JPH04284292A - Image receiving sheet for thermal transfer recording and thermal transfer recording method - Google Patents

Abstract

PURPOSE:To provide image receiving sheet for thermal transfer recording having excellent fixing property of thermodiffusive coloring matter, life of image, bleeding preventing property, and thermal transfer recording method capable of high speed printing with low energy. CONSTITUTION:An image receiving sheet for thermal transfer recording has a first image receiving layer and a second image receiving layer which is layered on the first layer. The first and second layers contain vinyl chloride resin. In a thermal transfer recording method, the image receiving sheet for thermal transfer recording and an ink sheet for thermal transfer recording are superposed and heated with semiconductor laser beam so as to record images on the image receiving sheet for thermal transfer recording.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to an image receiving sheet for thermal transfer recording.
More specifically, regarding the image receiving sheet for thermal transfer recording, which has excellent heat-diffusible dye fixing properties, image storage stability, and bleeding prevention properties, and the ability to form images at high speed with low energy. The present invention relates to a thermal transfer recording method that enables high-speed printing.

0002

BACKGROUND OF THE INVENTION Conventionally, color recording techniques such as inkjet, electrophotography, and thermal transfer recording have been studied as methods for obtaining color hard copies.

Among these, the thermal transfer recording method is particularly
It has advantages such as easy operation and maintenance, miniaturization of the device, and low cost.

[0004] There are two types of this thermal transfer recording system as follows. That is, a method in which a transfer sheet having a meltable ink layer on a support is heated imagewise (imagewise) by a laser or a thermal head, and the meltable ink layer is melt-transferred onto an image-receiving sheet for thermal transfer recording. and thermal diffusion transfer, in which the heat-diffusible dye is diffusely transferred to an image-receiving sheet for heat-sensitive transfer recording using an ink sheet for heat-sensitive transfer recording having an ink layer containing a heat-diffusible dye (sublimable dye) on a support. There are two types:

Among these, the thermal diffusion transfer method can control the gradation of the image by changing the amount of dye transferred in response to changes in the thermal energy of the thermal head, so it is possible to control the gradation of the image in cyan, magenta, and yellow. In recent years, it has been attracting attention as a method for obtaining color images with continuous changes in color shading by performing overlapping recording.

However, the conventional thermal diffusion transfer method has various problems.

For example, the main problems with conventional image-receiving sheets for thermal transfer recording are the fixability of heat-diffusible dyes,
Image storage and bleeding prevention properties are poor.

That is, during thermal transfer, the fixability of the heat-diffusible dye that migrates from the thermal transfer recording ink sheet is not necessarily good, and the heat resistance and light resistance are also insufficient, and the formed image cannot be exposed to high temperatures. If stored in an environment for a long period of time or left exposed to light, the dye may bleed out or ooze out onto the surface of the image-receiving sheet for thermal transfer recording, causing the image to deteriorate over time. It was difficult to maintain clarity over a period of time.

[0009] In addition to solving these problems, recently, image receiving sheets for thermal transfer recording and thermal transfer recording methods have been developed which have features that allow high-speed printing with low energy without reducing transfer density. Development is required.

The present invention has been made to improve the above situation. That is, the object of the present invention is to provide an image-receiving sheet for thermal transfer recording that has excellent dye fixing properties, image storage stability, and bleeding prevention properties, as well as an image-receiving sheet that allows high-speed printing with low energy without reducing transfer density. An object of the present invention is to provide a thermal transfer recording method.

[0011]

[Means for Solving the Problems] The present invention as set forth in claim 1 to achieve the above object comprises laminating a first image-receiving layer and a second image-receiving layer in this order on a support. , both of the first image-receiving layer and the second image-receiving layer mainly contain vinyl chloride resin, and in the vinyl chloride resin, the vinyl chloride resin contained in the first image-receiving layer contains vinyl chloride. An image receiving sheet for thermal transfer recording, characterized in that the content of vinyl chloride in the vinyl chloride resin contained in the second image receiving layer is smaller than the content of vinyl chloride in the vinyl chloride resin contained in the second image receiving layer. A first image-receiving layer and a second image-receiving layer are laminated in this order on the body, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin, and at least the second image-receiving layer contains a vinyl chloride resin. An image-receiving sheet for thermal transfer recording characterized in that one image-receiving layer contains a heat solvent and/or a plasticizer. and a second image-receiving layer laminated in this order, both the first image-receiving layer and the second image-receiving layer containing a vinyl chloride resin, and the first image-receiving layer containing microbubbles. An image-receiving sheet for thermal transfer recording, characterized in that the present invention according to claim 4 is characterized in that a first image-receiving layer and a second image-receiving layer are laminated in this order on a support; An image-receiving sheet for thermal transfer recording, characterized in that both the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin, and at least the second image-receiving layer contains an ultraviolet absorber. Yes, the present invention according to claim 5 has a structure in which a first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both the first image-receiving layer and the second image-receiving layer are The present invention according to claim 6 is an image receiving sheet for thermal transfer recording, characterized in that: contains a vinyl chloride resin, and at least the first image receiving layer contains a near-infrared absorber; The thickness of the first image-receiving layer is 3 μm or more, and the thickness of the second image-receiving layer is 3 μm or more.
The image-receiving sheet for thermal transfer recording according to claim 7 has an image-receiving sheet for thermal transfer recording according to claim 5, and the image-receiving sheet for thermal transfer recording according to claim 5, wherein Overlap the recording ink sheet and apply the semiconductor laser
This is a thermal transfer recording method characterized in that an image is recorded on an image receiving sheet for thermal transfer recording by heating with light.

[1] Image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording of the present invention is basically formed by laminating a first image-receiving layer and a second image-receiving layer in this order on a support.

-Support- Examples of the support include various papers such as paper, coated paper, and synthetic paper (polypropylene, polystyrene, or a composite material made of paper and paper), vinyl chloride resin sheets, and ABS. Various plastic films or sheets such as resin sheets, polyethylene terephthalate base films, polybutylene terephthalate base films, polyethylene naphthalate base films, films or sheets formed from various metals, films or sheets formed from various ceramics, etc. can be mentioned.

[0014] White pigments such as titanium white, magnesium carbonate, zinc oxide, barium sulfate, silica, talc, clay, calcium carbonate, etc. are contained in the support in order to improve the clarity of the image formed in a later step. Preferably, it is added.

[0015] The thickness of the support is usually 20 to 1000 μm,
Preferably it is 20 to 800 μm, and is appropriately selected from within this range.

-Image-receiving layer- The first image-receiving layer and the second image-receiving layer in the present invention both contain a vinyl chloride resin as a binder as a main component.

[0017] Both layers may be formed of only a vinyl chloride resin, or may be formed of a vinyl chloride resin and various additives. In any case, the thickness of the first image-receiving layer is preferably 3 μm or more, and the thickness of the second image-receiving layer is preferably 3 μm or less.

[0018] When the thickness of the first image-receiving layer is less than 3 μm,
The ability to retain the heat-diffusible dye may not be sufficient, resulting in poor image preservation.If the thickness of the second image-receiving layer exceeds 3 μm, the heat-diffusible dye may not diffuse sufficiently, resulting in poor image preservation. This is because sex may not be obtained.

Further, in a preferred embodiment of the present invention, in the vinyl chloride resin, the vinyl chloride content in the vinyl chloride resin contained in the first image receiving layer is lower than the vinyl chloride content in the vinyl chloride resin contained in the second image receiving layer. It is less than the vinyl chloride content in the system resin.

As mentioned above, the first image-receiving layer and the second image-receiving layer are basically made of vinyl chloride resin, and the vinyl chloride resin contained in the first image-receiving layer is If the second image-receiving layer contains less vinyl chloride than the vinyl chloride resin contained in the second image-receiving layer, the dyeability of the first image-receiving layer will be lower than that of the second image-receiving layer. Gender differences arise. In this case, if the dyeability of the vinyl chloride resin contained in the first image-receiving layer is superior to that of the vinyl chloride resin contained in the second image-receiving layer, the ink sheet for thermal transfer recording may be used during thermal transfer recording. The heat-diffusible dye that has migrated from the first image-receiving layer to the second image-receiving layer is further easily diffused in large quantities toward the first image-receiving layer. It can exhibit excellent preservability and high bleeding prevention properties of heat-diffusible dyes.

In this case, the dyeability of the vinyl chloride resin can be evaluated by the following measuring method.

A coating solution is prepared by mixing a vinyl chloride resin binder and a dye at a ratio of 100:1, and the coating solution is coated on a support to a dry film thickness of 4 μm and dried to form a first colored layer. A coating solution prepared by preparing a vinyl chloride resin binder different from that of the first colored layer and the dye used in the first colored layer at a ratio of 100:1 is applied thereon to a dry film thickness of 4.
A second colored layer is provided by layer coating and drying to a thickness of μm.

[0023] The colored layer laminated as above is heated at 100°C.
After leaving it for 24 hours, the thickness is 3μ in the direction perpendicular to the stacking direction.
The sample is sliced into 500 mm pieces, the tomographic plane is observed with a microtome, and the dyeability of the vinyl chloride resin binder is determined based on the degree of coloring of the dye.

1. Vinyl chloride resin Examples of the vinyl chloride resin include polyvinyl chloride resins and vinyl chloride copolymers.

Examples of the vinyl chloride copolymer include copolymers of vinyl chloride and other comonomers containing vinyl chloride as a monomer unit in a proportion of 50 mol % or more.

Examples of the other comonomers include vinyl esters of fatty acids such as vinyl acetate, vinyl propylate, vinyl palmate, and vinyl tallow; acrylic acid;
Acrylic acid or methacrylic acid and its alkyl esters such as methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, 2-hydroxyethyl methacrylate, 2-ethylhexyl acrylate, maleic acid, maleic acid Maleic acid and its alkyl esters such as diethyl, dibutyl maleate, dioctyl maleate, methyl vinyl ether, 2-
Examples include alkyl vinyl ethers such as ethylhexyl vinyl ether, lauryl vinyl ether, palmityl vinyl ether, and stearyl vinyl ether. Furthermore, the comonomers include ethylene, propylene, acrylonitrile, methacrylonitrile, styrene, chlorostyrene, itaconic acid and its alkyl esters, crotonic acid and its alkyl esters, monohalogenated vinyl such as fluoroethylene, dichloroethylene, and trifluoroethylene. Polyhalogenated olefins such as cycloolefins such as cyclopentene, glycidyl group-containing vinyl monomers such as allyl glycidyl ether, aconitic acid esters, vinyl benzoate, benzoyl vinyl ether, styrene, chlorostyrene, etc. Examples include saturated compounds.

The vinyl chloride copolymer may be a block copolymer, a graft copolymer, an alternating copolymer, or a random copolymer.

Among these, vinyl chloride resins that are difficult to dye include resins with a high content of vinyl chloride.
Among these, this tendency is more preferable when the monomer to be copolymerized is an aromatic unsaturated compound.

2. Compounding agents such as additives, microbubbles, the effects of the present invention, i.e. fixing properties of heat-diffusible dyes, image storage properties,
In order to more noticeably exhibit bleeding prevention properties, etc., (1)
It is preferable that at least the first image-receiving layer contains a heat solvent and/or a plasticizer. Furthermore, this first image-receiving layer preferably contains microbubbles.

(2) Furthermore, it is preferable that at least the second image-receiving layer contains an ultraviolet absorber. (3) Furthermore, an image-receiving sheet for thermal transfer recording suitable when a semiconductor laser beam, which will be described later, is used as a heat source during thermal transfer recording, has a first image-receiving layer containing a near-infrared absorbing substance. It is preferable.

The thermal solvent has the function of facilitating the dissolution and diffusion of the heat-diffusible dye into the image-receiving layer, and/or the function of plasticizing the binder forming the image-receiving layer. Various compounds can be used as long as they have the function of making the image-receiving layer highly sensitive. Generally speaking, examples of the heat solvent include heat-fusible substances, fatty acid amides, and the like.

Specific examples of the heat-melting substances include vegetable waxes such as carnauba wax, wood wax, auriculie wax, and espar wax; animal waxes such as beeswax, insect wax, shellac wax, and spermaceti wax; paraffin wax, and microcrystalline wax. , petroleum waxes such as polyethylene waxes, ester waxes and acid waxes; and
Examples include waxes such as mineral waxes such as montan wax, ozokerite and ceresin, polyester waxes, polyurethane waxes, wax chlorides, etc.
In addition to these waxes, palmitic acid,
Higher fatty acids such as stearic acid, margaric acid and behenic acid; palmityl alcohol, stearyl alcohol,
Higher alcohols such as behenyl alcohol, marganyl alcohol, myricyl alcohol and eicosanol;
Higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate and myricyl stearate; amides such as acetamide, propionic acid amide, palmitic acid amide, stearic acid amide and amide wax; and stearylamine, behenylamine and pallic acid. Examples include higher amines such as mitylamine.

Among these, preferred for the purpose of the present invention are dye-soluble heat-melting substances, such as polyester waxes, polyamide waxes, polyurethane waxes, and wax chlorides.

Furthermore, the exemplified compounds described in JP-A-61-162042, page 19, upper left column, line 13 to page 19, upper right column, line 10, and JP-A-59-2018
Publication No. 95, page 3, lower right column, line 4 to page 4, upper left column, 1
The exemplified compounds listed in line 4 can also be suitably used as heat solvents.

The content of the thermal solvent in the first image receiving layer is usually 0.1 to 40% by weight, preferably 0.5 to 20% by weight.
Weight%.

Examples of the plasticizer include phthalate esters (for example, dimethyl phthalate, dibutyl phthalate, dioctyl phthalate, didecyl phthalate, etc.), trimellitic acid esters (for example, octyl trimellitate, isotrimellitate, etc.). nonyl ester, isodesol trimellitate ester, etc.), adipate esters (dioctyl adipate, methyl lauryl adipate, di-2-ethylhexyl adipate, ethyl lauryl adipate, etc.), other oleic acid esters, succinic acid Esters, maleate esters, sebate esters, citric acid esters, epoxy stearate esters, phosphate esters such as triphenyl phosphate and tricresyl phosphate, ethyl phthalyl ethyl glycolate, butyl Examples include glycol esters such as phthalyl butyl glycolate, and rubber-based ones. Among these, preferred are phthalic acid esters and trimellitic acid esters.

The content of plasticizer in the first image-receiving layer is usually 0.01 to 30% by weight, preferably 0.5 to 2% by weight.
It is 0% by weight.

As a method for containing air bubbles in the first image-receiving layer, there is a method in which air bubbles are introduced into the coating solution by mechanical stirring, and the coating solution is coated on a support and dried, and chemical decomposition such as using a blowing agent is used. A method in which a substance that generates gas is added to the coating liquid and dried; a method in which a substance soluble in a solvent is added and the liquid is impregnated and extracted after the first image-receiving layer is formed; A method in which fine particles with voids inside are added and dried, and a coating liquid dissolved in an organic solvent and a non-solvent that is compatible with the organic solvent but insoluble in the binder resin are used. Examples include a method in which a mixed solution is applied and dried, or a method in which a resin kneaded with a foaming agent is melt-extruded and laminated onto a support.

The content of bubbles in the first image-receiving layer is 1 to 1.
40% by volume, preferably 5-25% by volume.

Examples of the ultraviolet absorber include 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2,2',4-trihydroxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone. benzophenone series such as phenyl salicylate, 2,4-ditertiarybutylphenyl-3,5-
Salicylate series such as ditertiarybutyl-4-hydroxybenzoate, (2'-hydroxyphenyl)benzotriazole, (2'-hydroxy-5'-methylphenyl)benzotriazole, (2'-hydroxy-3'-tertiary Butyl-5'-methylphenyl)-
Benzotriazole types such as 5-chlorobenzotriazole, acrylonitrile types such as ethyl-2-cyano-3,3-diphenylacrylate, methyl-2-carbomethoxy-3-(paramethoxy)acrylate, and metal complex salts such as nickel dibutyl dithiocarbamate. Various compounds of the series can be mentioned.

The content of the ultraviolet absorber in the second image-receiving layer is usually 0.1 to 30% by weight, preferably 0.5 to 30% by weight.
It is 20% by weight.

The ultraviolet absorber is usually contained in the second image-receiving layer, but unless the condition that the dyeability of the first image-receiving layer is greater than that of the second image-receiving layer is maintained,
It can also be contained in the first image-receiving layer.

As the near-infrared absorbing material, any conventionally known material can be used, but in the present invention, since heat is generated by irradiation with semiconductor laser light, 750 to 89
A near-infrared absorbing material exhibiting an absorption maximum in a wavelength band of 0 nm is more preferable.

Examples of near-infrared absorbing substances include carbon black, organic compounds such as polymethine, azulenium, squarylium, thiobyrylium, and anthraquinone, and organometallic complexes such as phthalocyanine, azo, and thioamide. Can be done.

[0045] These can be used singly or in combination of two or more.

The amount of the near-infrared absorbing substance contained in the first image-receiving layer is usually appropriately selected within the range of 1 to 10% by weight. However, a near-infrared absorbing substance may also be included in the second image-receiving layer, as long as the object of the present invention is not compromised. In that case, the amount of the near-infrared absorbing substance contained in the second image-receiving layer is appropriately selected within the range of 0.01 to 5% by weight.

When the content of the near-infrared absorbing substance contained in the first image-receiving layer is greater than the near-infrared absorbing substance contained in the second image-receiving layer, the first image-receiving layer is irradiated with laser light. The layer generates more heat than the second image-receiving layer, promoting diffusion of the heat-diffusible dye into the first image-receiving layer. Thereby,
The first image-receiving layer receives more heat-diffusible dye than the second image-receiving layer, and as a result, the image-receiving sheet for thermal transfer recording has high fixability of heat-diffusible dye, high image storage stability, It can exhibit high bleeding prevention properties of diffusible dyes.

In the present invention, as long as the effects of the invention are not impaired, the first image-receiving layer and the second image-receiving layer are
A release agent, an antioxidant, a light stabilizer, a filler (inorganic fine particles, organic resin particles), and a pigment may be added.

The release agent is used to improve the releasability between the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording, and in the present invention, it is particularly preferably added to the second image-receiving layer.

Such release agents include silicone oil (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; Among them, silicone oil is preferred. This silicone oil is a simple addition type (
There are two types: the simple addition type) and the curing or reaction type (hardening reaction type).

In the case of a simple addition type, it is preferable to use a modified silicone oil (for example, polyester modified silicone resin, urethane modified silicone resin, acrylic modified silicone resin, etc.) in order to improve the compatibility with the binder.

[0052] The amount of these simple addition type silicone oils cannot be uniformly determined because it may vary depending on the type of silicone oil, but generally speaking, it is usually The amount is 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

[0053] As curing reaction type silicone oil,
Reaction curing type (for example, reaction curing of amino-modified silicone oil and epoxy-modified silicone oil),
Examples include photo-curing type and catalyst-curing type.

The amount of these curable silicone oils added is preferably 0.5 to 30% by weight of the binder for the image-receiving layer.

[0055] A release agent layer can also be provided on a part of the surface of the image-receiving layer by dissolving or dispersing the above-mentioned release agent in a suitable solvent and applying the solution, followed by drying.

[0056] As the antioxidant, JP-A-59-1
No. 82785, No. 60-130735, JP-A-1-1
Antioxidants described in publications such as No. 27387, and compounds known to improve image durability in photographs and other image recording materials can be mentioned. As a light stabilizer used in combination with an ultraviolet absorber, JP-A-5
No. 9-158287, No. 63-74686, No. 63-
No. 145089, No. 59-19692, No. 62-22
No. 9594, No. 63-122596, No. 61-283
Examples include compounds described in publications such as No. 595 and JP-A-1-204788, and compounds known to improve image durability in photographs and other image recording materials.

[0057] Examples of the filler include inorganic fine particles and organic resin particles.

Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, etc., and examples of the organic fine particles include fluororesin particles, guanamine resin particles, acrylic resin particles, silicone resin particles, etc. The following resin particles can be mentioned. These inorganic/organic resin particles vary depending on their specific gravity, but are 0.1
Addition of ~70% by weight is preferred.

Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay, and acid clay.

[0060] In the present invention, the total amount of additives such as the above-mentioned release agent, antioxidant, light stabilizer, filler (inorganic fine particles, organic resin particles), pigment, etc. is usually determined based on the binder. It ranges from 0.1 to 50% by weight.

-Other Layers- An intermediate layer (
A sublayer) may also be provided.

Further, an overcoat layer may be laminated on the surface of the second image-receiving layer for the purpose of preventing fusion between the thermal transfer recording ink and the thermal transfer recording image-receiving sheet.

Furthermore, a backing layer may be provided on the surface opposite to both image-receiving layers (the back surface of the support) for the purpose of preventing charging, curling, and the like.

[2] Manufacture of image-receiving sheet for thermal transfer recording The image-receiving sheet for thermal transfer recording is prepared by dispersing or dissolving the forming components of the first image-receiving layer and the second image-receiving layer in a solvent, and coating the first image-receiving layer. A coating method in which a coating solution and a coating solution for a second image-receiving layer are prepared, and these coating solutions for an image-receiving layer are sequentially or simultaneously applied to the surface of a support and dried, and a component forming the first image-receiving layer. It can be formed by a lamination method, etc. in which the mixture and the mixture having the components forming the second image-receiving layer are melt-extruded and laminated on the surface of a support.

Solvents used in the above coating method include water, alcohols (for example, ethanol, propanol), cellosolves (for example, methyl cellosolve, ethyl cellosolve), aromatics (for example, toluene, xylene, chlorobenzene), ketones (for example, Examples include acetone, methyl ethyl ketone), ester solvents (eg, ethyl acetate, butyl acetate, etc.), ethers (eg, tetrahydrofuran, dioxane), chlorine solvents (eg, chloroform, trichlorethylene), and the like.

[0066] For the coating, conventionally known coating methods using a gravure roll, extrusion coating method, wire bar coating method, roll coating method, etc. can be employed.

The first image-receiving layer may be formed over the entire surface of the support, or may be formed on a part of the surface.

The method for incorporating air bubbles into the first image-receiving layer has already been described in detail.

[3] Ink sheet for thermal transfer recording An ink sheet for thermal transfer recording is basically formed by laminating ink layers on a support.

-Support- The support used in the present invention may be anything as long as it has good dimensional stability and can withstand the heat during recording with a thermal head, such as condenser paper or glassine paper. Tissue paper, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polycarbonate,
Heat resistant plastic films such as polysulfone, polyvinyl alcohol cellophane, polystyrene can be used.

The thickness of the support is not particularly limited, but is usually preferably 2 to 10 μm.

[0072] There are no particular restrictions on the shape of the support;
For example, it can be of any shape, such as wide sheets or films, or narrow tapes or cards.

-Ink layer- The ink layer contains a heat-diffusible dye and a binder as essential components.

1. Heat-diffusible dyes Examples of heat-diffusible dyes include cyan dyes, magenta dyes, and yellow dyes.

[0075] As the cyan dye, JP-A-59-7
No. 8896, No. 59-227948, No. 60-249
No. 66, No. 60-53563, No. 60-130735
No. 60-131292, No. 60-239289, No. 61-19396, No. 61-22993, No. 6
No. 1-31292, No. 61-31467, No. 61-3
No. 5994, No. 61-49893, No. 61-1482
No. 69, No. 62-191191, No. 63-91288
Examples include naphthoquinone dyes, anthraquinone dyes, and azomethine dyes described in publications such as No. 63-91287 and No. 63-290793.

[0076] As the magenta dye, JP-A-59-
No. 78896, JP-A-60-30392, JP-A-60
-30394, JP 60-253595, JP 61-262190, JP 63-5992, JP 63-205288, JP 64-159, JP 64-63194 Examples include anthraquinone dyes, azo dyes, azomethine dyes, etc., which are described in various publications such as No.

[0077] As the yellow dye, JP-A-59-
No. 78896, JP-A-60-27594, JP-A-60
-31560, JP-A-60-53565, JP-A-6
Examples include methine dyes, azo dyes, quinophthalone dyes, and anthrisothiazole dyes described in publications such as No. 1-12394 and JP-A-63-122594.

Particularly preferred as the heat-diffusible dye is a compound having an open-chain or closed-chain active methylene group, and an oxidized product of a p-phenylenediamine derivative or a p-phenylenediamine derivative.
Azomethine dye obtained by a coupling reaction with an oxidized product of an aminophenol derivative and indoaniline obtained by a coupling reaction with an oxidized product of a phenol or naphthol derivative or a p-phenylenediamine derivative or an oxidized product of a p-aminophenol derivative. It is a pigment.

The heat-diffusible dye contained in the 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 monochromatic. Furthermore, depending on the color tone of the image to be formed, it may contain two or more of the three types of dyes or other heat-diffusible dyes.

[0080] The amount of the heat-diffusible dye used is usually 0.1 to 20 g, preferably 0.2 to 20 g per m2 of support.
It is 5g.

2. Binder Binders for the ink layer include cellulose resins (e.g. nitrocellulose, ethyl cellulose, etc.), polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, styrene resins, acrylic resins, methacrylic resins, and other vinyl resins. , rubber resin, ionomer resin, olefin resin, etc. Among these resins, preferred are polyvinyl formal, polyvinyl butyral, polyvinyl acetoacetal, or cellulose resins, which have excellent dye retention ability. The above-mentioned various binders can be used alone or in combination of two or more.

The weight ratio of the binder to the heat-diffusible dye is preferably from 1:10 to 10:1, particularly preferably from 2:8 to 8:2.

3. Other Optional Components Furthermore, various additives may be added to the ink layer as long as they do not impede the object of the present invention.

The additives include fillers such as fine metal powder, silica gel, metal oxide, carbon black, and fine resin powder, mold release agents such as silicone resin and fluororesin, and curing agents that can react with the binder component ( Examples include radiation active compounds such as isocyanates, acrylics, and epoxies. Furthermore,
JP-A No. 59-1996, heat-melting substances such as wax and higher fatty acid esters are used as additives to promote transfer.
Examples include compounds described in Japanese Patent Publication No.-106997.

-Support- Any support for the ink sheet for thermal transfer recording may be used as long as it has good dimensional stability and can withstand the heat during recording with a thermal head, but condenser paper, glassine paper, etc. Heat-resistant plastic films such as tissue paper, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone, polyvinyl alcohol, cellophane, polystyrene can be used.

The thickness of the support is preferably 2 to 10 μm, and the support has a subbing layer for the purpose of improving adhesion with the binder and preventing transfer and dyeing of the dye to the support. You can leave it there. Furthermore, a backing layer may be provided on the back surface of the support (the side opposite to the ink layer) for purposes such as running stability, heat resistance, and antistatic properties.

The thickness of this subbing layer and backing layer is usually 0.1 to 1 μm.

[0088] There are no particular restrictions on the shape of the support;
For example, it can be of any shape, such as wide sheets or films, or narrow tapes or cards.

[4] Production of ink sheet for thermal transfer recording The ink sheet for thermal transfer recording is prepared by dispersing or dissolving the various components forming the ink layer in a solvent to prepare a coating liquid for forming the ink layer. It can be manufactured by coating this on the surface of a support and drying it.

[0090] The above-mentioned binders are used by dissolving one or more of them in a solvent or dispersing them in a latex form.

Examples of the solvent include water, alcohols (eg, ethanol, propanol), cellosolves (eg, methyl cellosolve, ethyl cellosolve), and aromatics (eg, methyl cellosolve, ethyl cellosolve).
(e.g., toluene, xylene, chlorobenzene), ketones (e.g., acetone, methyl ethyl ketone), ester solvents (e.g., ethyl acetate, butyl acetate, etc.), ethers (e.g., tetrahydrofuran, dioxane), chlorinated solvents (e.g., chloroform, trichloroethylene)
etc.

[0092] For the above-mentioned coating, conventional methods such as a surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method, a roll coating method, etc. can be employed.

The ink layer may be formed as a layer containing a monochromatic heat-diffusible dye on the entire surface or a part of the surface of the support, or may be formed as a layer containing a monochromatic heat-diffusible dye, or a yellow ink layer containing 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 in a constant repetition along the plane direction. You can leave it there.

The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm.
It is μm.

[0095] In the present invention, it is also possible to facilitate use by forming perforations on the ink sheet for thermal transfer recording, or providing detection marks for detecting the positions of areas with different hues. .

The ink sheet for thermal transfer recording is not limited to the structure consisting of a support and an ink layer formed thereon, and other layers may be formed on the surface of the ink layer.

For example, an overcoat layer may be provided for the purpose of preventing set-off (blocking) of the heat-diffusible dye.

[5] Image formation (thermal transfer recording) To form an image, the ink layer of the ink sheet for thermal transfer recording and the image-receiving layer of the image-receiving sheet for thermal transfer recording are overlapped, and the ink layer and image-receiving layer are combined. Apply thermal energy imagewise to the interface.

Then, the heat-diffusible dye in the ink layer is vaporized or sublimated in an amount corresponding to the applied thermal energy, transferred to the image-receiving layer side, and received, thereby forming an image on the image-receiving layer.

[0100] The heat source for providing the thermal energy is as follows:
A thermal head is generally used, but other known devices such as a laser beam, an infrared flash, and a thermal pen can also be used.

When a thermal head is used as a heat source for applying thermal energy, the applied thermal energy can be varied continuously or in multiple stages by modulating the voltage or pulse width applied to the thermal head.

In the thermal transfer recording method of the present invention, a semiconductor laser beam can be used as a heat source for providing thermal energy.

[0103] By using this semiconductor laser light, it is possible to realize high-speed printing with low energy, unlike when using other heat sources, and moreover, the light intensity and irradiation area of the laser light can be changed. The thermal energy provided can be changed by

In this case, an image-receiving sheet for thermal transfer recording is used in which the above-mentioned near-infrared absorbing substance is added to the first image-receiving layer or the first image-receiving layer and the second image-receiving layer in order to facilitate the absorption of semiconductor laser light. It is preferable.

[0105] Also, in the ink sheet for thermal transfer recording, a laser light absorbing material (for example, in the case of a semiconductor laser, carbon black, near-infrared absorbing material, etc.) is preferably present in the ink layer or near the ink layer.

When using semiconductor laser light, it is preferable to bring the ink sheet for thermal transfer recording and the image-receiving sheet for thermal transfer recording into close contact with each other.

[0107] If a dot generator incorporating an acousto-optic element is used, thermal energy can be applied depending on the size of halftone dots.

[0108] When an infrared flash lamp is used as a heat source for providing thermal energy, heating is preferably performed through a colored layer such as black, as in the case of using laser light.

[0109] Alternatively, heating may be performed through a pattern or halftone dot pattern that continuously expresses the shading of an image, such as black, or a colored layer such as black on one side and a negative of the above pattern. Heating may be performed in combination with negative patterns. Thermal energy may be applied from the ink sheet side for thermal transfer recording, from the image receiving sheet side for thermal transfer recording, or from both sides, but if priority is given to effective use of thermal energy, It is desirable to perform this from the ink sheet side for thermal transfer recording.

[0110] By the above thermal transfer recording, a one-color image can be recorded on the image-receiving layer of an image-receiving sheet for thermal transfer recording, but according to the method described below, it is possible to obtain a color photographic color image consisting of a combination of each color. You can also do it.

[0111] For example, by sequentially replacing yellow, magenta, cyan, and, if necessary, black thermal transfer recording sheets and performing thermal transfer according to each color, a color photo-like color image consisting of a combination of each color is obtained. You can also do that.

[0112] The following method is also effective. That is, instead of using ink sheets for heat-sensitive transfer recording of each color as described above, an ink sheet for heat-sensitive transfer recording is used that has areas pre-painted in each color.

[0113] First, the yellow area is used to thermally transfer the yellow color separation image, and then the magenta area is used to thermally transfer the magenta color separation image, and the process is repeated sequentially to create yellow, magenta, and cyan. , and, if necessary, a method of thermally transferring the black color image in this order.

[0114] Although it is possible to obtain a color photographic-like color image with this method, a further advantage is that this method does not require replacing the heat-sensitive sheet for heat-sensitive transfer recording as described above. There is.

Furthermore, after forming an image by the method described above, heat treatment may be performed by the method described above for the purpose of improving the image storage stability. For example, heat treatment is performed over the entire image forming surface using a thermal head using a portion of the ink sheet where no ink layer is provided, or heat treatment using a heat roll or the like. Furthermore, when a near-infrared absorber is contained, the image forming surface may be exposed using an infrared flash lamp. In either case, the heating means does not matter, but since the purpose is to further diffuse the dye into the image-receiving layer, it is effective and preferable to heat from the support side of the image-receiving layer.

[0116]

EXAMPLES Next, the present invention will be explained in more detail based on examples. Note that in the following, "parts" represent "parts by weight."

(Example 1) -Manufacture of image-receiving sheet for thermal transfer recording- The following coating liquids for forming a first image-receiving layer and coating liquids for forming a second image-receiving layer were prepared.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...1
0 parts [vinyl chloride content: 75%, Tg: 50°C]
Methyl ethyl ketone・・・・・・・・・・・・・・・
・・・・・・80 parts Cyclohexanone・・・・・・
・・・・・・・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 5 parts [vinyl chloride content: 81%, Tg: 61°C
] Polyester modified silicone resin・・・・・・・・・
...0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone...
・・・・・・・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・・・・
10 parts.

Next, a synthetic paper with a thickness of 150 μm [Yupo FPG-150 manufactured by Oji Yuka Synthetic Paper Co., Ltd.] was used as a base material.
On top, the coating liquid for forming the first image receiving layer is applied and dried,
A first image-receiving layer with a thickness of 10 μm was formed, and then the coating liquid for forming the second image-receiving layer was applied and dried to form a second image-receiving layer with a thickness of 2 μm.

- Manufacture of ink sheet for thermal transfer recording - A coating liquid for forming an ink layer having the following composition was applied to the corona-treated surface of a 6 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] as a support using a wire bar. Using the coating method, apply to a dry thickness of 1 μm, dry, and dropper a nitrocellulose solution containing silicone resin [SP-2105, manufactured by Dainichiseika Co., Ltd.] on the back side that has not been corona treated. One or two drops were applied and spread over the entire surface, and a backside treatment coat was applied to obtain an ink sheet for thermal transfer recording.

[0122] Coating liquid for forming ink layer; Heat-diffusible dye...
... 4.0 parts [Nippon Kayaku Co., Ltd., Kayaset Blue 714] Polyvinyl butyral 5.0 parts [
Sekisui Chemical Co., Ltd., S-LEC BX-1] Methyl ethyl ketone・・・・・・・・・・・・・・・
Part 81 Cyclohexanone・・・・・・・・・
...... 10 copies Next, the ink sheet for thermal transfer recording and the image receiving sheet for thermal transfer recording,
The former ink layer surface and the latter image-receiving layer surface are overlapped so that they are in contact with each other, and a thermal head is used to print an output of 0.4 W/dot, a pulse width of 0.3 to 10 msec, and a dot from the support side of the ink sheet for thermal transfer recording. Density 6 dots/m
Image recording was performed by heating under the conditions of m.

After the image was recorded, the transfer density on the surface of the image-receiving layer, heat-resistant storage stability, light-resistant storage stability, dye fixability, and bleeding prevention property of the image were evaluated according to the following criteria. The results are shown in Table 1. Transfer density: Reflection density OD value was measured using an optical densitometer. ◎...OD value is 2.5 or more〇...OD value is 2.0-2.5 △...OD value is 1.7-2.0 X...OD value is 1.7 or less.

Heat resistance (heat-resistant image storage stability): The image-receiving sheet for thermal transfer recording on which an image has been recorded is stored at 77°C and relative humidity 80%.
The specimens were kept in this environment for 72 hours, and the presence or absence of dye bleed-out and color change or fading (determined by visual inspection) was examined. ○...The pigment does not easily come off even if you rub the image with your hands. There is also no discoloration or fading. ×: When the image was rubbed by hand, the pigment was removed, or discoloration or fading was observed.

Light Resistance (Light Resistance Image Preservability) The image-receiving sheet for thermal transfer on which the image was recorded was exposed to light for 72 hours using a xenon weather meter, and then the image was visually judged. ○: No discoloration or fading of the pigment is observed. ×: Significant discoloration or fading of pigment.

Dye fixability: The image-receiving sheet for thermal transfer recording on which an image has been recorded is placed face to face with the image-receiving sheet for thermal transfer recording on which the image of the present invention is not recorded, and a load of 40 g/cm2 is applied to the image-receiving sheet for thermal transfer recording at 60°C. After standing for a period of time, judgment was made based on the transfer density of the dye transferred to the image-receiving sheet for thermal transfer recording on which no image was recorded. ◎・・・The transferred dye density was less than 0.10. ○・・・Transferred dye density is 0.10 or more, 0.15
It was below. x: The transferred dye density was 0.15 or more.

Prevention of dye bleeding: The image-receiving sheet for thermal transfer recording on which an image was recorded was left at 60° C. for one week, and then the degree of bleeding was visually judged. ○: Almost no bleeding is observed. ×: Bleeding was observed.

(Example 2) The same procedure as in Example 1 was carried out except that the composition of the coating solution for forming an image-receiving layer was changed to the following. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 5 parts [vinyl chloride content: 75%, Tg: 50°C
] Trimellitic acid alkyl ester...
...0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Methyl ethyl ketone...
・・・・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・・・
10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-(pt-butylbenzoate) copolymer...
・9.5 parts [vinyl chloride content: 86.9%, Tg
:79℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone......80 parts Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

(Example 3) The same procedure as in Example 1 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and the azoisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 0 parts [vinyl chloride content: 81%, Tg: 61°C
] Trimellitic acid alkyl ester...
......0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Azobisisobutyronitrile ......0.5 Part Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-allyl glycidyl ether copolymer...9
．． 5 parts [vinyl chloride content: 91.4%, Tg: 6
1℃] Polyester modified silicone resin...
・・・・・・・・・0.5 parts [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone ・・・・・・・・・・・・・・・ 80 parts
Cyclohexanone・・・・・・・・・・・・・・・・・・
... 10 parts.

(Example 4) The same procedure as in Example 1 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 0 parts [vinyl chloride content: 75%, Tg: 50°C
] Trimellitic acid alkyl ester...
......0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Azobisisobutyronitrile ......0.5 Part Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-benzyl methacrylate copolymer...8
．． 5 parts [vinyl chloride content: 83.7%, Tg: 5
1℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・・・・1.0 copy
[Manufactured by BASF, Uvinal N35] Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

(Example 5) The composition of the coating solution for forming an image-receiving layer was changed to the following, and azobisisobutyronitrile was decomposed and foamed during drying. Furthermore, instead of the thermal head, an ink sheet for thermal transfer recording and an image receiving sheet for thermal transfer recording are superimposed so that the surface of the ink layer of the former is in contact with the surface of the image receiving layer of the latter, and the support side of the ink sheet for thermal transfer recording is From, semiconductor laser LT090MD/M
The same procedure as in Example 1 was carried out, except that F [wavelength 830 nm, maximum optical output 100 mW, manufactured by Sharp Corporation] laser light was focused and a beam light having a diameter of about 80 μm was irradiated to form an image. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...8
．． 8 parts [vinyl chloride content: 75%, Tg: 50°C
] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd., DO
P] Near-infrared absorber・・・・・・・・・・・・・・・・
・・・・・・0.2 parts [manufactured by Mitsui Toatsu Dye Co., Ltd., S
IR-103] Azobisisobutyronitrile...
・・・・・・・・・・・・・・・0.5 parts Methyl ethyl ketone・・・・・・・・・・・・・・・ 80
Part Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...4
．． 5 parts [vinyl chloride content: 75%, Tg: 50°C
] PVC···············
......5.0 parts [vinyl chloride content: 10
0%, Tg: 82°C] Polyester modified silicone resin 0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone...・・・・・・・・・・・・・・・
80 parts cyclohexanone・・・・・・・・・
・・・・・・・・・ 10 parts.

(Example 6) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-vinyl propionate copolymer...8
．． 8 parts [vinyl chloride content: 86.8%, Tg: 6
7℃] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd.]
DOP] Near-infrared absorber・・・・・・・・・・・・・・・
・・・・・・0.2 parts [manufactured by Mitsui Toatsu Dye Co., Ltd., S
IR-103] Azobisisobutyronitrile...
・・・・・・・・・・・・・・・0.5 parts Methyl ethyl ketone・・・・・・・・・・・・・・・ 80
Part Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-dimethyl maleate copolymer...8
．． 0 parts [vinyl chloride content: 90.4%, Tg: 7
0°C] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・・・・1.5 copies
[Manufactured by BASF, Uvinal N35] Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

(Example 7) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; vinyl chloride-dimethyl maleate-acrylonitrile copolymer

・・・・・・・・・・・・・・・8.8 parts [Vinyl chloride content: 80.1%, Tg: 74°C] Trimellitic acid alkyl ester・・・・・・・・・...
...0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Near-infrared absorber ......
・・・・・・・・・・・・0.2 part [Mitsui Toatsu Dye (
Co., Ltd., SIR-103] Azobisisobutyronitrile ・・・・・・・・・・・・・・・・・・ 0.5 part Methyl ethyl ketone ・・・・・・・・・・・・・・・・・・
・ 80 parts cyclohexanone・・・・・・・・・
・・・・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-benzyl methacrylate copolymer...8
．． 5 parts [vinyl chloride content: 83.7%, Tg: 5
1℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・・・・1.0 copy
[Manufactured by BASF, Uvinal N35] Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

(Example 8) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

[0147] Coating liquid for forming the first image-receiving layer; Vinyl chloride-dimethyl fumarate copolymer......8
．． 2 parts [vinyl chloride content: 80.1%, Tg: 7
4℃] Trimellitic acid alkyl ester...
・・・・・・・・・1.0 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Near-infrared absorber...
・・・・・・・・・・・・・・・・・・0.3 copies [
Manufactured by Mitsui Toatsu Dye Co., Ltd., SIR-103] Azobisisobutyronitrile・・・・・・・・・・・・・・・・・・
0.5 parts Methyl ethyl ketone・・・・・・・・・
・・・・・・・・・ 80 parts Cyclohexanone...
・・・・・・・・・・・・・・・・・・ 10 parts.

[0148] Coating liquid for forming second image-receiving layer; Polyvinyl chloride resin...................................................................8
．． 4 parts [vinyl chloride content: 100%, Tg: 82
°C] Polyester modified silicone resin...
...0.5 part [Shin-Etsu Silicone Co., Ltd.]
manufactured by X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・1.0 copy
[Manufactured by BASF, Uvinal N35] Near-infrared absorber・・・・・・・・・・・・・・・・・・0
．． 1 part [manufactured by Mitsui Toatsu Dye Co., Ltd., SIR-103]
Methyl ethyl ketone・・・・・・・・・・・・・・・
・・・・・・80 parts Cyclohexanone・・・・・・
・・・・・・・・・・・・・・・ 10 parts.

(Example 9) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...8
．． 7 parts [vinyl chloride content: 75.0%, Tg: 5
0°C] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd.]
DOP] Near-infrared absorber・・・・・・・・・・・・・・・
...0.3 parts [manufactured by Mitsui Toatsu Dye Co., Ltd., S
IR-103] Azobisisobutyronitrile...
・・・・・・・・・・・・・・・0.5 parts Methyl ethyl ketone・・・・・・・・・・・・・・・ 80
Part Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

Coating liquid for forming second image-receiving layer; vinyl chloride-benzyl methacrylate-allyl glycidyl ether copolymer
・・・・・・・・・・・・・・・・・・8.
4 parts [vinyl chloride content: 75.4%, Tg: 54
°C] Polyester modified silicone resin...
...0.5 part [Shin-Etsu Silicone Co., Ltd.]
manufactured by X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・1.0 copy
[Manufactured by BASF, Uvinal N35] Near-infrared absorber・・・・・・・・・・・・・・・・・・0
．． 1 part [manufactured by Mitsui Toatsu Dye Co., Ltd., SIR-103]
Methyl ethyl ketone・・・・・・・・・・・・・・・
・・・・・・80 parts Cyclohexanone・・・・・・
・・・・・・・・・・・・・・・ 10 parts.

(Example 10) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...8
．． 7 parts [vinyl chloride content: 75%, Tg: 50°C
] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd., DO
P] Near-infrared absorber・・・・・・・・・・・・・・・・
...0.3 parts [manufactured by Mitsui Toatsu Dye Co., Ltd., S
IR-103] Azobisisobutyronitrile...
・・・・・・・・・・・・・・・0.5 parts Methyl ethyl ketone・・・・・・・・・・・・・・・ 80
Part Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

Coating liquid for forming second image-receiving layer; vinyl chloride-(pt-butylbenzoate)-vinyl propionate copolymer
・・・・・・・・・・・・・・・・・・8
．． 4 parts [vinyl chloride content: 80.2%, Tg: 6
8℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Ultraviolet absorber...
・・・・・・・・・・・・・・・・・・・・・1.0 copy
[Manufactured by BASF, Uvinal N35] Near-infrared absorber・・・・・・・・・・・・・・・・・・・・・
0.1 part [manufactured by Mitsui Toatsu Dye Co., Ltd., SIR-103
] Methyl ethyl ketone・・・・・・・・・・・・
・・・・・・80 parts Cyclohexanone・・・・・・
・・・・・・・・・・・・・・・ 10 parts.

(Comparative Example 1) The same procedure as in Example 1 was carried out except that the composition of the coating liquid for forming the first image-receiving layer was changed to the following. The results are shown in Table 1.

[0156] Coating liquid for forming the first image-receiving layer; Polyester resin 1
0 parts [manufactured by Toyobo Co., Ltd., Byron 103] Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
・ 80 parts cyclohexanone・・・・・・・・・
・・・・・・・・・・・・ 10 parts.

(Comparative Example 2) The same procedure as in Example 1 was carried out except that the composition of the coating solution for forming the first image-receiving layer was changed to the following. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...1
0 parts [vinyl chloride content: 81%, Tg: 61°C]
Methyl ethyl ketone・・・・・・・・・・・・・・・
・・・・・・80 parts Cyclohexanone・・・・・・
・・・・・・・・・・・・・・・ 10 parts.

(Comparative Example 3) The same procedure as in Example 1 was carried out except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below. The results are shown in Table 1.

[0160] Coating liquid for forming the first image-receiving layer; Polyester resin 9
．． 5th part [manufactured by Toyobo Co., Ltd., Byron 103]
Trimellitic acid alkyl ester・・・・・・・・・
...0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Methyl ethyl ketone...
・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-(pt-butylbenzoate) copolymer...
・9.5 parts [vinyl chloride content: 86.9%, Tg
:79℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone......80 parts Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

(Comparative Example 4) The same procedure as in Example 1 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 0 parts [vinyl chloride content: 81%, Tg: 61°C
] Trimellitic acid alkyl ester...
......0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Azobisisobutyronitrile ......0.5 Part Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

Coating liquid for forming second image-receiving layer; Polyester resin・・・・・・・・・・・・・・・・・・9
．． Part 5 [manufactured by Toyobo Co., Ltd., Byron 290]
Polyester modified silicone resin・・・・・・・・・・・・
...0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-
24-8300] Methyl ethyl ketone...
・・・・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・・・・ 1
0 copies.

(Comparative Example 5) The same procedure as in Example 1 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 0 parts [vinyl chloride content: 75%, Tg: 50°C
] Trimellitic acid alkyl ester...
......0.5 part [Adekaiser C-79, manufactured by Asahi Denka Kogyo Co., Ltd.] Azobisisobutyronitrile ......0.5 Part Methyl ethyl ketone・・・・・・・・・・・・・・・・・・
80 parts Cyclohexanone・・・・・・・・・・・・
・・・・・・・・・ 10 parts.

[0167] Coating liquid for forming second image-receiving layer; Polyester resin...................................................................8
．． Part 5 [manufactured by Toyobo Co., Ltd., Byron 290]
Polyester modified silicone resin・・・・・・・・・・・・
...0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-
24-8300] Ultraviolet absorber・・・・・・・・・
・・・・・・・・・・・・・・・1.0 copy [BAS
Manufactured by Company F, Uvinal N35] Methyl ethyl ketone 80 parts
Cyclohexanone・・・・・・・・・・・・・・・・・・
... 10 parts.

(Comparative Example 6) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. . The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...8
．． 8 parts [vinyl chloride content: 75%, Tg: 50°C
] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd., DO
P] Near-infrared absorber・・・・・・・・・・・・・・・・
・・・・・・0.2 parts [manufactured by Mitsui Toatsu Dye Co., Ltd., S
IR-103] Azobisisobutyronitrile...
・・・・・・・・・・・・・・・0.5 parts Methyl ethyl ketone・・・・・・・・・・・・・・・ 80
Part Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

Coating liquid for forming second image-receiving layer; Polyester resin・・・・・・・・・・・・・・・・・・9
．． Part 5 [manufactured by Toyobo Co., Ltd., Byron 290]
Polyester modified silicone resin・・・・・・・・・・・・
...0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-
24-8300] Methyl ethyl ketone...
・・・・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・・・・ 1
0 copies.

(Comparative Example 7) The same procedure as in Example 5 was carried out, except that the composition of the coating solution for forming an image-receiving layer was changed to the one shown below, and azobisisobutyronitrile was decomposed and foamed during drying. . The results are shown in Table 1.

Coating liquid for forming the first image-receiving layer; Vinyl chloride-isobutyl vinyl ether copolymer...9
．． 0 parts [vinyl chloride content: 75%, Tg: 50°C
] Phthalic acid alkyl ester...
...0.5 part [manufactured by Daihachi Chemical Co., Ltd., DO
P] Azobisisobutyronitrile・・・・・・・・・
...0.5 part Methyl ethyl ketone...
・・・・・・・・・・・・・・・ 80 parts Cyclohexanone・・・・・・・・・・・・・・・・・・
10 parts.

Coating liquid for forming second image-receiving layer; Vinyl chloride-(pt-butylbenzoate) copolymer...
・9.5 parts [vinyl chloride content: 86.9%, Tg
:79℃] Polyester modified silicone resin...
......0.5 part [manufactured by Shin-Etsu Silicone Co., Ltd., X-24-8300] Methyl ethyl ketone......80 parts Cyclohexanone・・・・・・・・・・・・・・・
... 10 parts.

[0174]

[Table 1]

[0175]

[Effect of the invention] The image-receiving sheet for thermal transfer recording of the present invention is
During thermal transfer, the dye from the ink sheet for thermal transfer recording has excellent fixability, and the obtained image has excellent storage stability, and the dye hardly bleeds during storage.

Furthermore, the thermal transfer recording method of the present invention can realize high-speed printing with low energy.

Claims (7)

[Claims] 1. A first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin. and the content of vinyl chloride in the vinyl chloride resin contained in the first image receiving layer is lower than the content of vinyl chloride in the vinyl chloride resin contained in the second image receiving layer. Image receiving sheet for thermal transfer recording. 2. A first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin. An image-receiving sheet for thermal transfer recording, characterized in that at least the first image-receiving layer contains a thermal solvent and/or a plasticizer. 3. A first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin. An image-receiving sheet for thermal transfer recording, characterized in that the first image-receiving layer contains microbubbles. 4. A first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin. An image-receiving sheet for thermal transfer recording, wherein at least the second image-receiving layer contains an ultraviolet absorber. 5. A first image-receiving layer and a second image-receiving layer are laminated in this order on a support, and both of the first image-receiving layer and the second image-receiving layer contain a vinyl chloride resin. An image-receiving sheet for thermal transfer recording, characterized in that at least the first image-receiving layer contains a near-infrared absorber. 6. The image-receiving sheet for thermal transfer recording according to claim 1, wherein the first image-receiving layer has a thickness of 3 μm or more, and the second image-receiving layer has a thickness of 3 μm or less. 7. Overlapping the image receiving sheet for thermal transfer recording according to claim 5 and the ink sheet for thermal transfer recording,
1. A thermal transfer recording method, characterized in that an image is recorded on an image-receiving sheet for thermal transfer recording by heating with semiconductor laser light.