JPH05270146A - Image receiving sheet for thermal transfer recording, thermal transfer recording ink sheet and thermal transfer recording method - Google Patents

Abstract

PURPOSE:To provide an image receiving sheet and an ink sheet thermal transfer recording not generating fusion, background staining and feed trouble and excellent in running stability and a thermal transfer method. CONSTITUTION:At least one kind of a resin selected from a group consisting of a silicone modified polyimide resin and a polyethyleneimine/ octadecylisocyanate adduct, at least one kind of a resin selected from a group consisting of a silicone resin, a silicone modified resin and a polyethyleneimine/ octadecylisocyanate adduct and silicone fine particles or at least one kind of a component selected from a group consisting of an alpha-olefin resin and wax are added. In a thermal transfer recording method, an outer layer containing at least one kind of a component selected from a group consisting of an alpha-olefin resin and wax is provided on the surface of a thermal transfer recording image receiving layer or ink layer in a printer immediately before both layers are combined.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-sensitive transfer recording image-receiving sheet, a heat-sensitive transfer recording ink sheet and a heat-sensitive transfer recording method. More specifically, the present invention relates to a heat-sensitive transfer recording image-receiving sheet and a heat-sensitive transfer recording ink sheet. The present invention relates to a heat-sensitive transfer recording image-receiving sheet, a heat-sensitive transfer recording ink sheet, and a heat-sensitive transfer recording method, which are free from fusing and conveyance troubles and have excellent running stability.

[0002]

2. Description of the Related Art Conventionally, the thermal diffusion transfer method, which is one of the thermal transfer recording methods, reduces the size and cost of the apparatus, and is easy to operate and maintain. For reasons, it has been widely used as a method for obtaining color hard copies. The thermal diffusion transfer system can control the gradation of the image by changing the transfer amount of the dye according to the change of the thermal energy of the thermal head. For example, the three primary colors of cyan, magenta, yellow, etc. are overlaid and recorded. By doing so, there is an extremely excellent advantage that a color image of multicolor printing having a continuous change in color shade can be easily formed, and therefore, in recent years, a thermal transfer recording method using a thermal diffusion transfer method has been adopted. For example, it has been actively used for producing an image recording body having a gradation color image such as a color photographic image.

However, when the heat-sensitive transfer recording method is used, fusion occurs between the heat-sensitive transfer recording image-receiving sheet and the heat-sensitive transfer ink sheet, transport troubles occur during printing, and running stability is poor. There were drawbacks such as.

Conventionally, as means proposed to solve the above-mentioned drawbacks, there are JP-A-60-34898, JP-A-60-212394, JP-A-61-177289, and JP-A-61-248791. Ibid.
No. 7, JP-A-63-82791, JP-A-1-25
7090, JP-A-59-79788, 5
9-101398, 61-262189, 62-50192 and 62-108091.
No. 62-208994, No. 62-283.
No. 1761, etc., a method of adding a release agent or fine particles to a receiving layer that receives a heat diffusible dye in an image-receiving sheet for thermal transfer recording, or an ink layer in an ink sheet for thermal transfer recording. There is.

However, when a release agent is added to the image receiving layer of the heat-sensitive transfer recording image-receiving sheet, there are problems that the image storability of the transferred image is deteriorated and the releasability is insufficient.
When a release agent is added to the ink layer of the thermal transfer recording ink layer, there are problems such as lack of storability such as dye bleeding out in the ink layer and insufficient releasability.

Therefore, the present invention solves the above-mentioned problems and can prevent the fusion between the image-receiving sheet for heat-sensitive transfer recording and the ink sheet for heat-sensitive transfer recording which are superposed, and at the time of printing. Without causing transport problems,
An object of the present invention is to provide an image-receiving sheet for thermal transfer recording, an ink sheet for thermal transfer recording, and a thermal transfer method, which are excellent in running stability and can maintain a beautiful image for a long period of time.

[0007]

The invention according to claim 1 for solving the above-mentioned problems comprises at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct. A heat-sensitive transfer recording image-receiving sheet comprising a support and an image-receiving layer for receiving a heat-diffusible dye, which is laminated on the support. An image-receiving layer that receives a diffusible dye, and an outer layer containing at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecylisocyanate adduct, which are laminated in this order. An image-receiving sheet for thermal transfer recording, wherein the invention described in claim 3 is a silicone-modified polyimide resin. And an ink layer containing at least one selected from the group consisting of polyethyleneimine-octadecylisocyanate adduct and containing a heat-diffusible dye, which is laminated on a support. According to the invention described in claim 4, at least one selected from the group consisting of an ink layer containing a heat diffusible dye on a support, a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct. An ink sheet for heat-sensitive transfer recording, comprising an outer layer containing one kind of layers laminated in this order, wherein the invention described in claim 5 is a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecyl. At least selected from the group consisting of isocyanate adducts An image-receiving sheet for heat-sensitive transfer recording, comprising an image-receiving layer containing one kind and silicone fine particles and receiving a heat-diffusible dye, which is laminated on a support. The invention comprises, on a support, an image-receiving layer that receives a heat-diffusible dye, at least one selected from the group consisting of a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicone fine particles. An image-receiving sheet for heat-sensitive transfer recording, comprising an outer layer laminated in this order, wherein the invention described in claim 7 comprises a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecyl isocyanate adduct. An image containing at least one selected from the group consisting of silicone fine particles and a diffusible dye. A heat-sensitive transfer recording ink sheet comprising a support layer and a heat-diffusing dye layer formed on the support. And a silicone resin, a silicone-modified resin, and at least one selected from the group consisting of a polyethyleneimine-octadecyl isocyanate adduct, and an outer layer containing fine silicone particles, laminated in this order. A recording ink sheet, wherein the invention according to claim 9 comprises an image-receiving layer that receives a heat-diffusible dye, and at least one selected from the group consisting of an α-olefin resin and a wax on a support. An image receiving sheet for heat-sensitive transfer recording, comprising: an outer layer to be contained in this order, and the invention described in the above item 10. An ink layer containing a heat-diffusible dye, and an outer layer, which is a layer containing at least one selected from the group consisting of α-olefin resins and waxes, laminated in this order on the body. An ink sheet for heat-sensitive transfer recording, wherein the invention according to claim 11 is for heat-sensitive transfer recording by heating the image-receiving sheet for heat-sensitive transfer recording and the ink sheet for heat-sensitive transfer recording in an imagewise manner. In a thermal transfer recording method in which a thermal diffusible dye in an ink sheet is diffusion-transferred to an image receiving layer in an image receiving sheet for thermal transfer recording, a thermal transfer recording is performed immediately before the image receiving sheet for thermal transfer recording and the ink sheet for thermal transfer recording are superposed. On the surface of the image-receiving layer of the image-receiving sheet for ink or the ink layer of the ink sheet for thermal transfer recording, from α-offine resin and wax. A thermal transfer recording method, which comprises laminating an outer layer containing at least one selected from the group that.

The present invention will be described in detail below. A. First embodiment: thermal transfer recording image-receiving sheet and ink sheet containing one selected from the group consisting of silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate adduct Silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate of the present invention An image-receiving sheet for heat-sensitive transfer recording and an image-receiving ink sheet for heat-sensitive transfer recording containing at least one selected from the group consisting of additives have the following two structures. (1) The first contains at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecylisocyanate adduct, and supports an image-receiving layer that receives a heat diffusible dye or an ink layer that contains it. (2) The second is a structure laminated on the body, and the second is an image-receiving layer or an ink layer containing a heat-diffusible dye on a support, a silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate. An outer layer containing at least one selected from the group consisting of additives is laminated in this order.

= Image-Receiving Sheet for Thermal Transfer Recording Having Structure (1) = At least One Structure Selected from Structure (1), that is, a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct. An image-receiving sheet for heat-sensitive transfer recording, which contains an image-receiving layer containing the heat-diffusible dye and laminated on a support, will be described below.

-Support-The support in the present invention is not particularly limited, and various materials, layer configurations, sizes, and thicknesses can be appropriately selected according to the purpose of use and the like. Paper, coated paper,
Various papers such as polypropylene, polystyrene, or synthetic paper made of laminated composite materials thereof, vinyl chloride resin, polystyrene, ABS resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, polycarbonate, polyether Ether ketone, polysulfone, polyether sulfone, polyetherimide, polyamide,
Various plastic films or sheets such as polyimide, films or sheets formed of various metals, films or sheets formed of various ceramics, or composite materials formed by laminating any combination of these. Can be used.

As the color of the support, any color can be selected, and any color can be selected according to its application. For example, when transparency is required, such as a transparent original such as an OHP or a sticker attached to glass or the like in that application, one having high transparency can be selected. Further, in other cases, it is possible to select a support of various colors or to color the support in various colors. An example of coloring the support is when the application is for a reflection image or the like, and a colored substance such as a white pigment can be added to the support in order to enhance the sharpness of the image formed.

Examples of the white pigment include titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate, barium sulfate, silica, talc, clay and the like. The thickness of the support is usually 20 to 1000.
μm, and preferably 20 to 800 μm.

-Silicone-modified polyimide resin-As the silicone-modified polyimide resin of the present invention, the silicone component may be any of graft, block, alternating and random copolymerization on the polyimide resin, but the silicone component has an imide skeleton. Those in which a silicone component is introduced into the polymer chain are particularly preferable.
These resins may be used alone or in a combination of two or more. In addition, these resins may be newly synthesized and used, or commercially available products may be used.

Examples of the silicone component include an organosiloxy group. An example of the silicone-modified polyimide resin can be represented by (Chemical formula 1).

[0015]

[Chemical 1]

The amount of the silicone-modified polyimide resin contained in the image-receiving layer is usually preferably 0.1 to 100 parts by weight, more preferably 0.5 to 70 parts by weight. -Polyethyleneimine-octadecyl isocyanate adduct-The polyethyleneimine-octadecyl isocyanate adduct in the present invention is not particularly limited, and a compound known per se can be used.

The amount of the polyethyleneimine-octadecyl isocyanate adduct contained in the image-receiving layer is usually preferably 0.1 to 100 parts by weight, more preferably,
It is 0.5 to 70 parts by weight.

In the present invention, the image-receiving layer contains at least one selected from the group consisting of the silicone-modified polyimide resin and the polyethyleneimine-octadecyl isocyanate adduct. The amount of one or more of these compounds contained in the image receiving layer is usually preferably 0.1 to 100 parts by weight, more preferably
It is 0.5 to 70 parts by weight.

-Image Receiving Layer- The image receiving layer in the image receiving sheet for thermal transfer recording of the present invention is
There is no particular limitation as long as it contains at least one of the silicone-modified polyimide resin and polyethyleneimine-octadecylisocyanate adduct and can receive a heat-diffusible dye described below, and a material appropriately selected according to the purpose of use and the like. For example, it can be formed using a resin that receives a heat diffusible dye or the like, or by adding various additives depending on the purpose and using various methods.

Examples of the dye-receptive resin include vinyl chloride resin, vinylidene chloride resin, polyester resin, styrene resin, acrylic or methacrylic resin, cellulose resin, polyvinyl acetal resin, epoxy resin, phenoxy resin. Resin, polyvinylpyrrolidone, polycarbonate, polysulfone, polyarylate, polyparabanic acid resin, urethane type resin, amide type resin, polyacrylonitrile resin and the like can be mentioned.

As the additives, antioxidants, UV absorbers, light stabilizers, optical brighteners, plasticizers as sensitizers,
Examples of the heat-melting substance include white particles and the like, in order to improve the sharpness and whiteness of the image when a reflection image is obtained.

The antioxidant is not particularly limited and known ones can be used. For example, JP-A-59-182785, JP-A-60-130735 and JP-A-1-127387 can be used. The antioxidants described in etc. can be used.

The UV absorber or light stabilizer is not particularly limited, and known ones can be used, for example, JP-A-59-158287 and JP-A-63-158287.
-74686, 63-145089, 59-196292, 62-229594, 63-122596, 61-28359.
The compounds described in JP-A No. 5 and JP-A No. 1-204788 can be used.

The fluorescent whitening agent is not particularly limited, and examples thereof include JP-A-61-237693 and 63-12.
Known compounds such as the compounds described in JP 2596, JP 63-147166 A, etc., or compounds used for improving the durability of images such as photographs can be used.

The plasticizer is not particularly limited, and known ones can be used. Examples thereof include phthalic acid esters, trimetic acid esters, adipic acid esters, and other saturated or unsaturated carboxylic acid esters. ,
Examples thereof include phosphite esters and glycol esters.

The heat-fusible substance is not particularly limited, and known substances can be used, for example, terpineol, menthol, 1,4-cyclohexanediol, alcohols such as phenol, acetaldehyde,
Amides such as benzamide, esters such as climane and benzyl cinnamate, ethers such as diphenylether and crown ether, camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, norbobornene, Hydrocarbons such as stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, higher fatty acid esters such as cetyl palmitate, higher fatty acid amides such as stearic acid amide, and higher amines such as behenylamine. Waxes such as molecular compounds, carnauba wax, beeswax, paraffin wax, ester wax, montan wax, amide wax, etc., rosin derivatives such as ester gum, rosin maleic acid resin and rosin phenol resin, phenol resin, kerosene Down resins, epoxy resins, diallyl phthalate resins, terpene resins, aliphatic hydrocarbon resins,
Examples thereof include polymer compounds represented by cycloolefin resins such as cyclopentadiene resins, polyolefin resins, polyethylene glycol and polypropylene glycol. In the present invention, it is preferable that the melting point or softening point of the heat-meltable substance is 10 to 150 ° C.

The white particles may be inorganic or organic particles, and known particles can be used. Examples of inorganic particles include titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, boron nitride, silica, alumina, lead white, molybdenum white, talc, clay, kaolin, Examples thereof include activated clay, acid clay, aluminum borate and the like. Examples of the organic particles include fluororesin particles, guanamine resin particles, styrene resin particles, styrene-acrylic resin particles, acrylic resin particles, silicone resin particles and melamine resin particles. These inorganic or organic resin particles differ depending on the specific gravity, but it is preferable to add 30% by weight or less to the image receiving layer. The average particle size of the white particles is usually 0.00
5 to 5.0 μm is preferable, and 0.01 is particularly preferable.
Is about 2.0 μm.

Further, as other additives, when a chelate dye image is formed by using a heat diffusible dye capable of forming a chelate as the image receiving layer forming component in forming the image receiving layer, it may be added as necessary. For example, US Pat.
A metal ion-containing compound or the like as described in the specification of 87049 can be contained. When the metal ion-containing compound is added, the addition amount thereof is preferably 5 to 70 parts by weight, more preferably 10 to 10 parts by weight in the image receiving layer forming composition.
40 parts by weight.

Generally, the total amount of the additives added is preferably 0.1 to 30 parts by weight based on the binder resin. Further, a mordant can be added as another additive, if necessary. Here, the mordant means that the dye forms a salt with the mordant and is fixed during image formation, or the dye is adsorbed and fixed to the mordant, or the dye forms a dye image in the presence of the mordant. Means an additive used as a mordant when it is fixed.

The mordant used in the present invention is not particularly limited, but an inorganic or organic basic compound is used, and examples of the inorganic compound include calcium carbonate, sodium carbonate, sodium acetate and the like. As a compound having an amino group, for example, alkylamine (decanoylamine, octylamine, dioctylamine, trioctylamine, etc.), arylamine (aniline and its derivatives, etc.), nitrogen-containing heterocyclic group (eg, pyridine, A compound having an imidazole ring), a compound containing an organic base represented by the following general formula (Formula 2) and a quaternary ammonium salt compound thereof, a Group 5B onium salt compound such as a phosphonium salt (the above-mentioned ammonium). 6B group, including salts), sulfonium salts, selenonium salts, telluronium salts, etc. Such as salt compounds.

[0031]

[Chemical 2]

The mordant described above may be a polymer. Examples of such polymer mordants include JP-A-48-28325, JP-A-54-74430, and JP-A-54-124726.
The thickness of the image receiving layer and the image receiving layer is usually 3 to 30 μm, preferably 5 to 20 μm. The structure of the image receiving layer may be a single layer or a multilayer structure of a plurality of layers having the same or different compositions.

-Formation of image-receiving layer- As a method for forming the image-receiving layer, a coating method in which the components for forming the image-receiving layer are dispersed or dissolved in a solvent to apply the image-receiving layer-forming coating liquid on the surface of the support and then dried. Alternatively, it can be formed by a laminating method or the like in which a mixture having the components for forming the image receiving layer is melt extruded and laminated on the surface of the support. Of these various methods, usually, the coating method can be preferably used.

Examples of the solvent used in the coating method include water, alcohols such as ethanol and propanol,
Methyl cellosolve, cellosolves such as ethyl cellosolve, aromatics such as toluene, xylene and chlorobenzene, acetone, ketones such as methyl ethyl ketone, ethyl acetate, ester solvents such as butyl acetate, ethers such as tetrahydrofuran, dioxane and diglyme, Examples thereof include chlorine-based solvents such as methylene chloride, chloroform and trichloroethylene, and nitrogen-containing solvents such as pyridine and N-methylpyrrolidone.

For the coating, various conventionally known methods such as a gravure roll coating method, an extrusion coating method, a wire bar coating method and a roll coating method can be used. By appropriately drying after this coating, an image receiving layer having a predetermined dry film thickness can be formed. The image receiving layer may be formed over the entire surface of the support, and
If necessary, it may be formed on one surface of a part thereof.

Further, a heat insulating property is provided between the image receiving layer and the supporting layer,
An intermediate layer may be provided for the purpose of adding properties such as barrier property, cushioning property, and adhesive property. When the intermediate layer is provided, its thickness is usually preferably 0.1 to 20 μm.

= Heat-sensitive transfer recording image-receiving sheet having the structure of (2) = In the heat-sensitive transfer recording image-receiving sheet having the structure of (2), the above-mentioned image-receiving layer is the above silicone-modified polyimide resin. And not containing at least one of polyethyleneimine-octadecylisocyanate adduct, and providing an outer layer containing at least one of the above silicone-modified polyimide resin and polyethyleneimine-octadecylisocyanate adduct on the image-receiving layer. The same as the image-receiving sheet for thermal transfer recording having the structure of (1) above.

-Outer Layer- The outer layer of the present invention is not particularly limited, except that it contains at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct, and various resins or additives are added. It is possible to form a single layer or a plurality of layers on the image-receiving layer by various methods using agents and the like. The thickness of this outer layer is usually 0.05 to 10 μm, preferably 0.1.
˜1 μm.

= Ink sheet for thermal transfer recording having the structure of the above (1) = One kind selected from the group of the structure of the above (1), that is, a silicone-modified polyimide resin and a polyethyleneimine-octadecylisosiatoate adduct. An ink sheet for heat-sensitive transfer recording, which comprises a support and an ink layer containing a heat-diffusible dye, will be described below. —Ink Layer— The silicone-modified polyimide resin or polyethyleneimine-octadecyl isocyanate adduct contained in the ink layer is as described above.

Examples of the heat diffusible dye include cyan dye, magenta dye and yellow dye. Examples of the cyan dye include, for example, JP-A-59-78896, JP-A-59-227948, and JP-A-60-2496.
6, gazette 60-53563 gazette, gazette 60-130.
No. 735, No. 60-131292, No. 60-
No. 239289, No. 61-19396, No. 6
No. 1-22993, No. 61-31292, No. 61-31467, No. 61-35994,
61-49893, 61-148269, 62-191191 and 63-91288.
No. 63-91287, No. 63-2907.
Naphthoquinone dyes described in Japanese Patent Publication No. 93, etc.,
Examples thereof include anthraquinone dyes and azomethine dyes.

Examples of the magenta dye include, for example, JP-A-59-78896, JP-A-60-30392, JP-A-60-30394, and JP-A-60-252595.
No. 61-262190, No. 60-535.
Anthraquinone dyes described in Japanese Patent No. 65, etc.,
Examples thereof include azo dyes and azomethine dyes.

Examples of the yellow dye include those disclosed in JP-A-59-59.
No. 78896, No. 60-27594, and No. 60
-31560, etc., methine dyes,
Examples thereof include azo dyes, quinophthalone dyes, and anthryothothiazole dyes.

When a chelate dye image is formed on a heat-sensitive transfer recording image-receiving sheet, the heat-diffusible dye is
A dye compound capable of forming a chelate with a metal ion-containing compound is preferable. Examples of the metal ions constituting the metal ion-containing compound include, for example, I to I of the periodic table.
There may be mentioned divalent and polyvalent metals belonging to Group VIII, among which Al, Co, Cr, Cu, Fe, Mg, M.
n, Mo, Ni, Sn, Ti, Zn and the like are preferable, and Ni, Cu, Co, Cr and Zn are particularly preferable. The compound containing these metal ions is preferably an inorganic or organic salt of the metal and a complex of the metal. Specific examples include Ni ²⁺ , Cu ²⁺ , Co ²⁺ , Cr ²⁺ and Zn.
A complex containing ²⁺ and represented by the following general formula is preferably used.

{M (Q ₁ ) _k (Q ₂ ) _m (Q ₃ ) _n } ^{p +}
p (L-) where M represents a metal ion, Q ₁ , Q ₂ , Q ₃
Each represents a coordination compound capable of forming a coordination bond with a metal ion represented by M, and these coordination compounds are selected from coordination compounds described in, for example, “Chelate Chemistry (5) (Nankodo)”. be able to. Particularly preferably, a coordination compound having at least one amino group that forms a coordinate bond with a metal can be mentioned, and more specifically, ethylenediamine and its derivatives, glycinamide and its derivatives, picolinamide and its derivatives can be mentioned. Be done.

L is a counter anion capable of forming a complex,
Examples thereof include inorganic compound anions such as Cr, SO ₄ , and ClO ₄ , and organic compound anions such as benzenesulfonic acid derivatives and alkylsulfonic acid derivatives. Particularly preferred are tetraphenylboron anion and its derivatives, and alkylbenzenesulfonic acid anion and its derivatives. It is a derivative. k represents an integer of 1, 2 or 3, m is 1,
2 or 0, and n represents 1 or 0, which are determined depending on whether the complex represented by the general formula is tetradentate or hexadentate, or Q ₁ , Q ₂ , Determined by the number of Q ₃ ligands. p represents 1, 2 or 3.

Examples of this type of metal ion-containing compound include
Mention may be made of those exemplified in US Pat. No. 4,987,049. When the above-mentioned metal ion-containing compound is added, the addition amount thereof is 0.5 to the image receiving layer.
Preferably ^{20g / m 2, 1~15g / m} 2 is more preferable.

As the compound forming a chelate with the metal ion-containing compound, various known compounds can be selected and used. For example, JP-A-59-78893.
Japanese Patent Publication No. 59-109349 and Japanese Patent Laid-Open No. 2-21.
No. 3303, No. 2-214719, No. 2-2
Examples thereof include cyan image forming dyes, magenta forming image dyes, and yellow forming image dyes described in JP-A No. 03742. Of these, a dye compound capable of forming a bidentate chelate with at least the metal ion-containing compound is preferable, and examples thereof include a dye represented by the following general formula (Formula 3).

[0048]

[Chemical 3]

In the formula, X ^{1 represents} an aromatic carbocycle in which at least one ring is composed of 5 to 7 atoms, or a group of atoms necessary for completing a heterocycle, At least one atom adjacent to the carbon atom bonded to the bond is a nitrogen atom or a carbon atom substituted with a chelating group. X ² has at least one ring of 5 to 7
Represents an aromatic heterocycle or aromatic carbocycle composed of atoms. G represents a chelating group. Whichever dye compound is used, depending on the color tone of the image to be formed, two or more of any of the above three dyes or another sublimable substance may be contained.

When the above-described mordant is contained in the image-receiving layer for heat-sensitive transfer recording, it is used as a heat-diffusible dye.
It is preferable to use a dye having a hydroxyl group and / or a dye formed by forming a salt with a nitrogen-containing organic base.

As the dye having a phenolic hydroxyl group, dyes such as azo dyes, azomethine dyes and anthraquinone dyes conventionally used in heat-sensitive transfer materials can be used, and in addition, JP-A-3-83685. , The same 3-83
687, 3-83688, 3-83689, 3-90397,
Examples thereof include dyes described in JP-A-3-92385, JP-A-3-92386 and JP-A-3-114890, and further, compounds I-1 to I-16 and 13 described in Japanese Patent Application No. 3-258005, pages 9 to 11. To compounds C-1 to C-17, M-1 to C-10, Y-2, Y-4, Y
-5 etc. can also be used conveniently.

The dye formed by forming a salt with a nitrogen-containing organic base is not particularly limited as long as it can form a salt with a nitrogen-containing organic base, and azo dyes and azomethine dyes conventionally used in heat-sensitive transfer materials. , Anthraquinone dyes and the like (for example, Kinki Chemical Society: Functional Dye Subcommittee Material No.
The dyes and their derivatives described on pages 16, 34 to 35, especially the derivatives having a phenolic hydroxyl group, are preferred from the viewpoints described later).

Among these dyes, a dye having a phenolic hydroxyl group is preferable in order to form a salt with a nitrogen-containing organic base while maintaining high sensitivity, that is, high transferability of the dye. Further, when an image is formed using a basic compound and / or a mordant, a dye having a phenolic hydroxyl group is preferable from the viewpoint of achieving both high transferability and mordability.
Examples of the dye having a phenolic hydroxyl group include a derivative of the phenolic hydroxyl group of the above-mentioned dye, JP-A-3-83685,
3-83687, 3-83688, 3-83689, 3-9039
No. 7, No. 3-92385, No. 3-92386, No. 3-114890 and the like.

Particularly preferred dyes having a phenolic hydroxyl group are dyes represented by the following general formula (Formula 4) (wherein R is
Represents a group forming an azomethine dye together with N—C ₆ H ₄ —OH, and the benzene ring may have a substituent. ), And specific examples thereof are JP-A-3-83685 and 3-83685.
687, 3-83688, 3-83689, 3-90397,
Examples thereof include dyes described in JP-A-3-92385, JP-A-3-92386 and JP-A-3-114890, and further, compounds I-1 to I-16 and 13 described in Japanese Patent Application No. 3-258005, pages 9 to 11. To compounds C-1 to C-17, M-1 to C-10, Y-2, Y-4, Y
-5 etc. can also be used conveniently.

[0055]

[Chemical 4]

The nitrogen-containing organic base forming the dye salt is preferably an organic base having a pka of 9 or more, and examples thereof include primary to tertiary alkylamines (eg octylamine, cyclohexylamine, dibutylamine, pyrrolidine, triethylamine). Etc.). Particularly preferred organic bases include the compounds represented by the above general formula (Formula 2). These compounds include amidine, guanidine, guanidine derivatives, and vinyl-type derivatives thereof.

In the formulas, R1, R2 and R3 each represent a hydrogen atom or an alkyl group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, an amino group (including an alkyl-substituted amino group) or a guanidine group. Represent R1 and R2 and / or R3 and R4 may be bonded to each other to form a ring. X
Represents a vinyl group, and n represents 0 or 1.

Specific examples of the base represented by the above general formula (Formula 2) include compounds B-1 to B-3 described in JP-A-64-3654, pages 3-4.
B-26 can be mentioned, and in addition, compounds A-1 to A-42 described in Japanese Patent Application No. 3-258005, pages 18 to 20 can be suitably used.

The content of the sublimable compound is usually preferably 10 to 70 parts by weight in the ink layer forming components,
More preferably, it is 30 to 60 parts by weight.

As the binder resin, vinyl chloride resin, polycarbonate resin, cellulose resin,
Polyvinyl acetal resin, polybutynyl pyrrolidone,
Polyvinyl acetate, polyacrylamide, styrene resin, acrylic or methacrylic resin, rubber resin,
Examples thereof include ionomer resins, olefin resins, polyester resins and the like. Among these, cellulose resins and polyvinyl acetal resins have good storage stability,
It can be preferably used. The binder resin is
They can be used alone or in combination of two or more.

Examples of the additive include a release agent, fine powder of metal, silica gel, metal oxide, carbon black, fine powder of resin, and the like, which can react with a binder component, such as isocyanates, acrylics, and epoxies. Examples thereof include hardeners such as radiation-active compounds and heat-melting substances such as waxes and higher fatty acid esters described in JP-A-59-106997 for promoting transfer.

The ink layer of the present invention may be composed of a single layer or a plurality of layers as long as it is formed on a support, and is used for thermal transfer recording. In order to prevent fusion with the image-receiving sheet and settling of the heat diffusible dye, an overcoat layer having a small dye content is provided on the surface of the ink layer, and on the contrary, the adhesion between the substrate or the undercoat layer and the ink layer is enhanced. Therefore, a lower ink layer having a small dye content may be provided. The thickness of the overcoat layer is usually 0.1 to 1 μm.

-Formation of Ink Layer- For the ink layer, an ink layer-forming coating liquid is prepared by dispersing or dissolving the above-mentioned various components forming the ink layer in a solvent, and coating this on the surface of a support. It can be manufactured by working and drying. The binders are used by dissolving one kind or two or more kinds in a solvent or dispersing them in a latex form.

Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, normal butyl acetate, N-methylpyrrolidone, dicryme and the like. For the coating, a conventionally known surface sequential coating method using a gravure roll, a wire bar coating method, a roll coating method, or the like can be used.

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, and a yellow ink layer, a magenta ink layer and a sheer ink layer may be formed. Alternatively, it may be formed on the entire surface or a part of the surface of the support at regular intervals along the plane direction. Further, in addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed. Regarding the black ink layer, a clear image can be obtained by either the diffusion transfer type or the melt transfer type.

The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3
μm. It should be noted that the transfer recording ink sheet can be conveniently used by forming a perforation or providing a detection mark for detecting the position of an area having a different hue.

-Support-The support is not particularly limited as long as it has good dimensional stability and can withstand the heat of a heat source such as a heat-sensitive head during image recording, and is not limited to condenser paper or glassine paper. Thin paper, polyethylene terephthalate, polyethylene naphthalate, polyamide, polyimide, polycarbonate, polysulfone, polyvinyl alcohol cellophane,
A heat resistant plastic film or sheet such as polystyrene can be used.

The thickness of the support is not particularly limited,
Preferably, it is 2 to 20 μm, more preferably 3 to 1
It is 0 μm. Any shape such as this sheet or film, narrow tape or card can be used.
Further, the support may have an undercoat layer for the purpose of improving the adhesiveness with the binder, transferring the dye to the support side, and preventing dyeing. Furthermore, the back surface of the support may have an energy A backing layer may be provided for the purpose of fusing to the support at the time of application, heat resistance, and preventing the formation of wrinkles in the thermal transfer recording ink sheet. The thickness of the backing layer is usually 0.1 to 1 μm.

= Thermal Transfer Recording Ink Sheet Having the Structure of (2) = In the thermal transfer recording ink sheet having the structure of (2) of the present invention, the ink layer has the above silicone-modified polyimide resin and Not containing at least one selected from the group consisting of polyethyleneimine-octadecyl isocyanate adduct, and an outer layer containing at least one selected from the group consisting of the above-mentioned silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate adduct. Is provided on the image receiving layer in the same manner as the thermal transfer recording ink sheet having the structure (1).

-Outer Layer-The outer layer of the present invention is not particularly limited, except that it contains at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct, and various resins or It is possible to form a single layer or a plurality of layers on the ink sheet by various methods using additives and the like. The thickness of this outer layer is usually 0.05 to 10 μm, preferably 0.1 to 1.0 μm.

B. Second embodiment: thermal transfer recording image-receiving sheet and ink sheet containing at least one selected from the group consisting of a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicon fine particles. An image-receiving sheet for thermal transfer recording and an ink sheet containing at least one selected from the group consisting of a resin, a silicone-modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicone particles have the following two structures.

(3) The first contains at least one selected from the group consisting of a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecylisocyanate adduct, and silicone fine particles, and at the same time, contains a heat diffusing dye. The image receiving layer or the ink layer containing the same is laminated on a support, and (4) the second is, on the support, the image receiving layer or the ink layer containing the heat diffusible dye, and the silicone. It has a structure in which at least one selected from the group consisting of a resin, a silicone-modified resin, and a polyethyleneimine-octadecyl isocyanate adduct, and an outer layer containing silicone particles are laminated in this order.

= Heat-sensitive transfer recording image-receiving sheet having the structure of (3) = In the heat-sensitive transfer recording image-receiving sheet of the present invention having the structure of (3), the above-mentioned image-receiving layer is a silicone-modified polyimide resin and polyethylene. Instead of at least one selected from the group consisting of imine-octadecyl isocyanate adduct, at least one selected from the group consisting of a silicone resin, a silicone modified resin and the above-mentioned polyethyleneimine-octadecyl isocyanate adduct, and silicone fine particles. It is the same as the image-receiving sheet for thermal transfer recording having the structure of (1) above except that it is contained.

—Silicone Resin and Silicone Modified Resin— The silicone resin has a siloxane bond and an alkyl group such as a methyl group at the silicon atom,
Examples thereof include what is called a resinous or solid organopolysiloxane at room temperature. An example of the organopolysiloxane that can be used in the present invention is shown below as (Chemical Formula 5).

[0075]

[Chemical 5]

The content of silicone resin is 0.1
It is preferably from 10 to 10 parts by weight, more preferably from 1 to 5 parts by weight. The silicone modified resin includes epoxy modified, olefin modified, ether modified, alcohol modified,
A modified polysiloxane resin in which various modifications such as fluorine modification, amino modification, mercapto modification and carboxyl modification are carried out on the alkyl group, and a part of urethane resin, acrylic resin and polyester resin is modified by the polysiloxane. Examples thereof include silicone-modified resins (preferably having a silicone portion in an amount of 5 to 40% by weight of the total resin). The structural formula of the modified polysiloxane resin is shown below.

[0077]

[Chemical 6]

[0078]

[Chemical 7]

[0079]

[Chemical 8]

[0080]

[Chemical 9]

[0081]

[Chemical 10]

[0082]

[Chemical 11]

In the formulas shown in the above Chemical Formulas 6 to 11, m, n,
a, b, c and x are integers of 0 or more, m and n are not 0 at the same time, R ¹ is an alkyl group, R
² and R ³ represent a divalent linking group. Me represents a methyl group.

-Silicone Fine Particles-The silicone fine particles have a network structure in which siloxane bonds are three-dimensionally extended, and have one alkyl group such as a methyl group bonded to a silicon atom. There can be mentioned fine particles having a different structure.

The silicone fine particles have an average particle diameter of 0.2 to 5.0 μm, a water content of 5% or less, a pH of 7 to 8, and a true specific gravity (25 ° C.) of 1 It is preferably 0.3 to 1.35, the bulk specific gravity is 0.2 to 0.3, the specific surface area is 50 to 90 m ² / g, and the linseed oil absorption is 80 to 110 ml / 100 g. The content of the silicone fine particles is 1 to
It is preferably 20 parts by weight, more preferably 2 to 10 parts by weight.

= Thermal Transfer Recording Ink Sheet Having Structure (4) = In the thermal transfer recording ink sheet having structure (4) of the present invention, the outer layer has the above silicone-modified polyimide resin and polyethylene. Instead of at least one selected from the group consisting of imine-octadecyl isocyanate adduct, at least one selected from the group consisting of the above silicone resin, silicone modified resin and polyethyleneimine-octadecyl isocyanate adduct, and the above silicone fine particles. It is the same as the ink sheet for heat-sensitive transfer recording having the structure of (2) above, except that it contains and.

-Outer Layer-The outer layer of the present invention is not particularly limited, except that it contains at least one selected from the group consisting of the above-mentioned silicone resin, silicone-modified resin and polyethyleneimine-octadecyl isocyanate adduct. It is possible to form a single layer or a plurality of layers on the ink sheet by various methods using various resins or additives.

C. Third embodiment: thermal transfer recording image-receiving sheet and ink sheet containing at least one selected from the group consisting of α-olefin resin and wax At least one selected from the group consisting of α-olefin resin and wax of the present invention The heat-sensitive transfer recording image-receiving sheet and the ink sheet containing the ink have the following two structures.

(5) The first contains at least one selected from the group consisting of α-olefin resins and waxes, and an image receiving layer or an ink layer containing a heat diffusible dye is provided on a support. It is a laminated structure,
(6) Secondly, an image receiving layer or an ink layer containing a heat diffusible dye, and an outer layer containing at least one selected from the group consisting of α-olefin resins and waxes are provided on a support. The structure is formed by stacking layers in this order.

= Heat-sensitive transfer recording image-receiving sheet having the structure of (5) = In the heat-sensitive transfer recording image-receiving sheet of the present invention having the structure of (5), the outer layer is a silicone-modified polyimide resin and polyethyleneimine. -A sensation having the structure of (2) above, except that at least one selected from the group consisting of α-olefin resins and wax is contained in place of at least one selected from the group consisting of octadecyl isocyanate adduct. This is the same as the image receiving sheet for thermal transfer recording.

-Α-Olefin Resin- The α-olefin resin of the present invention is not particularly limited, and various known ones such as polyethylene, polypropylene and polybutene-1 can be used. Is preferably 1 to 100 parts by weight, more preferably 30 to 100 parts by weight.

-Wax- The wax of the present invention is not particularly limited and includes, for example,
Various known waxes such as polyethylene wax, polypropylene wax, paraffin wax, microcrystalline wax, animal wax, mineral wax and vegetable wax can be used.
1 to 100 parts by weight is preferable, and more preferably 30
~ 100 parts by weight.

The thickness of the outer layer containing at least one selected from the group consisting of α-olefin resins and wax is usually 0.01 to 10 μm, preferably 0.01 to 2 μm.

= Thermal Transfer Recording Ink Sheet Having Structure (6) = In the thermal transfer recording ink sheet having structure (6) of the present invention, the outer layer is a silicone-modified polyimide resin and polyethyleneimine- In addition to containing at least one selected from the group consisting of the above α-olefin resin and wax instead of at least one selected from the group consisting of octadecyl isocyanate adduct, it has the structure of (2) above. It is the same as the thermal transfer recording ink sheet.

-Outer Layer- The outer layer of the present invention is not particularly limited, except that it contains at least one selected from the group consisting of α-olefin resins and waxes, and various outer layers such as various resins and additives may be used. A single layer or multiple layers can be formed on the ink sheet by the method. The thickness of the outer layer is preferably 0.01 to 10 μm, more preferably 0.01 to 2 μm.

D. Thermal Transfer Recording Method The thermal transfer recording method of the present invention is a thermal diffusible dye in a thermal transfer recording ink sheet obtained by superimposing an image receiving sheet for thermal transfer recording and an ink sheet for thermal transfer recording and heating them imagewise. In the heat-sensitive transfer recording method for forming an image by diffusively transferring to the image-receiving layer of the heat-sensitive transfer recording image-receiving sheet, the above-mentioned support is provided immediately before the heat-sensitive transfer recording image-receiving sheet and the heat-sensitive transfer recording ink sheet are superposed. An outer layer containing at least one selected from the group consisting of the α-olefin resin and wax is laminated on the surface of the above-mentioned image-receiving layer or ink layer laminated thereon.

-Formation of Image- To form an image, the ink layer of the thermal transfer recording ink sheet and the image-receiving layer of the thermal transfer recording image-receiving sheet are superposed, and an image is formed on the interface between the ink layer and the image-receiving layer. Gives heat energy. Then, the heat-diffusible dye in the ink layer is thermally diffused or sublimated by an amount according to the amount of heat energy applied to the image formation, and is transferred to the image-receiving layer side to be received, resulting in the dye in the image-receiving layer. An image (chelate dye image) is formed.

As a heat source for giving heat energy, a thermal head is generally used, but in addition to this, known sources such as a loser light, an infrared flash, and a heat pen can be used. When a thermal head is used as a heat source for applying heat energy, the applied heat energy can be changed continuously or in multiple steps by modulating the voltage or pulse width applied to the thermal head.

When laser light is used as a heat source for giving heat energy, the heat energy to be given can be changed by changing the light amount of the laser light or the irradiation area. In this case, in order to make it easier to absorb the laser light, for example, in the case of a semiconductor laser, a laser light absorbing material such as carbon black or a near infrared absorbing substance may be present in the ink layer or in the vicinity of the ink layer.

When a laser beam is used, it is advisable to bring the thermal transfer recording ink sheet and the thermal transfer recording image receiving sheet into close contact with each other. Further, if a dot generator with a built-in acousto-optic element is used, it is possible to give heat energy according to the size of the halftone dot. When an infrared flash lamp is used as a heat source for giving heat energy, it is preferable to perform heating through a black colored layer, as in the case of using laser light. When an infrared lamp is used as a heat source for providing heat energy, heating may be performed as in the case of using a laser beam, or a negative layer corresponding to the negative of the above pattern and a colored layer such as black on one surface. You may heat by combining.

The thermal energy may be applied from the thermal transfer recording ink sheet side, the thermal transfer recording image receiving sheet side or both sides, but the effective use of thermal energy is prioritized. If this is done, it is preferable to carry out from the side of the thermal transfer recording ink sheet. By the above-mentioned thermal transfer recording, an image of one color can be recorded on the image receiving layer of the image receiving sheet for thermal transfer recording. However, according to the following method, it is also possible to obtain a color photographic tone color image formed by combining the respective colors. For example, by replacing the yellow, magenta, cyan, and, if necessary, black thermal transfer recording thermal sheets in sequence, and instead of using thermal transfer recording ink sheets for each color, pre-separate areas are formed by separately coating each color. You may use the thermal transfer recording ink sheet which has. With this method, it is possible to obtain a color photograph-like color image, but more advantageously, this method has an advantage that the above-mentioned replacement of the thermal transfer recording ink sheet is unnecessary. Furthermore, after forming an image by the above-mentioned method, for the purpose of improving image storability,
You may heat-process by the above-mentioned method. For example, over the entire surface of image formation, heat treatment may be performed using a portion of the ink sheet where the ink layer is not provided, or heat treatment such as a heat roll may be newly performed. Further, when the near infrared ray absorbent is contained, the image forming surface may be exposed by using an infrared flash lamp. In any case, the heating means is not limited, but since the purpose is to further diffuse the dye inside the image receiving layer, it is effective and preferable to heat from the support side of the image receiving layer.

-Lamination of Outer Layer- The outer layer containing at least one selected from the group consisting of α-olefin resins and waxes is subjected to thermal transfer recording image reception in a printing apparatus by using various coating methods as described above. It is applied and formed on the surface of the image receiving layer of the sheet or the ink layer of the thermal transfer recording ink sheet, immediately before the thermal transfer recording image receiving sheet and the thermal transfer recording ink sheet are combined. As the thickness of the outer layer,
0.01 to 10 μm is preferable, and more preferably 0.
It is 01 to 2 μm.

[0103]

EXAMPLES Next, the present invention will be described more specifically based on examples. In the following, "part" means "part by weight". (Example 1) As a base material, a synthetic paper having a thickness of 150 μm (trade name: YUPO FPG-150; manufactured by Oji Yuka Synthetic Paper Co., Ltd.) was coated with a coating solution for forming an image receiving layer having the following composition by a wire-bar coating method. After applying and temporary drying with a dryer,
By drying in an oven at a temperature of 100 ° C. for 1 hour, an image-receiving sheet for heat-sensitive transfer recording was obtained in which an image-receiving layer having a thickness of 5 μm was formed on synthetic paper.

Coating Liquid for Forming Image Receiving Layer Silicone-Modified Polyimide Resin ... 0.5 Part {Sumitomo Bakelite Co., Ltd., CRC-7025X} Polyvinyl Butyral ...・ ・ ・ 9.5 parts {Brand name BX-1: Sekisui Chemical Co., Ltd.} Methyl ethyl ketone ・ ・ ・ ・ ・ 45 parts Dioxane ・ ・ ・........ 45 copies Image recording was performed by heating with a thermal head under the conditions of output of 0.35 W / dot and dot density of 8 dots / mm. ..

After image recording, background stains on the unprinted portion (white background portion) of the image receiving layer surface of the thermal transfer recording image receiving sheet, transfer density on the image receiving layer surface, thermal transfer recording ink sheet and thermal transfer recording image receiving sheet. The fused state was evaluated according to the following criteria. The results are shown in Table 1.

Background stain: ∙ ... Contamination by the dye was not found in the unprinted portion of the surface of the image receiving layer or the ink layer. X: The same unprinted area was contaminated with dye. Transfer density: The reflection density OD value was measured with an optical densitometer. ◎ ・ ・ ・ ・ OD value is 2.3 or more. 〇 ・ ・ OD value is 2.0 or more. X ... OD value is 2.0 or less.

Fusing: ◯ ... Only the dye was transferred to the image receiving layer, and the image receiving layer or the ink layer was not peeled from the support. X ... The entire image receiving layer or ink layer was peeled from the support and transferred.

(Example 2) The coating liquid for forming an image receiving layer of Example 1 was prepared by using at least one selected from the group consisting of silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate adduct. After the image-receiving layer is formed by applying the following coating liquid for forming an outer layer on the image-receiving layer and drying,
An image receiving sheet for thermal transfer recording having an outer layer of mm was obtained. Coating liquid for outer layer: Silicone-modified polyimide resin: 5 parts {Sumitomo Bakelite Co., Ltd., CRC-7025X} Polyvinyl butyral ... .. 5 parts {Brand name BX-1: Sekisui Chemical Co., Ltd.} Methyl ethyl ketone ... 45 parts Dioxane ... ........... 45 parts Example 1 of the obtained image-receiving sheet for thermal transfer recording
The same test was performed and the test results are shown in Table 1.

(Example 3) As a support, AST was formed on the back surface.
A coating liquid for ink layer formation having the following composition was dried on the surface of a polyethylene terephthalate film (trade name: Lumirror 6CF-531: manufactured by Toray Industries, Inc.) having a layer and a thickness of 6.0 μm by a wire bar coating method. An ink sheet for thermal transfer recording was obtained by coating and drying so that the thickness would be 1 μm.

Coating liquid for forming ink layer Silicone-modified polyimide resin: 0.12 parts {Sumitomo Bakelite Co., Ltd., CRC-7025X} Disperse dye:・ ・ ・ ・ ・ ・ ・ ・ ・ 3 parts {Kayaset Blue 136 manufactured by Nippon Kayaku Co., Ltd.} Polyvinyl acetal ・ ・ ・ ・ ・ ・ 2.88 parts {Product name KY-24: manufactured by Denki Kagaku Kogyo Co., Ltd.} Methyl ethyl ketone ... 47 parts Dioxane ... .. 47 parts The obtained thermal transfer recording ink sheet was subjected to the same test as in Example 1, and the test results are shown in Table 1.

(Example 4) The coating liquid for forming the ink layer of Example 1 was prepared without using at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct. After forming the ink layer, the following outer layer forming coating liquid was applied onto the ink layer and dried to obtain an ink sheet for thermal transfer recording having an outer layer having a thickness of 0.5 μm. Coating liquid for ink layer formation Silicone-modified polyimide resin ・ ・ ・ ・ ・ ・ ・ ・ 3 parts {Sumitomo Bakelite Co., Ltd., CRC-7025X} Polyvinyl acetal ・ ・ ・ ・ ・ ・ ・ ・ ・ ・・ ・ ・ 3 parts {Product name KY-24: manufactured by Denki Kagaku Kogyo KK} Methyl ethyl ketone ・ ・ ・ 47 parts Dioxane ・ ・ ・ ・ ・ ・47 parts The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example 1 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecyl isocyanate adduct, an acrylic-modified silicone (Cymac US- 270) and polyester-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. (X-
An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 1 except that (24-8301) was used. The heat-sensitive transfer recording image-receiving sheet thus obtained was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example 2 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecylisocyanate adduct, an acrylic-modified silicone (Cymac US- 270) and polyester-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. (X-
An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 2 except that (24-8301) was used. The heat-sensitive transfer recording image-receiving sheet thus obtained was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example 3 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecylisocyanate adduct, an acrylic-modified silicone (Cymac US- 270) and polyester-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. (X-
An ink sheet for thermal transfer recording was obtained in the same manner as in Example 3 except that (24-8301) was used. The same test as in Example 1 was performed on the obtained thermal transfer recording ink sheet, and the test results are shown in Table 1.

Comparative Example 4 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecylisocyanate adduct, an acrylic-modified silicone (Cymac US- 270) and polyester-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. (X-
An ink sheet for thermal transfer recording was obtained in the same manner as in Example 4 except that (24-8301) was used. The same test as in Example 1 was performed on the obtained thermal transfer recording ink sheet, and the test results are shown in Table 1.

Example 5 As a silicone resin, X-
24-8301 0.4 parts, CRC-7025X as silicone modified resin 0.1 part, as silicone fine particles, Tospearl 120 manufactured by Toshiba Silicone Co., Ltd. 0.5 part, polyvinyl butyral 9.0 parts In the same manner as in Example 1, except that at least one selected from the group consisting of the silicone resin of the present invention, the silicone-modified resin, and the polyethyleneimine-octadecyl isocyanate adduct, and the silicon fine particles, and an image-receiving sheet for thermal transfer recording. Formed. The same test as in Example 1 was conducted on the obtained thermal transfer recording image-receiving sheet,
The test results are shown in Table 1.

Example 6 As a silicone resin, X-
1 part of 24-8301, CR as silicone modified resin
The silicone resin of the present invention, the silicone-modified resin, and the silicone-modified resin of the present invention were prepared in the same manner as in Example 2 except that 4 parts of C-7025X, 1 part of Tospearl 120 manufactured by Toshiba Silicone Co., Ltd., and 4 parts of polyvinyl butyral were used as silicone fine particles. At least one selected from the group consisting of polyethyleneimine-octadecyl isocyanate adduct,
An image-receiving sheet for thermal transfer recording containing silicon fine particles was formed. The heat-sensitive transfer recording image-receiving sheet thus obtained was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Example 7 As a silicone resin, X-
Other than using 0.02 part of 24-8301, 0.1 part of CRC-7025X as a silicone-modified resin, 0.3 part of Tospearl 120 manufactured by Toshiba Silicone Co., Ltd., and 2.58 part of polyvinyl acetal as silicone fine particles. In the same manner as in Example 3, a thermal transfer recording ink sheet containing at least one selected from the group consisting of the silicone resin, the silicone-modified resin and the polyethyleneimine-octadecylisocyanate adduct of the present invention, and silicon fine particles is prepared. Formed.

The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1 and the test results are shown in Table 1.
It was shown to.

(Example 8) As a silicone resin, X-
24-8301 0.3 parts, CRC-7025X 2.7 parts as silicone modified resin, Toshiba Silicone Co., Ltd. Tospearl 120 0.3 parts as polyvinyl fine particles, and polyvinyl acetal 2.7 parts. The same procedure as in Example 4 except that the silicone resin of the present invention, the silicone-modified resin and the polyethyleneimine-
An ink sheet for thermal transfer recording containing at least one selected from the group consisting of octadecyl isocyanate adduct and silicon fine particles was formed. The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Comparative Example 5) An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 1 except that Tospearl 120 as silicone fine particles was not contained. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Comparative Example 6) An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 2 except that Tospearl 120 as silicone fine particles was not contained. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Comparative Example 7) An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 3 except that Tospearl 120 as fine particles of silicone was not contained. The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Comparative Example 8) An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 4 except that Tospearl 120 as the silicone fine particles was not contained. The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Example 9) As a coating liquid for forming an outer layer, a polyethylene resin emulsion {trade name: E-1000 was used.
0, manufactured by Toho Kagaku Co., Ltd.} was used in the same manner as in Example 2 to form an image-receiving sheet for thermal transfer recording containing at least one selected from the group consisting of the α-olefin resin and the wax of the present invention. did. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

(Example 10) As an outer layer forming coating solution,
Polyethylene resin emulsion {Product name: S-625
4, manufactured by Toho Kagaku Co., Ltd.} was used to form an image-receiving sheet for thermal transfer recording containing at least one selected from the group consisting of the α-olefin resin and the wax of the present invention in the same manner as in Example 4. did. The heat-sensitive transfer recording image-receiving sheet thus obtained was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example 9 An image-receiving sheet for thermal transfer recording was obtained in the same manner as in Example 2 except that at least one selected from the group consisting of α-olefin resin and wax was not contained. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Comparative Example 10 An ink sheet for thermal transfer recording was obtained in the same manner as in Example 4 except that it did not contain at least one selected from the group consisting of α-olefin resin and wax. The obtained thermal transfer recording ink sheet was tested in the same manner as in Example 1, and the test results are shown in Table 1.

Example 11 An image-receiving sheet for thermal transfer recording and an image-receiving sheet for thermal transfer recording were prepared in the same manner as in Example 1 except that at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct was not contained. An ink sheet was obtained. Immediately before printing by combining the heat-sensitive transfer recording image-receiving sheet and the heat-sensitive transfer recording ink sheet, at least one selected from the group consisting of silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate adduct -Polyethylene wax emulsion (E-1000) as an olefin resin was used as a coating liquid for forming an outer layer, which was applied to the surface of the image receiving layer, and then printing was performed. Then, the same test as in Example 1 was performed, and the test results are shown in Table 1.

(Example 12) An image-receiving sheet for thermal transfer recording and an image-receiving sheet for thermal transfer recording were prepared in the same manner as in Example 1 except that at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct was not contained. An ink sheet was obtained. Immediately before printing by combining the heat-sensitive transfer recording image-receiving sheet and the heat-sensitive transfer recording ink sheet, at least one selected from the group consisting of silicone-modified polyimide resin and polyethyleneimine-octadecyl isocyanate adduct -Polyethylene wax emulsion (E-1000) was used as an olefin resin as a coating liquid for forming an outer layer, and this was applied to the surface of an ink sheet, and then printing was performed. Then, the same test as in Example 1 was performed, and the test results are shown in Table 1.

(Comparative Example 11) Printing was carried out in the same manner as in Example 11 except that the α-olefin resin was not contained. Then, the same test as in Example 1 was performed, and the test results are shown in Table 1.

Comparative Example 12 Printing was carried out in the same manner as in Example 12 except that the α-olefin resin was not contained. Then, the same test as in Example 1 was performed, and the test results are shown in Table 1.

(Example 13) {Preparation of image-receiving sheet for thermal transfer recording} Thickness 125 μm,
12 parts of titanium oxide having an average particle diameter of 0.3 μm and 1.5 parts of an antistatic agent (Elex 334, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) using Beck smoothness 1500 sec. Contains, the density is 0.90 g / cm ³ ,
A composition containing polypropylene as a main component and having a melt flow rate of 7 g / 10 min was melted and sufficiently kneaded, and then 40 g / m ² on the image receiving layer side and 30 g / m ² on the back side.
A support was prepared by hot-melt extrusion laminating so that the amount of stickiness was.

The surface of the support thus prepared on which the image receiving layer was to be laminated was subjected to corona discharge treatment, and then an intermediate layer composition solution having the following composition was applied and dried to form an intermediate layer having a thickness of 0.2 μm.

Intermediate layer composition Polyester resin: 18 parts {Unitika KK-made Elitel UE3300} Curing agent: ····································· 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Part Subsequently, an image receiving layer forming composition solution having the following composition was applied onto the intermediate layer so that the thickness after drying was 10 μm and dried to form an image receiving layer to obtain an image receiving sheet for thermal transfer recording.

Image-Receiving Layer-Forming Composition Solution Phenoxy Resin ... 5 parts {PKHH manufactured by Union Cover Co., Ltd.} Mordant ...・ ・ ・ ・ ・ ・ 4 parts {Tetrabutylammonium benzoate} Silicone modified polyimide resin ・ ・ ・ ・ ・ ・ ・ ・ 1 part {Sumitomo Bakelite Co., Ltd., CRC-7025X} Methyl ethyl ketone ・ ・ ・ ・ ・ 80 parts Methyl cellosolve ・ ・ ・ ・ ・..10 parts Cyclohexanone ........ 10 parts {Preparation of ink sheet for thermal transfer recording} Polyethylene terephthalate film with a thickness of 6 μm {Lumirror, manufactured by Toray Industries, Inc. 6CF53N} with a back coat composition having the following composition By over bar coating method,
It was applied and dried so that the thickness after drying was 0.3 μm.

Backcoat composition Silicone resin: 5 parts {Dairo Seika Co., Ltd., Dialomer SP-712} Nitrocellulose:・ ・ ・ 5 parts Methyl ethyl ketone ・ ・ ・ 85 parts Cyclohexanone ・ ・ ・・ ・ ・ 5 parts Next, a coating solution for forming an ink layer having the following composition was applied to the surface opposite to the surface coated with the back coat by a wire bar coating method to obtain a thickness after drying. An ink sheet for thermal transfer recording was obtained by coating and drying so as to have a thickness of 1 μm.

Ink layer forming coating solution Thermal diffusible dye 50 parts {Exemplified compound M-2 described in Japanese Patent Application No. 3-258005} Polyvinyl butyral ······································································ 2 2 2 2/2 Chemical Industry Co., Ltd., Cymac US-270} Using the obtained thermal transfer recording ink sheet and thermal transfer recording image-receiving sheet, the same test as in Example 1 was conducted, and the results shown in Table 1 were obtained. Was obtained. Further, when printing was carried out after each of the obtained thermal transfer recording ink sheet and thermal transfer recording image receiving sheet was stored at 60 ° C. for 62 hours, it was possible to print at high speed without fusing. No background stain was found on the surface of the image receiving sheet for use.

Comparative Example 13 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecylisocyanate adduct, an acrylic-modified silicone resin (manufactured by Toagosei Kagaku KK, Cymac) is used. An image receiving sheet for thermal transfer recording was obtained in the same manner as in Example 13 except that US-270} was used. The same test as in Example 13 was carried out on the obtained thermal transfer recording image-receiving sheet, and the test results are shown in Table 1.

(Example 14) The coating liquid for forming an image receiving layer of Example 13 was prepared without using at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct. After forming the image-receiving layer by applying the same coating solution for forming an outer layer as in Example 2 to the upper layer of the image-receiving layer and drying, an image-receiving sheet for thermal transfer recording having an outer layer having a thickness of 0.5 μm was obtained. The same test as in Example 1 was conducted using the ink sheet of Example 13 and the obtained image-receiving sheet, and the test results are shown in Table 1.

(Comparative Example 14) Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecyl isocyanate adduct, an acrylic-modified silicone resin (Toa Gosei Kagaku KK, Cymac) An image receiving sheet for thermal transfer recording was obtained in the same manner as in Example 14 except that US-270} was used. The same test as in Example 13 was carried out on the obtained thermal transfer recording image-receiving sheet, and the test results are shown in Table 1.

(Example 15) {Preparation of image-receiving sheet for heat-sensitive transfer recording} Thickness 125 μm,
12 parts of titanium oxide having an average particle diameter of 0.3 μm and 1.5 parts of an antistatic agent (Elex 334, manufactured by Matsumoto Yushi-Seiyaku Co., Ltd.) using Beck smoothness 1500 sec. Contains, the density is 0.90 g / cm ³ ,
A composition containing polypropylene as a main component having a melt flow rate of 7 g / 10 min was melted and sufficiently kneaded, and then 40 g / m ² on the image receiving layer side and 30 g / m ² on the back side.
A support was prepared by hot-melt extrusion laminating so that the amount of stickiness was.

After corona discharge treatment was applied to the surface of the prepared support on which the image receiving layer was laminated, an intermediate layer composition solution having the following composition was applied and dried to form an intermediate layer having a thickness of 0.2 μm.

Intermediate layer composition Polyester resin: 18 parts {Unitika KK-made Elitel UE3300} curing agent: ··································· 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 Then, an image receiving layer forming composition solution having the following composition was applied onto the intermediate layer so that the thickness after drying was 10 μm, and dried,
An image receiving sheet for thermal transfer recording was obtained by forming an image receiving layer.

Image-Receiving Layer Forming Composition Solution Phenoxy Resin ... 6 parts {PKHH manufactured by Union Cover Co., Ltd.} Mordant ...・ ・ ・ ・ ・ ・ 4 parts {Tetrabityl ammonium benzoate} Methyl ethyl ketone ・ ・ ・ ・ 80 parts Methyl Cellosolve ・ ・ ・ ・ 10 parts Cyclohexanone ・ ・ ・ ・ 10 parts {Ink sheet for thermal transfer recording Preparation of 6 μm thick polyethylene terephthalate film {Lumirror 6CF53N manufactured by Toray Industries, Inc.} with a back coat composition having the following composition by a wire bar coating method.
It was applied and dried so that the thickness after drying was 0.3 μm.

Backcoat composition Silicone resin: 5 parts {Dairo Seika Co., Ltd., Dialomer SP-712} Nitrocellulose:・ ・ ・ 5 parts Methyl ethyl ketone ・ ・ ・ 85 parts Cyclohexanone ・ ・ ・・ ・ ・ 5 parts Next, a coating solution for forming an ink layer having the following composition was applied to the surface opposite to the surface coated with the back coat by a wire bar coating method to obtain a thickness after drying. An ink sheet for thermal transfer recording was obtained by coating and drying so as to have a thickness of 1 μm.

Ink Layer-Forming Coating Liquid Thermal Diffusive Dye ... 50 parts {Exemplary Compound C described in Japanese Patent Application No. 3-258005] -1} Polyvinyl butyral ... 47 parts {Sekisui Chemical Co., Ltd., S-REC BX-1} Silicone modified polyimide resin ...・ ・ ・ ・ ・ ・ 3 parts {Sumitomo Bakelite Co., Ltd., CRC-7025X} Using the obtained thermal transfer recording ink sheet and thermal transfer recording image receiving sheet, the same test as in Example 1 The results shown in Table 1 were obtained. Further, when printing was carried out after each of the obtained thermal transfer recording ink sheet and thermal transfer recording image receiving sheet was stored at 60 ° C. for 62 hours, it was possible to print at high speed without fusing. No background stain was found on the surface of the image receiving sheet for use.

Comparative Example 15 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecyl isocyanate adduct, an acrylic-modified silicone resin (manufactured by Toagosei Kagaku Co., Cymac) is used. An ink sheet for thermal transfer recording was obtained in the same manner as in Example 14 except that US-270) was used. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 15, and the test results are shown in Table 1.
It was shown to.

(Example 16) 1. Preparation of image-receiving sheet for thermal transfer recording 125 μm in thickness, Beck smoothness 1500 sec.
Titanium oxide with an average particle size of 0.3 μm
Part, and 1.5 parts of antistatic agent {Matsumoto Yushi-Seiyaku Co., Ltd., Elex 334}, density 0.90 g
/ Cm ³ and melt flow rate is 7 g / 10 min
Melt the composition containing polypropylene as the main component,
After sufficiently kneading, a support was prepared by hot-melt extrusion laminating so that the image-receiving layer surface side had a coverage of 40 g / m ² and the back surface side had a coverage of 30 g / m ² .

The surface of the support thus prepared on which the image receiving layer was laminated was subjected to corona discharge treatment, and then an intermediate layer composition solution having the following composition was applied and dried to form an intermediate layer having a thickness of 0.2 μm. Intermediate layer composition Polyester resin: 18 parts {Unitika Ltd., Elitel UE3300} Curing agent:・ ・ ・ ・ ・ ・ ・ ・ ・ 2 parts {Nippon Polyurethane Co., Ltd., Coronate HX} methyl ethyl ketone ・ ・ ・ 100 parts An image receiving layer forming composition solution having the following composition is applied onto the intermediate layer so that the thickness after drying is 10 μm, and dried,
An image receiving layer was formed.

Image-Receiving Layer-Forming Composition Alkyl phthalate ester ... 10 parts {DOP} manufactured by Daihachi Chemical Co., Ltd. Mordant ...・ ・ ・ ・ ・ ・ ・ ・ 40 parts {Tetrabutylammonium acetate} phenoxy resin ・ ・ ・ ・ ・ ・ ・ ・ 50 parts {Union Carbite Manufactured by PKHJ} Methyl ethyl ketone ...... 400 parts Further, a polyethylene resin emulsion {S-6254 manufactured by Toho Kagaku Co., Ltd.} as an outer layer forming coating liquid is used as an image receiving layer. An outer layer was formed by coating and drying the composition so that the thickness after drying would be 0.5 μm to obtain an image-receiving sheet for thermal transfer recording.

Using the same thermal transfer recording ink sheet as in Example 14 and the obtained thermal transfer recording image receiving sheet, the same test as in Example 1 was carried out, and the results shown in Table 1 were obtained. Further, when printing was carried out after each of the obtained thermal transfer recording ink sheet and thermal transfer recording image receiving sheet was stored at 60 ° C. for 62 hours, it was possible to print at high speed without fusing. No background stain was found on the surface of the image receiving sheet for use.

Comparative Example 16 Instead of at least one selected from the group consisting of the silicone-modified polyimide resin of the present invention and the polyethyleneimine-octadecylisocyanate adduct, an acrylic-modified silicone resin (manufactured by Toagosei Kagaku Co., Ltd., Cymac) is used. An ink sheet for thermal transfer recording was obtained in the same manner as in Example 14 except that US-270} was used. The obtained thermal transfer recording image-receiving sheet was tested in the same manner as in Example 15, and the test results are shown in Table 1.
It was shown to.

[0154]

[Table 1]

[0155]

The image-receiving sheet for heat-sensitive transfer recording of the present invention comprises
Even if the platen pressure during printing is increased, it is possible to prevent fusion between the ink layer and the image receiving layer that are in close contact, so it is possible to print at high speed and high density with a small amount of power. The ink sheet for heat-sensitive transfer recording of the present invention has the technical effect that the surface gloss of the printing surface can be maintained for a long period of time, and the ink adheres even if the platen pressure during printing is increased. Since fusion between the image-receiving layer and the image-receiving layer can be prevented, printing can be performed at high speed and high density with a small amount of power, and the background of the surface of the image-receiving sheet for thermal transfer recording after printing can be performed. The thermal transfer recording method of the present invention has the technical effect of preventing the generation of stains, and even when the platen pressure during printing is increased, fusion between the intimate ink layer and the image receiving layer is prevented. Because it can be prevented
It is possible to print at high speed and high density with a small amount of power, and to maintain the gloss of the surface of the image-receiving sheet for thermal transfer recording after printing for a long period of time and prevent the occurrence of scumming. It has a technical effect.

Front Page Continuation (72) Inventor Tomoki Kawamura 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

Claims (11)

[Claims] 1. An image receiving layer containing at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct and receiving a heat diffusible dye is laminated on a support. Characteristic image-receiving sheet for thermal transfer recording. 2. An image receiving layer for receiving a heat diffusible dye, and an outer layer containing at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct on a support. An image-receiving sheet for heat-sensitive transfer recording, characterized by being laminated in order. 3. An ink layer containing at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecylisocyanate adduct and containing a heat-diffusible dye is laminated on a support. Characteristic thermal transfer recording ink sheet. 4. An ink layer containing a heat diffusible dye, and an outer layer containing at least one selected from the group consisting of a silicone-modified polyimide resin and a polyethyleneimine-octadecyl isocyanate adduct on a support. An ink sheet for thermal transfer recording, characterized by being laminated in order. 5. An image receiving layer containing at least one selected from the group consisting of a silicone resin, a silicone modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicone fine particles and receiving a heat diffusible dye on a support. An image-receiving sheet for heat-sensitive transfer recording, characterized by being laminated on. 6. An image receiving layer for receiving a heat diffusible dye, at least one selected from the group consisting of a silicone resin, a silicone modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicone fine particles on a support. An image-receiving sheet for thermal transfer recording, comprising an outer layer and an outer layer contained in this order. 7. An ink layer containing at least one selected from the group consisting of a silicone resin, a silicone-modified resin and a polyethyleneimine-octadecylisocyanate adduct, silicone fine particles and a heat diffusing dye is laminated on a support. An ink sheet for thermal transfer recording characterized by the following. 8. An ink layer containing a heat diffusible dye, at least one selected from the group consisting of a silicone resin, a silicone modified resin and a polyethyleneimine-octadecyl isocyanate adduct, and silicone particles on a support. An ink sheet for thermal transfer recording, comprising an outer layer and an outer layer contained in this order. 9. An image receiving layer for receiving a heat diffusible dye and an outer layer containing at least one selected from the group consisting of α-olefin resins and waxes are laminated in this order on a support. An image receiving sheet for thermal transfer recording. 10. An ink layer containing a heat-diffusible dye and an outer layer, which is a layer containing at least one selected from the group consisting of α-olefin resins and waxes, are laminated in this order on a support. An ink sheet for thermal transfer recording characterized by the following. 11. A thermal transfer recording image-receiving sheet and a thermal transfer recording ink sheet are superposed and heated imagewise so that the heat diffusible dye in the thermal transfer recording ink sheet is transferred to the thermal transfer recording image receiving sheet. In a heat-sensitive transfer recording method of diffusively transferring to the image-receiving layer, immediately before the heat-sensitive transfer recording image-receiving sheet and the heat-sensitive transfer recording ink sheet are superposed, on the surface of the image-receiving layer in the heat-sensitive transfer recording image-receiving sheet, or for the heat-sensitive transfer recording. A thermal transfer recording method comprising laminating an outer layer containing at least one selected from the group consisting of α-olefin resins and waxes on the surface of the ink layer of the ink sheet.