JPS60218643A - Process for forming heat developing type color picture image - Google Patents

Abstract

PURPOSE:To obtain a positive color picture image directly by a simple treatment and using simple materials by executing heat development of a heat development color sensitive element by contacting with an image receiving element. CONSTITUTION:A heat development color photosensitive element contg. a silver salt oxidizing agent, reducing agent, a dye donating material capable of forming or discharging a diffusive dye by the heat development, and a binder is image- exposured. After heat development of the photosensitive element by contacting with an image receiving element, the image receiving element is released. The heat development color photosensitive element treated by the above described process is then heat developed by contacting with the image receiving element.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method of forming a color image 1# using a hot mass II, and more specifically, a method of forming a color image 1# using a hot mass II, and more specifically, a method of forming a color image 1# using a hot mass II, and more specifically, a method of forming a color image 1# using a hot mass II, and more specifically, a method for forming a color image 1# using a hot mass II, and more specifically, a method of forming a color image 1# using a hot mass II, and more specifically, a method of forming a color image 1# using a hot mass II, and more specifically, a method for forming a color image 1# using a hot mass II, and more specifically, a method for forming a color image 1# using a hot mass II, and more specifically, a method for forming a color image 1# using a hot mass II. Concerning the method of formation. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to Ike's photographic method in terms of photosensitivity, gradation, image preservation, etc., and is the most widely put into practical use. This is a photography method that has been around for a long time. However, in this method, wet processing is used for processing steps such as fixation and washing, so the processing is time-consuming and labor-intensive, and there are concerns that the processing chemicals may cause pollution to the human body. There are many problems, such as concerns about contamination of the process room and workers by the above-mentioned chemicals, and consideration of pollution caused by waste liquid. Therefore, there has been a demand for the development of a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photography method, and among them, heat-developable photosensitive materials in which the developing step can be performed by heat treatment have attracted attention as photosensitive materials that meet the above-mentioned requirements. Regarding such heat-developable photosensitive materials, for example,
No. 3-4921 and Japanese Patent Publication No. 43-4924 disclose photographic materials comprising an organic silver salt, a silver halide, and a reducing agent. These technologies form #iron by exposing a photosensitive silver salt such as silver halide to light, use this latent image as a catalytic nucleus, and conduct a redox reaction (VC) between an organic iron salt and a reducing agent during heating. This gives it a silver edge. Attempts have also been made to obtain color images by using color-forming iron herbal medicines and couplers in the thermal mass-sensitizing source material. Regarding such technology, for example, U.S. Pat. No. 3,53
1.286, 3,761,270 and 3
, 764, 328, etc., disclose a photosensitive material comprising an organic acid silver salt, silver halide, an aromatic primary amine phenolic agent, and a coupler. With these techniques, it is possible to make one negative image superior to the original image 11i1. In contrast, direct positive W
Techniques for obtaining J jobs have been proposed. For example, Research Disclosure (R
e5earch Dlscjoure) (hereinafter referred to as R
D) April 1976 issue A14433, 1976
December issue Bian 15227, U.S. Patent No. 4,235,95
No. 7 and other publications describe useful dyes and bleaching methods. However, this method requires extra materials such as overlapping and heating activator sheets to speed bleaching of the dye. Furthermore, useful compounds and methods for directly forming a positive iron by incorporating a nitroxyl compound into a light-sensitive material are described in U.S. Pat. No. 4,124,387. However, the positive steel obtained by this method has a high degree of turnip IJ di, so it is difficult to say that this method is practical. In addition, RD January 1979 issue A1770 regarding the method of directly forming positive iron by using a dye reducing agent.
6 describes useful dye reducing agents and auxiliary developing agents. However, this method has the problem that a magenta color image and a cyan color image cannot be obtained. [Object of the Invention] Therefore, the object of the present invention is to provide a method for forming a pus by a silent viewing method, which allows a positive color image to be directly obtained using simple processing and materials. Another object of the present invention is to provide a method for forming a single image using the close viewing method, which allows a practical positive color image with low capri density to be obtained. Also, the purpose of the pond of the present invention is cyan, magenta and yellow positive II! The object of the present invention is to provide a method for forming images using a thermal phenomenon method that can obtain a till effect. [Structure of the Invention] As a result of extensive studies, the present inventors have found that the above object is to provide a silver salt oxidizing agent, a reducing agent, a dye-donating substance that is formed with or released from a diffusible dye by heat development, and a binder. Contains heat-developable color photosensitive material! After the element is imagewise exposed, it is thermally developed in close contact with a receiving element, the image receiving element is peeled off, and the heat-developed color photosensitive element after the above treatment is closely adhered to a receiving element to form a thermal mass, a single image color image. We have discovered what can be achieved by the iron forming method. The dye-providing substance used in the thermal one-image color photosensitive element used in the present invention (hereinafter referred to as the photosensitive element of the Sewer invention) is one that can be used to form a one-image diffusion transfer type dye-one image. Regardless of the type, such as dye-releasing type or dye-forming type, the dye is released by the oxidative coupling reaction described in, for example, JP-A No. 59-12431, Japanese Patent Application No. 57-224883, etc. Chemical attachment, special request 1977
No. 8-33363, No. 5B-34083, No. 58-1
Compounds that form dyes through oxidative coupling reactions, such as those described in No. 09293, can be used. Examples of preferred dye-donating substances are listed below [Dye-donating substances] [l] H C,, H,. [2] H [3] 0 units [4 units ■ 1lHH [5] H [6] H [7] H Cl8HjII

[9] R 80, H [10] C/ [11] [12] Cl [13] (4 [14] [15] [I6] [17] C,, H,. [19] NHCOCH30H C10”3! [Add] C7! C,, H2S [21] [22] OCH. 14- [Ta] OH O No. CH. [24] [5] [26] OHN [A] - 0 CH. [(9)] CH OCR. [31] OSO, Na CH. [32] 11 H, N, I O [A] H [A] H NHCOC,, H3゜ [36] H NHCOC+aHsi [37] A] 0 0H. The above book of invention The dye-salting substance used in the photosensitive element varies depending on the current photosensitive composition, coating conditions, processing method, etc., but is generally used in the range of 0.01 mol to 10 mol per mol of the silver salt oxidizing agent. The amount is preferably from 0.1 mol to 2.0 mol.In order to incorporate the dye dissipating substance into the heat-developable photosensitive layer of the photosensitive element of the present invention or its adjacent layer, for example As described in Japanese Patent No. 2,322.027, it can be dissolved and contained in a high-boiling point solvent. Examples of the above-mentioned high-boiling point solvent include di-n-butyl phthalate, tricresyl phosphate, and dichloromethane. -octyl phthalate, n-nonylphenol, etc. In order to incorporate the dye dissipating substance into the thermal mass II photosensitive layer of the thermal development color photosensitive material or its adjacent layer, the Fischer dispersion method can also be used. Fischer dispersion is also called Agefer dispersion (UK patent 45F).
, No. 556, No. 465,823, No. 298.979, and Japanese Patent Application No. 104901/1988 can be referred to. In this way, there is no need for grinding using a ball mill or sand mill as in the conventional method, and the dye image can be finely and stably dispersed in the heat-developable photosensitive layer in a short time. Transfer density can be improved. In addition, in the present invention, a hydrophilic binder can be used as the binder for the one-image photosensitive layer as described later, so when coating the heat-developable photosensitive layer on a support, a non-organic solvent, that is, an aqueous solvent is used. In particular, when gelatin is used as one of the binders, its setting property can be utilized, so it is non-polluting and does not necessarily require horizontal coating, which simplifies the process for manufacturing photosensitive materials. be converted into Examples of the reducing agent used in the photosensitive element of the present invention include U.S. Pat.
No. 0 and No. 3,764.328, U.S. Pat.
137.079-j), lfl*4.138,265 British Patent No. 2.018.453, JP 51-6016
2.6. -dichloro-4-aminophenol, 2.6
-dipromo-4-aminophenol, 2+6-di-4-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminephenol, or their salts such as hydrochloride and sulfate , and N,N-dimethyl-p-phenylenediamine, N,N-diethyl-
p,-phenylenediamine, N-ethyl-N-carboxymethyl-2-methyl-p-7enylenediamine, 3
-acetylamino-4,-aminodimethylaniline, N
-ethyl-N-β-methanesulfonamidoethyl-4-
aminoa, niline, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline, N
-ethyl-N-β-hydroxyethyl-3-methyl-4
-aminoaniline, N-ethyl-N-β-methoxyethyl-3-methyl-4-aminoaniline, or the like. Examples include salts such as hydrochloride, sulfate, and p-toluenesulfonate. Further useful reducing agents include Japanese Patent Application No. 58-104901.
No. 58-236075, No. 58-'23607
No. 6, No. 5B-236077, No. 58-236078
No., February 29, 1981 patent application "Thermal phenomenon 1 phenomenon color photosensitive material" sulfonoa epsilon doaniline,
Examples include sulfonamide draenol, sulfonamide pyrazolone, alkylaminophenylsulfacic acid, sulfaminobi-razolone, and sulfaminophenol. Specific examples of particularly useful reducing agents will be given below. □〔
Reducing agent] C,)i. (5) H3 (6) C1H. (7) (8) (9) (10) (1) (14) (15) (16) The reducing agents used in the photosensitive element of the present invention can be used alone or in combination of two or more. Also, the amount used is
Although it depends on the type of silver salt oxidizing agent used, the type of photosensitive silver halide, and the type of other additives added as necessary, it is usually per mole of organic silver salt (oxidizing agent). The amount ranges from 0.05 mol to 10 mol, preferably from 0.1 mol to 3 mol. Examples of the organic silver salt (oxidizing agent) used in the photosensitive element of the present invention include Japanese Patent Publications Nos. 43-4921, 44-26582, 45-18416, 45-12700, and 4
No. 5-22185, JP-A No. 49-52626, No. 52
-31728, 52-137321, 52-1
No. 41222, No. 53-36224, No. 53-376
Publications such as No. 10 and U.S. Patent No. 3.330,63
No. 3, No. 3.794.496, No. 4.105.4
No. 51, No. 4.123.274, No. 4.168,
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, silver behenate, α- (1-phenyltetrazolethio)
Silver aromatic carboxylates, such as silver acetate, e.g. silver benzoate,
Silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 45-
No. 12700, No. 45-18416, No. 45-221
No. 85, JP-A-52-31728, JP-A No. 52-1373
Publications No. 21, Japanese Patent Application No. 57-1065, No. 57-1
Silver salts of imino groups as described in specifications such as No. 066, such as benzotriazole silver, 5-nitrobenzotriazole silver, 5-chlorobenzotriazole silver,
5-methoxybenzotriazole silver, 4-sulfobenzotriazole fi14-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nidrobenzimidazole silver, pyrazole silver, urazole silver, 1.2.4-triazole silver,
IH-tetrazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., and 2-mercagutopenzoxazole silver, mercaptooxadiazole silver, 2-mercagutopenzothiazole silver, 2-mercaptobenzimidazole, etc. Silver, 3-mercapto-4-phenyl-1゜2,4-triazole silver, 4-hydroxy-6-methyl-1+3s3a+7-titrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4゜6-
Examples include silver pentazaindene. Among the above organic silver salts, imino group silver salts are preferred, and benzotriazole spinner silver salts are particularly preferred. When it is safe to increase the sensitivity of the photosensitive element of the present invention, it is preferable to number the photosensitive silver halide. Examples of photosensitive silver halides include silver chloride, silver bromide,
Examples include silver iodide, silver chlorobromide, silver chlorobromoiodide, silver chloroiodide, silver chloride, and mixtures thereof. These can be used in combination of one or more types. Preparation of silver halide can be carried out by any method known in the photographic field, such as the single jet method, double jet method, or 1-method. The photosensitive silver halide may be chemically sensitized by any method known in the photographic field. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The photosensitive silver halide prepared in advance in this manner can be added to serve as a component of the photosensitive element used in the present invention. If gelatin is used as one of the binders in the present invention, there is an advantage that such a sensitization method can be easily carried out. Furthermore, as a method for preparing a pond, a photosensitive silver halide forming component is allowed to coexist with the organic silver m (al2 converting agent), and an organic steel base C
It is also possible to form photosensitive silver norogenide in a part of the #R-forming agent). The photosensitive silver halide-forming components used in this preparation method include inorganic) halogen crops, such as M
A halogen compound represented by 1. When M is a metal atom, its valence is shown. The metal atoms here include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, macinatum, calcium, strontium, /(
IJium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, lead, antisulfur, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, rhodium, palladium, osmium,
Examples include iridium, platinum, and cerium. ];]Norogen-containing metal complexes such as PtCJ6,
K, PtBr6. HkuC7l, . (NH,), Ir('/, , (NH,), Ir
CJ, , (NHa)*RuCA! s. (NH4)S RuC41(NH4)l RhCAl5
+ (NH4)l RhBr. etc.], onium nolides (e.g., quaternary ammonium nolides such as tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, tetraethyl 7-osphonium quaternary phosphonium halides such as bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, N-ethylthiazolium bromide, etc.); halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, -bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromphthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromphthalazinone, N-chlorophthalazinone) , N-bromoacetanilide, N,N-cyfromobenzenesulfonamide, N-promoN-methylbenzenesulfonamide, 1゜3-dibromo-4,4-dimethylhydantoin, etc.); triphenylmethyl, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). These photosensitive silver halide and photosensitive silver halide forming components can be used in combination in various methods, and the number used is 0.001 mol to 4.0 mol per 1 mol of organic silver salt (oxidizing agent). molar range, preferably 0.01 e
It is ~1°0 mole. Additives such as development accelerators used in the photosensitive element of the present invention include dicarboxylic acids and phthalazine described in JP-A-57-207245;
Carboxylic acids and carbonamides containing a thioether group as described in JP-A-58-3763
6, triazoles having a mercapto group described in JP-A No. 58-184156, etc.
Examples include polyhydroxy compounds described in No. 8038. Components other than those mentioned above that can be used in the photographic constituent layers of the light-sensitive element of the present invention include a spectral sensitizer, an antihalation agent, a non-mercury-based anticapri agent, a printout inhibitor, a water release agent,
Various known additives such as water sampling agents can be optionally added. As the spectral sensitizer, one that is effective for the silver halide emulsion is used. Examples include cyanine, merocyanine, rhodacyanine, and styryl pigments. Binders used in the photosensitive element of the present invention include synthetic or natural polymeric substances such as polyvinylpyrrolidone, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, gelatin, and phthalated gelatin. These can be used alone or in combination of two or more. For example, a combination of gelatin or a derivative thereof and polyvinylpyrrolidone or polyvinyl alcohol is effective for V9u. Examples of the support used in the photosensitive element of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film, and paper supports such as photographic base paper, printing paper, baryta paper, and resin-coated paper. can give. The above-mentioned components are coated on these supports together with a binder and an appropriate solvent to form a hot lump iron sensitizing layer. These components do not necessarily need to be contained in a single layer, and may be separated and contained in separate layers as long as they are in a state where they can react with each other. When the photosensitive element of the present invention has a multilayer structure, for example, a yellow dye-providing substance is contained in a blue-sensitive thermal block iron photosensitive layer, a magenta dye-donating substance is contained in a green-sensitive heat-developable photosensitive layer, and a red-sensitive thermal block iron photosensitive layer. In the case of the multilayer structure described above, the thickness of each photosensitive layer is 1 μm to 1000 μm after drying.
m, preferably 3 μm to 20 μm. If necessary, an intermediate layer may be provided, and an undercoat layer or a topcoat layer may be formed. After the photosensitive element of the present invention produced in this way is exposed to positive image as it is, it is brought into close contact with the first image receiving element, and usually
Color development and transfer can be achieved simply by heating for 1 to 120 seconds in the temperature range of .degree. C. to 200.degree. (The first image-receiving element may be in close contact with the photosensitive element before image exposure.) Peel off the first image-receiving element and add the second image-receiving element to the IC.
1! 1 in the temperature range of 120°C to 250°C.
Heat for ~120 seconds. By such an operation, a clear positive image can be obtained on the second image receiving element. Furthermore, if necessary, the entire surface may be exposed to light before the second thermal block weaving, or a capri agent may be used, but a single thermal phenomenon at a high temperature is sufficient to form a positive image. To further explain the process of forming the painting according to the present invention, first,
Exposure to the photosensitive element forms a negative latent image on the image. When this occurs as a thermal phenomenon, a color negative iron is produced by the reaction between the oxidized form of the reducing agent produced by the redox reaction between the organic silver salt and the reducing agent and the dye-donating substance (cobler) using this latent image as a catalyst nucleus. can get. This is transferred to the first image receiving element. In the photosensitive element remaining after the above processing, organic silver salts, reducing agents, dye-providing substances, etc. remain in a positive relationship with respect to exposure. Then, by carrying out capri development by second heating, a positive color transfer is obtained by the reaction between the oxidized reducing agent and the dye-providing substance (fogger), and this is transferred to the second image-receiving element. The receiving elements (first and second) used in the present invention consist of a support and an image receiving layer, and the support may be the same as that used in the photosensitive element described above. The image-receiving layer may be any material as long as it can receive the thermally transferred dye, preferably polyester, polycarbonate,
A layer made of at least one kind of polymer selected from polyvinyl chloride and polyvinylidene chloride may be mentioned. These polymers are dissolved and coated onto a support using a suitable solvent. Further, if necessary, an adhesive layer or a dye-impermeable layer may be provided between the support and the image-receiving layer. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. However, embodiments of the present invention are not limited thereto. Example-1 20Ii of 4-sulfobenzotriazole and 4I of sodium hydroxide in alcohol/water = (1/1) solution 2
00IIL1. To this solution, 20 mm of a 5N aqueous silver nitrate solution was added dropwise. At this time, a 5N sodium hydroxide water bath solution was added dropwise to maintain the pH at 7-8. The solution was stirred for 1 hour, water was removed, and the solution was finished to 300% to prepare a 4-sulfobenzotriazole silver dispersion. 1.3II of the following dye-providing substance (1) was mixed with 4M ethyl acetate and 1.5g of dioctyl phthalate, and dissolved by heating. This bath was mixed with an 8% gelatin solution containing a surfactant at 17,5 mA! The mixture was mixed with water, the volume was made up to 3 Q ml, and stirred with a homogenizer for 5 minutes to prepare a milk dispersion. . Dye-providing substance (1) C,,H 3 The above 4-sulfobenzotriazole silver solution 5d and dye-providing substance dispersion 6p were mixed, and further polyvinylpyrrolidone (molecule 3130000) 7301v, pentaerythritol 5201#, Polyethylene glycol (molecule 31400) 310 da, water 3 d and the following 3A imager 20
After adding 0 Da, the pH was adjusted to 5.5 with 8 citric acid. Silver iodobromide with an average particle size of 0.05 μm was added to this dispersion in 3×10-'E-le in terms of silver, and the mixture was coated onto a polyethylene terephthalate support using a wire paper so that the wet film thickness was 65 μm. did. EXAMPLE 1 A sample obtained by drying the above coating was exposed to % 30.000 CM8 through a step wedge. Next, the following ammonium chloride (1
) were piled up and pressed and heated for a leap second using a metal heat block with a surface temperature of 140° C., and the receiving edge element (1) was peeled off. Next, stack the following receiver (11! element (2)) until the surface temperature is 170.
℃ heating for 90 seconds with a metal heat block and peeled off the element (2) with one negative element (1) and one positive element (2) with one negative element. Ta. The positive results obtained for the first element (2) are shown in Table 1 below. The receiving elements (1) and (2) used here are both the same and were coated onto photographic baryta paper using a 10% vinyl chloride solution in tetrahydrofuran to a dry film thickness of 50 μm. be. Example-2 The dye-donor shown below was used in place of the diocugul phthalate in Dye-donor (1) 1.3.9 and 1.511 used in Example-1! (2) It was operated in the same manner as in Example-1 except that 2, 3 g and 2.09 dioctyl 7-talate were used. Dye-providing substance (2) Example-3 Dye-providing substance (1) used in Example-1 In place of 1.3 g and 1.5 g of dioctyl phthalate, dye-providing substance (3) shown in F below 1.51! The same procedure as in Example 1 was conducted except that 2.0 g of dioctyl phthalate was used.・→ The results of one positive image obtained in Examples 1 to 3 are summarized in Table 1. In addition, the submerged positive image II was measured by the reflection density for red light in Example-1, the reflection density for blue light in Example-2, and the reflection density for green light in Example-2. did. Table 1 From Table 1, it can be seen that according to the present invention, positive images of '/7' magenta and yellow with low capri density can be obtained. [Effects of the Invention] According to the present invention, a practical color positive with low capri density can be obtained using simple processing and materials. Agent Patent Attorney No 1) Parent-in-law

Claims (1)

[Claims] ゛ After exposure to a thermal mass II color photosensitive agent containing a silver hydrochloride additive, a reducing agent, a dye depleting substance that forms or releases a diffusible dye by applying heat fA1, and a binder, 111! The thermal mass in close contact with the element is separated, and the heat-sensitive element is peeled off, and the thermally applied color photosensitive element after the above treatment is transferred to the thermal mass in close contact with the matrix element. A method for forming a thermal mass ■Color image II, characterized by