JP3225365B2 - Thermal transfer recording method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording method, a thermal transfer recording medium, and a recording medium.
To transfer a high-resolution image onto a recording medium by superimposing a thermal transfer recording medium having a heat-fusible ink layer on a support and a recording medium, and irradiating light that can be converted to heat imagewise. The present invention relates to a thermal transfer recording method that can be performed, and a thermal transfer recording medium and a recording medium used in such a thermal transfer recording method.

[0002]

2. Description of the Related Art Conventionally, as a thermal transfer recording method, a pressure heating method using a thermal head has been put to practical use. This method has a low noise level and can be implemented with a simple mechanism. In addition, an apparatus that executes the above method has excellent features in that it is maintenance-free and is a dry process. Moreover, according to this method, the density of the thermal head has been increased in terms of resolution, and in recent years, a resolution of 400 to 600 dpi has been obtained. However, it is more difficult to increase the density of the thermal head, and it is difficult to form an image having a resolution higher than the above-mentioned resolution depending on the thermal transfer recording method using the thermal head.

On the other hand, as a method capable of recording a high-resolution image, a laser beam is applied to a thermal transfer recording medium, the laser beam is converted into heat in the thermal transfer recording medium, and the heat transfer recording is performed by the heat. Is known. Since such a laser thermal transfer recording method can focus the laser beam used for energy supply down to about several microns, it has a dramatic resolution compared to a thermal transfer recording method that supplies heat with a thermal head. Can be improved.

However, in the laser thermal transfer recording method, there is a limit to the laser output, so that it is desired to increase the sensitivity of the material in the thermal transfer recording medium. In addition, since the adhesion between the thermal transfer recording medium and the recording medium greatly affects the resolution of the image, how to increase the adhesion is a problem particularly in obtaining a high-resolution image. .

[0005] In the laser thermal transfer recording system, when performing a planar scan, a transparent pressing member is put on a laminate of a thermal transfer recording medium and a recording medium by applying a transparent pressing member.
The adhesion between the thermal transfer recording medium and the recording medium can also be improved.

However, in order to reduce the space required for high-speed recording and the optical system, a thermal transfer recording medium and a recording medium are wound around the surface of a cylindrical drum, and the thermal transfer recording medium is scanned with a laser beam to form an image. When recording,
When only the laser beam irradiation area on the cylindrical drum is pressed, when the cylindrical drum is rotated at a high speed, the thermal transfer recording medium and the recording medium cannot be uniformly brought into close contact, and only partial adhesion can be obtained. Absent. To prevent this,
There is a method in which a cover sheet is attached to a thermal transfer recording medium and a recording medium that have been wound around a cylindrical drum, and an attempt is made to achieve close contact between the thermal transfer recording medium and the recording medium by tension of the cover sheet. Although this method is effective in pressing a large area, it is difficult to achieve perfect adhesion between the thermal transfer recording medium and the non-recording medium, and a high quality transfer image cannot be obtained.

Therefore, in a scanner or the like using a silver halide photograph, the inside of a cylindrical drum having a through-hole is evacuated to reduce the adhesion between a member mounted on the outer peripheral surface of the cylindrical drum and the outer peripheral surface of the cylindrical drum. Since this technology is applied, the non-recording medium and the heat-sensitive transfer recording medium are wound around a cylindrical drum having a large number of through holes, and the inside of the cylindrical drum is depressurized. Investigations have been made to improve the adhesion to the thermal transfer recording medium. However, since air stagnation or undulation of the sheet occurs between the non-recording medium and the thermal transfer recording medium, it is not possible to ensure perfect adhesion between the thermal transfer recording medium and the non-recording medium.

As a method of preventing the air accumulation, it is conceivable to include fine particles of several to several tens of μm called a mat material in the image receiving layer of the recording medium or the heat-meltable ink layer of the thermal transfer recording medium. In this case, by roughening the surface of the image receiving layer of the recording medium or the surface of the heat-meltable ink layer of the thermal transfer recording medium, problems such as air pockets can be solved. U.S. Pat. No. 4,772,582 discloses that in a sublimation type laser thermal transfer recording method, a spacer bead-containing layer is provided above an ink layer in an ink sheet.
No. 6,235 discloses that fusion of an ink layer and an image receiving layer is prevented by adding spacer beads to an image receiving layer of a non-recording medium. These are all aimed at preventing the fusion of the two layers by roughening the surface of the ink layer or the surface of the image receiving layer.

However, when a mat material is used, the surface of the heat-meltable ink layer or the image receiving layer becomes rough, so that fine adhesion is impaired, thereby causing a new problem that transfer unevenness occurs.

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and to superimpose a heat-sensitive transfer recording medium and a non-recording medium and irradiate the heat-transferable light with an image to the non-recording medium. In a thermal transfer recording method for transferring and forming
A thermal transfer recording method capable of stably outputting a high-resolution image by realizing sufficient adhesion between the thermal transfer recording medium and the recording medium, a thermal transfer recording medium used in the method, and a non-transferable recording medium. It is intended to provide a recording medium.

[0011]

The invention according to claim 1 for solving the above problems SUMMARY OF THE INVENTION may, the recording medium disposed opposite to the heat-meltable ink layer in a thermal transfer recording medium, a laser
In thermal transfer recording method for recording an image on more the recording medium to scan the light, one of the thermal transfer recording media and the recording medium, a heat-meltable ink layer on a support having a cushioning A heat-sensitive transfer recording medium in which a cushioning layer and a heat-fusible ink layer are laminated in this order on a heat-sensitive transfer recording medium or a non-cushioning support, or an image-receiving layer on a support in which the recording medium has cushioning properties a recording medium formed by laminating a cushion layer and the image receiving layer in this order on a recording medium or non-cushioned support having, image and said thermal transfer recording medium and the recording medium is a vacuum contact on a substrate A thermal transfer recording method comprising performing recording, wherein the invention according to claim 2 is arranged such that a recording medium is opposed to a heat-fusible ink layer of the thermal transfer recording medium. In thermal transfer recording method for recording an image on a recording medium by scanning a laser beam, at least one of the image-receiving surface of the surface or the recording medium of the thermal transfer recording medium, crushed by pressurizing pressure or heating mat A thermal transfer recording method, comprising superimposing a thermal transfer recording medium containing a material and a recording medium, and performing thermal transfer recording while applying pressure or heat and pressure in vacuum contact on a substrate. The invention described in 3 is:
In a thermal transfer recording method in which a recording medium is arranged opposite to a heat-fusible ink layer of a thermal transfer recording medium and an image is recorded on the recording medium by scanning with a laser beam , restoration is performed between a support and an image receiving layer. A recording medium having a cushion layer formed of a shape memory resin having a possible cushioning property and a thermal transfer recording medium are overlapped, and a vacuum is applied on the substrate.
Forming a multicolor image by repeating the step of performing thermal transfer recording in close contact , and thereafter, the step of restoring the shape of the cushion layer by pressurizing or heating and pressing the recording medium. in the heat-sensitive transfer recording method in which
is there.

Hereinafter, the present invention will be described in detail.

According to the method of the present invention, (1) a laminate of a thermal transfer recording medium and a recording medium is arranged on a substrate, and the laminate is brought into close contact with the substrate by a decompression action on the substrate, and converted into heat. Irradiating possible light to form a transfer image on the recording medium, and (2) superimposing the thermal transfer recording medium on the recording medium while the recording medium is in close contact with the substrate by depressurization. In this state, a transfer image is formed on the recording medium by irradiating heat that can be converted to heat in that state, and then a photosensitive material having a color material different from that of the thermal transfer recording medium except for the used thermal transfer recording medium is used. The thermal transfer recording medium is superimposed on the recording medium, and in this state, a transfer image is formed on the recording medium by irradiating light that can be converted to heat, and thereafter, the same operation is repeated to transfer a multicolor transfer image having a desired color. And (3) obtained by the above two aspects. Superposing a recording medium and another recording medium having a transferred image, comprising a third aspect of forming a re-transferred image by re-transferring the transfer image to another recording medium by heating and pressing.

In any of the above embodiments, any of a cylindrical drum and a flat substrate can be used as the substrate. Preferred is a cylindrical drum. When a cylindrical drum is used as a substrate, a transfer image can be formed at a high speed by high-speed rotation, a space for a light irradiation system is reduced, and when a laser beam or the like is used by simplifying an optical system, This is because energy efficiency can be increased and the device can be downsized.

The means for bringing the thermal transfer recording medium or the recording medium into close contact with the substrate is not particularly limited. For example, a large number of through holes are provided in the substrate, and the substrate is evacuated from the through holes by the exhaust means, and the suction force is thereby generated. And means for fixing a sheet such as a thermal transfer recording medium or a non-recording medium.

A thermal transfer recording medium may be superimposed on the surface of the substrate, and a recording medium may be superimposed thereon, or may be superimposed in the reverse order. When stacking, the pressure may be reduced by using a cover sheet, or the size of the sheet that wraps around the outside of the cylindrical shape should be slightly increased in order to increase the adhesion between the thermal transfer recording medium and the recording medium. Thereby, the cover sheet may be used.

In the case where a monochrome image is transferred and formed on a recording medium using a thermal transfer recording medium, there is no particular problem even if a cover sheet is used. In the case of transferring and forming a full-color image or a multicolor image on a recording medium, it is necessary to replace the thermal transfer recording medium many times in a state where the recording medium is suction-contacted on the substrate. It is preferable not to use a cover sheet to form an image. That is, when forming a full-color image or a multicolor image, two sheets of a thermal transfer recording medium and a recording medium are used without using a cover sheet.

In order to transfer and form a full-color image or a multi-color image, it is necessary to fix a recording medium on a substrate so as not to cause a color shift while exchanging a plurality of thermal transfer recording media. For this purpose, it is desirable that the surface of the substrate be formed of, for example, an adhesive material, and that the recording medium be fixed on the substrate by the suction force by exhaust even when the thermal transfer recording medium is replaced.

A method for separately adhering and detaching two sheets is disclosed in Japanese Utility Model Laid-Open No. 63-87031.

In any of the above embodiments, it is important that at least one of the thermal transfer recording medium and the recording medium has a cushioning support or cushion layer. By this cushioning property, it is possible to make the support less susceptible to subtle undulations and the like.

However, although the adhesion is improved by providing the cushion layer, the time required for depressurization when performing vacuum contact does not change much, and a too rapid depressurization induces the formation of air pockets. Therefore, the time required for vacuum adhesion can be reduced by roughening the surface of either or both of the thermal transfer recording medium and the recording medium.

As a method for roughening the surface, the surface of the cushion layer is subjected to a roughening treatment in advance and a heat-meltable ink layer or an image receiving layer is provided on the surface of the cushion layer. The surface is roughened, and the surface that has been roughened in the state of vacuum adhesion is to be smooth again. The matte material is contained on the surface of either or both of the thermal transfer recording medium and the recording medium. And the like. Thus,
Due to the synergistic effect between the roughened surface and the cushion layer,
The time required for vacuum adhesion can be shortened, and the adhesion can be sufficiently ensured.

Further, in order to shorten the contact time, it is preferable to apply a reduced pressure while squeezing the thermal transfer recording medium and the recording medium. In addition, once the squeeze is performed while strongly reducing the pressure, the degree of vacuum required to maintain the close contact may be reduced by providing the cushion layer. Therefore, once the degree of vacuum is sufficiently increased in the contact step, the degree of vacuum at the time of recording is not required so much, which is advantageous in terms of apparatus design.

As described above, even if the surface of the thermal transfer recording medium and the surface of the recording medium are roughened in order to shorten the time required for vacuum adhesion, the complete transfer between the thermal transfer recording medium and the recording medium at the time of transfer is completed. Achieving close contact is made possible by the cushion layer. However, in order to obtain a multi-color image and a full-color image, for example, when each color such as yellow, magenta, cyan, and black is overprinted, the cushion layer used once cannot maintain the conventional performance, that is, the second color In the subsequent image formation, the time required for vacuum adhesion may be long, or sufficient adhesion may not be easily obtained. In this case, the cushion layer is 1
After the first transfer, the part roughened by the mat material or the like is absorbed and the shape is retained, and the function is not sufficient after the second transfer.

[0025] Before such a case, when molded at a certain temperature (T ₁₎ above, stressed at a low temperature can hold any shape, applying a certain temperature (T ₂₎ until the warming stress The problem can be solved by using a shape memory resin that restores the shape (T ₁ > T ₂ ). In this case, each time one color is transferred, a step of heating the cushion layer made of the shape memory resin to recover the shape is required.

When the surface of the thermal transfer recording medium and the surface of the recording medium are appropriately roughened by the above-described methods, the degree thereof is determined by the elasticity of the cushion layer, the film thickness, the pressing force (degree of vacuum), the thermal transfer recording medium and It is determined by the surface roughness of the recording medium, the particle size of the mat material, and the amount added.

The degree of vacuum required for vacuum adhesion depends on the degree of surface roughening of the thermal transfer recording medium and the recording medium.
0.1 to 350 torr, and may be lower after the close contact.

The surface roughness of the cushion layer depends on the material for forming the cushion layer.
A range of from 10 to 10 μm is preferred. The same applies to the case where the surfaces of the thermal transfer recording medium and the recording medium are roughened immediately before the close contact.

The particle size and amount of the matting material differ depending on whether the matting material is included in the heat-meltable ink layer of the thermal transfer recording medium or the image receiving layer of the recording medium. The particle size of the mat material is usually
0.3 to 30 μm, preferably 0.5 to 20 μm
And the amount of addition is 0.1 to 100 mg / m ² . The pressing force when pressing the laminate of the thermal transfer recording medium and the recording medium in which such a mat material is blended is usually 0.1.
It is 1 to 5 kg / cm ² . In this case, when a mat material having a small particle size is used, it is necessary to increase the amount (weight per m ² ) of the mat material. In this case, the pressing force may be small, and conversely, the pressing force may be large. When a mat material is used, the amount of the mat material may be small, but the pressing force needs to be increased. However, since the cushion layer is provided, the pressure does not become so large.

Examples of the matting material include inorganic fine particles and organic fine particles. Examples of the inorganic fine particles include silica, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, barium sulfate, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, metal salts such as boron nitride, kaolin, clay, talc, zinc oxide, and the like. Examples include lead white, ziglite, quartz, diatomaceous earth, perlite, bentonite, mica, and synthetic mica. Examples of the organic fine particles include fluorine resin particles, guanamine resin particles, acrylic resin particles, styrene-acryl copolymer resin particles, silicon resin particles, melamine resin particles, and epoxy resin particles.

The surface of the heat-sensitive transfer recording medium and / or recording medium used in the present invention (the surface of the heat-sensitive transfer recording medium which is superimposed on the recording medium, and the surface of the recording medium which is superposed on the heat-sensitive transfer recording medium) The mat surface is included in the heat transfer recording medium or the recording medium by providing an appropriate gap on the contact surface between the thermal transfer recording medium and the recording medium. The present invention prevents the occurrence of air pockets and wrinkles that occur when suction bonding is performed, but in the present invention, in order to prevent a decrease in resolution and color turbidity caused by the generation of the space, thermal transfer recording is performed. By making the medium cushioning or the recording medium cushioning, the density of the thermal transfer recording medium and the recording medium during image transfer can be improved. To guarantee the sex.

However, in the present invention, even when the thermal transfer recording medium and / or the recording medium are not provided with cushioning properties, the image is transferred while the thermal transfer recording medium and the recording medium are overlapped and pressed, or The same effect can be obtained even when the mat material that is crushed by the pressure when heated and pressed is contained in the thermal transfer recording medium and / or the recording medium.

Examples of the matting material which can be crushed when pressurized include fine particles formed of a material having rubber elasticity, and specifically, acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene, and the like. Rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber, silicone rubber, acrylic rubber,
Elastomers such as fluoro rubber, neoprene rubber, chlorosulfonated polyethylene, epichlorohydrin and EPDM can be mentioned. Further, as the matting material which is crushed by heating and pressing, fine particles made of low-hardness wax such as paraffin wax, beeswax, wax having a large oil content, and wax having a large low molecular weight component can be used. The thermal transfer recording medium and the recording medium roughened by the wax fine particles can be manufactured by forming at a temperature lower than the melting start temperature of the wax forming the fine particles by 10 ° C. or more.

[0034] Regardless of using a mat material which does not crush or is crushed when pressurized or heated and pressed,
In order to provide the thermal transfer recording medium and / or the recording medium with cushioning properties, (1) impart cushioning properties to the support of the thermal transfer recording medium, and (2) use the heat-meltable ink layer in the thermal transfer recording medium. Providing a cushioning layer (cushion layer) between the support and the support; (3) providing cushioning to the support in the recording medium; and (4) between the support and the image receiving layer in the recording medium. A method of providing a layer having a cushioning property (cushion layer), (5) providing an image receiving layer having a cushioning property on a support of a recording medium, and the like can be employed.

Regardless of the layer, in order to impart cushioning properties, it is preferable to use a material having a low elastic modulus or a material having rubber elasticity for the layer. In other words, a support is formed using a material having a low elastic modulus or a material having rubber elasticity, or a cushion layer is formed.

When dimensional stability is required or when a material having a low elastic modulus is used, the support and the heat-meltable ink are used for the heat-sensitive transfer recording medium rather than forming the support in a cushioning property. It is preferable to provide a cushion layer between the support and the image receiving layer for the recording medium.

In order to impart cushioning properties, the support or the cushion layer is preferably formed of the following materials.

That is, natural rubber, acrylate rubber, butyl rubber, nitrile rubber, butadiene rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, urethane rubber,
Elastomers such as silicone rubber, acrylic rubber, fluorine rubber, neoprene rubber, chlorosulfonated polyethylene, epichlorohydrin, EPDM, and urethanelastomer, polyethylene, polypropylene, polybutadiene, polybutene, high-impact ABS resin, polyurethane, ABS resin, and acetate , Cellulose acetate,
Amide resin, polytetrafluoroethylene, nitrocellulose, polystyrene, epoxy resin, phenol-formaldehyde resin, polyester, impact-resistant acrylic resin, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, acrylonitrile-butadiene copolymer And vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, vinyl chloride containing a plasticizer, vinylidene chloride resin, polyvinyl chloride, polyvinylidene chloride, and the like, and resins having a small elastic modulus.

Examples of the shape memory resin usable as the cushion layer include polynorbornene and a styrene-based hybrid polymer in which a polybutadiene unit and a polystyrene unit are combined.

The thickness of the support or cushion layer having cushioning properties depends on various factors such as the type of resin or elastomer used, the suction force at the time of close contact, the particle size of the mat material, and the amount of the mat material used. Since it is different, it cannot be determined unconditionally, but it is usually 10 to 100 μm.

As a method of forming a cushion layer using these materials, a material dissolved or dispersed in a latex form in various solvents may be used as a blade coater, a roll coater, or the like.
It can be formed by a coating method using a bar coater, curtain coater, gravure coater, or the like, or lamination by an extrusion lamination method.

In the present invention, as described above, the thermal transfer recording medium and / or the recording medium employ various configurations as long as the thermal transfer recording medium and / or the recording medium has a cushioning property by providing a cushioning support or cushion layer. be able to.

Hereinafter, the thermal transfer recording medium and the recording material used in the present invention will be generally described.

-Thermal transfer recording medium- The thermal transfer recording medium used in the present invention has a structure in which at least a heat-fusible ink layer is laminated on a support, and the light irradiated imagewise is converted to heat. It has a function of converting, in some cases, a backing layer may be provided on the surface of the support opposite to the surface on which the heat-fusible ink layer is provided, and a release layer is provided between the support and the heat-fusible ink layer. May be provided.
When a cushion layer is provided between the support and the hot-melt ink layer, the release layer can be provided between the cushion layer and the hot-melt ink layer.

The function of converting light radiated imagewise into heat is achieved by incorporating a high heat conversion substance into the heat fusible ink layer or adjacent to the heat fusible ink layer. This can be realized by providing a high heat conversion layer.

Hereinafter, each layer will be described.

Support Any material may be used as long as it has good dimensional stability and can withstand heat during image formation. Specifically, the lower left column on page 2 of JP-A-63-193886 is used. The films or sheets described in lines 12 to 18 can be used.

If an image is formed by irradiating a laser beam from the support side, it is desirable that the support is transparent. The support does not need to be particularly transparent as long as an image is formed by irradiating a laser beam from the image receiving layer side.

The thickness of the support is not particularly limited, but is usually 2 to 300 μm, preferably 5 to 200 μm.

If a cushioning property is imparted to the support, it is preferable to form the support with the above-described substance imparting cushioning property, or to mix the substance imparting cushioning property.

Backing layer The backing layer (the surface opposite to the surface on which the heat-fusible ink layer is provided) of the support is provided with a backing layer to impart functions such as running stability, heat resistance and antistatic properties. Can be provided.

The backing layer may be a coating solution for a backing layer in which a resin such as nitrocellulose is dissolved in a solvent, or a coating solution for a backing layer obtained by dissolving or dispersing a binder resin and fine particles of 20 to 30 μm in a solvent. It can be formed by applying a working liquid to the surface of the support.

Cushion Layer The cushion layer is as described above. The cushion layer is not an essential layer as long as the cushioning property is imparted to the support itself.

Light-to-heat conversion layer The light-to-heat conversion layer is provided adjacent to the heat-fusible ink layer. However, as described above, when the high heat conversion substance is contained in the heat fusible ink layer, the light-heat conversion layer may not be particularly provided.

As the high heat conversion material, although it differs depending on the light source, a material that absorbs light and efficiently converts it to heat is preferable. For example, when a semiconductor laser is used as a light source, it has an absorption band in the near infrared. Substances are preferred, and specifically, carbon black, graphite, phthalocyanine dyes, squarylium dyes, nitroso compounds and metal complexes thereof, polymethine dyes, thiol nickel salts, triallylmethane dyes, immonium dyes, naphthoquinone dyes And anthracene dyes can be used. Specific examples include the compounds described in JP-A-63-139191 and the compounds described in JP-A-3-103476.

As the binder in the light-to-heat conversion layer,
Resins with high glass transition points and high thermal conductivity, such as polymethyl methacrylate, polycarbonate, polystyrene, ethyl cellulose, nitrocellulose, polyvinyl alcohol, polyvinyl chloride, amide resins, polyimide, polyetherimide, polysulfone, and polyethersal General heat-resistant resins such as phone and aramid can be used. Among these, polyvinyl alcohol is particularly preferable because scattering of the light-heat conversion layer hardly occurs. The thickness of the light-to-heat conversion layer is 0.1 to 3 μm, and the content of the light-to-heat conversion substance in the light-to-heat conversion layer is such that the absorbance at the wavelength of the light source usually used for image recording is 0.5 to 3.0. Can be determined.

The light-to-heat conversion layer can also be formed as a vapor-deposited film in addition to carbon black, gold, silver, nickel described in JP-A-52-20842.
An example is a deposition layer of metal black such as anchmon, tellurium, bismuth, and selenium. The light-to-heat conversion material is not limited to these, and there are various materials.
You can use them.

Heat-meltable ink layer The heat-meltable ink layer in the present invention means an ink layer that can be transferred or melted or softened upon heating to transfer a layer containing a colorant and a binder. It is not necessary to transfer in a completely molten state.

Examples of the coloring material include pigments such as inorganic pigments and organic pigments, and dyes. Examples of the inorganic pigment include titanium dioxide, carbon black, zinc oxide, Prussian blue, cadmium sulfide, iron oxide, and chromates of lead, zinc, barium, and calcium.

Examples of the organic pigment include azo-based, thioindigo-based, anthraquinone-based, anthranthrone-based, triphenedioxazine-based pigments, vat dye pigments, phthalocyanine pigments such as copper phthalocyanine and its derivatives, and quinacridone pigments. Examples of the organic dye include an acid dye, a direct dye, a disperse dye, an oil-soluble dye, a metal-containing oil-soluble dye, and a sublimable dye. As the sublimable dye, a conventionally known sublimable dye can be used. In the present invention, when this sublimable dye is referred to, it includes a heat sublimable dye. As the sublimable dye, for example, a cyan dye,
Magenta dyes and yellow dyes can be mentioned. Examples of the cyan dye include JP-A-59-78896, JP-A-59-227948, JP-A-60-24946, and JP-A-60-24966.
No. -53563, No. 60-130735, No. 60-1
No. 31292, No. 60-239289, No. 61-19
No. 396, No. 61-22993, No. 61-31292
No. 61-31467, No. 61-35994, No. 61-49893, No. 61-148269, No. 62
No. 191191, No. 63-91288, No. 63-9
Examples thereof include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in JP-A Nos. 1287 and 63-290793.

The magenta dye is described in JP-A-59-1984.
No. 78896, JP-A-60-30392, JP-A-60-60
-30394, JP-A-60-253595, JP-A-61-262190, JP-A-63-5992, JP-A-63-205288, JP-A-64-159, JP-A-64-63194 Anthraquinone dyes, azo dyes, azomethine dyes, etc. described in each publication such as No.

As the yellow dye, JP-A-59-78 can be used.
896, JP-A-60-27594, JP-A-60-3
No. 1560, JP-A-60-53565, JP-A-61-61
Methine dyes, azo dyes, quinophthalone dyes and anthrisothiazole dyes described in JP-A Nos. 12394 and 63-122594.

Particularly preferred as the sublimable dye are a compound having an open or closed type active methylene group and an oxidized product of a p-phenylenediamine derivative or p-phenylenediamine derivative.
An azomethine dye obtained by a coupling reaction with an oxidized form of an aminophenol derivative, and an India obtained by a coupling reaction with an oxidized form of a phenol or naphthol derivative or a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative It is an aniline dye.

The sublimable dye contained in the hot-melt ink layer may be any of a yellow dye, a magenta dye and a cyan dye as long as the image to be formed is a single color. The content of the coloring material in the hot-melt ink layer is usually in the range of 5 to 70% by weight, preferably in the range of 10 to 60% by weight.

Examples of the binder include a heat-meltable substance, a heat-softening substance, and a thermoplastic resin. The heat-fusible substance is usually a solid or semi-solid substance having a melting point in the range of 40 to 150 ° C. measured using a Yanagimoto MJP-2 type.

Specific examples of the heat-fusible substance include, for example,
Vegetable waxes such as carnauba wax, wood wax, ouriculi wax and Espal wax; animal waxes such as beeswax, insect wax, shellac wax and whale wax; paraffin wax, microcrystalline wax, polyethylene wax,
Examples include waxes such as petroleum waxes such as ester waxes and acid waxes; and mineral waxes such as montan wax, ozokerite and ceresin. In addition to these waxes, palmitic acid, stearic acid, margaric acid, and wax Higher fatty acids such as henic acid; higher alcohols such as palmityl alcohol, stearyl alcohol, behenyl alcohol, marganyl alcohol, myristyl alcohol and eicosanol; higher fatty acids such as cetyl palmitate, myristyl palmitate, cetyl stearate and myristyl stearate ester;
Amides such as acetamide, propionamide, palmitic amide, stearic amide and amide wax; and higher amines such as stearylamine, behenylamine and palmitylamine, which may be used alone or in combination May be.

Specific examples of the heat-softening substance include waxes such as vegetable wax, animal wax, petroleum wax, and mineral wax. In addition to these waxes, higher fatty acids, higher alcohols, Examples include higher fatty acid esters, amides and higher amines. Examples of the thermoplastic resin include ethylene copolymer, polyamide resin, polyester resin, polyurethane resin, polyolefin resin, acrylic resin, vinyl chloride resin, cellulose resin, rosin resin, ionomer resin, and petroleum oil. Resins such as base resins; elastomers such as natural rubber, styrene butadiene rubber, isoprene rubber and chloroprene rubber; rosin derivatives such as ester gum, rosin maleic resin, rosin phenol resin and hydrogenated rosin; and phenol resins and terpene resins And high molecular compounds having a softening point of 50 to 150 ° C., such as cyclopentadiene resin and aromatic hydrocarbon resin.

The hot-melt ink layer further contains, in addition to the above components, a surfactant, inorganic or organic fine particles (metal powder, silica gel, etc.), oils (linseed oil, mineral oil, etc.) and the like. Good. Unless you get a black image,
By including a substance that absorbs the wavelength of the light source used for image recording, energy required for transfer can be reduced. Substances that absorb the wavelength of the light source include pigments,
Any colorant may be used, but if a color image is to be obtained, use an infrared light source such as a semiconductor laser to record the image, and use a dye with low absorption in the visible part and high absorption at the wavelength of the light source. Is preferable in terms of color reproduction.
Examples of near infrared dyes include compounds described in JP-A-3-103476. These near-infrared dyes are preferably added so as to have an absorbance of 0.5 to 3.0 with respect to light having a wavelength of a light source used for image recording. In this case, it is not necessary to particularly provide the light-to-heat conversion layer as described above.

The thickness of the hot-melt ink layer is usually 0.1
３3 μm, preferably 0.1-1.0 μm
m.

Anti-scattering layer When the high-density energy of a laser or the like is used as a light source, the anti-scattering layer does not contain a light-to-heat conversion substance in the heat-fusible ink layer. When the light-to-heat conversion layer has a layer structure, the light-to-heat conversion layer rapidly absorbs light energy and generates heat, thereby preventing the light-to-heat conversion material or the binder from being scattered by the generated heat. The anti-scattering layer has a thermal conductivity so that the light-to-heat conversion layer can be scattered in a thin film and the heat generated in the light-to-heat conversion layer can be quickly transferred to the heat-fusible ink layer. It is desirable that the material be made of a material having a high density. The scattering prevention layer is formed of a general heat-resistant resin or the like in the same manner as the light-to-heat conversion layer binder. Among them, polyvinyl alcohol has a large scattering prevention effect,
It can be applied by dissolving in water, and is preferably mixed with a hot-melt ink layer or a light-to-heat conversion layer with little mixing. When light is irradiated from the support side of the thermal transfer recording medium, the scattering prevention layer may be opaque, and a metal deposition film of aluminum or the like also has a scattering prevention effect.

The smaller the thickness of the scattering prevention layer, the higher the sensitivity.
The greater the thickness, the more effective it is in preventing scattering.
1.0 μm.

Release Layer The release layer can be provided at an appropriate position between the support and the hot-melt ink layer. The presence of the release layer facilitates the release of the heat-fusible ink layer during thermal transfer recording, so that a high-quality image can be obtained. The release layer can be composed of the heat-fusible compound itself, but is usually preferably composed of the heat-fusible compound and / or a binder resin such as a thermoplastic resin.

The heat-meltable compound used as a main component of the release layer may be appropriately selected from known compounds and used. Specific examples thereof include, for example, JP-A-63-1.
The exemplified substances can be used from page 4, upper left column, line 8 to page 12, upper right column, line 12 of 93886. Specific examples of the thermoplastic resin include, for example, an ethylene-based copolymer such as an ethylene-vinyl acetate-based resin, a polyamide-based resin, a polyester-based resin, a polyurethane-based resin,
Examples thereof include polyolefin-based resins, acrylic resins, and cellulose-based resins. In addition, for example, resins such as vinyl chloride resin, rosin resin, petroleum resin and ionomer resin, elastomers such as natural rubber, styrene butadiene rubber, isoprene rubber and chloroprene rubber, ester gum, rosin maleic resin, rosin Rosin derivatives such as phenolic resins and hydrogenated rosins, as well as phenolic resins, terpene resins, cyclopentadiene resins, aromatic resins, and the like can be used as appropriate.

In the present invention, the thermoplastic resin used as a component of the release layer has a melting point or a softening point of usually 50 to 50 among the various thermoplastic resins exemplified above.
Those having a temperature in the range of 150 ° C., particularly 60 to 120 ° C., or those in the range obtained by mixing two or more kinds are preferably used. -Manufacture of Thermal Transfer Recording Medium- To manufacture the thermal transfer recording medium of the present invention, first, the various components forming the heat-meltable ink layer are mixed while heating, or dispersed or dissolved in a solvent. To prepare a coating liquid for forming an ink layer. Then, a coating liquid for forming an ink layer is applied to the surface of the support, and the solvent is dried if necessary, thereby obtaining a desired heat-sensitive transfer recording medium. When the various layers are formed on a support, it is preferable to prepare a coating solution for forming such layers and apply them sequentially.

Solvents for preparing the coating liquid for forming the ink layer include water, alcohols (eg, ethanol, methanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), and aromatics (eg, toluene, Xylene, chlorobenzene, ketones (eg, acetone, methyl ethyl ketone), ester solvents (eg, ethyl acetate, butyl acetate), ethers (eg, tetrahydrofuran, dioxane), chlorinated solvents (eg, chloroform, trichloroethylene), etc. Can be.

For the coating, a conventionally known coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted.

The hot-melt ink layer may be formed as a layer containing a monochromatic coloring material on the entire surface or a part of the surface of the support, or may be formed as a yellow ink layer having a binder and a yellow dye. A magenta ink layer containing a binder and a magenta dye, and a cyan ink layer containing a binder and a cyan dye are formed on the entire surface or a part of the surface of the support at a constant repetition along a planar direction. It may be.

The thermal transfer recording medium can be conveniently used by forming perforations or providing detection marks for detecting the positions of different areas of the color layer.

The thermal transfer recording medium may have a single-color heat-meltable ink layer on a support, or a cyan heat-meltable ink layer and a magenta heat-meltable ink layer on a support. The ink may have a water-soluble ink layer and a yellow heat-meltable ink layer in a plane-sequential manner.

-Recording Medium- (1) Recording Medium as Final Image Recording Medium The recording medium receives the heat-meltable ink layer peeled imagewise from the thermal transfer recording medium to form an image. . Normal,
This recording medium has a support and an image receiving layer, and may be formed only from the support.

Since the heat-meltable ink layer melted by heat is transferred to the recording medium, the recording medium must have appropriate heat resistance and excellent dimensional stability so that an image can be formed properly. Is desirable.

The surface of the recording medium which comes into contact with the thermal transfer recording medium during image formation has severe smoothness or is appropriately roughened. More specifically, when the surface of the heat-fusible ink layer of the thermal transfer recording medium is roughened by the mat material or the like described above, the surface of the recording medium that contacts the heat-fusible ink layer has a good surface. It is desirable to have smoothness, and when the hot-melt ink layer is not roughened, the surface of the recording medium that contacts the hot-melt ink layer is roughened by the mat material described above. It is desirable that the surface is flat. Further, both the heat-fusible ink layer and a surface of the recording medium that contacts the heat-fusible ink layer may be roughened.

The mat material is the same as in the description of the thermal transfer recording medium. Therefore, the detailed description is omitted.

According to the present invention, a mat material is used for a thermal transfer recording medium or a recording medium, so that the contact surface between the thermal transfer recording medium and the recording medium is appropriately roughened so that the mutual surfaces are in close contact with each other. On the other hand, the problem caused by the use of the matting material, that is, the problem caused by the use of the matting material, that is, the occurrence of uneven adhesion, a decrease in resolution, and the occurrence of color turbidity is eliminated by imparting cushioning properties to the recording medium.

Here, the support is made of polyethylene, polypropylene or polyethylene terephthalate so that the image (transmitted image) can be seen through the surface opposite to the surface having the transferred image. And resin sheets without a resin film such as polystyrene, polyvinyl chloride, and polyimide. or,
As the support, if forming an image (reflection image) that cannot be seen through from the surface opposite to the surface having the transferred image and can be seen only from the transfer surface side,
Examples thereof include white films formed by adding a white pigment such as barium sulfate, calcium carbonate, and titanium oxide to the resin film or the resin sheet, and papers such as coated paper, art paper, and RC paper.

In order to impart cushioning properties to the support, the support may be formed of the above-described material imparting cushioning properties, or the resin film or resin sheet may be formed of a material imparting cushioning properties. The support may be formed of a composite film or sheet that is composited with the resulting film or sheet.

The image receiving layer can be formed of a binder, various additives added as required, and the above-mentioned material for imparting cushioning properties.

Examples of the binder include an adhesive such as an ethylene-vinyl chloride copolymer adhesive, a polyvinyl acetate emulsion adhesive, a chloroprene adhesive, an epoxy resin adhesive, natural rubber, chloroprene rubber, and butyl rubber. Type, polyacrylate type, nitrile rubber type,
Polysulfide-based, silicone rubber-based, rosin-based resin,
Adhesives such as vinyl chloride resin, petroleum resin and ionomer resin, recycled rubber, SBR, polyisoprene, polyvinyl ether, and the like can be given.

The cushion layer interposed between the support and the image receiving layer is the same as the cushion layer described in the thermal transfer recording medium, and therefore, detailed description thereof is omitted. The thickness of the support in the recording medium having the support, the cushion layer, and the image receiving layer, or the thickness of the support in the recording medium formed only of the support is not particularly limited. The thickness of the cushion layer is the same as the thickness of the cushion layer in the thermal transfer recording medium. The thickness of the image receiving layer is usually 0.1 to 20 μm, but is not limited to the case where the cushion layer is used as an image receiving layer.

The recording medium described above can be used as a final image recording medium when an image is transferred and formed on a thermal transfer recording medium.

In addition, a single color heat-meltable ink layer is formed imagewise for each thermal transfer recording medium by using various types of thermal transfer recording media having different color materials and one recording medium. When a multi-color or full-color transfer image is formed by transferring the recording medium, the recording medium needs to have cushioning properties. In particular, the support or cushion layer having cushioning properties is preferably formed of a shape memory resin that can be restored.

Examples of the shape memory resin include polynorbornene, a styrene-based hybrid polymer in which a polybutadiene unit and a polystyrene unit are combined, and the like.

(2) Recording medium for retransfer as an intermediate transfer member Generally, when a heat-meltable ink layer is image-transferred imagewise to a recording medium by a thermal transfer recording medium, a transfer image of high image quality is obtained. For this purpose, it is desirable that the surface of the recording medium is smooth. In other words, a high-quality image cannot be recorded on a recording medium having a low surface smoothness.

To form a high quality image on a recording medium having a low surface smoothness, a thermal transfer recording medium is used.
It is desirable to temporarily transfer an image to a recording medium as an intermediate transfer medium having a high surface smoothness, and then retransfer the image of the intermediate transfer medium to a recording medium having a low surface smoothness.

In the present invention, the recording medium can be used as an intermediate transfer medium. When the recording medium of the present invention is used as an intermediate transfer medium, it is possible to record a high-definition image on paper having a small surface smoothness, which is difficult to directly transfer an image with a thermal transfer recording medium. When a recording medium is used as the intermediate transfer medium, the recording medium needs to have cushioning properties.
This is because, by having a cushioning property, even if a transfer receiving body for obtaining a final image has a poor surface smoothness, a recording medium as an intermediate transfer body and a final image recording body can be obtained. This is because sufficient adhesion to the recording medium can be ensured.

When the recording medium of the present invention is used as the intermediate transfer member, an image without voids can be retransferred. The thickness of the cushion layer of the recording medium of the present invention as the intermediate transfer member is preferably at least 20 μm or more, since, for example, when high-quality paper is used, it usually has a swell of 10 to 20 μm.

It is desired that the recording medium as such an intermediate transfer member has good receptivity to the heat-fusible ink layer and good retransferability to the final recording medium.
Recording media having such properties are polyethylene,
Polypropylene, low VA type ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer (E
EA), ethylene-methacrylate copolymer (EM
A), ethylene-methyl methacrylate copolymer (E
MMA), ethylene-vinyl acetate copolymer, ionomer resin, chlorinated ethylene, chlorinated polypropylene, chlorinated polyolefin, butadiene rubber, isoprene rubber,
SBR, SBS, SIP, polyvinyl butyral, polyvinyl acetal, polyvinyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, olefinic polymers such as various acrylic resins, polyester resins, polyuriethane resins, polyamide resins, nitrocellulose, cellulose acetate, ethyl cellulose, etc. Cellulose, fluorine resin, silicone resin and the like can be mentioned.

The recording medium as the intermediate transfer member is superimposed on the final recording medium, and the image of the intermediate transfer member is re-transferred to the surface of the final recording medium by pressing or heating and pressing.

If a monochrome image is to be retransferred, one type of recording medium as an intermediate transfer member and one type of final recording medium are used. If a multicolor retransfer image or a full-color retransfer image is transferred to the final recording medium, a plurality of types of intermediate transfer members may be used for one final recording medium. Alternatively, a multi-color or full-color transfer image may be transferred and formed on one intermediate transfer medium, and then re-transferred to the final recording medium.

Regardless of whether a monochrome image is retransferred or a multicolor image or a full color image is retransferred,
The entire image receiving layer of the recording medium as an intermediate transfer member is
Both the method of retransfer to the final recording medium and the method of retransferring only the image transferred on the recording medium as an intermediate transfer, that is, the image on the image receiving layer without transferring the image receiving layer, can be used. Can be adopted.

If only the image is to be retransferred without retransfer of the image receiving layer, the image receiving layer of the intermediate transfer member is desirably non-adhesive to the final recording medium.

If the retransfer is performed while heating, it is desired that the image receiving layer of the intermediate transfer member is not heat-sealing during the retransfer. When employing the technique of retransferring while heating, the image receiving layer and the cushion layer of the intermediate transfer body are not easily separated by heat, for example, an adhesive layer is interposed between the image receiving layer and the cushion layer. It requires some ingenuity.

When the image is retransferred together with the image receiving layer,
Contrary to the above, it is preferable to interpose a release layer between the image receiving layer and the cushion layer.

(3) Production of Non-Recording Medium The recording medium according to the present invention or used in the present invention, particularly the recording medium having an image receiving layer on a support, includes the above-described various components forming the image receiving layer. Are mixed with heating or dispersed or dissolved in a solvent to prepare a coating solution for forming an image receiving layer, and then coating the coating solution for forming an image receiving layer on a support, if necessary. It can be obtained by drying the solvent.

A recording medium having a cushion layer on a support and an image receiving layer thereon may be mixed with various components for forming the cushion layer while heating, or dispersed or dissolved in a solvent. To prepare a coating solution for forming a cushion layer, and then apply the coating solution for forming a cushion layer on a support and, if necessary, drying the solvent, thereby first forming a cushion layer on the support. And then mixing the various components for forming the image receiving layer while heating, or dispersing or dissolving in a solvent to prepare a coating solution for forming the image receiving layer, and then applying the coating solution for forming the image receiving layer. A liquid can be obtained by applying a liquid onto the cushion layer and, if necessary, drying the solvent.

Examples of the solvent used for the coating include:
Water, alcohols (eg, ethanol, propanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.), aromatics (eg, toluene, xylene, chlorobenzene, etc.), ketones (eg, acetone,
Methyl ethyl ketone, etc.), ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), chlorinated solvents (eg, methylene chloride, chloroform, trichloroethylene, etc.).

For the coating, a conventionally known coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method and the like can be adopted. The image receiving layer can be formed by a hot melt extrusion lamination method in which a mixture having components for forming the image receiving layer is melt-extruded and laminated, in addition to the coating method.

Lamination by the hot melt extrusion lamination method is disclosed in Japanese Patent Laid-Open No. 1-263081.
No. 1-271289, No. 2-106397, No. 2-111586, No. 2-305688, No. 3-4
It can be carried out by a usual method described in, for example, Japanese Patent Application No. 9991.

-Image Formation- The thermal transfer recording method of the present invention is performed as follows.
That is, the thermal transfer recording medium and the recording medium are arranged on the substrate so as to overlap each other. In this case, the thermal transfer recording medium may be placed first on the substrate, or the recording medium may be placed first. At this time, either the thermal transfer recording medium or the recording medium is fixed on the substrate by suction by the decompression means. If necessary, a cover sheet is placed on the laminate of the thermal transfer recording medium and the recording medium.

If the substrate is transparent, light, for example, a laser beam is irradiated imagewise from the back side of the substrate or the cover sheet side. The laser light is converted into heat by the high heat conversion material in the thermal transfer recording medium, and the heat-fusible ink layer is melted imagewise and adheres to the recording medium. Thereafter, when the thermal transfer recording medium is separated from the recording medium, a recording medium adhered imagewise to the recording medium can be obtained.

By the above operation, a recording medium having a monochrome image is obtained.

A multi-color image or a full-color image is obtained as follows.

First, a heat-sensitive transfer recording medium having a heat-meltable ink layer of cyan, a heat-meltable ink layer of magenta, and a heat-meltable ink layer of yellow formed on a support in a sequential manner is prepared. Alternatively, a single-color heat-sensitive transfer recording medium having a cyan heat-meltable ink layer on a support, a single-color heat-sensitive transfer recording medium having a magenta heat-meltable ink layer on a support, and a yellow heat-meltable ink layer Is prepared on the support.

Obtaining multi-color images or full-color images;
A recording medium is fixed on a substrate by a suction action. A thermal transfer recording medium is superimposed on the recording medium, and light is irradiated imagewise to form a cyan image on the surface of the recording medium, as described above. Next, the thermal transfer recording medium is peeled from the surface of the recording medium, the thermal transfer recording mediums of different colors are overlapped, and light is irradiated imagewise in the same manner as described above to form, for example, a magenta image. After the image is formed, the thermal transfer recording medium is peeled off from the recording medium, and another color of the thermal transfer recording medium is overlaid on the recording medium. Next, light is irradiated imagewise to form, for example, a yellow image.

The thus-obtained transfer medium having an image on the surface is used as an intermediate transfer member, and the image is re-transferred to another recording medium, whereby the surface is not smooth. A fine image can be formed on a recording medium.

[0116]

The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to the following embodiments, and it goes without saying that design changes can be made appropriately within the scope of the present invention.

As a matter common to the following examples, a semiconductor laser [LT090MD / MF (wavelength: 0.83 μm, maximum output: 100 mW, manufactured by Sharp Corporation) was oscillated on a thermal transfer recording medium prepared as described below. The laser beam is focused so that the beam system becomes 20 μm, and the irradiation time for recording one dot is set to 40, 30, 20,
Exposure was performed at 10 and 5 μsec, and a recordable irradiation time was obtained. A line was recorded with a dot pitch of 10 μm, and the line pitch was set to 10 μm, and solid printing was performed. All observations were made using a microscope. The evaluation was carried out on the adhesion required from the time required for the adhesion and the transferability by solid printing, and the results are summarized in a table.

Example 1 Production of Thermal Transfer Recording Medium and Recording Medium A light-to-heat conversion layer having the following composition was formed on a support having a cushion layer and a support having no cushion layer prepared by the following method. The coating liquid for coating and the coating liquid for forming an ink layer have a thickness of 0.
A thermal transfer recording medium was manufactured by applying the solution to a thickness of 5 μm (0.5 g / m ² ) and drying. An image receiving layer forming coating solution having the following composition was dried on a support having a cushion layer and a support having no cushion layer by a wire bar coating method to a thickness of 1 μm (1 g / m 2).
A recording medium was manufactured by coating and drying to satisfy ² ).

-Production of Cushion Layer- A polyethylene terephthalate film (manufactured by Toray Industries, Inc.) having a thickness of 100 μm as a support (hereinafter referred to as PET base) having a thickness of 20 μm by extrusion lamination.
m, a low-density polyethylene layer was provided as a cushion layer, and a corona discharge treatment was performed to further improve coatability.

-Coating liquid for forming photoelectric conversion layer- Carbon black aqueous dispersion 6 parts Polyvinyl alcohol 14 parts Water ······· 80 parts-Coating liquid for forming ink layer-Paraffin wax [Nippon Seiro Co., Ltd., HNP-11] ··· 0.5 part Rosin resin [Harima Chemical Co., Ltd. , DS-90] ... 4 parts Ethylene-vinyl acetate copolymer [Mitsui-DuPont Polychemical Co., Ltd., EV-40
Y] 1 part Magenta pigment dispersion [Mokoku Dye Co., Ltd.] 2.5 parts Methyl ethyl ketone (MEK) 90 parts-Coating solution for image receiving layer-Ethylene-vinyl chloride copolymer [AD37P295J manufactured by Toyo Morton Co., Ltd.]
10 parts Water 90 parts-Adhesion method-Thermal transfer recording medium described above Into a cylindrical drum with a drum diameter of 13 cm having a large number of fine through holes on the outer peripheral surface,
A recording medium was overlaid on the surface of the thermal transfer recording medium. Next, the inside of the cylindrical drum was vacuumed at 1, 10, 5
0, 100, 400 torr. The pressure was reduced so that the heat-sensitive transfer recording medium and the recording medium were fixed by suction (also referred to as vacuum adhesion) on the outer peripheral surface of the cylindrical drum.

-Combination of Thermal Transfer Recording Medium and Recording Medium- The following combinations were examined for the prepared samples, and the same results were obtained in all cases.

1. Thermal transfer recording medium with cushion layer
1. Recording medium with cushion layer 2. Thermal transfer recording medium with cushion layer-recording medium without cushion layer Thermal transfer recording medium without cushion layer-Recording medium with cushion layer

[0123]

[Table 1]

Example 2 The cushion layer had a thickness of 50 μm.
m, a heat-sensitive transfer recording medium and a recording medium were prepared in the same manner as in Example 1 except that the coating solution for forming an image receiving layer shown below was prepared. did. The results are shown in Table 2.

-Coating solution for image receiving layer- Ethylene-vinyl chloride copolymer [AD37P295J, manufactured by Toyo Morton Co., Ltd.]
············ 10 parts Silica fine particles [Average particle size of 3.5 μm, manufactured by Fuji Devison Co., Ltd., Syloid 244]・ ・ ・ ・ ・ ・ ・ ・
0.01 to 1 part (addition amount of fine particles is 0.01, 0.10, 0.2, 0.
6, 0.6 and 1.0 parts by weight. Water: 90 parts

[0126]

[Table 2]

Example 3 A heat-sensitive transfer recording medium and a recording medium were prepared in the same manner as in Example 1 except that the following coating solution for forming an ink layer was prepared.
Was performed in the same manner as described above. The results are shown in Table 3.

-Coating liquid for forming ink layer-Paraffin wax [HNP-11, manufactured by Nippon Seiro Co., Ltd.] 0.5 parts Rosin-based resin [DS-90, manufactured by Harima Chemicals, Inc.] ... 4 parts ethylene-vinyl acetate copolymer [Mitsui-Dupont Polychemical Co., Ltd., EV-40
Y] 1 part Magenta pigment dispersion [Mokoku Dye Co., Ltd.] 2.5 parts Silica fine particles [Average particle size 3.5 μm, manufactured by Fuji Devison Co., Ltd., Syloid 244]
0.01 to 1 part (addition amount of fine particles is 0.01, 0.10, 0.2, 0.
6, 0.6 and 1.0 parts by weight. ) Methyl ethyl ketone (MEK): 90 parts

[0129]

[Table 3]

Example 4 The procedure of Example 1 was repeated except that the coating solution for the image receiving layer described in Example 2 and the coating solution for forming the ink layer described in Example 3 were used. A heat-sensitive transfer recording medium and a recording medium were prepared and carried out in the same manner as in Example 1. The results are shown in Table 4.

[0131]

[Table 4]

(Examples 5 to 7) In the same manner as in Example 1 except that the vacuum adhesion was performed while squeezing using a pressure roller instead of performing the vacuum adhesion in Example 1 described above. did. The results are shown in Tables 5 to 7.

[0133]

[Table 5]

[0134]

[Table 6]

[0135]

[Table 7]

Example 8 A heat-sensitive transfer recording medium and a recording medium were prepared in the same manner as in Example 2 except that the cushion layer shown below was provided, and a degree of vacuum of 50 torr. Was carried out in the same manner as in Example 1 above. The results are shown in Table 8.

-Production of Cushion Layer- A polyethylene terephthalate film having a thickness of 100 μm (manufactured by Toray Industries, Inc.) (hereinafter referred to as a PET base) having a thickness of 20 was formed by extrusion lamination as a support.
A low-density polyethylene layer having a thickness of 50 or 100 μm was provided, this was used as a cushion layer, and a corona discharge treatment was performed to further improve applicability.

Also, a carboxyl group-modified styrene-butadiene latex (solid content: 50%) was applied using a blade coater so that the thickness after drying became 20, 50, and 100 μm, and dried to form a cushion layer (see Table 1). Now, it is displayed as SB).

[0139]

[Table 8]

Example 9 A thermal transfer recording medium and a recording medium were prepared in the same manner as in Example 2 except that the cushion layer shown below was provided, and the degree of vacuum was set to 50 torr. In the same manner as in Example 2 above. The results are shown in Table 9.

-Production of Cushion Layer- A latex and a melt of the following material are applied to a PET base having a thickness of 100 μm as a support using a blade coater so that the thickness after drying becomes 20 μm or 50 μm, and dried. Thus, a cushion layer was formed. The materials used for the cushion layer are as follows.

Ethylene-vinyl acetate copolymer (shown as EVA in the table) [E1403, manufactured by Du Pont-Mitsui Chemicals Co., Ltd.] Soft polyvinyl chloride [GR-2500S, manufactured by Shin-Etsu Chemical Co., Ltd.] Carboxyl group modification Styrene-butadiene latex [Nippon Synthetic Rubber Co., Ltd., 0617] Acrylic emulsion [Nippon Synthetic Rubber Co., Ltd., AE948] 1,2-polybutadiene [Nippon Synthetic Rubber Co., Ltd., RB810] Polyisoprene rubber [Nippon Gosei Rubber Co., Ltd., IR2200] Polybutadiene rubber [Japan Synthetic Rubber Co., Ltd., BR02] Butyl rubber [Japan Synthetic Rubber Co., Ltd., Butyl065] Acrylonitrile-butadiene rubber [Nippon Synthetic Rubber Co., Ltd., N250S] Ethylene- Propylene terpolymer (EPDM) [Nippon Synthetic Rubber Co., Ltd. EP43]

[0143]

[Table 9]

Example 10 A heat-sensitive transfer recording medium and a recording medium were prepared in the same manner as in Example 2 except that the following coating solution for forming an image receiving layer was prepared.
orr. In the same manner as in Example 2 above. The results are shown in the table.

-Coating solution for image receiving layer- Ethylene-vinyl chloride copolymer [AD37P295J, manufactured by Toyo Morton Co., Ltd.]
... 10 parts Silica fine particles [Types of fine particles are shown below. ]
... 0.01 to 1 part (The addition amount of the fine particles is 0.01, 0.10, 0.2, 0.
6, 0.6 and 1.0 parts by weight. 90 parts of water * Type of fine particles Silicon resin with average particle diameter of 0.3 μm, [Tospearl 103 manufactured by Toshiba Silicone Co., Ltd.] Average particle diameter 0.8 μm silicon resin, [Tospearl 108, manufactured by Toshiba Silicone Co., Ltd.] Silicon resin with an average particle size of 2.0 μm, [Tospearl 120, manufactured by Toshiba Silicone Co., Ltd.] Silica with an average particle size of 3.5 μm [Fuji Devison Siloid 244, manufactured by Co., Ltd.] Silica having an average particle size of 7.0 μm [Syloid 244, manufactured by Fuji Devison Co., Ltd.] Silica having an average particle size of 12 μm [MR-13G, manufactured by Soken Chemical Co., Ltd.] Silica [Soken Chemical Co., Ltd., MR-20G]

[0146]

[Table 10]

Example 11 A thermal transfer recording medium and a recording medium were prepared in the same manner as in Example 1 except that the cushion layer shown below was provided.
r. The procedure was the same as in Example 1 except for the above. Table 1 shows the results
It is shown in FIG.

-Production of Cushion Layer- A low-density polyethylene layer (denoted as PE in the table) or polypropylene having a thickness of 50 μm by extrusion lamination on a polyethylene terephthalate film having a thickness of 100 μm (manufactured by Toray Industries, Inc.) as a support. A layer (shown as PP in the table) was provided and used as a cushion layer. This cushion layer has a surface roughness Ra of 0.1,
Matt processing was performed to 0.5, 1, 3, 5, 10, and 20 μm, and corona discharge treatment was performed to improve applicability.

For comparison, polyester (indicated as PES in the table) was used as the cushion layer. This cushion layer made of polyester has a small cushion property.

[0150]

[Table 11]

(Example 12) The following coating liquid for forming an image receiving layer was applied to the PET base on which the cushion layer formed in Example 2 was formed, with an adhesive, by wire bar coating to have a dry film thickness of 5 µm. And dried to obtain a recording medium.

Except that this recording medium was used, the same operation as in Example 2 was carried out. Further, a recording medium on which an image has been recorded is overlaid on a special art paper made by Mitsubishi Paper, and the pressure is 3 kg / cm ² ,
Retransfer was performed at a temperature of 150 ° C. and a speed of 20 mm / sec. Table 12 shows the results.

-Coating solution for image receiving layer- Ethylene-vinyl acetate copolymer [EV-450, manufactured by DuPont Mitsui Chemicals, Inc.]
············ 10 parts Silica fine particles [Average particle size 3.5μm, TR-6]
... 0.01 to 1 part (addition amount of fine particles is 0, 0.01, 0.10, 0.2,
0.4, 0.6, and 1.0 parts by weight. Toluene 90 parts (Example 13) Same as Example 11 except that the coating solution for forming the image receiving layer was changed to the following composition. And recorded again. The results are shown in Table 12.

-Coating solution for image receiving layer- 1,2-polybutadiene [RB-810]
10 parts of silica fine particles [average particle size of 3.5 μm, manufactured by Fuji Devison Co., Ltd., Syloid 244] ...
..0.01 to 1 part (addition amount of fine particles is 0, 0.01, 0.10, 0.2,
0.4, 0.6, and 1.0 parts by weight. ) Toluene 90 parts

[0155]

[Table 12]

(Example 14) An image receiving layer lower layer of a recording medium,
Under the cushion layer, on the back of the PET base, 1,000
ア ル ミ aluminum vapor deposition film was provided, and the degree of vacuum was 50 torr. Image recording was performed in the same manner as in Example 2. Table 13 shows the results.

[0157]

[Table 13]

Example 15 A thermal transfer recording medium was manufactured using the following coating liquid for forming an ink layer, and a recording medium was prepared using the following coating liquid for forming an image receiving layer. Image recording was performed in the same manner as in Example 8. Table 14 shows the results.

-Coating liquid for forming ink layer-Paraffin wax [HNP-11, manufactured by Nippon Seiro Co., Ltd.] 0.5 parts Rosin-based resin [DS-90, manufactured by Harima Kasei Co., Ltd.] ... 4 parts ethylene-vinyl acetate copolymer [Mitsui-Dupont Polychemical Co., Ltd., EV-40
Y] 1 part Magenta pigment dispersion [Mokoku Dye Co., Ltd.] 2.5 parts Acrylic-urethane spherical fine particles [Average particle size 10 μm, manufactured by Nippon Shokubai Co., Ltd., SP-104
S] 0.0
1 to 1 part (the addition amount of the fine particles is 0, 0.01, 0.10, 0.
7, 0.4, 0.6, and 1.0 parts by weight. 90 parts of methyl ethyl ketone (MEK)-Coating solution for forming image receiving layer-Ethylene-vinyl chloride copolymer [AD37P295J manufactured by Toyo Morton Co., Ltd.]
········································································································································································································································ − ······················ − · − · − ···· A ____________ at_ at_ at_ at_ at__ at_ at_
S]....
01 to 1 part (the addition amount of the fine particles is 0, 0.01, 0.10, 0.2,
0.4, 0.6, and 1.0 parts by weight. 90 parts of water (Example 16) The thickness of the cushion layer was set to 50 μm, and the following coating solution for forming an image receiving layer was prepared. The procedure was the same as in Example 1 to prepare a thermal transfer recording medium and a recording medium, and the degree of vacuum was set to 50 torr. Image recording was performed in the same manner as in Example 8 above. The results are shown in Table 14.

-Coating liquid for forming image receiving layer- Ethylene-vinyl chloride copolymer [AD37P295J, manufactured by Toyo Morton Co., Ltd.]
········································································································································································································································ − ······················ − · − · − ···· A ____________ at_ at_ at_ at_ at__ at_ at_
S]....
01 to 1 part (the addition amount of the fine particles is 0.01, 0.10, 0.2, 0.
6, 0.6 and 1.0 parts by weight. Water: 90 parts

[0161]

[Table 14]

(Example 17, Comparative Example) At a temperature lower than about 40 ° C. or less, an arbitrary shape is maintained when deformed.
Polynorbornene, which restores its original shape when heated to 0 ° C or higher, is formed into a 50 μm smooth film,
To form a cushion layer. This was provided with the image receiving layer described in Example 1 to obtain a recording medium. The photothermal conversion layer described in Example 1 and the following coating liquid for forming an ink layer were laminated on a 100 μm PET base to obtain a thermal transfer recording medium. The heat-sensitive transfer recording medium and the recording medium were vacuum-adhered at 10 Torr, and an image was recorded by irradiating the first color laser beam. Subsequently, the recording medium is heated to 40 ° C.
After heating to restore the smoothness of the cushion layer, image recording was performed by the next laser light irradiation. Such an operation was repeated for four or more colors of YMCK to obtain a full-color image. For comparison, a full-color image was similarly formed using a recording medium having a polyethylene cushion layer of 50 μm. The time required for close contact and the transferability were observed, and the results are shown in Table 15.

-Coating liquid for forming ink layer- Paraffin wax [HNP-11, manufactured by Nippon Seiro Co., Ltd.] 0.5 parts Rosin-based resin [DS-90, manufactured by Harima Kasei Co., Ltd.] ... 4 parts ethylene-vinyl acetate copolymer [Mitsui-Dupont Polychemical Co., Ltd., EV-40
Y] 1 part Magenta pigment dispersion [Mokoku Dye Co., Ltd.] 2.5 parts Silica fine particles [Average particle size 3.5 μm, manufactured by Fuji Devison Co., Ltd., Syloid 244]
0.01 parts methyl ethyl ketone (MEK) 90 parts Example 18 Instead of polynorbornene in Example 17, a styrene-based hybrid polymer in which a polybutadiene unit and a polystyrene unit are compounded [Asahi Kasei Corporation 50 μm
One of the surfaces was formed into a smooth film while the other surface was formed into a roughened film, and the resulting film was bonded to a 100 μm PET base with a smooth surface to form a cushion layer. This was provided with the image receiving layer described in Example 1 to obtain a recording medium. The recording medium was provided with the image receiving layer described in Example 1. This recording medium and the heat-sensitive transfer recording medium described in Example 17 were replaced with 10T.
A vacuum contact was made at orr, and image recording by laser light irradiation was performed. Then, while recovering the shape of the cushion layer in the same manner as in Example 17, image recording was performed a plurality of times, and the time required for close contact and the transferability were observed.
It was shown to.

[0164]

[Table 15]

[0165]

According to the present invention, when an image is transferred from a thermal transfer recording medium to a recording medium by converting light irradiated imagewise into heat, a cushion is applied to the thermal transfer recording medium and / or the recording medium. Is imparted to the recording medium and / or the recording medium to prevent excessive mutual adhesion due to the inclusion of the mat material in the recording medium. Transfer recording method capable of forming a perfect image,
A thermal transfer recording medium and a recording medium can be provided.

Continuation of the front page (72) Inventor Sota Kawakami 1 Konica Co., Ltd., Sakura-cho, Hino-shi, Tokyo (56) References JP-A 64-14081 (JP, A) JP-A 64-5885 (JP, A) JP-A-63-87286 (JP, A) JP-A-61-110592 (JP, A) JP-A-2-52794 (JP, A) JP-A-2-147397 (JP, A) 87031 (JP, U) (58) Field surveyed (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (1)

(57) [Claims] 1. A thermal transfer recording method for recording an image on a recording medium by scanning a laser beam with a recording medium facing a heat-fusible ink layer of the thermal transfer recording medium. One of the recording medium and the heat-sensitive transfer recording medium having a heat-meltable ink layer on a support having a cushioning property or a non-cushioning support on a heat-sensitive transfer recording medium. A thermal transfer recording medium formed by laminating, or a recording medium formed by laminating a cushion layer and an image receiving layer in this order on a recording medium having an image receiving layer on a support having cushioning properties or a non-cushioning support. A recording medium, and the thermal transfer recording medium and the recording medium face each other
The thermal transfer recording medium so that a mat material is arranged on the surface; and
A thermal transfer recording method, characterized in that at least one of the recording media contains a mat material, and the thermal transfer recording medium and the recording medium are vacuum-contacted on a substrate to perform image recording.