JPH0228134B2 - NETSUGENZOKARAAKAKUSANTENSHAGAZONOKEISEIHOHO - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a heat-developable color diffusion transfer image, and more specifically, an image-forming method for obtaining a clear color image by sublimating and transferring an image formed from a specific color-providing substance into a heat-developable photosensitive material. Regarding. Color image forming methods using a photosensitive substance (silver halide) include, for example, a method using a dye formed by an oxidized color developing agent and a coupler, and a method to obtain an image by bleaching the dye with silver (silver dye). Bleaching method) or color diffusion transfer method, which uses an alkaline processing solution to diffusely transfer pigments used in so-called instant photography, are known, but both require a water-soluble processing solution and are difficult to form images. This has the disadvantage that the processing required to do so is complicated. Therefore, it is desired to develop a new photosensitive and thermal development color image forming method that forms color images using a dry process and simple processing. As a heat development color image forming method, for example, Japanese Patent Publication No. 7782, U.S. Patent No. 3761200, U.S. Pat.
No. 3764328, JP-A-56-27132, and JP-A No. 56-
As described in No. 27133, there is a color image forming method using an oxidized color developing agent and a coupler, but in these methods, a silver image is also formed where a dye image is formed. This may cause color turbidity, and staining of the white background may occur due to printouts after development. To eliminate these problems, desilvering and fixing steps are required, which impairs the simple and dry processing method that is an advantage of thermal development photography. Other thermal development color image forming methods include, for example, JP-A Nos. 52-105821, 52-105822, and 56-
There are silver dye bleaching methods described in No. 50328 and US Pat. No. 4,235,957. However, these methods require the use of an activation sheet containing a strong acid or a silver halide complexing agent for dye image bleaching, and have drawbacks such as complicated processing and the use of strong acids. There is. Still another heat-developable color image forming method is, for example, the dye silver salt method described in Research Disclosure No. 16966 published in May 1978. This method is attracting attention as a method that compensates for the drawbacks of the two methods mentioned above, but since the dye is transferred to a solvent when transferring the dye, not only the dye but also other undesirable additives are transferred. The dye silver salt itself is also transferred, which has the disadvantage of causing image fogging. Therefore, a first object of the present invention is to provide a novel image forming method that eliminates the various drawbacks of the conventional heat-developable color diffusion transfer image forming method described above. A second object of the present invention is to provide a method for forming heat-developable color diffusion transfer images that provides vivid color images by using specific color-donor materials that can release sublimable dyes or precursors as a function of development. It is about providing. The above-mentioned object of the present invention is to provide a thermally non-diffusible material represented by the following general formula (1) capable of releasing a sublimable dye or a sublimable dye precursor by reacting with an oxidized product of a developing agent produced by thermal development. After imagewise exposing a photothermographic material having a layer containing a color-providing substance,
An image-wise distribution of the sublimable dye or precursor is formed from the color-providing material by thermal development, and at least a portion of the image-wise distribution is thermally transferred to an image-receiving layer in a stacked relationship with the light-sensitive material. This is achieved by General formula (1) Dye-(J) _o -X (wherein, Dye represents a sublimable dye or precursor residue, and X is a 5-pyrazolone derivative residue and a group having a ballasting group, or When the binder is hydrophilic, it represents a group having a ballasting group and/or a hydrophilic group, J represents a divalent bonding group, and is bonded to the 4-position of the pyrazolone derivative. n is (Represents 0 or 1.) "Sublimability" generally refers to "the property of changing from a solid to a gas without passing through a liquid state," and many pigments that exhibit this sublimability are known in the industry. (Specific examples are shown in "Dye Handbook" (Maruzen)). Sublimable dyes are immobile solids at low temperatures and non-diffusible in the absence of a solvent. When it is heated and exceeds a certain temperature, it sublimates and becomes a gas, exhibiting diffusivity and being able to move through space. The sublimable dye of the present invention can also be transferred in a gaseous state by sublimating and melting and then vaporizing, and vaporization accompanied by this melting is also included in the sublimation transfer in the present invention. For example, a sublimable dye coated on a support vaporizes when heated, leaves the support, and diffuses. If there is an image-receiving layer nearby, the pigment will be adsorbed and deposited on the surface or inside the image-receiving layer, forming a dye image even if it is not in close contact with the support. Sublimable dyes also have the ability to diffuse between layers in a gaseous state. That is, even if there is an intermediate layer between the layer in which the sublimable dye is released and the image-receiving layer, the dye can be diffused and transferred without requiring a solvent. Therefore, by utilizing this property, it is easy to design a multilayer color heat-developable photosensitive material. In the present invention, the sublimable dye or sublimable dye precursor released in the heat development reaction has a low molecular weight, a small dipole moment, and is highly hydrophobic, so that the interaction with the hydrophilic binder is small, that is, the sublimable dye precursor is hydrophilic. It has low solubility in a hydrophilic binder and easily diffuses in a hydrophilic binder without the need for a solvent. Therefore, in the present invention, the combination of a sublimable dye or a sublimable dye precursor with a hydrophilic bander is advantageous for diffusion and transfer, i.e. the color from which the sublimable dye or sublimable dye precursor can be released. Preferably, the donor material is added into a hydrophilic binder. When a hydrophilic binder is used in this manner, the color-providing substance is non-diffusible (having a ballast group and/or a hydrophilic group) in order to be non-sublimable in the binder. In addition,
It is also possible to add a hydrophobic binder to the hydrophilic binder insofar as it does not interfere with the non-diffusibility of the color-providing substance and does not interfere with the diffusibility of the dye or dye precursor. According to the method of the present invention, an image is generated and fixed only by thermal processing, and a color image can be obtained with very simple processing. The present invention will be explained in more detail below. The present inventors have disclosed a method of forming a color image using a color-providing substance that releases a sublimable dye or precursor as a function of development in Japanese Patent Application No. 57-122599.
No. 57-160698. The former previously proposed technology is a method of obtaining a cyan colored image using a color donor using a phenol derivative or naphthol derivative as Dev [X in general formula (1)], and the latter previously proposed technology is , using a color-donor material capable of releasing a chelatable sublimable dye or precursor as a function of development, and applying a sublimable dye or precursor chelated with the multivalent metal ion to an image-receiving layer containing a multivalent metal ion. This is a method to obtain imagewise distribution. The present invention is improved over the previously proposed technology in that it uses a specific color-providing substance that is highly reactive with the oxidized form of a developing agent and has excellent release properties of sublimable dyes or precursors. . Furthermore, the present invention allows the latter previously proposed technique to be applied as is, which is rather preferable. The thermal non-diffusible color-providing substance represented by the general formula (1) used in the present invention will be explained next. The sublimable dye in the present invention has a sublimation temperature of 50
It is a dye such as an azo dye, anthraquinone dye, azomethine dye, indigo dye, triphenylmethane dye, xanthene dye, etc., which has a temperature of -250°C, more preferably 50 - 170°C, and may be a precursor thereof. In particular, it is preferable to use a sublimable dye that can be chelated, as shown in the latter previously proposed technique, and in this case, the image-receiving layer contains polyvalent metal ions [e.g. Platinum (), palladium () or cobalt ()
etc.], a metal chelate dye can be formed in the image-receiving layer after sublimation transfer, and a dye image with excellent fixing properties and light resistance can be obtained. In general formula (1), the divalent bonding group represented by J is -O-, -S-, -NH-, -OCO
--,

【formula】

【formula】

【formula】

[Formula] etc. can be mentioned. The bonding group on the left side has the general formula (1).
The bonding part on the right side is bonded to Dye in . Further, a preferable pyrazolone derivative represented by X can be represented by the following general formula (2). General formula (2) In the formula, R' represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group (preferably a phenyl group, 2,4,6-trichlorophenyl group, or 4-sulfamidophenyl group), R ² is an alkyl group having 1 to 24 carbon atoms, an aryl group, an alkylamino group, an arylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, a cyano group, a carboxy group, etc., and R ¹ and R ² At least one of them is a group that makes the compound represented by the general formula (1) and the pyrazolone derivative compound after dye release non-thermal diffusible (non-sublimable). The above-mentioned pyrazolone derivatives can be any magenta couplers known in the art as magenta couplers in the conventional photography field. Compared to the conventional so-called instant photography method, in which an image is formed by dyes diffusing in a concentrated alkaline solution that is harmful to the human body, the color thermal diffusion transfer method of the present invention creates a transferred image simply by heating at a fixed temperature for a fixed period of time. It is excellent in terms of safety and other aspects. Furthermore, in the conventional method of transferring dyes formed or released in a heat-developable photosensitive material using a thermal solvent, it is difficult to achieve a multilayer system, but with the method of the present invention, This is easily possible. In the present invention, the color-providing substance is thermally non-diffusive and does not substantially cause intralayer or interlayer diffusion even when heated. Furthermore, in the present invention, the color-providing substance is one that can release a sublimable dye or a sublimable dye precursor as a function of development, and can directly or indirectly control the redox reaction that occurs during development, or indirectly through a cross-oxidizing agent or the like. A release reaction occurs when the substance acts on the substance. Next, the heat-developable photosensitive material of the present invention will be explained. Heat-developable photosensitive materials have traditionally been used to form black and white images using silver.
43-4924, 43-19166, 46-4728, 43-19166, 46-4728,
No. 44-26582, No. 45-12700, No. 45-18416,
As described in JP-A No. 49-52626, etc., it is composed of a support, a photosensitive silver halide, a metal (silver) salt or complex of an organic compound, a developer, and a binder. The above-mentioned conventionally known photothermographic materials can also be used. Particularly preferred as the developer are color developing agents or their precursors known in the photographic field, such as p-phenylenediamine derivatives and p-aminophenol derivatives, such as 2-methyl-
4-(N-methylsulfonamidoethyl-N-ethylamino)-aniline, 4-(N,N-diethylamino)-aniline, 4-(phenylsulfonamide-aniline, 4-morpholinoaniline, 4-
These include phenylsulforamidophenol, 3,5-dichloro-4-aminophenol, and the like. Heat-developable photosensitive materials include color toning agents, chemical sensitizers, development regulators, antifoggants, spectral sensitizers,
Filter dyes, antihalation dyes, etc. may also be added. Substances constituting the above-mentioned heat-developable photosensitive material - support, photosensitive silver halide, metal (silver) salt or complex of organic compound, developer, binder, toning agent,
Chemical sensitizers, development modifiers, antifoggants, spectral sensitizers, filter dyes, antihalation dyes, etc. are described in more detail on pages 9 to 15 of Research Disclosure published in June 1978. These can also be referred to for the structure of the photothermographic material used in the present invention. Next, an example of the structure of the photothermographic material used in the present invention will be explained. The photothermographic material used in the present invention comprises at least one layer (A) provided on a support. The layer (A)
is represented by general formula (1) as a function of (a) photosensitive silver halide, (b) silver salt of an organic compound, (c) heat developing material such as a developing agent, and (d) heat development in a binder. It has at least one color-providing substance, and comprises components (a), (b),
(c) and (d) may be contained in the same layer or in separate layers as long as they are in a state where they can react with each other, and the absorption wavelength of the color donor substance If the wavelength range overlaps with the sensitive wavelength range of the photosensitive silver halide, the color donor is placed in a position that does not reduce the sensitivity of the combined silver halide, i.e. in the direction of exposure relative to the photosensitive (silver halide) layer. Preferably, it is contained in the layer located on the opposite side. However, if the absorption wavelength of the color-providing substance is different from that of the dye produced in the image-receiving layer and does not overlap with the photosensitive range of the combined photosensitive silver halide, the color-providing substance and the photosensitive silver halide, etc. can be contained in the same layer. In a preferred embodiment of the present invention, the photothermographic material has a layer (A) consisting of the following three different layers on a support. That is, three different layers (A) each containing a color-donor releasing dye or precursor capable of forming yellow, magenta, and cyan dye images in the image-receiving layer, and correspondingly spectrally sensitized silver halide. Since the released dye is in a gaseous state, only the dye can move between the overlaid layers, preventing undesirable interlayer effects and movement of other substances between layers during transfer. A multicolor image can be obtained without any interference. In addition to the layer (A) containing the photosensitive layer, the heat-developable photosensitive material used in the present invention may optionally include a subbing layer,
It may have an intermediate layer, a protective layer, a reflective layer, etc. Various binders can be used in the present invention. Examples include proteins such as gelatin, gelatin derivatives, casein, sodium caseinate, and albumin, cellulose derivatives such as ethylcellulose, polysaccharides such as dextran and agar, natural substances such as gum arabic and gum tragacanth, and the dimensional stability of photographic materials. These include latex-like vinyl compounds and synthetic polymers such as those described below. For example, US Patent No. 3142586, US Patent No. 3193386
No. 3062674, No. 3220844, No. 3220844, No. 3062674, No. 3220844, No.
Examples include those described in the specifications of No. 3287289 and No. 3411911. Examples of useful polymers include water-insoluble polymers based on alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates. Also, polyvinyl butyral,
Polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate,
Polymethyl methacrylate, polyvinyl pyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride, chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alkote, polyvinyl acetate, Examples include benzylcellulose, cellulose acetate, cellulose propionate, and cellulose acetate phthalate. Preferred hydrophilic binders that can be used in the present invention to non-diffuse the color-providing substance and diffuse the released sublimable dye or sublimable dye precursor include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxylic Examples include methylcellulose, polyethylene glycol, polyethylene glycol ester, sodium alginate, propylene glycol alginate ester, polyvinyl alcohol, water-soluble polyvinyl butyral, polyvinylpyrrolidone, starch, agar, dextran, and gelatin. If necessary, two or more types may be used in combination. The amount of binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts per part of organic silver salt for each photosensitive layer. Next, the image receiving layer of the present invention will be explained. The image-receiving layer of the present invention basically has only to have the function of stopping the transfer of the imagewise distribution of the sublimated and transferred dye and fixing it. For example, it may simply be a layer of gelatin or other synthetic polymer, or it may be a layer of wood pulp or other synthetic pulp fibers. In addition, in order to improve the efficiency of sublimation and transfer, inorganic compounds such as titanium white, silica, and acid clay are added to the image-receiving layer, and PH
You may also adjust. Further, the image-receiving layer may be integrated with the photosensitive layer, or may be in a form that can be separated from the photosensitive layer. Furthermore, after being imagewise exposed without having an image-receiving layer, it is overlaid with any cloth (handkerchief, shirt, sheet) or paper and thermally developed, and an image is formed using the cloth or paper as an image-receiving layer. You may be When the sublimable dye used in the present invention is a sublimable dye that can be chelated, it is sufficient to contain polyvalent metal ions in the image-receiving layer. A valent metal ion donating substance may be included, or only polyvalent metal ions may be included, and the multivalent metal ion donating substance itself may also serve as an image-receiving layer.
As a preferable polyvalent metal ion donating substance, Tokkosho
No. 36-11535, JP-A-55-48210, JP-A No. 55-129346
No. 57-122596, and Japanese Patent Application No. 57-160698. Preferably, the polyvalent metal ion contained in the image-receiving layer reacts quickly with the released dye, forms a complex with a desired hue, strongly coordinates with the ligand,
It is substantially colorless in an image receiving layer such as an image receiving sheet.
Polyvalent metal ions having such properties include copper (), nickel (), palladium (), zinc (), platinum (), and cobalt (), but particularly preferred are copper () and nickel (). (). The image-receiving layer according to the present invention may be in a stacked relationship with the heat-developable photosensitive material before exposure, or may be stacked on the heat-developable photosensitive material after exposure and before development,
Further, after development, the image-receiving layer may be laminated with the heat-developable photosensitive material to transfer the dye image. After transfer, the image may be observed (through the support) without peeling off the image-receiving layer, but it is preferable to separate it from the photothermographic material by peeling off the image-receiving layer. An example of the method for forming a thermal color diffusion transfer image of the present invention is shown below. (1) The above-mentioned heat-developable photosensitive material, or a recording material made by laminating the photosensitive material and an image-receiving layer (or image-receiving sheet), is cut into a suitable size and then imagewise exposed. Light sources for image exposure include sunlight, tungsten lamps, fluorescent lamps, mercury lamps,
A light source such as a halogen lamp (such as an iodine lamp or a xenon lamp) or a laser beam can be used. (2) About 50 to 250°C, preferably 100 to 200°C, when the photosensitive layer of the photosensitive material is in contact with the image-receiving layer.
Heat at a temperature of Heating time is 5 seconds to 180 seconds,
Preferably it is 15 to 90 seconds. As a heating method, conventionally known methods used for heat-developable photosensitive materials can be used. There are methods of heating the material by passing through it, or by using high frequency heating or a laser beam. (3) Subsequently, a color image is obtained by peeling off the image-receiving layer from the photosensitive layer. In the present invention, in order to form a multicolor image, yellow, yellow and
A light-sensitive material is described above comprising at least three distinct layers, each containing a color-donor material that releases dyes capable of forming magenta and cyan dye images, and correspondingly spectrally sensitized silver halide and other heat-developable materials. This is achieved by exposing the image to light in the same manner as above, heat developing it in a stacked relationship with the image-receiving layer, sublimating it, and transferring it. Specific examples of color-providing substances used in the present invention are listed below. however,

[Formula] or

[Example color-donor substance]

The amount of the color-providing substance used in the present invention is not limited, but is generally 0.1 mg to 100 ^cm2 .
It may be 500 mg, preferably 0.5 mg to 50 mg. Further, the method of addition is arbitrary, and for example, it may be added by grinding with a sand mill or ball mill, or by dissolving it in a solvent and adding it into the binder. Hereinafter, the image forming method of the present invention will be explained by giving specific examples. Example 1 To 7.26 g of 4-hydroxybenzotriazole silver, 24 c.c. of a 25% aqueous solution of water-soluble polyvinyl butyral (Sekisui Chemical Co., Ltd., ESLETSUKU W-201), 116 c.c. of water, and 70 c.c. of methanol were added, and an alumina ball mill was added. The mixture was pulverized and dispersed to obtain a silver salt dispersion. To 25 c.c. of this silver salt dispersion, 0.21 g of phthalic acid, 0.16 g of phthalazine, and 1.11 g of the above-mentioned color-providing substance CPM-(2)
g, 0.42 g of the following developer, 5 c.c. of a 25% aqueous solution of water-soluble polyvinyl butyral, 10 c.c. of water, and 36 mg of silver iodide gelatin emulsion with an average particle size of 0.04 μ in terms of silver, It was applied onto photographic baryta paper using a wire bar so that the wet film thickness was 55 μm. [Developer] The dried sample was exposed to white light at 30,000 CMS through a step wedge. Separately, an image-receiving paper was prepared by applying a 10% acetone solution of cellulose diacetate to ivory paper so that the amount of cellulose diacetate was 1.20 g per square meter. The coated surface of the exposed sample and the coated surface of the image-receiving paper were brought into close contact, and after heating and pressing with an iron having a surface temperature of 150° C. for 30 seconds, the sample and the image-receiving paper were peeled off. An orange step wedge image with a maximum reflection density of 0.88 and a minimum reflection density of 0.13 was obtained on the surface of the receiving paper. Comparative Example 1 A sample obtained in the same manner as in Example-1 except that the following CPM compound was used as a color-providing substance was subjected to the same exposure as in Example-1, and the same image-receiving paper as in Example-1 was used. As in Example 1, the material was thermally developed for 30 seconds with an iron at 150°C for sublimation and transfer, and the maximum reflection density was 0.76 and the minimum reflection density was 0.11. In order to increase the maximum reflection density to 0.85 or higher, it was necessary to heat the film at 150°C for 1 minute, but the minimum density in this case was 0.25. Example 2 4.5 g of silver behenate, 20 ml of alcohol, 5 ml of water, and 15 ml of a 25% aqueous solution of water-soluble polyvinyl butyral.
and make a dispersion liquid [1] using an ultrasonic homogenizer.
was prepared. Meanwhile, 0.20 g of phthalic acid, 0.13 g of phthalazine, 1.12 g of the above-mentioned exemplary color donor CPM-(3), and 2.55 g of the following developer were mixed with 40 c.c. of a water-soluble polyvinyl butyral 8% water-alcohol (1:1) solution. Ball mill dispersion was performed for 24 hours to obtain solution-[1]. [Developer] Further, silver trifluoroacetate and lithium bromide were reacted in a 10% water-alcohol (1:1) solution of water-soluble polyvinyl butyral to obtain emulsion-[1]. Dispersion - [1] 0.3 cc of a 0.05% methanol solution of the following sensitizing dye and 20 mg of mercuric acetate were added to 10 cc. [Sensitizing dye] Finally, the above solution-[1] was added and coated onto a transparent polyester film using a wire bar so that the wet film layer had a thickness of 74 μm to form a photosensitive layer. A white reflective layer and an image-receiving layer having the following compositions were provided thereon, and another transparent polyester film was adhered onto the image-receiving layer. [White reflective layer] (Unit: g/m ² ) Titanium dioxide (average particle size 1.5μ) 15 Cellulose diacetate 1.2 Sodium dodecyl sulfate 0.08 Ethanol 25 Water 30 [Image-receiving layer] (Unit: g/m ² ) Cellulose diacetate 1.5 Acetone 20 The photosensitive layer side of this sample was exposed to 30,000 CMS through a step wedge, and the photosensitive layer side was pressed with an iron having a surface temperature of 130°C for 30 seconds. The image receiving layer has a maximum reflection density of 0.82 and a minimum reflection density of 0.82.
A lemon yellow image of 1.0 was obtained. Example 3 5-nitrobenzotriazole 7.80g Exemplary color-providing substance CPM-(14) 1.45g Ossein gelatin 10% aqueous solution 84c.c. Water 120c.c. Methanol 96c.c. The above composition was dispersed in an alumina ball mill. hand,
A dispersion liquid [3] was obtained. Similarly, a solution [2] having the following composition was prepared.

[Table] After mixing the above dispersion liquid - [3] 25 c.c. and solution - [2] 15 c.c., add 0.11 g of silver bromide gelatin emulsion with an average particle size of 0.04 μm in terms of silver. The mixture was coated on photographic baryta paper and dried to obtain a photosensitive layer. The dried sample was exposed to white light at 40,000 CMS through a step wedge. On the other hand, an aqueous solution containing 15% water-soluble polyvinyl butyral and 10% nickel chloride was placed on ivory paper so that the amount of polyvinyl butyral per square meter was
An image receiving paper containing nickel chloride was prepared by applying 1.40 g of nickel chloride. The coated surface of the exposed sample and the coated surface of the receiver paper were brought into close contact and heated with an iron at a surface temperature of 150℃ for 30 minutes.
After pressing and heating for seconds, when the photosensitive layer and receiver paper were peeled off, the maximum reflection density was 0.92, and the minimum reflection density was 0.92.
A magenta dye image chelated with nickel ( ) ions of 0.15 was obtained. These results show that according to the present invention, stable color images can be obtained through simple processing.

Claims (1)

[Scope of Claims] 1. A thermally non-diffusible compound represented by the following general formula (1) capable of releasing a sublimable dye or a sublimable dye precursor by reacting with an oxidized form of a developing agent produced by thermal development. A photothermographic material having a layer containing a color-providing substance is imagewise exposed and then thermally developed to form an imagewise distribution of the sublimable dye or precursor from the color-providing substance. A method for forming a heat-developable color diffusion transfer image, comprising thermally transferring at least a portion of the distribution to an image-receiving layer in a stacked relationship with the photosensitive material. General formula (1) Dye-(J) _o -X (where Dye leaves a residue of a sublimable dye or precursor, and X is a 5-virazolone derivative residue and a group having a ballasting group, or When the binder is hydrophilic, it represents a group having a ballasting group and/or a hydrophilic group, J represents a divalent bonding group, and is bonded to the 4-position of the pyrazolone derivative. n is (represents 0 or 1)