JPH07270992A - Heat-developed color picture forming image receiving paper - Google Patents

Abstract

PURPOSE:To provide a heat-developed color picture forming image receiving paper to form a color hard copy easy to handle, excellent in curling characteristic and especially having the dependency of curling on the environmental humidity reduced. CONSTITUTION:A moistening water is applied on the photosensitive layer face of a heat-developing photosensitive material having a photosensitive silver halide, reducing agent, binder and dye-donative compd. on a substrate, the material is put on an image receiving paper and heated to form a color picture on the image receiving layer of the paper in the heat-developed color picture forming material. The substrate has a polyolefin resin-laminated layer having >=15mum thickness on the image receiving layer on the image receiving layer- coated face of the base paper and at least one hydrophobic polymer layer on the face opposite to the coated face, and the solid coating amt. of the hydrophobic layer is controlled to <=15g/m in this heat-developed color picture image forming receiving paper.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image-receiving paper for heat-development color image formation, which has excellent curling characteristics, and in particular, curling has little dependency on environmental humidity.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver salt photograph edition (1982, published by Corona Publishing Co., Ltd.), pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by being oxidized and reduced by the reducing agent remaining without being oxidized. In European Patent Publication No. 220746A and Kokai Giho No. 87-6199 (Vol. 12, No. 22), NX bond (X is oxygen atom, nitrogen atom or sulfur) is used as a compound that releases a diffusible dye by a similar mechanism. Photothermographic materials are described which use compounds which release diffusible dyes by the reductive cleavage of (representing atoms).

[0006]

As a simple image forming method using such a photothermographic material, a small amount of dampening water is applied to the surface of the photosensitive layer of the photosensitive material, which is then superposed on the image receiving material and heated. JP-A No. 64-13546 discloses a method of forming a color image on the image receiving layer by developing silver halide and transferring the dye in one step. When such an image forming method is compared with a conventional so-called conventional photographic method such as color paper development processing, there is no operation corresponding to the final washing step which is indispensable in liquid development processing. A relatively large amount of water-soluble salts remains on the image-receiving material, which easily absorbs moisture.
Presumably as a result of this, the image-receiving material after processing has a large dependence of curling on environmental humidity. Particularly, in the case of a paper support, there is a drawback that the curling becomes stronger because the rigidity of the support itself is low.

As a method for solving this problem, the rigidity of the support is increased by increasing the thickness or changing the material to make it less susceptible to the expansion and contraction of the image receiving layer, or the surface opposite to the surface coated with the image receiving layer has a similar moisture absorption property. There is known a method of improving the property by providing a hydrophilic binder layer having properties and balancing the front surface and the back surface. However, the former has a limit in its implementation because it is too thick or too hard to be handled by people, and the latter has a high manufacturing cost and is composed of hydrophilic binders on both front and back surfaces. In addition, when the image receiving material is in contact with the front surface and the back surface of the image receiving material, the image receiving material tends to adhere when it is stored.

Accordingly, it is an object of the present invention to provide an image-receiving paper for heat-development color image formation for obtaining a color hard copy which is easy to handle and has excellent curling properties, and in particular, curling has little dependency on environmental humidity. .

[0009]

As a result of intensive experiments, the present inventor has found that the above problems can be solved by the following color image forming method. That is, (1) after dampening water is applied to the photosensitive layer surface of a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donating compound on a support, the resulting layer is heated on an image receiving paper. In the heat-developable color image-forming material for forming a color image on the image-receiving layer of the image-receiving paper, the support of the image-receiving paper has a polyolefin resin laminate layer having a thickness of 15 μm or more on the image-receiving layer coated surface of the base paper. And a surface opposite to the surface coated with the image receiving layer (hereinafter referred to as the back surface) has at least one hydrophobic polymer layer having a hydrophobic polymer as a binder, and the solid polymer coating amount of the hydrophobic polymer layer. Is 15 g or less per 1 m ^2, and the image-receiving paper for heat development color image formation is characterized in that. (2) In the image-receiving paper for heat development color image formation of (1), the polyolefin resin layer is a polyethylene resin laminate layer containing 10% by weight or more of a white pigment,
Moreover, the solid coating amount of the hydrophobic polymer layer is 1 per 1 m ^2.
An image-receiving paper for heat-development color image formation, which has a weight of 0 g or less. (3) In the image-receiving paper for heat-development color image formation according to (1) and (2), the hydrophobic polymer layer is a hydrophobic polymer layer using an acrylic resin as a binder, thereby forming a heat-development color image. Image receiving paper.

The present invention will be described in detail below.

The polyolefin resin laminate layer on the coated surface of the image receiving layer in the present invention means a resin layer formed by laminating a heat-melted polyolefin resin on a base paper in a thin film state. The laminate layer thus formed has good water resistance, but in order to obtain sufficient water resistance in the image receiving paper of the present invention, it is preferable to use it with a thickness of 15 μm or more, more preferably 20 μm or more. Further, when only water resistance is intended, various hydrophobic polymer layers of the present invention can be used, but in the heat-developable image forming material of the present invention, a polyolefin resin laminate, which easily causes stains due to various causes, Among them, the polyethylene resin laminate showed the most stable and good properties.

The hydrophobic polymer layer coated on the back surface in the present invention is a layer using a hydrophobic polymer as a binder, but a hydrophobic polymer having a relatively high moisture permeability is preferable for the purpose of the present invention. Specific examples of the binder of the polymer layer, polyvinyl chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, fluororesin such as polyvinylidene fluoride, butadiene rubber, chloroprene rubber, Rubbers such as natural rubber, esters of acrylic acid or methacrylic acid such as polymethyl methacrylate and polyethyl acrylate, polyester resins such as polyethylene phthalate, polyamide resins such as nylon 6 and nylon 66, cellulose resins such as cellulose triacetate, silicone resins And water-insoluble polymers such as or derivatives thereof. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used.

Particularly preferred binders are copolymers of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid (preferably 5 mol% or less of acrylic acid or methacrylic acid), styrene-butadiene copolymers, styrene-butadiene-acrylic acid copolymers ( Acrylic acid is preferably 5 mol% or less),
Styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrile-methyl methacrylate-ethyl acrylate. -Acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer, and the like. These may be used alone or in combination of two or more.

In the polymer layer of the present invention, a photographic additive such as a matting agent, a surfactant, a dye, a slipping agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica may be added, if necessary. May be added.

The polymer layer of the present invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the polymer layer is too large, the water vapor permeability of the polymer layer will be insufficient, and the moisture absorption and desorption of the base paper layer will be impeded, resulting in poor curling. Of course, the thickness of the polymer layer also depends on the physical properties of the binder used. Therefore, it is necessary to determine the thickness of the polymer layer in consideration of both of them. The preferred solid coating amount of the polymer layer depends on the type of binder of the polymer layer, but is in the range of 10 g or less, preferably 6 g or less per 1 m ² . When the polymer layer of the present invention comprises two or more layers, the sum of the coating amounts of all the polymer layers is the coating amount of the polymer layer of the color image forming material of the present invention.

In the heat-developable color light-sensitive material of the present invention, basically, a photosensitive silver halide, a reducing agent, a binder and a dye-donating compound (which may also serve as a reducing agent as described later) are formed on a support. In addition, an organic metal salt oxidizing agent and the like can be added as necessary. These components are often added to the same layer,
If it is in a state where it can react, it can be divided and added to another layer. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.
The reducing agent is incorporated in the photothermographic material, and further, for example, by a method of diffusing from a dye fixing element described later,
You may use together the method supplied from the outside. By incorporating a reducing agent in the light-sensitive material, an effect of promoting color image formation can be obtained.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, there are a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The photothermographic material may be provided with various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer, in addition to the above-mentioned protective layer.

The silver halide emulsion (emulsion containing photosensitive silver halide) in the present invention may have various shapes. Examples of these are cubes, octahedra,
Examples thereof include regular grains having regular crystals such as tetradecahedrons, tabular grains, spherical grains, and grains having irregular crystal forms such as potato grains. The silver halide composition of the grains is silver bromide,
Although any silver halide such as silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride may be used, silver bromide or silver chlorobromide is preferable. Further, it may contain silver thiocyanate, silver cyanate and the like. The silver halide composition in the grain may be uniform, may have different halogen compositions inside and outside, or may have a layered structure (JP-A-57-154232 and JP-A-58-58). 108
No. 533, No. 58-248469, No. 59-4875.
5, 59-52237, US Pat. No. 3,505,
068, 4,433,048, 4,444,8
77, European Patent 100,984, and British Patent 1,027,146).

The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 3 μm. Here, a monodisperse silver halide emulsion is defined as 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably within ± 30%. To be done.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging.

In the present invention, two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and they can be used in different emulsion layers and / or the same emulsion layer. It is possible to use.

In particular, tabular silver halide grains have already been reported in US Pat. Nos. 4,434,226 and 4,4.
39,520, 4,414,310, 4,43
3,048, 4,414,306, 4,45
9,353, JP-A-59-99433, 62-2.
No. 09445 discloses the production method and use technique. Further, JP-A-63-220238 and JP-A-1-
No. 201649 discloses tabular silver halide grains in which dislocations are intentionally introduced.

The ratio of average grain diameter to average grain thickness (hereinafter referred to as grain diameter / thickness) in the tabular grains is preferably 2 or more, more preferably 3 to 12, and particularly 5
It is preferably -8. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains, but a simple method is to use the ratio of the average diameter of all tabular grains to the average thickness of all average grains. You can also ask. The diameter of the tabular grains (corresponding to a circle) is 0.3 μm or more, preferably 0.3 to 10 μm, and more preferably 0.5 to
The thickness is 5.0 μm, more preferably 0.5 to 2.0 μm. The particle thickness is less than 1.0 μm, preferably 0.05
To 0.5 μm, more preferably 0.08 to 0.3 μm
Is.

In the present invention, the tabular grains account for 50% or more of the projected area of all grains in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more. The grain diameter and grain thickness of tabular grains can be measured by electron micrographs of grains as described in US Pat. No. 4,434,226. Specific examples of the halogen composition of tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Alternatively, silver chlorobromide is preferable. It may also contain silver thiocyanate, silver cyanate and the like. Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

In the tabular grains, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver thiocyanate and oxides. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395, 478, No. 4,433, 501
Issue 4,463,087, Issue 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

The silver halide grains used in the present invention are
Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.
hysique Photographique, Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In addition, 2 formed separately
A mixture of two or more silver halide emulsions may be used.

The silver halide emulsion consisting of the regular grains can be obtained by controlling the pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photog
radical Science and Engine
ering), Vol. 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

During the production of emulsions containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,67
2,900, 3,650,757, 4,24
No. 2,445, JP-A Nos. 55-142329 and 55-
The description of No. 158124 can be referred to.

To accelerate the ripening of silver halide grains,
Silver halide solvents are useful. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, introduction of a silver halide solution into the reactor can accelerate ripening. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. In addition, JP-A-53-8
It is also possible to use thione compounds as disclosed in 2408 and 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The characteristics of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), compounds such as gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 1977.
As described on pages 19 to 27, the silver halide emulsion can reduce-sensitize the inside of the grain during the precipitation formation process.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, JP-A-62-253159 and Duffin, "Photographic Emulsion Chemistry", pages 138 to 143 (published by Focal Press, 1966).

The silver halide grains used in the present invention are
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The additives used in such a process are Research Disclosure No. 17643 and N
o. 18716.

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc .; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 2-11, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, polo polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. Nos. 3,615,641 and JP-A-63-23145).

The timing of adding these sensitizing dyes to the emulsion may be during or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666, the silver halide grains may be added. It may be before or after nucleation. In particular, the presence of a sensitizing dye at the time of chemical sensitization often gives a preferable effect. The addition amount is generally about 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,1.
No. 97, No. 3,713, 828, No. 3, 615, 64
No. 3, No. 3,615, 632, No. 3,617, 293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Nos. 3,713,828 and 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ^{3 to} 10 g / m ^{3 in} terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220746A2. US Patent No. 303986
Combinations of various reducing agents such as those disclosed in No. 9 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent is optionally added to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the photosensitive element.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.1 to 20 mol, per mol of silver.
It is from 01 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound which produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. It may also contain a sex compound. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
For specific examples of color developers and couplers, see TH James “Th
e Theory of the Photographic Process "4th Edition 291
To 334 and 354 to 361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility from n-Z, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. Good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. In addition, the following items (1) to (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, 3544545.
No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and US Pat. No. 4,199.
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example, US Pat. No. 4,133,938
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat.
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, U.S. Pat. Nos. 4,343,893 and 4619.
Compounds that release a diffusible dye by cleavage of a single bond after reduction, as described in U.S. Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 which release a diffusible dye after electron acceptance, and the like.

As more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having a —X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, SO ₂ —X (X has the same meaning as above) in one molecule described in JP-A-1-26842. Compound having electron-withdrawing group, JP-A-63-271344
Compounds having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-27.
C-X 'bond (X' in marked within one molecule in 1341 issue X synonymous or or -SO ₂ - and represented) include compounds having an electron-withdrawing group.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2
(3), (7) to (10), (12), (13), (15), (23) to (26), (3
1), (32), (35), (36), (40), (41), (44), (53) to (5
9), (64), (70), compound (1) of Open Technical Report 87-6199
1) to (23).

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 3443940, 4474867, 448.
3914 and the like.

A compound (DRR compound) which is reducing to a silver halide or an organic silver salt, and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312 and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
939, JP-A-58-116537, 57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44, among which the compounds (1) to (3) described in the U.S. patents, (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, p. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
Year 4 issue, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, based on 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
The dispersion method using a polymer described in 59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When dispersing the hydrophobic compound in the hydrophilic colloid as the binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be applied separately on a support different from the photosensitive element, or may be applied on the same support as the photosensitive element. Regarding the relationship between the light-sensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

In order to include such a form in which the light-sensitive element and the dye-fixing element are coated on the same support, the light-sensitive material of the present invention will be referred to as the light-sensitive element hereinafter for the sake of convenience. explain. The dye fixing element is also called a dye fixing material.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. If necessary, a protective layer, a release layer,
An auxiliary layer such as an anti-curl layer can be provided. In particular, it is useful to provide a protective layer.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye-fixing element. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly 10 g or less, more preferably 7 g or less.

As the hardener used in the constituent layers of the light-sensitive element and the dye-fixing element, US Pat. No. 4,678,739, No. 4 can be used.
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the present invention, an image formation accelerator can be used in the light-sensitive element and / or the dye-fixing element.
The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to enhance the storage stability of the light-sensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210660 and a compound (referred to as a complex forming compound) capable of forming a complex reaction with a metal ion constituting the sparingly soluble metal compound, JP-A-61-2
The compounds that generate a base by electrolysis as described in No. 32451 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image with respect to changes in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

The constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

In the constituent layers of the light-sensitive element and the dye-fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in “Modified Silicone Oil” technical data P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. In addition, JP-A-6
The silicone oils described in JP-A No. 2-219553 and JP-A No. 63-46449 are also effective.

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.

Examples of antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A Nos. 54-48535 and 62-
There are compounds described in Nos. 136641 and 61-8256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat.
55, 42425018, columns 3 to 36, 4,25
4,195, columns 3 to 8, JP-A-62-174741.
No. 61-88256, pages (27) to (29), JP-A-1-75568, JP-A-62-31096, JP-A-1.
There are compounds described in, for example, -74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other.

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable that the dye-fixing element contains a fluorescent whitening agent or is supplied from the outside of the light-sensitive element. As an example, K. Veenkataraman edited by "The Chem
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based carboxy compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

Various surfactants can be used in the constituent layers of the light-sensitive element and the dye-fixing element for the purpose of coating aid, improvement of releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving peelability. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444 and JP-A-62-135826, or oily fluorine-based compounds such as fluorine oil or solid fluorine-based compound resins such as tetrafluoroethylene resin And the hydrophobic fluorine compound.

A matting agent can be used in the light-sensitive element and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

As the support of the photosensitive element of the present invention, a support that can withstand the processing temperature is used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (PET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and polypropylene. Film-type synthetic paper made from etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass etc. Used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As the base paper used for the image receiving paper of the present invention, in addition to ordinary paper using natural pulp, film-processed synthetic paper made of polypropylene or the like, or mixed paper made of synthetic resin pulp such as polyethylene and natural pulp. , Yankee paper, baryta paper, coated paper (particularly cast coated paper) can be used.

As a method for exposing and recording an image on a light-sensitive element, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on the photosensitive element,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

In the present invention, water is used to accelerate the migration of the dye released during the development process (this water is referred to as dampening water in the present invention). That is, JP-A-59-21
As described in detail in No. 8443, No. 61-238056 and the like, development and transfer are carried out simultaneously or successively by heating in the presence of a small amount of solvent (particularly water). In this method,
The heat development temperature is preferably 50 ° C. or higher and 100 ° C. or lower. In this case, the amount of water used is equal to or less than the weight of water corresponding to the maximum swelling volume of the entire coated film (especially, less than or equal to the amount of water corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film). A small amount is enough.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. is contacted. And passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and the resistance heating element layer may be energized for heating. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye-fixing element,
The pressure condition and the method for applying the pressure when closely contacting each other are disclosed in Japanese Patent Laid-Open Publication No.
The method described in page 1-147244 (27) can be applied.

Any of a variety of thermal development equipment can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0108]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1 A method for preparing a zinc hydroxide dispersion will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution,
30 using glass beads with an average particle size of 0.75 mm in a mill
Grind for minutes. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. 10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Was used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0111]

[Chemical 1]

[0112]

[Chemical 2]

Next, a method for preparing a dye trapping agent dispersion will be described. Polymer latex (1) (13% solid content)
108 ml, nonionic surfactant (1) 20 g, water 123
While stirring 2 ml of the mixed solution, 600 ml of a 5% aqueous solution of anionic surfactant (1) was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next 1500 ml
Water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0114]

[Chemical 3]

[0115]

[Chemical 4]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. Cyan, magenta, yellow, and electron donor gelatin dispersions were prepared according to the formulations in Table 1, respectively. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, and this solution and an aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed, followed by a homogenizer for 13 minutes,
Dispersed at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0117]

[Table 1]

[0118]

[Chemical 5]

[0119]

[Chemical 6]

[0120]

[Chemical 7]

[0121]

[Chemical 8]

[0122]

[Chemical 9]

[0123]

[Chemical 10]

[0124]

[Chemical 11]

[0125]

[Chemical 12]

[0126]

[Chemical 13]

[0127]

[Chemical 14]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 480 ml of water, 0.5 g of potassium bromide, 3 parts of sodium chloride).
g and 30 mg of silver halide solvent (1) were added, and the temperature was 45 ° C.
The solution (I) and the solution (II) shown in Table 2 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 20 minutes. After 5 minutes, (III) in Table 2
Solution and (IV) solution were added simultaneously at the same flow rate for 25 minutes. Also (I
II), 10 minutes after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a pigment (containing 1 g of gelatin, 70 mg of pigment (1), 139 mg of pigment (2), and 5 mg of pigment (3) in 105 ml of water at 45 ° C) Which was kept warm) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and 4.1 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Add 1,250 mg of -1,3,3a, 7-tetrazaindene and 1.8 mg of chloroauric acid, and add 60 ° C.
Optimally chemically sensitized with, then antifoggant (3) 200
After adding mg, the mixture was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm
Got

[0131]

[Chemical 15]

[0132]

[Table 2]

[0133]

[Chemical 16]

Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] An aqueous solution of well-stirred gelatin (in 783 ml of water, 20 g of gelatin, 0.5 g of potassium bromide and 6 parts of sodium chloride).
and 30 mg of silver halide solvent (1) were added, and the mixture was heated to 65 ° C.
The solution (I) and the solution (II) shown in Table 3 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 30 minutes. After 5 minutes, (III) in Table 3
Solution and (IV) solution were added simultaneously at an equal flow rate for 15 minutes. Also (I
II), 2 minutes after the start of the addition of solution (IV), an aqueous solution of a gelatin dispersion of dye (containing 0.9 g of gelatin, 76 mg of dye (1), 150 mg of dye (2), and 5 mg of dye (3) in 95 ml of water) (Incubated at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.8, and 2.8 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Add 175 mg of -1,3,3a, 7-tetrazaindene and 1.2 mg of chloroauric acid, and add 60 ° C.
Chemistry optimally with, then antifoggant (2) 163mg
And then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0136]

[Chemical 17]

[0137]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride in 690 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 48 ° C.
The solution (I) and the solution (II) shown in Table 4 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 8 minutes. 10 minutes later (III) in Table 4
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin and 250 mg of the dye (4) in 100 ml of water and kept at 45 ° C.) was added all at once. .

After washing and desalting in the usual way, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.6, and sodium thiosulfate 9.4 mg and 4-hydroxy-6-methyl were added. Add 263 mg of -1,3,3a, 7-tetrazaindene and optimally perform chemical sensitization at 68 ° C,
After adding 163 mg of the antifoggant (2), the mixture was cooled.
Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0140]

[Table 4]

[0141]

[Chemical 18]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and 15 mg of silver halide solvent (1) are added, and the temperature is 55 ° C.
The solution (I) and the solution (II) shown in Table 5 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 20 minutes. After 10 minutes, (II in Table 5
Solution (I) and solution (IV) were added simultaneously at an equal flow rate for 20 minutes. In addition, 1 minute after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (a mixture of 1.8 g of gelatin and 180 mg of the dye (4) in 95 ml of water and kept at 45 ° C.) was collectively added. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 1.0 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. -1,3,3a, 7-Tetrazaindene (46 mg) and chloroauric acid (0.6 mg) were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (2) 163 m.
After adding g, it was cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm
Got

[0144]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 51 ° C.
The solution (I) and the solution (II) shown in Table 6 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 8 minutes. After 10 minutes, (III) in Table 6
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
One minute after the addition of the solutions (II) and (IV) was completed, an aqueous solution of the dye (water
The dye (5) (220 mg) and the dye (6) (110 mg), which were kept warm at 45 ° C., were added all at once to 100 ml of methanol and 5 ml of methanol.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate 4.8 mg and 4-hydroxy-6-methyl were added. Add 1,3,3a, 7-tetrazaindene (250mg) and optimally chemically sensitize at 68 ° C.
Next, 163 mg of antifoggant (2) and 94 mg of potassium iodide were added, and the mixture was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.30 μm
35 g were obtained.

[0147]

[Table 6]

[0148]

[Chemical 19]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 695 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 63 ° C.
The solution (I) and the solution (II) shown in Table 7 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 10 minutes. After 10 minutes, (II in Table 7
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 30 minutes. One minute after the addition of the solutions (III) and (IV) was completed, an aqueous solution of the dye (66 ml of water and 4 ml of methanol, containing 155 mg of the dye (5) and 78 mg of the dye (6) and kept at 60 ° C.) was put together. Added.

After washing and desalting in the usual way, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and 1.6 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. Addition of 95 mg of -1,3,3a, 7-tetrazaindene and 0.31 mg of chloroauric acid at 68 ° C
Optimally chemically sensitized with, then antifoggant (2) 163
After adding mg and potassium iodide 94 mg, it cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0151]

[Table 7]

A light-sensitive material D shown in Table 8 using the above materials
Made 101.

[0153]

[Table 8]

[0154]

[Table 9]

[0155]

[Table 10]

[0156]

[Chemical 20]

[0157]

[Chemical 21]

[0158]

[Chemical formula 22]

Next, a method of making the image receiving material will be described. An image receiving material R101 having a structure shown in Table 9 and an image receiving material R102 having a structure shown in Table 10 were produced.

[0160]

[Table 11]

[0161]

[Table 12]

[0162]

[Chemical formula 23]

[0163]

[Chemical formula 24]

[0164]

[Chemical 25]

[0165]

[Chemical formula 26]

[0166]

[Chemical 27]

[0167]

[Chemical 28]

[0168]

[Chemical 29]

[0169]

[Chemical 30]

[0170]

[Table 13]

[0171]

[Table 14]

[0172]

[Chemical 31]

Next, in the support (2) of Table 10 used in the image receiving material R102, a hydrophobic polymer layer shown in Table 11 was applied instead of removing the back surface PE layer and the back surface undercoat layer to form a table. 12 image receiving materials R103 to 10
9 was created.

[0174]

[Table 15]

[0175]

[Table 16]

The above light-sensitive material D101 and image-receiving material R10
1 to R109 were processed using the image recording apparatus described in JP-A-2-84634. That is, a full-color original image is scanned and exposed through a slit, and the exposed photosensitive material is exposed to 40
After immersing in water kept at ℃ for 2.5 seconds, it was squeezed with a roller and immediately superposed so that the image receiving material and the film surface were in contact with each other.
Then, using a heat drum whose temperature has been adjusted to 80 ° C on the water-absorbed film surface, the photosensitive material is peeled off from the image receiving material by heating for 17 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

Next, the A4 size color print prepared by the above method was left in the environment of 25 ° C. and 55% Rh for half a day or more, and then transferred to the environment of 25 ° C. and 20% Rh, and the curling after 1 hour was measured. The measurement results are also shown in Table 12. The measured values are obtained by placing the above color print on a smooth table and measuring the heights of the four corners lifted up in mm units and averaging them. Numerical plus (+) means curling with the image receiving layer surface inside, and minus (-) means curling with the image receiving layer surface outside. The results in Table 12 show that the image-receiving material of the present invention can provide a color print with less curling even at low humidity.

Example 2 An instant print system manufactured by Fuji Photo Film Co., Ltd., a Pictrostat 200 (PS200) apparatus was used.
When a print was made using the dedicated light-sensitive material PS donor (PS-DS) and the image receiving materials R101 to R109 of Example 1 and curling was measured, the image receiving material of the present invention curled in a low humidity environment as in Example 1. And good results were obtained.

Example 3 A method for preparing the emulsion (7) will be described. (Emulsion for Fifth Layer) Solution I and solution II having the compositions shown in Table 14 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 13 which was well stirred, and then the emulsion having the composition shown in Table 14 was added. Liquid III and IV 3
Added over 5 minutes.

[0180]

[Table 17]

[0181]

[Table 18]

From 18 minutes after the start of addition of the solution III,
75cc of 0.5% methanol solution of dye (7) over a period of time
Was added. Washing with water, desalting (using the precipitating agent (1), pH =
4.1) and then add 22 g gelatine to pH
= 6.0, pAg = 7.9, and then chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 15. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic emulsion having a grain size variation coefficient of 10.2%, and the average grain size was 0.31 micrometer.

[0183]

[Table 19]

[0184]

[Chemical 32]

[0185]

[Chemical 33]

The method for preparing the emulsion (8) will be described. (Emulsion for Third Layer) Solution I and solution II having the composition shown in Table 17 were simultaneously added over 10 minutes to an aqueous solution having the composition shown in Table 16 which was well stirred, and then the emulsion having the composition shown in Table 17 was added. Liquid III and IV 4
Added over 5 minutes.

[0187]

[Table 20]

[0188]

[Table 21]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent (1) at pH = 3.9), 12 g of gelatin was added to pH = 5.9 and pAg = 7.8. Then, it was chemically sensitized at 70 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of dye (8) (gelatin 5%, sensitizing dye 0.5%) was added. The compounds used for the chemical sensitization are shown in Table 18. The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a grain size variation coefficient of 12.6%, and the average grain size was 0.32 micrometer.

[0190]

[Table 22]

[0191]

[Chemical 34]

A method for preparing the emulsion (9) will be described. (Emulsion for First Layer) Solution I and solution II having the composition shown in Table 20 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 19 which was well stirred, and then the composition shown in Table 20 was added. Solution III and IV solution 2
Added over 5 minutes.

[0193]

[Table 23]

[0194]

[Table 24]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent (1) at pH = 3.8), 20 g of gelatin was added to pH = 6.6 and pAg = 8.0. Then, it was chemically sensitized at 58 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of dye (9) (gelatin 5%, sensitizing dye 1%) was added. The compounds used for the chemical sensitization are shown in Table 21. The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.22 micrometer.

[0196]

[Table 25]

[0197]

[Chemical 35]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Magenta dye donating compound (2) 14.64 g, reducing agent (1) 0.8 g, antifoggant (4) 0.20 g, anionic surfactant (2) 0.
4 g and 5.1 g of high boiling point solvent (2) were weighed, and ethyl acetate 7
0 ml was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution, 71 g of a 14% lime-processed gelatin solution, and 220 cc of water were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a magenta dye-donor compound.

[0199]

[Chemical 36]

7.3 g of the cyan dye-donating compound (3),
Cyan dye donating compound (4) 10.6 g, reducing agent (1) 1.0 g, antifoggant (4) 0.30 g, anionic surfactant (2) 0.4 g, high boiling point solvent (2) 9.
8 g was weighed, 40 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. After stirring and mixing this solution with 71 g of a 14% solution of lime-processed gelatin and 260 cc of water,
Disperse with a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a cyan dye-donor compound.

[0201]

[Chemical 37]

Yellow dye-donor compound (2) 18.8
g, reducing agent (1) 1.0 g, antifoggant (4) 0.1
3 g, anionic surfactant (2) 1.5 g, dye (1)
2.1 g and 7.5 g of the high boiling point solvent (2) were weighed, 45 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 71% of this solution and 14% of lime-processed gelatin
g and 160 cc of water by stirring and mixing, and then 1 with a homogenizer
Dispersed for 0 minutes at 10,000 rpm. This dispersion is referred to as a yellow dye-donor compound dispersion.

[0203]

[Chemical 38]

From these, the light-sensitive material D as shown in Table 22 was obtained.
201 was configured.

[0205]

[Table 26]

[0206]

[Table 27]

[0207]

[Chemical Formula 39]

[0208]

[Chemical 40]

[0209]

[Chemical 41]

[0210]

[Chemical 42]

[0211]

[Chemical 43]

The high boiling point solvent (5) is triisononyl phosphate. A method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide having an average particle size of 0.15 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate are added to 100 ml of a 4% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm are milled. Was crushed for 30 minutes. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, evaluation was performed by the following exposure and processing. Japanese Patent Application Nos. 63-281418 and 6) for the above light-sensitive material.
Using the laser exposure apparatus described in 3-204805,
Exposure was performed under the conditions shown in Table 23. Exposed photosensitive material D20
(1) After supplying dampening water to the emulsion surface with a wire bar, the emulsion was placed so that the image receiving materials R101 to R109 of Example 1 were in contact with the film surface, and the temperature of the heat-absorbed film was adjusted to 85 ° C. After heating for 30 seconds using the, the image receiving material was peeled off from the photosensitive material to obtain an image on the image receiving material.

[0214]

[Table 28]

When the curling characteristics of the color print thus produced were measured, good results were obtained with less curling in a low humidity environment with the image receiving material of the present invention as in Example 1.

Example 4 Pictrography 3000 manufactured by Fuji Photo Film Co., Ltd.
(PG3000) device, special sensitive material PG donor (PG
-D) and prints using the image receiving materials R101 to 109 of Example 1 were made and curling was measured. As with Example 1, the image receiving material of the present invention gave good results with less curling in a low humidity environment. Was given.

Example 5 The support (2) shown in Table 10 used in the image receiving material R102 of Example 1 was coated with the hydrophobic polymer layer shown in Table 24 instead of removing the backside PE layer and the backside undercoat layer. By doing so, image receiving materials R110 to 116 in Table 25 and image receiving materials R117 to 120 in Table 26 were prepared.

[0218]

[Table 29]

[0219]

[Table 30]

[0220]

[Table 31]

Tables 25 and 26 also show the results of evaluation of curling of the obtained prints by the same method as in Example 1 except that the above image receiving materials were used. From these results, it can be seen that by using the image receiving material of the present invention, it is possible to obtain a good color print having good curling characteristics even when the humidity of the environment changes. It is considered that the result of the image receiving material R120 in Table 26 is that when the thickness of the polyethylene resin waterproof layer on the coated surface of the image receiving layer is too thin, water penetrates into the base paper layer during thermal development to cause stain.

[0222]

As described above, by using the image receiving material of the present invention, it is possible to obtain a good color print having good curling characteristics even if the humidity of the environment changes.

Claims (3)

[Claims] 1. A dampening water is applied to the photosensitive layer surface of a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donating compound on a support, and the resultant is superposed on an image-receiving paper and heated. In the heat-developable color image-forming material for forming a color image on the image-receiving layer of the image-receiving paper, the support of the image-receiving paper has a polyolefin resin laminate layer having a thickness of 15 μm or more on the image-receiving layer coated surface of the base paper. And a hydrophobic polymer layer having at least one layer of a hydrophobic polymer as a binder is provided on the surface opposite to the surface coated with the image receiving layer, and the solid polymer coating amount of the hydrophobic polymer layer is 1 m ²
An image receiving paper for heat-development color image formation, characterized in that it is 15 g or less per unit. 2. The polyolefin resin layer is a polyethylene resin laminate layer containing 10% by weight or more of a white pigment, and the hydrophobic polymer layer has a solid coating amount of 1 m ^2.
Claim 1 characterized in that per 10g or less
Image receiving paper for heat development color image formation. 3. The image-receiving paper for heat-developable color image formation according to claim 1, wherein the hydrophobic polymer layer is a hydrophobic polymer layer containing an acrylic resin as a binder.