sensitive materials, the inverse relationship between the size of silver salt crystal grains and their covering power also holds in the heat-developable photosensitive recording material of the present invention, that is, thermal development. When the size of the organic silver salt particles as the image forming portion of the photosensitive recording material is large, it means that the covering power is small and the image density is low. In the present invention, the minor axis is from 0.01 μm to 0.20 μm, and the major axis is from 0.10 μm to 5.0.
μm or less, more preferably from 0.01 μm to 0.15 μm in the short axis, and more preferably from 0.10 μm to 4.0 μm in the long axis. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is the minor axis, the percentage of the value obtained by dividing the standard deviation of the length of each major axis by the minor axis and major axis, respectively, is preferably 100% or less, more preferably 80% or less, and still more preferably 50% or less. is there.
The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring the monodispersity, there is a method of obtaining the standard deviation of the volume weight average diameter of the organic silver salt, the percentage of the value divided by the volume weight average diameter (coefficient of variation) is preferably 100% or less, more It is preferably at most 80%, more preferably at most 50%. As a measuring method, for example, a particle size obtained by irradiating a laser beam to an organic silver salt dispersed in a liquid and obtaining an autocorrelation function with respect to a time change of fluctuation of the scattered light.
(Mean volume load average diameter).

Silver semi-soaps have also been found to be useful, especially the equimolar amounts of silver behenate and behenic acid having a silver content of about 14.5% prepared by precipitation from a commercially available aqueous solution of behenic acid. Mixtures are a preferred example. Transparent film materials require a transparent coating, and therefore contain no more than about 40% of free behenic acid and have an analytical silver content of about 2%.
A behenic acid total soap of 5.2% may be used. The methods used to make silver soap dispersions are well known in the art and are described in "Research Disclosure", April 1983, Item No. 22812,
"Research Disclosure" October 1983,
Item No. 23419 and US Pat. No. 3,985,5
No. 65.

A silver salt of a compound containing a mercapto or thione group and derivatives thereof can also be used. Preferred examples of these compounds include a silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver salt of 2-mercaptobenzimidazole, a silver salt of 2-mercapto-5-aminothiadiazole, Silver salts of thioglycolic acid such as silver salts of (ethyl glycolamide) benzothiazole, silver salts of S-alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithioacetic acid, etc. Silver salt of dithiocarboxylic acid, silver salt of thioamide, 5-carboxyl-1-methyl-2-phenyl-
Silver salts of 4-thiopyridine, silver salts of mercaptotriazine, silver salts of 2-mercaptobenzoxazole, silver salts described in U.S. Pat. No. 4,123,274, for example, 3-amino-5-benzylthio-1,2 Silver salts of 1,2,4-mercaptothiazole derivatives, such as silver salts of 1,4-thiazole;
And silver salts of thione compounds such as the silver salt of 3- (3-carboxyethyl) -4-methyl-4-thiazoline-2-thione described in U.S. Pat. No. 3,301,678. further,
A silver salt of a compound containing an imino group can be used.
Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazoles such as silver 5-chlorobenzotriazole, and US Pat. 4,220,709, silver salts of 1,2,4-triazole or 1-H-tetrazole, and silver salts of imidazole and imidazole derivatives. For example, US Pat. No. 4,761,361
And various silver acetylide compounds as described in U.S. Pat. No. 4,775,613.

The binder used in the photosensitive layer (emulsion layer) of the present invention may be a known natural or synthetic resin, for example, gelatin, polyvinyl alcohol, polyvinyl acetal, polyvinyl chloride, polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene. , Polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are included in such definitions. Preferred polymers are polyvinyl butyral, butyl ethyl cellulose, methacrylate copolymer, maleic anhydride copolymer, polystyrene, polyethylene, polypropylene and butadiene-
It is a styrene copolymer. If necessary, two or more of these polymers can be used in combination. Such a polymer is used in an amount sufficient to hold the components therein. That is, it is used in an effective range to function as a binder. The effective range can be appropriately determined by those skilled in the art. As a guide when at least the organic silver salt is retained, the ratio of the binder to the organic silver salt is 15: 1 to 1: 5 by weight, particularly 1: 1.
The range of 0: 1 to 1: 2 is preferred.

In the present invention, a binder obtained by dispersing a hydrophobic polymer in an aqueous solvent may be used as the binder for the emulsion layer. The aqueous solvent here is water or a mixture of water and 70% by weight or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include methanol, ethanol, propanol, ethyl acetate, dimethylformamide, methyl cellosolve, butyl cellosolve and the like. Specific examples of the solvent composition include water / methyl alcohol = 90/10 or 70/30 or 50/50, water / isopropyl alcohol = 90/10, water / butyl cellosolve = 95/5, and water / dimethylformamide = 95.
/ 5, water / methyl alcohol / dimethylformamide =
90/5/5 or 80/15/5 (weight ratio).

The term "dispersion" as used herein refers to a state in which the polymer is not thermodynamically dissolved in the solvent but is dispersed in the aqueous solvent in a latex, micelle state, or molecular dispersion state.

In the present invention, it is preferable to use such an aqueous latex (polymer latex) in a dispersed state.

The polymer latex of the present invention is described in "Synthetic Resin Emulsion (edited by Tadashi Okuda and Hiroshi Inagaki, published by Kobunshi Kanko (1978))" and "Application of Synthetic Latex (Takaaki Sugimura, Yasuo Kataoka, Soichi Suzuki, Edited by Keiji Kasahara, published by the Society of Polymer Publishing (1993)), and "Synthesis of Synthetic Latex (Souichi Muroi, published by the Society of Polymer Publishing (1970))". The average particle size of the dispersed particles is preferably in the range of 1 to 50,000 nm, more preferably in the range of about 5 to 1000 nm. There is no particular limitation on the particle size distribution of the dispersed particles, and they may have a wide particle size distribution or a monodispersed particle size distribution.

The polymer latex of the present invention may be a so-called core / shell type latex other than a polymer latex having a normal uniform structure. In this case, it may be preferable to change the glass transition temperature of the core and the shell.

The minimum film forming temperature (MFT) of the polymer latex of the present invention is from -30 ° C. to 90 ° C., more preferably 0 ° C.
The temperature is preferably about 70C. A film-forming auxiliary may be added to control the minimum film-forming temperature. The film forming aid is an organic compound (usually an organic solvent) which is also called a plasticizer and lowers the minimum film forming temperature of the polymer latex. For example, the above-mentioned "Synthetic Latex Chemistry (Souichi Muroi, published by Kobunshi Kankokai (1970)") )"It is described in.

As the binder of the present invention, among these polymers, those having an “equilibrium water content at 25 ° C. and 60% RH” of 2 wt% or less are particularly preferred. The lower limit of the equilibrium water content is not particularly limited, but is preferably 0.01 wt%, more preferably 0.03 wt%. Here, the “equilibrium moisture content at 25 ° C. and 60% RH” refers to the weight W _{1 of} the polymer that has reached the humidity control equilibrium in an atmosphere of 25 ° C. 60% RH and the weight W ₀ of the polymer that is in a completely dry state at 25 ° C. Can be expressed as “Equilibrium moisture content at 25 ° C and 60% RH” = {(W ₁ -W ₀ ) / W ₀ } × 100
(wt%)

The polymer of the present invention is not particularly limited as long as it can be dispersed in the above-mentioned aqueous solvent. For example, acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin, vinylidene chloride resin, rubber resin (for example, SBR resin) , NBR resin, etc.), vinyl acetate resin, polyolefin resin, polyvinyl acetal resin and the like. As the polymer, either a homopolymer or a copolymer obtained by polymerizing two or more monomers may be used. The polymer may be linear or branched. Further, the polymers may be crosslinked. The number average molecular weight of the polymer is 1,000 to 1,000,000, preferably 3,000 to 500,000
Is desirable. Those having a number average molecular weight of less than 1,000 generally have a low film strength after coating, which may cause inconvenience such as cracking of the photosensitive material. Of these, styrene-butadiene copolymers are preferred, although they are included in the above SBR resin.

The "styrene-butadiene copolymer" used in the present invention is a polymer containing styrene and butadiene in the molecular chain. The molar ratio of styrene-butadiene is 99: 1 to 40:60, and more preferably 95: 5 to 50: 5.
0, particularly preferably 90:10 to 60:40.

The "styrene-butadiene copolymer" of the present invention also includes esters of acrylic acid or methacrylic acid such as methyl methacrylate and ethyl methacrylate, acids such as acrylic acid, methacrylic acid and itaconic acid, or acrylonitrile. Other vinyl monomers such as divinylbenzene may be copolymerized. Styrene-butadiene is 50% by weight or more, and more preferably 50 to 9%.
It is preferably present at 9% by weight, especially 60-97% by weight.

The styrene-butadiene copolymer used in the present invention has a number average molecular weight of 2,000 to 1,
1,000,000, more preferably 5,000-500,
A range of 000 is preferred.

The styrene-butadiene copolymer of the present invention is usually a random copolymer, but these copolymers may be linear polymers, branched or crosslinked. Usually, it is used as particles having an average particle size of about 0.01 to 1 μm.

Specific examples of the polymer of the present invention include acrylic resins such as Sebian A-4635, 46683, and 4601 (all manufactured by Daicel Chemical Industries, Ltd.) and Nipol LX811, 814, 820, 821, and 857.
(Nippon Zeon Co., Ltd.), etc., and as the polyester resin, FINETEX ES650, 611, 679, 675, 525, 801, 85
0 (all manufactured by Dainippon Ink and Chemicals, Inc.) and Wdsize WMS (manufactured by Eastman Chemical). Specific examples of the rubber-based (SBR) resin or styrene-butadiene copolymer are as follows.

Latex of P-1-St ₇₀ -Bu _30- (Mn = 30
_{000) P-2 -St 60 -Bu} 37 -MAA 3 - latex (Mn = 45000) P-3 -St 50 -Bu 40 -AN 7 -AA 3 - latex (Mn = 70000) P-4 -St ₇₀ -Bu ₂₀ -DVB ₅ -MAA ₅ - latex (Mn = 100000) P-5 -St 50 -Bu 30 -AN 15 -IA 5 - latex (Mn = 60000)

The abbreviations here represent structural units derived from the following monomers, the numerical values are% by weight, and Mn is the number average molecular weight.

St: styrene, Bu: butadiene, MA
A: methacrylic acid, AN: acrylonitrile, AA: acrylic acid, DVB: divinylbenzene IA: itaconic acid

Further, the Luck Star 3307B, DS-205, 6
02, Rack Star DS203, 7132C, DS807
(Dai Nippon Ink Chemical Co., Ltd.), Nippol 2507,
Lx416, Lx433, Lx410, Lx430, L
x435 (manufactured by Nippon Zeon Co., Ltd.), DL-670,
L-5702 and 1235 (all manufactured by Asahi Kasei Corporation).

In the present invention, when a styrene-butadiene copolymer which is preferably used as a binder is used, a coating solution having a solid content of 0.5 to 12 wt% using the above-mentioned solvent is used.
More preferably, it is in the range of 1 to 8% by weight.

As described above, application with an aqueous solvent is preferable from the viewpoint of environment and cost. When an aqueous latex, particularly a latex of a polymer having an equilibrium water content of 2% by weight or less, is used, an increase in fog in a high humidity atmosphere is suppressed. Is preferred.

Photothermographic emulsions such as the silver halide emulsions of the present invention can be coated on a variety of substrates. Typical substrates are polyester film, primed polyester film, poly (ethylene terephthalate) film, cellulose nitrate film, cellulose ester film, poly (vinyl acetal) film,
Includes polycarbonate films and related or resinous materials, as well as glass, paper, metal, and the like. Flexible substrates, especially partially acetylated or baryta and / or α-olefin polymers, especially polyethylene terephthalate, are typically used. The support may be transparent or slightly opaque, but is more preferably transparent.

In the heat-developable photosensitive recording material of the present invention, a surface protective layer can be provided on the photosensitive emulsion layer.

Suitable binders for the surface protective layer of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)),
Poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, and poly (amide) s. Binder is water or organic solvent or latex,
A coating may be formed from the emulsion.

The matting agent usually used is fine particles of an organic or inorganic compound. Any matting agent can be used, for example, U.S. Pat. Nos. 1,939,213, 2,701,245, 2,322,037, 3,262,782, and 3,539. Nos. 3,344, 3,767,448, etc., and organic matting agents described in 1,260,772, 2,192,241.
No. 3,257,206 and 3,370,951
Nos. 3,523,022, 3,769,020, etc., and those well known in the art such as inorganic matting agents described in each specification can be used. For example, specifically, examples of organic compounds that can be used as a matting agent include, as examples of water-dispersible vinyl polymers, polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, acrylonitrile-α-methylstyrene copolymer, and polystyrene. , Styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, etc., and starch derivatives such as carboxy starch, carboxynitrophenyl Starch, urea-formaldehyde-starch reactants, etc.
Gelatin hardened with a known hardener and hardened gelatin coacervated into microcapsule hollow granules can be preferably used. Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. . The above matting agents can be used by mixing different types of substances as necessary. The size of the matting agent is not particularly limited, and those having an arbitrary particle size can be used. However, in the practice of the present invention, those having a particle size of 0.1 μm to 30 μm are preferably used. Those having a particle size of 15 μm are more preferred. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze of the coating film and the surface gloss, the particle size, the shape, and the particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. Although it is possible, it is preferable to use a spherical one, and further, for example, a true spherical one such as Sildex H-31, H-51, H-121 manufactured by Dokai Chemical Co., Ltd. or Tospearl 145, 120 manufactured by Toshiba Silicone Co., Ltd. is particularly preferable. preferable.

In the present invention, the matting agent comprises the outermost surface layer of the photosensitive recording material or a layer functioning as the outermost surface layer;
Alternatively, it is preferably contained in a layer near the outer surface. The degree of matting can be controlled by changing the matting agent particle size / addition amount. Increasing the particle size of the matting agent,
Alternatively, by increasing the amount of the matting agent, the matte degree becomes a small numerical value. In particular, increasing the particle size of the matting agent is effective in reducing the matting degree to a small value. The matte degree is preferably a Beck smoothness of 250 seconds or less and 10 seconds or more, more preferably 180 seconds or less and 50 seconds or more.

The photothermographic recording material of the present invention may have a backing layer (back layer) on the surface of the support opposite to the silver halide emulsion layer (photosensitive layer).

Suitable binders for the backing layer of the present invention include transparent or translucent and generally colorless natural polymer synthetic resins and polymers and copolymers, and other film-forming media such as: gelatin, gum arabic,
Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) ), Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)),
Poly (ester) s, poly (urethanes), phenoxy resin, poly (vinylidene chloride), poly (epoxide)
, Poly (carbonate) s, poly (vinyl acetate), cellulose esters, poly (amide) s and the like. The binder may be coated from water or an organic solvent or emulsion.

In the present invention, it is preferable to use a reducing agent.

The reducing agent for the non-photosensitive silver salt may be any substance that reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but bisphenol and hindered phenol reducing agents are preferred. Preferably, the reducing agent is present as 2 to 30% by weight of the image forming layer.

Disclosed are reducing agents for non-photosensitive silver salts, including amide oximes such as phenylamido oxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; for example, 4-hydroxy-3, Azines such as 5-dimethoxybenzaldehyde azine; combinations of aliphatic carboxylic acid arylhydrazides such as 2,2'-bis (hydroxymethyl) propionyl-β-phenylhydrazine with ascorbic acid and ascorbic acid; polyhydroxybenzene And a combination of hydroxylamine, reductone and / or hydrazine (such as a combination of hydroquinone and bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine); Ruhidorokisamu acid, p- hydroxy hydroxamic acids such as phenyl hydroxamic acid and β- ants Nin hydroxamic acid; combinations of azines and sulfonamidophenols (for example, phenothiazine and 2,
6-dichloro-4-benzenesulfonamidophenol, etc.); α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenyl acetate, ethyl-α-cyanophenyl acetate; 2,2′-dihydroxy-1, Bis-β-naphthol as exemplified by 1′-binaphthyl, 6,6′-dibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane; bis A combination of -β-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); and 5-, such as 3-methyl-1-phenyl-5-pyrazolone. Pyrazolone; dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and ann Reductones as exemplified by hydrodihydropiperidone hexose reductone; sulfonamide phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1, 2,2-dimethyl-7 and the like;
Chromans such as -t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarbethoxy-
1,4-dihydropyridines such as 1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-
3-tert-butyl-5-methylphenyl) methane, 2,2
-Bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-
Methylphenol) and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like); ascorbic acid derivatives (for example, 1-ascorbyl palmitate, ascorbyl stearate and the like); and aldehydes such as benzyl and biacetyl And ketone; 3
-Including pyrazolidone and certain indane-1,3-diones.

These reducing agents may be contained as a solid in the image forming layer or in a layer adjacent thereto. The size of the solid particles is preferably in a range that cannot be visually recognized, and the average diameter is preferably 5 μm or less, particularly preferably 1 μm or less.
The lower limit is not particularly limited, but is usually about 0.1 μm.

In the present invention, it is preferable to use a color tone material.

The toning agent used in the present invention can be used as a photothermographic material as disclosed in US Pat. Nos. 3,080,254, 3,847,612 and 4,123,282. Common color toning agents can be used.

For example, phthalimide and N-hydroxyphthalimide; succinimide, pyrazolin-5-one, and quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione Cyclic imide; naphthalimide (for example, N-hydroxy-1,8
-Naphthalimide); cobalt complex (e.g., cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4-triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2 ,
4-triazole and 2,5-dimercapto-1,3,
Mercaptans exemplified by 4-thiadiazole; N-
(Aminomethyl) aryldicarboximides, such as (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,
3-dicarboximide); and blocked pyrazoles, isothiuronium derivatives, and certain photobleaching agents (eg, N, N'-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- ( 3,6-
Diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-
(Benzothiazole)); and 3-ethyl-5 [(3-
Ethyl-2-benzothiazolinylidene) -1-methylethylidene] -2-thio-2,4-oxazolidinedione; phthalazinone, a phthalazinone derivative or metal salt, or 4- (1-naphthyl) phthalazinone, 6-chlorophthala Derivatives such as dinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione; phthalazine and phthalic acid derivatives (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetraphthalic acid) Quinazolinedione, benzoxazine or naphthoxazine derivatives; rhodium complexes, such as hexachloro, which function not only as tone modifiers but also as sources of halide ions for silver halide formation in situ. Rhodium (III) ammonium, rhodium bromide, nitric acid Indium and potassium persulfates such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-1 , 3-Benoxazine-2,4-dione and 6-nitro-1,3-benzoxazine-2,
Benzoxazine-2,4-dione such as 4-dione;
Pyrimidines and asymmetric-triazines (eg 2,4-
Dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4
-Diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene and 1,4-di (o-chlorophenyl)
-3,6-dimercapto-1H, 4H-2,3a, 5,6a
-Tetraazapentalene).

Among these, the most preferred color tone agents include phthalimides, phthalazinones, and combinations of phthalazines and phthalic acids.

These toning agents may be contained in the image forming layer or in a layer adjacent thereto as a solid. The size of the solid particles is preferably in a range that cannot be visually recognized, and the average diameter is preferably 5 μm or less, particularly preferably 1 μm or less.
The lower limit is not particularly limited, but is usually about 0.01 μm.

As the sensitizing dye in the present invention, any dye can be used as long as it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE Item 17
Item 643IV-A (p.23, December 1978), Item 1831X (August 1979)
p.437) or in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers, scanners, imagesetters and plate making cameras can be advantageously selected.

Examples of spectral sensitization to red light include He-Ne
For a so-called red light source such as a laser, a red semiconductor laser or an LED, a compound of I-1 to I-38 described in JP-A-54-18726, and a compound of I-1 described in JP-A-6-75322. I-3
5 and the compounds I-1 to I- described in JP-A-7-287338.
34 compounds, dyes 1 to 20 described in JP-B-55-39818,
The compounds I-1 to I-37 described in JP-A-62-284343 and the compounds I-1 to I-34 described in JP-A-7-287338 are advantageously selected.

For semiconductor laser light sources in the wavelength range of 750 to 1400 nm, various known dyes including cyanine, merocyanine, styryl, hemicyanine, oxonol, hemioxonol and xanthene dyes are spectrally advantageously sensitized. Can be done. Useful cyanine dyes are, for example, cyanine dyes having basic nuclei such as thiazoline nuclei, oxazoline nuclei, pyrroline nuclei, pyridine nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei and imidazole nuclei. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including. Among the above cyanine and merocyanine dyes, those having an imino group or a carboxyl group are particularly effective. For example, U.S. Pat.
No. 3,719,495, No. 3,877,943, British Patent No. 1,466,
No. 201, No. 1,469,117, No. 1,422,057, No. 3-10391
No. 6-52387, JP-A-5-341432, 6-94781,
It may be appropriately selected from known dyes as described in JP-A-6-301141.

Particularly preferred as the structure of the dye used in the present invention is a cyanine dye having a thioether bond-containing substituent (for example, JP-A-62-58239 and JP-A-3-13863).
No.8, No.3-138642, No.4-255840, No.5-72659, No.5-
72661, 6-222491, 2-230506, 6-258757
No., 6-317868, 6-324425, Tokuyohei 7-500926,
Dyes described in U.S. Pat.No. 5,541,054), dyes having a carboxylic acid group (for example, JP-A-3-163440, 6-301
No. 141, dyes described in U.S. Pat.No. 5,441,899), merocyanine dyes, polynuclear merocyanine dyes and polynuclear cyanine dyes (JP-A-47-6329, JP-A-49-105524, JP-A-51-127719)
No. 52-80829, No. 54-61517, No. 59-214846, No. 6
Nos. 0-6750, 63-159841, JP-A-6-35109, 6-5938
No. 1, 7-146537, No. 7-146537, Tokiohei 55-50111
Dyes described in US Pat. No. 5,467,638 and U.S. Pat. No. 5,281,515).

Further, as dyes forming J-band, dyes described in Example 5 of US Pat. Nos. 5,510,236 and 3,871,887, JP-A-2-96131, and JP-A-59-48753 are disclosed. It can be preferably used in the present invention.

These sensitizing dyes may be used alone.
Two or more kinds may be used in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are
Research Disclosure Volume 176, 17643 (December 1978) No. 23
Section IV of Page IV, or JP-B-49-25500, 43-43933,
These are described in JP-A-59-19032 and JP-A-59-192242.

The sensitizing dyes used in the present invention may be used in combination of two or more. To add sensitizing dyes to a silver halide emulsion, they may be directly dispersed in the emulsion,
Or water, methanol, ethanol, propanol,
Acetone, methyl cellosolve, 2,2,3,3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol , N, N-dimethylformamide or the like, alone or in a mixed solvent, and added to the emulsion.

As disclosed in US Pat. No. 3,469,987 and the like, a dye is dissolved in a volatile organic solvent, and this solution is dispersed in water or a hydrophilic colloid. Method of adding into the inside, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and this solution is added to the emulsion, or an acid or base is added to the emulsion as an aqueous solution in the presence of an acid or base. A method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to a emulsion as disclosed in U.S. Patent Nos. 3,822,135 and 4,006,025, 102733, a method of directly dispersing a dye in a hydrophilic colloid as disclosed in JP-A-58-105141, and adding the dispersion to an emulsion, JP-A-51-746.
As disclosed in JP-A No. 24, a method of dissolving a dye using a compound that causes a red shift and adding this solution to an emulsion can also be used. Also, ultrasonic waves can be used for dissolution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat.Nos. 2,735,766 and 3,628,960
No. 4,183,756, No. 4,225,666, JP-A-58-184142
And JP-A-60-196749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Until the emulsion is coated just before chemical ripening or during the process, before chemical ripening and before coating, as disclosed in the specification such as JP-A-58-113920. It may be added at any time in the process. Also, as disclosed in U.S. Patent No. It may be divided and added during the process or after the completion of chemical ripening, or divided before or during the chemical ripening or after the completion. You may change and add.

The sensitizing dye may be added at any time described above, but is preferably before adding silver halide to the coating solution. The amount of the sensitizing dye used in the present invention may be a desired amount in accordance with the performance such as sensitivity and fog, but is preferably 10 ^-6 to 1 mol per mol of silver halide in the photosensitive layer.
One mole is preferable, and 10 ^-4 to 10 ^-1 mole is more preferable.

The silver halide emulsions of the present invention are further protected against the formation of additional fog and can be stabilized against reduced sensitivity during storage in inventory. Suitable antifoggants, stabilizers and stabilizer precursors which can be used alone or in combination are described in US Pat.
Thiazonium salts described in U.S. Pat. Nos. 1,038 and 2,694,716; azaindenes described in U.S. Pat. Nos. 2,886,437 and 2,444,605; U.S. Pat. No. 2,728,663. Mercury salt described in U.S. Pat.
287,135, U.S. Pat. No. 3,2,135.
No. 35,652, sulphocatechol, British Patent 623,448, oxime, nitrone, nitroindazole, U.S. Pat. No. 2,839,405, polyvalent metal salt, U.S. Pat. , 839, and palladium, platinum and gold salts described in U.S. Patent Nos. 2,566,263 and 2,597,915; U.S. Patent Nos. 4,128,557 and No. 4,137,079, 4,138,365 and 4,459,350, and the phosphorus compounds described in U.S. Pat. No. 4,411,985.

Emulsions in the present invention may include plasticizers and lubricants such as polyhydric alcohols (eg, glycerin and diols of the type described in US Pat. No. 2,960,404), US Pat. No. 2,588,765. No. 3
The fatty acid or ester described in U.S. Pat. No. 121,060 and the silicone resin described in British Patent No. 955,061 may be included.

The heat-developable photosensitive recording material of the present invention may contain an image dye stabilizer. Such image dye stabilizers are described in GB 1,326,889, US Pat.
No. 32,300, No. 3,698,909, No. 3,57
No. 4,627, No. 3,573,050, No. 3,76
4,337 and 4,042,394.

The photothermographic recording material of the present invention may contain an antistatic or conductive layer such as a soluble salt (eg, chloride,
Nitrate, etc.), deposited metal layer, US Pat. No. 2,861,05
No. 6,206,312 or a layer containing an insoluble inorganic salt as described in U.S. Pat. No. 3,428,451. Is also good.

[0132]

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

First, preparation of a polymer fine particle dispersion and a microcapsule dispersion containing the dye of the present invention will be described.

<< Preparation of Dispersion of Dye-Containing Polymer Fine Particles >> The above-exemplified dye D-7 (2 g) of the present invention and a methyl methacrylate-methacrylic acid copolymer (85:15)
(6 g) and 40 ml of ethyl acetate
After heating and dissolving at 0 ° C., it is added to 100 ml of an aqueous solution containing 5 g of polyvinyl alcohol, and finely dispersed by a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho) at 12,000 rpm for 5 minutes to obtain fine polymer particles having an average particle diameter of 0.3 μm. An emulsified dispersion P-1 was obtained.

Using the exemplary dye D-10 (2 g) of the present invention in place of the dye D-7 of P-1, an emulsified dispersion of polymer fine particles P-2 was obtained in exactly the same manner.

Using the exemplified dye D-14 (2 g) of the present invention instead of the dye D-7 of P-1, a polymer fine particle emulsified dispersion P-3 was obtained in exactly the same manner.

Instead of the methyl methacrylate-methacrylic acid copolymer of P-1, polybutyl methacrylate (6
Using g), a polymer fine particle emulsified dispersion P-4 was obtained in exactly the same manner.

<< Preparation of Dye-Containing Microcapsule Dispersion >> Exemplified dye D-7 (2 g) of the present invention shown above,
85 ml of an aqueous solution containing 5 g of polyvinyl alcohol was added to a solution consisting of 24 ml of ethyl acetate and Takenade D110N (22 g), and emulsified and dispersed with a high-speed stirrer (homogenizer, manufactured by Nippon Seiki Seisakusho) at 6000 rpm for 5 minutes. 15 ml of water was added to the obtained emulsified dispersion, mixed uniformly, and stirred at 40 ° C. for 3 hours to obtain a microcapsule dispersion C-1.

A microcapsule dispersion C-2 was obtained in exactly the same manner as described above except that the dye D-10 (2 g) of the present invention was used in place of the dye D-7 of C-1.

Example 1 << Preparation of Silver Halide Particles >> 22 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and p was dissolved at a temperature of 35 ° C.
After adjusting H to 5.0, 159 ml of an aqueous solution containing 18.6 g of silver nitrate and 0.9 g of ammonium nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 92: 8 by a control double jet method while maintaining the pAg at 7.7. It was added over a minute. Then, 55.4 g of silver nitrate and 2 g of ammonium nitrate
476 ml of an aqueous solution containing 10 μmol / L of dipotassium hexachloridate and 1 μmol / L of potassium bromide at 1 mol / L while maintaining the aqueous solution at a pAg of 7.7 by a control double jet method over 30 minutes, followed by adding 4-hydroxy -6
1 g of -methyl-1,3,3a, 7-tetrazaindene was added, and the pH was further lowered to coagulate and settle to desalinate. Thereafter, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and pAg8.2, and the silver iodobromide grains (iodine content core 8 mol%, average 2 mol%, average size 0.05 μm, projected area variation coefficient 8%, (100 ) Area ratio 88
% Cubic particles).

The silver halide grains thus obtained were heated to 60 ° C. to obtain 85 μm mole of sodium thiosulfate per mole of silver.
11 μm mol of 2,3,4,5,6-pentafluorophenyldiphenylphosphine selenide, 3.5 μm mol of chloroauric acid and 270 μm mol of thiocyanic acid were added, and after aging for 120 minutes, 30
The mixture was quenched to give a silver halide emulsion.

<< Preparation of Organic Acid Silver Emulsion >> Stearic acid 7 g,
While vigorously stirring 4 g of arachidic acid, 36 g of behenic acid and 850 ml of distilled water at 90 ° C., 187 ml of a 1N-NaOH aqueous solution was added and reacted for 60 minutes. After adding 65 ml of 1N-nitric acid, the temperature was lowered to 50 ° C. Then, with more vigorous stirring, N-bromosuccinimide
0.62 g was added, and 10 minutes later, silver halide grains prepared in advance were added so that the amount of silver halide was 6.2 mmol. Further, 125 ml of an aqueous solution of 21 g of silver nitrate was added over 100 seconds, stirring was continued for 10 minutes, 0.62 g of N-bromosuccinimide was added, and the mixture was allowed to stand for 10 minutes. afterwards,
The solid content is separated by suction filtration, and the solid content is 30%.
Washed with water until it reached μS / cm. 150 g of a 0.6% by weight solution of polyvinyl acetate in butyl acetate was added to the solid content thus obtained, and the mixture was stirred. The stirring was stopped, the mixture was allowed to stand, the mixture was separated into an oil layer and an aqueous layer, and the aqueous layer was removed together with the contained salts to obtain an oil layer. Next, 80 g of a 2.5 wt% 2-butanone solution of polyvinyl butyral (Denka Butyral # 3000-K, manufactured by Denki Kagaku Kogyo KK) was added to the oil layer and stirred. Furthermore, after adding pyridinium bromide perbromide 0.1 mmol and calcium bromide dihydrate 0.15 mmol together with 0.7 g methanol, 2-butanone 200 g and polyvinyl butyral (Monsanto BUTVAR ^TM B-76) 59 g And dispersed with a homogenizer, and the organic acid silver salt emulsion (average minor axis 0.04 μm)
m, average major axis 1 μm, and variation coefficient 30%).

<< Preparation of Emulsion Layer Coating Solution >> Each of the chemicals was added to the above-obtained organic acid silver emulsion in the following amount per mol of silver. Sodium phenylthiosulfonate 10 at 25 ° C
mg, 80 mg of the following sensitizing dye (1), 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 580 g, dimethylformamide
220 g were added with stirring. Then, 2 g of the following disulfide compound (1), 140 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, Megafax F-176P (Dainippon Ink Chemical Industry 1.1 g, 2-butanone 590 g, and methyl isobutyl ketone 10 g were added with stirring.

[0144]

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[0145] Dyes, dye-containing polymer fine particle dispersions or dye-containing microcapsule dispersions of the types and amounts shown in Table 1 were added to each to obtain coating solutions. The structure of the dye (1) is as shown below. Further, the coating amounts in Table 1 are all coating amounts as dyes.

[0146]

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<< Emulsion Surface Protective Layer Coating Solution >> 75 g of CAB171-15S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.), 4-g
5.7 g of methylphthalic acid, 1.5 of tetrachlorophthalic anhydride
g, phthalazine 10 g, tetrachlorophthalic acid 5.1 g, 0.3 g of Megafax F-176P, Sildex H31 (Torkai Chemical Co., Ltd., spherical silica average size 3 μm) 2 g, sumidur N3500 (Sumitomo Bayer Urethane Co. polyisocyanate) A solution prepared by dissolving 6 g in 3000 g of 2-butanone and 30 g of ethyl acetate was prepared.

<< Back Surface Coating Liquid >> First, 12 g of tricyclohexylguanidine as a solid base, 1.6 g of polyvinyl alcohol, and 27 g of water were dispersed in a 1/16 G sand grinder mill (manufactured by Imex Co., Ltd.) to obtain a base solution.

Next, 2 g of the following basic dye precursor (1), 2 g of the following acidic compound (1), 18 g of a 3: 1 adduct of xylylene diisocyanate and trimethylolpropane, 24 g of dibutyl phthalate, and 5 g of ethyl acetate were mixed. The dissolved organic solvent phase was mixed with an aqueous phase composed of 5.2 g of polyvinyl alcohol and 58 g of water, and emulsified and dispersed at room temperature (average particle size 2.5 μm). 100 g of water was added to this emulsion, the temperature was raised to 60 ° C. with stirring, and the mixture was allowed to stand for 2 hours to obtain a colored microcapsule solution.

[0150]

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20 g of the base solution, 20 g of the colored microcapsule solution, 21 g of gelatin, 0.6 g of sodium dodecylbenzenesulfonate, 1,3-divinylsulfone-2-propanol
0.6 g was mixed to obtain a back surface coating solution.

Gelatin 10 g, polymethyl methacrylate
0.6 g (average particle size: 7 μm), 0.4 g of sodium dodecylbenzenesulfonate, and 1 g of X-22-2809 (silicone compound manufactured by Shin-Etsu Silicone Co., Ltd.) were dissolved in 500 g of water to obtain a coating solution for a back surface protective layer.

<< Preparation of Photothermographic Material >> The emulsion layer prepared as described above was coated on the undercoating side of vinylidene chloride of a 175 μm polyethylene terephthalate support having one surface coated with moisture-resistant vinylidene chloride and the other surface coated with gelatin. after the liquid silver was applied, respectively, as a 2.3 g / m ^2, the amount of the back surface coating solution and dry thickness of the coating amount of the 650nm optical density of 0.5 on the surface opposite to the emulsion layer is 0.9μm Was applied simultaneously and in layers. Further, an emulsion surface protective layer coating solution was applied on the emulsion surface to a dry thickness of 2 μm. The coated samples of the photothermographic material thus obtained were rated 1-1 to 1-8, and the following evaluations were made.

(Evaluation of fog) The coated samples 1-1 to 1-8 were developed without exposure at 115 ° C. for 25 seconds, the density was measured according to a conventional method, and the value obtained by subtracting the undeveloped density was ΔFog. As shown in Table 1.

(Evaluation of Discoloration During Light Irradiation) The coated sample which was unexposed and developed in the same manner as in the evaluation of photographic properties was irradiated with a xenon lamp through an ultraviolet cut filter for 24 hours (70,000 lux), the absorption spectrum was measured, and the absorption maximum was measured. Table 1 shows changes in absorbance at wavelengths before and after irradiation. Table 1 shows that the maximum absorption concentration before irradiation is D (λmax) (Fresh), the maximum absorption concentration after irradiation is D (λmax) (Xe 1d), and the maximum absorption concentration before irradiation D (λmax) (Fresh). Absorption maximum concentration D after irradiation
The percentage of the ratio of (λmax) (Xe 1d) was shown as a residual rate (%).

[0156]

[Table 1]

It can be seen that Samples 1-3 to 1-8 of the present invention are clearly excellent in light fastness.

Example 2 A coating sample was prepared in the same manner as in Example 1 except that an additional 5 g of tribromomethylsulfonylbenzene (II-2) was added before the addition of the disulfide compound to prepare an emulsion layer coating solution.
1 to 2-8 were created.

The obtained samples were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0160]

[Table 2]

In this case, the effect is further remarkable, and it can be seen that the samples 2-3 to 2-8 of the present invention are very stable to light irradiation.

Example 3 (Preparation of silver halide grains A) 22 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and p was dissolved at a temperature of 40 ° C.
After adjusting H to 5.0, 159 ml of an aqueous solution containing 18.6 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 92: 8 at a pAg of 7.7 by a controlled double jet method over 10 minutes. Was added. Then 476 ml of an aqueous solution containing 55.4 g of silver nitrate and 8 μm of dipotassium hexachloride iridate
An aqueous solution containing mol / l and potassium bromide at 1 mol / l was added over 30 minutes by a controlled double jet method while maintaining the pAg at 7.7. After that, the pH was lowered to perform coagulation sedimentation and desalting treatment, and phenoxyethanol 0.1 g.
Was adjusted to pH 5.9 and pAg 8.0. Silver iodide content core 8
It was a cubic grain having a mol% of 2 mol% on average, a grain size of 0.07 μm, a variation coefficient of projected area diameter of 8%, and a (100) plane ratio of 86%.

To the prepared silver halide grains A, potassium iodide was added at 1 mol% based on silver, and the mixture was stirred at 35 ° C. for 1 hour. Thereafter, the temperature was raised to 60 ° C., and the following sensitizing dye A was used in an amount of 7 × 10 ^-4 mol based on silver halide, and
× 10 ^-4 mol was added with stirring. Then, 85 mol of sodium thiosulfate per mol of silver and 2, 3, 4, 5,
11 μm mol of 6-pentafluorophenyldiphenylphosphine selenide, 2 μm mol of the following tellurium compound 1,
3.3 μm mol of chloroauric acid and 230 μm mol of thiocyanic acid were added, and the mixture was aged for 120 minutes, and then rapidly cooled to 30 ° C. to complete the preparation of silver halide grains A.

[0164]

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(Preparation of Organic Acid Silver Microcrystal Dispersion) Behenic Acid
40 g, 7.3 g of stearic acid and 500 ml of water were stirred at a temperature of 90 ° C. for 15 minutes, 187 ml of 1N NaOH was added over 15 minutes, 61 ml of a 1N aqueous nitric acid solution was added, and the temperature was lowered to 50 ° C. Next, 124 ml of a 1N silver nitrate aqueous solution was added over 2 minutes, and the mixture was stirred as it was for 30 minutes. Then, the solid content is separated by suction filtration, and the conductivity of the filtrate is measured.
The solid content was washed with water until it reached 30 μS / cm. The solid content thus obtained was treated as a wet cake without drying, and to a wet cake equivalent to 34.8 g of dry solid content, 12 g of polyvinyl alcohol and 150 ml of water were added,
The slurry was mixed well to form a slurry. Prepare 840 g of zirconia beads having an average diameter of 0.5 mm, put them in a vessel together with the slurry, disperse them in a dispersing machine (1 / 4G sand grinder mill: manufactured by Imex Co., Ltd.) for 5 hours, and observe an average minor diameter of 0.04 by electron microscopic observation. Preparation of a microcrystalline dispersion of silver organic acid, which is needle-shaped particles having a diameter of 0.8 μm, an average major axis of 0.8 μm, and a projected area variation coefficient of 30%, was completed.

(Preparation of Material Solid Fine Particle Dispersion) Tetrachlorophthalic acid, 4-methylphthalic acid, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
Solid fine particle dispersions of 5-trimethylhexane, phthalazine, and tribromomethylphenylsulfone (II-2) were prepared. 0.81 g of hydroxypropylmethylcellulose and 94.2 cc of water were added to tetrachlorophthalic acid, stirred well, and left as a slurry for 10 hours. Thereafter, 100 ml of zirconia beads having an average diameter of 0.5 mm was prepared, placed in a vessel together with the slurry, and dispersed in the same dispersing machine as used for preparing the organic acid silver microcrystal dispersion for 5 hours to prepare tetrachlorophthalic acid. Was obtained. Particle size is 70
wt% was 1.0 μm or less. For other materials, the amount of the dispersant used and the dispersion time were changed to obtain the desired average particle size, and solid fine particle dispersions were obtained for each material.

(Preparation of Emulsion Layer Coating Solution) The silver halide grains A were added to the previously prepared organic silver microcrystal dispersion (equivalent to 1 mol of silver) by adding 10 mol% of silver halide / equivalent to organic acid silver, 5 g of phthalic acid, 98 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 9.2 g of phthalazine, 12 g of tribromomethylsulfonylbenzene, Dyes of the indicated type and amount, dispersion of polymer fine particles containing the dye or dispersion of microcapsules containing the dye, and 108 g of Luckstar 3307B (manufactured by Dainippon Ink and Chemicals, Inc .; SBR latex) as a polymer latex were added. To obtain an emulsion coating solution. The dye (1) in Table 3 is the same as that of Example-1. In addition, Luck Star 3307B is styrene-
It is a polymer latex containing a butadiene-based copolymer, and the dispersed particles have an average particle size of 0.1 to 0.15 μm.
m.

(Preparation of Coating Solution for Emulsion Surface Protective Layer) For 10 g of inert gelatin, 0.26 g of the following surfactant A, 0.09 g of the following surfactant B, and 0.9 of silica fine particles (average particle size 2.5 μm) 0.9
g, 1,2- (bisvinylsulfonylacetamido) ethane and 0.3 g of water were added to form a surface protective layer.

[0169]

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(Preparation of colorant dispersion) 35 g of ethyl acetate
2.5 g, 7.5 of the following compounds 1 and 2 respectively
g was added and stirred to dissolve. 50 g of a 10% by weight solution of polyvinyl alcohol dissolved in advance was added to the solution, and the mixture was stirred with a homogenizer for 5 minutes. Thereafter, the ethyl acetate was volatilized by removing the solvent, and finally diluted with water to prepare a color former dispersion.

[0171]

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(Preparation of Back Surface Coating Solution) The color former dispersion 35 prepared above was added to 30 g of polyvinyl alcohol.
g, the following compound 20 g, water 250 g and Sildex H121 (Spherical silica manufactured by Dokai Chemical Co., Ltd., average size 12 μm)
m) 1.8 g was added to obtain a back surface coating solution.

[0173]

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(Preparation of Emulsion Layer Coating Sample) The emulsion layer coating solution prepared as described above was coated on a transparent 175 μm polyethylene terephthalate support at a silver concentration of 1.9 g / m ^2, and then the emulsion coating layer was coated. The emulsion surface protective layer coating solution was coated thereon such that the coating amount of gelatin was 1.8 g / m ² . After drying, a coating solution for the back surface was coated on the surface opposite to the emulsion layer so as to have an optical density of 660 nm of 0.5 to prepare Samples 3-1 to 3-8.

The obtained sample was evaluated in exactly the same manner as in Example-1, and the results are shown in Table 3.

[0176]

[Table 3]

In this case, the effect is further remarkable, and it can be seen that the samples 3-3 to 3-8 of the present invention are very stable to light irradiation.

Example-4 << Preparation of Organic Acid Silver Emulsion >> Behenic acid 840 g, stearic acid 95
g was added to 12 liters of water, and while maintaining the temperature at 90 ° C., a solution prepared by dissolving 48 g of sodium hydroxide and 63 g of sodium carbonate in 1.5 liters of water was added. After stirring for 30 minutes, set to 50 ° C,
1.1 L of a 1% aqueous solution of N-bromosuccinimide was added, and then 2.3 L of a 17% aqueous solution of silver nitrate was gradually added with stirring. Further, the liquid temperature was 35 ° C., and 1.5 liters of a 2% aqueous solution of potassium bromide was added over 2 minutes with stirring, followed by stirring for 30 minutes.
4 liters were added. While stirring this aqueous mixture
After adding 3300 g of 1.2 wt% polyvinyl acetate in butyl acetate, the mixture was allowed to stand for 10 minutes, separated into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. The thus obtained mixture of gel-like behenic acid / silver stearate and silver bromide was dispersed in 1800 g of a 2.6% isopropyl alcohol solution of polyvinyl butyral (Denka butyral # 3000-K, manufactured by Denki Kagaku Kogyo Co., Ltd.). Butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) 600 g, dispersed together with 300 g of isopropyl alcohol, silver salt of organic acid emulsion (needle particles having an average minor axis of 0.05 μm, an average major axis of 1.2 μm, and a variation coefficient of 25%) I got

<< Preparation of Emulsion Layer Coating Solution >> Each of the chemicals was added to the above-obtained organic acid silver emulsion in the following amount per mol of silver. Sodium phenylthiosulfonate 10 at 25 ° C
mg, 50 mg of sensitizing dye C, 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 580 g, dimethylformamide 220 g
Was added with stirring and left for 3 hours. Then, 5-tribromomethylsulfonyl-2-methylthiadiazole (I
I-12) 8 g, 2 g of disulfide compound (1), 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 140 g, tetrachlorophthalic acid 5 g, hydrazine compound A of 2.1 g, Megafax F-176P (Fluorine manufactured by Dainippon Ink and Chemicals, Inc.) 1.1 g of a dye and the kind and amount of the dye shown in Table 4, a dispersion of fine polymer particles containing the dye or a dispersion of microcapsules containing the dye, 590 g of 2-butanone, and 10 g of methyl isobutyl ketone were added with stirring. did. Dye (1) in Table 4 is the same as that of Example-1.

<< Emulsion Surface Protective Layer Coating Solution >> 75 g of CAB171-15S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.), 4-g
5.7 g of methylphthalic acid, 1.5 of tetrachlorophthalic anhydride
g, Phthalazine 12 g, 0.3 g of Megafax F-176P, Sildex H31 (Doukai Chemical's spherical silica average size 3μ)
m) 2 g, 5 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co.) 3070 g of 2-butanone and 30 g of ethyl acetate
Was prepared.

<< Preparation of Support Having Back Surface >> 6 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK), Sildex H121 (average size of true spherical silica 12 μm manufactured by Dokai Chemical Co., Ltd.) 0.2 g, Sildex H51 (0.2 g of true spherical silica, manufactured by Dokai Chemical Co., Ltd., average size: 5 μm) and 0.1 g of Megafax F-176P2-propanol (64 g) were added with stirring to dissolve and mix. Further, a coating solution was prepared by adding a solution of 420 mg of the dye (3) in 10 g of methanol and 20 g of acetone and a solution of 1 g of 3-isocyanatomethyl-3,5,5-trimethylhexyl isocyanate in 7 g of ethyl acetate.

A coating solution for the back side was applied on a polyethylene terephthalate film having a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 0.7 at 633 nm.

The structural formula of the compound used in the above is as shown below, and the dye (1) is the same as that of Example-1.

[0184]

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(Preparation of Emulsion Layer Coating Sample) The emulsion layer coating solution was coated on the support prepared as described above so that the silver concentration was 2 g / m ^2, and then the emulsion surface protective layer coating solution was coated on the emulsion surface. Was applied to a dry thickness of 2 μm to prepare Samples 4-1 to 4-8.

The obtained sample was evaluated in exactly the same manner as in Example 1, and the results are shown in Table 4.

[0187]

[Table 4]

In this case, the effect is remarkable, and Sample 4 of the present invention was used.
It can be seen that -3 to 4-8 are very stable to light irradiation.

[0189]

According to the present invention, it is possible to obtain a heat-developable photosensitive recording material having good image color tone, no discoloration due to light irradiation, and excellent color tone stability during storage.

Claims (7)

[Claims] 1. A photothermographic recording material having a support and a binder, wherein at least one of the constituent layers contains polymer fine particles containing a dye and / or microcapsules containing a dye. Heat-developable photosensitive recording material. 2. The photothermographic recording material according to claim 1, wherein at least one of the constituent layers contains a photosensitive silver halide and a reducing agent. 3. The photothermographic recording material according to claim 1, wherein at least one of the constituent layers contains a non-photosensitive organic silver salt and a color tone agent. 4. The photothermographic recording material according to claim 1, wherein at least one of the constituent layers contains a polyhalogen compound. 5. A transparent support comprising, as a constituent layer, a photosensitive layer containing photosensitive silver halide and a binder, wherein at least one of the photosensitive layers contains polymer fine particles containing a dye and / or a dye. The heat-developable photosensitive recording material according to any one of claims 1 to 4, comprising a microcapsule and a polyhalogen compound. 6. Polymer fine particles containing a dye having at least one absorption maximum between 500 and 700 nm and / or
The heat-developable photosensitive recording material according to any one of claims 1 to 5, further comprising a microcapsule containing a dye having at least one absorption maximum at 500 to 700 nm. 7. The photothermographic recording material according to claim 1, wherein an aqueous latex is used as a binder.