JPS59159161A - Thermodevelopable diffusion transfer color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of forming an image good in color balance and superior in storage stability by using a specified compd. as a dye donor for each photosensitive layer of said material. CONSTITUTION:A thermodevelopable color diffusion transfer photosensitive material is formed by laminating three photosensitive layers each contg. photosensitve silver halide, an org. silver salt, a binder, and one of yellow, magenta, and cyan on a support. Each of said photosensitive layers contains one or dye donors releasing diffusive yellow, magenta, and cyan dyes, respectively, each represented by formulae I , II, and III in which R is alkyl or aryl; J is a joint group; and each of Dyes 1, 2, 3 is one of diffusive yellow, magenta, and cyan dyes, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a heat-developable color photosensitive paulownia material for forming color images by heat development.

More specifically, the present invention relates to a heat-developable color diffusion transfer photosensitive material containing a dye-providing substance that releases or forms a spreading dye upon heat development.

More specifically, the present invention relates to dye-donating substances that emit diffusive colors of V, magenta and cyan, and that also obtain ij-type t+y, L.

(Prior art 2) Color sensitization using silver halide is an example of a method using a dye formed from an oxidized product of mulberry, a coupler, and G; There are methods such as the method of making a 1lI111 pattern (silver dye?whitening method), or the method of diffusion-transferring the dye released by oxidation-reduction, which is used in all types of instant photography, using a Ryukari processing solution. I don't know.

71. All of these methods have been developed using wet processing methods in which images are formed using alkaline or pickling processing solutions.

In recent years, in contrast to these wet treatments, a simple and rapid treatment method using dry treatment such as heating has been developed.

Heat development 1. As for yC materials and their processing power methods, U.S. Patent No. 3,152,904, No. 3,30n, 67
No. 8, No. 3,392,020; g, No. 3,457
, No. 075 and Research Disclosure Magazine (Re5
17029;
It is described in the June 1978 issue, pages 9 to 15.

Regarding a method of obtaining a color image by thermal development, a method of forming a color image by coupling an oxidized product of J-1 developer with a coupler is described in U.S. Pat. No. 3,531,286.
No. 3. '761,270, same number 4,021,2
No. 40 and Belgian Patent No. 802. ．． No. 519, etc. However, this method has the disadvantage that a silver image and a color image after heat development occur simultaneously, making it impossible to obtain a clear color image.

In order to solve this problem, there are methods in which silver marking is performed using a liquid treatment or an activator sheet, but these methods are not preferred.

On the other hand, a method is known in which the dye is liberated by heat development using a dye silver salt, but the separability of the exposed portion and the unexposed portion is poor and clear images cannot be obtained.

Furthermore, methods for forming color images using leuco dyes are described, for example, in U.S. Pat. No. 3,985,565 and U.S. Pat. No. 4,022,617. It has the disadvantage that it is difficult to incorporate and gradually discolors.

On the other hand, there is a method of releasing the dye through diffusion 1 by heat development using a reducing dye-donating substance and a reducing agent.
IM (5'y-179a No. 40 and 57-198
It is described in No. 458. Furthermore, this reducing dye donor i
Coupling with the oxidized form of the developer instead of the trivalent substance,
Coupling dye that is more diffusive than the coupling position)
A method is known in which a dye is formed using an oxidized developer and a coupler, and a method in which the formed dye is transferred by heat is disclosed in Japanese Patent Application No. 5'7.
There is a description in No.-229671.

The method of L et al. has been improved in various respects. For example, silver painting for thermal transfer of released dye]
There is no clouding of colors due to color distortion, and the image can be easily manipulated to create a color image.

However, the color i
To obtain iM, diffusive yellow, magenta, and cyan dichromatic color donor materials are sensitized to at least three limited wavelength ranges.
applied in a heat-developable photosensitive material in combination with silver halide,
By heat development after exposure, a color image can only be obtained by releasing (or forming) diffusive yellow, magenta and cyan dyes. They have the disadvantage that some dyes have little or no pigmentation, and some of them release quickly, resulting in a poor balance with other dye-donating substances and the inability to obtain stable color tones.

In addition, some dye-donating substances have the disadvantage of relatively high diffusivity and poor color separation from the released dye, and some have poor stability during storage and gradually release the dye. Some of them have various drawbacks, such as converting into compounds with no release properties at all.However, one method that is still satisfactory is the ability to obtain images, superior storage stability, and thermal development color diffusion. An object of the present invention is to provide a transfer photosensitive 4N material.

(Structure of the Invention) As a result of extensive study, the present invention has been developed to suit the purpose of the present invention and to be able to embody at least one
A photosensitive layer containing photosensitive silver halide, a binder, and a dye-donating substance that releases a diffusible yellow dye represented by the following general formula [I], and at least one layer of photosensitive halogen. A photosensitive layer containing silver oxide, an organic silver salt, a binder, and a dye-donating substance that emits a diffusible magenta dye represented by the following general formula [■], and further at least one layer of photosensitive silver halide, organic, silver A heat-developable color diffusion transfer material C having a binder and a photosensitive layer containing a dye-donating substance that releases a diffused 1t cyan dye represented by the following general formula I is constituted. I was able to achieve this.

General formula [I] H -Dyel General formula [n] H General formula [11] In the formula, R represents an alkyl group or a aryl group, and J represents a divalent divalent group. Dyel is a diffusible yellow dye, Dye2 is a diffusible magenta dye, and D7θ3 is a diffusible cyan dye.The alkyl group represented by 0 may or may not have a substituent, and is preferably having 1 to 20 carbon atoms, such as butyl group, hekynyl group, octyl group, or dodecyl group, and aryl group such as phenyl group, naphthyl 2k, p-butylphenyl &, 2,4.6-)lichlorophenyl group, 0-
Tetradecyloxyphenyl group, etc.

As the divalent divalent group represented by J, a divalent group substituted at the active site of a coupler used in ordinary silver halide color light-sensitive materials can be used, for example, -0-1-S. -1-SO,, -N=H-1-0-0
-1-0C! O-, -0SO,-, -NH3O2-11
1100 -OCNR1- and -NHCO- groups, and l represents an alkyl group or an aryl group. The alkyl group preferably has 1 to 20 carbon atoms, and the alkyl group is preferably a methyl group, an ethyl group, a butyl group, a 5eC-
The aryl group represented by R1 is,
For example, phenyl group, tolyl group, chlorophenyl group, etc.

Next, the compounds represented by the general formulas [I], [II] and [[] used in the present invention are shown below, but are not limited to stiff compounds.

(Compound n represented by general formula [I]) -1 -3 -4 0H (Compound n-2 represented by general formula [II] H 00H.

-3 00H.

-5 H OCR.

Engineering (-6 H M-7 -8 H 00H.

(Compound represented by the general formula [1])0-3 H -4 H O,H.

-8 H 00H.

The photosensitive material according to the present invention is produced by heat-developing the image-receiving material in close contact with the image-receiving interest after exposure of the image (in the case of a method in which the image-receiving material and the photosensitive material are already integrated, In the foggy light area, silver grain sand is formed, and in contrast to γt, a diffusive dye is released or formed.This diffusible dye diffuses in the binder and further diffuses into the image receiving frame F. If the unreacted dye-providing substance is not diffused into the image layer and is released, but the dye is released or formed, and the dye is of low molecular weight, Various techniques can be used, such as using a compound with a relatively large molecular weight as the dye-donating substance, or, if the dye is hydrophobic, adding four hydrophilic groups to the dye-donating substance.

The organic silver salt used in the present invention reacts with a reducing agent to form a silver image when heated from 80° C. to 250° C. in the presence of photosensitive silver halide. As the organic silver salt, Japanese Patent Publication No. 43-4924, No. 44-
No. 26582, [Tsukasa No. 45-18416, No. 45-12
No. 700, No. 45-22185 and JP-A-49-52
No. 6.26, No. 52-31.728, No. 52-137
No. 31, No. 52-141222, No. 53-36224
No. 53-3622, U.S. Patent No. 3,330
Silver salts of aliphatic carboxylic acids described in specifications such as No. 633 and No. 4,168,980, such as silver laurate, myristic acid, silver acid, silver valmitate, stearic acid, arachidonic acid Silver, behenriI silver, etc., and also aromatic carboxylic acid silver, such as anion,! , silver fragrant, silver phthalate, etc., and silver salts containing an imino group, such as silver benztriazole,
614 salts of compounds having mercapto or thione groups, such as silver zacharin, silver 7-thallazinone, silver 7-talimide, etc., such as 2-mercaptobenz-oxazole 6, IJ M mercaptooxadiazole silver, mercaptobenzdeazole silver, 2-mercaptobenz silver imidazole, 3-mercapto-phenyl-1,2,4-)riazole silver, and as others 4-hydroxy-6-methyl-1,3,3
a.

Examples include silver 7-thitrazaindene, silver 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene, and the like. Also, RD16966, 16907, British Patent No. 1,590,956, British Patent No. 11.590.95
It is also possible to use silver compounds such as those described in Specification No. 7.

Among them, a silver salt having an imino group such as Mat of benzolyl silver (for example, benzolyl silver) is preferable, and silver salts of benztriazole A include alkyl-substituted penztriazole silver such as methylbenztriazole silver, e.g. bromo-benzol silver. triazole silver, amide-substituted benztriazole silver such as chlorobenztriazole silver, amide-substituted benztriazole silver, such as chlorbenztriazole silver, 454 benztriazole silver, such as 5-acetamidobenztriazole silver, and British Patent No.
, 590,956 and 1.590,957, such as N-[6-chloro-4-N(3,
5-dichloro-4-hydroxyphenyllimino-1-
Oxo-5-methyl-2,5-cyclohexadiene-2
- ylyo5-carbamoylbenztriazole silver salt,
2-penztriazole-5-ylazo-4-methoxy-1-naphthol silver salt, 1-penztriazole-5-
Silver salts of 2-naphthol, N-benztriazol-5-yl-4-(4-dimethylaminophenylazonobenzamide, etc.) are available.

Further, nitrobenztriazoles represented by the following general formula (12) and benztriazoles represented by the following general formula (13) can be advantageously used.

General formula (12) In the formula, R1? represents nitro), and the present number may be the same or different.
Salts, bromine, iodine, hydroxy groups, sulfo groups or their salts (e.g. sodium salts, potassium salts, ammonium salts, carboxy groups or their salts (e.g. sodium salts, potassium salts, ammonium salts, nitro groups,
Cia/group or its n, -%' 11. A carmoyl group, a sulfamoyl group, an alkyl M group (for example, a methyl group, an ethyl group, a propyl group), an alkoxy group (for example, a methoxy group, an ethoxy group,
It represents an aryl group (for example, a phenyl group) or an amide group, m is an integer of 0 to 2, and n is an integer of O-1.The lj'+ substituent of the carbamoyl pongee is, for example, a methyl group. , ethyl group, acetyl group, etc. Substituents for sulfamoyl group include, for example, methoxy group, ethyl group, acetyl group, etc. Substituents for 1 of alkyl group include, for example, carboxy group, Ethoxycarbonyl group, etc., substituents for aryl groups include, for example, sulfo groups, nitro groups, etc. substituents for alkoxy groups include, for example, carboxyl group and ethoxycarbonyl group, and substituents for ryomino groups include, for example, acetyl group. , methanesulfonyl group, and hydroxy group.

The compound represented by the general formula (1z) is a silver salt of a benzotriazole derivative having at least one nitro group, and specific examples thereof include the following compounds.

For example, silver 4-nitrobenzotriazole, silver 5-nitrobenzotriazole, silver 5-nitro-6-chlorobenzotriazole, silver 5-nitro-6-methylbenzotriazole, silver 5-nitro-6-methylbenzotriazole, -nitro-7-phenylbenzotriazole silver,
4-Hydroxy-5-nitrobenzotriazole silver, 4
-H)" o Silver xy-7-nitrobenzotriazole, silver 4-hydroxy-5,7-sinitrobenzotriazole, silver 4-bitroxy-5-nitrobenzotriazole, 4-hydroxy-5- Nitro 6-methylbenzotriazole mJ, 4-sulfo-6-nitrobenzotriazole silver, 4-carboxy-6-nitrobenzotriazole silver, 5-carboxy-6-nitrobenzotriazole 廝艮, 4- Carbamoyl-6-nitrobenzotriazolezotriazole, 5-carboxymethyl-6-nitrobenzotriazole silver, 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole silver 5-nitro-
Silver 7-nitrobenzotriazole, silver 5-amino-6-nitrobenzotriazole, silver 5-nidroa - (
p-nitrophenylbenzotriazole silver, 5,7-
Dinitro-6-chlorobenzotriazole silver, 5,7-
Examples include silver dinitro-6-methoxybenzotriazole.

General formula (13) In the formula, R2. is a hydroxy group, a sulfo group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), a carboxy group or a salt thereof (e.g., sodium salt, potassium salt, ammonium salt), a carbamoyl group which may have an il substituent and a sulfamoyl group which may have a substituent, and R□ is a halogen atom (for example,
Chlorine, bromine, iodine, hydroxy group, sulfo group or its salt (e.g. sodium salt, potassium salt, ammonium salt), carboxy group or its salt (e.g. sodium salt, potassium salt, ammonium m), nitro group,
a cyano group, or an alkyl group that may have a substituent (for example, a methyl group, an ethyl group, a propyl group),
aryl group (e.g., 7-ethyl group), 7 represents a koxy group (e.g., methoxy group, ethoxy group) or amide group, p is 1 or G or 2, and q represents an integer from 0 to 2. 〕vinegar.

Also, t) 41 R. carbamoyl group shield,
Examples of substituents include methyl, ethyl, acetyl, etc., and examples of substituents for sulfamoyl include methyl, ethyl, acetyl, and the like. Furthermore, as a substituent for the acylekyl group in R1I, for example, a carboxyl group, an ethoxycarbonyl group, etc., as a substituent for an aryl group, for example, a sulfo group, a nitro group, etc., and as a substituent for an alkoxy group, for example, a carboxy group, an ethoxycarbonyl group, etc. Examples of the groups and substituents of the amino pattern include an acetyl group, a methanesulfonyl group, and a hydroxy group.

Specific examples of the organic silver salt represented by the general formula (Part 3) include the following compounds.

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sodium sulfonate, benzotriazole silver-sodium 5-sulfonate, Silver benzotriazole-4-potassium sulfonate, silver benzotriazole-5-potassium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, 4-carboxybenzotriazole silver, 5-carboxy benzotriazole silver, benzotriazole silver-4-sodium carboxylate, benzotriazole silver-5-sodium carboxylate,
Potassium benzotriazole silver-4-carboxylate, Potassium benzotriazole silver-5-carboxylate, Ammonium benzotriazole silver-4-carboxylate, Pen'1
Silver triazole - ammonium 5-carboxylate, silver 5-carbamoylbenzotriazole, silver 4-sulfo7amoylbenzotriazole, silver 5-carboxy-6-hydroxybenzotriazole, silver 5-carboxy-7-sulfobenzotriazole, 4-hydroxy -5-sulfobenzotriazole silver, topedroxy-7-sulfobenzotriazole silver, 5,6-dicarboxybenzo) I
J Azole silver, 4.6-cyhydroxybenzotriazole silver, 4-hydroxy-5-chlorobenzotriazole silver, 4-hydroxy-5-methylbenzotriazole silver, 4-hydroxy-5-methoxybenzotriazole silver length, 4- Hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-5-cyanobenzotriazole silver,
4-Hydroxy-5-aminobenzotriazole silver, 4
-Hydroxy-5-acetamidobenzotriazole silver, 4-hydroxy-5-benzenesulfonamide benzotriazole silver, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4 -Hydroxy-5-carboxymethylbenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethylbenzotriazole silver, 4-hydroxy-5-,
Phenylbenzotriazole silver, 4-hydroxy-5-
(p-nitrophenylnobenzotriazole/l' silver, 4
-hydroxy-5-, (p-sulfophenylnobenzotriazole silver, 4-sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5-methoxybenzotriazole silver, 4
-Sulfo-5-cyanobenzotriazole silver, 4-sulfo-5-ami/benzotriazole silver, 4-sulfo-5
-acetamidobenzotriazole silver, 4-sulfo-5
-benzenesulfonamidobenzotriazole silver, 4-
Sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5-carboxymethylbenzotriazole silver, 4-sulfo -5-ethoxycarbonylmethylbenzotriazole silver, 4-sulfo-5-phenylbenzotriazole silver, 4-sulfo-5-(p-nitrophenylnobenzotriazole silver,
4-Sulfo-5-(p-sulfophenyl)benzotriazole silver, 4-sulfo-5-methoxy-6-chlorobenzotriazole silver, 4-sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy- 5-chlorobenzotriazole silver, 4-carboxy-5-methylbenzotriazole silver, 4-carboxy-5-nitrobenzotriazole silver, 4-carboxy-5-amine benzotriazole silver, 4-carboxy-5-methoxybenzo Triazole silver, 4-carboxy-5-acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-5-carboxymethylbenzotriazole silver,
4-Carboxy-5-phenylpenzoto1. azole silver, 4-carboxy-5-(p-nitrophenylnohenzotriazole silver, 4-carboxy-5-methyl-7-
Examples include silver sulfobenzotriazole. These compounds may be used alone or in combination of two or more.

The preparation method of the silver salt used in the present invention will be described later, or the organic silver salt according to the present invention may be isolated and used by dispersing it in a binder by an appropriate means, Alternatively, a silver salt may be prepared in a suitable binder and used as is without isolation.

The amount of the organic silver salt used is 0.05g per 1771 supports.
~10.0g, preferably 0.2. @~2. Og
It is.

Examples of reducing agents used in developing the photosensitive material of the present invention include those disclosed in US Pat. No. 3,531,286 and US Pat. '
No. 761,270, same No. 3. '764, 3289 specifications, RD 12146, RD 15108, RD15
127 and JP-A-56-27132, JP-A No. 56-146
p-phenylenediamine type and p-aminophenol type developing agents, 7-osfluoramide phenol type and sulfonamide phenol thread developing agents, and hydrazone type color developing agents described in Japanese Patent No. 133 and the like can be used.

Diffusible dyes are released by oxidative coupling of the reducing agent in this case with these thermally transferable dye-providing substances. Also, U.S. Patent Nos. 3,342,599 and 3,719,49
No. 2, JP-A-53-135628, JP-A No. 54-7903
Color developing agent precursors described in Japanese Patent Application No. 5'7-163234 and the like can also be advantageously used. In this case, a reducing agent as described below can be used in combination with the above-mentioned reducing agent.

NO13 phenols (e.g., p-phenylphenol, p-methoxyphenol, 2,6-sheet tθrt-
butyl-p-cresol, N-methyl-p-aminophenol, etc.], sulfonamidophenol [(e.g. 4-
Benzenesulfonamidophenol, 2-penzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-
(p-”toluenesulfonamide)phenol'J
), and hapolyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, 2.6-
trimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxylic acid tefur, etc.), naphthols (such as α-naphthol,
β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols (e.g. 1,1'-dihydroxy-
2,2'-binaphthyl, 6,6'-dibromo-2,21
-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2゜2'-dihydroxy-1,1'-binaphthyl, 4,41-dimethoxy-1,11-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1-naphthyltumethane, etc.), methylenebisphenols (for example, 1,1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5, 5-) IJ Methylhexane, 1.1-bis(2-hydroxy-3-tert-butyl-5-methylphenyltumethane, 1.1-bis(2-
hydroxy-3,5-di-tert-butylphenyl)
Methane, 2,6-methylenebis(2-hydroxy-3-
tert-butyl-5-methylphenyl)-4-methylphenol α-phenyl-α, α-bis(2-hydroxy-3,5-di-tert-butylphenyltumethane,
α-phenyl-α, α-bis(2-human ot-cy 3
-tert-butyl-5-methylphenyltumethane1.
1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1. l, 5゜5-tetrakis (2-hydroxy-3,5-dimethylphenyl J-2,
4-ethylpenkune, 2,2-his(4-hydroxy-
3,5-dimethylphenyldipropane, 2,2-bis(
4-Hydroxy-3-methyl-5-tert-butylphenylribroban, 2,2-bis(4-hydroxy-3
5-di-tert-butylphenylnobroban, etc., ascorbic acids, 3-pyrazolidones, pyrazolones,
Mention may be made of hydrazones and heterophenylene diamines.

These reducing agents may be used alone or in combination of two or more. The amount of reducing agent used depends on the type of organic acid silver salt used, the type of photosensitive silver salt, and the types of other additives, but it is usually 0.05 per mole of organic acid silver salt. It ranges from mol to 10 mol, preferably 0.
It is 1 to 3 moles.

Photosensitive silver halides used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide/silver iodobromide, silver chloroiodobromide, etc. Ran. The photosensitive tin halide can be prepared by any method known in the photographic field, such as a single jet method or a double jet method, but in the present invention, a conventional method for preparing a silver halide gelatin emulsion is used. A light-sensitive silver halide emulsion prepared according to the method gives favorable results.

The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization.

The silver halide in the light-sensitive emulsion may have coarse or fine grains, but the preferred grain size is about 1.5 microns to about 0001 microns, more preferably about 0.000 microns. 5 microns - about 0.01 microns.

The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention.

Furthermore, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The n'6 photosensitive silver salt forming component used in this preparation method is an inorganic halide, for example, an n' halide represented by MXn (
Here, M represents an H atom, an NH4 group, or a metal atom;
, 1 when Q is 1, and 15 where M is a metal atom indicates its valence. Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, and ship. , antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, cerium, etc. ], halogen-containing metal buttons (e.g., PtC4, K, PtBr, , HAuC
e4. (NH4) 1 engineering rCj16° (NH4 fly r
e, e, , (NH4)1Ru04,
(NH4)IRuC! 74.

CMH4), RhC16, (NH4), RhBr6, etc., onium/%ride (e.g. tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide,
3-Methylthiazolium bromide, quaternary ammonium halides such as trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethyl bromide, 1-ethylthiazolium bromide, etc. tertiary sulfonium halides, halogenated hydrocarbons (e.g. iodoform, bromoform carbon tetrabromide,
2-bromo-2-methylpropane, etc.), N-710 compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalic acid imide, N-bromocetamide, N-iotocholic acid imide, N-Bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-promo N-methylbenzenesulfonamide, 1
, 3-dibromo-4,4-dimethylhydantoin, etc.),
Other halogen-containing compounds (e.g. triphenylmethyl chloride, triphenylmethyl chloride, 2-bromobutyric acid, 2-bromobutyric acid,
(bromoethanol, etc.).

These 11 C-type silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount used is 0,001 to 1.0 mol per mol of silver salt. 001 to 03 mol.

Further, the heat-developable color diffusion transfer light-sensitive material of the present invention has layers sensitive to blue light, green light, and red light, namely, a heat-developable blue-sensitive layer, a heat-developable green-sensitive 70 layer, and a heat-developable red-sensitive layer. The blue I6 silver halide emulsion, the green-sensitive silver halide emulsion, and the red-sensitive silver halide emulsion each used may have a multilayer structure as a color layer. It can be obtained by adding a sensitizing agent.

Typical spectral sensitizing dyes used in the present invention include
For example, cyanine, merocyanine, and
trinuclear or tetranuclear] cyanine, holopholarianine,
Styryl, hemicyanine, oxonol, etc. are suppressed. Among cyanine dyes, those with a basic nucleus such as thiazoline, oxazoline, hyroline, pyridine oxanol, thiazole, selenazole, and imitazole are more preferred. This younger nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkylcarboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a carbon atom or a complex atom. . Moreover, it may be symmetrical or asymmetrical, and methines and polymethines may be substituted with an alkyl group, a phenyl group, an enamine group, or a heterosubstituted group.

In addition to the basic nuclei mentioned above, merocyanine dyes have acidic nuclei such as naohitanotoin, rotanine, oxazoline nonion, thiazolidinedione, no(rubitur ah, thiazolinthione, malononitrile, and hirazolone). These acidic nuclei can also be substituted with an alkyl group, an alkylene group, a phenyl group, a carboxyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxypurkyl end, a pulkylamine group, or a heteroterminal modification. It is also possible to use a combination of these colored threads if the number of threads is different.Furthermore, ascorbic W
u*I4i, asa 1 ten cadmiwam salt, im sul/'
j−+ 7 # Qj , -l1olli Eha tree L! !
I Ship RL-No. 2 +933.390, No. 2,9
37. It is written in the specifications of Li2Q that it seems to be talented = J type, absorbs light / good layered feeling) 8〉Machining 1〕It is Tamiru.

Usukafu of these pigments is hanke/kaeiga or... 1 mole of the dyestuff forming component is 1 mole (47 to 1 mole. Preferably 4 moles to 1 mole of lff) Al.

To the heat-machine color diffusion transfer light-sensitive material of the present invention, additives may be added to the above-mentioned tube components as a dust image accelerator. It's rice!! l Special old-No.: U, 22 (+, 846, same No. 3, 5)
No. 31,285, No. 4,012,260+j, No. 4
．． 06f], No. 420, No. 4.0″88,496,
No. 4,207,392 Tanibei Homare Zutaba RD 157
33, same 1! '+ 734, 15776, etc., 60 grains of alkaline field spray, a commercial mechanism described in Japanese Patent Publication No. 12700/1973, US Patent No.

-CO-, -802-, -SO described in No. 667.959
- Non-aqueous chronic solvent compound with door, Komekoshi 1 Patent No. 3.
Meltformer-1 described in No. 438,776, published in U.S. Patent No. 3,666.477, in Japanese Patent Application Laid-Open No. 1982-19525^
There are polyalkylene glycols and other products.

In addition, as a color thickening agent, for example, Toku-Sho 46-4928 sword,
No. 46-6077, No. 49-5019, No. 49-5
No. 020, No. 49-91215, No. 49-10111
No. 1, No. 50-2524, No. 1 Tsukasa 50-67132 sword,
No. 50-67641, No. 50-114217, No. 5
2-33722g, 16j 52-99813%, fi3-1040-q, fi3-55115, four F1
No. 3-76020, No. 53-125 (1149, No. F+
4-156523+f, 54-156524, 54-IF+6525, 54-156526, 55-4060, 554061, 1-cho 55-
Publications such as No. 32015 and West German Patent No. 2.140,4
No. 06, No. 2,147,063, No. Z, 220.
f u 18 N I, Thu L! ! + Patent No. 3,08t
l, No. 254, same No.: U, 847. i] 12 bows,
laj No. 3, 7) 32. '-+41-, same 4t8J3
, 994 , 732 +:j, w4. lz3. z8
2-q, 4th + 20] + 582 +5%
') % details & Fc qe +, 6 compound phthalafone, phthalicide, hirazolo/, quinacrine/, N-hydrogycinnaphthalimito, benzoxane, naphthomaxacymene, 2,3-di Hitorou Futarashi/Zion, 2,','i-/Hitorou]
, 3-Oki → Tsunono 2.4-N-O/, Oxypyridine, Aminoquirinno, Hydroxyquinolino, Aminoquinoline, Incalphostyryl, Sulfo/Amino), 21(-1
, 3-pentthiazine-2,4-(314)one, peztriazine, merkaftotriazole, merkaftotetoshizabe/sauce/, phthalic acid, naphthalate, phthalamine, etc., and one of these or , or more with an imitasol compound or a mixture of at least one phthalic acid, a nanotalin compound or an acid anhydride and a phthalazine compound, as well as notalazine and maleic acid, itaconic acid, quinolinic acid, kenthidine. Combinations of acids, etc. can also be mentioned.
3-Amino-5-mercapto-1,2,4-) lyazoles, 3-acylamino-5-mercapto 1.2.4 described in No. 3215 and Ministry of Specification No. 57-76838
-Triazoles are also effective.

Furthermore, as an anti-fogging agent, flJ Eha Special Publication
-11113, JP-A No. 49-90118, JP-A No. 49-
No. 10724, lij No. 49-97613, lij No. 50-
No. 101019, No. 49-130720, No. 50-
No. 12331, No. 51-47419, No. 51-574
35'\T1 No. 51-78227, No. 51-1043
No. 38, No. 53-19825, No. 53-20923, No. 51-50725, No. 51-3223, No. 51
No. 42529, No. 51-81124, No. 54-518
Publications such as No. 21 and No. 55-93149, as well as British Patent No. ¥1.4F15,271 and U.S. Patent No. 3.8.
No. 85,968, No. 3,700.4F17, No. 4
．． No. 137,079, No. 4,138,265, West German No. 1v-F No. 2,617,907, etc. Qi 1
j (for example, N-halokene acetamide, N-halokene acetamide, N-halokene acetamide, asXB substrate and its salts, 11. 1 remainder (・” Sultin a (,
Laughlin' lithium, rosin, noterbeno [kai thiosulpone la'49], or A:
: Mercanoto compound releasing compound 'I/7), thiouranyl, disulfide, simple sulfur, Mercanoto-1,
2,4-trianol, thiasolinthione, polysulfidated 1>n, H, etc.), other ogisazoline, l,
2.4-1) There is no combination of anol and phthalimide (cut protection).

Also, as a female foot agent, after treatment, c°-2 / flint out prevention sharpening may be used at the same time.
624 +fj, 1rg 5 1) -1
20:i 28 Jr:T, 1ri453 46 (1
In Publication No. 20, etc., 4 saponified hydrocarbons, Hyogo 1, tetodinerombutane, trifluoroethanol, 2-noro-7-2-tolylaceto, 2-pro(-
Examples include 2-tolylsulfonylacetamyl-12-19 furo-7methylsulfonylbenzothiazole, 2,4-his(tribromomethyl)-6-methyltriazine, and the like.

Further, post-treatment may be carried out using a sulfur compound as described in Japanese Patent Publication Nos. 46-3593, 50-4329, and 5Cl-77034.

Furthermore, Yoneyama Patent No. 3,301,678 Bow, Yoneyama Patent No. 3.
No. 506,444, No. 3,824,103, No. 3
．． 844,788, and U.S. Pat. The activator stabilizer precursor etc. described in the specification etc. may also be included.

In addition to the above-mentioned reasons, the heat-developable color diffusion transfer light-sensitive material of the present invention may further contain a spectral sensitizing dye,...
'Gin prevention paste, firefly'''lt, mortar agent, hardening agent, phlegm fixing agent, river qt)-+ agent, thickening agent, etc.6 ω-to addition, coating aid, etc. is added.

In the heat-developable color diffusion transfer photosensitive material of the present invention, a hydrophilic or IK aqueous natural or synthetic binder is used as the binder. In the present invention, the hydrophilic binder refers to one that is in an OJ bath due to water or a mixture of water and a solvent. The list includes natural substances and effective polymers such as Serachi, Seratin fat conductors, cellulose fats, Horisac light such as Dextran, Arabic com, etc., -〇, polyvinyl acetal (preferably, Preferred are polyacrylamide, polyvinylpyrrolidone, ethyl cellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), etc., but only these There is no limitation.If necessary, two or more types/1Ill may be used in combination.

The amount of binder is 1/10 to 0, preferably 1/4 to 4 parts by weight per 1 part of organic silver salt per valley photosensitive layer.

The layers containing the components of the invention and other layers can be coated on a wide variety of supports. Supports used in the present invention include binding or plastin film such as cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polyethylene film, polyethylene terephthalate film, polycarbonate film, and metal bridges such as glass, paper, and aluminum. etc. can be opened. Furthermore, baryta paper, resin coated paper and water-resistant paper can also be used.

In addition to the photosensitive layer, the heat-developable color diffusion transfer photosensitive material of the present invention can be provided with a top coat polymer layer, an F coating layer, a backing no. .

The W photophase can be used to form a dye image by imagewise exposure and heat treatment, or can be applied to an image-receiving layer for a dye image using a solvent such as methanol or a heat-melted solution such as methyl anthedate. Thermal transfer can be performed using various heat bath agents.

It is also possible to use a thermal transfer method as described in British Patent No. 1,590,957.

The light-sensitive material according to the present invention is imagewise exposed and then thermally developed to form a sparrow-like distribution of ascending color cords or ascending dye flexors from the dye donor k, and forming a sparrow-like distribution of ascending color cords or ascending dye flexors from the dye donor k. When applied to the Cassie thermal ambiguous transfer method, in which at least a portion of the photosensitive material is thermally transferred to the image receiving layer in a stacked relationship with the photothermographic material, the lI! formed on the image receiving layer is applied. Provides an image of the thigh with improved tl image density.

In the photoreceptor according to the present invention, the dye used in the process for dye images can be used as the image-receiving layer. The image-receiving layer may also be a separate image-receiving element comprising a receptor i# layer on a non-conventional support, or the receptor layer may be part of the heat-developable photographic material element described above. One layer may be used. If necessary, an opacifying layer can be wrapped in a shadow-sensitive material, such that the Jm can be used to obtain the desired amount of axillary radiation, e.g. It is used to reflect Kaso light. The opaque layer can contain a persimmon reagent that provides the necessary reflection, and the layer can contain titanium dioxide. For the q layer, bank layer, and other layers, respective coating methods are prepared and applied by dipping method, air knife method, curtain coating method, bomber coating method described in U.S. Pat. No. 3,681,294, etc. Photosensitive materials can be created using various coating methods.

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 for the heat-developable photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation containing '5'J radiation. In general, light sources used for color printing with appropriate sound, such as tungsten lamps, water button lamps, xenon lamps, racer Mototai, CRT beams, etc., can be used as the light source.

The original drawing may be a line image such as a technical drawing, or a photograph im+IM with one level. Furthermore, the burning from the original drawing may be either accumulated burning or reflective burning.

In addition, the images projected by a video camera, etc., or the images sent from a television station (↑) are sent directly to a CRT or FOT, and this image is displayed on a heat-developed photosensitive material using 9 lenses into a dense layer. It is also possible to make an image and print it.

In addition, there has been a great deal of progress recently], E D (Vuramoto Daimanchido) (・yo, death) 1! As an exposure means in the electrifying device of 1.
l] Irretsu\ there is. It is difficult to make this L F; Using something that emits light or infrared light, I made a dye that emits yellow, macenta, and cyan dyes, respectively (the first one is good. The green Δ originally contains a yellow dye, and the photosensitive layer contains a magenta dye-releasing image-forming substance, so that the extra photosensitive layer contains a cyan dye [ Middle school
It would be good if you could say that the image forming thing is a heron.

Other than the above method of close contact with the original drawing or projection 1-p
- The original image irradiated by the original source is read by the original power source, CCD, etc., and input into a computer, etc., and this official gazette is processed into 8 pieces. After applying the image location, the information to the artist 1 is transmitted to the CRT, and this can be used as an image palpitation, or it can be directly used based on the processed information. There is also a method of exposing by emitting ED light.

The fl obtained after exposure of the heat-developable color photosensitive material of the present invention
For example, the heating time is approximately 800 to 250°C for 03 to 12 seconds.
Developed by heating the entire surface of the photosensitive paulownia with 0 sand.
-I can do something. As long as the temperature falls within the above range, the basket can be used at both high and low temperatures by increasing or shortening the heating time. Particularly for temperatures in the range of about 110°C to 200''C, the heating means may be a hot plate, iron, hot roller or the like.

In case of misfire ψ3, the specific method for forming a color image by image bearing is 1" thermal diffusion transfer of a dynamic dye,
For 7 purposes, a heat-developable color photosensitive material is formed of a photosensitive layer containing on a support at least...silver rokenide, an organic @chloride oxidizing agent and its reducing agent, a dye-donating substance, )<inter, and the photosensitive layer. It consists of an image-receiving layer capable of receiving mobile dyes.

The above-mentioned optical layer and image-receiving layer may be formed on the same support, or may be formed on separate supports.

The image receiving layer can be peeled off from the photosensitive layer.

The arrangement is the same as that of heat-machine twisted color photosensitive materials. - Heating condition 1: After swimming, the dye can be transferred by heating the layer at a lower temperature than the ambient temperature.

The image-receiving layer that supports the coloring matter released from the light-sensitizing method of the present invention is not particularly limited, and it is possible to use a layer that can be used in the known heat-developed color diffusion transfer method. So, for example, Polynisdel film specialized for polyethylene terephthalate film, Holika Hoi: -1,
jA vinylite/vinyl chloride, cellulose triacetate, cellulose diacetate, polyethylene, polystyrene, polyamide (nylon) bone boot film, polymer containing one dye mordant component in the molecule, hydrophilic or hydrophobic It is possible to use a binder containing a dye mortar in one layer.

A useful mordant can be selected depending on the physical properties of the dye, transfer conditions, other components contained in the dye, etc. Useful mordants are polymers bearing ammonium salts and are described in US Pat. No. 3,709.690. Examples of polymers containing an ammonia water ring include holistile/-co-N,N,N-)ly-n-hexyl-N-vinylpe/silammonium chloride;
The ratio of styrene to vinylpeneyl ammonium chloride is 124-421, preferably 1:1.

A preferred N in the image-receiving layer is obtained by mixing a polymer containing an ammonium salt with seratin and coating it on a transparent ψJ support layer. A transfer electric medium can be used to transfer the dye from the thermal development one-stop color impression layer to the receiver DI). As the transfer medium, a low-boiling temperature medium such as methanol, ethyl acetate, or diyne butyl ketone, and a Tsutsuna point medium such as tri-n-cresyl phosphate, trilononyl phosphate, or sea-n-butyl phthalate are used. For the MA base of the cylinder boiling point electric medium, an appropriate emulsifier can be used to emulsify gelatin and add it to the mordant layer.

Another specific method involves providing a layer of titanium dioxide in which seratin is dispersed on a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer (7. By viewing the transferred color image 1W from the side of the transparent support I4-, a reflection-type shell can be obtained.

(Practical sequence) 2i1: An example is shown below, but the actual implementation is as follows.
It is not limited to these.

How to prepare silver benzotriazole, which is commonly used by Matsu)% vero.

Preparation of 4-hydroxybenzotriazole silver salt 3. I, 0.9 was bathed in water 450+, t/:, and while stirring, ammonia water was poured into the form, and the droplet F was discontinued when the silver was intoxicated. . 4-Hydroxybenzotriazole (Patent application 1986-1065)
-Synthesized by the method described in Q) 27.5 P with ethanol 3
5 (1mt was added to the ammoniacal silver nitrate bath to stir the bath. The reaction number was filtered for 9J, and dried under conditions of water and methanol. 46.4% of white crystals were obtained. Ta.

1J1 4-Hydroxybenztriazole silver 7.26.9% water-soluble polyvinylbutylene 2-5% (Okonsui Kagaku Elex W 2Lll) 24 cc, water 11
6 cc.

70 cc of methanol was added and the rice was crushed and dispersed in an alumina ball mill to obtain a silver salt dispersion.

25 cc of this silver salt dispersion, 0.21 phthalate & 0.16.9 phthalazine, the present compound C-30,95
, 9 and further dispersed in a hole mill, the following active agent 0.42. ! ? Red sensitized silver chlorobromide seratin emulsion (Silver chloride (Silver) mole%) is converted into scissors and is 36~ and water f6i't', polyvinyl butyral 5% water Sa (
Same as above) 5 cc of water, LO cc of water was dispersed, and the wet film was dimpled on photographic baryta paper so that the wet film was 551 mm, and a red-sensitive diffusive cyan dye-releasing heat-transferable photosensitive layer was obtained. I swallowed.

Furthermore, on top of this, C-3 used in the red-sensitive photosensitive layer is applied.
-20,82,! ? and red sensitized emulsion to line color sensitized silver chlorobromide seratin emulsion (silver chloride 6()).
mol %) to silver, replace it with C36η, and add 0.42% of the developer. ! i' was added to obtain a dispersion, and the wet @ membrane was 6b.
Y-10,97
A color dye-releasing thermally sensitive 9 layer was foil-faced to a blind-sensitive diffusive layer in the same manner as the dispersion number described above except that y and a sensitive silver chloride seditine emulsion (50 mol% silver bromide) were used. Nessaizuka obtained diffusion transfer photosensitive publication.

[Desk image agent]

This sample was passed through a Ste 7 Nowafield and exposed to white light.

10,000, 7 tons of 0% cellulose diacetate was dissolved on Ipoly paper, and 1.0% cellulose diacetate per square meter.
I applied it so that it was 20.9 and made a 1" 4! paper case.

49 Futa of the above-mentioned 1-light sample] and the coating surface of the protection layer are densely layered,
Rescue 1: The bales were pressed and heated for seconds on an iron with a temperature of 8o''c, and the receptor layer was peeled off.
65 (manufactured by Konishi Rokureishin Kogyo Co., Ltd.).

The results are shown below.

Table 1 From Table 1, it can be seen that the samples according to the invention exhibit a well-balanced color balance.

Example 2 The dye-providing substance in the photosensitive layer was not listed in Table 2 and was used as a raw material.
Each photosensitive layer was coated in the same manner as @Shiori 1, and the thermal dust image color diffusion transfer photosensitive material was prepared.

Table 2 The sushi rice was processed in the same manner as in 1 and 7J' in Table 3.

From the third hole, it can be seen that the sample according to the invention has a poor color balance in each sample.

(Dynamic bed of the invention) The present invention has achieved the object of the invention, and at the same time, a method has been developed to create an R color base by unifying the bases of the dye-donating substances of the three primary colors. .

Agent Yoshi Eihara Written amendment for lost procedures May 1981 24L1 '+, +1. I'f+'+long' Kazuo Shirawakasugi Displaying 111 items 1982'I"NjfI Application No. 34083"':2
Name of the invention Heat-developable color diffusion transfer photosensitive material 3 Relationship with 144 persons making corrections Patent applicant II Address: 26-2, Nishi-Shinjuku 1-J, Shinjuku-ku, Tokyo Name (+27) Konishiroku Photo Industry Co., Ltd. 1 Nobuhiko Moto for representative director 4 Agent Address: 191 Address: 11 Kuchimachi, Tokyo Sakura-cho 1if+-Chikonishiroku Photography Voluntary within Yugyo Co., Ltd. 6 Detailed description of the invention in the specification to be amended Column 7: Contents of the amendment The detailed description of the invention is amended as follows.

(1) On page 11 of the specification, the structural formula of Y-6 is corrected as follows.

(2) The description is corrected as follows.

Claims (1)

[Claims] On a support, at least one photosensitive halogenated layer;
: Hei machine silver background, binder and the following -1 throw type 1-I
] and a photosensitive C layer containing a dye-donating substance that releases a diffusible or color dye; at least one layer of photosensitive silver halide, an organic silver salt, a binder, and
] A sensitive C layer containing a dye-donating substance capable of emitting a diffusible magenta dye represented by the formula [LIT]; 1. A heat-developable color diffusion transfer-sensitive yC material, characterized in that it has a yC layer containing a dye-donating flow that releases a diffusible cyan dye. General formula [, I] H J-1)yel General formula [II] H, T-Dye2 General formula [1■] H [wherein R represents an alkyl group or an aryl group, J
represents a divalent divalent group. Dye represents a diffusive yellow color patch, Dye2 represents a diffusive magenta dye, and Dye3 represents a diffusive cyan dye. ]