JPH0251496B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a completely dry image forming method using a silver halide photosensitive material. More specifically, the present invention relates to a method of fixing a color image obtained by heat development onto a dye fixing layer by heating, without using a system containing a solvent. Photography using silver halide is different from other photographic methods,
For example, compared to electrophotography and diazo photography, it has superior photographic characteristics such as sensitivity and gradation adjustment.
It has traditionally been the most widely used. In recent years, a technology has been developed that allows images to be formed easily and quickly on photosensitive materials using silver halide by changing from the conventional wet processing using a developing solution to a dry processing using heating, etc. It's here. Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see
“For example, the basics of photographic engineering (published by Corona Publishing, 1979)
pages 553-555, video information published in April 1978, page 40,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand Reinhold
Company) pages 32-33,
U.S. Patent Nos. 3152904, 3301678, 3392020
No. 3457075, British Patent No. 1131108, No.
No. 1167777 and Research Disclosure Magazine, June 1978, pages 9 to 15 (RD-17029). Many methods have already been proposed for obtaining color images using a dry method. Regarding a method of forming a color image by combining an oxidized form of a developer with a coupler, U.S. Pat. p-
Aminophenol reducing agent received Belgian patent no.
Issue 802519 and Research Disclosure Magazine
In the September 1975 issue, pages 31-32, sulfonamide phenolic reducing agents are described, and in U.S. Pat. No. 4,021,240,
A combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler has been proposed. However, in such a method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the color image becomes cloudy. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer. Another method is to introduce a nitrogen-containing heterocyclic group into a dye, form a silver salt, and release the dye by heat development.
Research Disclosure Magazine May 1978 Issue 54
Pages 58 to 58 (RD-16966). This method is not a common method because it is difficult to suppress the release of dye in areas not exposed to light, making it impossible to obtain clear images. Further, regarding the method of forming positive color images by thermal silver dye bleaching method, for example, Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-
14433), December 1976 issue of the same magazine, pages 14-15 (RD-
15227) and US Pat. No. 4,235,957, useful dyes and bleaching methods are described. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color image is gradually reduced by coexisting free silver, etc. Since it is bleached, it has the disadvantage of not being able to withstand long-term storage. Further, regarding methods of forming color images using leuco dyes, for example, U.S. Pat.
Described in No. 4022617. However, this method has the disadvantage that it is difficult to stably incorporate the leuco dye into the photographic material, and the material gradually becomes colored during storage. The present inventors have already provided a new photosensitive material capable of solving the drawbacks of these conventional methods, and provided an image forming method therefor. This is a photosensitive material that can release a mobile hydrophilic dye by a simple method of heating in a substantially water-free state, and this mobile hydrophilic dye can be released mainly in the presence of a solvent. The invention relates to an image forming method characterized by transferring the dye to a fixing layer. As a result of further research into this earlier invention, the present inventors have discovered that an image formed by a mobile hydrophilic dye, which is formed by heating in a state substantially free of water, can be formed by using no solvent at all. It was discovered that the movement can be easily achieved by heating without heating, and the present invention was achieved based on this discovery. Therefore, the first object of the present invention is to provide a method for fixing a dye fixing layer without supplying a solvent to a hydrophilic dye image produced by heat development performed after exposure or simultaneously with exposure. be. Furthermore, a second object of the present invention is to contain a dye-donating substance capable of reacting with photosensitive silver halide by heating in a substantially solvent-free state to release a mobile hydrophilic dye. The object of the present invention is to provide a method for forming a high-quality dye image on a dye fixing layer by using a heat-developable photosensitive material and simply by heating without supplying any solvent in all steps. That is, the present invention provides at least a photosensitive silver halide, a binder, and a binder that is reducible to the photosensitive silver halide, and reacts with the photosensitive silver halide by heating to form a mobile material. By heating a photosensitive material having a dye-donating substance that releases a hydrophilic dye in the presence of a hydrophilic thermal solvent after or simultaneously with heat development, without supplying a particular solvent, imagewise exposure can be achieved. This is a dry image forming method characterized by forming a dye image by moving a mobile hydrophilic dye imagewise generated by the action of heating to a dye fixing layer. In the photosensitive material according to the present invention, the exposed photosensitive silver halide is converted into a photosensitive silver halide by using the exposed photosensitive silver halide as a catalyst by heating in a substantially water-free state after or simultaneously with the imagewise exposure. Because an oxidation-reduction reaction occurs with the reducing dye-donating substance, in addition to the silver image in the exposed area, there is also a silver image released from the dye-donating substance that has been oxidized by silver halide and turned into an oxidant. A hydrophilic dye image can also be obtained at the same time. In the present invention, this development step is called "heat development," but since unreacted dye-providing substances coexist when heat development is performed, it can be distinguished from the detached mobile hydrophilic dye image. It is difficult and undesirable to do so. However, in the present invention, since the dye of the dye image obtained at this time is a hydrophilic mobile dye, it cannot be moved to the dye fixed layer in an atmosphere to which the hydrophilic dye has affinity. As a result, a dye image with excellent image quality and storage stability can be obtained. This step is the "dye fixation" step in the present invention. In this case, it has already been disclosed that an atmosphere having affinity with the hydrophilic dye can be realized mainly by supplying a solvent (Japanese Patent Application Laid-Open No. 58-58543), but furthermore, in the present invention, By making a hydrophilic thermal solvent exist, we have created an atmosphere that has affinity with hydrophilic dyes, so there is no need to supply any particular solvent, and therefore all processes from exposure to heat development and dye fixation can be performed completely. A dye image with good color reproducibility can be formed by completely dry processing that does not require the supply of a solvent. This principle remains essentially the same whether a negative-tone emulsion or an auto-positive emulsion is used as the emulsion for the light-sensitive material. A dye image with good color reproducibility can be obtained in the same manner as when using a negative emulsion, except that only the dye image among the silver image and mobile dye image is transferred to the dye fixing layer. In the present invention, the redox reaction between the photosensitive silver halide and the dye-donating substance and the subsequent dye-releasing reaction can be caused by heating in a substantially solvent-free state; means heating at 80°C to 250°C, and a state substantially free of water means that the reaction system is in equilibrium with moisture in the air, and no water is present to cause or accelerate the reaction. This means that there is no special supply of This condition is explained by “The theory of the photographic
process”4th Ed. (Edited by THJames,
Macmillan) on page 374. In the present invention, the dye to be released can be selected by selecting the dye-donating substance, so that various colors can be reproduced. Therefore, it is possible to create multiple colors by selecting a combination of them, so the dye image in the present invention includes not only a single color but also a multicolor image, and a monochrome image also includes a monochrome image obtained by mixing two or more colors. be done. Conventional dye release reactions are thought to be caused by attack by so-called nucleophiles, and given that they are usually carried out in an aqueous solution with a high pH of 10 or higher.
It is extremely unusual for the photosensitive material used in the present invention to exhibit a high reaction rate only by heating in a state substantially free of water. Furthermore, based on conventional knowledge obtained from wet development at around room temperature, it is possible that the dye-donating substance used in the present invention can undergo a redox reaction with silver halide without the aid of a so-called auxiliary developer. It is also extremely unusual (Japanese Patent Application Laid-Open No. 58-58543). The above reaction proceeds particularly well when an organic silver salt oxidizing agent is present, and high image density can be obtained. Therefore, it is a particularly preferred embodiment to coexist an organic silver salt oxidizing agent. The reducing dye-donating substance that releases the hydrophilic diffusible dye used in the present invention is represented by the following general formula Ra-SO ₂ -D (). Here, Ra represents a reducing substrate that can be oxidized by silver halide, and D represents an image-forming dye portion having a hydrophilic group. The reducing substrate (Ra) in the dye-donating substance Ra-SO ₂ -D has a redox potential of 1.2 with respect to a saturated calomel electrode in polarographic half-wave potential measurement using acetonitrile as a solvent and sodium perchlorate as a supporting electrolyte. V or less is preferable.
The preferred reducing substrate (Ra) has the following general formula ()
~(). Here, R ¹ _a , R ² _a , R ³ _a , and R ⁴ _a are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, and an alkylsulfonyl group. Amino group, arylsulfonylamino group, aryloxyalkyl group, alkoxyalkyl group, N-substituted carbamoyl group, N-substituted sulfamoyl group,
Represents a group selected from a halogen atom, an alkylthio group, and an arylthio group, and the alkyl group and aryl group moiety in these groups can further be an alkoxy group, a halogen atom, a hydroxyl group, a cyano group, an acyl group, an acylamino group, and a substituted carbamoyl group. , a substituted sulfamoyl group, an alkylsulfonylamino group, an arylsulfonylamino group, a substituted ureido group or a carbalkoxy group. Furthermore, the hydroxyl group and amino group in Ra may be protected with a protecting group that can be regenerated by the action of a nucleophilic reagent. In a more preferred embodiment of the present invention, the reducing substrate Ra is represented by the following formula (). Here, G represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. R ¹⁰ _a represents an alkyl group or an aromatic group. n represents an integer from 1 to 3. X ¹⁰ represents an electron-donating substituent when n=1; when n=2 or 3, it may be the same or different substituent, and when one of them is an electron-donating group, it represents an electron-donating substituent; 3 is an electron-donating group or a halogen atom, and may form a condensed ring with X ¹⁰ itself or may form a ring with OR ¹⁰ _a .
The total number of carbon atoms in both R ¹⁰ _a and X ¹⁰ is 8 or more. Among those included in formula () of the present invention, in a more preferred embodiment, the reducing substrate Ra is represented by the following formulas (a) and (b). Here, Ga represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis. R ¹¹ _a and R ¹² _a may be the same or different, each an alkyl group, or R ¹¹ _a and R ¹² _a may be linked to form a ring. R ¹³ _a represents a hydrogen atom or an alkyl group, and R ¹⁰ _a represents an alkyl group or an aromatic group. X ¹¹ and X ¹² may be the same or different and each represents a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group or an alkylthio group, and
R ¹⁰ _a and X ¹² or R ¹⁰ _a and R ¹³ _a may be linked to form a ring. Here, Ga is a hydroxyl group or a group that provides a hydroxyl group by hydrolysis, R ¹⁰ _a is an alkyl or aromatic group, X ² is a hydrogen atom, an alkyl group, an alkyloxy group, a halogen atom, an acylamino group, or an alkylthio group, ² and R ¹⁰ _a may be connected to form a ring. Specific examples included in (), (a), and (b) are described in US Pat. In another further preferred embodiment of the present invention,
The reducing substrate (Ra) is represented by the following formula (XI). (However, the symbols Ga, X ¹⁰ , Ra ¹⁰ _a and n have the same meanings as Ga, X ¹⁰ , R ¹⁰ _a n in formula ().) More preferred embodiments of those included in (XI) of the present invention In , the reducing substrate (Ra) is represented by the following formulas (XIa) to (XIc). However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; R ²¹ _a and R ²² _a may be the same or different and each represents an alkyl group or an aromatic group; R ²¹ _a and R ²² _a may combine to form a ring; R ²⁵ _a represents a hydrogen atom, an alkyl group, or an aromatic group; R ²⁴ _a represents an alkyl group or an aromatic group; R ²⁵ _a represents an alkyl group , represents an alkoxy group, an alkylthio group, an arylthio group, a halogen atom, or an acylamino group; p is 0, 1 or 2; R ²⁴ _a and R ²⁵ _a may be bonded to form a condensed ring; ; R ²¹ _a and R ²⁴ _a may be combined to form a condensed ring; R ²¹ _a and R ²⁵ _a may be combined to form a condensed ring, and R ²¹ _a , ^R22a _, ^R23a _, ^R24a _{_}
and (R ²⁵ _a ) _p has a total number of carbons greater than 7. However, Ga is a hydroxyl group or a group that gives a hydroxyl group by hydrolysis; R ³¹ _a represents an alkyl group or an aromatic group; R ³² _a represents an alkyl group or an aromatic group; R ³³ _a is an alkyl group, an alkoxy group, represents an alkylthio group, an arylthio group, a halogen atom or an acylamino group; q is 0, 1 or 2; R ³² _a and R ³³ _a may combine to form a condensed ring; R ³¹ _a and R ³² _a may be combined to form a fused ring; R ³¹ _a and R ³³ _a may be combined to form a fused ring; and R ³¹ _a , R ³² _a , (R ³³ _a ) The total number of carbon atoms in _q is greater than 7. In the formula, Ga represents a hydroxyl group or a group that provides a hydroxyl group through hydrolysis; R ⁴¹ _a represents an alkyl group or an aromatic group; R ⁴² _a represents an alkyl group, an alkoxy group, an alkylthio group, an arylthio group, or a halogen atom , or represents an acylamino group; r is 0, 1 or 2;

[Formula] The group represents a condensation of 2 to 4 saturated hydrocarbon rings, and the carbon atom in the condensed ring participates in bonding to the phenol (or its precursor) core.

[Formula] is a tertiary carbon atom constituting one element of a condensed ring, and some of the carbon atoms in the hydrocarbon ring (excluding the tertiary carbon atoms mentioned above) are substituted with oxygen atoms. or the hydrocarbons may have a substituent,
Furthermore, an aromatic ring may be fused; R ⁴¹ _a or R ⁴² _a and the above

[Formula] The group may form a fused ring. However, R ⁴¹ _a , (R ⁴² _a ) _r and

[General formula]

In the above formula, A ₁ , A ₂ , A ₃ , and A ₄ may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and Represents a substituent selected from heterocyclic residues, and also represents A ₁ and
A ₂ or A ₃ and A ₄ may be linked to form a ring. Specific examples include H ₂ NSO ₂ NH ₂ , H ₂ NSO ₂ N
( _{CH3 ) 2 , H2NSO2N} ( _{C2H5 ) 2} , _{H2NSO2NHCH3 ,
H2NSO2N ( C2H4OH ) 2 , CH3NHSO2NHCH3 ,} etc. The above compounds can be used in a wide range of applications. A useful range is 20% by weight or less of the coated dry film of the photosensitive material, more preferably,
It is 0.1-15% by weight. In the present invention, it is advantageous to use a water-releasing compound because it accelerates the dye-releasing reaction. A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are particularly known for transfer printing of textiles, and are
NH ₄ Fe(SO ₄ ) 2.12H ₂ O described in _Publication No. 88386 is useful. The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. Includes film or resin materials. US Patent No.
The polyesters described in No. 3634089 and No. 3725070 are preferably used. Particularly preferably, polyethylene terephthalate film is used. The coating solution used in the present invention can be prepared by mixing separately formed silver halide and organometallic salt oxidizing agent before use, but it is also possible to prepare the coating solution by mixing the two separately. Mixing in a ball mill for hours is also effective. Also effective is a method in which a halogen-containing compound is added to the prepared organic silver salt oxidizing agent to form halogen silver with silver in the organic silver salt oxidizing agent. For information on how to make these silver halides and organic silver salt oxidizing agents, how to mix them, etc., see Research Disclosure No. 17029 and JP-A-1973
No. 32928, No. 51-42529, U.S. Patent No. 3700458,
It is described in JP-A-49-13224, JP-A-50-17216, etc. In the present invention, the coating amount of photosensitive silver halide and organic silver salt oxidizing agent is 50 mg in total in terms of silver.
~10g/ ^m2 is suitable. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, improvement of slipperiness, emulsion dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization), etc. Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. agent; alkyl carboxylate,
Alkyl sulfonate, alkylbenzene sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-
Carboxy groups such as N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc.
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups;
Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonium salts, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide. Nonionic surfactants that meet the above conditions are
It is widely used outside the field, and its structure, properties, and synthesis method are well known. Representative known documents include Surfactant Science Series
Volume1.Nonionic Surfactants (Edited by
Martin J.Shich, Marcel Dekker Inc.1967),
Surface Active Ethylene Oxide Adducts
(Schoufeldt.N, Pergamon Press 1969), and the nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention. These nonionic surfactants can be used alone,
It can also be used as a mixture of two or more types. The polyethylene glycol type nonionic surfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably 50% or less. The photosensitive material of the present invention can contain a cationic compound having a pyridinium salt. An example of a cationic compound with a pyridinium group is
PSA Journal, Section B36 (1953),
USP2648604, USP3671247, Special Publication Showa 44-30074,
It is described in Special Publication No. 44-9503, etc. In the light-sensitive material used in the present invention, a compound that activates development and simultaneously stabilizes the image can be used. Among them, isothironiums represented by 2-hydroxyethyl isothiuronium and trichloroacetate described in U.S. Patent No. 3301678, 1,8-(3,6
-dioxaoctane)bis(isothiuronium)
bisisothiuroniums such as trifluoroacetate), thiol compounds described in West German Patent No. 2162714, 2-amino-2-thiazolium trichloroacetate described in U.S. Patent No. 4012260, 2
-thiazolium compounds such as amino-5-bromoethyl-2-thiazolium trichloroacetate, bis(2-amino-2-thiazolium)methylenebis(sulfonylacetate) described in U.S. Pat. No. 4,060,420, 2-amino-2-thiazolium Preferably used are compounds having α-sulfonylacetate as an acidic moiety, such as lium phenylsulfonylacetate, and compounds having 2-carboxycarboxamide as an acidic moiety, as described in US Pat. No. 4,088,496. In the case of the present invention, since the dye-providing substance is colored, it is not so necessary to further include anti-irradiation, anti-halation substances, or various dyes in the light-sensitive material, but the sharpness of the image can be improved. In order to improve the quality of the product, we have published the Publication No. 48-3692, U.S. Patent No. 3253921, U.S. Patent No. 2527583,
Filter dyes, absorbent substances, etc. described in specifications such as No. 2956879 can be contained. In addition, it is preferable that these dyes are thermally decolorizable, such as those described in US Pat. No. 3,769,019 and US Pat.
Dyes such as those described in No. 3745009 and No. 3615432 are preferred. The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH It can contain layers, release layers and the like. Various additives include those described in Research Disclosure Magazine Vol. 170, No. 17029, June 1978, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes,
Additives include matting agents, surfactants, fluorescent whitening agents, and anti-fading agents. In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, back layer, and other layers are prepared for each layer, and coated using the dipping method, air knife method, curtain coating method, or the U.S. Patent No.
Hopper coating method described in specification No. 3681294, etc.
A photosensitive material can be produced by sequentially coating a support material using various coating methods and drying it. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. In the present invention, the latent image obtained after exposure to a light-sensitive material is exposed to light over the entire element for about 0.5 seconds to about 300 seconds at a moderately elevated temperature, e.g. It can be developed by heating. As long as the temperature is within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time. Especially about 110℃~approx.
A temperature range of 160°C is useful. As the heating means, ordinary means such as a simple hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc., or a similar method can be used. In the image forming method of the present invention in which a mobile hydrophilic dye is transferred to a dye fixing layer under high temperature conditions in the presence of a hydrophilic thermal solvent, even if the transfer of the mobile dye starts at the same time as the release of the dye, It may be after the release of Therefore, heating for transfer may be performed after or simultaneously with heat development. Simultaneously with heat development,
This means that the heating for development also acts at the same time as the heating for the migration of the released dye. Since the optimal temperature for development, the optimal temperature for dye migration, and the heating time required for each do not necessarily match, the temperatures can be set independently. In the present invention, "under high temperature conditions in the presence of a hydrophilic thermal solvent" means under a condition in which an atmospheric temperature is 60° C. or higher in the presence of a hydrophilic thermal solvent. Heating for dye migration improves the storage stability of photosensitive materials,
From the viewpoint of workability, etc., the temperature is between 60℃ and 250℃, so
In the present invention, it is possible to appropriately select a solvent that can function as a hydrophilic thermal solvent within this temperature range. It goes without saying that hydrophilic thermal solvents must be able to quickly assist the movement of dyes upon heating, but if we also consider the heat resistance of photosensitive materials, the requirements for hydrophilic thermal solvents are The melting point is 40
The temperature is preferably 40°C to 200°C, more preferably 40°C to 150°C. In the present invention, a "hydrophilic thermal solvent" is a compound that is in a solid state at room temperature but becomes a liquid state when heated, and has an (inorganic/organic) value>1, and
It is defined as a compound with one or more solubility in water at room temperature. Inorganicity and organicity are concepts for predicting the properties of compounds, and the details thereof are described in, for example, Chemistry Region 11, p. 719 (1957). Since the hydrophilic thermal solvent has the role of assisting the movement of the hydrophilic dye, it is considered preferable that it is a compound that can act as a solvent for the hydrophilic dye. It is generally known from experience that preferred solvents for dissolving organic compounds have an (inorganic/organic) value close to the (inorganic/organic) value of the organic compound. On the other hand, the (inorganic/organic) value of the dye-donating substances used in the present invention is approximately 1, and the (inorganic/organic) value of the hydrophilic dyes that are separated from these dye-donating substances. teeth,
It has a value larger than the (inorganic/organic) value of the dye-donating substance, preferably 1.5 or more, particularly preferably 2 or more. The hydrophilic thermal solvent used in the present invention is preferably one that moves only the hydrophilic dye and does not move the dye-providing substance, so its (inorganic/organic) value is /organic) value. That is, as a hydrophilic thermal solvent,
It is an essential condition that the (inorganic/organic) value is 1 or more, preferably 2 or more. On the other hand, considering the melting point of the size of the molecule, it is considered preferable that there be molecules around the moving dye that can move by themselves without interfering with the movement. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 100 or less. The hydrophilic thermal solvent of the present invention only needs to be able to substantially assist the movement of the hydrophilic thermal dye generated by heat development to the dye fixing layer, so it can not only be included in the dye fixing layer. The hydrophilic heat-sensitive material can be contained in a photosensitive material such as a photosensitive layer, in both a dye fixing layer and a photosensitive layer, or in a photosensitive material or in an independent dye fixing material having a dye fixing layer. A separate layer containing a solvent can also be provided. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto. The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols such as methanol, ethanol, etc. The hydrophilic heat solvent used in the present invention is 5 to 500% by weight, preferably 20 to 200% by weight, particularly preferably 20 to 200% by weight of the total coating amount of the photosensitive material and/or dye fixing material
It can be used in a coating amount of 30 to 150% by weight. Examples of the hydrophilic heat solvent used in the present invention include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Next, specific examples of the hydrophilic heat solvent used in the present invention will be shown. Among these, ureas (1), (2), (3), (10), pyridines (17), (19), amides (26),
(30), (33), sulfonamides (34), (36),
Imides (40), (41), (43), (44) and alcohols (46) and (54) are particularly preferred. Further, the hydrophilic heat solvent used in the present invention can be used alone or in combination of two or more. In the present invention, a hydrophilic mobile dye generated in an imagewise manner is moved by heat development simultaneously with imagewise exposure or subsequent to imagewise exposure, and a dye image is fixed by receiving this mobile dye. layers are required. For this purpose, the photosensitive material of the present invention
a photosensitive layer () containing at least silver halide on a support, optionally an organic silver salt oxidizing agent and a dye-donating substance which is also a reducing agent thereof, and a binder;
It is composed of a dye fixing layer () that can receive a hydrophilic and mobile dye formed by the () layer. Such a photosensitive layer () and a dye fixing layer () may be formed on the same support,
They can also be formed on separate supports. The dye fixing layer ( ) and the photosensitive layer ( ) can also be peeled off. For example, after imagewise exposure, uniform heat development can be carried out, and then the dye fixing layer (2) or the photosensitive layer can be peeled off. In addition, when a photosensitive material in which a photosensitive layer () is coated on a support and a fixing material in which a fixing layer () is coated on a support are formed separately, the photosensitive material is imagewise exposed to uniform light. After heating, the fixing material can be layered to transfer the mobile dye to the fixing layer (). There is also a method in which only the photosensitive material (2) is imagewise exposed, and then a dye fixing layer (2) is superimposed and uniformly heated. For adhesion between the photosensitive material and the dye-fixing material, a conventional method such as using a pressure roller can be used, but in order to ensure sufficient adhesion, heating can also be used at the time of adhesion. If the surface of the photosensitive material and the dye-receiving surface of the dye-fixing material are brought into close contact and heated after image exposure or after heat development at the same time as image exposure, the heating need only contribute to dye migration. Therefore, from this point of view, the heating temperature and heating time can be set independently of the heating for development. When this method is adopted, it is preferable that the heating for development completes the reaction for development within a short period of time so as not to contribute to dye migration as much as possible, while at the same time allowing the dye to be released in an imagewise manner. In order to obtain a clear image, it is preferable to keep the heating for transferring the dye to the dye transfer layer as low as possible within an appropriate transfer time range so as not to cause a thermal reaction in the unexposed area. The dye fixing layer () may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided on a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained. A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. As the dye transfer aid, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used. Also used are low boiling point solvents such as methanol, N,N-dimethylformamide, acetone and diisobutyl ketone, or mixed solutions of these low boiling point solvents and water or basic aqueous solutions. The dye transfer aid may be used by moistening the image-receiving layer with a solvent, or may be incorporated into the material in the form of crystal water or microcapsules. The dye fixing layer contains a dye mordant for fixing the dye,
It may contain a hydrophilic heat solvent to aid the movement of the dye, a base and/or a base precursor to promote the dye release reaction, etc., and a binder to bind them together. When the dye fixing layer is provided on a support separate from the light-sensitive material, it is a particularly preferred embodiment to contain a base and/or a base precursor. When the dye mordant is a polymer mordant,
Since this also functions as a binder, the amount of binder may be reduced or no binder may be used in such cases. Conversely, if the binder also functions as a mordant,
Similarly, dye mordants can also be omitted.
As the binder, the same kind of binder as used in photosensitive materials can be used. The mordant used in the dye fixing layer of the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, polymer mordants refer to secondary and tertiary mordants.
Polymers containing a class amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cation groups, etc., with a molecular weight of 5,000 to 200,000, especially
10,000 to 50,000. For example, U.S. Pat.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 2548564, US Pat. No. 2484430, US Pat. No. 3148061, US Pat.
Crosslinkable polymer mordants such as gelatin disclosed in U.S. Pat. No. 4,128,538 and British Patent No. 1,277,453;
No. 2798063, JP-A-54-115228, No. 54
-145529, 54-126027, etc.; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No.) A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification; furthermore, US Pat.
No. 3788855, No. 3642482, No. 3488706, No. 3557066, No. 3271147, No. 3271148,
JP-A-50-71332, JP-A No. 53-30328, JP-A No. 52-
155528, 53-125, and 53-1024, as well as the mordants disclosed in
The mordants described in No. 2675316 and No. 2882156 can also be mentioned. Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used. Particularly preferred polymer mordants are shown below. (1) Groups that have a quaternary ammonium group and can be covalently bonded to gelatin (for example, aldehyde groups, chloroalkanoyl groups, chloroalkyl groups, vinylsulfonyl groups, pyridinium propionyl groups,
Polymers having vinyl carbonyl groups, alkylsulfonoxy groups, etc.) For example, (2) A reaction product of a copolymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer, and a crosslinking agent (for example, bisalkanesulfonate, bisarenesulfonate). R ^b ₁ : H, alkyl group R ^b ₂ : H, alkyl group, aryl group Q: divalent group R ^b ₃ , R ^b ₄ , R ^b ₅ : alkyl group, aryl group, or R ^b ₃ to ^{R b} ₅ At least two of these may be combined to form a heterocycle. X: Anion (The above alkyl group and aryl group include substituted ones.) (3) Polymer represented by the following general formula x: about 0.25 to about 5 mol% y: about 0 to about 90 mol% z: about 10 to about 99 mol% A: monomer having at least two ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated Monomer Q: N, PR ^b ₁ , R ^b ₂ , R ^b ₃ : alkyl group, cyclic hydrocarbon group,
Furthermore, at least two of R ^b ₁ to R ^b ₃ may be combined to form a ring. (These groups and rings may be substituted.) (4) Copolymer consisting of (a), (b) and (c) (a)

[Formula] or

[Formula] 3
Water-insoluble polymer having more than R ^b ₁ , R ^b ₂ , R ^b ₃ : each represents an alkyl group,
The total number of carbon atoms from R ^b ₁ to R ^b ₃ is 12 or more. (The alkyl group may be substituted.) X: Anion Various known gelatins can be used as the gelatin used in the mordant layer. For example, it is also possible to use gelatin manufactured by different methods such as lime-treated gelatin and acid-treated gelatin, or gelatin obtained by chemically modifying the obtained gelatin such as phthalation or sulfonylation. Moreover, if necessary, it can be used after being subjected to desalting treatment. The mixing ratio of the polymer mordant and gelatin of the present invention and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordanted, the type and composition of the polymer mordant, and the image forming process to be used. However, the mordant/gelatin ratio is 20/80 to 80/20 (weight ratio), and the amount of mordant applied is 0.5
Preferably it is used at ~8 g/ ^m2 . Typical dye fixing materials used in the present invention are:
It is obtained by mixing a polymer containing an ammonium salt with gelatin and coating it on a transparent support. When the dye fixing layer is located on the surface, a protective layer can be further provided if necessary. As such a protective layer, one generally used as a protective layer for photosensitive materials can be used as is, but if the dye fixing layer is provided on the dye fixing material separately from the photosensitive material, In order not to inhibit the movement of the hydrophilic dye, it is preferable to impart hydrophilicity to the protective layer as well. The photographic light-sensitive material and dye-fixing material of the present invention include:
The photographic emulsion layer and other binder layers may contain an inorganic or organic hardener. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), activated vinyl compound (1,3,5
-triacrylonitrile-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.),
Mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination. Further, as the heating means for moving the dye, various means similar to the heating means used in heat development as described above can be employed. In the present invention, coating solutions are prepared for the dye fixing layer, protective layer, intermediate layer, undercoat layer, back layer, and other layers, respectively, and the dipping method, as in the case of the photosensitive layer and other layers described above, is applied. A photosensitive material having a dye fixed layer or a photosensitive material can be formed by sequentially coating it on a support using various coating methods such as the air knife method, curtain coating method, or hopper coating method described in U.S. Pat. No. 3,681,294 and drying it. A dye-fixing material can be produced in which a dye-fixing layer is provided on a separate support. In the present invention, various exposure means can be used. The latent image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for normal color printing include tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, and CRTs.
A light source, a fluorescent tube, a light emitting diode, etc. can be used as the light source. The original drawing may be a line image such as a technical drawing, or a photographic image with gradation. It is also possible to photograph portraits of people and landscapes using a camera. The printing from the original drawing may be carried out by contact printing over the original drawing, reflection printing, or enlargement printing. In addition, images taken with a video camera, etc., and image information sent from a television station can be directly transmitted to a CRT or
It is also possible to print the image on a heat-developable photosensitive material by exposing it to a FOT and then forming the image on a heat-developable photosensitive material either in close contact or through a lens. Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, are being used as exposure means or display means in various devices. this
It is difficult to make LEDs that emit blue light effectively, so in order to reproduce color images using LEDs, three types of LEDs that emit green, red, and infrared light are used. The portions of the photosensitive material that are sensitive to light may be designed to emit yellow, magenta, and cyan dyes, respectively. That is, the green-sensitive portion (layer) may contain a yellow dye-providing substance, the red-sensitive portion (layer) may contain a magenta dye-providing substance, and the infrared-sensitive portion (layer) may contain a cyan dye-providing substance. . Other combinations are possible as required. In addition to the method described above, in which the original drawing is directly attached or projected, the original drawing illuminated by a light source is read by a light receiving element such as a phototube or CCD, and this information is stored in a memory such as a computer and processed as necessary. After performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source, or there is a method of directly causing three types of LEDs to emit light based on the processed information and exposing the image. . The image forming method of the present invention includes steps from exposure to heat development,
This is an extremely simple image forming method, as all steps up to fixation of the dye can be completely dry-processed without supplying any solvent from the outside. , furthermore,
Not only can the sensitivity of conventional silver halide photographic light-sensitive materials be maintained, but since the formed dye image is fixed to a dye fixing material, the quality and storage stability of the dye image are extremely good, and the color reproducibility is excellent. often,
Although it is a completely dry process, it is extremely useful because it can reproduce color images satisfactorily. The image forming method of the present invention having such characteristics can meet not only the field of photography but also the recent demand for converting so-called soft images to hard images. Since the dye is fixed in the dye fixing layer, the image has good storage stability, so it can be easily used even when long-term storage is required, which is superior to conventional photographic technology. Therefore, the present invention has great significance. The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto. Example 1 Preparation of Photosensitive Material D-1 A silver iodobromide emulsion was prepared as follows. Dissolve 40g of gelatin and 26g of KBr in 3000ml of water,
This solution was stirred while being maintained at 50°C. Next, a solution of 34 g of silver nitrate dissolved in 200 ml of water was added to the above solution over a period of 10 minutes, followed by a solution of 3.3 g of potassium iodide dissolved in 100 ml of water over a period of 2 minutes. The pH of the silver iodobromide emulsion thus prepared was adjusted, the pH was adjusted to 6.0 after sedimentation and excess salt was removed, and the yield was 400g.
A silver iodobromide emulsion was obtained. Next, a benzotriazole silver emulsion was prepared as follows. 28g gelatin and 13.2g benzotriazole in water
After dissolving in 3000 ml, the mixture was stirred while being kept at 40°C. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over a period of 2 minutes. The pH of the thus obtained benzotriazole silver emulsion was adjusted and the pH was adjusted to 6.0 by sedimentation to remove excess salt, yielding 400 g of benzotriazole silver emulsion. Next, a gelatin dispersion of a dye-providing substance was prepared as follows. Weigh out 5 g of magenta dye-donating substance (42), 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate as a surfactant, and 5 g of trire cresyl phosphate (TCP), and add 20 ml of ethyl acetate. The mixture was heated to approximately 60°C to dissolve and form a homogeneous solution. 10 of this solution and lime-processed gelatin
% solution and then dispersed with a homogenizer at 10,000 rpm for 10 minutes to prepare a dispersion of magenta dye-providing substance. In addition, the photosensitive layer contains (a) 20 g of silver iodobromide emulsion, (b) 10 g of silver benzotriazole emulsion, (c) 33 g of gelatin dispersion of dye-providing substance (68), and (d) 2.5% of compound (A) having the following structure. Aqueous solution 10ml (e) 12.5 ml of 10% ethanol solution of guanidine trichloroacetic acid (f) 4 ml of 10% dimethylsulfamide aqueous solution After mixing above (a) to (f) and heating and dissolving to prepare a photosensitive coating, This was applied onto a polyethylene terephthalate film having a thickness of 180 μm to a wet film thickness of 30 μm. Furthermore, as a protective layer on top of this, (g) 35 g of 10% aqueous gelatin solution (h) 5 ml of 10% guanidine trichloroacetic acid solution in ethanol (i) 4 ml of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (j) Water A mixed solution of 56 ml was applied onto the photosensitive layer to a wet film thickness of 25 μm, and then dried to form the photosensitive material D-
1 was produced. Example 2 Preparation of photosensitive material D-2 A dye-donating substance (68) was used in place of the dye-donating substance (42) used in Example 1, and 10 g of benzotriazole silver emulsion was used in the photosensitive coating. A photosensitive material D-2 was prepared in exactly the same manner as in Example 1, except that 5 g of silver iodobromide emulsion was used. Example 3 Preparation of photosensitive material D-3 6.5 g of benzotriazole and 10 g of gelatin were added to water.
The solution was stirred while maintaining the temperature at 50°C. Next, a solution of 8.5 g of silver nitrate dissolved in 100 ml of water was added to the above solution for 2 minutes, and then potassium bromide was added to the solution.
A solution of 1.2 g dissolved in 50 ml of water was added over 2 minutes.
The prepared emulsion was precipitated by pH adjustment, and after removing excess salt, the pH of the emulsion was adjusted to 6.0. The yield was 200g. In place of the silver iodobromide emulsion and silver benzotriazole emulsion used in the photosensitive coating material of Example 1, silver benzotriazole emulsion 25 containing the photosensitive silver bromide was used.
A photosensitive material D-3 was prepared in exactly the same manner as in Example 1, except that the dye-donating substance (21) was used in place of the dye-donating substance (42). Example 4 Preparation of photosensitive materials D-4 to D-6 Photosensitive materials D-4 to D-6 were prepared in exactly the same manner as in Examples 1 to 3, except for the guanidine trichloroacetic acid used in Examples 1 to 3. . Example 5 Preparation of photosensitive material D-7 Guanidine trichloroacetic acid used in Example 1
A photosensitive material D-7 was prepared in exactly the same manner as in Example 1, except that the amount of 220 mg was reduced to 1/2 (110 mg). Example 6 Preparation of dye fixing material R-1 The dye fixing material R-1 used in the present invention was prepared as follows. Poly(methyl acrylate-co-N,N,N,-
10 g of trimethyl-N-vinylbenzylammonium chloride (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
100g 10% lime processed gelatin dissolved in 200ml water
mixed evenly. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 90 μm. On top of the film formed in this way, the following
After mixing and dissolving (k) to (o), the mixture was coated uniformly to a wet film thickness of 60 μm and dried.
Hereinafter, this second layer will be referred to as a hydrophilic thermal solvent layer. (k) Urea (hydrophilic heat solvent) 4g (l) Water 10ml (m) Polyvinyl alcohol (saponification degree 98%)
10% by weight aqueous solution 12g (n) Compound A used in Example 1 100mg (o) 5% of sodium dodecylbenzenesulfonate
Aqueous solution 0.5ml Examples 7 to 9 Preparation of dye fixing materials R-2, R-3 and R-4 Urea 4 used in Example 6 as a hydrophilic thermal solvent
Dye fixing material R-2 was prepared in exactly the same manner as in Example 6, except that 4 g of pyridine N-oxide was used instead of g. Similarly, dye fixing materials R-3 and R-4 were prepared using 4 g of sulfonamide and 4 g of acetamide as hydrophilic thermal solvents, respectively. Examples 10-11 Preparation of dye fixing materials R-5 and R-6 4 g of urea used in Example 6 as a hydrophilic thermal solvent
Instead, 2 g of urea and 2 g of N-methylurea were mixed and used, but in the same manner as in Example 6,
A dye fixing material R-5 was produced. Similarly, instead of 4 g of urea used in Example 6, 1 g of urea, 1 g of N-methylurea, 1 g of ethyl urea
A dye fixing material R-6 was prepared by mixing and using 1 g of ethylene urea. Examples 12 to 14 Preparation of dye fixing materials R-7 to R-9 The procedure of Example 6 was repeated except that 0.8 g of guanidine trichloroacetic acid was added to the coating solution for the second layer (hydrophilic heat solvent layer) of Example 6. Pigment fixing material R in exactly the same manner as
-7 was produced. Similarly, 0.4 g of guanidine trichloroacetic acid and 0.4 g of sodium carbonate were added to the coating solution for the second layer of Example 6, and dye fixing materials R-8 and R- were added, respectively.
9 was produced. Example 15 Using photosensitive material D-1 with a tungsten light bulb,
Imagewise exposure was made for 10 seconds at 2000 lux. then 140
The mixture was heated uniformly for 20 seconds on a heat block heated to ℃. Next, place the dye fixing materials R-1 to R-9 in close contact with the coated surfaces facing each other, and place them on a heat block.
Heated at 120°C for 30 seconds. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta color image was obtained on the dye-fixing material.
The density of the negative image thus formed was measured using a Macbeth densitometer (RD-504). The results are shown in Table-1.

[Table] The above results show that by using a dye fixing material containing a hydrophilic thermal solvent, images with high maximum density can be obtained without supplying any water, and that two or more types of hydrophilic thermal solvents can be used. It has been demonstrated that particularly sharp images can be obtained when dye fixing materials (R-5 and R-6) are used in combination. Example 16 The photosensitive materials D-1 to D-3 of Examples 1 to 3 were exposed and heat-developed in the same manner as in Example 5. These were brought into close contact with the dye fixing material R-1 of Example 6 with the coated surfaces facing each other, and placed on a heat block.
Heated at 120°C for 30 seconds. When the dye-fixing material was peeled off from the photosensitive material sheet, negative magenta, yellow and cyan images were obtained on the dye-fixing material, respectively. Table 2 shows the results of measuring the negative image thus formed using a Macbeth densitometer (RD-504).

[Table] The above results demonstrate that by using a dye fixing material containing a hydrophilic thermal solvent, images with high maximum density of cyan, magenta or yellow can be obtained without supplying any water. Example 17 Each of the photosensitive materials D-4 to D-6 of Example 4 was subjected to imagewise exposure at 2000 lux for 10 seconds using a tungsten light bulb. Each of these light-sensitive materials was brought into close contact with the dye fixing material R-8 of Example 13, with their coated surfaces facing each other, and heated at 130 DEG C. for 30 seconds on a heat block. When the dye-fixing material was peeled off from the photosensitive material sheet, negative magenta, yellow and cyan color images were obtained on the dye-fixing material. The density of these negative images was measured using a Macbeth densitometer (RD-504). The results are shown in Table 3.

[Table] The above results demonstrate that images with high maximum density can be obtained even when heat development and dye transfer are performed simultaneously. Example 18 Exposure, heat development and transfer were carried out in the same manner as in Example 17, except that R-9 was used instead of the dye fixing material R-8 used in Example 17. As a result R-
Similarly to the case where No. 8 was used, negative color images of magenta, yellow and cyan were obtained on the dye fixing material. Example 19 The photosensitive material D-8 was prepared in the same manner as in Example 1 except that 1.5 g of urea (hydrophilic heat solvent (1)) was added to the photosensitive coating of the photosensitive material D-1 of Example 1.
was created. Furthermore, in the dye fixing material R-1 of Example 6,
A dye fixing material R-10 was prepared in exactly the same manner as in Example 1 except that the amount of urea applied in the hydrophilic thermal solvent layer was reduced to 1/2. Photosensitive material D-8 using a tungsten light bulb
Imagewise exposure for 10 seconds at 2000 lux, then at 130°C.
Heat evenly for 20 seconds. Next, dye fixing material R-10
Place each coated surface in close contact with each other, facing each other.
Heated at 120°C for 20 seconds. When the dye-fixing material was peeled off from the photosensitive material, a high density negative magenta color image was obtained on the dye-fixing material. When the density of this negative color image was measured using a Macbeth densitometer (RD-504), the maximum density was 1.22 and the minimum density was 0.19. It has been demonstrated that even by incorporating a hydrophilic thermal solvent into a photosensitive material, a dye image with high density can be obtained by heating for a short time without supplying any water at all. Example 20 Dye fixing material R-11 used in the present invention was produced as follows. 200 ml of 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride 1:1) and 25 g of hydrophilic heat solvent (1) of water and mixed uniformly with 100 g of 10% lime-treated gelatin. Spread this mixture onto a polyethylene terephthalate film.
It was applied uniformly to a wet film thickness of 90 μm. A dye fixing material R-11 was prepared by applying polyvinyl alcohol to a dry film thickness of 1.5 μm on the film thus formed. Using photosensitive material D-1 with a tungsten light bulb,
Imagewise exposure was made for 10 seconds at 2000 lux. then 140
The mixture was heated uniformly for 20 seconds on a heat block heated to ℃. Next, place the dye fixing material R-11 in close contact with the coated surfaces facing each other, and place on a heat block for 120 minutes.
Heat at ℃ for 30 seconds. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta color image on the dye-fixing material was obtained.
The density of the negative image thus formed was measured using a Macbeth densitometer (RD-504) and the maximum density was 1.26 and the minimum density was 0.18. Thus, it has been demonstrated that by using a dye fixing material containing a hydrophilic thermal solvent in the dye fixing layer, an image with high maximum density can be obtained without supplying any water at all. Comparative Example A photosensitive material D-9 was prepared in the same manner as in Example 1 except that 4 g of urea (a hydrophilic thermal solvent) was added to the photosensitive coating of the photosensitive material D-1 of Example 1. Furthermore, in the dye fixing material R-1 of Example 6,
A dye fixing material R-11 was prepared in the same manner as in Example 6 except that the amount of urea applied was 0. Photosensitive material D-9 using a tungsten light bulb
130℃ after imagewise exposure for 10 seconds at 2000 Lux
Heat evenly for 20 seconds. Next, dye fixing material R-
No. 11 was placed in close contact with the coated surfaces facing each other and heated at 120°C for 20 seconds. When the dye-fixing material was peeled off from the photosensitive material, the coated layer of the photosensitive material partially adhered to the dye-fixing material, staining the screen. As described above, if a hydrophilic thermal solvent in an amount necessary for dye transfer is added only to a light-sensitive material, a clear image cannot be obtained.

Claims (1)

[Claims] 1. On the support, at least the photosensitive silver halide, the binder, and the photosensitive silver halide are reducible and react with the photosensitive silver halide under heating to release a hydrophilic dye. A mobile hydrophilic dye formed imagewise by heating a photosensitive material having a dye-providing substance after imagewise exposure or simultaneously with imagewise exposure is coated with at least one hydrophilic thermal solvent in the dye-fixing layer or the dye-fixing layer. 1. A dry image forming method, which comprises moving a dye fixing material contained in an adjacent layer to a dye fixing layer under high temperature conditions by the action of the hydrophilic thermal solvent, and fixing the dye to the dye fixing layer.