JPH04107548A - Dye image receiving material - Google Patents

Abstract

PURPOSE:To prevent the devitrification of films by specifying the weight ratio of a hydrophilic binder and polymer particles and the water absorption quantity of dye image receiving layers in the hydrophilic binder. CONSTITUTION:At least one layer of the dye image receiving layers contg. at least the hydrophilic binder and the polymer particles are provided on a base. The weight ratio of the hydrophilic binder and the polymer particles is 1:0.5 to 1:20 and the water absorption quantity at 30 deg.C of the dye image receiving layers in the hydrophilic binder is specified to <=800wt.%. Polymer latex is preferably used as the polymer particles and the dye image receiving layers preferably contain the hydrophilic binder and a hardener which can harden the films. The devitrification is obviated in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a dye image-receiving material, and particularly to a dye image-receiving material used in a heat-developable color light-sensitive material or a heat-sensitive transfer method.

[Background of the Invention] Heat development processing in which the development step is performed by heating is well known, and methods for obtaining black and white images and color images are known. Furthermore, so-called transfer-type heat-developable photosensitive materials, in which an image obtained by heat development is transferred from the photosensitive material to an image receiving layer, are also well known.

A heat-developable color photosensitive material usually has at least one photosensitive layer on a support, containing a binder, a photosensitive silver halide emulsion, a dye-providing substance, and a reducing agent, and if necessary, an organic silver salt or other additives. Various photographic additives are added. Further, in a transfer type heat-developable color photosensitive material, an image receiving material having an image receiving layer capable of receiving a dye is used in combination with the above photosensitive material.

The present invention particularly relates to a dye image-receiving material that is preferably used in combination with such a heat-developable color photosensitive material.

Conventionally, dye image-receiving materials have been broadly divided into two types based on the structure of their image-receiving layers. One is an image-receiving material in which the image-receiving layer is made of a heat-resistant hydrophobic polymer, and the other is an image-receiving layer in which the image-receiving layer contains a dye mordant in a hydrophilic binder. No. 60643, No. 60-119557, No. 60-122942, No. 6
It is described in No. 0-122940, No. 60-122941, etc.

In the former, the binder itself has dye-receiving properties by utilizing the high dye-dying ability of hydrophobic polymers, for example,
Examples include polyvinyl chloride described in JP-A-60-60643, polyester as described in JP-A-59-124332, and polycarbonate as described in JP-A-60-19138. Image-receiving materials having an image-receiving layer made of these hydrophobic polymers have high dye-receptivity, but because the polymer is made of a thermoplastic resin, the heat resistance of the image-receiving layer is poor during thermal development at high temperatures. This has the drawback that the image-receiving layer is likely to be damaged, resulting in uneven development. In order to improve this shortcoming,
Conventionally, attempts have been made to use thermoplastic resins with high heat resistance, but these have had the disadvantage that, even if the heat resistance of the image-receiving layer is improved, the dye-receiving ability is reduced.

On the other hand, in a dye image-receiving material having an image-receiving layer in which a mordant is contained in a hydrophilic binder, since the color photosensitive material is usually composed of a hydrophilic binder, the photosensitive material and the dye image-receiving material after heat development are Special care was required when peeling. That is, since thermal development and dye transfer are carried out substantially in the absence of water, it is necessary to bring the light-sensitive material and the image-receiving material into close contact with each other. For this purpose, it is necessary to use a large amount of a suitable thermal solvent, but since this thermal solvent has the property of being easily diffused in a hydrophilic binder, it is difficult to absorb the binder of both the photosensitive material and the image-receiving material. If the film is mainly composed of a hydrophilic binder, there is a drawback that the light-sensitive material and the image-receiving material cannot be peeled off neatly after development, and a part of the light-sensitive layer or the image-receiving layer is likely to be destroyed. Ta.

On the other hand, in a system using such a photosensitive material and an image-receiving material, it is also known that thermal development is carried out by supplying a small amount of water to the photosensitive material and/or image-receiving material immediately before thermal development. In this case, by controlling the degree of hardness of both hydrophilic binders to some extent, the releasability after heat development was improved compared to when a large amount of hot solvent was used, but the amount of water supplied was small. In some cases, there was a drawback that peeling defects were likely to occur.

On the other hand, it is already known to add polymer latex to the image-receiving layer. In Japanese Patent Application Laid-Open No. 61-156045,
It is described that a hydrophilic binder, a dye mordant, and a polymer latex are added to the image-receiving layer in order to prevent cracking of the image-receiving layer.

However, in this publication, the effect of the polymer latex is only to prevent cracking of the film, and the effect of improving the peelability of the photosensitive material and image-receiving material after heat development is not obtained from the image-receiving layer. It turned out that it was not possible. Furthermore, JP-A No. 62-245257 also discloses that a polymer latex is added onto the dye mordant layer in order to prevent cracking of the film, but this publication also discloses the above-mentioned prior art. Similarly, it was found that no improvement effect could be obtained with respect to the above-mentioned problems.

[Problems to be Solved by the Invention] The purpose of the present invention is to improve the above-mentioned problems, and in particular, when heat development is performed with a color photothermographic material,
It is an object of the present invention to provide a dye image-receiving material that improves the peelability between a photosensitive material and an image-receiving material after thermal development, and provides a high dye density without uneven development.

Another object of the present invention is to provide a dye image-receiving material that provides a high maximum density and prevents thermal fusion with an ink sheet in a sublimation dye thermal transfer system.

A further object of the present invention is to provide a dye image-receiving material in which devitrification of the film is prevented or reduced.

[Means for Solving the Problems] The object of the present invention is to provide a dye-receiving material having at least one dye-receiving layer containing at least a hydrophilic binder and polymer particles on a support. A dye image receiving layer characterized in that the weight ratio of the binder to the polymer particles is 0.05 to 1:20, and the amount of water absorbed by the dye image receiving layer at 30°C is 800% by weight or less with respect to the hydrophilic binder. Achieved through materials.

Hereinafter, a specific configuration of the present invention will be explained in detail.

The dye image-receiving material of the present invention basically consists of a support and at least one dye image-receiving layer provided thereon,
The dye image-receiving layer contains at least a hydrophilic binder and polymer particles.

The polymer particles used in the dye image-receiving layer of the present invention include:
There are so-called polymer latex formed by emulsion polymerization and fine particles made by mechanically crushing a resin made of a hydrophobic polymer and dispersing it in a hydrophilic colloid liquid.In the present invention, polymer latex is used from the viewpoint of stability. It is preferable to use

The polymer latex preferably used in the present invention is an aqueous dispersion of a polymer, and such polymers are mainly classified into condensation polymers and vinyl polymers. Examples of condensation polymers include polyamide, polypeptide, polyester,
Examples include polycarbonate, polyacid anhydride, polyurethane, polyurea, polyether, and the like. Vinyl polymers include addition polymers with vinyl groups, such as aliphatic hydrocarbons, aromatics, vinyl alcohols, nitrile, acrylic, methacrylic, acrylonitrile, and halogen-based monopolymers, as well as single polymers of these. Examples include copolymers based on combinations.

Polyester or vinyl polymers are preferably selected from the viewpoint of ease of production of polymer latex. The polymerizable unsaturated compound serving as a raw material for these polymers may be a polymerizable unsaturated ethylenic compound or a diolefin compound. For example, acrylic acid and its esters, methacrylic acid and its esters, crotonic acid and its esters, vinyl esters, maleic acid and its diesters, fumaric acid and its diesters, itaconic acid and its diesters, olefins. , styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, polyfunctional monomers, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, and the like.

To give specific examples of these polymerizable unsaturated compounds, examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 5ec-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate,
Tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2.2
-dimethyl-3-hydroxypropyl acrylate, 2
-Methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 21s
o-propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1- Examples include bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, inbutyl methacrylate, 5ec-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate. , chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate-1
・, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate,
2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-
Ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate , ω-methoxypolyethylene glycol methacrylate (number of added moles n=6), and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, etc. Can be mentioned.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3-dimethylbutadiene, and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, vinylbenzoic acid methyl ester, etc. can be mentioned.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate, and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Examples include methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, and N-(2-acetoacetoquinethyl)acrylamide.

Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, and te
'r t-Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide Examples include amide, N-(2-acetoacetoxyethyl)methacrylamide, and the like.

Examples of allyl compounds include allyl acetate, allyl caproate, allyl laurate, and allyl benzoate.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl vinyl ketone.

Examples of the vinyl heterocyclic compound include vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, and N-vinylpyrrolidone.

Examples of glycidyl esters include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylate trile.

Examples of polyfunctional monomers include divinylbenzene, methylene bisacrylamide, and ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates, such as monomethyl maleate, monoethyl maleate, maleic acid; monobutyl acids, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid; acrylamide alkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, e.g.
-Methacrylamide-2-methylethanesulfonic acid, 2
- methacrylamide-2-methylpropanesulfonic acid,
2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl phosphates, such as methacryloyloxyethyl phosphate, 3-methacryloyl Examples include oxypropyl-2-phosphate and the like; sodium 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions. Furthermore, other polymerizable unsaturated compounds include U.S. Pat.
Crosslinkable monomers described in JP-A No. 4,215°195, JP-A-57-205735, and the like can be used. An example of such a crosslinking monomer is specifically N-(2-
acetoacetoxyethyl)acrylamide, N-(2-
(2-acetoacetoxyethoxy)ethyl)acrylamide and the like can be mentioned.

Among the polymers constituting the polymer latex used in the present invention, particularly preferred ones include polymethyl acrylate, polyethyl acrylate, poly-n-butyl acrylate, copolymer of ethyl acrylate and acrylic acid, vinylidene chloride and butyl Examples include copolymers of acrylate, copolymers of butyl acrylate and acrylic acid, copolymers of vinyl acetate and butyl acrylate, copolymers of vinyl acid and ethyl acrylate, copolymers of ethyl acrylate and 2-acrylamide, and the like. These polymer latexes can generally be produced by polymerizing monomers forming hydrophobic polymers with vigorous stirring in the presence of a high concentration of a surfactant containing a hydrophilic group.

The method for producing these polymer latexes is described in detail, for example, in "Experimental Methods of Polymer Synthesis" by Tsuyoshi Otsu and Masayoshi Kinoshita, Kagaku Dojinsha (1975).

In the production of the polymer latex used in the present invention, general anionic, cationic, nonionic, and amphoteric surfactants are used as surfactants. These may be used alone or in combination of two or more.

The polymer latex used in the present invention has an average molecular weight of 5
It is preferable to use a dispersoid containing a polymer of at least 10,000,000, particularly from 200,000 to 500,000. In addition, the particle size of the polymer latex used in the present invention can be arbitrarily adjusted depending on the manufacturing conditions (monomer amount, surfactant amount, polymerization temperature, stirring speed, etc.), but preferably the average particle size is 0.02 μm. ~02 μm water dispersion.

Hydrophilic binders used in the dye image-receiving layer of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethacrylate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, and starch. , synthetic or natural polymeric substances such as gum arabic, etc., and these can be used alone or in combination of two or more, but at least one of the hydrophilic binders can be hardened with a hardening agent. In particular, gelatin is preferably used, and gelatin and a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol are also preferably used in combination.

The amount of binder used is usually 0.05g per 1d of support.
~50g, preferably 0.2g~20g.

In the dye image-receiving material of the present invention, the ratio of the polymer particles to the hydrophilic binder is particularly important in terms of dye concentration and releasability between the photosensitive material and the image-receiving material after heat development.
The weight ratio of hydrophilic binder to polymer particles is 1+0.5~
It is necessary to keep it in the range of 1:20. When the amount of hydrophilic binder is more than twice that of the polymer particles,
The ability of the polymer particles to accept dyes decreases rapidly, and when heat development is performed using a hot solvent, the releasability between the photosensitive area and the image receiving area after heat development decreases. On the other hand, if the polymer particles are used in an amount exceeding 20 times the hydrophilic binder, although a sufficiently high dye concentration can be obtained, the heat resistance of the image-receiving layer decreases during thermal development, and the film It becomes easy to cause uneven development due to destruction.

The preferred ratio of polymer particles to hydrophilic binder is 1
:1 to 1:15% by weight, particularly preferably 1:2 to
The range is 1:10.

The amount of polymer particles added per 1rrl' of the image-receiving material is approximately 0.
It ranges from 5 to 50 g, preferably from 1 to 25 g.

The dye image-receiving layer of the present invention has a water absorption amount of 800% by weight or less, preferably 600% by weight relative to the hydrophilic binder at 30°C.
It is necessary that the amount is below % by weight. By controlling the amount of water absorption to a certain value or less in this way, it is possible to significantly improve development unevenness or transfer unevenness due to film destruction or sticking of the image-receiving layer during thermal development or heat-sensitive recording.

In order to make the amount of water absorbed by the dye image-receiving layer in pure water at 30° C. to be 800% by weight or less, preferably 600% by weight or less, a hydrophilic binder and a hardening agent that can be hardened are added to the dye-receiving layer. As the hardening agent preferably used in the present invention, those conventionally known as photographic hardening agents are preferably used, such as epoxy-based, aldehyde-based, vinyl sulfone-based, aluminum compounds, metal salts such as chromium compounds, acryloyl Hardeners such as halogen-substituted S-triazine, ethyleneimine, methanesulfonic acid, N-methylol, and isocyanate can be used.

Preferred are vinyl sulfone hardeners, epoxy hardeners, and aldehyde hardeners.

Specific compounds of the hardening agent preferably used in the present invention are shown below.

Cl-10 Below, bottom - margin OOH -5 COCH=CH.

Y(-6 Na C-fCH2SO, CH=CH, L 0C82CH,OH (CH,=CH8O, CH2hO (CH= = CHS Ot CH2CH2h OH-
11 CH,=CH5O,CH,CHCH,SO,CH=CH
.

1:0.75 molar ratio of reactants with CH,SO,CH=CH,L and KO,SCH,CH,Na2H-18H-24Co-+NHC)! ,0)1h CH,S○=(CH2)3SO-CH50ONg C○N Pi しFiz N MCU(,tl 2(,
M z S (J zC = shi h2C) l, SO, CH
2CH, OCH, CH, SO, CH.

The amount of the hardener added varies depending on the type of hydrophilic binder, the ratio of polymer particles to the hydrophilic binder, the type of hardener, and the characteristics of various additives added to the image-receiving layer. Approximately 0.00 per gram of hydrophilic binder
The amount ranges from 1g to 0.2g, preferably from 0.01 to 0.1g.

The dye image-receiving layer of the present invention preferably contains a high-boiling organic solvent having a boiling point of 170'C or more from the viewpoint of preventing devitrification of the dye image-receiving layer. The polymer particles used in the dye image-receiving layer of the present invention have a relatively high glass transition temperature and contain a hydrophilic binder in addition to the polymer particles.
When formed into a dye image-receiving layer, the film has a strong tendency to devitrify, and in order to prevent or reduce this, it is preferable to add a high-boiling point organic solvent to the dye-image-receiving layer.

The high boiling point organic solvent that can be used in the present invention can be appropriately selected from those conventionally used for photography, but is preferably liquid at room temperature and containing polar groups such as ester groups. It is preferable to have the following.

Specific examples of high boiling point organic solvents preferably used in the present invention include the following compounds.

Below margin 1 111go liquid paraffin Chlorinated paraffin CH, -CHCooC ,H3゜ C,H.

C, it.

(C,H,0+-P=0 (1 day) CG, H, 10+-P=0 (iso-C,.H2++vP=0 (n-C,, f-1,, O+-P=0 C,H,, -0-C,H C,H,C00C2H,OC,H,0COCH.

C,H,COOC,H,OC,H,0COC,H.

C,H.

\ NC0C,,H,.

/ C,H.

C2H.

\ N-C0C,,H,.

/ C7 Summer-I.

(CzHsO)-P (CH-),. C00C-Hl
(!so) These high boiling point organic solvents are used in an amount of about 5 to 100% by weight, preferably 10 to 50% by weight, based on the polymer particles. These high boiling point organic solvents are
It is usually emulsified and dispersed in a hydrophilic colloid aqueous solution and added to the coating solution for the dye image-receiving layer. It can also be added together with a hydrophobic substance such as an agent or a fluorescent brightener.

Further, the dye image-receiving layer of the image-receiving material of the present invention may contain a known mordant within a range that does not impair the effects of the present invention, such as tertiary amine or quaternary ammonium. Polymers containing salts are preferred, and include, for example, the compounds described in US Pat. No. 3,709,690 and JP-A-64-13546. These mordants are preferably used in combination with the polymer particles of the present invention.
It can be used in an amount of 0% by weight or less, particularly preferably 10% by weight or less.

The support for the dye image-receiving material of the present invention includes a transparent support,
It may be any reflective support. Specifically, for example, polyethylene terephthalate, polycarbonate,
Polystyrene, polyvinyl chloride, polypropylene, supports containing white pigments such as barium sulfate, calcium carbonate, titanium dioxide, etc., art paper,
Cast coated paper, baryta paper, laminated paper in which a paper support is coated with a thermoplastic resin (polyethylene, etc.) containing a white pigment, cloth, glass, metal foil such as aluminum, etc. can be used. A support on which an electron beam curable resin composition containing a pigment is coated, hardened, and cured, a reflective support having type 2 diffuse reflection, and the like can also be used as supports for the dye image-receiving material of the present invention. It can be used as

The dye image-receiving material of the present invention may be provided with a single dye image-receiving layer on a support, or may be coated with a plurality of constituent layers, in which case all of the dye image-receiving layers are It is also possible for only a part of the constituent layers, including a protective layer, a subbing layer, etc., to be a dye image-receiving layer.

Various known additives can be added to the dye image-receiving material of the present invention. Such additives include, for example, stain preventive agents, ultraviolet absorbers, optical brighteners, image stabilizers, development accelerators, antifoggants, pH 8 moderators (acids and acid precursors, base precursors, etc.), thermal Examples include solvents, organic fluorine compounds, oil droplets, surfactants, hardeners, matting agents, and various metal ions.

The heat-developable color photosensitive material (hereinafter referred to as the heat-developable color photosensitive material of the present invention) which is preferably used in combination with the dye image-receiving material of the present invention will be described below.

The heat-developable color photosensitive material of the present invention has at least one photosensitive layer on a support, the photosensitive layer having at least a binder photosensitive silver halide emulsion and a dye-providing substance that forms or releases a diffusible dye during thermal development; A reducing agent or reducing agent precursor, organic silver, etc. are included as necessary.

Examples of dye-providing substances that can be used in the heat-developable color photosensitive material of the present invention include JP-A-62-44737;
Couplers that form diffusible dyes, such as those described in Japanese Patent Application No. 62-129852, No. 62-169158, and Japanese Patent Application No. 1-200859, such as JP-A-61-882
54 or, for example, U.S. Pat.
Examples include azo dyes used in the heat-developable dye bleaching method described in No. 235-957. Preferably, a dye-providing substance that forms or releases a diffusible dye is used, particularly preferably a compound that forms a diffusible dye by a coupling reaction.

Hereinafter, the dye-providing substance that forms or releases a diffusible dye that is preferably used in the present invention will be explained.

The dye-providing substance that forms or releases a diffusible dye may be one that responds to or inversely responds to the reduction reaction of photosensitive silver halide and/or organic silver salt, and is capable of forming or releasing a diffusible dye. There are type dye-donating substances and positive-type dye donating substances.

As a negative dye-donating substance, for example, U.S. Pat.
No. 63,079, No. 4,439,513, JP-A-59
-60434, 59-65839, 59-71
No. 046, No. 59-87450, No. 59-88730
Examples include reducing dye-releasing compounds described in the specifications of No. 59-123837, No. 59-124329, No. 59-165054, and No. 59-165055.

Other negative dye-donating substances include, for example, U.S. Pat.
, No. 474,867, JP-A-59-12431, No. 5
No. 9-48765, No. 59-174834, No. 59-
No. 159159, No. 59-231040, JP-A-1-
Examples include coupling type dye-forming compounds described in various specifications such as No. 185630.

Still another preferred negative-tone dye-providing substance of the coupled dye-forming compound is one represented by the following general formula (a).

General formula (A) cp (J) (B) In the formula, Cp represents a coupler residue that can form a diffusible dye by coupling reaction with the oxidized form of the reducing agent, and J represents the oxidized form of the reducing agent. represents a divalent organic group bonded to the active position of Cp that reacts with the body, and B represents a ballast group.

The ballast group referred to here is a group that makes the dye-providing substance non-diffusible during thermal development; for example, a group having 8 or more carbon atoms, preferably 12 or more carbon atoms, or a group that has a non-diffusive function depending on the nature of the polymer chain or molecule. (for example, a sulfo group in heat development in the absence of water). The most preferred ballast group is a polymer chain.

The coupled dye-donating substance having a polymer chain as a ballast group is preferably one having a polymer chain derived from a monomer represented by general formula (b).

General formula (b) Cp-(J)-(Y>i-(Z)-, (L)
In the formula, CpSJ is the same as defined in general formula (a), Y represents an alkylene group, arylene group, or aralkylene group, 2 represents 0 or 1, and Z represents a divalent organic group. and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group.

Specific examples of the coupling type dye-forming compound represented by the general formula (a) or (b) include, for example, JP-A No. 5
No. 9-124339, No. 59-181345, No. 60-2950, No. 61-57943, No. 61-593
No. 36, Japanese Patent Application No. 1-200859, U.S. Patent No. 4,63
No. 1,251, No. 4,650,748, No. 4,656
, 124, particularly U.S. Pat. Nos. 4,656,124 and 4,631,251.
The polymeric dye-providing substances described in the specifications of No. 1 and No. 4,650,748 are preferred.

As a positive dye-donating substance, for example, JP-A-59-
No. 55430, No. 59-165054, No. 59-15
No. 4445, No. 59-116655, No. 59-124
No. 327, No. 59-152440, No. 64-1354
There are compounds described in various publications such as No. 6.

These dye-providing substances may be used alone or in combination of two or more, and the amount used can vary widely depending on the type of dye-providing substance and the circumference of the photothermographic material. The amount is generally in the range of 0.05 to 10 g, preferably 0.1 to 5 g, per 1 photosensitive material.

The above-mentioned dye-providing substance is included in the photographic constituent layer of the heat-developable light-sensitive material.
The method of dispersing it in a hydrophilic colloid solution using a known high-boiling point organic solvent such as dibutyl phthalate, dioctyl phthalate or tricresyl phosphate, or dissolving it in an alkaline hydrophilic colloid aqueous solution. Thereafter, a method of neutralizing with an acid and dispersing, or a method of mechanically dispersing into a solid state in a hydrophilic colloid aqueous solution by a known method, and the like can be appropriately selected from known methods.

As the photosensitive silver halide used in the heat-developable photosensitive material of the present invention, conventionally known silver halides can be used, such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloride iodo Silver bromide can also be used.

These silver halides have a uniform composition from the inside of the grain to the surface, or have a core/shell type in which the composition differs between the inside and the surface, or have a multilayer structure in which the composition changes in a step or continuous manner. There may be.

The shapes of silver halide are cubic, spherical, octahedral, and 12
It is possible to use a crystal wall having a clear crystal wall, such as a hedron or a tetradecahedron, or a crystal wall without such a crystal wall.

For example, JP-A-58-111933, JP-A No. 58-1
No. 11934, Research Disclosure 22,
A particle having two parallel crystal planes, each of which has a larger area than the other crystal planes, such that the diameter-to-thickness ratio of the particle is approximately 5
: One or more tabular silver halides can also be used.

Furthermore, for example, U.S. Patent No. 2.592.250;
, 220.613, 3.271,257, 3.
No. 317,322, No. 3511゜622, No. 3,53
No. 1,291, No. 3,447,927, No. 3761.
No. 266, No. 3,703,584, No. 3,736,1
No. 40, No. 3761.276, JP-A-50-8524
It is also possible to use internal latent image type silver decagenide emulsions in which the grain surfaces are not fogged in advance, as described in Japanese Patent Nos. 50-38525, 52-15661, and 55-127549.

In addition, in the grain formation stage of photosensitive silver halide,
Metal ionic species such as iridium, gold, rhodium, iron, lead, etc. can be added in the form of suitable salts.

The grain size of the photosensitive silver halide emulsion is approximately 0.02 to 2μ.
m, preferably about 005-05 μm.

In the present invention, as a method for preparing photosensitive silver halide, a photosensitive silver salt-forming component is allowed to coexist with an organic silver salt described below, and a part of the organic silver salt is converted into a part of photosensitive silver halide. It can also be formed.

The surface of the silver halide grains of the photosensitive silver halide emulsion can be chemically sensitized using a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate, etc.).

Chemical sensitization can also be carried out in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

Furthermore, the photosensitive silver halide can be spectral sensitized to blue, green, red, and infrared light using known spectral sensitizing dyes. Typical sensitizing dyes include cyanine, merocyanine, trinuclear or tetranuclear cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like.

The amount of these sensitizing dyes used is per mole of silver halide,
1μmoi to 10mo, 9, preferably 10μmo, g
~0.1mo'i.

The sensitizing dye may be added at any stage of the silver halide emulsion, specifically when silver halide grains are formed, when soluble salts are removed, before the start of chemical sensitization, during chemical sensitization, or during chemical sensitization. It may be any time after the end.

The amount of these photosensitive silver halides and photosensitive silver salt forming components is about 0.01 to 50 g, preferably 0.1 g, per 1 photosensitive material.
It is used in the range of ~10g.

In the heat-developable photosensitive material of the present invention, a known organic silver salt can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Organic silver salts that can be used in the present invention include, for example, JP-A-53-4921, JP-A-49-52626, JP-A-52-141222, JP-A-53-36224, JP-A-53
-37626, 53-36224, 53-37
Publications such as No. 610 and U.S. Patent No. 3,330,633
Silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having heterocycles (for example, silver behenate, , α-(1-phenyltetrazolethio)silver acetate, etc.), or Japanese Patent Publication No. 1982-26582, No. 45-12
No. 700, No. 45-18416, No. 45-22815
No., JP-A-52-137321, JP-A No. 58-11863
No. 8, No. 5'8-118639, U.S. Patent No. 4.123
There are silver salts of compounds having an imino group, which are described in publications such as No. 274. Furthermore, JP-A No. 61-24904
Acetylene silver described in No. 4 can also be used.

Among these, silver salts of compounds having an imino group are preferred, and silver salts of benzotriazole and derivatives thereof (eg, silver benzotriazole, silver 5-methylbenzotriazole, etc.) are particularly preferred.

The above organic silver salts can be used alone or in combination of two or more, and they can be prepared in an aqueous solution of a hydrophilic colloid such as gelatin and used as is after removing soluble salts. Alternatively, the organic silver salt can be isolated, mechanically pulverized and dispersed into fine solid particles, and then used. The amount of organic silver salt used is 0.01g to 20g per 1 photosensitive material.
Preferably it is in the range of 0.1 to 50 g.

The reducing agent used in the photothermographic material of the present invention is selected from among those conventionally known for use in photothermographic materials depending on the development mechanism and dye formation or release mechanism. The reducing agent mentioned here also includes a reducing agent precursor that releases a reducing agent during thermal development.

Examples of reducing agents that can be used in the present invention include:
U.S. Patent No. 3,351.286, U.S. Patent No. 3,761,270
No. 3,764,328, No. 3,342,599, Specification No. 3,719,492, Research Disclosure No. 12,146, No. 15,108, No. 15
, No. 127, and JP-A-56-27132, No. 53-
p-Fuynylene diamine type and p-aminophenol type developing agents, monotonic acid amide phenol type developing agents, sulfonamide aniline type developing agents, and hydrazone type developing agents described in No. 135628 and No. 57-79035 , phenols, sulfonamidophenols, polyhydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the various reducing agents mentioned above. There is.

Furthermore, the dye-donating substance can also serve as a reducing agent.

Particularly preferable reducing agents are N-(p-N', N
'Dialkylamino) phenylsulfamate and its derivatives.

Two or more types of reducing agents may be used in combination, and the amount of reducing agent used is in the range of 0.01 to 10 mmol per 1M of light-sensitive material.

It is preferable to use a thermal solvent in the heat-developable photosensitive material of the present invention for the purpose of promoting dye transfer and other purposes.

The thermal solvent is a compound that liquefies during thermal development and has the effect of promoting thermal development and thermal transfer of the dye, and is preferably in a solid state at room temperature.

Examples of thermal solvents that can be used in the present invention include:
U.S. Patent No. 3,347,675, U.S. Patent No. 3,667.959
No. 3,438,776, No. 3,666.477, Research Discology + - (No. 17,643
No. 51-19325, No. 53-24829, No. 53-60223, No. 58-118640, No. 58-198038, No. 59-229556, No. 5
No. 9-68730, No. 59-84236, No. 60-1
No. 91251, No. 60-232547, No. 60-14
No. 241, No. 61-52643, No. 62-78554
No. 62-42153, No. 62-44737, No. 63-53548, No. 63-161446, JP-A No. 1-224751, No. 2-863, etc. .

Specifically, urea derivatives (dimethylurea, diethylurea, phenylurea, etc.), amide derivatives (e.g., acetamide, stearylamide, benzamide, p-toluamide, p-acetoxyethoxybenzamide, p-butanoyloxyethoxybenzamide, etc.), Sulfonamide derivatives (eg, p-toluenesulfonamide, etc.) and polyhydric alcohols (eg, 1,6-hexanediol, pentaerythritol, polyethylene glycol, etc.) are preferably used.

Among the above-mentioned thermal solvents, water-insoluble solid thermal solvents are particularly preferably used, and specific examples thereof include, for example, JP-A-62-136645, JP-A No. 62-139545, JP-A No. 62-139545, and JP-A No. 62-139545.
No. 3-53548, No. 63-161446, JP-A-1
-224751, 2-863, 2-12073
No. 9, No. 2-123354, and the like.゛The above thermal solvent can be added to any layer such as a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, a dye image receiving layer of an image receiving member, and the amount added is usually based on the binder.
10% to 500% by weight, more preferably 30% by weight
~300% by weight.

Binders that can be used in the heat-developable photosensitive material of the present invention include polyvinyl butyral, polyvinyl acetate,
There are synthetic or natural polymeric substances such as ethyl cellulose, polymethacrylate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, gelatin derivatives such as phthalated gelatin, cellulose derivatives, proteins, starch, gum arabic, etc., and these can be used alone or 2
Although more than one type of binder can be used in combination, at least one of the binders is preferably a binder that can be hardened with a hardening agent, and gelatin is particularly preferably used. Further, the combined use of gelatin and a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol is also preferably used in the present invention.

The amount of binder used is usually 0.005 m/rn” of support.
g to 50 g, preferably 0.2 g to 20 g.

In addition to the above, various additives can be added to the photothermographic material of the present invention, if necessary.

Examples of the development accelerator that can be used in the present invention include JP-A-59-177550 and JP-A-59-1
No. 11636, No. 59-124333, No. 61-72
No. 233, No. 61-236548, JP-A-1-152
The compound described in No. 454 is useful, and the compound described in JP-A-61
-159642, JP-A-1-104645, and JP-A-1-110767, or the electronegativity is 4 as described in JP-A-1-104645.
The above metal ions can also be used.

Examples of antifoggants that can be used in the present invention include higher fatty acids described in U.S. Pat. No. 3,645,739, and
mercuric salts described in No. 1, N-halides described in JP-A-51-47419, U.S. Patent No. 3,700,457,
and mercapto compound releasing compounds described in JP-A No. 51-50725, arylsulfonic acids described in JP-A No. 49-125016, carboxylic acid lithium salts described in JP-A No. 51-47419, British Patent No. 1,455,271, and Oxidizing agent described in JP-A No. 50-101019, No. 53-1
Sulfinic acids and thiosulfonic acids described in No. 9825, thiouracils described in No. 51-3223, No. 51-
Sulfur described in No. 26019, No. 51-42529, No. 5
Disulfides and polysulfides described in No. 1-81124 and No. 55-93149, No. 51-57435
Rosin or diterpenes described in No. 51-104
Polymer acids having a carboxyl group or sulfonic acid group as described in No. 338, thiacyrithione as described in U.S. Pat.
142331, triazoles described in U.S. Patent No. 4,137,079, thiosulfinic acid esters described in JP-A-55-140883, JP-A-59-46641
No. 59-57233 and No. 59-57234, JP-A-59-111
Thiol compound described in No. 636, No. 60-198540
and the hydroquinone derivatives described in No. 60-227255. Further preferred antifoggants include the antifoggant having a hydrophilic group described in JP-A-62-78554, the polymer antifoggant described in JP-A-62-121452, and JP-A-62-12345.
The antifoggant having a ballast group described in No. 6 can be mentioned. Also preferably used are colorless couplers described in JP-A-1-161239.

Examples of base precursors that can be used in the present invention include compounds that release basic compounds by decarboxylation upon heating (such as guanidine trichloroacetic acid), and compounds that decompose by intramolecular nucleophilic substitution reaction to release amines. , and base precursors that release a base through the reaction of a basic metal compound (such as zinc hydroxide) that is sparingly soluble in water with a compound (such as picolinic acid) that can form a complex with the metal ion that forms it. , specifically, for example, JP-A-56-13
No. 0745, No. 59-157637, No. 59-166
No. 943, No. 59-180537, No. 59-1748
No. 30, No. 59-195237, No. 62-10824
No. 9, No. 62-174745, No. 62-187847
No. 63-97942, No. 63-96159, and Japanese Unexamined Patent Publication No. 1-68746.

Various known photographic additives other than those mentioned above can be used in the heat-developable photosensitive material of the present invention, such as antihalation dyes, colloidal silver, optical brighteners, hardeners, antistatic agents, and interface agents. It can contain an activator, an inorganic or organic matting agent, an anti-fading agent, an ultraviolet absorber, a white background color tone adjusting agent, etc.

Specifically, RD (Research Disclosure) Magazine Vol. 1.170. It is described in the following publications: June 1978 Publication No. 17029, JP-A No. 62-135825, and JP-A No. 64-13546.

These various additives can be appropriately added not only to the photosensitive layer but also to any constituent layers such as an intermediate layer, undercoat layer, protective layer, or backing layer.

The support used in the heat-developable photosensitive material of the present invention includes:
For example, glass, transparent or opaque synthetic plastic films such as polypropylene film, cellulose acetate film, polyethylene terephthalate film, and polyethylene naphthalate film, various coated papers such as art paper, cast coated paper, and baryta paper, polyethylene resin-coated paper, and Examples include supports obtained by coating and curing electron beam curable resin compositions on these various supports.

The heat-developable photosensitive material of the present invention contains (a) a photosensitive silver halide emulsion, (b) a dye-providing substance, (c) a binder, and further contains (d) organic silver and (e) a reducing agent. It is preferable to do so. These may be contained in a single photographic constituent layer, or may be added separately to two or more layers.

Specifically, components (a), (b), (c), and (d) are added to one layer, and (e) is added to an adjacent layer, or (a), It is also possible to add (b), (c), and (e) to a single layer and (d) to another layer.

Further, the photosensitive layer having substantially the same color sensitivity may be composed of two or more photosensitive layers, and each may be a low-sensitivity layer and a high-sensitivity layer.

When the heat-developable photosensitive material of the present invention is used as a full-color recording material, it usually has three photosensitive layers with different color sensitivities, and dyes with different hues are formed or released in each photosensitive layer by heat development. Ru. In this case - for boat fishing,
The blue-sensitive layer (B) contains a yellow dye (Y), the green-sensitive layer (G) contains a magenta dye (M), and the red-sensitive layer (R).
) is combined with cyan dye (C), but the present invention is not limited to this, and any combination is possible.

Specifically, (B-C)-(G-M)-(RY), (
Combinations such as infrared sensitive -C)-(G-Y) to (RM) are also possible.

The layer structure of each layer is arbitrary, and in order from the support side, R-G
-BSG, -R-BSR-G-infrared, GR-infrared, etc. layer arrangements are possible.

In addition to the photosensitive layer, the heat-developable photosensitive material of the present invention can optionally be provided with non-photosensitive layers such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer.

The heat-developable photosensitive material of the present invention can be exposed by a known exposure means suitable for the color sensitivity of the photosensitive material.

Exposure light sources that can be used include tungsten lamps, halogen lamps, xenon lamps, mercury lamps, and CR lamps.
A T light source, an FO-CRT light source, a light emitting diode, a laser light source (for example, a gas laser, a dye laser, a YAG laser, a semiconductor laser, etc.), etc. can be used singly or in combination. In addition, semiconductor laser and SH
A light source in combination with a G element (second harmonic generation element) can also be used. Others: electron beam, X-ray, γ-ray, α
Exposure can also be achieved by light emitted from a phosphor excited by a ray or the like.

The exposure time is one screen per exposure, or one
Digital exposure is performed for each pixel, but in the former case, it is usually 0.01 seconds to 10 seconds, and in the latter, it is carried out in the range of 10-' to 1o-1 seconds per pixel. .

During exposure, a color filter may be used to adjust the color temperature of the exposure light source, if necessary, or scanner exposure may be performed using a laser or the like.

After imagewise exposure, the heat-developable photosensitive material of the present invention preferably has
70-200'C1, more preferably 90-170'C
preferably for 1 to 180 seconds, more preferably for 2 to 1
Heat development is performed for 20 seconds to form a dye image.

Transfer of the diffusible dye to the dye image-receiving member may be carried out simultaneously with heat development by bringing the dye-receiving layer surface of the image-receiving member into close contact with the photosensitive layer side of the photosensitive material during heat development, or transfer of the dye image-receiving member after heat development. The dye may be transferred by bringing the member into close contact with the photosensitive material, or furthermore, after water is supplied, the photosensitive material and the dye image receiving member may be brought into close contact with each other. Also, before exposure,
Immediately before development, at least one of the photosensitive material and the dye image-receiving member is heated, as described in JP-A-60-143338 and JP-A-62041, in which the photosensitive material is preheated in the range of 0 to 160°C. Preheating can also be carried out in the temperature range of 80 to 120°C.

When thermally developing the photothermographic material of the present invention, known heating means can be applied, such as contacting with a heated heat block or surface heater, or contacting with a heated roller or heated drum. , a method that passes through an atmosphere maintained at a high temperature, a method that uses a high-frequency heating method, or a method that uses a heat-generating conductive material such as a carbon black layer on the back side of a photosensitive material or image receiving member, and Joule heat generated by applying electricity. It is possible to apply methods such as using .

There are no particular restrictions on the heating pattern during thermal development, such as a method of performing at a constant temperature, a method of performing the initial stage of development at a high temperature and a method of performing the second half at a low temperature, or the opposite method, or even changing the temperature range in three or more steps. This can be carried out by any method such as a method in which the temperature is changed continuously or a method in which the temperature is continuously changed.

The dye image-receiving material of the present invention can be used not only as an image-receiving material for the above-described heat-developable photosensitive material, but also as a dye image-receiving material for a sublimation dye transfer system. In this case, when the dye image-receiving material of the present invention is used, sticking between the ink sheet and the image-receiving layer is reduced during thermal transfer recording, and high-sensitivity recording becomes possible.

The dye image-receiving material of the present invention can be used as it is as an image-receiving material for thermal development, or can be used by appropriately changing the amount of polymer particles and hydrophilic binder used, but in general, Those prepared for use in heat-developable photosensitive materials can be used as they are.

When the dye image-receiving material of the present invention is used in a sublimation dye transfer system, the ink sheet used in combination with the dye image-receiving material of the present invention is coated with yellow, magenta, cyan, and, if necessary, on a support. Each layer has a separate black ink layer, which is sequentially recorded by a thermal head.

[Example] Hereinafter, specific examples of the present invention will be described. However, it goes without saying that the present invention is not limited to the following examples.

Example 1 (1) A dye image-receiving layer having the composition shown below was provided on photographic baryta paper having a weight of 150 g/rrr to prepare dye image-receiving material 1 (comparative sample). (Unless otherwise specified, the amount added is expressed per unit of material.) (Composition of dye image-receiving layer) Polyvinyl chloride (average degree of polymerization 5oo) io g
Image stabilizer - 107 g Image stabilizer - 205 g Image stabilizer - 303 g Image stabilizer - 408 g Development accelerator - 105 g The dye image-receiving layer was applied by extrusion coating with a coating solution having the above composition (solvent: methyl ethyl ketone).

On the other hand, a dye image-receiving layer having the following composition was coated on the photographic baryta paper (coating was carried out using a slide hopper coater using a water-soluble coating solution having the following composition in an aqueous system).

) to prepare dye image-receiving material-2 (comparative sample).

Gelatin 4g Dye mordant - 18g Image stabilizer - 107g Image stabilizer - 2o, s g Image stabilizer - 30, 3g Image stabilizer - 4o, s g Development accelerator - 105g Dye mordant - 1 Image stabilizer - 1 Image stabilization Agent-2 n'', 100 Image Stabilizer-3 Next, polyvinyl chloride latex (glass transition temperature Tg = 110°C) shown in Table-1, gelatin, and exemplary hardening agent H-12 were used as a hardening agent. Dye image-receiving materials 3 to 33 were prepared by coating the above photographic baryta paper as a dye image-receiving layer.In addition, in dye image-receiving materials 3 to 33, image stabilizers -1, -2°-3, -4, and and development accelerator-1
was added to the dye image-receiving layer in the same amount as dye-receiving material-2.

(Coating was carried out in the same manner as for dye image-receiving material-2.

) The obtained dye image-receiving material was stored at 35° C. and 60% relative humidity for 3 days to harden it.

(2)! !　　　　...　;.

A heat-developable color photosensitive material having the layer structure shown in Table 2 was prepared on a transparent polyethylene phthalate film support having a thickness of 180 μm, which had been subjected to undercoating treatment on both sides. Table -
2, the amount of each additive used is determined in the heat-developable photosensitive material IM
Indicates the winning amount. (However, the photosensitive silver halide emulsion and benzotriazole silver are each shown in terms of silver.

) Image stabilizer development accelerator-1 (HOC2F(, 5CI (2 amount = h, margin below) The infrared-sensitive, green-sensitive, and red-sensitive emulsions used in the heat-developable photosensitive material are as follows. there was.

Infrared-sensitive silver iodobromide emulsion: average grain size 0.15 μm (grain size distribution 8%), silver iodide composition 2
Iridium hexachloride (rV) potassium was added at the time of particle formation, and the shape was approximately cubic with slightly rounded corners and sides. Chemical sensitization was carried out to the optimum point in the presence of sodium thiosulfate, sodium chloroaurate, the following mercapto compound-1, and the following sensitizing dye (a).

Green-sensitive silver iodobromide emulsion: average grain size 0.25 μm (grain size distribution 9%), silver iodide composition 2
Potassium iridium hexachloride (TV) was added at the time of grain formation, and the shape was approximately cubic with slightly rounded corners and sides. Chemical sensitization was carried out to the optimum point in the presence of sodium thiosulfate, sodium chloroaurate, the following mercapto compound-1, and the following sensitizing dye (b).

Red-sensitive silver iodobromide emulsion: average grain size 0.15 μm (grain size distribution 8%), silver iodide composition 2
Potassium iridium (IV) hexachloride was added at the time of grain formation, and the shape was approximately cubic with slightly rounded corners and sides. Chemical sensitization was carried out to the optimum point in the presence of sodium thiosulfate and the following sensitizing dye (e).

To the three types of photosensitive silver halide emulsions mentioned above, 1 g of 4-hydroxy-6-methyl-1,3°3a,7-titrazaindene was added per mole of silver halide at the end of chemical sensitization.

Sensitizing dye (,) Sensitizing dye (b) Sensitizing dye (C) Mercapto compound-1 Dye-donating substance (1) Benzotriazole silver emulsion: Ammoniacal silver nitrate aqueous solution and Prepared by simultaneous mixing of benzotriazole (containing 0.2 mol of ammonia water with respect to benzotriazole), and after addition, the pH of the solution was adjusted.
is reduced, agglomerated and desalted to form needle-like crystals (medium 01-0.
2 μm 1 length 05-2 μm) was obtained.

x = 60% by weight y = 40% by weight 壬 = knee 1 Below - White dye-providing substance (2) Dye-providing substance (3) Anti-capri agent - 1 Anti-capri agent - 2 H Heat solvent ultraviolet absorber - 1 Reducing agent -1 AP-1 Reducing agent -2 Irradiation silane prevention dye -1 Irradiation prevention dye -2 Irradiation prevention dye -3 The obtained heat-developable photosensitive material was heated at 35°C and relative humidity 60%
It was stored for several days and allowed to harden.

(3) ゛ Support image ■ Material side ■ Top image-receiving material After conditioning the humidity at 25°C and 55% relative humidity for 2 hours,
The weight was measured (Wl). After immersing this in pure water kept at 30° C. for 2 minutes, the water adhering to the surface was wiped off with a filter paper, and the weight was measured (W2).

The water absorption amount was calculated using the following formula.

(W2−Wl) Water absorption amount = 100 Each image-receiving material was continuously subjected to heat development every 10 times at 150° C. for 75 seconds using a drum-belt type heat development device.

After the obtained sample was returned to room temperature, the light-sensitive material and the image-receiving material were peeled off and the peelability was evaluated. In addition, the number of uneven spots due to film damage or poor transfer on the image-receiving material after peeling was counted. on the other hand,
The reflection density (maximum density) of the dye image formed on the image-receiving material was measured, and the results shown in Table 1 were obtained. In the table, B, G, and R at the highest and lowest densities indicate that the densities were measured using blue, green, and red monochromatic lights, respectively.

Note that peelability was evaluated based on the following criteria.

○: It can be easily peeled off, and at the edge of the photosensitive material,
The photosensitive layer is not transferred to the image-receiving layer at all.

Δ: Peeling is relatively easy, but in some cases smooth peeling is not possible, or a very small portion of the photosensitive layer is transferred to the image-receiving layer at the edges.

×: Considerable peeling strength was required for peeling off, and in most cases of peeling, a portion of the photosensitive layer was observed to be transferred to the image-receiving layer.

XX: It was almost impossible to separate the photosensitive material and image-receiving material.

From the results shown in Table 1, dye image-receiving material-1°8, which has only polyvinyl chloride as the dye image-receiving layer, has excellent peelability and high dye-receiving ability (high maximum density); It can be seen that unevenness is likely to occur on the surface of the dye image-receiving layer during development. On the other hand, dye image receiving material 2, which has a dye image receiving layer consisting of gelatin and mordant 1 (without polyvinyl chloride polymer latex), has insufficient peeling between the photosensitive material and the dye image receiving material after heat development. I understand.

It also contains polyvinyl chloride polymer latex,
It can be seen that dye image-receiving materials-3, 9, 14, 19, 24, and 29 containing only the amount specified in the present invention have insufficient improvement in releasability after heat development.

On the other hand, in image-receiving materials (Image-receiving materials-3 to 13) that contain the polymer latex of the present invention within the scope of the present invention but have a water absorption of more than 800% at 30°C, film destruction after thermal development occurs. It can be seen that there are many occurrences of uneven development due to uneven transfer and the like.

In contrast, the image-receiving material of the present invention (image-receiving material-15 to 1
8. 20-23. 25-28 and 30-33) have good releasability after heat development, and there is little occurrence of development unevenness.
Moreover, it can be seen that it gives a high maximum concentration. In particular, an image-receiving material with a water absorption of 600% or less at 30°C (Image-receiving material-2
0-23, 25-28 and 30-33), it can be seen that the releasability is good and the development unevenness is extremely small.

Example-2 In image-receiving material-12 prepared in Example-1, the hardener was H-1°5, 16 compared to H-12 used in Example-1.
．． Image-receiving materials (34-53) changed to 22 and listed in Table-3
It was created. In the same manner as in Example-1, water absorption, releasability, uneven development, and maximum density were examined. The results are shown in Table-3.

From the results shown in Table 3, it can be seen that the image-receiving material of the present invention, which has a water absorption of 80% by weight or less, is excellent in terms of releasability and development unevenness.

Example-3 Example-2 was repeated. However, here, polyvinyl chloride is used as the polymer latex, and polyester (
Glass transition temperature Tg=115°C) was used.

Water absorption, releasability, development unevenness, and maximum density were measured in the same manner as in Example 2, and the results shown in Table 4 were obtained.

From the results shown in Table 4, it is clear that the effect of the present invention is as follows:
It can be seen that this can also be obtained when polyvinyl chloride is used.

Chilled 1 below 1゛−−〜”−.

Example-4 Dye image-receiving material prepared in Example-1 6.12.17゜2
2, 27.32 (gelatin 2g, polymer latex 1
Dye image-receiving materials 74 to 79 were prepared by replacing the polymer latex with a dispersion obtained by dispersing polyvinyl chloride powder in a ball mill for 72 hours according to the following formulation.

Ball Mill Dispersion Prescription Similar to Example 1, water absorption, peelability, development unevenness, and the results shown in Table 5 show that even if mechanically pulverized polyvinyl chloride dispersion is used as the polymer particles of the image-receiving layer, water absorption is not observed. It can be seen that the image-receiving material of the present invention in which the amount is 800% or less has good releasability and less uneven development.

Example 5 Dye image receiving materials 80 to 86 were prepared by adding the compounds shown in Table 6 as high boiling point organic solvents to the dye image receiving layer of dye image receiving material 27 prepared in Example 1.

However, here, a transparent polyethylene terephthalate support having a thickness of 100 μm and subjected to undercoating was used as the support for the dye image-receiving material.

The obtained image-receiving material was examined for releasability, development unevenness, and photographic performance in the same manner as in Example 1, and the results are shown in Table 6. In addition, the devitrification property of the image-receiving material after heat development was visually examined. The devitrification property was evaluated as follows.

Items that are not devitrified at all...○ Items that are slightly devitrified...△ Items that are completely devitrified...× The results are shown in Table-6.

From the results in Table 6, it can be seen that devitrification is improved by adding a high boiling point organic solvent.

Claims (8)

[Claims] (1) In a dye image-receiving material having at least one dye image-receiving layer containing at least a hydrophilic binder and polymer particles on a support, the weight ratio of the hydrophilic binder to the polymer particles is 1:0. .5 to 1:20, and the dye image-receiving layer has a water absorption amount of 800% by weight or less relative to the hydrophilic binder at 30°C. (2) The dye image-receiving material according to claim (1), wherein the polymer particles are polymer latex. (3) The dye image-receiving material according to claim 1, wherein the dye image-receiving layer has a water absorption amount of 600% by weight or less with respect to the hydrophilic binder at 30°C. (4) Claims (1) to (3) characterized in that the dye image-receiving layer contains a hydrophilic binder and a hardening agent capable of hardening.
) The dye image-receiving material according to any one of the above. (5) Weight ratio of hydrophilic binder and polymer particles is 1:1
The dye image-receiving material according to claim 1, characterized in that the ratio is 1:10 to 1:10. (6) Claim (1), (2) or (
5) The dye image-receiving material described above. (7) The dye image-receiving layer containing polymer particles further has a boiling point of 1
The dye image-receiving material according to any one of claims (1) to (6), characterized in that it contains an organic solvent with a high boiling point of 70°C or higher. (8) Claim (1) characterized in that the polymer particles are polyvinyl chloride or polyester polymer latex.
The dye image-receiving material according to any one of (7) to (7).