JPS59174833A - Dry type image forming method - Google Patents

Abstract

PURPOSE:To obtain a dry type image high in quality by imagewise exposing a positive type photosensitive material contg. photosensitive silver halide, a dye donor capable of releasing a mobile dye, etc., heating it, and transferring the mobile dye produced in the unexposed area to a fixing layer with a hot solvent to fix the dye to the layer. CONSTITUTION:A positive type silver halide photosensitive material is prepared by forming on a support a layer contg. photosensitive silver halide, a hydrophilic binder, a diffusion resistant reducing dye donor, e.g. formula I or II, capable of releasing a mobile hydrophilic dye, but made incapable of releasing the hydrophilic dye when it reacts with photosensitive silver halide on being heated, and the like. This material is imagewise exposed, heat developed, a mobile dye formed in the unexposed areas is transferred in the presence of a hydrophilic hot solvent, e.g. N-methylurea in a high temp. state, and it is fixed in a dye fixing layer to form an intended dry method image.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a completely dry image forming method. More specifically, in the present invention, the dye obtained in the unexposed area by heat development treatment is
In particular, the present invention relates to a method of fixing the dye to a dye fixing layer by heating without supplying a solvent from the outside.

Photography using silver halide has traditionally been the most widely used method because it has superior photographic properties such as sensitivity and gradation control compared to other photographic methods, such as electrophotography and diazo photography. Ta. 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, "Fundamentals of Photographic Engineering" (published by Corona Publishing, 1979), pages 553-55.
5 pages, video information published in April 1978, 40 pages, Neble
tts Hand-book of Photo
graphy and reprography 7
thEd.

(Van Nostrand ReinholdC
US Pat. No. 3,152,904, No. 3.301.6.
No. 78, No. 3.392.020, No. 3,457,07
No. 5, British Patent No. 1.131゜108, No. 1,167
．． No. 777 and Research Disclosure Magazine 19
It is described in the June 1978 issue, pages 9 to 15 (RD-17029).

Many methods have already been proposed for obtaining color images using a dry method. U.S. Pat.
No. 31,286, p-phenylene diamine reducing agents and phenolic or active methylene couplers; U.S. Pat. No. 3,761.270, p-aminophenolic reducing agents; Research Disclosure Magazine September 1975 Issue 31-32
In US Pat. No. 4,021,240, a combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler is proposed.

However, in this method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, resulting in a problem 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.

In addition, a nitrogen-containing heterocyclic group is introduced into the dye to form a silver salt,
A method of releasing dyes by heat development is described in Research Disclosure magazine, May 1978 issue, pages 54-5B (R
D~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, see, for example, Research Disclosure magazine, April 1976 issue, pages 3o to 32 (RD-14433).
), December 1976 issue of the same magazine, pages 14-15 (RD-1
5227) 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 gradually deteriorates due to coexisting free silver, etc. Since it is reductively 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.
No. 022,617. 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 (Japanese Patent Application No. 1988-157).

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 a dye-fixing layer that releases this mobile dye mainly in the presence of a solvent. The invention relates to an image forming method characterized by moving the image.

As a result of further research into the above invention, the present inventors have discovered that a mobile hydrophilic dye formed in an unexposed area by heating in a state substantially free of water can be produced without using any solvent at all. It was discovered that the movement can be easily performed by heating without supplying it, and the present invention was achieved.

Therefore, the first object of the present invention is to produce a hydrophilic dye in the form of a positive image in the unexposed area by heat development treatment performed after exposure or at the same time as exposure, without supplying a transparent solvent from the outside. A second object of the present invention is to provide a method for fixing a plurality of hydrophilic dyes on a fixing layer, which is produced in the form of a positive image in an unexposed area by heat development treatment carried out after or simultaneously with exposure. An object of the present invention is to provide a method for fixing a dye to a dye fixing layer without specifically supplying a solvent from the outside.

A third object of the present invention is to provide an image forming method capable of improving the quality and storage stability of images obtained using heat-developable positive-working silver halide photographic materials. The object of the present invention is to provide a completely dry image forming method that does not require the supply of any solvent in all steps leading to dye fixation.

That is, the present invention provides at least a photosensitive silver halide binder and a reducible compound capable of releasing a hydrophilic dye upon heating, which is oxidized by reacting with the photosensitive silver halide upon heating. A positive silver halide photosensitive material containing a diffusion-resistant dye-providing substance that does not release hydrophilic dye (hereinafter simply referred to as a dye-providing substance) is heated after image exposure or simultaneously with image exposure, so that it is not exposed to light. The mobile hydrophilic dye formed on the dye is fixed to the dye fixing layer by moving it under high temperature conditions in the presence of at least one type of hydrophilic heat solvent without particularly supplying a solvent from the outside. This is a dry image forming method characterized by the following.

In the light-sensitive material according to the present invention, heating in a substantially water-free state after image exposure or simultaneously with image exposure allows not only silver images but also undeveloped silver halide in unexposed areas to be treated. As a result, a hydrophilic mobile dye is obtained. In the present invention, this step is called "heat development treatment", but in this case, since the dye obtained in the unexposed area is a hydrophilic mobile dye, it is used in an atmosphere to which the hydrophilic dye has affinity. In the process, this can be transferred to the dye fixing layer, thereby making it possible to obtain a dye image with excellent image quality and storage stability. 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 No. 56-157, 7
98) Furthermore, in the present invention, by making a hydrophilic thermal solvent exist, an atmosphere having affinity with the hydrophilic dye is realized, so there is no need to supply any particular solvent, and therefore, from exposure to development and fixing, there is no need to supply any solvent. A dye image with good color reproducibility can be formed by completely dry processing in which there is no need to supply any solvent in all the steps.

This principle remains essentially the same whether an autopositive emulsion or a negative type emulsion is used as an emulsion for a light-sensitive material. A dye image with good reproducibility can be obtained in the same manner as when a negative emulsion is used, except that only the dye image among the silver image and the mobile dye image is transferred to the dye fixing layer.

In the present invention, 'C' is a dye-donating substance, and the dye to be released can be selected by selecting various compounds, so that various colors can be reproduced. Therefore, by selecting a combination, it is possible to create a colored image, so the dye image in the present invention includes not only a monochrome image but also a multicolor image, and a monochrome image also includes a monochrome image obtained by mixing two or more colors. .

In the present invention, a diffusion-resistant 9 dye-providing substance that originally releases hydrophilic dyes but does not release hydrophilic dyes when oxidized is used. In this method, an oxidation-reduction reaction occurs between the photosensitive silver halide and the dye-donating substance using the photosensitive silver halide as a catalyst, and at the same time a silver image is formed in the exposed area, the diffusion-resistant dye-donating substance is oxidized. As a result, the hydrophilic dye is no longer released in the exposed area, and a mobile hydrophilic dye is obtained only in the unexposed area. At this time, the presence of a dye release aid promotes the above reaction. A positive dye image can be obtained by moving this mobile dye to, for example, a dye fixing layer. The above results apply when a negative type emulsion is used, but when an autopositive emulsion is used, a silver image is obtained in the unexposed areas and a mobile dye is obtained in the exposed areas, but the result is the same as when a negative type emulsion is used. It is.

The redox reaction and dye release reaction between the dye-donating substance and the photosensitive silver halide used in the present invention are carried out at high temperatures.
Moreover, it is characterized in that it is caused by a heat development process that produces a dry state that does not substantially contain water.

Here, "high temperature" refers to a temperature condition of 80°C or higher (t), and "dry state, which does not substantially contain water" refers to a state in which the system is in equilibrium with moisture in the air, but without water being supplied from outside the system. say. This situation is called “The theory of t
he photographic process
``4th Ed, (Edited by T.

H. James, Macmillan Jan)
It is described on page 374.

Conventionally, the dye release reaction is thought to be caused by attack by a so-called nucleophile, and is usually carried out in a high 1)H liquid with a pH of 10 or higher. However, it is unexpected that the present invention exhibits a high reaction rate at high temperatures and in a dry state substantially free of water.

The above reaction proceeds particularly well in the presence of an organic silver salt oxidizing agent, resulting in high image density. Therefore, the presence of an organic silver salt oxidizing agent is particularly preferred. Examples of dye-providing substances used in the present invention include compounds represented by the general formula IA or IB.

5 (Nu)' and (Nu)2 are each a nucleophilic group (for example, 10H
group, NR2- group), -2Z represents a divalent atomic group (e.g. sulfonyl group) that is electronegative with respect to the carbon atom on which R4 and R5 are substituted, and Q represents a dye moiety. . R1, R2 and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group, and when R1 and R2 are at adjacent positions on the ring,
The remainder of the molecule forms a fused ring, and R2 and R3 form a fused ring, and each of R4 and R5, which may be the same or different, represents hydrogen, a hydrocarbon group, or a substituted hydrocarbon group. , R1, R2, R':5, R4 and R5 contain a group of sufficient size to prevent said compound from migrating in the layer, i.e. a diffusion-resistant group. .

Residues that confer diffusion resistance are residues that are capable of inhibiting the migration of compounds bearing them in hydrophilic colloids commonly used in photographic materials.

Organic residues which generally bear straight-chain or branched aliphatic groups or which can carry carbocyclic or heterocyclic or aromatic groups, generally having 8 to 20 carbon atoms, are preferably used for this purpose. Ru. These residues may be attached directly or indirectly to the rest of the molecule, e.g. -NHCO-1-NH3O2-1NR-
Niko R represents hydrogen or an alkyl group, -0-1-
Bonded via S- or -5o2-. The diffusion-resistant residues may additionally carry groups 1, such as sulfo groups or carboxyl groups, which may be present in anionic form, conferring solubility in water. Mobility is determined by the size of the compound's molecules as a whole, so in some cases, for example, when the molecule as a whole is large enough, "diffusion-resistant residues"
It is also quite possible to have a base aroma with a shorter chain length.

The method for synthesizing the compound (IA) is described in US Pat. No. 3,980.
No. 479, and the compound (IB) can be synthesized by the method described in JP-A-53-11.0827.

Specific examples of these compounds include reduced forms of the following compounds.

However, R: " 02 (IB-3) However, Cog': However, Co12: (And CoA3 is the same as in the case of (IB-6>).

4 is the same as for IB-master.

However, Coβ4 is controlled by d in the case of (■d−a:+).

However, Coβ5: Shil/r'l/coAs a second example of the dye-donating substance of the present invention, the general formula (
Examples include those shown in n).

However, Nu is a nucleophilic group (e.g. -NH2 group, -〇l (group)
and GH is an oxidizable group (eg, amine (including alkylamino) group, sulfonamide group). GH is R
11 or RI3 or any group specified for Nu, preferably GH is in the para position to Nu in the above formula.

E is an electrophilic group which can be either carbonyl-CO- or thiocarbonyl-C8-, preferably carbonyl; Q provides a monoatomic bond between E and RI5 Here, the monoatom is a non-metal atom in the -2 or -3 valence state of group Va or group IIa of the periodic table, such as nitrogen atom, oxygen atom, sulfur atom, selenium atom. , where said atoms provide two covalent bonds linking E to R16, and when Q is a trivalent atom it is a hydrogen atom, an alkyl group (containing from 1 to 10 carbon atoms) ( (including substituted alkyl groups), aromatic groups (containing 5 to 20 carbon atoms) (including aryl groups and substituted aryl groups), or atomic groups necessary to form a 5- to 7-membered ring with R15 (e.g. (Pyridine or piperidine group); R1 is an alkylene group containing 1 to 3 carbon atoms in the bonding group (represents an alkylene group having a substituent)
, or at least one methylene in said linking group is a dialkyl or diarylmethylene linking group, and preferably an alkylene group containing 11) carbon atoms in the divalent linking group, such as a megoolene linking group or a dialkyl- or diaryl linking group. )(・-substituted methylene bonding group; n
is %'E@ of 1 or 2; R16 can be an aromatic group containing at least 5 atoms, preferably 5 to 20 atoms, including heterocyclic groups such as pyridine, tetrazole, henzimidazole, benzo Also included are groups containing a nucleus such as triazole or isoquinoline, or 6 to 2
Also included are carbocyclic di-lene groups containing 0 carbon atoms (preferably also including phenylene and naphthylene groups substituted with phenylene or naphthylene groups). Or R
16 can also be an aliphatic hydrocarbon group such as an alkylene group containing 1 to 12 carbon atoms. This also includes substituted alkylene groups; R15 is an alkyl group containing 1 to 40 carbon atoms (also includes substituted alkyl groups and cycloalkyl groups), an aryl group containing 6 to 40 carbon atoms (substituent or it can function as a ballast group.

R13, R11 and R, +2 may each be a monoatomic substituent such as a hydrogen atom or a halogen atom, but preferably a polyatomic substituent such as an alkyl group containing 1 to 40 carbon atoms (substituted alkyl group and cycloalkyl group). (including groups),
Alkoxy group, aryl group containing 6 to 40 carbon atoms (
substituent groups), carbonyl groups, sulfamyl groups, and sulfonamide groups. However, when RI6 is an aliphatic hydrocarbon group such as an alkylene group, R12 and R
11 must be a polyatomic substituent and preferably R12 is a polyatomic substituent. and R14 is selected to provide substantial proximity to the nucleophilic group to permit an intramolecular nucleophilic reaction favoring the release of Q from E, and preferably selected to provide from 3 to 5 atoms between the atom that is the reactive center of the nucleophilic reaction of the group and the atom that is the reactive center of the electrophilic reaction of the electrophilic group, so that the compound is 5- to 8-membered ring,
Most preferably, a 5- to 6-membered ring can be formed by intramolecular nucleophilic substitution of the group -(Q-RI 6-X3) from the electrophilic group.

Compounds of the above general formula, when RI 5 is a pallic substituent that provides steric hindrance, exhibit improved Dmin and overall imaging properties with increased stability after processing. Representative groups that can be RI5, and particularly useful pulpy groups, include cycloL1-\xyl, isopropyl, isophthyl, and benzyl. R
Improvements in imaging properties are also obtained when R1, 2 and R13 contain a parky substituent that provides steric hindrance to the adjacent portion of the quinone ring. Representative substituents include α- and β-substituted alkyl groups such as α-methylalkylcyclohexyl, isopropyl, α-methylbenzyl and p-t-
Includes butyl-α-phenethyl and the like.

Although it may be more advantageous for this halky substituent to be present in compounds of the structure described above, they can also be used to occupy other analogous positions in the compound; gives improved photographic properties.

Examples of the compound of general formula (U) include the following specific examples.

Onko [-33) (n-35) (n-36) (II-40> In the present invention, the amount of the dye-providing substance added is 0.01 mol to 4 mol per mol of silver halide, More preferably, the amount is 0.05 mol to 2 mol.

Examples of the dye moiety contained in the compound of the present invention include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes,
Examples include groups such as carbonyl dyes, phthalocyanine dyes, and metal complex salts thereof.

Typical dye precursors contained in the compounds of the present invention are those that give dyes by hydrolysis, such as JP-A-48-125818 and U.S. Pat. No. 3,222,19.
As described in No. 6 and No. 3,307,947, dyes with acylated auxochromes (transient short-wave dyes) can be mentioned. By temporarily shortening the dye absorption during exposure through acylation,
When these color image forming agents are mixed with a photosensitive emulsion and coated, desensitization due to light absorption can be prevented. Note that for this purpose, it is also possible to use a dye that has different hues when transferred onto the mordant and when present in the emulsion layer. The dye moiety can have a group that imparts water solubility, such as a carboxyl group or a sulfonamide group.

The properties required of the diffusion-resistant dye-donating substance of the present invention include the following.

10 In the dye-donating substance, silver halide and/or
Or, it is rapidly oxidized by an organic silver salt oxidizing agent and efficiently fixes a mobile dye for image formation by the action of a dye release aid.

2. The diffusion-resistant dye-providing substance must be immobilized in a hydrophilic or hydrophobic binder, and only the released dye must be mobile.

3. Easy to synthesize/Yokoto.

etc. can be mentioned.

Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,
There are styryl pigments, 21-mouth pigments, quinoline pigments, carbonyl pigments, phthalocyanine pigments, etc., and representative examples are shown below by hue. It should be noted that these dyes can be used in a temporarily short-wave form that can be restored during development.

Yellow Fuki 12 R12 i/l'IJ'1 Cyan In the above formula, R11-Rl5 are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group. group, cyano group, hydroxyl group, alkylsulfonylamino group, arylsulfonylamino group, alkylsulfonyl group, hydroxyargyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen atom , rufamoyl group, N-substituted sulfamoyl group, carbamoyl group, N-substituted carbamoyl group, aryloxyalkyl group, amino group, substituted amino group, alkylthio group 1
．． Represents a substituent selected from ruthio groups, and the alkyl and aryl groups in these substituents further include halogen atoms, hydroxyl groups, cyano groups, acyl groups, acylamino groups, alkoxy groups, carbamoyl groups, Substituted carbamoyl group, sulfamoyl group 1. substituted sulfamoyl group,
carboxyl group, alkylsulfonylamino group,
It may be substituted with a sulfonylamino group or a ureido group.

The dye-donating substance of the present invention is disclosed in U.S. Patent No. 2,322.0.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 27. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used.

For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters ( high-boiling organic solvents such as octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesate esters (e.g. tributyl trimesate); After dissolving in an organic solvent at 30°C to 160°C, such as lower alkyl acetate such as ethyl acetate or butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. , hydrophilic colloid C. is dispersed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Special Publication No. 51-39853, Japanese Patent Publication No. 51-59943
It is also possible to use the dispersion method using a compound described in the above issue.

In addition, various surfactants can be used when dispersing the dye-donating substance in the hydrophilic colloid, and these surfactants include those listed as surfactants elsewhere in this specification. You can use it.

The bar of the high boiling point organic solvent used in the present invention is 1 g of the dye-donating substance used, and is 10 g or less, preferably 5 g.
It is as follows.

Silver halides used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, and silver iodobromide.1. Silver chloroiodobromide, silver iodide, etc.

In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, it is preferable to use silver halide containing silver iodide crystals in some of its grains.

Such silver halide exhibits a pattern of pure silver iodide as its X-ray diffraction pattern.

Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary halide emulsions, silver halide grains form perfect crystals. For example, when measuring X-ray diffraction of a silver iodobromide emulsion, no pattern of silver iodide crystals or silver bromide crystals appears, but an X-ray diffraction pattern appears at positions corresponding to the mixing ratio.

In the present invention, particularly preferred silver halides are silver chloroiodide, silver iodobromide, and silver chloroiodobromide, which contain silver iodide crystals in their grains and therefore exhibit an X-ray pattern of silver iodide crystals. .

Such silver halide, for example silver iodobromide, can be obtained by first adding a silver nitrate solution to a potassium bromide solution to form silver bromide grains, and then adding potassium iodide.

Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination.

The average grain size of the silver halide used in the present invention is from 0.001 μm to 10 μm, preferably from o, oot μm to 5 μm.

Although the silver halide used in the present invention may be used as it is, chemical sensitizers such as compounds such as sulfur, selenium, tellurium, gold, platinum, palladium, rhodium, iridium, etc.) Chemical sensitization may be carried out by using reducing agents such as tin halide or a combination thereof. For more information, see “The Theory of the
"Photo-graphic Process" 4th edition, T6H, James, Chapter 5, pages 149 to 169.

In a particularly preferred embodiment of the present invention, an organic silver salt oxidizing agent is used in combination, but the silver halide used in this case is pure silver iodide crystals when silver halide is used alone. All silver halides known in the art can be used;

The organic silver salt oxidizing agent used in the present invention is produced at a temperature of 80°C or higher, preferably 100°C in the presence of photosensitive silver halide.
When heated above, it reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance if necessary, to form a mirror image.

By coexisting with an in-house silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density.

Examples of such organic silver salt oxidizing agents include silver salts of organic compounds having a carboxyl group, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. There is.

Examples of aliphatic carboxylic acids include silver salts of behenic acid, silver salts of stearic acid, silver salts of oleic acid, silver salts of lauric acid, silver salts of capric acid, silver salts of myristic acid, and silver salts of valmitic acid. , silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, silver salt of oleic acid, silver salt of adipic acid, silver salt of sebacic acid, succinic acid. There are silver salts of , silver salts of acetic acid, silver salts of butyric acid, silver salts of N solid number, etc. Also, silver salts substituted with halogen atoms or hydroxyl groups are also effective.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3゜5-dihydroxybenzoic acid, silver salts of 0-methylbenzoic acid 1, m,
- Substitution of silver salt of methylbenzoic acid, silver salt of p-6 methylbenzoic acid, silver salt of 2,4-dichlorobenzoic acid, silver salt of Y-cetamidobenzoic acid, silver salt of p-phenylbenzoic acid, etc. Silver salt of benzoic acid, silver salt of gallic acid, silver salt of tannic acid 1. Tin salt of phthalic acid, silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid 1, US Patent No. 3. Silver salts such as 3-carboxymethyl-4-methyl-4-thiapurin-2-thione described in US Pat. No. 185.830 and thioether groups as described in US Pat. 'J1 !iJ
j There are silver salts of carboxylic acids, etc.

In addition, there are silver salts of compounds having a mercapto group or a 1,000-ion group and derivatives thereof.

For example, 3-mercapto-4-phenyl-1゜2.4-
Silver salt of triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2-mercaptobenzthiazole, 2-
Silver salt of (s-ethyl glycolamide) benzthiazole, S-alkyl (alkyl group having 12 to 22 carbon atoms)
Silver salts of thioglycolic acid described in JP-A-48-28221, such as thioglycolic acetic acid, silver salts of dithiocarboxylic acids such as silver salt of dithioacetic acid, silver salts of thioamides, 5-
Silver salt of carboxy-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzthiazole, silver salt of mercaptooxadiazole, US Pat. No. 4,123,274 Silver salts described in the literature, such as the 1,2,4-mercaptotriazole derivative 3-amino-5-pendylthio 1.2°4
-Silver salts of triazoles, U.S. Pat. No. 3,301.678
It is a silver salt of a 1,000 ion compound such as a silver salt of 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-1,000 ion described in the specification of No.

In addition, there are silver salts of compounds having imino groups. For example, silver salt 14 of benzotriazole and its derivatives described in Japanese Patent Publication No. 44-30270 and Publication No. 45-18416.
For example, alkyl-substituted silver salts such as benzotriazole silver salts and methylbenzotriazole silver salts, halogen-substituted silver salts such as nzotriazole silver salts, and 5-chlorohencytriazole silver salts, and nzotriazole silver salts2. silver salts of carbimidobenzotriazoles, such as butylcarbo, silver salts of imidobenzotriazole, U.S. Pat. No. 4,220
．． No. 709 specification (7) 1,2.4-) Silver salts of srzole and 1-H-tetrazole, carbazole salts, silver salts of sacca 11, imitasol and imidazole derivatives There are silver salts, etc.

In addition, in the present invention, Riji - 1,000 j', f Suffragian Vo 1. 170. June 1978 Ha 17
Organic gold W4 salts such as silver salts and copper snoorate described in No. 029 (151!) can also be used in the same way as the various tin salts mentioned above. Organic silver salt oxidizing agents should be used in combination with Hffi or more. I can do it.

In the present invention, a reducing agent can be used as necessary. The reducing agent in this case is a so-called auxiliary developer,
It is oxidized by a silver halide and/or organic silver salt oxidizing agent, and its oxidized product has the ability to oxidize the reducing substrate in the dye-donating substance.

Useful auxiliary developers include hydroquinone, t-dimethylhydroquinone, furkyl-substituted hydroquinones such as 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, methoxyhydroquinone, etc. There are polyhydroxybenzene derivatives such as alkoxy-substituted hydroquinones and methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid,
Ascorbic acid derivatives, hydroxylamines such as N,N'-di(2-ethoxyethyl)hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroquinemethyl-1-phenyl-3-pyrazolidone Pyrazolidones, reductones, hydroxytetronic acids, etc. are useful.

Auxiliary developers can be used in a range of concentrations. A useful concentration range is 7 o, oo for silver.

Particularly useful concentration ranges are 5 times molar to 20 times molar.
It is 0.001 times mole to 4 times mole.

Although the thermal development process during heating of the present invention is not fully clarified, it can be considered as follows.

When a photosensitive material is irradiated with light, a latent image is formed on the photosensitive silver halide. Regarding this, T.H.
The Theory of the P by s.
photographyProcess”3rd E
dition, pages 105 to 148.

Furthermore, by heating the photosensitive material, the dye-donating substance releases a hydrophilic dye, but if exposed photosensitive silver halide is present, the photosensitive silver halide is used as a catalyst to release the photosensitive halogen. It reacts with silver oxide, becomes oxidized, and no longer releases hydrophilic dyes. Therefore, by heating after exposure, only the dye-providing substance in the unexposed area releases the hydrophilic dye to form a positive dye image.

When using an organic silver salt oxidizing agent, it is necessary to use silver halide and oxidizing agent to start the reaction quickly. It is necessary that the silver halide oxidizing agent be present at a substantially effective distance from the silver salt oxidizing agent, and therefore it is desirable that the silver halide and the organic silver salt oxidizing agent be present in the same layer.

Development by heating differs from so-called wet development in that the reaction requires time because the diffusion of reactive molecular species is restricted.

In the present invention, a hot solvent can be used as one means for improving such disadvantages. Here, "thermal solvent" is solid at ambient salinity,
A non-hydrolyzable organic material that exhibits a mixed melting point with other components at or below the heat treatment temperature used, and when developed by heat in the presence of a hot solvent, the development rate It is possible to speed up the process and improve the image quality. As such a thermal solvent used in the present invention, a compound that can serve as a solvent for a developer, a compound that is a substance with a high dielectric constant and is known to accelerate the physical development of a silver salt, and the like are useful. Useful thermal solvents include polyglycols described in U.S. Pat. No. 3,347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax 1, monostearin, -3O2 -1
Compounds with a high dielectric constant containing a -CO・- group, such as acetamide, succinimide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate (・,
Polar substances described in U.S. Pat. No. 3,667,959, 4-
Lactone of hydroxybutanoic acid, methylsulfinylmethane, tetrahydrothiophene-1,l-dioxide, 1,10-decanediol, methyl anisate, biphenyl perate described in Research Disclosure magazine, December 1976 issue, pages 26-28 etc. are preferably used.

Although the role of the thermal solvent in the present invention is not necessarily clear, it is understood that its main role is to promote the diffusion of reactive molecular species during development.

The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. A dye-providing substance is also dispersed in the binder described below.

The binders used in the present invention can be used alone or in combination. This binder has
Hydrophilic materials can be used. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, and cellulose derivatives, and natural substances such as polysaccharides such as starch, gum arabic, pullulan, and dextrin. Substances and other synthetic polymeric compounds, including synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, particularly in the form of latex, increase the dimensional stability of photographic materials. There are dispersed vinyl compounds that can

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
Contains pigments belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Migzol nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered i# such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiono<rubituric acid nucleus, etc.
A ring nucleus can be applied.

As a sensitizing dye for coalescence, for example, German Patent No. 929
．． No. 080, U.S. Patent No. 2. 'L31. No. 658, No. 2,493.748, No. 2.503, '77
No. 6, No. 2,519,001-+, No. 2.912.
No. 329, No. 3.656.959, No. 3.672
．． No. 897, 5, No. 3.694゜217, No. 4,0
No. 25,349, No. 4°046.572, British Patent No. 1. 242. No. 588, Special Publication Showa 44-14030
No. 52-24844.

These sensitizing dyes may be used alone or in combination (combinations of sensitizing dyes are often used, particularly for the purpose of supersensitization).

Representative examples are U.S. Patent No. 2,688,545 and U.S. Pat.
, No. 977.229, No. 3.397.060, No. 3,522,052, No. 3.527.641, No. 3.6'17,293, No. 3,628. No. 964, No. 3.666.480, No. 3,672,898
No.-1 No. 3,679.428, No. 3,703,3
No. 77, No. 3.769.301, $3.814,
No. 609, No. 3,837.862, No. 4,026
゜707, British Patent No. 1.344,281, British Patent No. 1
．． No. 507,803, Special Publication No. 43-4936, No. 53
-12375, JP-A-52-110618, JP-A No. 52
-109925.

Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933.390, U.S. Pat. No. 3.635,7)
21), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3. '615,613, same No. 3
, 615,641, 3,617°295, and 3,635,721 are particularly useful.

In the present invention, various dye release aids are used in various ways,
For example, it can be used by being included in any layer of a photosensitive material or any layer of a dye fixing material. A dye release aid is a photosensitive silver halide and/or
Or an organic silver salt that can promote the redox reaction between the oxidizing agent and the dye-donating substance, or act nucleophilically on the dye-donating substance to promote dye release, and the base or base precursor is used. In the present invention, in order to promote the reaction,
It is particularly advantageous to use these dye-releasing aids, but when these dye-releasing aids are incorporated into a light-sensitive material, it is necessary to select one that does not affect the storage stability of the light-sensitive material. . Examples of preferable bases that can be used in the light-sensitive material include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl-substituted aromatic amines, N-alkyl-substituted aromatic amines,
-Hydroxyalkyl-substituted aromatic amines, and His(
Examples include p, -(diflukylamino)fe, -ru]me 97 cheek. Also, U.S. Patent No. 2゜410.644
M-(tetramethylammonium iodide, diaminobutane dihydrochloride; 1, U.S. Pat. Organic compounds containing are described and useful. The base precursor releases a basic component when heated. Examples of typical base precursors are described in British Patent No. 998.949. Preferred base precursors are salts of carboxylic acids and organic bases.1. Useful carboxylic acids include I.Rif 1:10 acetic acid, trifluoroI.
! 3 acids, useful bases include guanidine, piperidine,
Examples include morpholine, p-toluidine, 2-picoline, and the like.

Guanidine trichloroacetic acid, described in US Pat. No. 3,220,84.6, is particularly useful.

Aldonamides described in JP-A No. 50-22625 are preferably used because they decompose at high temperatures to produce bases.

These dye release aids can be used and used in a wide variety of ways. The useful range is 50% by weight or less of the coated bellows of the photosensitive material converted into M amount2. Preferably 0.01% by weight
-4o% by weight.

In the heat-developable light-sensitive material of the present invention, it is particularly advantageous to use a compound represented by the following general formula because development is accelerated and the release of dye 9 is also promoted.

[General formula]

In the above formula, AI, A2, A3, and A4 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 a heterocyclic residue. It represents a substituent selected from among them, and A1 and A2 or A3 and A4 may be linked to form a ring.

Specific examples include H2N502NH2, H2N502N
(C,H3)2,H2N502N(C2H5)2,H
2N502NHCH3,](2N S 02N (C2
H40H)' 2, CH3NH302NHCH3.2H2, and the like.

The above compounds can be used in a wide range of applications.

The useful range is 7, 20% by weight or less of the coating buffing film of the photosensitive material, more preferably 0.1 to 15%.
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 in the transfer printing of fibers, and include N 114 Fe (S O, : Ri 2 12 H
20 etc. is useful.

The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports used include glass, paper, metal and their supporting bodies, as well as acetic acid. cellulose film, cellulose ester soil film, polyvinyl acetal film, -1
2 Listyrene film, polycarbonate i-film,
Included are polyethylene terephthalate films and their related films or resin materials. U.S. Patent No. 3,
The polyesters described in No. 634.089 and No. 3,725,070 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 an mM organic silver salt oxidizing agent to form halogen silver with the 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, JP-A-50-32928, and JP-A-50-32928.
No. 1-42529, U.S. Patent No. 3,700.458;
It is described in JP-A-49-13224, JP-A-50-17216, etc.

In the present invention, the coating amount of the photosensitive silver halide and organic silver salt oxidizing agent is 50 mg to 10 g in terms of silver using a ζ needle.
/'m2 is appropriate.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic agents, slippery improvement, emulsification dispersion,
Preventing adhesion and improving photographic properties (e.g. development acceleration, hardening,
Various surfactants may be included for various purposes such as sensitization).

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene: meglycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol realkylaryl ethers, polyethylene glycol esters, polyethylene glycol Sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyenalene oxide adducts>, glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides) fatty acid esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as
Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl 1a! Carboxyl esters such as esters, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene)'lkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. basis,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups; amino Mi,
Ampholytic surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, furkyl betaines, amine oxides, etc.; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridium, imidazolium, etc. Cationic surfactants such as heterocyclic quaternary ammonia J, salts, and phosphoniuno 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 widely used outside the field, and their structures, properties, and synthesis methods are well known. Representative known documents include 5ur
factant Science 5eries Volume,
Non1onic 5urfactants (Edi
ted by Martin J.

5hick, Marcel Dekker Inc, 1
967), 5surface Active Ethylene OxideAd
ducts (Schoufeldt, N. Perga
mon 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 may be used alone or as a mixture of two or more.

4. The polyethylene glycol type nonionic surfactant has an equal weight or less to the hydrophilic binder. Preferably 50%
Used below.

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 JO+xr.
nal, Scc, tion B36 (1953),
USP2,648,604, USF'3. G71,24
7, described in Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 44-9503, etc.

In the light-sensitive material used in the present invention, a compound that stabilizes the image at the same time as inactivating the development can be used. Among them, isothiuroniums represented by 2-hydroxyethylisothiuronium and trichloroacetate described in U.S. Patent No. 3,301°678, and U.S. Pat.
1.8=(3,6-shiokira・
Octane) bis(isothiuronium trifluoroacetate)! Q? Bisisothiuronium compounds, West German patent No. 2
thiol compounds disclosed in No. 162.714, 2-amino-2-thiazolium trichloroacetate and 2-amino-5-bromoethyl-2-thiazolium trichloroacetate described in U.S. Pat. No. 4,012,260, etc. Thiazolium compounds, U.S. Patent No. 4,060,4
Bis(2-amino-2-thiazoliumone methylene bis(sulfonylacetate)), 2-γminor 2-thiazolium phenylsulfonylacetate, etc. described in No. Compounds having 2-carboxydicarboxamide as an acidic moiety as described in US Pat. No. 4,088,496 are preferably used.

In the case of the present invention, since the color-providing substance is color-increasing, it also contains anti-irradiation and anti-halation substances.
Alternatively, it is necessary to incorporate various dyes into light-sensitive materials, but in order to improve the sharpness of images, the methods disclosed in Japanese Patent Publication No. 48-3692 and U.S. Patent No. 3.
No. 253,921, No. 2,527,583, No. 2. 956. Filter dyes, absorbent substances, etc. described in various specifications such as No. 879 can be contained.

Further, these dyes are preferably thermally decolorizable, such as those described in U.S. Pat. Nos. 3,769,019 and 3,745.
Dyes such as those described in US Pat. No. 3,615,432 are preferred.

The photosensitive material used in the present invention may optionally contain various additives known as °C1 heat-developable photosensitive materials, layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer,
AI layer 1. It can contain a release layer and the like. Various additives are listed in Linarch Disclosure Magazine Vol.
No. 170, June 1978, No. 17029, such as plasticizers, sharpness-improving dyes, A
Additives include H dyes, sensitizing dyes, capping agents, surfactants, fluorescent whitening agents, and antifading agents.

In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, bank layer, and other layers are prepared for each layer using the dipping method, the air knife method, the curtain coating method, or the U.S. A light-sensitive material can be prepared by sequentially coating onto a support by various coating methods, such as the hopper coating method described in Japanese Patent No. 3,681.294, and drying.

Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in U.S. Pat. No. 2,761,791 and British Patent No. 837,095.

In the present invention, the latent image obtained after exposure of the photosensitive material is maintained at a moderately elevated temperature, e.g., from about 80'C to about 250'C, at a temperature of about 0.5 seconds to about 300'C. Developing can be carried out by heating the element as a whole.As long as the temperature falls within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time. A temperature range of 10°C to about 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 an image formed by a mobile hydrophilic dye is transferred to a dye fixing layer under high temperature conditions in the presence of a hydrophilic thermal solvent, the transfer of the mobile dye is initiated simultaneously with the release of the dye. It may also be carried out after the release of the dye is completed. Therefore, the heating of the moving reservoir may be performed after the heat development or at the same time as the heat development. Simultaneously with thermal development means that the heating for development also acts as heating for the transfer 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 a condition in which a hydrophilic thermal solvent is present and the ambient temperature is 60° C. or higher.

Heating for dye transfer is from 60'C to 250°C from the viewpoint of storage stability and workability of the photosensitive material, so in the present invention, it exhibits its action as a hydrophilic @solvent in this temperature range. You can choose what you want to do. It goes without saying that hydrophilic thermal solvents must be able to quickly aid the movement of dyes when heated, but if we also consider the heat resistance of photosensitive materials, we need to consider the melting point required for hydrophilic thermal solvents. is 40°C to 250°C, preferably 40"C to 200°C
"C1" is more preferably 40°C to 150°C.

The "hydrophilic thermal solvent" in the present invention is a compound that is in a solid state at room temperature but becomes a liquid state when heated,
(Inorganic/Organic) Value〉■, and is defined as a compound having a solubility in water at room temperature of 1 or more. Here, inorganic and organic are concepts for predicting the properties of compounds, and details can be found, for example, in the area of chemistry, page 1171.9 (
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.

In general, preferred solvents for dissolving organic compounds are those whose (inorganic/organic) value is the (inorganic/organic) value of the organic compound.
It is empirically known that the value is close to the inorganic/organic) value. On the other hand, the (inorganic/organic) value of the dye-donating substances used in the present invention is around 1, and the (inorganic/organic) value of the hydrophilic dyes released from these dye-donating substances is approximately 1.
The value is 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)
Must be greater than the 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, from the viewpoint of molecular size, it is considered preferable that there be molecules around the moving dye that can move by themselves without inhibiting the movement. Therefore, it is preferable that the molecular size of the hydrophilic heat solvent is small, about 2
00 or less, more preferably about 100 or less intermolecular distance. Therefore, it is sufficient that it can be contained not only in the dye fixing layer, but also in the photosensitive material such as the photosensitive layer, or in both the dye fixing layer and the photosensitive layer, or in the photosensitive material. It is also possible to provide an independent layer containing a hydrophilic thermal solvent in the dye fixing material or in an independent dye fixing material having a dye fixing layer.From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, hydrophilic The heat solvent is preferably 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 thermal solvent used in the present invention has a coating amount of 5 to 500% by weight, preferably 20 to 200% by weight, particularly preferably 30 to 150% by weight of the total coating amount of the photosensitive material and/or dye fixing material. It can be used.

Examples of the hydrophilic heat solvent used in the present invention include ureas,
Pyridines, amides, sulbonamides, imides,
Mention may be made of alcohols, oximes, and other heterocycles.

Next, specific examples of the hydrophilic heat solvent used in the present invention will be shown.

Margin below (work 1) (12)? H2N CN (CH3)2 ti (34) (35) CH3SO2NH2, HOCH2SO2NH2 (36)
(37) H2NS02NH2,3HCNIiSO7,NH2(3
B) (39) (40) (41) (43) (44) +71 ♂H, (47) HOCH2(CHOH) 3CH20H.

(48) (49) CJI3C<c
r+2oH)-5, C2)f5c (CH20H)
3(50) (51)02NC(C
H20H)3, Sorbit <52)
(53) (54) HOCIip -CH=CH-C)IzOH (55)
(56) CH3CH=NOH, HON=CHCH-NOH (59
) (60) (61) (62) Among these, ureas (1), (2), (3), (
10), pyridines (17), (19), amide Fs (26), (30), (33), sulfone)'mides (34), (36), imides (40) , (41
), (43), (44) and alcohol (46),
(54 N is particularly preferable. The hydrophilic heat solvent used in the present invention can be used alone, and 7.2
Can also be used together.

In the present invention, 1. Dye fixation involves moving a hydrophilic mobile dye generated in an imagewise manner under high temperature conditions in the presence of a hydrophilic thermal solvent, and fixing the dye image by blocking this mobile dye. layers are required. For this purpose, the photosensitive material of the present invention has a support L L'-/! / a photosensitive layer (1) containing at least silver halide, optionally an organic silver hydrochloride ratio agent and a dye-donating substance which is also its reducing agent, and a binder;
It is composed of a dye-immobilized Btf (IT) that can accept a hydrophilic and mobile dye formed by 13 strands.

In this way, the photosensitive layer <I> and the dye fixing layer (■) are 1.
They may be formed on the same support or on separate supports. The dye fixing layer (II) and the photosensitive layer (1) can also be separated. For example, after imagewise exposure, the dye fixing layer (II) or the photosensitive layer can be peeled off after being level-heated and developed.

Furthermore, when a photosensitive material in which the photosensitive layer (1) is coated on the support and a fixing material in which the fixing layer (It) is coated on the support are formed separately, the photosensitive material is imagewise exposed. After uniform heating, the fixing material can be layered to transfer the mobile dye to the fixing layer (n). There is also a method in which only the light-sensitive material (I) is imagewise exposed, and then a dye fixing layer (■) 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.
In order to achieve sufficient adhesion, heating can also be used during 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 to transfer the dye to the dye transfer layer as low as possible within a reasonable transfer time so as not to cause a thermal reaction in the unexposed area. .

The dye fixing layer (U) 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.

Further, a low boiling point solvent such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, or a mixed solution of these low boiling point solvents and water or a basic aqueous solution is used. 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, a hydrophilic heat solvent for aiding the movement of the dye, a rounded base and/or a base precursor for promoting the dye release reaction, etc., and further,
A binder may be included to bind these 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, it also functions as a binder, so in such cases the amount of binder may be reduced or no binder may be used. Conversely, if the binder also functions as a mordant, the dye mordant may not be used.

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, the polymer mordant refers to a polymer containing secondary and tertiary amine groups,
Polymers having a nitrogen-containing heterocyclic moiety and polymers containing these quaternary cation groups, etc., with a molecular weight of 5,000 to 5,000.
200°,000, especially 10,000 to 50,000. For example, U.S. Pat. No. 2,548,564;
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Patent No. 2.484.430, U.S. Pat. , No. 694, No. 3. No. s59,096, No. 4,128,538, British Patent! Polymer mordants capable of crosslinking with gelatin etc. disclosed in US Pat. No. 3.958.995, US Pat. No. 2,721,852,
No. 2,798.063, JP-A-54-115228
No. 54-145529, No. 54-126027, etc.; U.S. Patent No. 3.898. A water-insoluble mordant disclosed in OBa No. M; a reactive mordant capable of forming a covalent bond with a dye disclosed in the specification of U.S. Patent No. fjS4,168,976 (Japanese Unexamined Patent Publication No. 54-137333), etc. ; further U.S. Pat. No. 3.709, . No. 690, No. 3,188.855,
Same No. 3.642,482, Same No. 3.4.88,706
No. 3.557,066, No. 3,2'll, 1
No. 47, No. 3.271.1413, JP-A-50-
No. 71332, No. 53-30328, No. 52-155
No. 528, No. 53-125, and No. 53-125, as well as the mordants disclosed in U.S. Pat.
．． 3z6, No. 2.882, 15 (mordants described in the specification of No. 3) may 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) A group that has a quaternary ammonium group and can be covalently bonded to gelatin (for example, an aldehyl 1' group, a chloroalkanoyl group, a chloroargyl group, a vinylsulfonyl group,
(2) 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. , reaction products with crosslinking agents (e.g. bisalkanesulfonates, bisarenesulfonates).

R2: H, alkyl group, aryl group They may be combined to form a petero ring.

X-anion (the above-mentioned alkyl groups and aryol groups also include substituted ones) (3) Polymer (A) x (B) V (CH2Cl)z- expressed by the following general formula
Y: About 0.25 to about 5 mol% Y: About 0 to about 90 mol% 2: About 10 to about 99 mol% A: Monomer having at least two ethylenically unsaturated bonds B: Copolymerizable ethylene Polymer unsaturated monomer Q: N, P may be bonded to form a ring (these groups and rings may be substituted).

or X: a hydrogen atom, an alkyl group, or a halogen atom (the alkyl group may be substituted) (b) Niacrylic acid ester (C) Niacrylonitrile (5) 1/3 of the repeating unit represented by the following general formula A water-insoluble polymer having the above ((CH2Cl)- may be mixed).

X-: As the gelatin used for the anion mordant layer, various known gelatins can be used. For example, it is also possible to use gelatin produced by different gelatin manufacturing methods, such as lime-treated gelatin and acid-treated gelatin, or gelatin that has undergone chemical benign treatment such as phthalate (IZ, 4, sulfonylation, etc.). Also, if necessary, it can be desalted before use.

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)
The mordant is preferably applied in an amount of 0.5 g/m2 to 8 g/m2.

A typical dye-fixing material used in the present invention 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 that is 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 may contain an inorganic or organic hardening agent in the photographic emulsion layer or other binder layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, cultaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), diochirin derivatives (2,3-dihydrokididioxide, etc.) active vinyl compound (L 3,5-triacryloyl-hexahydro-5-) riazine 1.1
, 3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
5-1-riazine, 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, the dye fixing layer, the protective layer, the intermediate layer, the undercoat layer, the bank layer and other layers are coated with respective coating solutions, and the dipping method is applied in the same manner as in the case of the photosensitive layer and other layers described above. , air knife method, curtain coating method, or hopper coating method of U.S. Pat.
A photosensitive material having a dye fixing layer or a dye fixing material in which the dye fixing layer is provided on a support separate from the photosensitive material can be produced.

In the present invention, various exposure means can be used. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing include tungnut lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources,
and CRT light sources, fluorescent tubes, light emitting diodes, etc. as light sources.
It can be used with 7.

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 are sent directly to a CRT or FOT,
It is also possible to form this image on a heat-developable photosensitive material either in close contact with it or through a lens, and then print it.

Furthermore, LEI (light emitting diode, light emitting diode), which has recently seen significant progress, is being used as an exposure means or display means in various types of equipment. ■This ED is difficult to make that effectively emits blue light, so LED
In order to reproduce color images using LEDs, three types of LEDs are used that emit green, red, and infrared light, and the parts of the photosensitive material that are sensitive to these lights emit yellow, magenta, and cyan dyes, respectively. It is good if it is designed to do so.

That is, the green-sensitive portion (layer) contains a yellow dye-donating substance, the red-sensitive portion (layer) contains a magenta dye-donating substance, and the infrared-sensitive portion (layer) contains a cyan dye-donating substance. . Other combinations are also 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 COD, and this information is stored in the memory of a computer or other device 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 for exposure. .

The image forming method of the present invention is an extremely simple image forming method that can perform completely dry processing in all steps from exposure to heat development and dye fixation without supplying any solvent from the outside. It is. Furthermore, not only can the sensitivity of conventional silver halide photographic light-sensitive materials be maintained, but also the quality and storage stability of the dye image are extremely good, as the formed dye image is fixed to the dye fixing material. It has good reproducibility and is extremely useful because it can reproduce color images satisfactorily even though it is a completely dry process.

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 into heart images. Since the image is fixed on 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. This is larger than the four sets of the present invention.

The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

(Emulsion Preparation Example-1) Preparation of Silver Iodobromide Emulsion 40 g of gelatin and 26 g of KBr were dissolved in 3000 ml of water, and after stirring the solution while keeping it at 50°C, 34.0 g of silver nitrate was dissolved. g dissolved in 3QQmρ of water was added to the above solution over 10 minutes.

Next, a solution prepared by dissolving 3.3 g of potassium chloride in 100 mff of water was added over 2 minutes.

The p 11 of the silver iodobromide emulsion thus prepared was adjusted, precipitated, excess salt was removed, and the pH was adjusted to 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g.

(Emulsion Preparation Example-2) Preparation of benzotriazole silver emulsion 28 g of gelatin and 13.2 g of benzotriazole were mixed with 3 parts of water.
000+n! ! After stirring this solution while keeping it at 40°C, add 17g of silver nitrate to this solution and add 100ml of water.
The solution dissolved in Step 5 was added over 2 minutes.

The pH of this benzo I-lyazole silver emulsion was adjusted, and the emulsion was precipitated to remove excess salt, and then the pH was adjusted to 6.0, yielding 1400 g of a ----nzotriazole chain emulsion.

(Emulsion Layering Example-3) Preparation of benzo-1-lyazole silver emulsion containing photosensitive silver bromide: 6.5 g of hensitosu gamma sol and 1 g of gelaginjO are mixed with 1 part of water.
0 Q Om / Mix 2 volumes of rice and 50jt of peel:
After stirring, add 8.5 g of silver nitrate to 10 Q of water.
The saliva was added to the above solution over a period of 2 minutes.

Next, a solution of 1.2 g of potassium bromide dissolved in 5 QmA of water was added over a period of 2 minutes, and the resulting emulsion was precipitated by adjusting pT-I. After removing excess salt, the pH of the 1L preparation was adjusted.
was adjusted to 6.0. The yield was 200g.

(Example of preparation of dye fixing material) Preparation of dye fixing material R--1 Poly(methyl acrylate-ni-1-N, tCN-to+,
I Methyl-N-vinylbenzylano JE: Niumku 1
Collide) (Ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) 10g to 200
mj! 10% lime-processed gelatin dissolved in water of 100%
It was evenly mixed with g. This mixed solution was uniformly applied onto a polyethylene terephthalate film to a wet film thickness of 20 ttrn.

On top of this, the following (a) to (S) were further mixed and dissolved, and then a dye transfer aid layer was uniformly applied to a wet film thickness of 60 μm (2) and dried.

(a) Urea 4g (b) Water
8mff (C)°1 of polyvinyl alcohol (saponification degree 98%)
0% aqueous solution 12g (d) 5% aqueous solution of the following compound 2mg aqueous solution
0.5mA! (Photosensitive material preparation example-1) Preparation of photosensitive material E-1 Preparation of dispersion of dye-donating substance 5 g of reduced form of dye-donating substance IA-(9), succinic acid-
Sodium 2-ethyl-hexyl ester sulfonate 0.5
g, l-leak resyl phosphate (TCP) 15g
was weighed, 30 mβ of ethyl acetate was added, and the mixture was heated and melted at about 60°C. 10 of this homogeneous solution and lime-processed gelatin.
After stirring and mixing with 100 g of % solution, the mixture was dispersed using a homogenizer for 10 minutes at 10.OOORPM. This dispersion is referred to as a dye-donating substance dispersion DP-1.

Next, the method for producing the photosensitive coating will be described.

(a) Photosensitive silver iodobromide emulsion (emulsion preparation example-1) 25 [ (b) Dispersion of dye-providing substance, P-13g (C) guanidine trichloride 109'l of acetic acid;
J-Knorr solution 15'nβ (d) 2.5% aqueous solution of the following compound 10m/H solution 4+nj! or more (7)'
After mixing and dissolving (a) to (e), the mixture was applied onto a polyethylene terephthalate film to a wet film thickness of 30 μm and dried.

Furthermore, the following composition was applied as a VAN protector on top of this film.

(f) Gelatin 10% aqueous solution 35g (g) Guanidine trichloroacetic acid 10% ethanol solution
6 m 1 (h) 1% aqueous solution of sodium succinate-2-ethylhexyl ester sulfonate m 1 (i) A mixture of 55 m# of water was applied to a wet film thickness of 25 μm, and then dried. , a photosensitive material E-i was prepared.

(Example 1) The photosensitive material E-1 prepared in Photosensitive Material Preparation Example-1 was imagewise exposed for 10 seconds at 2,000 lux using a tank sten lamp, and then exposed to light for 30 minutes on a heat block heated to 130°C.
Heat evenly for seconds.

Next, use this photosensitive material and the dye-fixing material prepared in Production Example-1)? The film surfaces of -1 were brought into close contact with each other facing each other, and heated uniformly for 30 seconds on a heat block heated to 120°C. When the dye-fixing material was peeled off from the photosensitive material, a positive magenta color image was obtained on the dye-fixing material. The density of this positive image was measured using a Maches transmission densitometer (D-504), and the maximum density for green light was 1.63 and the minimum was 0.52. In addition, the gradation of the sensitometric curve is that in the straight line part, the density difference is 1°07 for a 10 times the exposure amount difference.
Met.

(Example 2) 1-phenyl-4-methyl-4-oxymethyl-3 was added as an electron transfer agent to the coating liquid used in Photosensitive Material Preparation Example-1.
- Photosensitive material E-2 was produced in exactly the same manner as in Production Example-1, except that 0.4 g of pyrazolidone was added.

Next, dye fixing materials R and R were prepared in exactly the same manner as dye fixing material R-1, except that the dye transfer aid shown in Table 1 was used instead of urea used in dye fixing material preparation example -1. −
2 to RG were prepared.

Except that photosensitive material E-2 was used in place of photosensitive material E-1 used in Example-1, and dye fixing materials R-2 to R-6 were used in place of dye fixing material R-1. Example-1
Exposure, heating, and density measurement of the positive color image were carried out in exactly the same manner as described above. The results are shown in Table 1.

Margin table below-1 Dye surface Dye transfer aid Maximum minimum fixed material
Concentration Concentration R' 2
N-methylurea (4g) 1.65 0.58R-3pyridi>'-N-oxide (4g) i,,68 0.53R
-4 sulfonamide (4g) 1.69 0.5OR-5 urea/
N-methylurea (2g/2g) 1.59 0.56R-
6 urea/N-methylurea/ethyl urea/ethyl urea 1.63 0.61 (Ig/
i g/l g/l g) (Example 3) Instead of 25 g of silver iodobromide emulsion used in Photosensitive Material Preparation Example 1, 20 g of silver iodobromide emulsion and silver benzotriazole (Emulsion Preparation Example 2) were used. ) 10g, and the dye-donating substance TA
- Dye-donating substance (23) 5 instead of the reduced form of (9)
A photosensitive material E-3 was prepared in exactly the same manner as in Photosensitive Material Preparation Example-1 except that G was used.

Exposure, heating, and determination of the density'/J1 of a positive color image were carried out in exactly the same manner as in Example-1, except that photosensitive material E-3 was used in place of the photosensitive materials E and 1 used in Example-1. As a result, the maximum density was 1.43 and the minimum density was 0°59.

(Example 4) Silver benzotriazole containing silver bromide (emulsion preparation example -
3) °ζ Photosensitive material E-4 was prepared in exactly the same manner as Photosensitive material preparation example-1 except that 25 g was used.

Light, heating, and density measurements were carried out in exactly the same manner as in Example-1, except that Photosensitive Material B-4 was used in place of Photosensitive Material E-1 used in Example-1.

The maximum density of the positive magenta color image on the dye-fixing material was 1.49, and the minimum density was 0.50.

(Example 5) Photosensitive material E-5 was produced in exactly the same manner as in Production example 1, except that the guanidine trichloroacetic acid used in Photosensitive material production example 1 was removed.

Further, dye fixing material R-7 was prepared in exactly the same manner as in dye fixing material preparation example 1, except that 0.8 g of guanidine trichloroacetic acid was added to the coating liquid used in dye fixing material preparation example 1.

The above photosensitive material E-5 was heated for 20 minutes using a tungsten light bulb.
After imagewise exposure for 10 seconds at 00 lux, dye fixing material R
-7 with the film surfaces facing each other, and heated on a heat block at 130° C. for 45 seconds.

When the dye-fixing material was peeled off from the light-sensitive material, a positive color image was obtained on the dye-fixing material. The density of this positive color image was measured using a Macbeth densitometer (TD-504). As a result, the maximum density of this Bhopal color image was 1.38, and the minimum density was 0.43.

Procedural Amendment Special 1 Office Commissioner Kazuo Wakasugi 1, Indication of the case 1982 Patent layer No. 048751 2, Name of the invention Dry image forming method 3, Person making the amendment Relationship with the case Patent applicant Minamia Shigara Nakanuma Address Kanagawa 210 Nakanuma, Minamiashigara City, Prefecture Name (52”) Minoru Onishi Fuji Photo Film Co., Ltd. 'Se Onishi Minoru 4, Agent ■ 160 Address 4-29-11-6 Koenji Kita, Suginami-ku, Tokyo
, Subject of amendment Column 7 of "Detailed Description of the Invention" of the specification. Contents of Sode Masa 1) On page 9, line 5 of the Detailed Description of the Invention, the phrase ``out of the image and the 0J mobile dye image'' has been replaced with ``the image and the mobile dye image obtained in the exposed area.'' Among them,” he corrected.

Claims (1)

[Claims] On the support, at least a photosensitive silver halide, a binder and a reducing compound capable of releasing a mobile hydrophilic dye by heating, react with the photosensitive silver halide by heating to form a hydrophilic dye. A positive-working silver halide photosensitive material having a diffusion-resistant dye-donating substance that no longer releases
By heating after image exposure or simultaneously with image exposure, the mobile hydrophilic dye formed in the unexposed area is moved under high temperature conditions in the presence of at least one type of hydrophilic thermal solvent, thereby fixing the dye. A dry image forming method characterized by fixing in layers.