JPH0363733B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new method for forming dye images by heating in a substantially water-free state. The present invention further relates to a new photographic material containing a dye-donating substance that reacts with photosensitive silver halide upon heating in a substantially water-free state to release a hydrophilic dye. The present invention particularly relates to a new method for obtaining dye images by transferring dyes released by heating to a dye fixing layer. Photography using silver halide has superior photographic properties such as sensitivity and gradation control compared to other photographic methods such as electrophotography and diazo photography.
It has traditionally been the most widely used. In recent years, a technology has been developed that allows images to be easily and quickly obtained by changing the image forming method for photosensitive materials using silver halide from the conventional wet processing using a developer to a dry processing using heating, etc. It has been. Heat-developable photosensitive materials are well known in the art, and for more information on heat-developable photosensitive materials and their processes, see, for example, Fundamentals of Photographic Engineering (published by Corona Publishing, 1979).
Pages 553-555, 40 pages of video information published in April 1978,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand Reinhold
Company), pages 32-33, US Pat. No. 3,152,904,
No. 3301678, No. 3392020, No. 3457075, British Patent No. 1131108, No. 1167777, and Research Disclosure Magazine, June 1978 issue, pages 9-15 (RD-17029). Many methods have been proposed for obtaining color images using a dry method. A method of forming a color image by combining an oxidized developer and a coupler is described in U.S. Pat. No. 3,531,286,
Phenylenediamine reducing agents and phenolic or active methylene couplers are used in U.S. Pat. , sulfonamide phenolic reducing agents are also disclosed in U.S. Patent No.
No. 4021240 proposes a combination of a sulfonamidophenolic reducing agent and a 4-equivalent coupler. 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. In addition, a method of introducing a nitrogen-containing heterocyclic group into a dye, forming a silver salt, and releasing the dye by heat development is described in Research Disclosure Magazine, May 1978 issue 54.
Described on page 58 RD-16966. With this method, it is difficult to suppress the release of dye in areas not exposed to light, and a clear image cannot be obtained, so it is not a common method. 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 30-32 (RD-14433), December 1976 issue, pages 14-15 of the same magazine. Page (RD-15227), U.S. Pat. No. 4,235,957, and others, 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 images may coexist during long-term storage. It had the disadvantage of being gradually reductively bleached by free silver and the like. Further, regarding the method of forming color images using leuco dyes, for example, US Pat. No. 3,985,565,
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. Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the disadvantage of only high capri and low density. The present invention provides a new method for forming dye images by heating in a substantially water-free state and overcomes the drawbacks of hitherto known materials. That is, an object of the present invention is to provide a new image forming method in which a mobile hydrophilic dye released by heating in a substantially water-free state is transferred to a dye fixing layer to obtain a dye image. be. The purpose of the present invention is to improve fog density in a new image forming method in which a mobile hydrophilic dye released by heating is transferred to a dye fixing layer in a substantially water-free state to obtain a dye image. The purpose of the present invention is to provide a method for increasing the density of a dye image formed by promoting a hydrophilic dye release reaction without increasing the dye density or deteriorating storage stability. An object of the present invention is to provide a method for quickly obtaining clear color images using a simple method. These purposes include disposing on the support at least a photosensitive silver halide, a binder, which is reducible to the photosensitive silver halide, and which reacts with the photosensitive silver halide by heating to release a mobile hydrophilic dye. After or simultaneously with imagewise exposure, a photosensitive material containing a dye-providing substance and a hydroquinone derivative that releases a mercapto group-containing compound when oxidized is heated in a substantially water-free state to make it mobile. This is achieved by a method of forming a dye into an image. The compound of the present invention does not release a mercapto group-containing compound until the redox reaction with silver halide occurs during heating, so it does not affect the photographic properties of the light-sensitive material and does not deteriorate the storage stability of the light-sensitive material.
This is advantageous in that it can accelerate the dye release reaction and increase the color density. Furthermore, since the mercapto compound is intensively released at the location where the dye release reaction occurs, it is advantageous in that the dye release reaction is promoted without increasing fog. Further, compounds having a mercapto group normally inhibit development, but surprisingly, in the system of the present invention, they actually promote the dye release reaction. The hydroquinone derivative according to the present invention that releases a compound having an oxidized mercapto group includes one represented by the following general formula (). General formula () In the formula, R ₁ and R ₂ are each a hydrogen atom or a base-removable group (for example, an alkoxycarbonyl group,
R ₁ and R ₅ or R ₂ and R ₆ may be bonded to each other to form a ring (for example, an oxathiol ring). R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an alkyl group (e.g. methyl, ethyl, 1,1,3,3
-tetramethyl-butyl, n-pentadecyl, 2
-propenyl group), aryl group (e.g. phenyl, p-tolyl, o-carboxy-phenyl, o-methoxycarbonyl-phenyl, p
-methoxy-phenyl group, etc.), hydroxyl group, halogen atom (e.g. chlorine, iodine, etc.), -
Represents an OW group or a -S-Z group. here,
Z and W each represent an alkyl group (e.g. methyl, ethyl, 1,1,3,3,-tetramethyl-butyl,
2-ethylhexyl, n-dodecyl, n-hexadecyl, n-octadecyl, hydroxycarbonylmethyl, ethoxycarbonylmethyl, 2-hydroxyethyl group, etc.), aryl group (such as phenyl, p-tolyl, o-tolyl, o-nitropheyl group), R ₃ , R ₄ , R ₅ Or at least one of R ₆ is -S-Z group. or
R ₃ and R ₄ or R ₅ and R ₆ may form a ring. In the general formula (), it is particularly preferred when Z is a nitrogen-containing heterocyclic group (particularly a nitrogen-containing 5-membered heterocyclic group). As the nitrogen-containing heterocyclic group having a mercapto group, a group represented by the following general formula () is particularly preferred. General formula () In the general formula (), Q is an oxygen atom, a sulfur atom, or a -NR′′′′ group (wherein R′′′′ is a hydrogen atom,
It represents an alkyl group, an unsaturated alkyl group, or a substituted or unsubstituted aryl group or aralkyl group, respectively. ), Y represents C-R ₁₂ or a nitrogen atom, G represents C-R ₁₃ or a nitrogen atom, R ₁₂ and R ₁₃ are each a hydrogen atom, alkyl,
Unsaturated alkyl group, substituted or unsubstituted aryl group, or substituted or unsubstituted aralkyl group -
SR′′′′, _-NH2 group (wherein R′′′′ group is a hydrogen atom, alkyl, aryl, aralkyl, alkylcarboxylic acid or alkali metal salt thereof, alkylsulfonic acid or alkali metal salt thereof ) When Y and G are C- _R12 and C- _R13 , respectively, _R12 and _R13 may form a substituted or unsubstituted aromatic ring. Among the groups represented by the above general formula (), examples of the 5-membered ring include a tetrazolyl group, a triazinyl group, a triazolyl group, an oxazolyl group, an oxadiazolyl group, a diazolyl group, a thiazyl group, a thiadiazolyl group, an imidazolyl group, and a penzooxazolyl group. These groups include various groups such as nitrohalogen (chlorine, bromine, iodine, fluorine), lower alkyl, lower alkylamide, lower alkoxy, lower alkylsulfonamide, α-chloroacetyl group, benzothiazolyl group, benzimidazolyl group, etc. It may be substituted with thio, lower alkylcarbamylamino, etc. Representative -S-Z is shown below in the form of H-S-Z. C ₁₃ H ₂₇ SH Specific examples of the compound represented by the general formula () used in the present invention are listed below. Compound-1 2-n-dodecylthio-5-(1'-phenyltetrazol-5'-ylthio)hydroquinone Compound-2 2-n-octadecylthio-5-(1'-phenyltetrazol-5-ylthio)hydroquinone Compound-3 2-n-hexadecylthio-5-(1'-phenyltetrazol-5-ylthio)hydroquinone Compound-4 2-(2,5'-dihydroxy-6'-(1''-phenyltetrazole-5'') -ylthio)-4′-(1・1
・3,3-tetramethylbutyl)phenylthiobenzoic acid compound-5 2-{2',5'-dihydroxy-6'-(1'-phenyltetrazol-5''-ylthio)-3-(1,1
・3,3-tetramethylbutyl)}phenylthiobenzoic acid compound-6 2-(1′-phenyltetrazol-5′-ylthio)-3-phenylthio-6-(1″・1″・3″・3″ −
Tetramethylbutyl)hydroquinone compound-7 2-(1′-phenyltetrazol-5′-ylthio)-3-phenylthio-5-(1″・1″・3″・3″-
Tetramethylbutyl)hydroquinone compound-8 2,5-dihydroxy-6-(1'-phenyltetrazol-5'-ylthio)-4-(1″・1″・3″・
3″-tetramethylbutyl) phenylthioacetic acid compound-9 2-{2′・5′-dihydroxy-3′-n-hexadecylthio-6′-(1″, phenyltetrazole-
5″-ylthio)}phenylthiobenzoic acid compound-10 2-n-hexadecylthio-5-(1′-phenyltetrazol-5′-ylthio)-6-phenylthiohydroquinone compound-11 4-(1′-ylthio) enyltetrazol-5′-ylthio)-5-hydroxy-7-(1″・3″・3″・3″-tetramethylbutyl)benzoxaol-2-one compound-12 2-{2′・5′ -dihydroxy-6′-(1″-phenyltetrazol-5″-ylthio)-3′-(1・1
・3-tetramethylbutyl)} phenylthiobenzoic acid methyl ester compound-13 2-{2′・5′-dihydroxy-6′-(1″-phenyltetrazol-5″-ylthio)-4′-(1・1
・3,3-tetramethylbutyl)}phenylthiobenzoic acid methyl ester compound-14 2-{2',5'-dihydroxy-3'-n-pentadecylthio-6'-(1''-phenyltetrazole-
5″-ylthio)} phenylthiobenzoic acid methyl ester compound-15 2-n-octylthioxycarbonylmethylthio-6-phenyl-3-(1′-phenyltetrazol-5′-ylthio)hydroquinone compound-16 2-p -Nitrophenylthio-3-(1′-phenyltetrazol-5′-ylthio)-6-(1″・
1″・3″・3″-tetramethylbutyl)hydroquinone compound-17 2-(2′-methylthio-1′・3′・4′-thiadiazol-5′-ylthio)-6-(1″・1″・3″・3″−
Tetramethylbutyl)hydroquinone compound-18 3-(2'-methylthio-1', 3', 4'-thiadiazol-5'-ylthio)-6-(1'', 1'', 3'', 3''-
Tetramethylbutyl)hydroquinone compound-19 2,3-bis(2'-methylthio-1',3',4'-
Thiadiazol-5-ylthio)-6-(1″・1″・
3″・3″-tetramethylbutyl)hydroquinone compound-20 2-(3′-n-pentyl-4′-phenyl-1′・
2′・4′-triazole-5′-ylthio)-5-
(1′・1″・3″・3″-tetramethylbutyl)hydroquinone compound-21 2-(6′-methyl-1′・3′・3a′・7′-tetraazainden-4′-ylthio) −6−(1″・1″・3″・
3″-tetramethylbutyl)hydroquinone compound-22 2,3-bis(6′-methyl1′・3′・3a′・7′-tetraazaindene-4′-ylthio)-6-(1″・
1″・3″・3″-tetramethylbutyl)hydroquinone compound-23 2-n-hexadecylthio-5-(2′-methylthio-1′・3′・4′-thiadiazol-5′-ylthio)hydroquinone compound− 24 2-{2′・5′-dihydroxy-6′-(2″-methylthio-1″・3″・4″-thiadiazol-5″-ylthio)-3′-(1・1・3・3− Tetramethylbutyl) phenylthiobenzoic acid compound -25 2-(2'-amino-1', 3', 4'-thiadiazol-5'-ylthio)-5-(1'', 1'', 3'', 3'' -Tetramethylbutyl)hydroquinone compound-26 2-{2′・5′-dihydroxy-6′-(2″-amino-1″・3″・4″-thiadiazole-5″-ylthio)
-4-(1,1,3,3-tetramethylbutyl)}phenylthiobenzoic acid compound-27 2-(2'-amino-1', 3', 4'-thiadiazol-5'-ylthio)-3- n-dodecylthio-6-
(1″・1″・3″・3″-tetramethylbutyl)hydroquinone compound-28 2-(6′-t-butyl-1・3・3a・7′-tetraazainden-4-ylthio)6- (1″・1″・
3″・3″-tetramethylbutyl)hydroquinone compound-29 2-(6′-n-nonyl-1′・3′・3a′・7′-tetraazainden-4′-ylthio)-6-(1 ″・1″・
3″・3″-tetramethylbutyl)hydroquinone compound-30 2-(4′-phenyl-1′・2′・4′-triazol-5′-ylthio)-5-(1″・1″・3″・3″-tetramethylbutyl)hydroquinone compound-31 2-(2′-phenyl-1′・3′・4′-oxadiazol-5-ylthio)-5-(1″・1″・3″・3″-tetramethylbutyl)hydroquinone compound-32 2-(1′-phenyltetrazol-5′-ylthio)-5-n-octyloxycarbonylmethylthiohydroquinone compound-33 2-t-dodecylthio-5-(1′ -Phenyltetrazol-5'-ylthio)hydroquinone compound-34 2-(benzoxazol-2'-ylthio)-5
-n-octadecylhydroquinone compound-35 2-(2'-methylphenylthio)6-n-octadecylthio-3-(1'-phenyltetrazol-5''-ylthio)hydroquinone compound-36 2-n-octyl Oxycarbonylmethylthio-3-(1'-phenyltetrazol-5'-ylthio)-6-p-tolylhydroquinone compound-37 2-ethoxycarbonylmethylthio-6-n-
Hexadecylthio-3-(1'-phenyltetrazol-5'-ylthio)hydroquinone compound-38 2-Phenylthio-3-(1'-phenyltetrazol-5'-ylthio)-5-n-dodecylthiohydroquinone compound- 39 2-t-octyl-5-(1'-phenyltetrazol-5'-ylthio)hydroquinone compound-40 2-t-octyl-6-(1'-phenyltetrazol-5'-ylthio)hydroquinone compound- 41 2-n-pentadecyl-5-(1'-phenyltetrazol-5'-ylthio)hydroquinone compound-42 2-n-octadecylthio-2.(X)-bis-
(1'-phenyltetrazol-5'-ylthio)hydroquinone compound-43 2-(4'-methylphenyl)-(X)-(1'-phenyltetrazol-5'-ylthio)hydroquinone compound-44 2-t -octyl-6-(2'-methylthio-
1′・3′・4′-thiodiazol-5′-ylthio)hydroquinone compound-45 2-n-pentadecyl-5-(2′-methylthio-1′・3′・4′-thiadiazol-5′-ylthio)
Hydroquinone compound-46 2-t-octyl-5-(2'-amino-1', 3',
4'-Thiadiazol-5-'-ylthio)hydroquinone compound-47 2-n-hexadecylthio-5-(2'-methylthio-1', 3', 4'-thiadiazol-5'-ylthio)hydroquinone compound-48 2 -t-octyl-5-(2'-n-pentyl-
1′-phenyl-1′・3′・4′-triazole-5′-
ylthio)hydroquinone compound-49 2-(penzothiazole-5'-ylthio)-5-
(1″・1″・3″・3″-tetramethylbutyl)hydroquinone compound-50 2-(penzimidazol-5'-ylthio)-5
-(1″・1″・3″・3″-tetramethylbutyl)hydroquinone compound-51 2-(benzoxazol-5′-ylthio)-5
-(1″·1″·3″·3″-tetramethyl)hydroquinone The compounds used in the present invention are not limited to the above. Hydroquinone derivatives used in the present invention can be obtained by the method described in US Pat. No. 3,379,529. When a heterocyclic compound having a mercapto group represented by the general formula () is added as it is to the heat-developable photosensitive material of the present invention, it has a concentration of 10 ^-6 to 1 mol (preferably 10 ^{- 5} ~ 0.1 mol)
In this case, development is promoted, but if the amount added is too large, development is significantly inhibited. However, when a hydroquinone derivative represented by the general formula () of the present invention, that is, a compound that releases a mercapto group-containing heterocyclic compound when oxidized, is added, development is not inhibited at all even if a large amount is added. It significantly accelerates development and increases sensitivity without causing. The hydroquinone derivative represented by the general formula () can be contained in a light-sensitive material by being dispersed in the same emulsion dispersion together with the dye-donating substance, or it can be separately incorporated in the same emulsion dispersion method as the dye-donating substance. It can also be emulsified and dispersed and incorporated into a light-sensitive material. Furthermore, water or methanol, ethanol,
It can also be dissolved in a water-miscible organic solvent such as acetone or dimethylformamide and added to the coating solution. The hydroquinone derivative of the general formula () according to the present invention is preferably used in an amount of 10 ^-6 to 10 mol per mol of silver.
10 ^-5 to 1 mol can be added. The hydroquinone derivative may be added to the same layer as the silver halide, or may be added to an adjacent layer. In order to stably dissolve, emulsify, coat, etc. the hydroquinone derivative without being oxidized, and to stably preserve the photosensitive material containing the hydroquinone derivative, it is preferable to coexist with a reducing compound. In particular, when the hydroquinone derivative is emulsified and dispersed separately from the dye-donating substance, it is preferable to coexist with a reducing compound. The reducing compound used in the present invention may be an inorganic compound or an organic compound, and can be selected from the group of commonly-called "antioxidants."
Among them, phenol derivatives, especially dihydroxybenzene derivatives, such as pyrocatechols, tocoherols, trihydroxybenzene derivatives, such as pyrogallols, naphthol derivatives, especially dihydroxynaphthalene derivatives and trihydroxynaphthalene derivatives, ascorbic acid derivatives, and reductones. , aromatic amino compounds, hydroxyamino compounds, stannous salts, diothi compounds, and the like are useful. The water-soluble reducing compound used in the present invention can be added as an aqueous solution to a dispersed colloidal aqueous solution of "DIR-hydroquinone derivative". The oil-soluble reducing compound can be dissolved in an organic solvent as a dispersion medium and used in coexistence with the hydroquinone derivative of the general formula (). The reducing compound used in the present invention can also be mixed before the process of synthesizing the hydroquinone derivative of general formula () or before the dispersion process. These compounds are described in U.S. Patent No. 2,360,290, no.
No. 2418613, No. 2675314, No. 2701197, No.
No. 2704713, No. 2728659, No. 2732300, No.
It is described in No. 2735765, No. 2710801, and No. 2816028. U.S. Patent Nos. 3457079 and 3069262;
Japanese Patent Publication No. 43-13496, U.S. Patent No. 2735765, Japanese Unexamined Patent Publication No. 4738-1987, U.S. Patent No. 3432300, No. 3573050
No. 3574627, Japanese Patent Application No. 121454/1980, etc. Compounds according to the invention are described by Gerald Scott.
Atomospheric oxidation and autooxidants,
A book published by Elsevier Publishing Company in 1965, and also by NMEmanuel and Yu N.
Written by Lyaskovskaya, translated into English by KA Allen The
Inhibition of Fat Oxidation Process,
You can choose from the reducing compounds listed in the book published by Pergamon Press in 1967. As the reducing compound used in the present invention, a phenol derivative having an aliphatic group having 8 or more carbon atoms and represented by the general formula () is particularly useful. General formula () In the formula, R ₁ represents a hydrogen atom or a straight chain or branched alkyl group having 8 to 20 carbon atoms, and R ₂ represents a hydrogen atom or a straight chain or branched alkyl group having 8 to 20 carbon atoms. A A' represents a hydrogen atom or a group that can be removed by alkali, such as an acetyl group or an alkoxycarbonyl group. The benzene ring may be substituted with another alkyl group having 8 or less carbon atoms, a halogen atom, an aryl group, a hydroxyl group, or a heterocycle. These compounds are described, for example, in US Pat. No. 2,336,327
No. 2728659, No. 2835579, and Japanese Patent Application Laid-open No. 1972-2128.
This is what is written in the number etc. Specific examples of these compounds are shown below. 2,5-Di-tert-octyl-hydroquinone 2-n-octadecylthio-hydroquinone 2-n-hexadecyl-hydroquinone 2-n-octadecylthio-5-tert-octyl-hydroquinone Hydroquinone 2-(3'-methyl-phenyl )-hydroquinone ascorbic acid ascorbyl palmitate 2,3-dihydroxynaphthalene 7,7'-dimethyl-6,6'-dihydroxy-4,
4,4',4'tetramethylbis-2,2'-spirochroman 2,3,5-trimethylhydroquinone sodium bisulfite and the like. The useful concentration range of these reducing compounds is based on 1 mole of hydroquinone derivative of general formula ().
A particularly useful concentration range is 0.001 molar to 20 times molar.
The amount is 0.01 to 2 moles. The dye image of the present invention refers to multicolor and monochrome dye images, and the monochrome image in this case includes a monochrome image resulting from a mixture of two or more types of dyes. In the image forming method of the present invention, a silver image and a dye can be simultaneously provided in the area corresponding to the silver image by simply heating the image after exposure. That is,
In the color image forming method of the present invention, image exposure is performed, and heat development is performed in a state substantially free of water, whereby the exposed photosensitive silver halide is used as a catalyst to form a bond between the photosensitive silver halide and the reducing dye-donating substance. An oxidation-reduction reaction takes place, producing a silver image in the exposed area. In this step, the dye-donating substance is oxidized by silver halide to become an oxidant, and as a result a hydrophilic mobile dye is released, and a silver image and mobile dye are obtained in the exposed area. At this time, the presence of a dye release aid accelerates the above reaction. A dye image is obtained by moving this mobile dye to, for example, a dye fixing layer. The above is a case where a negative type emulsion is used, but when an autopositive emulsion is used, the process is the same as when a negative type emulsion is used, except that a silver image and mobile dye are obtained in the unexposed areas. . The oxidation-reduction reaction between the photosensitive silver halide and the dye-donating substance of the present invention and the subsequent dye-releasing reaction are characterized in that they occur at high temperatures and in a dry state substantially free of water. Here, "high temperature" refers to a temperature condition of 80°C or higher, and "dry state, which does not substantially contain water" refers to a state in which the system is in equilibrium with the moisture in the air, but there is no water supply from outside the system. . This situation is explained by “The theory of the
photographic process”4th Ed. (Edited by T.
H.James, Macmillan) on page 374. The fact that a sufficient reaction rate is exhibited even in a dry state that does not substantially contain water can be confirmed from the fact that the reaction rate of a sample vacuum-dried for one day at 10 ^-3 mmHg did not decrease. Conventionally, the dye release reaction is thought to be due to attack by a so-called nucleophile, and is usually carried out in a liquid with a high 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. Furthermore, the dye-donating substance of the present invention can undergo a redox reaction with silver halide without the aid of a so-called auxiliary developer. This is an unexpected result based on previous knowledge of wet development at temperatures around room temperature. The above reaction proceeds particularly well in the presence of an organic silver hydrochloride oxidizing agent, resulting in high image density. 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 . ^R10a _and
The total number of carbon atoms in both 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 (). (However, the symbols Ga, X ¹⁰ , R ¹⁰ _a and n have the same meanings as Ga, X ¹⁰ and R ¹⁰ _a n in formula ().) In a more preferred embodiment of what is included in () of the present invention is the reducing substrate (Ra)
is expressed by the following formulas (a) to (c). 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 ) The total carbonity of _p is greater than y. 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 be combined 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 by 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

[Formula] The total number of carbon atoms in the group is 7 or more. Specific examples included in the above (), (a) to (b) are Japanese Patent Applications No. 56-16131, No. 57-650, No. 57
−4043. Formula () and the essential part of formula () are para-(sulfonyl)aminophenol moieties.
Specific examples include US3928312, US4076529,
US Published Patent Application B 351,
673, US4135929, and US4258120, which are also effective as the reducing substrate (Ra) of the present invention. In another further preferred embodiment of the present invention,
The reducing substrate (Ra) is represented by the following formula (). Here, Ballast represents a diffusion-resistant group. Ga represents a hydroxyl group or a hydroxyl group precursor. G ¹ _a represents an aromatic ring and represents a group forming a naphthalene ring together with a benzene ring. n and m represent different integers of 1 or 2. Examples encompassed above are described in US-4053312. The reducing substrates of formulas (), (), (), and () are characterized by containing a heterocycle, and specific examples include US4198235, JP-A-53-46730,
Examples include those described in US4273855.
A specific example of a reducing substrate represented by the formula () is
It is described in US4149892. The following properties are required for the reducing substrate Ra. 1. To be rapidly oxidized by silver halide and to efficiently release a diffusible dye for image formation through the action of a dye release aid. 2. The dye-donating substance is diffusible in a hydrophilic or hydrophobic binder, and only the released dye needs to be diffusible. Therefore, the reducing substrate R must have large hydrophobicity. . 3. Excellent stability against heat and dye release aids, and should not release image-forming dyes until oxidized. 4. Easy to synthesize. Next, a preferred specific example of Ra that satisfies these conditions will be shown. In the examples, NH- represents a linkage with the dye moiety. Dyes that can be used as image-forming dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes, and representative examples are shown for each dye. In addition,
These dyes can also be used in the form of a temporarily shortened wavelength that can be multicolored during development. In the above formula, R ⁵¹ _a to R ⁵⁶ _a each represent 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, a cyano group, a hydroxyl group, or an alkylsulfonylamino group. group, arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen, sulfamoyl group, N-substituted sulfamoyl group, carbamoyl group, Represents a substituent selected from N-substituted carbamoyl group, acyloxyalkyl group, amino group, substituted amino group, alkylthio group, and arylthio group, and the alkyl group and aryl group moiety in these substituents are further halogen atom,
hydroxyl group, cyano group, acyl group, acylamino group,
It may be substituted with an alkoxy group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or a ureido group. Hydrophilic groups include hydroxyl group, carboxyl group, sulfo group, phosphoric acid group, imide group, hydroxamic acid group, quaternary ammonium group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, sulfamoylamino group, substituted Examples include a sulfamoylamino group, a ureido group, a substituted ureido group, an alkoxy group, a hydroxyalkoxy group, and an alkoxyalkoxy group. In the present invention, those whose hydrophilicity is significantly increased by proton dissociation under basic conditions are particularly preferred, including phenolic hydroxyl groups, carboxyl groups, sulfo groups, phosphoric acid groups, imide groups, hydroxamic acid groups, ( (substituted) sulfamoyl group, (substituted) sulfamoylamino group, etc. The characteristics required for image-forming dyes are (1) having a hue suitable for color reproduction, (2) having a large molecular extinction coefficient, and (3) being sensitive to light, heat, and a dye release aid contained in the system. Examples include stability against other additives, and (4) ease of synthesis. Specific examples of preferred image-forming dyes satisfying these conditions are shown below. Here, H ₂ N-SO ₂ represents a bonding site with a reducing substrate. Next, specific examples of preferred dye-providing substances will be shown. In addition to the above-mentioned specific examples, the dye-donating substances of the present invention include US4055428, JP-A-56-12642,
56-16130, 56-16131, 57-650, 57-
4043, US3928312, US4076529, US Published
Patent Application B351673, US4135929,
US4198235, JP-A-53-46730, US4273855,
Compounds described in US4149892, US4142891, US4258120, etc. are also effective. In addition, US4013633, US4156609,
US4148641, US4165987, US4148643,
US4183755, S4246414, US4268625,
US 4245028, JP 56-71072, JP 56-25737, JP
55-138744, 55-134849, 52-106727, 51
Dye-donating substances that emit yellow dyes, such as those described in US Pat. Also
US3954476, US4932380, US3931144,
US3932381, US4268624, US4255509, JP-A-56
-73057, 56-71060, 55-134850, 55-
40402, 55-36804, 53-23628, 52-
Dye-donating substances that release magenta dyes, such as those listed in No. 106727, No. 55-33142, and No. 55-53329, are also effective in the present invention. Also US3929760,
US4013635, US3942987, US4273708,
US4148642, US4183754, US4147544,
US4165238, US4246414, US4268625, JP-A-56
-71061, 53-47823, 52-8827, 53-
Dye-donating substances that release cyan dyes, such as those listed in No. 143323, are also effective in the present invention. Two or more types of dye-donating substances may be used in combination. In this case, two or more types may be used in combination to express the same pigment, and cases in which two or more types are used in combination to express black are also included. The total amount of dye-donating substances is 10 mg/ ^m2 to 15
Suitably, it is used in a range of 20 mg/m ² to 10 g/m ² , preferably in a range of 20 mg/m 2 to 10 g/m ² . Next, the method for synthesizing the dye-donating substance will be described. Generally, the dye-donating substance of the present invention is a reducing substrate.
It is obtained by condensing the amino group of Ra with the chlorosulfonyl group of the image-forming dye. Depending on the type of substrate, the amino group of the reducing substrate Ra can be introduced by reduction of nitro, nitroso, or azo groups or ring opening of benzoxazole, and can be used as a free base or as a salt of an inorganic acid. . On the other hand, the chlorosulfonyl group in the image-forming dye moiety can be derived from the sulfonic acid or sulfonate of the dye by a conventional method, ie, by the action of a chlorinating agent such as phosphorus oxychloride, phosphorus pentachloride, or thionyl chloride. The condensation reaction between the reducing substrate Ra and the image-forming dye D is generally carried out in an aprotic polar solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, acetonitrile, etc. using pyridine, picoline, lutidine, triethylamine, It can be carried out in the presence of an organic base such as diisopropylethylamine at a temperature of 0 to 50°C, and the desired dye-donating substance can usually be obtained in a very good yield. An example of its synthesis is shown below. Synthesis Example 1 Synthesis of 6-hydroxy-2-methylbenzoxazole 306 g of 2,4-dihydroxyacetophenone,
164 g of hydroxyraumine hydrochloride, 328 g of sodium acetate, 1000 ml of ethanol, and 500 ml of water were mixed and heated under reflux for 4 hours. The reaction solution was poured into 10 g of water, and the precipitated crystals were collected to obtain 314 g of 2,4-dihydroxyacetophenone oxime. Dissolve 30g of this oxime in 400ml of acetic acid and heat to 120°C.
Hydrogen chloride gas was blown into the mixture for 2 hours while heating and stirring. After cooling, the precipitated crystals were collected and washed with water to obtain 17 g of 6-hydroxy-2-methylbenzoxazole. Synthesis Example 2 Synthesis of 6-hexadecyloxy-2-methylbenzoxazole 18.0 g of 6-hydroxy-2-methylbenzoxazole synthesized in Synthesis Example 1, 36.9 g of 1-bromohexadecane, 24.0 g of potassium carbonate, N,N- 120 ml of dimethylformamide was stirred at 90°C for 4.5 hours. The solid was separated from the reaction solution, and the solution was poured into 500 ml of methanol. Take the precipitated crystals and
45.0 g of -hexadecyloxy-2-methylbenzoxazole was obtained. Synthesis Example 3 Synthesis of 2-acetylamino-5-hexadecyloxyphenol 6-hexadecyloxy-2- obtained in Synthesis Example 2
Methylbenzoxazole 111g, ethanol
Mix 1300ml, 33% hydrochloric acid 110ml, and 550ml water, 55~
The mixture was stirred at 60°C for 4 hours. After cooling, the precipitated crystals were collected to obtain 113 g of 2-acetylamino-5-hexadecyloxyphenol. Synthesis Example 4 Synthesis of 2-acetylamino-4-t-butyl-5-hexadecyloxyphenol 30.0 g of 2-acetylamino-5-hexadecyloxyphenol obtained in Synthesis Example 3, Amberlyst 15 (Rohm, USA) & Haas Inc. registered trademark)
20.0 g and 300 ml of toluene were mixed, and while stirring and heating at 80 to 90°C, isobutene was blown into the mixture for 5 hours. After removing the solid, the liquid was concentrated and 350 ml of n-hexane was added to the residue to precipitate crystals.
23.5 g of 2-acetylamino-4-t-butyl-5-hexadecyloxyphenol was obtained. Synthesis Example 5 Synthesis of 2-amino-4-t-butyl-5-hexadecyloxyphenol 2-acetylamino-4-t- obtained in Synthesis Example 4
Butyl-5-hexadecyloxyphenol 23.0
g, 120 ml of ethanol, and 96 ml of 35% hydrochloric acid,
The mixture was stirred and refluxed for 5 hours. After cooling the reaction solution, the precipitated crystals were collected to obtain 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride.
23.2g was obtained. Synthesis example 6 4-t-butyl-5-hexadecyloxy-2
Synthesis of -[2-(2-methoxyethoxy)-5-nitrobenzesulfonylamino]phenol 2-amino-4-t-butyl- obtained in Synthesis Example 5
5-hexadecyloxyphenol hydrochloride 4.4g
and 3.1 g of 2-(2-methoxyethoxy)-5-nitrobenzenesulfonyl chloride were dissolved in 12 ml of N,N-dimethylacetamide, and 2.5 g of pyridine
ml and then stirred at 25°C for 1 hour. When the reaction solution was poured into dilute hydrochloric acid, an oily substance precipitated. When 30 ml of methanol was added to this oil, it crystallized and was collected. Yield 4.5g. Synthesis Example 7 Synthesis of 2-[5-amino-2-(2-methoxyethoxy)benzenesulfonylamino]-4-t-butyl-5-hexadecyloxyphenol 10g of the compound obtained in Synthesis Example 6 above was added to 60% ethanol.
Approximately 0.5 g of 10% palladium-carbon catalyst dissolved in ml
After adding hydrogen, pressurize hydrogen to 55Kg/cm ² and
Stirred at ℃ for 6 hours. Next, the catalyst was removed while hot, and when it was allowed to cool, crystals precipitated and were collected. Yield 7.5g. Synthesis Example 8 Synthesis of 3-cyano-4-[4-(2-methoxyethoxy)-5-sulfophenylazo]-1-phenyl-5-pyrazolone In a solution of 8.0 g of sodium hydroxide and 200 ml of water, 5-
Add 49.4 g of amino-2-(2-methoxyethoxy)benzenesulfonic acid, and add sodium nitrite.
A 13.8g aqueous solution (50ml) was added. Concentrated hydrochloric acid 60% separately
ml and 400 ml of water was prepared, and the above solution was added dropwise to this at 5°C or lower. Thereafter, the reaction was completed by stirring at 5° C. or lower for 30 minutes. Separately, prepare a solution of 16.0 g of sodium hydroxide, 200 ml of water, 33.0 g of sodium acetate and 200 ml of methanol, add 37.0 g of 3-cyano-1-phenyl-5-pyrazolone, and add the diazo solution prepared above at 10°C. dripped. After the completion of the dropwise addition, the mixture was stirred for 30 minutes at 10° C. or lower, and then for 1 hour at room temperature. The precipitated crystals were collected, washed with 200 ml of acetone, and air-dried. Yield 52.0g mp263-265℃ Synthesis Example 9 3-cyano-4-[4-(2-methoxyethoxy)-5-chlorosulfonylphenylazo]-1
-Synthesis of phenyl-5-pyrazolone 3-cyano-4-[(4-methoxyethoxy-5-sulfophenylazo]-1 obtained in Synthesis Example 8 above)
-Phenyl-5-pyrazolone 51.0g, acetone
N,
50ml of N-dimethylacetamide was added dropwise at below 50°C. After the addition, the mixture was stirred for about 1 hour and gradually poured into 1.0 ml of ice water. After separating the precipitated crystals, they were washed with 100 ml of acetonitrile and air-dried. Yield 46.7g mp181-183℃ Synthesis Example 10 Synthesis of dye-donating substance (1) 2-[5-amino-2-(2-methoxyethoxy)benzenesulfonylamino-4 obtained in Synthesis Example 7
-t-butyl-5-hexadecyl oxyphenol
6.3g was dissolved in 30ml of N,N-dimethylacetamide to obtain 3-cyano-4-[4-(2
-methoxyethoxy)-5-chlorosulfonylphenylazo]-1-phenyl-5-pyrazolone 4.6
Then, 5 ml of pyridine was added. After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallization from N,N-dimethylacetamide-methanol gave 7.5 g. mp189-191℃ Synthesis Example 11 Synthesis of dye-donating substance (2) 2-[5-Amino-2-(2-methoxyethoxy)benzenesulfonylamino-4 obtained in Synthesis Example 7
Dissolve 6.3 g of -t-butyl-5-hexadecyloxyphenol in 30 ml of N,N-dimethylacetamide. 5.0 g of chlorosulfonylphenyl-5-pyrazolone was added, followed by 5 ml of pyridine. After stirring at room temperature for 1 hour, the reaction solution was poured into dilute hydrochloric acid, and the precipitated crystals were collected. Recrystallize with acetonitrile
8.4g was obtained. mp144-149℃ Synthesis Example 12 Synthesis of dye-donating substance (10) 4.4 g of 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride and 4-[3-
Chlorosulfonyl-4-(2-methoxyethoxy)
[phenylazo]-2-(N,N-diethylsulfamoyl)-5-methylsulfonylamino-1-naphthol (6.5 g) was dissolved in N,N-dimethylacetamide.
The solution was dissolved in 20 ml and 4.2 ml of pyridine was added. 1 hour 25
After stirring at °C, the reaction solution was poured into dilute hydrochloric acid. The precipitated solid was collected and purified by silica gel column chromatography (eluted with a mixed solvent of chloroform-ethyl acetate (2:1)). Yield: 5.2g. Synthesis Example 13 Synthesis of dye-donating substance (17) Dissolve 11.6 g of 2-amino-4-t-butyl-5-hexadecyloxyphenol hydrochloride in 100 ml of N,N-dimethylacetamide, and add 12 ml of pyridine.
added. This was added to 5-(3-chlorosulfonylbenzenesulfonylamino)-2-(N-t-butylsulfamoyl)-4-(2-methylsulfonyl-
4-nitrophenylazo)-1-naphthol 20g
added. After stirring for 1 hour, the mixture was poured into 500 ml of ice water, and the precipitate was recrystallized from isopropyl alcohol-acetonitrile (1:1) to obtain 6.8 g. Synthesis Example 14 Synthesis of dye-donating substance (19) 2-[5-amino-2-(2-methoxyethoxy)benzenesulfonylamino]-4-t-butyl-5-hexadecyloxyphenol 31.5 g,
39.1 g of 5-(3-chlorosulfonylbenzenesulfonylamino)-4-(2-methylsulfonyl-4-nitrophenylazo)-1-naphthol with N,
It was dissolved in 100 ml of N-dimethylacetamide, and 21 ml of pyridine was added. After stirring for 80 minutes, methanol 250
ml and 100 ml of water were added. The precipitated resinous material solidified after a while and was removed. This was recrystallized from a toluene-methanol-water (16:4:3) mixed system to obtain 41.5 g. Synthesis Example 15 Synthesis of Compound 40 (a) Synthesis of 2,5-dihydroxy-4-t-butylacetophenone 83 g of t-butylhydroquinone was dissolved in 400 ml of acetic acid, and boron trifluoride ( BF ₃ ) was introduced for about 3 hours. After the reaction 1
The precipitated viscous solid was collected by pouring it into ice water. This solid was dissolved in 600 ml of 2N-NaOH and the insoluble portion was removed. The solution was made acidic with dilute hydrochloric acid, and the precipitated crystals were collected, washed with water, and then recrystallized from aqueous methanol. Yield 68g (65%) (b) Synthesis of 2,5-dihydroxy-4-t-butylacetophenone, oxime 21g of the ketone obtained in (a) above was dissolved in ethanol 70g.
ml, heat and dissolve with 24g of sodium acetate, and add 12g of hydroxylamine hydrochloride while stirring.
A solution dissolved in 70 ml of water was added and refluxed for about 1 hour. After the reaction was completed, it was poured into 500 ml of ice water to collect precipitated crystals and recrystallized from benzene-hexane. Yield 17g (76%) (c) Synthesis of 6-t-butyl-5-hydroxy-2-methylbenzoxazole Dissolve 14g of the oxime obtained in (b) above in 100ml of acetic acid and introduce dry hydrochloric acid gas while heating. death,
Refluxed for 1.5 hours. After the reaction was completed, the mixture was poured into 500 ml of ice water, and the precipitated crystals were collected and washed with water. Yield 9g (70%) (d) 6-t-butyl-5-hexadecyloxy-
Synthesis of 2-methylbenzoxazole 6.9 g of the benzoxazole obtained in (c) above was dissolved in 50 ml of dimethylformamide and stirred with 8 g of anhydrous potassium carbonate and 11 g of hexadecyl bromide at 80 to 90°C for 6 hours. After the reaction is complete,
After removing inorganic substances, 150 ml of methanol was added to the solution, and the mixture was cooled on ice to precipitate crystals. By taking this, the title compound was obtained. Yield: 8.8 g (62%) (e) Synthesis of 2-amino-5-t-butyl-4-hexadecyloxyphenol hydrochloride 7.3 g of the benzoxazole compound obtained in (d) above
The mixture was refluxed for 3 hours with 30 ml of ethanol and 20 ml of concentrated hydrochloric acid. After the reaction was completed, the mixture was allowed to cool, and the precipitated crystals were collected, washed with water, and then washed with acetone. Yield: 6.9 g (92%) (f) Synthesis of Compound Example 40 6 g of the hydrochloride obtained in (d) above and 8.8 g of the sulfonyl chloride of the structural color shown below were dissolved in 50 ml of dimethylacetamide, 4 ml of pyridine was added, and the mixture was heated at room temperature. The mixture was stirred for 1 hour. After the reaction was completed, the precipitated crystals were poured into dilute hydrochloric acid and washed with water. After drying, the residue was purified by silica gel chromatography to obtain 2.2 g of the title compound, which was essentially one component. Dye sulfonichloride: Synthesis Example 16 Synthesis of dye-donating substance (42) In the above Synthesis Example 15(d), 6-t-butyl-5
-6-t-octyl-5-hydroxy-2 instead of hydroxy-2-methylbenzoxazole
O-hexadecylation was performed using -methylbenzoxazole. Then Synthesis Example 15(e) and (f)
A dye-donating substance (42) was obtained by the same treatment as above. The dye-donating substance of the present invention is disclosed in US Pat. No. 2,322,027.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in the above. 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) ,
High-point organic solvents such as benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate) , or boiling point approximately 30℃ to 160℃
After dissolving in an organic solvent 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., it is converted into a hydrophilic colloid. distributed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. 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 amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less per 1 g of the dye-providing substance used. In the present invention, an auxiliary developer can be used as necessary. The auxiliary developer is oxidized by a silver halide and/or an organic silver salt oxidizing agent, and its oxidized product has the ability to oxidize the reducing substrate Ra in the dye-donating substance. Useful auxiliary developers include alkyl-substituted hydroquinones such as hydroquinone, t-butylhydroquinone, and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, and alkyl-substituted hydroquinones such as methoxyhydroquinone. There are substituted hydroquinones and polyhydroxybenzene derivatives such as methylhydroxynaphthalene. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, N,N'-
Hydroxylamines such as di-(2-ethoxyethyl)hydroxylamine, 1-phenyl-3
Pyrazolidones such as -pyrazolidone, 4-methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone, reductones, and hydroxytetronic acids are useful. Auxiliary developers can be used in a range of concentrations. The useful concentration range is 0.0005 times molar to 20 times molar relative to silver, and particularly useful concentration ranges are:
It is 0.001 times mole to 4 times mole. Silver halides used in the present invention include silver chloride, silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, and silver iodide. In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, particularly preferred silver halide is one containing silver iodide crystals in part of the grains. That is, it is particularly preferable that a pattern of pure silver iodide appears when the silver halide is subjected to X-ray diffraction. Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary silver halide emulsions, silver halide grains form a complete mixed crystal. For example, in a silver iodobromide emulsion, the X
When line diffraction is measured, patterns of silver iodide crystals and silver bromide crystals do not appear, but X-ray patterns appear at positions corresponding to the mixing ratio. Particularly preferred silver halides in the present application include silver chloroiodide, silver iodobromide, which contain silver iodide crystals in their grains, and therefore exhibit an X-ray pattern of silver iodide crystals.
Silver chloroiodobromide. 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 grains used in the present invention is preferably from 0.001 .mu.m to 10 .mu.m, more preferably from 0.001 .mu.m to 5 .mu.m. The silver halide used in the present invention may be used as it is, but it may also be compounded with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, etc., gold, platinum, palladium, rhodium, iridium, etc., and tin halide. Chemical sensitization may be achieved by the use of reducing agents such as or combinations thereof. For more information, see “The
Theory of tho Photographic Process” 4th edition,
TH James, Chapter 5, pages 149-169. In a particularly preferred embodiment of the present invention, an organic silver salt oxidizing agent is coexisted, and the temperature is preferably 80°C or higher in the presence of exposed silver halide.
When heated to 100° C. or higher, it reacts with the image-forming substance or a reducing agent coexisting with the image-forming substance if necessary to form a silver image. By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density. The silver halide used in this case does not necessarily have the characteristic of containing pure silver iodide crystals when silver halide is used alone, and all silver halides known in the art may be used. be able to. Examples of such organic silver salt oxidizing agents include the following. It is a silver salt of an organic compound having a carboxyl group, and representative examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. 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, silver salts of palmitic 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,
These include silver salts of adipic acid, silver salts of sebacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, and silver salts of camphoric acid. Furthermore, 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 salt of 3,5-dihydroxybenzoic acid, silver salt of o-methylbenzoic acid, silver salt of m-methylbenzoic acid,
Silver salt of p-methylbenzoic acid, silver salt of 2,4-dichlorobenzoic acid, silver salt of acetamidobenzoic acid, p
-Silver salts of substituted benzoic acids such as silver salts of phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, silver salts of phthalic acid, silver salts of terephthalic acid, silver salts of salicylic acid, silver salts of phenyl acetic acid. , silver salt of pyromellitic acid, 3-carboxymethyl-4-methyl-4-thiazoline-2 described in U.S. Pat. No. 3,785,830
-silver salts such as thione, silver salts of aliphatic carboxylic acids having thioether groups as described in US Pat. No. 3,330,663, and the like. In addition, there are compounds having a mercapto group or a thione group, and silver salts of derivatives thereof. For example, 3-mercapto-4-phenyl-1,
Silver salt of 2,4-triazole, Silver salt of 2-mercaptobenzimidazole, 2-mercapto-5-
Unexamined patent publications such as silver salt of aminothiadiazole, silver salt of 2-mercaptobenzthiazole, silver salt of 2-(s-ethylglycolamido)benzthiazole, s-alkyl (alkyl group having 12 to 22 carbon atoms) thioglycol acetic acid, etc. Silver salt of thioglycolic acid, silver salt of dithiocarboxylic acid such as silver salt of dithioacetic acid, silver salt of thioamide, 5-
silver salt of carboxy-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole,
Mercaptooxadiazole silver salt, US patent
Silver salts described in 4123274, for example 1, 2,
Silver salt of 3-amino-5-benzylthio 1,2,4-triazole, which is a 4-mercaptotriazole derivative, 3- as described in U.S. Pat. No. 3,301,678
It is a silver salt of a thione compound such as a silver salt of (2carboxyethyl)-4-methyl-4-thiazoline-2thione. In addition, there are silver salts of compounds having imino groups. For example, silver salts of benzotriazole and its derivatives described in Japanese Patent Publications No. 44-30270 and No. 45-18416, silver salts of benzotriazole, silver salts of alkyl-substituted benzotriazoles such as methylbenzotriazole silver salt, 5-chlorobenzo Silver salts of halogen-substituted benzotriazoles such as silver salts of triazoles, silver salts of carboimidobenzotriazoles such as silver salts of butylcarboimidobenzotriazoles, 1,2,4-triazoles described in US Pat. No. 4,220,709, and Examples include silver salts of 1-H-tetrazole, silver salts of carebazole, silver salts of saccharin, and silver salts of imidazole and imidazole derivatives. Also Research Day Closure Vol170,
Organometallic salts such as silver salts and copper stearate described in No. 17029, June 1978 are also organometallic salt oxidizing agents that can be used in the present invention. Two or more kinds of organic silver salt oxidizing agents can be used. Although the thermal development process during heating of the present invention is not fully understood, 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,
“The Theory of the
Photographic Process” 3rd Edition page 105~
It is described on page 148. By heating the photosensitive material, a reducing agent, in the case of the present invention, a dye-donating substance, uses latent image nuclei as a catalyst to reduce silver halide or silver halide and an organic silver salt oxidizing agent to produce silver, itself is oxidized. This oxidized dye-donating substance is cleaved to release the dye. For information on how to make these silver halides and organic silver salt oxidizing agents, and how to mix both, please refer to Research Disclosure No. 17029, JP-A-50-32928, JP-A-51-42529, U.S. Patent No. 3,700,458, Japanese Patent Application Publication 1973-
No. 13224 and JP-A-50-17216. In the present invention, the total coating amount of photosensitive silver halide and organic silver salt oxidizing agent is 50 mg or more in terms of silver.
10g/ ^m2 is suitable. 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 contained alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, natural substances such as starch, polysaccharides such as gum arabic, and polyvinylpyrrolidone. , synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds, which increase the dimensional stability of photographic materials, especially in the form of latexes. 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 dye, hemicyanine dye,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the basic heterocyclic nuclei commonly used for cyanine dyes can be applied to these dyes. That is, pyrroline nucleus,
Oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nucleus in which aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus , indole, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. 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-thioxazoline-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, as a nucleus having a ketomethylene structure. A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful ring-enhancing dyes include, for example, the German patent
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748, U.S. Patent No.
No. 2503776, No. 2519001, No. 2912329, No. 2519001, No. 2912329, No.
No. 3656959, No. 3672897, No. 3694217, No.
No. 4025349, No. 4046572, British Patent No. 1242588,
Examples include those described in Japanese Patent Publication Nos. 44-14030 and 52-24844. These ring-enhancing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
Typical examples are U.S. Patent No. 2688545, U.S. Patent No. 2977229,
3397060, 3522052, 3527641, 3527641, 3522052, 3527641,
No. 3617293, No. 3628964, No. 3666480, No.
No. 3672898, No. 3679428, No. 3703377, No. 3672898, No. 3679428, No. 3703377, No.
No. 3769301, No. 3814609, No. 337862, No.
4026707, British Patent No. 1344281, British Patent No. 1507803,
Special Publication No. 43-4936, No. 53-12375, Japanese Patent Publication No. 52-
No. 110618 and 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.,
2933390 and 3635721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3743510), cadmium salts, azaindene compounds, and the like. US patent
No. 3615613, No. 3615641, No. 3617295, No. 3615613, No. 3615641, No. 3617295, No.
The combination described in No. 3635721 is particularly useful. The support used in the present invention is one that can withstand the 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. Contains film or resin materials. Polyesters described in US Pat. No. 3,634,089 and US Pat. No. 3,725,070 are preferably used. Various dye release aids can be used in the present invention. What is a dye-releasing aid? A dye-releasing agent is one that promotes the redox reaction between a photosensitive silver halide and/or organic silver salt oxidizing agent and a dye-donating substance, or that aids in the oxidized dye-donating substance in the subsequent dye-releasing reaction. A base or a base precursor is used as a substance that can act nucleophilically to promote dye release. In the present invention, it is particularly advantageous to use these dye release aids to accelerate the reaction. Examples of preferred bases include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted aromatic amines and bis[ Examples include p-(dialkylamino)phenyl]methanes. U.S. Pat. No. 2,410,644 describes tetramethylammonium betaine iodide and diaminobutane dihydrochloride, and U.S. Pat. No. 3,506,444 describes organic compounds containing amino acids such as urea and 6-aminocaproic acid, which are useful. The base precursor releases a basic component when heated. Examples of typical base precursors are listed in British Patent No.
Described in No. 998949. Preferred bases are salts of carboxylates and organic bases; useful carboxylic acids include trichloroacetic acid and trifluoroacetic acid; useful bases include guanidine, piperidine, morpholine, p-toluidine, and 2-picoline. Guanidine trichloroacetic acid, described in US Pat. No. 3,220,846, is particularly useful. Aldonamides described in JP-A-50-22625 are preferably used because they decompose at high temperatures to produce bases. These dye release aids can be used in a wide variety of ways. A useful range is 50% by weight or less, more preferably from 0.01% to 40% by weight, based on the weight of the coated dry film of the light-sensitive material. In the heat-developable color light-sensitive material of the present invention, it is advantageous to use a compound represented by the following general formula because development is accelerated and dye release is also promoted. [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
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 ,}

Examples include [Formula]. The above compounds can be used in a wide range of applications. A useful range is 20% by weight or less, more preferably 0.1 to 15% by weight of the dry coated film of the light-sensitive material. 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 were patented in Japan in 1970.
−NH ₄ Fe (SO ₄ ) ₂・12H ₂ O described in Publication No. 88386
etc. are useful. Further, in the present invention, it is possible to use a compound that activates the development and stabilizes the image at the same time. Among them, isothiuroniums represented by 2-hydroxyethylisothiuronium trichloroacetate described in U.S. Patent No. 3301678, 1,8-(3,6-dioxaoctane)bis(isothiuronium・Bisisothiuroniums such as trifluoroacetate),
Thiol compounds disclosed in West German Patent No. 2162714, 2-amino-2- described in U.S. Patent No. 4012260
Thiazolium compounds such as thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiazolium trichloroacetate,
Bis(2-amino-
Compounds having α-sulfonylacetate as an acidic moiety such as 2-thiazolium)methylenebis(sulfonylacetate) and 2-amino-2-thiazolium phenylsulfonylacetate, as an acidic moiety described in U.S. Pat. No. 4,088,496. Compounds having 2-carboxycarepoxyamide are preferably used. In the present invention, a hot solvent can be contained. As used herein, a "thermal solvent" is a non-hydrolyzable organic material that is solid at ambient temperature but exhibits mixed melting points with other components at or below the heat treatment temperature used. Useful examples of the thermal solvent include a compound that can serve as a solvent for a developer, and a compound that is a substance with a high dielectric constant and is known to accelerate the physical development of silver salt. 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,
Monostearin, -SO ₂ -, high dielectric constant compounds having -CO- groups, 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-1,1-dioxide, 1,10-decanediol described in Research Disclosure Magazine, December 1976 issue, pages 26-28,
Methyl anisate, biphenyl suberate, and the like are preferably used. In the case of the present invention, since the dye-providing substance is colored, it is not so necessary to incorporate anti-irradiation or anti-halation substances or dyes into the light-sensitive material. −3692 publication, U.S. Patent No. 3253921,
Filter dyes and absorbent substances described in specifications such as No. 2527583 and No. 2956879 can be contained. Preferably, these dyes are thermally decolorizable, such as those described in U.S. Pat. No. 3,769,019, U.S. Pat.
Dyes such as those described in No. 3,615,432 are preferred. The photosensitive material used in the present invention may 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 layer, etc., as necessary. It can contain a chestnut layer and the like. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, 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 non-ionic compounds such as alkyleamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), aliphatic esters of polyhydric alcohols, alkyl esters of sugars, etc. surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, Acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants containing; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts Cationic surfactants such as heterocyclic quaternary ammonium salts such as , pyridinium, imidazolium, 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
volume 1.Nonionic Surfactants (Edited by
Martin J. Schick, Marcel Dekker Inc.1967),
Surface Acive Ethylene Oxide Adducts
(Schoufelds.N, Pergamon Press 1969), and the nonionic surfactants described in these documents that meet 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 light-sensitive 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 B 36 (1953),
USP2648604, USP3671247, Special Publication Showa 44-30074,
It is described in Special Publication No. 44-9503, etc. In the photographic light-sensitive material of the present invention, an inorganic or organic hardening agent may be contained in the photographic emulsion layer and the hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane etc.), activated vinyl compounds (1,3,5-
triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucochloric acid, Cofenoxychloroic acid, etc.), etc. can be used alone or in combination. “Research Disclosure” for various additives
Additives such as plasticizers, sharpness improving dyes, AH
These include dyes, sensitizing dyes, matting agents, 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 U.S. Patent No.
A light-sensitive material can be prepared by coating on a support using various coating methods such as the hopper coating method described in No. 3,681,294 and drying. 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. Various exposure means can be used in the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for normal color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, and
CRT light sources, fluorescent tubes, light emitting diodes, etc. can be used as light sources. 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 done by overlaying the original drawing by contact printing, by reflection printing, or by enlarging printing. In addition, images taken with video cameras and image information sent from television stations can be directly processed.
It is also possible to output the image to a CRT or FOT, form the image on a heat-developable material using a contact lens or a lens, and then print it. Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means or display means in various devices. this
It is difficult to create an LED that effectively emits blue light. In this case, to play a color image,
Three types of LEDs that emit green, red, and infrared light may be used, and the parts of the sensitive material that are sensitive to these lights 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 above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After reading the information using a light-receiving element such as a CCD and storing it in the memory of a computer, processing this information as necessary and performing so-called image processing, this image information is reproduced on a CRT and used as an image-like light source. There is also a method of directly causing the three types of LEDs to emit light based on the processed information. In the present invention, after exposure of the photosensitive material, the resulting latent image is heated by heating the element at a moderately elevated temperature, e.g., from about 80°C to about 250°C for about 0.5 seconds to about 300 seconds. It can be developed by
As long as the temperature is within the above range, either high or low temperatures can be used by increasing or shortening the heating time. A temperature range of about 110°C to about 160°C is particularly useful. The heating means may be a simple hot plate, an iron, a hot roller, a heating element using carbon or titanium white, or the like. In the present invention, a specific method for forming a color image by heat development is to move a hydrophilic mobile dye. To this end, the light-sensitive material of the present invention comprises a light-sensitive layer () containing at least silver halide, optionally an organic silver hydrochloride oxidizing agent and a dye-donating substance which is also its reducing agent, and a binder on a support; It is composed of a dye fixing layer () that can receive the hydrophilic and diffusible dye formed by the () layer. The above-mentioned photosensitive layer () and dye fixing layer () are:
They may be formed on the same support or on separate supports. The dye fixing layer ( ) and the photosensitive layer ( ) can also be peeled off. For example, it is possible to carry out uniform heat development after imagewise exposure, and then peel off the dye fixing layer () or the photosensitive layer. When the fixing material and the fixing material coated on the support are formed separately, the light-sensitive material can be imagewise exposed and heated uniformly, and then the fixing material can be overlapped to transfer the mobile dye to the fixing layer (2). 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. The dye fixing layer ( ) can contain, for example, a dye mordant for dye fixation. Various mordants can be used as the mordant, and polymer mordants are particularly useful. In addition to the mordant, a base, a chloride precursor, etc., and a hot solvent may be included. Especially the photosensitive layer () and the dye fixing layer ()
It is particularly useful to include a base, a base precursor, in the fixed layer () when the base and base precursor are formed on separate supports. The polymer mordants used in the present invention are polymers containing secondary and tertiary amino groups, polymers having nitrogen-containing heterocyclic moieties, polymers containing these quaternary cation groups, etc., and have a molecular weight of 5,000 to 200,000, particularly 10,000 to 10,000. 50,000. For example, US Patent No. 2548564, US Patent No. 2484430, US Patent No.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in U.S. Patent Nos. 3148061 and 3756814;
Polymer mordants capable of crosslinking with gelatin etc. disclosed in US Pat. No. 3859096, US Pat.
No. 2798063, Japanese Unexamined Patent Publication No. 115228, No. 54-
Aqueous sol-type mordant disclosed in No. 145529, No. 54-126027, etc.; Water-insoluble mordant disclosed in U.S. Pat.
A reactive mordant capable of forming a covalent bond with the dye disclosed in the specification of No. 4168976 (Japanese Unexamined Patent Publication No. 137333/1983);
No. 3642482, No. 3488706, No. 3557066, No.
No. 3271147, No. 3271148, JP-A-50-71332,
No. 53-30328, No. 52-155528, No. 53-125,
The mordant disclosed in the specification of 53-1024 can be mentioned. Other mordants described in US Pat. No. 2,675,316 and US Pat. No. 2,882,156 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) A group that has a quaternary ammonium group and can be co-supplied with gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylesulfonyl group, pyridiniumpropionyl group, vinylcarbonyl group, alkylsulfonoxy group, etc.) For example, a polymer with (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 (eg, bisalkanesulfonate, bisarenesulfonate).

[Formula] 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,
Alternatively, at least two of R ^b ₃ to R ^b ₅ 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 7 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, P R ^b ₁ , R ^b ₂ , R ^b ₃ : Alkyl group, cyclic hydrocarbon group, or 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)

[Formula] or

[Formula]
Water-insoluble polymer having 3 or more R ^b ₁ , R ^b ₂ , R ^b ₃ : Each represents an alkyl group, and the total number of carbon atoms in 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 . The dye fixing layer () may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided over 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 typical fixative 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. A dye transfer aid can be used to transfer the dye from the photosensitive layer to the dye fixed layer. Dye transfer aids include water, caustic soda, caustic potash,
A basic aqueous solution containing 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 as crystal water or microcapsules. Hydrophilic heat solvents can also be used as dye transfer aids. That is, the dye can be transferred from the photosensitive layer to the dye fixing layer by heating in the presence of a hydrophilic hot solvent. The heating for transferring the mobile dye may be performed simultaneously with the heat development or after the heat development is completed. The hydrophilic thermal solvent is a compound that is solid at room temperature but becomes liquid when heated;
It is defined as a compound with an organic property value>1 (preferably 2) and a solubility in water at room temperature of 1 or more. Here, inorganic and organic are concepts for predicting the properties of compounds, and the details are, for example,
It is described in Chemistry Area 11, page 719 (1957).
The molecular weight of the hydrophilic heat solvent is preferably small;
It is about 200 or less, more preferably about 100 or less. 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 aid the movement of dyes upon heating, but if we also consider the heat resistance of the photosensitive material, we need a hydrophilic thermal solvent to The melting point is 40℃
-250°C, preferably 40°C - 200°C, more preferably 40°C - 150°C. It is sufficient that the hydrophilic thermal solvent can substantially assist the movement of the hydrophilic dye generated by heat development to the dye fixing layer, so it can not only be contained in the dye fixing layer, but also be included in the photosensitive layer. A hydrophilic heat solvent can be contained in a photosensitive material such as, in both a dye fixing layer and a photosensitive layer, or in a photosensitive material or in an independent dye fixing sheet having a dye fixing layer. It is also possible to provide an independent layer. 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. Examples of the hydrophilic heat solvent include ureas, pyridines, amides, sulfonamides, imides,
Mention may be made of alcohols, oximes, and other heterocycles. These hydrophilic heat solvents can be used alone or in combination of two or more. The hydrophilic thermal solvent is used in an amount of 10 to 300% by weight, preferably 20 to 200% by weight, particularly preferably 30% by weight of the total coating thickness excluding the hydrophilic thermal solvent in the photosensitive material or dye fixing material. It can be used in a range of 150% by weight. <Example of Preparation of Photosensitive Material> Preparation of Photosensitive Materials D-1 to D-4 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. 5 g of magenta dye-donating substance (10), 0.5 g of compound-3 of the present invention, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate, and tricreasyl phosphate (TCP) as a surfactant. Weigh out 5g, add 20ml of ethyl acetate,
The mixture was heated to about 60°C to dissolve and form a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, use a homogenizer for 10 minutes.
Dispersion was performed at 10,000 rpm to prepare magenta dye-providing substance dispersion-1. Further, the photosensitive layer contains (a) 20 g of silver iodobromide emulsion, (b) 10 g of silver benzotriazole emulsion, (c) dye-donating substance (10) and compound-3 of the present invention.
gelatin dispersion - 33g (d) 2.5% aqueous solution of compound (A) with the following structure 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% gelatin aqueous solution (h) 5 ml of 10% geanidine trichloroacetic acid solution in ethanol (i) 4 ml of 10% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (j) A mixture of 56 ml of water was applied onto the photosensitive layer to a wet film thickness of 25 μm, and then dried.
1 was produced. Photosensitive material D-2 was prepared in exactly the same manner as photosensitive material D-1 except that (b) 10 g of silver benzotriazole was replaced with 5 g of silver iodobromide emulsion and 5 ml of water. In producing photosensitive materials D-1 and D-2, photosensitive materials D-1 and D-2 were prepared in exactly the same manner as photosensitive materials D-1 and D-2, except for excluding compound-3 of the present invention.
3 and D-4 were produced. <Example of preparation of dye fixing material> Preparation of dye fixing materials R-1 and 2 Poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (methyl acrylate and vinylbenzylammonium chloride) The ratio is 1:1) 10g
100g 10% lime processed gelatin dissolved in 200ml water
was mixed evenly. This mixed solution was uniformly applied to a wet film thickness of 90 μm on a paper support laminated with polyethylene dispersed with titanium dioxide and dried. The sample prepared in this way was dye-fixed material R.
-1. On top of this dye fixing material R-1, the following (k)
After mixing and dissolving (o), it was applied uniformly to a wet film thickness of 60 μm and dried. Hereinafter, this second layer will be referred to as a hydrophilic thermal solvent. (k) Urea (hydrophilic heat solvent) 4g (l) Water 10ml (m) Polyvinyl alcohol (saponification degree 98%)
10% by weight aqueous solution 12g (n) Compound with the following structure 100mg (o) 0.5 ml of 5% aqueous solution of sodium dodecylbenzenesulfonate The sample thus prepared is referred to as dye fixing material R-2. Example 1 Photosensitive materials D-1 to D-4 were imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb.
Thereafter, it was heated uniformly for 20 seconds on a heat block heated to 140°C. Next, the dye fixing material is soaked in water, and the film surface of the wetted dye fixing material R-1 is brought into contact with the film surface of the photosensitive materials D-1 to D-4 that have been heat-treated. Overlaid. After heating for 6 seconds on a heat block at 80° C., the dye-fixing material was peeled off from the light-sensitive material, and a negative magenta color image was obtained on the dye-fixing material. The density of this negative image against green light was measured using a Macbeth reflection densitometer (RD519).
The results measured using this are shown in the table below.

[Table] From the above results, it was found that Compound-3 of the present invention has a remarkable development accelerating effect. Example 2 The same method as used for photosensitive material D-1 was used except that the compound of the present invention listed in the table below was used in place of the compound-3 of the present invention used in photosensitive material D-1 in Photosensitive Material Preparation Example. Photosensitive materials D-5 to D-10 were produced. Photosensitive materials D-5 to D-10 and D-3 were processed in exactly the same manner as in Example-1, and the results shown in the table below were obtained. The amount of the compound of the present invention used is shown in the table below.

[Table] From the above results, it was found that the compound of the present invention has a remarkable development accelerating effect. Example 3 Photosensitive material D-1 in Photosensitive Material Preparation Example except that yellow dye-donating substance (33) and cyan dye-donating substance (48) were used instead of magenta dye-donating substance 10. Photosensitive materials D-11 and D-12 were produced in exactly the same manner as material D-1. For comparison, photosensitive materials D-13 and D-14, which do not use the compound of the present invention, were prepared in the same manner as photosensitive materials D-11 and D-12, respectively. Using these photosensitive materials D-11 to D-14, the same operations and treatments as in Example 1 were carried out to obtain the results shown in the table below. However, the density of yellow cyan was determined based on the density of blue light and red light, respectively.

[Table] From the above results, it was found that Compound-3 of the present invention has a development accelerating effect regardless of the type of dye-providing substance. Example 4 Photosensitive materials D-1, D-3, D-11 to D-14 were exposed to 1000 lux at 2000 lux using a tungsten bulb.
Imagewise exposure was made for seconds. Thereafter, these photosensitive materials were brought into close contact with dye fixing material R-2 with their film surfaces facing each other and heated for 25 seconds on a heat block heated to 130°C, and then the dye fixing material was peeled off from the photosensitive material. Negative magenta, yellow and cyan color images were obtained on top. The densities of this negative image with respect to green light, blue light, and red light were measured using a Macbeth reflection densitometer (RD519), and the results are shown in the table below.

[Table] From the above results, it can be seen that the compound-3 of the present invention significantly accelerates development even in a system in which thermal development and dye transfer are performed simultaneously in the presence of a hydrophilic hot solvent.

Claims (1)

[Claims] 1 At least photosensitive silver halide on the support,
A binder, a dye-donating substance that is reducing to photosensitive silver halide and releases a mobile hydrophilic dye by reacting with photosensitive silver halide upon heating, and a compound having a mercapto group when oxidized. A method of heating a photosensitive material containing a hydroquinone derivative to be released in a substantially water-free state after or simultaneously with imagewise exposure to form a mobile dye in the form of an image.