JPS5955429A - Method for forming color image by thermal development - Google Patents

Abstract

PURPOSE:To easily obtain a sharp color image, by thermally developing a silver salt photosensitive material contg. a dye to imagewise harden said material, and controlling diffusion of the dye from the hardened part to an image receiving layer. CONSTITUTION:The thermodevelopable photosensitive layer B is obtained by forming a dye layer (d) contg. a dye 1 dispersed in gelatin on baryta paper (c), and laminating on the layer (d) an emulsion layer (c) contg. a photosensitive silver halide, a tanning developing agent, and a silver salt or an org. acid salt of silver represented, e.g., by the shown formula in which R<1> is NO2; R<2>, R<3> are each halogen, OH, sulfo, its salt, COOH, CN, carbamoyl, alkyl, alkoxy, aryl, NH2, or the like; m is 0, 1, or 2; and n is 0 or 1. A photosensitive material is obtained by laminating on the layer B, a polyethylene base sheet (a) coated with an image receiving layer (b) having dispersed titanium white. It is exposed (C) from the layer (A) and then, heated (D) from the baryta paper (e) at 80-200 deg.C for 1-60sec. The layer (c) at the exposed parts is developed by tanning to restrict diffusion of the dye 1 to the layer (b), and the dye 1 at the unexposed parts diffuses to the layer (b) to fix 3 it, thus obtaining a sharp color image.

Description

[Detailed description of the invention] The present invention relates to a thermal development color image forming method.

In general, silver salt photosensitive materials have the excellent property of being able to obtain high image quality at high temperatures by utilizing the light-responsive properties of silver salts, which are unparalleled in other photosensitive materials. Due to the complexity of the process, there was a need for faster processing.

Conventionally, in contrast to this complexity, black and white silver salt photosensitive materials can be processed easily without impairing the light-responsive properties of silver salt.
Photosensitive materials using the so-called heat development processing method were published in 1973.
It is disclosed in Japanese Patent No. 4921, No. 43-4924, etc. Furthermore, Japanese Patent Publication No. 45-12700 proposes a heat-developable photosensitive material containing an organic carboxylate, but the effect of improving developability was insufficient. Therefore, there has been a strong desire to develop a color image forming method using a more superior thermal development processing method. One of the reasons for the delay in the development of such color image forming methods is that, in color image forming methods using heat development processing, the technology for forming clear images with dye materials is still incomplete. As a result of intensive research, the inventors discovered a structure of a light-sensitive material that can easily produce clear images using a simple operation method, and established the thermal development process color image forming method of the present invention.

A first object of the present invention is to provide a color image forming method using thermal development processing, which allows a clear dye image to be obtained through simple development processing.

A second object of the present invention is to provide a heat development color image forming method in which a color image and a silver image can be efficiently separated by tanning development of a silver salt photosensitive material.

The above object of the present invention is to thermally develop a silver salt photosensitive material containing a dye, to perform tanning development, to imagewise harden the binder of the silver salt photosensitive material, and to transfer the dye from the binder to the image-receiving layer. This is achieved by a thermal development process color image forming method characterized by controlling diffusion and forming an image-wise color image in an image-receiving layer.

The present invention will be explained in detail below.

In the heat-developable photosensitive material used in the heat-developable color image forming method of the present invention, the heat-developable photosensitive layer (photosensitive emulsion layer) preferably contains, for example, (a) an organic silver salt, (b) a photosensitive silver halide , (c) a tanning developing agent, (d) a color image-forming dye, and (e) other additives and a binder.

The formation of a color image and the reaction system according to the heat development process color image forming method of the present invention are as follows.

By exposing the silver salt photosensitive material imagewise and then thermally developing it,
The gelatin binder reacts and hardens in the silver salt emulsion layer to form imagewise tanned areas.

The physical properties of the tanned area are significantly different from those of the untanned area, which causes the dye to diffuse from the binder of the dye layer through the binder of the silver salt emulsion layer and transfer to the image-receiving layer during thermal development. A color image is formed on the image-receiving layer in the form of an exposed image by utilizing the change in speed. Therefore, the type of pigment or
Differences in dye diffusion methods (sublimation diffusion, diffusion using hot solvent)
The physical properties of the hardening degree of the tanned part and the unhardened degree of the untanned part, that is, the affinity with the dye such as hydrophilicity and lipophilicity, change depending on the It is possible to create a positive or negative image in layers.

Direct dyes, acid dyes, basic dyes, mordant dyes, disperse dyes, oil-soluble dyes, etc. can be used as color image-forming dyes, but are not particularly limited to the above. Examples include azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, but are not limited to these.

As the tanning developing agent, any tanning developing agent known in the photographic industry can be used. Specifically, developing agents with two or more hydroxy groups, such as hydroquinone, pyrogallol, catechol, or developing agents with one hydroxy group, such as amidol, metol, p-aminephenol, ascorbin. Examples include acids, but are not particularly limited to the above.

Examples of organic silver salts used in the heat-developable photosensitive layer material used in the present invention include Japanese Patent Publication Nos. 43-492 and 44-2.
No. 6582, No. 45-18416, No. 45-1270
No. 0, No. 45-22185, JP-A No. 49-52626
No. 52-31728, No. 52-137321,
No. 52-141222, No. 53-36224, No. 5
No. 3-37610, U.S. Patent No. 3,330,633,
Compounds described in publications and specifications such as No. 4,168,980, i.e. silver salts of aliphatic carboxylic acids, such as silver laurate, silver myristate, silver palmitate, silver stearate, arachidone Acid silver, silver behenate, silver salts of aromatic carboxylic acids, such as silver benzoate, silver phthalate, etc. Silver salts of organic compounds having amino groups, such as silver benzotriazole, silver saccharin, silver phthalazinone, silver phthalimide Silver salts of compounds having mercapto or thione groups, such as 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl -1,2
, 4-triazole silver, others 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaintene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaintene silver Examples include. Among these, silver salts having an imino group such as silver salts of benzotriazoles are preferred.

Examples of silver salts of benzotriazoles include benzotriazole silver, alkyl-substituted benzotriazole silver such as methylbenzotriazole silver, halogen-substituted benzotriazole silver such as prom-benzotriazole silver and chlorobenzotriazole silver, For example 5
- More amide-substituted silver benzotriazoles than silver acetamidobenzotriazole are mentioned, and nitrobenzotriazoles represented by the following general formula [I] and benzotriazoles represented by the following general formula [II] are advantageously used. can.

General formula [I] In the formula, R2 represents a nitro group, R2 and R5 may be the same or different, and each represents a halogen atom (e.g. chlorine, bromine, iodine), a hydroxy group, a sulfo group or a salt thereof (e.g. sodium salt, potassium salt, ammonium salt), carboxy group or its salt (e.g. sodium salt, potassium salt, ammonium salt), nitro group, cyano group, or carbamoyl group, sulfamoyl group, alkyl group, each of which may have a substituent. groups (e.g. methyl group,
ethyl group, propyl group), alkoxy group (e.g. methoxy group, ethoxy group), aryl group (e.g. phenyl group)
Alternatively, it represents an amine group, m represents 0 to 2, and n represents a divisor of 0 to 1. Further, examples of substituents for the carbamoyl group include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. Examples of substituents for alkyl groups include carboxy and ethoxycarbonyl groups; examples of substituents for aryl groups include sulfo and nitro groups; and examples of substituents for alkoxy groups include carboxy and ethoxy groups. Examples of substituents for the carbonyl group and the amino group include an acetyl group, a methanesulfonyl group, and a hydroxy group.

The compound represented by the general formula [I] 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-methoxybenzotriazole, silver Nitro-7-phenylbenzotriazole silver,
4-Hydroxy-5-nitrobenzotriazole silver, 4
-Hydroxy-7-nitrobenzotriazole silver, 4-
Hydroxy-5,7-dinitropensotriazole silver, 4-hydroxy-5-nitro-6-chlorobenzotriazole silver, 4-hydroxy-5-nitro-6-methylbenzotriazole silver, 4-sulfo-6- Nitrobenzotriazole silver, 4-carboxy-6-nitrobenzotriazole silver, 5-carboxy-6-nitrobenzotriazole silver, 4-carbamoyl-6-nitrobenzotriazole silver, 4-sulfamoyl-6-nitrobenzotriazole silver, 5 -Carboxymethyl-6-nitrobenzotriazole silver, 5-hydroxycarbonylmethoxy-6-nitrobenzotriazole silver, 5-nitro-7-
Silver cyanobenzotriazole, silver 5-amino-6-nitrobenzotriazole, silver 5-nitro-7-(p-nitrophenyl)benzotriazole, 5,7-dinitro-
6-Metelbenzotriazole silver, 5,7-dinitro-
6-chlorobenzotriazole silver, 5,7-sinitro-
Examples include silver 6-methoxybenzotriazole.

General formula [II] In the formula, R4 is a hydroxy group, a sulfo group or a salt thereof (
For example, sodium salt, potassium salt, ammonium salt),
It represents a carboxy group or a salt thereof (e.g. sodium salt, potassium salt, ammonium salt), a carbamoyl group which may have a substituent, and a sulfamoyl group which may have a substituent, and R5 represents a halogen atom (e.g. 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 salt), nitro group, cyano group, or each Represents an alkyl group (e.g. methyl group, ethyl group, propyl group), aryl group (e.g. phenyl group), alkoxy group (e.g. methoxy group, ethoxy group) or amino group which may have a substituent, and p is 0. Represents an integer between ~2.

Further, examples of substituents for the carbamoyl group in R4 include methyl group, ethyl group, acetyl group, etc., and examples of substituents for sulfamoyl group include methyl group, ethyl group, acetyl group, etc. I can do it. Furthermore, examples of substituents for the alkyl group in R5 include carboxy group, ethoxycarbonyl group, etc., examples of substituents for aryl group include sulfo group, nitro group, etc., and examples of substituents for alkoxy group include, for example, Examples of substituents for carboxy groups, ethoxycarbonyl groups, and amino groups include acetyl groups, methanesulfonyl groups, and hydroxy groups.

Specific examples of the organic silver salt represented by the general formula [I] include the following compounds.

For example, silver 4-hydroxybenzotriazole, silver 5-hydroxybenzotriazole, silver 4-sulfobenzotriazole, silver 5-sulfobenzotriazole, silver benzotriazole-4-sodium sulfonate, silver benzotriazole-5-sodium sulfonate, benzotriazole silver Silver triazole-4-potassium sulfonate, silver benzotriazole-5-sodium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benzotriazole-5-ammonium sulfonate, silver 4-carboxybenzotriazole, 5- Carboxybenzotriazole 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, ammonium benzotriazole silver-5-carboxylate, silver 5-carbamoylbenzotriazole, 4-sulfur fuamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy-7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4-hydroxy-7-sulfobenzotriazole silver, 5,6-dicarpoxybenzothiliazole silver, 4,6-dihydroxybenzotriazole silver,
4-Hydroxy-5-chlorobenzotriazole silver, 4
-Hydroxy-5-methylbenzotriazole silver, 4-
Hydroxy-5-methoxybencitriazole silver, 4-
Hydroxy-5-nitrobenzotriazole silver, 4-hydroxy-5-cyanobenzotriazole silver, 4-hydroxy-5-aminobenzotriazole silver, 4-hydroxy-5-acetamidobenzotriazole silver, 4-hydroxy-5-benzenesulfone Amidobenzotriazole silver, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-
Hydroxy-5-carboxymethylbenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethelbenzotriazole silver, 4-hydroxy-5-phenylbenzotriazole silver, 4-hydroxy-5-(p-nitrophenyl)benzotriazole silver , 4-hydroxy-
5-(p-sulfophenyl)benzotriazole silver, 4
-sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5
-methoxybenzotriazole silver, 4-sulfo-5-cyanobenzotriazole silver, e-sulfo-5-aminobenzotriazole silver, 4-sulfo-5-acetamidobenzotriazole silver, 4-sulfo-5-benzenesulfonamidobenzotriazole silver, 4 -sulpo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-
sulfo-5-ethoxycarboxylmethoxybenzotriazole silver, 4-hydroxy-5-carboxydibenzotriazole silver, 4-sulfo-5-carboxymethylbenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-Sulfo-5-phenylbenzotriazole silver, 4-sulfo-5-(p-nitrophenyl)benzotriazole 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-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5 -acetamidobenzotriazole silver, 4-carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-5-carboxymethylbenzotriazole silver, 4-carboxy-
5-phenylbenzotriazole silver, 4-carboxy 5-(p-nitrophenyl)benzotriazole silver, 4
-carboxy-5-methyl-7-sulfobenzotriazole silver and the like. These compounds may be used alone or in combination of two or more.

In the heat-developable photosensitive material used in the present invention, the photosensitive silver halide used is specifically silver bromide, silver iodide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, silver iodine Mixtures of silver iodide and silver chloride, mixtures of silver iodide and silver chloride, mixtures of silver iodide and silver iodobromide, mixtures of silver iodobromide and silver bromide, silver bromide epitaxially bonded to silver iodide. Examples include silver halides having the following.

The photosensitive silver 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 particular, in the present invention, it is preferable to prepare a gelatin-silver halide photographic emulsion. The use of gelatin-silver halide emulsions prepared according to such techniques gives favorable results.

This photosensitive silver halide may have coarse or fine grains, but the preferred grain size is approximately 1.5 in major diameter.
micron to about 0.001 micron, more preferably about 0.5 micron to about 0.05 micron.

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 photosensitive silver salt forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, an NF4 group, and a metal atom group, and
represents Cl, Br, and I atoms; n represents 1 when M is an H atom or NH4 group; and represents the valence when M is a metal atom. 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, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, cerium, etc.), halogen-containing metal complexes (such as K2PtCl6,
K2PtBr6, HAuCl4, (NH4)2IrCl
6, (NH4)3IrCl6, (NH4)2RuCl6
, (NH4)3RuCl6, (NH4)3RhCl6,
(NH4)3RhBr6, etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromite, trimethylbenzylammonium bromide, and other quaternary ammonium halides), tetraethyl Quaternary phosphonium halides such as phosphonium bromide, tertiary sulfonium halides such as benzylethylmethyl bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform,
bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalic acid imide, N-bromoacetamide, N-iodosuccinic acid) imide, N-fromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethyl hydantoin, etc.), other halogen compounds (e.g. triphenylmethyl chloride, triphenylmethyl bromide),
2-frombutyric acid, 2-fromethanol, etc.).

These photosensitive silver halides and photosensitive silver salt forming components can be used in combination in various methods, and the amount used is 0.1 to 30 mol, preferably 0.3 to 30 mol, per 1 mol of organic silver salt. It is 5 moles.

Although the silver halide emulsion used in the present invention can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the methods described by Glafki-des or Zelikman et al. Frie-se
r edition de grundlagen der fotografisien brotsese mid zilbel halogennieden (Di
e Grundlagen der Photogra
phischen Yrozesse mit Sil
berhalogeniden) (Akademisc)
he Verlagsgesellschaft, 19
68) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a four-metal sensitization method using gold or other noble metal compounds, etc. may be used alone or in combination. Can be used. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rotanines, and other compounds can be used, and specific examples thereof include U.S. Pat. No. 410,689, No. 2.278,947
No. 2,728,668, No. 3,656,95
It is fully described in issue 5. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used.
Specific examples of these are U.S. Pat. No. 2,487,850 and U.S. Pat.
, No. 419,974, No. 2,518,698, No. 2.983.609, No. 2.983.610, and No. 2,694,637. For noble metal sensitization, complex salts of metals in group VIII of the periodic table, such as gold complex salts, platinum, iridium, and palladium, can be used; specific examples thereof include US Pat. No. 2,399.083;
No. 2,448.050, British Patent No. 618,061
It is written in the number etc.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes,
Included are merocyania dyes, complex cyanine dyes, complex merocyanine dyes, holobolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. For these dyes, any gold nucleus commonly used for cyanine dyes can be used as a basic heterocyclic nucleus. Namely, viroline nucleus, oxazole nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, pyridine nucleus, imidazole nucleus, tetrazole nucleus, pyridino nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei fused with aromatic hydrocarbons, i.e. indolenine nucleus, penzindolenine nucleus, indole nucleus, benzoxazole nucleus, rat oxisazole 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, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nuclei, thiazolinone-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc., can be applied. Useful sensitizing dyes are described, for example, in German Patent No. No. 929.080, U.S. Patent No. 2,231,658, U.S. Patent No. 2,493,
No. 748, No. 2,503,776, No. 2,519
, No. 001, No. 2,912,329, No. 3.65
5.394, 3.656,959, 3.6
These sensitizing dyes may be used alone. However, combinations thereof may also be used, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Pat.
3.527.641, 3,617.293, 3.628.964, 3,666,480
No. 3,679.428, No. 3,703, 37
No. 7, No. 3.769.301, No. 3,814.6
No. 09, No. 3,837.862, British Patent Nos. 1 and 3
44,281, Japanese Patent Publication No. 43-4936, etc.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with fluorine-containing heterocyclic groups (for example, U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,
635,721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743.5);
10) may contain cadmium salts, azaintene compounds, etc. U.S. Patent No. 3,615,613
No. 3.615.641, No. 3.617,29
The combinations described in No. 5, No. 3,635,721 are particularly useful.

Other additives used in the heat-developable photosensitive material used in the present invention include, for example, development accelerators:
U.S. Patent No. 3,220,846, U.S. Patent No. 3,531,2
No. 85, No. 4,012,260, No. 4.060,
No. 420, No. 4,088,496, No. 4,207
, 392 or Research Disclosures 15733, 15734, 15776, etc., organic acids described in Japanese Patent Publication No. 54-127110, and US Pat. No. 3,667,959. Non-aqueous polar solvent compounds having -CO-, -SO2-, -SO- groups as described, melt formers described in U.S. Pat. No. 3,438,776, U.S. Pat. No. 3,666,
There are polyalkylene glycols described in JP-A No. 477 and JP-A-51-19525. In addition, as a color toning agent, for example, JP-A No. 46-4928, JP-A No. 46-60
No. 77, No. 49-5019, No. 49-5020, No. 49-91215, No. 49-107727, No. 50
-2524, 50-67132, 50-676
No. 41, No. 50-114217, No. 52-33722
No. 52-99813, No. 53-1020, No. 5
No. 3-55115, No. 53-76020, No. 53-1
No. 25014, No. 54-156523, No. 54-15
No. 6524, No. 54-156525, No. 54-156
No. 526, No. 55-4060, No. 55-4061,
Publications such as No. 55-32015 and West German Patent No. 2,
No. 140,406, No. 2,147.063, No. 2
, 220,618, U.S. Patent No. 3,080.254, U.S. Patent No. 3,847,612, U.S. Patent No. 3,782.941
No. 3,994,732, No. 4.123,28
2. Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which are compounds described in the specifications of No. 2, No. 4,201,582, etc.
3-dihydro-phthalazinedione, 2,3-dihydro-
1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, °aminoquinoline, incarbosnoryl, sulfonamide, 2H-1
, 3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazabentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., and one or more of these and an imidazole compound Also, mixtures of at least one acid or acid anhydride such as phthalic acid and naphthalic acid or an acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, kentisic acid, etc. .

Further, as an antifoggant, for example,
No. 11113, JP-A-49-90118, JP-A No. 49-1
No. 0724, No. 49-97613, No. 50-1010
No. 19, No. 49-130720, No. 50-12333
No. 1, No. 51-47419, No. 51-57435,
No. 51-78227, No. 51-104338, No. 5
No. 3-19825, No. 53-20923, No. 51-5
No. 0725, No. 51-3223, No. 51-42529
No. 51-81124, No. 54-51821, No. 55-93149, and British Patent No. 1,
No. 455.271, U.S. Pat. No. 3,885,968;
No. 3,700,457, No. 4,137.079, No. 4,138,265, West German Patent No. 2.617.
No. 907 and other specifications, oxidizing agents (e.g. N-halogenoacetamide, N-halokenosuccinimide, perchloric acid and its salts, inorganic peroxides, persulfuric acid) salts, etc.), acids and their salts (e.g. sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), sulfur-containing compounds (e.g. mercapto compound-releasing adducts, thiouracil, disulfide, simple sulfur, mercapto- 1,2,4-triazole, thiazolinthione,
polysulfide compounds, etc.), others, oxazoline, 1
, 2,4-triazole, phthalimide and the like.

In addition, as a stabilizer, a printout preventive agent may be used in combination, for example, JP-A No. 48-45228, No. 50-119624, No. 50-120328, No. 5
Halogenated hydrocarbons described in Publication No. 3-46020, specifically tetrabromobutane, trifluoroethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromo Examples include methylsulfonylbenzotheazole and 2,4-bis(tribromomethyl)-6-methyltriazine.

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
Post-treatment may be carried out using a sulfur-containing additive as described in each publication.

Furthermore, U.S. Patent No. 3,301,678;
506.444, 3.824.103, 3
, No. 844.788, as well as the inthiuronium-based squabilizer recursor described in U.S. Patent No. 3.6.
No. 69.670, No. 4,012,260, No. 4,
It may also contain the activator stabilizer breaker described in No. 060,420.

Examples of water-retentive compounds include hydroxyethyl cellulose, carboxymethyl cellulose, polyalkylene oxide (polyglycol), and organic acids.

As the binder used in the present invention, any polymeric substance capable of causing tanning by reacting with the oxidized product of the tanning developing agent can be used. Particularly preferred binders include gelatin and its derivatives.

The image-receiving layer used in the present invention is formed of titanium white, ZnO, SiO2, Al2O3, etc. alone or in a suitable ratio in a mixture on a transparent support to a desired thickness by a method such as coating or vapor deposition. can be done.

As the transparent support on which the image-receiving layer is formed, synthetic plastic films such as polyethylene base sheets, polycellulose acetate films, polyethylene terephthalate films, etc. are used.

Examples of the photosensitive layer support used in the heat-developable photosensitive material of the present invention include synthetic plastic films such as polyethylene film, cellulose acetate film, and polyethylene terephthalate film, as well as photographic base paper, printing paper, baryta paper, and resin coated paper. I can give you some paper. These supports may have a subbing layer.

The above composition is coated on these supports together with a binder and a suitable solvent to form a heat-developable photosensitive layer. The thickness of the coating after drying is 1 to 1000μ, preferably 3 to 20μ
It is. Furthermore, an overcoat layer may be formed on the heat-developable photosensitive layer, if necessary.

A portion of each component of the present invention (a) organic silver salt, (b) photosensitive silver halide, (c) tanning developing agent, (d) color image forming dye, and (e) other additives are: It may be contained in the support by permeation from the heat-developable photosensitive layer. In addition, each component of the present invention (
Parts of a) to (e) may be contained in the overcoat layer and/or subbing layer by penetration from the heat-developable photosensitive layer.

The pH of the coating solution for the heat-developable photosensitive layer in the heat-developable photosensitive material used in the present invention is in the range of 2 to 7, with a particularly preferable pH range of 3 to 5. If the pH of the coating solution is lower than 2, the developability is good, but print-out after processing increases, and the object of the present invention is not achieved. Also, the pH of the coating solution
If the value is higher than 7, there will be very little cutting out after processing, but fog during development will increase and developability will deteriorate, making it impossible to obtain high sensitivity and high maximum density, and the object of the present invention will not be achieved.

To adjust the pH of the coating solution for the heat-developable photosensitive layer, add an acid such as nitric acid, sulfuric acid, acetic acid, or trichloroacetic acid, or an alkali such as ammonia, potassium hydroxide, sodium hydroxide, or quanidine to an appropriate solvent. This can be done by doing.

Further, the pAg of the coating solution for the heat-developable photosensitive layer in the heat-developable photosensitive material used in the present invention is in the range of 4 to 10.5, and the particularly preferable pAg range is 5 to 9. It is closely related to pH and changes in conjunction with pH, but generally when pAg is lower than 4, developability is good but print-out after processing increases, and pAg is lower than 4.
If it is higher, there will be less print-out after processing, but capri will increase during development, and developability will deteriorate, making it impossible to obtain high sensitivity and high maximum density, and in either case, the object of the present invention will not be achieved.

The heat-developable photosensitive material of the present invention produced as described above is usually exposed at 80°C to 20°C after imagewise exposure as a photosensitive material as it is.
The film can be developed by simply being heated for 1 to 60 seconds in the temperature range of 00°C. If necessary, the water-impermeable layer may be brought into contact and developed. Also, if necessary, heat the temperature at 70°C to 180°C before exposure.
Preheating may be performed in the temperature range of °C. Suitable light sources for image exposure include tungsten lamps, fluorescent lamps, mercury lamps, iodine lamps, xenon lamps, and C.
Examples include RT light sources and laser light sources.

According to the heat development color image forming method of the present invention, a dye image on an image plate can be easily obtained on the image receiving layer by a simple heat development process of heating after exposure, so that the dye image and silver image can be clearly distinguished. The present invention can be used in a wide range of applications as an unprecedented image forming method. Furthermore, since the color image forming method of the present invention is one of the dry methods, it can be incorporated into the device alone, and in particular, the color image forming method of the present invention can be incorporated into the device in combination with a recording device and a printing device. It also has the additional effect of expanding the functions of the system.

The invention will now be illustrated by way of examples.

Example 1 As shown in Figure 1 (1), an acid dye [X] dispersed in gelatin was applied as a lower layer on baryta paper (e) to form a dye layer (d), and the ingredients shown in Table 1 were coated on baryta paper (e). A silver salt emulsion layer (c) partially containing gelatin is coated as an upper layer, and a polyethylene base sheet (a) having an image-receiving layer (b) containing titanium white dispersed thereon is further laminated to produce a photosensitive material. It was adjusted. In the figure, A represents an image-receiving layer, and B represents a heat-developable photosensitive layer.

Acid dye [X] Table 1 After exposing this photosensitive material through an optical wedge, 18
A heat development process was performed at 0°C for 30 seconds.

Figure 1 (II) shows the layer structure and reaction system during thermal development, and the exposed area is tannin-developed and hardened under the conditions of 180°C and 30 seconds, forming the hardened silver salt emulsion layer (f). Therefore, the acid dye [X], that is, dye 1 in the figure, has an extremely low diffusion rate in the hardened silver salt emulsion layer (f), and becomes diffused dye 2 in the uncured silver salt emulsion layer (g). , reaches the image-receiving layer (b) made of titanium white and is fixed thereon.

In this way, an imagewise pattern with different image density according to the density of the optical wedge was formed by the dye. After development, the polyethylene base sheet with the image-receiving layer is peeled off,
The dye concentration was measured.

FIG. 2 shows the relationship between the silver image density of the silver salt emulsion layer on the light-sensitive material and the color image density of the image-receiving layer, based on the density of the optical wedge.

It was confirmed that a clear dye image was obtained on the image-receiving layer.

[Brief explanation of the drawing]

FIG. 1 shows the layer structure of a photosensitive material in the heat development process color image forming method of the present invention, in which (I) shows the layer structure during exposure, and (II) shows the layer structure and reaction during heat development. Display the system. FIG. 2 shows an image density characteristic curve obtained by the heat development color image forming method of the present invention. In the figure, A represents an image-receiving layer, B represents a heat-developable photosensitive layer, C represents light, D represents thermal energy, a represents a polyethylene base sheet,
b is the image receiving layer, c is the silver salt emulsion layer, d is the dye layer, e is baryta paper, f is the hardened silver salt emulsion layer, g is the uncured silver salt emulsion layer, h is the color image density curve of the image receiving layer , i represents the silver image density curve of the silver salt emulsion, 1 represents the dye, 2 represents the diffused dye, and 3 represents the fixed dye, respectively.

Claims (1)

[Claims] By subjecting the dye-containing silver salt photosensitive material to heat development treatment, tanning development is performed to harden the silver salt photosensitive material binder in an imagewise manner, and the diffusion of the dye from the binder to the image-receiving layer is controlled, thereby producing an image-receiving layer. A color image forming method using thermal development processing, which is characterized by forming an image-like color image on a layer.