JPH01241493A - Color transfer recording method - Google Patents

Abstract

PURPOSE:To transfer uniform and high-density images, by laminating an ink sheet and a mask sheet with each other, breaking imagewise a light-reflective layer of the mask sheet, bringing an image-receiving sheet into close contact with a thermally transferable solid ink layer, irradiating the ink layer with optical energy to transfer the ink layer onto the image- reiceiving sheet, and repeating these operations for each color to perform color superposition. CONSTITUTION:A mask sheet 16 and an ink sheet 17 are laminated with each other by passing between rollers 18a, 18b, whereas a transfer recording medium is passed between earthing rollers 19a, 19b, and the surface of a light reflective layer of the mask sheet is maintained at the earth potential. The medium reaches a position between an electric discharge recording head 20 and a platen roller 21, and the light-reflective layer corresponding to an ink is subjected to imagewise discharge breakdown. An image-receiving sheet 5 fixed by a gripper 23 is brought into close contact with the surface of a thermally transferable solid ink layer by rotating a transfer drum 24, and is fed between the drum 24 and a glass plate 25, followed by irradiation with light from a flash lamp 27, whereby the first color ink corresponding to the part broken away by electric discharge is transferred onto the image-receiving sheet 5. The sheet 5 is held by the gripper 23 in close contact with the drum 24, which is rotated by one rotation. Color superposing transfer is conducted in the same manner as for the first color.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a transfer recording method suitable for recording high-resolution characters or images, and particularly to a color transfer recording method suitable for multi-color or full-color recording.

2. Prior Art As shown in FIG. 6, a conventionally proposed transfer recording medium has a light-reflecting layer 2 on the upper surface of a light-transmitting support 1 and a photothermal layer containing a photodegradable compound on the lower surface for improving transferability. The conversion layer 3 has a structure in which a thermally transferable solid ink layer 4 is provided on the lower surface of the light-to-heat conversion layer 3. To perform recording using this transfer recording medium, the light reflecting layer 2 is
is removed according to the information pattern, and as shown in FIG. 7, the surface coated with thermally transferable solid ink N4 is brought into close contact with the image receiving sheet 5, and a xenon flash lamp 6 is used to illuminate the light reflective layer 2 with ultraviolet rays and visible light. and emit a flash of light containing infrared rays.

As a result, the flash of light irradiated onto the portion where the light reflection PJ2 remains is reflected, and the flash of light irradiated onto the portion from which the light reflection layer has been removed passes through the support 1 and reaches the photothermal conversion layer 3. The photothermal conversion layer absorbs flash energy and effectively converts it into thermal energy. As a result, the thermally transferable solid ink layer 4 starts thermal melting or thermal sublimation and is transferred onto the surface of the image receiving sheet 5. Thereafter, a transferred image was obtained by peeling off the discharge recording medium and the image receiving sheet.

When layering colors, perform each of the above steps with yellow,
A subtractive color mixing method was employed in which the above steps were repeated for each monochromatic heat transferable solid ink layer consisting of magenta, cyan, and, if necessary, black.

Problems to be Solved by the Invention However, the above-mentioned conventional transfer recording media include yellow,
Magenta and cyan inks have major deficiencies in their subtractive color mixing properties, that is, in their color overlapping characteristics and density uniformity.

That is, when the first color ink is transferred, the ink is transferred very well due to the volume expansion of the gas generated as a result of photodecomposition of the photodegradable compound, but on the other hand, the ink is As a result, the air permeability of the transferred ink surface increases significantly due to the strong pressing force of The sudden ejection force of the gas and the retention of the gas in the ink layer cause the ink to solidify in a roughened state.
A smooth surface cannot be maintained.As a result, when the second color ink is transferred onto the first color ink layer surface, it is transferred onto a surface with high air permeability and low smoothness. .

Therefore, it becomes extremely difficult to dissipate the gas generated as a result of photolysis, and the transferred ink surface becomes even rougher than in the case of the first color. Furthermore, due to the rapid ejection force of gas,
As a result of the second color ink being strongly mixed with the first color ink, a trapping problem occurs in which a portion of the first color ink adheres to the medium side and is separated from #1 depending on the degree of surface roughening. . Furthermore, since the transfer is to a surface with low smoothness, the situation is disadvantageous for the transfer of the second color ink.

For the same reason, the transferability of the third color becomes even more difficult, and a satisfactory color result becomes impossible. Furthermore, if there is a distribution of light energy over the irradiated area, and before separating the image receiving sheet and the transfer recording medium,
When light is irradiated twice, there will be a large difference in the air permeability and smoothness of the surface between the part that has been irradiated with light once and the part that has been irradiated with light twice. As a result, density unevenness will occur. Therefore, when a color transfer image is obtained by repeating light irradiation, it is difficult to obtain a uniform density without unevenness.

In view of the above-mentioned circumstances, the present invention is a color transfer system that is faithful to discharge breakdown recording and has improved color transfer characteristics (subtractive color mixture characteristics) so as to obtain a uniform, high-density transferred image with no density unevenness. The purpose is to provide a recording method.

Means for Solving the Problems In view of the above circumstances, the present invention has been made as a result of intensive studies to solve the problems.

The first aspect of the present invention is to provide a photothermal conversion material on one side of a photothermal conversion support having a thickness of 10 mm or less, which is formed by providing a photothermal conversion substance as a separate layer on the support or blending it into the support. An ink sheet is provided with a foam layer containing a compound, and on the other side, monochromatic color thermal transfer solid ink layers of yellow, magenta, cyan, or a combination of these and black are sequentially arranged in a two-dimensional manner, and a light-transmitting layer is provided. A light-reflecting layer removable by discharge rupture recording is provided on the grained layer of the transparent support, and the other surface of the light-transmitting support has room temperature adhesiveness, heat-sensitive adhesiveness, or pressure-sensitive adhesiveness. Using a mask sheet provided with an adhesive layer that is solid or semi-solid at room temperature, (a) bonding the foam layer surface of the ink sheet and the adhesive layer surface of the mask sheet using a heat roller or a pressure roller to create a transfer recording medium; (b) After destroying the light-reflecting layer of the mask sheet imagewise by discharge destruction recording, an image-receiving sheet is brought into close contact with the surface of the thermally transferable solid ink layer of the ink sheet to form a light-reflecting layer. A step of selectively generating heat and melting the thermally transferable solid ink layer by irradiating the entire surface with light energy from the side and transferring it onto the image receiving sheet; A step of producing a monochromatic transfer recorded image on an image receiving sheet by repeating steps (1) and (c) for each monochromatic color. A color transfer recording method characterized by subtractive color mixing.

Furthermore, the second invention provides a photothermal conversion layer and a foaming layer containing a photothermal conversion substance and a photodegradable compound on one side of a support having a thickness of 10 mm or less using the ink sheet used in the first invention, Except that the first ink sheet was replaced with an ink sheet in which, on the other side of the support, single-color heat transferable solid ink layers of yellow, magenta, and cyan, or a hue consisting of these and black were sequentially arranged in a two-dimensional manner. A color transfer recording method characterized in that subtractive color mixing is performed in the same manner as in the invention.

The ink sheet and mask sheet used in the color transfer recording method of the present invention will be explained below based on the drawings.

Figures 2 (a), (b), and (c) show the structure of the ink sheet used in the first invention;
In b), the photothermal conversion layer 12a containing the photothermal conversion substance 13 is provided on the support 9, and the foamed layer 8 containing the photodegradable compound is provided on the support 9, and then the photothermal conversion layer 12a is provided on the other side of the support. This is an ink sheet in which a thermally transferable τ ink layer 4 is provided.

FIG. 2(B) shows that after a foam layer 8 containing a photodegradable compound is provided on a support 9, a photothermal conversion layer 12b containing a photothermal conversion material 2r13 is provided on the other side of the support. This is an ink sheet on which a thermally transferable solid ink layer 4 is provided.

FIG. 2(c) shows a photothermal conversion support 12c containing a photothermal conversion substance 13 in the support itself, and a foamed layer 8 containing a photodegradable compound provided on this support. This ink sheet has a heat transferable solid ink layer 4 provided on the other side of the body.

FIG. 3 shows the structure of the ink sheet used in the second invention, in which a photothermal conversion layer/foaming layer 10 containing a photothermal conversion substance and a photodegradable compound is provided on a support 9,
A thermally transferable solid ink, 1
This is an ink sheet provided with 4.

The materials used for the above ink sheet are as follows. [Photothermal conversion support #-] (A) When the photothermal conversion material is formulated as a separate layer, i.e., photothermal conversion 1, (Fig. 2 (a), (b) [Support] The support used in the present invention is , polyethylene terephthalate, polyimide, polycarbonate, cellophane, and various other heat-resistant and i-resin films.

In this case, in the case of the structure shown in FIG. 2(B), the support must be transparent, but in the case of the structure shown in FIG. 2(B), it may be transparent or opaque.

The thickness of the support is an important requirement in the present invention. That is, it is essential that it is 10 or less, and it is particularly preferable that it is in the range of 1 to 4.

This is because, if the thickness of the support is 1ρ or less, during the production of the ink sheet, the support may be damaged by sharpness and wrinkles during transportation, unevenness and coating streaks during the coating of each layer, and furthermore, when the ink sheet is produced, This is because many problems such as wrinkles will occur. In this case, since the heat capacity is small and the mechanical strength is weak, the support material is significantly altered and deteriorated due to the heat generated by the photothermal conversion material and the pressing action caused by the volume expansion of the photodecomposition gas.
This is because it can become deformed and even burst. This is because when the thickness of the support is greater than 10, the heat generated is absorbed by the support itself due to the large cursor l, resulting in a decrease in thermal sensitivity. In addition, the mechanical strength is too strong, which significantly impedes the effect of pressure accompanying the volumetric expansion of the photolyzed gas, resulting in a significant drop in performance.

[Light-to-heat conversion layer] The light-to-heat conversion layer in the present invention is formed by dissolving or dispersing a light-to-heat conversion substance that absorbs light energy and converts it into thermal energy in a binder. It is essential for a photothermal conversion material to absorb light energy including ultraviolet rays, visible light, infrared rays, etc. over a wider wavelength range and convert it into thermal energy more effectively, and carbon black is a suitable material system for this purpose. , graphite, various metal powders and their oxide powders, and various organic pigments and dyes.

These photothermal conversion substances can be used alone or in combination of two or more types. The amount of photothermal conversion material used is
The appropriate amount is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of the total solid content in the light-to-heat conversion layer.

The coating material for the light-to-heat conversion layer is obtained by adding a binder, a light-to-heat conversion substance, and various additives as necessary, and dissolving or dispersing the mixture in an appropriate solvent. This coating material for the light-to-heat conversion layer is formed on the surface of the support by a solvent coating method. The thickness of the photothermal conversion layer is 0601 to 10
ρ, preferably in the range of 0.1 to 5 ρ.

(B) When the photothermal conversion substance is blended in the support as a mixed layer (Figure 2 (c)) In this case, the photothermal conversion support is a support in which the photothermal conversion substance is dispersed in the binder. Use your body.

As the binder in this case, resins with high mechanical strength, heat resistance, and chemical resistance are desirable, and specific examples include polyarylate resin, polysulfone resin, polyacrylate resin, polycarbonate resin, polyimide resin,
Examples include polyurethane resins, polyester resins, silicone resins, fluororesins, polystyrene resins, and various cellulose resins. As the photothermal conversion substance, the above-mentioned material systems can be used as they are.

In this case, the photothermal conversion support can be formed by mixing the binder and the photothermal conversion material, and then applying various molding methods commonly used in the plastic industry. That is, specific examples thereof include compression molding, transfer molding, injection molding, extrusion molding, and calender molding.

On the other hand, it can also be obtained by dissolving or dispersing the binder and the photothermal conversion substance in a suitable solvent, forming a film by cast coating on a releasable separator, and then peeling it off. In this case, the separator is
It must have high heat resistance, chemical resistance, and surface smoothness, and must satisfy removability after being cast coated and dried. Specific examples include various fluororesins, polyester resins, silicone resins, etc. Can be done.

In this case, for the same reason as in case (A), it is essential that the thickness of the photothermal conversion support is 10 mm or less, and it is particularly preferably in the range of 1 to 4 mm.

[Foamed Layer] The foamed layer in the present invention is formed by dissolving or dispersing at least a photodegradable compound in a binder. In this case, suitable binder materials for the foam layer include organic solvent-soluble resins such as acrylic resins, styrene resins, and vinyl resins, and water-soluble resins such as polyvinyl alcohol, polyvinyl butyral, and imbutylene/maleic anhydride copolymers. The material can be appropriately selected from among polyester resins, various waxes, and rubbers.

Next, it is essential that the photodegradable compound added to the foam layer be photodecomposed by light including ultraviolet rays, visible rays, infrared rays, and the like. Material systems suitable for this purpose include diazo compounds and azide compounds. Among these, the diazo compounds include those conventionally used in the field of diazo copying materials.

That is, specific examples thereof include 4-diazo-1-dimethylaminobenzene, 4-diazo-1-diethylaminobenzene, 4-diazo-1-benzoylamino-2,5
-jethoxybenzene, 4-diazo-1-morpholinobenzene, 4-diazo-1-morpholino-2,5-dimethoxybenzene, 4-diazo-1-morpholino-2,5-
Jetoxybenzene, 4-diazo-1-pyrrolidino-3
-Methylbenzene, 4-diazo-1-pyrrolidino-2-
Methylbenzene, 4-diazo-1-dimethylamino-2
-(4'-chlorophenoxy)-5-chlorobenzene and the like can be mentioned.

The above-mentioned diazo compound can be stabilized by forming a double salt of its chloride and a metal halide such as zinc chloride, cadmium chloride, and tin chloride.

Further, the diazo compound may be stabilized by forming a complex salt with a fluoride acid such as tetrafluoroboric acid, hexafluorophosphoric acid, or fluorosulfuric acid, or an organic boron salt such as sodium tetraboronate.

On the other hand, as the azide compound, aromatic azide compounds are particularly effective, but in addition, 4,4'-diazide-diphenylsulfone, 4,4'-diazidebenzosulfone,
, 4'-Diazidostilbene, 4.4'-Diazidobenzalacetone, 2゜6-di(4-azidobenzal)-
4-methylcyclohexanone and the like can be applied to the present invention.

The above-mentioned diazo compounds and azide compounds can be used alone or in combination of two or more. The appropriate amount of these photodegradable compounds to be used is 0.1 to 80 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the total solid content in the foam layer.

The paint for the foam layer is obtained by adding the above-mentioned binder, photodegradable compound, and various additives as necessary, dissolving or dispersing it in a suitable solvent, and applying it by a solvent coating method to a concentration of 0.01 to 20 ρ. , preferably to a coating thickness of 0.1 to 10 a.

[Photothermal conversion/foaming layer] The photothermal conversion/foaming layer in the second invention is formed by dissolving or dispersing the above-mentioned photothermal conversion substance and photodegradable compound in a binder. The binder material used for the foam layer can be used as is.

The photothermal conversion/foaming layer is made in exactly the same way as the foaming layer.
By solvent coating method, 0.01~20ρ,
It is preferably applied to a coating thickness of 0.1 to 10 tIM.

[Thermal Transferable Solid Ink Layer] The thermal transferable solid ink layer is mainly composed of a binder, a colorant, and, if necessary, a softener. In this case, binders include waxes, higher fatty acids, higher fatty acid esters, higher alcohols, amides, ester gums, rosin derivatives such as rosin phenol resins, polymeric compounds such as terpene resins and cyclopentadiene resins, stearylamine, and valmityl. Examples include higher amines such as amines, polyethylene glycol, polyethylene oxide, and the like.

The colorant can be selected from conventionally known dyes or pigments. As a specific example, cyan color pigments include magenta color pigments such as Diaceriton Fast Brilliant Blue R (manufactured by Mitsubishi Kasei Co., Ltd., trade name), Kayalon Polyester Blue B-3F Conc (manufactured by Nippon Koyaku Co., Ltd., trade name), etc. As for Diaceriton Fast Red R (manufactured by Mitsubishi Kasei Corporation,
Yellow pigments include Kayalon Polyester Light Yellow 5G-3 (manufactured by Nippon Koyaku Co., Ltd., trade name), Kayalon Polyester Pink RCL-E (manufactured by Nippon Koyaku Co., Ltd., trade name), Eisens Viron Yellow GRH (manufactured by Hodogaya Chemical Co., Ltd., trade name). In addition, cyan pigments include cerulean blue and phthalocyanine blue, magenta pigments include brilliant carmine and alizarin lake, yellow pigments include Hansa yellow and bisazo yellow, and black pigments include carbon black, graphite, and Oil black etc. can be mentioned.

Heat-sublimable or heat-vaporizable colorants include disperse dyes, oil-soluble dyes, acid dyes, mordant dyes, vat dyes, basic dyes, etc., which are generally used in transfer printing of textiles and heat transfer inks. You can choose.

Specific examples include azo, anthraquinone, nitro, styryl, naphthoquinone, quinophthalone,
Examples include azomethine dyes, coumarin dyes, and condensed polycyclic dyes. The sublimation starting temperature of these dyes is 150℃
The following are desirable.

In the above heat transferable solid ink layer, thermoplastic resins such as ethylene/vinyl acetate copolymer, butyral resin, polyamide resin, plasticizers, oil agents such as bamboo oil, vegetable oil, etc. may be added, or as necessary. Depending on the situation, anti-blocking agents, inorganic and organic pigments, antioxidants, ultraviolet absorbers, antistatic agents, surfactants, etc. may be added. The thermally transferable solid ink layer, which may have a multilayer structure with separate functions, is formed by a hot melt coating method or a solvent coating method. The thickness of the thermally transferable solid ink layer is 0.
A suitable range is 1 to 10-1, preferably 1 to 5a+.

In FIGS. 2 and 3, the thermally transferable solid ink layer has a structure in which monochromatic thermally transferable solid ink layers of yellow, magenta, cyan, and, if necessary, black are sequentially arranged in a plane. (hereinafter referred to as "field sequential shape").

For example, as shown in FIG. 4(A), each monochromatic color thermally transferable interlayer ink layer 4a is sequentially applied along the flow direction of the support.
, 4b, 4C and 4d, or a fourth
As shown in Figure (B), the heat transferable solid ink layers of each grass color color may be sequentially provided along the width direction of the support. In this case, each single color heat transferable solid ink layer 4a
, 4b, 4C, and 4d correspond to, for example, yellow, magenta, cyan, and black.

FIG. 5 shows the structure of the mask sheet used in the present invention, in which a roughened layer 11 is placed on a light-transmitting support 1, and a light-reflecting layer 2 that can be removed by discharge destruction recording is placed on top of the roughened layer 11. The mask sheet is provided with an adhesive layer 14 that is solid or semi-solid at room temperature and has heat-sensitive or pressure-sensitive adhesive properties on the other side of the light-transmissive support.

The materials used for the above mask sheet are as follows. [Light-transparent support] Various heat-resistant resin films such as polyethylene terephthalate, polybutylene terephthalate, polyimide, polycarbonate, seven-mouth fan, aromatic polyamide, etc. are used as the light-transparent support used in the present invention. The appropriate thickness is 1 to 1100 mm, preferably 4 to 30 mm.

[''fA Surface roughening layer] The roughening layer in the present invention is formed by dispersing at least an inorganic or organic pigment or fine particles in a binder. In this case, a suitable binder for the roughening layer is used. The material system is preferably a resin with high mechanical strength and stability, heat resistance strength and stability, and chemical resistance. Specific examples thereof include polyester resin, polyurethane resin, polystyrene resin, various cellulose resins, and polyimide. Examples include various thermoplastic resins and thermosetting resins such as resins, silicone resins, fluororesins, polyarylate resins, epoxy resins, alkyd resins, etc.If the above can be cured, for example, curing When the means of curing is heat, a curing agent, a chain extender, a catalyst, etc. can be added to the base resin.When the means of curing is light, especially ultraviolet rays, resin monomers ( Alternatively, oligomers), photopolymerization initiators, thermal polymerization inhibitors, and various sensitizers can be added.When the curing means is electron beam, various sensitizers can be added to the base resin. can.

Next, the pigments or fine particles to be blended into the roughening layer include inorganic pigments such as silica, alumina, tin dioxide, hydrated alumina, and glass peas, crosslinked polystyrene resin, phenol resin, polymethyl methacrylate resin, silicone resin,
Examples include organic pigments or fine particles such as benzoguanamine, benzoguanamine/formaldehyde condensation polymer resin, and melamine/formaldehyde condensation polymer resin. These pigments or fine particles preferably have relatively high transparency, and may be used alone or in combination of two or more types.

The appropriate amount of these to be used is 0.1 to 60 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total solid content in the roughened layer. The coating material for the roughened layer can be obtained by adding the above-mentioned binder, pigment or fine particles and, if necessary, various additives such as a curing agent and a catalyst, and dissolving or dispersing the mixture in a suitable solvent. The paint is coated onto a light-transmitting support using a solvent coating method.
．． It is applied to a coating thickness of 0.01 to 20a+, preferably 0.1 to 10IEn.

[Light Reflection Layer] A gold R vapor-deposited film of aluminum, zinc, tin, etc., which is easily destroyed by discharge, is applied. As the vapor deposition method, a resistance heating vapor deposition method, a direct current or high frequency sputtering method, an ion blating method, an ion beam vapor deposition method, a cluster ion beam vapor deposition method, etc. can be used. The thickness of the light reflective layer is o, o
A suitable range is oi to 1 μm, preferably 0.01 to 0.1.

[Adhesive Layer] The adhesive layer in the present invention is made of a substance that is solid or semi-solid at room temperature and has room temperature adhesiveness, heat-sensitive adhesiveness, or pressure-sensitive adhesiveness.

Room-temperature adhesive substances include polymeric materials with a low glass transition temperature that are conventionally known as adhesives, such as polystyrene, polyolefin, polyester, polyurethane, polyamide, polyvinyl, polyvinylidene, and epoxy. Resins such as acrylic resins, acrylic resins, and rosin resins can be used as they are. On the one hand, water-soluble polymeric materials, such as vegetable-based viscous substances such as gum arabic, locust bean gum, sodium alginate, and agar, animal-based viscous substances such as hyaluronic acid and gelatin, and fibers such as methylcellulose, cellulose phosphate, and carboxymethylcellulose, base resins, and polyvinyl alcohol,
Examples include synthetic viscous substances such as polyacrylic acid and polyvinylpyridine.

The heat-sensitive adhesive substance has a melting point or softening point of 30°C to 7.
0°C, and materials that develop or increase the degree of tackiness or adhesiveness when heated are preferred. Specific examples of thermomeltable resins include carnauba wax, paraffin wax, microcrystalline wax, Waxes such as ester wax, oxidized wax, and montan wax, higher fatty acids such as stearic acid and behenic acid, higher alcohols such as palmityl alcohol and stearyl alcohol, higher fatty acid esters such as cetyl palmitate and cetyl stearate, acetamide, and stearin. Examples include amides such as acid amides.

Specific examples of resins that exhibit supercooling properties after hot melting include Santicizer-9 (a mixture of orthotoluenesulfonamide and baratoluenesulfonamide), chlorinated diphenyl, benzotriazole, tribenzylamine, polyethylene glycol, and benzoin. Examples include acids.

Specific examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, polyvinyl resins such as polyvinyl acetate, polyvinyl alcohol, and ethylene-vinyl acetate copolymer resins, as well as polyesters, polyurethanes, and polyamides. Examples include resins such as resins.

As the pressure-sensitive adhesive substance, polymeric materials conventionally known as pressure-sensitive adhesives, such as polyolefin-based, acrylic-based, and various rubber-based resins, can be used as they are.

The above adhesive layer materials can be used alone or in combination of two or more.

The above adhesive layer material can be used without special treatment, but if necessary, it may be encapsulated in microcapsules. Encapsulation can be achieved by conventionally known methods. . That is, U.S. Patent No.
Coacervation method using hydrophilic wall material disclosed in Publication No. 800457 etc., US Patent No. 328715
Interfacial polymerization method disclosed in Publication No. 4 etc., British Patent No. 9
Electrolytic dispersion cooling method disclosed in Publication No. 52807 etc.
Any method such as the spray drying method disclosed in US Pat. No. 3,114,07 etc. can be applied.

As the wall material of the microcapsule, polyurethane resin, polyamide resin, urea/formaldehyde copolymer resin, melamine resin, polystyrene/acrylate copolymer resin, gelatin, polyvinylpyrrolidone resin, polyvinyl alcohol resin, etc. may be used alone or in combination. Can be used together.

The particle size of the microcapsules is suitably in the range of Q, 01 to 20, preferably 0.05 to 2a.

The adhesive layer is coated by a solvent coating method or a non-solvent coating method such as a hot melt method by adding the above-mentioned adhesive layer material and various additives as necessary. The thickness of the layer is suitably in the range of 0.01 to 5, preferably 0.05 to 2a+. In addition, the interfacial adhesive force after bonding the mask sheet and the ink sheet through the layer is preferably in the range of 0.1 to 20 g W/an, preferably 0.5 to 10 g vt/■. be.

Next, the case where the color transfer recording method of the present invention is carried out using the above-described ink sheet and mask sheet will be explained below based on the drawings.

FIG. 1 is a diagram schematically explaining a process for carrying out the color transfer recording method of the present invention.

In FIG. 1, a mask sheet 16 is first wound around a mask sheet core 16a so that the light reflecting layer is on the inside, and a mask sheet 16 is wound around an ink sheet core 17a so that the thermally transferable solid ink layer is on the inside. The enclosed ink sheet 17 passes between hot or pressure rollers 18a, 18b. At this time, the adhesive layer surface of the mask sheet and the foam layer surface of the ink sheet or the photothermal conversion and foam layer are overlapped and bonded together. The thus bonded transfer recording medium passes between ground rollers 19a and 19b. At this time, the light-reflecting layer surface of the mask sheet is held at ground potential.

Next, the transfer recording medium reaches between the discharge recording head 2o and the platen roller 21, where the light reflection layer corresponding to the first color (for example, yellow ink) is destroyed by discharge in the form of an image. After that, the image receiving sheet conveying roller 2
As the transfer drum 24 rotates, the image-receiving sheet 5, which is conveyed between 2a and 22b and fixed by the "claws" 23 provided across the surface of the transfer drum 24, is transferred to the surface of the thermally transferable solid ink layer of the transfer recording medium. It is closely followed. In this state of close contact, the transfer drum 24 and the glass plate 25 are conveyed, and at this position, a flash lamp 27 such as a xenon lamp or an iodine lamp with a reflection plate 26 is used to irradiate the entire surface of the light reflection layer. will be done.

As a result, the thermally transferable solid ink of the first color (for example, yellow ink) corresponding to the discharge destruction removed portion recorded in the form of an image on the light reflection layer of the transfer recording medium is transferred onto the image receiving sheet. The image receiving sheet to which the colored ink has been transferred is held by the claw 23 and rotates once in close contact with the transfer drum.

The transferred recording medium is transferred to the capstan roller 28a.
, 28b, and is wound around the bobbin winding core 29. Meanwhile, during this time, the second color (
For example, the light-reflecting layer corresponding to the ink (magenta ink) is similarly destroyed by electrical discharge in the form of an image, and then, just as in the case of the first color, overlapping color transfer is performed on the surface to which the first color ink was transferred. Ru.

Next, the image receiving sheet onto which the second color ink has been transferred is rotated once while being held by the claw 23 in close contact with the transfer drum. While the transferred medium is wound onto a bobbin core, the light-reflecting layer corresponding to the third color (for example, cyan ink), which is provided in a plane-sequential manner, is similarly destroyed by electric discharge in an imagewise manner, and then the first Color overlapping transfer is performed in exactly the same way as in the case of the first color and the second color. Through the above steps, subtractive color mixing is completed, and a color transfer recorded image can be obtained. At this time, if necessary, black ink can also be transferred using the same process to increase the contrast of the image. is rotated and released from the transfer drum 24.

Effects Since the present invention has the above-mentioned configuration, it performs the following effects.

1. Regarding the non-blocking effect when pulling out a mask sheet that has been spring-cold in a roll form, the light-reflecting layer of the mask sheet is provided on the roughened layer, so when pulling out a mask sheet that has been spring-cold in a roll form, there is no blocking effect. The contact area with the adhesive layer provided on one surface is relatively significantly small, so blocking with the light reflective layer does not occur.

2. Regarding the bonding effect of the mask sheet and the ink sheet, when the mask sheet and the ink sheet are passed through a heat roller or a pressure roller, the adhesive layer generates tackiness or adhesion, and as a result, the mask sheet and the ink sheet are bonded to form an integrated transfer recording medium.

Otherwise, the coefficient of kinetic friction at the interface will be significantly higher.
The occurrence of "misalignment" and "wrinkles" at the interface during conveyance can be avoided, and smooth m-feeding is possible.

3. Regarding the effect of thermally transferable solid ink during transfer In the present invention, after the light-reflecting layer is destroyed by electrical discharge in an imagewise manner and the image-receiving sheet is brought into close contact with the surface of the thermally-transferable solid ink layer, light energy is applied from the light-reflecting layer side. Illuminate the entire surface. Then, the photothermal conversion layer, the photothermal conversion support, or the photothermal conversion material in the photothermal conversion/foaming layer absorbs light, which is effectively converted into thermal energy and generates heat. This thermal energy is thermally conducted in the layer thickness direction of the small support of 10 IEA or less, and causes the thermally transferable solid ink layer provided on the surface to be in a thermally molten state or a thermally sublimated state.

At the same time, the photodecomposable compound in the foam layer and the photothermal conversion/foam layer also absorbs light and generates photodecomposition gas. As a reaction to the remarkable volumetric expansion of the photodecomposed gas, temporary "stretching" occurs in the 10- or less-sized support, and the thermally transferable solid ink provided on this surface is transferred to the surface of the image-receiving sheet. Press along the surface profile. Furthermore, due to the generation of photodecomposition gas from the foam layer or the photothermal conversion and foam layer, the adhesive layer effectively reduces the culm of thermal and mechanical connection at the interface between the mask sheet and the ink sheet during light irradiation. As a result, the following effects are particularly achieved.

1) As a result of preventing the generated thermal energy from dissipating to the mask sheet side, the efficiency of thermal energy is improved. (Insulating effect) 2. IX# is dominated by the mask sheet and has a strong
As a result, the "stiffness" becomes weak "stiffness" of only the ink sheet, and as a result, the pressing effect of the ink layer due to the volume expansion of the photolytic gas is significantly improved. (Press action) 3) As a result of the ink layer being pressed through the support, the transferred ink surface has a high degree of smoothness. (Smooth transfer action) Examples The present invention will be specifically explained with reference to Examples below. However, these Examples are not intended to limit the present invention.
All blended parts indicate parts by weight.

Example 1 <A) Preparation of mask sheet [Formation of roughened layer] Binder: 180 parts Polyester resin 40% methyl ethyl ketone/toluene = 60/40 solution (manufactured by Toyobo Co., Ltd., trade name Vylon MT-240) Pigment 220 Amorphous silica with a part average particle size of 4p (manufactured by Fuji Davison Chemical Co., Ltd., trade name Thyroid 978) Hardening agent for binder = 10 parts 75% ethyl acetate solution of incyanate resin (manufactured by Nippon Polyurethane Co., Ltd., trade name Coronate) Solvent 2190 parts of methyl ethyl ketone After dispersing the above mixed solution in an attritor for 4 hours, this was used as a coating material for the roughened layer.

Next, one side of a polyethylene terephthalate film with a thickness of 12 mm was surface-modified by corona treatment, and then a reverse roll coating method was applied to the surface of the polyethylene terephthalate film, which had a coating weight of 4.5 mm after drying.
A roughened layer was formed by coating to obtain g1rd. Thereafter, the curing reaction of the roughened layer was completed by performing a curing treatment for 2 days at a temperature of 50°C. The Bekk smoothness value of the obtained roughened layer surface was 58 parts 4 seconds, and the surface roughness was 6.0 ± 1.3 ρ with a ten-point average roughness (Rz) according to the test method of JIS 80601-1982. The centerline smooth roughness (Ra) is 1.0±0.3, and the critical height (RIl) is 1.0±0.3.
aX) was 8.5±2.2μ.

[Formation of light-reflecting layer] A light-reflecting layer made of an aluminum vapor-deposited film having a thickness of approximately 500 mm was formed on the roughened layer using a resistance heating type winding type vacuum evaporation apparatus. The surface resistance value of the light reflective layer is JIS C
-2318-1335 test method 4. :Te0.52+0
It was 0.03Ω.

[Formation of adhesive layer] Adhesive substance: 15 parts Microcrystalline wax (manufactured by Kuchimoto Seiro Co., Ltd., trade name Himic 1070) Solvent: 8
5 parts toluene After dissolving and dispersing the above mixed solution in a disper for 2 hours, this was used as a coating for the adhesive layer on the opposite side of the light-transmitting support of the mask sheet where the light-reflecting layer was provided. The coating thickness after drying was 1.21 mm using the rod coating method on the surface of
A mask sheet was obtained by coating to obtain M. This was wound to form a mask sheet roll so that the light reflective layer was on the inside.

(B) Preparation of ink sheet [Formation of light-to-heat conversion layer] Binder = 175 parts 40% methyl ethyl ketone of polyester resin/toluene = 60740'/g liquid (manufactured by Toyobo Co., Ltd., trade name: Vylon MT-240) Light-to-heat conversion substance = 60 15% toluene dispersion of carbon black (manufactured by Toyo Ink Co., Ltd., trade name Multilac^-903 Black) Solvent: 180 parts Methyl ethyl ketone After dispersing the above mixture in a disper for 2 hours, it was heated with light. It was used as a paint for the conversion layer.

Next, a light-to-heat conversion layer was formed by coating on a polyethylene terephthalate film having a thickness of 2.6 μm using a rod coating method so that the coating thickness after drying was 2.0 μ.

[Formation of foam layer] Binder 20 parts Polyester resin 30% methyl ethyl ketone/toluene =
20/80 solution (manufactured by Toyobo Co., Ltd., product name: Vylon 30S
S) Photodegradable compound = 4 parts 4
-Diazo-1-diethylamino-2-(4'-chlorophenoxy)-5-chlorobenzene/hexafluorophosphorus salt: 56 parts methyl ethyl ketone After dissolving the above mixture in a disper for 1 hour, this was used as the foam layer paint.

Next, the paint was applied to the surface opposite to the surface provided with the light-to-heat conversion layer so that the coating thickness after drying was 1.5a to form a foam layer.

[Formation of thermally transferable solid ink layer (A) Yellow ink (Y) Binder: Carnauba wax (N, P, 73°C) 12 parts Paraffin wax (RA, P, 60°C) 20 parts Additives = 9 parts Olein Acid pigment: 9 parts bisazo yellow (B) magenta ink (M) Binder: 12 parts carnauba wax (m, p, 73°C) 20 parts paraffin wax (n, p, 60°C) Additives:
9 parts Oleic acid pigment: 9 parts Brilliant carmine (c) Cyan ink (c) Binder: Carnauba wax (1, p, 73°C) 12 parts Paraffin wax (RA, p, 60°C) 20 parts Additives: 9 parts Oleic acid M charge 2
9 parts Phthalocyanine blue (D) black ink (8K) Binder: Carnauba wax (RA, p, 73°C) 12 parts Paraffin wax (ri, p-60"C,) 20 parts Additives = 9 parts Oleic acid pigment: 9 Part Carbon Black Each mixture consisting of the above (^), (B), (c) and (D) was melt-mixed at 95° C., and then stirred for 2 hours using a homomixer to obtain a hot-melt ink.

The melting points of Y, M, C and BK inks are 75.74.
The respective melt viscosities at 72 and 69°C and 100°C are:
It was 126.34.22 and 120 cP.

Next, each of the inks described above is applied onto the photothermal conversion layer by a hot-melt coating method in a plane-sequential manner along the flow direction of the support as shown in FIG. 320
It was coated to give a thickness of mm. At this time, the order in which the inks were applied was black (BK), cyan (c), magenta (M), and yellow (Y).6Then, the obtained ink sheet was coated with a thermally transferable solid ink layer on the core. The ink sheet roll was obtained by winding the ink sheet so that it was on the inside.

Thereafter, transfer recording was performed using the apparatus shown in FIG. 1 according to the transfer recording method described above.

At this time, the pressure of the pressure roll is 1000 f/d, and the platen pressure is 700 g/+! The pressure between the transfer drum and the glass plate was 100 g/-, and the image receiving sheet was bond paper with a surface Bekk smoothness of 4 to 6 seconds, 50 to 6 seconds.
Four types of paper were used: copy paper for 0 seconds, thermal transfer paper for 300 to 320 seconds, and OHP sheet for 10,000 seconds or more. The conveyance speed was kept constant at 2 m/min, and the flash lamp energy was kept constant at 13 nJ/-.

On the other hand, the discharge recording head uses a line head consisting of a plurality of radial electrodes, and the image signals input thereto are Y,
In addition to M, C, and BK single colors, two-color and three-color overlapping transfers of red, green, blue-violet, and black were used as subtractive color mixture solid patterns and character patterns.

Example 2 (A) Preparation of mask sheet In the same manner as in Example 1, a roughened layer and a light reflective layer were provided on one side of a polyethylene terephthalate film having a thickness of 12ρ.

[Formation of adhesive layer] Hot-melt thermoplastic resin: 10 parts 800 <n<900 (molecular weight 50,000 to 70,000, +9.
p, 60° C.) Solvent: 90 parts of methyl ethyl getone The above mixed solution was dissolved in a disper for 2 hours, and then used as a coating material for the adhesive layer.

Next, on the opposite side of the light-transmitting support of the mask sheet on which the light-reflecting layer was provided, coating was applied using a rod coating method so that the coating thickness after drying was 1.5 mm. A mask sheet roll was obtained which was wound so that the light reflective layer was on the inside.

(B) Preparation of ink sheet [Formation of photothermal conversion and foam layer] Binder: 260 parts 25% cyclohexanone solution of polyurethane resin (manufactured by Mitsubishi Chemical Industries, Ltd., trade name Mytic MX-4001) Photothermal conversion substance = 67 parts Carbon black 15% toluene dispersion (manufactured by Toyo Ink Manufacturing Co., Ltd., trade name Multitic A-903 Black) Photodegradable compound: 25 parts 4-diazo-1-diethylamino-2-(4'-chlorophenoxy)-5- Chlorobenzene/phosphorus hexafluoride salt solvent = 650 parts Methyl ethyl getone After dispersing and dissolving the above mixed solution in a disper for 2 hours, this was used as a coating for photothermal conversion and foaming layer.

Next, the above paint was applied onto the surface of a polyethylene terephthalate film with a thickness of 2.6ρ using a rod coating method so that the coating thickness after drying was 1.3μ to form a photothermal conversion and foaming layer. Don't form it.

Next, on the surface opposite to the surface on which the photothermal conversion/foaming layer was provided, color ink was coated in a sequential manner in the same manner as in Example 1, so that the thermal transfer lN1 ink layer was placed on the inside. An ink sheet roll was obtained.

Next, transfer recording was performed using the apparatus shown in FIG. 1 in the same manner as in Example 1, except that the pressure roll was changed to a hot pressure roll set at 62°C.

Comparative Example 1 Color transfer recording was attempted in the same manner as in Example 1 except that no adhesive layer was provided on the polyethylene terephthalate surface of the mask sheet. However, in this case, a significant "misalignment" occurred between the mask sheet and the ink sheet when passing through the ground roller. Furthermore, when the image-receiving sheet and the ink surface were brought into close contact with each other, the "wrinkles" of the ink sheet were involved, making it impossible to obtain uniform transfer. Furthermore, upon transfer of the second and subsequent colors, the degree of "misalignment J" and "wrinkles" between the mask sheet and the ink sheet increased, and significant "color misregistration" occurred. From the above, it was found that color transfer recording is impossible with this method.

Comparative Example 2 Color transfer recording was carried out in the same manner as in Example 2 except that the photothermal conversion/foaming layer did not contain a photodegradable compound.

When the color image quality obtained from the transfer recording method of each of the Examples and Comparative Examples described above was evaluated, the results shown in Table 1 were obtained. The image quality evaluation methods shown in Table 1 are based on visual inspection and visual judgment using enlarged photographs (25x magnification), and the evaluation criteria are as follows.

Y, M, C, BK, Y-M, Y-+C, M-+C1Y-
In all cases of M → C, there is no "printing blur", "blurring", "staining", "repelling", "color unevenness", "shading unevenness in solid areas", etc., and the two-color overlapping area is Each color is uniform red, green, and blue-violet, and the three-color overlapping part is uniform black, and the Macbeth reflection density value of this black part is 1.
◎ If the value is 5 or higher and an overall extremely high quality color image is obtained, ◎ means that at least one of the above problems occurs, but the severity is small and the two-color overlap area is , if subtractive color mixing is uniform and the Macbeth reflection density value of the black part of the three-color overlap is 1.2 or more, and an overall acceptable color image is obtained, ○, the above △: If the problem is very noticeable and the Macbeth reflection density value of the black part of the three-color layer is 0.9 or more, and the quality is difficult to accept overall, △: If the above problem is very noticeable and the density is insufficient was marked as ×.

As is clear from Table 1, the color transfer recording method of the present invention not only provides excellent subtractive color mixing properties for solid patterns, but also provides clear color transfer images even for patterns that require high resolution, such as letters. be able to.

Table 1 Effects of the Invention Since the present invention has the above-described structure, image information recorded by discharge destruction at high resolution on the light reflection layer of a mask sheet can be
It is possible to faithfully and reliably transfer the image onto the image receiving sheet. In particular, since the mask sheet and ink sheet are integrated in everything from discharge destruction recording to the transfer process,
It can be transported smoothly as a transfer recording medium, and colors can be overlapped without wrinkles or "color misregistration." In addition, due to the pressing force associated with the photodegradable compound, ink can be applied to a wide variety of image-receiving sheets, from highly smooth image-receiving sheets (including OHP sheets) to bond paper with extremely low smoothness. It has a high adhesion amount and allows for color overlapping with good mutual adhesion between inks.

Furthermore, since the ink is transferred through the support,
The transferred ink surface has a high level of smoothness and allows for uniform color overlapping with high density.

Therefore, by the color transfer recording method of the present invention, it is possible to obtain multi-color, full-color transfer recorded images of extremely high quality.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram schematically showing a process for carrying out the color transfer recording method of the present invention, FIGS. 2 and 3 are cross-sectional views of an ink sheet used in the present invention, and FIG. In the present invention, a plan view of an ink sheet in which monochromatic thermal transferable solid ink layers are provided in a plane-sequential manner, FIG. 5 is a cross-sectional view of a mask sheet used in the present invention, and FIG. 6 is a transfer diagram of a conventional example. A cross-sectional view of a recording medium, FIG. 7, is an explanatory diagram showing a conventional transfer recording method. 1... Light-transmitting support, 2... Light-reflecting layer, 3...
Light-to-heat conversion layer, 4... thermal transferable solid ink layer, 4a, 4
b, 4C14d... Monochromatic color thermal transferable solid ink layer, 5... Image receiving sheet, 6... Light source, 7... Flash light,
8... Foaming layer, 9... Support, 10... Light-to-heat conversion/foaming layer, 11... Roughened layer, 12a, 12b...
Photothermal conversion layer, 12c... Photothermal conversion support, 13...
Photothermal conversion material, 14... Adhesive layer, 15... Thermal FI contact part or heat sublimation part, 16a... Winding core for mask sheet,
16... Mask sheet, 17... Ink sheet, 1
7a... Ink sheet core, 18a, 18b...
Heat roller or pressure roller, 19a, 19b...
・Earth roller, 20...Discharge recording head, 21・
...Platen roller, 22a, 22b...Image receiving sheet conveyance roller, 23...Claw, 24...Transfer drum, 25...Glass plate, 26...Reflector, 27...
・Flash lamp, 28a, 28b... Capstan roller, 29... Winding core for bobbin. Patent applicant: 1 representative from outside Tomegawa Paper Mills Co., Ltd. Patent attorney Liquid department Close (A) (B) ()\) Figure 2 (A) Figure 4

Claims (2)

[Claims] (1) A foam layer containing a photodegradable compound is provided on one side of a photothermal conversion support having a thickness of 10 μm or less, which is formed by providing a photothermal conversion substance as a separate layer on the support or blending it into the support. On the other side, yellow, magenta and cyan,
Alternatively, an ink sheet comprising a thermal transferable solid ink layer of each monochromatic color having a hue of black arranged one after another on a plane, and a light that can be removed by electrical discharge destruction recording on a roughened layer of a light-transmitting support. A mask sheet is used in which a reflective layer is provided, and an adhesive layer that is solid or semi-solid at room temperature and has room temperature adhesiveness, heat-sensitive adhesiveness, or pressure-sensitive adhesiveness is provided on the other side of the light-transmitting support. (a) forming a transfer recording medium by bonding the foam layer surface of the ink sheet and the adhesive layer surface of the mask sheet using a heat roller or a pressure roller; (b) destroying the light reflective layer of the mask sheet by electrical discharge; After destroying the thermally transferable solid ink layer in the form of an image by recording, an image receiving sheet is brought into close contact with the surface of the thermally transferable solid ink layer of the ink sheet, and the entire surface of the thermally transferable solid ink layer is irradiated with light energy from the light reflecting layer side, thereby destroying the thermally transferable solid ink layer. A step of selectively generating heat and melting and transferring it onto an image receiving sheet; and (c) a step of peeling and separating the transfer recording medium and the image receiving sheet to produce a monochrome transfer recorded image on the image receiving sheet. , A color transfer recording method characterized in that steps (b) and (c) are repeated for each single color to perform color overlapping to perform subtractive color mixing. (2) A photothermal conversion/foaming layer containing a photothermal conversion substance and a photodegradable compound is provided on one side of a support with a thickness of 10 μm or less, and the other side is made of yellow, magenta, and cyan, or these and black. An ink sheet is formed by sequentially arranging thermally transferable solid ink layers of each monochromatic color on a plane, and a light reflecting layer removable by discharge destruction recording is provided on the roughened layer of a light-transmitting support. Using a mask sheet comprising an adhesive layer that is solid or semi-solid at room temperature and has room temperature adhesiveness, heat-sensitive adhesiveness, or pressure-sensitive adhesiveness on the other side of a transparent support, (a) the ink is (b) forming a transfer recording medium by bonding the photothermal conversion/foaming layer surface of the sheet and the adhesive layer surface of the mask sheet using a heat roller or a pressure roller; (b) forming an image on the light reflection layer of the mask sheet by discharge destruction recording; After destroying the thermally transferable solid ink layer of the ink sheet, an image receiving sheet is brought into close contact with the surface of the thermally transferable solid ink layer, and the entire surface of the thermally transferable solid ink layer is irradiated with light energy from the light reflecting layer side, thereby selectively generating heat in the thermally transferable solid ink layer. , a step of melting and transferring it onto an image receiving sheet, and (c) a step of peeling and separating the transfer recording medium and the image receiving sheet to create a monochrome transfer recorded image on the image receiving sheet, A color transfer recording method characterized in that subtractive color mixing is performed by repeating steps (b) and (c) for each single color and overlapping the colors.