JPH0633006B2 - Thermal transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a cured film having excellent heat resistance and slipperiness on one side of a plastic film by a novel coating material that forms a cured film having excellent heat resistance and slipperiness by heat or radicals. The present invention relates to a thermal transfer sheet having a material layer formed on the opposite surface of the plastic film and transferred to the transfer target by heating.

In order to obtain an image according to image information by a thermal head, in recent years, a heat-sensitive melt transfer type transfer sheet having a heat-fusible wax layer in which pigments and dyes are dispersed on a base sheet, or a sublimable dye in a binder is used. Heat-sensitive sublimation transfer sheets having a layer included in the above have been used.

As the base sheet of such a heat-sensitive transfer sheet, there are condenser paper, polyester film, polypropylene film, cellophane, cellulose acetate film and the like, and those having a thickness of 5 to 12 [mu] are used. Among these substrate sheets, the polyester film is preferably used because of its thickness uniformity, surface smoothness, and ease of operation in a printer. By the way, when this polyester film is provided with the heat-sensitive melting transfer layer or the heat-sensitive sublimation transfer layer, and heat printing is performed from the back surface of the film with a thermal head, when printing is performed with energy necessary for obtaining sufficient print density, If the transfer film becomes inoperable or is so remarkable that the sheet itself is fused with the thermal head, that is, so-called staking occurs, the film is broken from that part.

In order to solve these problems, some attempts have been proposed to provide a heat-resistant protective layer on the back surface of the base sheet, but some examples are given, and a silicon oxide layer as a metal layer or wear-resistant layer on the back surface of the base. Method (Japanese Patent Application Laid-Open No. 54-143)
152, JP-A-57-74195) A method of providing a heat resistant resin layer such as silicone or epoxy (JP-A-55-74).
67), a method of forming a resin layer to which a solid or semi-solid surfactant or the like is added at room temperature (JP-A-57-129789).
Alternatively, there is a method of providing a layer in which a lubricating inorganic pigment is contained in a heat resistant resin (JP-A-56-155794).

However, these proposals require expensive processes such as vapor deposition, require a large amount of thermal energy for thermosetting, or require long-term aging to obtain sufficient heat resistance, or The thermal head was not sufficiently slippery for smooth running.
In addition, the addition of a lubricant such as a surfactant has a drawback that it promotes the attachment of dirt to the thermal head.

Therefore, an object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, that is, it is stable to the thermal energy of the thermal head at the time of printing and is necessary for smooth running. To obtain a coating material for forming a resin film having

The present inventors provide a copolymer containing an acrylic acid ester or a methacrylic acid ester of a higher alcohol having 12 or more carbon atoms, which has extremely excellent thermal stability when the copolymer is cured by heat or radical polymerization. The present inventors have found that a film having a slip property is formed and have reached the present invention.

The present invention contains a vinyl polymer having a structure represented by the following general formula (I) in the molecule, and a layer of a coating material curable by heat or radicals is provided on one side of a plastic film, The present invention relates to a heat-sensitive transfer sheet having a heat-sensitive transfer ink layer formed on the opposite surface of a plastic film.

The coating material according to the present invention is a polymer having an acrylic ester or methacrylic ester of a higher alcohol having 12 or more carbon atoms and a thermosetting functional group as structural units, respectively. Or a blend of homopolymers having respective structural units, or a blend of a copolymer containing both structural units and a polymer not containing these structural units. Further, a radically polymerizable unsaturated monomer can be added.

Examples of the acrylic or methacrylic acid ester of a higher alcohol having 12 or more carbon atoms as the first structural unit include, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, myristyl alcohol, pentadecyl alcohol, nonadecyl alcohol, eicosyl alcohol, Examples thereof include oleyl alcohol, elaidyl alcohol, linoleyl alcohol, linolenyl alcohol, and behenyl alcohol, and esters of acrylic acid or methacrylic acid. Further, in the present invention, esters of the above alcohols and unsaturated carboxylic acids such as itaconic acid, maleic acid and fumaric acid can also be used. From the viewpoint of the effect of slipperiness, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate and the like are particularly preferable.

In order to introduce the thermosetting functional group which is the second structural unit, the following monomers are copolymerized.

(1) Monomer having hydroxyl group: N-methylol acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate,
2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy, 3-phenoxypropyl methacrylate, 2-hydroxy, 3-phenoxypropyl acrylate, and the like.

(2) Monomer having a carboxyl group: acryloyloxyethyl monosuccinate and the like.

(3) Epoxy group-containing monomer: glycidyl methacrylate and the like.

(4) Monomers having an aziridinyl group: 2-aziridinylethyl methacrylate, allyl 2-aziridinylpropionate and the like.

(5) Monomers having amino groups: acrylamide, methacrylamide, diacetone acrylamide, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.

(6) Sulfon group-containing monomer: 2-acrylamido-2-methylpropane sulfonic acid.

(7) Monomer having isocyanate group: an addition product of a diisocyanate such as 2,4-toluene diisocyanate and 2-hydroxyethyl acrylate in an amount of 1 mol to 1 mol and a radial polymerizable monomer having active hydrogen.

Further, in order to adjust the glass transition point of the copolymer or the physical properties of the cured film, the following copolymerizable monomers can be used for copolymerization. For example, methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate,
Isobutyl methacrylate, t-butyl acrylate,
t-butyl methacrylate, isoamyl acrylate,
Isoamyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate,
Etc. are usually used, but methyl methacrylate, ethyl methacrylate, etc., which is a high glass transition point polymer, are preferable in order to obtain good heat resistance.

A monomer comprising an acrylic acid ester or a methacrylic acid ester of a higher alcohol having 12 or more carbon atoms, a monomer for introducing a thermosetting functional group, and other copolymerizable monomer as necessary. Is polymerized by a usual method such as solution polymerization, emulsion polymerization and pearl polymerization.

The polymer having a thermosetting functional group obtained as described above is heated only after the polymer solution is applied to a base material; two types of thermosetting polymers are mixed to form a group. After application to the material, it is heated; a thermosetting crosslinking agent such as a polyisocyanate group compound, a polyepoxy compound, a polyaziridinyl group compound, a polyamino group compound is added and cured; if necessary, various catalysts such as dibutyltin lauri Curing is performed by a method such as adding rate or pyridine.

Further, the polymer having an alkyl group having a radically polymerizable unsaturated group as X in the second structure is prepared by the method described below after producing the above-mentioned polymers having various thermosetting functional groups. It is obtained by reacting a polymer.

(A) In the case of a copolymer of a monomer having a hydroxyl group, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is subjected to a condensation reaction.

(B) In the case of a copolymer of a monomer having a carboxyl group and a sulfone group, the above-mentioned monomer having a hydroxyl group is subjected to a condensation reaction.

(C) In the case of a copolymer of a monomer having an epoxy group, an isocyanate group or an aziridinyl group, the above-mentioned monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction.

(D) In the case of a copolymer of a monomer having a hydroxyl group or a carboxyl group, a pair of a monomer having an epoxy group, a monomer having an aziridinyl group or a diisocyanate compound and a hydroxyl group-containing acrylate monomer 1
It is also possible to carry out an addition reaction with a mole of an adduct.

In order to carry out the above reaction, it is preferable to add a trace amount of a polymerization inhibitor such as hydroquinone and to send it by sending dry air.

Furthermore, in the present invention, a radically polymerizable unsaturated monomer can be added as a third component to the copolymer. This is one which improves the crosslink density and the heat resistance upon irradiation with ionizing radiation, and in addition to the above-mentioned monomers, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol. Dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol trimethacrylate. Acrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaac Rate, dipentaerythritol hexamethacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate, propylene glycol Diglycidyl ether dimethacrylate, polypropylene glycol diglycidyl ether diacrylate, polypropylene glycol diglycidyl ether dimethacrylate, sorbitol tetraglycidyl ether tetraacrylate,
Sorbitol tetraglycidyl ether tetramethacrylate, etc. can be used, and 0.1 to 100 parts by weight is preferable with respect to 100 parts by weight of the solid content of the copolymer mixture.

As a method of curing the above coating material, there are a method of irradiating with ionizing radiation and a method of using a radical polymerization initiator, but a method using ionizing radiation is preferable in the sense that curing is completed in a short time. Ionizing radiation includes electron beams, ultraviolet rays, and γ
Rays and the like can be used, and in the case of electron rays and γ rays, 1 to 20 Mrad is preferable. In the case of curing by ultraviolet irradiation, sensitizers such as benzoin ethers such as benzoquinone, benzoin, benzoin methyl ether, halogenated acetophenones, and biacyl which generate radicals by ultraviolet irradiation can also be used. As the radical polymerization initiator, various peroxides such as benzoyl peroxide, α, α′-azobisisobutyronitrile, etc. are added in an amount of 0.1 to 1% by weight of the solid content, and the mixture is heated to a temperature above the decomposition temperature. .

In addition, a solvent may be used as necessary to adjust the coating suitability. Further, the solvent used for the polymerization may be used as it is. A polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether can be used as a stabilizer for improving storage stability.

In order to produce a coating material, the above-mentioned copolymer or copolymer mixture, and optionally a radically polymerizable unsaturated monomer are added and additives such as a sensitizer are appropriately added and uniformly dissolved. .

The coating material may have a solid content of 0.1 to 4 g / polyester film, polypropylene film, cellophane, cellulose acetate film, etc. by a coating method such as a roll coating method, a gravure coating method, a screen coating method, and a fountain coating method.
After coating so as to have m ³ and drying the solvent and the like, a cured film having both heat resistance and slipperiness is formed by a method such as irradiation with ionizing radiation. The film is extremely useful as a base sheet for a thermal transfer sheet provided with a material which is transferred to the opposite surface of the cured film layer by heating and transferred to a transfer target.

A heat-fusible wax layer in which a pigment or a dye is dispersed or a layer containing a sublimable dye in a binder is formed on the substrate sheet by a conventional method to obtain a heat-sensitive transfer sheet.

Next, the present invention will be described with reference to examples.

Example 1 The following composition was refluxed for 6 hours to obtain a polymer (A) Stearyl methacrylate 324 parts by weight Glycidyl methacrylate 15 〃 Toluene 700 〃 α, α'-azobisisobutyronitrile 0.7 〃 Polymer ( A) Immediately before use, 1 part by weight of amine-boron trifluoride complex was added to 100 parts by weight, and a solid content of 1.5 g / m was applied to a polyester film 6 μ (Toray “Lumirror”) with a plate depth of 40 μ. ^After being evenly coated so as to have a thickness of ² , the solvent was dried, and then heated to 100 ° C. to be cured.

Then, a wax ink in which carbon black is dispersed on the opposite surface of the cured film was heated to 120 ° C. and coated at a rate of 3 g / m ² by a reverse roll coating method to obtain a heat-sensitive transfer sheet. When the wax surface and 75 Kg base form paper were overlaid and printed with a thermal printer (manufactured by NEC), stable running performance was obtained without any problems such as staking.

Comparative Example For comparison, a polymer obtained from the following composition was tested in the same manner, but the film was not fused to the thermal head and did not run.

Glycidyl methacrylate 140 parts by weight Toluene 300 〃 α, α'-azobisisobutyronitrile 0.3 〃 Example 2 The following composition was refluxed for 6 hours to obtain a polymer (B).

Behenyl methacrylate 350 parts by weight Methyl methacrylate 100 〃 2-aziridinylethyl methacrylate 100 〃 Toluene 650 〃 Methyl ethyl ketone 650 〃 Benzoyl peroxide 1 〃 Separately, the following composition was polymerized to obtain a polymer (C).

Methyl methacrylate 100 parts by weight Methacrylic acid 10 〃 Toluene 220 parts by weight Methyl ethyl ketone 220 〃 Benzoyl peroxide 0.5 〃 Polymer (B) 100 parts by weight Immediately before use Polymer (C) 15
When 0 parts by weight were mixed and the same test as in Example 1 was performed,
Both runnability and printability were stable.

Example 3 1 mol of 2.4 toluene diisocyanate was placed in a flask, and 1 mol of 2-hydroxyethyl methacrylate was dropped therein to react at 50 to 60 ° C. to give 2,4-
A 1: 1 to 1 mole addition product of toluene diisocyanate and 2-hydroxyethyl acrylate (2-HEMA-TD1) was obtained. Then, the following composition was polymerized to obtain a polymer (D).

Addition product (2HEMA-TD1) 300 parts by weight Stearyl acrylate 160 〃 ・ Methyl methacrylate 300 〃 ・ Toluene 1500 〃 ・ Methyl ethyl ketone 1500 〃 α, α'-azobisisobutyronitrile 1.5 〃 Polymer (D) By reverse roll coating method, polyester film 6μ (Toray “Lumirror”) has a solid content of 0.
8 / m ² was applied, the solvent was dried, and then the wound coating material was cured while spraying mist with a humidifier. Then, a gravure ink containing a sublimable dye (Kayasettsu B Co., Ltd. made by Nippon Kayaku Co., Ltd.) was printed on the opposite side of the polyester film so that the solid content was 2 g / m ² to obtain a heat-sensitive transfer sheet.

The heat-sensitive transfer sheet thus obtained was superposed on a 75 kg-based foam paper coated with polybutylmethacrylate and applied to a thermal printer manufactured by Matsushita Electric Industrial Co., Ltd. to obtain stable running performance and a clear red printed matter. .

Example 4 The following composition was polymerized to obtain a polymer (E).

Lauryl acrylate 200 parts by weight Methacrylic acid 50 〃 Methyl methacrylate 100 〃 Toluene 350 〃 Methyl ethyl ketone 350 parts by weight Benzoyl peroxide 0.7 〃 Immediately before use 1: 1 by weight with the polymer (A) used in Example (1) When mixed with and tested in the same manner as in Example 1, a heat-sensitive transfer sheet having stable running properties was obtained.

Example 5 The following composition was polymerized to obtain a polymer (F).

Stearyl methacrylate 180 parts by weight 2-hydroxyethyl methacrylate 13 〃 methyl methacrylate 200 〃 toluene 400 〃 methyl ethyl ketone 400 〃 α, α'-azobisisobutyronitrile 0.8 〃 The polymer used in Example 3 immediately before use (D ) 100 parts by weight and 500 parts by weight of the polymer (F) were mixed and tested in the same manner as in Example 3. As a result, a thermal transfer sheet having stable transferability and running property was obtained.

Example 6 10 parts by weight of a polyisocyanate group compound (Coronate L made by Nippon Polyurethane Co., Ltd.) was added to 100 parts by weight of the polymer (F) obtained in Example 5, and the same test as in Example 2 was conducted. A heat-sensitive transfer sheet excellent in running property was obtained.

Example 6 A copolymer (G) was obtained by polymerizing the following composition at a bath temperature of 90 ° C to 100 ° C for about 6 hours.

Stearyl acrylate 324 parts by weight Glycidyl methacrylate 426 〃 Methyl methacrylate 600 〃 α, α'-azobisisobutyronitrile 3.3 〃 Methyl ethyl ketone 2,000 〃 Toluene 2,000 〃 To these, 35 parts by weight of diethylenetriamine as an epoxy curing agent Partial coating material was used. The obtained coating material is a 6μ polyester film (Toray “Lumirror”)
Approximately 1 g / m ^{2 was} applied on one side by gravure coating, the solvent was dried, and the film was wound and allowed to stand at room temperature for 4 days to be cured. Next, about 1.2 g / m ^{2 of} ink in which a sublimation dye (KST-B-314 Nippon Kayaku Co., Ltd.) was dissolved using ethyl hydroxyethyl cellulose (Herky Yures Co., Ltd.) as a binder was applied on the opposite side of the film to form a heat-sensitive sublimation transfer sheet. Obtained.

Thermal printer (made by Matsushita Electric) using the sheet
When printed on synthetic paper coated with polyester resin, the film ran smoothly and a vivid image was obtained. In addition, no head dust was attached.

Example 7 The following composition was polymerized at a bath temperature of 90 to 100 ° C. for about 6 hours to obtain a copolymer (H).

Glycidyl methacrylate 426 parts by weight Methyl methacrylate 600 〃 α, α'-azobisisobutyronitrile 2.5 〃 Ethyl acetate 3,000 〃 The copolymer (G) obtained in Example 6 and the above copolymer (H)
35 parts by weight of diethylenetriamine as an epoxy curing agent was added to the above two kinds of copolymers to prepare a coating material. The obtained coating material was coated on the film in the same manner as in Example 6 and then coated with an ink to obtain a heat-sensitive transfer sheet. When printing was performed using this sheet, the sheet traveled smoothly, a vivid image was obtained, and no head dust was attached.

Example 8 The following composition was polymerized at a bath temperature of 90 to 100 ° C. for about 6 hours to obtain a copolymer (I).

Stearyl acrylate 324 parts by weight 2-hydroxymethacrylate 390 〃 methyl methacrylate 600 〃 α, α'-azobisisobutyronitrile 3.3 〃 methyl ethyl ketone 2,000 〃 toluene 2,000 〃 Tolylene diisocyanate adduct as an organic isocyanate compound The body (Nippon Polyurethane "Coronate L") was added in an amount of 4.6 parts by weight (1.0 mol of the hydroxyl group) in terms of solid content to obtain a coating material. About 1 g / m ^{2 of the} obtained coating material was applied to one side of a 6 μ polyester film (Toray “Lumirror”) by gravure coating, the solvent was dried and wound up, and aged at 40 ° C. for 48 hours, Cured. Then, a hot melt type ink in which carbon black was dispersed in a wax binder was applied by gravure coating at about 3 g / m ² to obtain a heat-sensitive melt transfer sheet. When the obtained thermal transfer sheet was used to print on high-quality paper with a thermal printer manufactured by Nippon Denki Co., Ltd., the thermal head was running smoothly and was printed at a sufficient density without adhering to head debris.

Example 9 A copolymer (J) was obtained by polymerizing the following composition at a warm bath temperature of 90 to 100 ° C. for about 6 hours.

2-Hydroxymethacrylate 390 parts by weight Methylmethacrylate 600 〃 α, α'-azobisisobutyronitrile 2.5 〃 Ethyl acetate 3000 〃 The copolymer (I) obtained in Example 8 and the above copolymer
To the two types of copolymers (J), 4.6 parts by weight (1.0 times moles of hydroxyl groups) of tolylene diisocyanate adduct (“Coronate L” manufactured by Nippon Polyurethane) as an organic isocyanate compound is added in solid content. It was used as a coating material.
The obtained coating material was coated on the film in the same manner as in Example 8 and then coated with ink to obtain a heat-sensitive transfer sheet. When printing was performed using this sheet, the sheet traveled smoothly, a vivid image was obtained, and no head dust was attached.

Example 10 The following composition was refluxed for 6 hours to carry out copolymerization.

Methyl methacrylate 320 parts by weight Stearyl methacrylate 267 parts by weight Glycidyl methacrylate 284 parts by weight Toluene 1290 〃 Methyl ethyl ketone 1290 〃 α, α'-azobisisobutyronitrile 2.5 〃 Then 0.2 parts by weight of hydroquinone is added to stop the reaction. After that, 158 parts by weight of acrylic acid and 10 parts by weight of pyridine were added, and the reaction was carried out at 90 ° to 100 ° C. for 8 hours while feeding dry air.

The obtained coating material is uniformly applied to a polyester film 6μ (Toray “Lumirror”) with a gravure solid plate having a plate depth of 40μ so as to have a solid content of 1.5 g / m ² , and the solvent is dried, and a titanium gas atmosphere is applied. Then, it was cured by irradiating it with an electron beam accelerated to 175 KV by 5 Mrad.

Then, a wax ink in which carbon black is dispersed on the opposite surface of the cured film was heated to 120 ° C. and coated at a rate of 3 g / m ² by a reverse roll coating method to obtain a heat-sensitive transfer sheet. When the wax surface and 75 kg base form paper were overlaid and printed with a thermal printer (manufactured by NEC), stable running performance was obtained without any problems such as staking. For comparison, a polyester film 6 .mu.m (Toray, "Lumirror") coated with wax ink in the same manner was applied to a printer, and the film was fused to the thermal head and could not run.

Example 11 The following composition was refluxed for 6 hours for copolymerization.

Methyl methacrylate 284 parts by weight Stearyl acrylate 162 parts by weight 2-Hydroxyethyl methacrylate 130 〃 Ethyl acetate 1100 〃 α, α'-azobisisobutyronitrile 2 〃 Then 0.1 parts by weight of paramethoxyphenol was added to stop the reaction. 100 parts by weight of 2-hydroxyethyl acrylate and 1,4-toluene diisocyanate
A mole to 1 mole adduct was added, and further 5 parts by weight of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 5 hours while sending dry air.

After the reaction solution was cooled to room temperature, 15 parts by weight of an ultraviolet sensitizer (Irgaki Yua 184 manufactured by Ciba-Gaiki) was added and uniformly dissolved to obtain an ultraviolet-curable coating material. The coating material was cured in the same manner as in Example 10 except that it was passed through a UV lamp having an output of 80 KW / cm instead of an electron beam 10 cm under a running speed of 10 m / min, and then a wax ink was applied in the same manner. A heat-sensitive transfer sheet was obtained. When the obtained heat-sensitive transfer sheet was applied to a thermal printer in the same manner as in Example 10, it ran smoothly.

Example 12 The following composition was refluxed for 6 hours for copolymerization.

Methyl methacrylate 100 parts by weight Methacrylic acid 22 parts by weight Behenyl methacrylate 10 parts by weight α, α'-azobisisobutyronitrile 1 part by weight Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight Then, 0.05 parts by weight of hydroquinone is added to stop the reaction. Then, 28 parts by weight of glycidyl methacrylate and 1 part by weight of pyridine were added, and dry air was blown into
The reaction was carried out at 0 ° to 100 ° C for 8 hours.

The obtained coating material was applied to a polyester film 6 μ (Toray “Lumirror”) by a reverse roll coating method so that the solid content was 2 g / m ² , and the solvent was dried.
The coating material was cured by irradiating it with an electron beam in the same manner as in Example 1. Then, a gravure ink containing a sublimable dye (Kayasettsu B Co., Ltd. made by Nippon Kayaku Co., Ltd.) was printed on the opposite side of the polyester film so that the solid content was 2 g / m ² to obtain a heat-sensitive transfer sheet.

The heat-sensitive transfer sheet thus obtained was superposed on a 75 kg-based foam paper coated with polybutylmethacrylate and applied to a thermal printer manufactured by Matsushita Electric Industrial Co., Ltd. to obtain stable running performance and a clear red printed matter. .

Example 13 The coating material obtained in the same manner as in Example 10 was applied to a polyester film 6 μ (Toray “Lumirror”) to give a solid content of 1.5 g.
/ M ² was applied uniformly and the solvent was dried to obtain a wound state.

Then, while being wound, the coating material was cured by irradiating with 5 Mrad of γ ray.

A wax ink was applied to the opposite surface of the film in the same manner as in Example 1 to obtain a heat-sensitive transfer sheet. As a result of conducting a printing test in the same manner as in Example 1, very stable running performance was obtained.

Example 14 The following composition was refluxed for 6 hours to carry out copolymerization.

Methyl methacrylate 320 parts by weight Stearyl methacrylate 267 〃 Glycidyl methacrylate 284 〃 Toluene 1290 〃 Methyl ethyl ketone 1290 〃 α, α'-azobisisobutyronitrile 2.5 〃 Then 0.2 parts by weight of hydroquinone was added to stop the reaction. Then, 158 parts by weight of acrylic acid and 10 parts by weight of pyridine were added, and the reaction was carried out at 90 ° to 100 ° C. for 8 hours while feeding dry air.

50 parts by weight of trimethylolpropane triacrylate was added to the reaction solution and uniformly dissolved.

The obtained coating material was applied to a polyester film and cured in the same manner as in Example 10, and ink was applied to the opposite surface of the cured film to obtain a heat-sensitive transfer sheet. This product had stable running performance without any problems such as staking.

Example 15 The following composition was refluxed for 6 hours to carry out copolymerization.

Butyl methacrylate 284 parts by weight Stearyl acrylate 162 parts by weight 2-Hydroxyethyl methacrylate 130 〃 Ethyl acetate 1100 〃 α, α'-azobisisobutyronitrile 2 〃 Then 0.1 parts by weight of paramethoxyphenol was added to stop the reaction. 100 parts by weight of 2-hydroxyethyl acrylate and 1,4-toluene diisocyanate
A mole to 1 mole adduct was added, and further 5 parts by weight of dibutyltin dilaurate was added, and the mixture was reacted at 80 ° C. for 5 hours while sending dry air. To the reaction solution, 100 parts by weight of dipentaerythritol hexaacrylate and 30 parts by weight of an ultraviolet sensitizer (Irgakiure 184, an ultraviolet sensitizer manufactured by Ciba-Geigy) are added and uniformly dissolved to prepare an ultraviolet curable coating material. Obtained. The coating material was cured in the same manner as in Example 14 except that it was passed under an ultraviolet lamp having an output of 80 KW / cm instead of an electron beam at a distance of 10 cm at a running speed of 10 m / min and then coated with a wax ink in the same manner. A heat-sensitive transfer sheet was obtained. The heat-sensitive transfer sheet thus obtained was used in Example 1.
When I applied it to a thermal printer in the same manner as above, I ran smoothly.

Example 16 The following composition was refluxed for 6 hours for copolymerization.

Methyl methacrylate 100 parts by weight Methacrylic acid 22 parts by weight Behenyl methacrylate 10 parts by weight α, α'-azobisisobutyronitrile 1 part by weight Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight Then, 0.05 parts by weight of hydroquinone is added to stop the reaction. Then, 28 parts by weight of glycidyl methacrylate and 1 part by weight of pyridine were added, and dry air was blown into
The reaction was carried out at 0 ° to 100 ° C for 8 hours. After the reaction liquid was cooled to room temperature, 50 parts by weight of trimethylolpropane trimethacrylate was added and uniformly dissolved to obtain a coating material.

The obtained coating material was applied to a polyester film and then cured in the same manner as in Example 12, and ink was applied to the opposite surface of the cured film to obtain a heat-sensitive transfer sheet. This one has no trouble such as staking and has stable running performance.

Example 17 The coating material obtained in the same manner as in Example 14 was applied to a polyester film 6 μ (Toray “Lumirror”) to give a solid content of 1.5 g.
/ M ² was applied uniformly and the solvent was dried to obtain a wound state.

Then, while being wound, the coating material was cured by irradiating with 5 Mrad of γ ray.

A wax ink was applied to the opposite surface of the film in the same manner as in Example 1 to obtain a heat-sensitive transfer sheet. As a result of conducting a printing test in the same manner as in Example 1, very stable running performance was obtained.

Example 18 The following composition was refluxed for 6 hours to carry out copolymerization.

Methyl methacrylate 320 parts by weight Stearyl methacrylate 267 parts by weight Glycidyl methacrylate 284 parts by weight Toluene 1290 parts by weight Methyl ethyl ketone 1290 〃 α, α'-azobisisobutyronitrile 2.5 〃 Then 0.2 parts by weight of hydroquinone is added to stop the reaction. After that, 158 parts by weight of acrylic acid and 10 parts by weight of pyridine were added, and the mixture was reacted at 90 ° to 100 ° C. for 8 hours while sending dry air to obtain a copolymer (K).

Separately, the following compositions were polymerized in the same manner. Methyl methacrylate 100 parts by weight Glycidyl methacrylate 70 parts by weight Ethyl acetate 600 parts by weight α, α'-azobisisobutyronitrile 1 part by weight 0.05 parts by weight of hydroquinone and 35 Acrylic acid of 2.5 parts by weight and pyridine of 2.5 parts by weight were added and reacted to obtain a copolymer (L).

The copolymer (K) and the copolymer (L) were uniformly dissolved or dispersed to obtain a coating material. The ratio of the copolymer (K) to the copolymer (L) was 40 parts by weight: 60 parts by weight.

The obtained coating material was applied to a polyester film and cured in the same manner as in Example 10, and ink was applied to the opposite surface of the cured film to obtain a heat-sensitive transfer sheet. This has no trouble such as staking and has stable running performance.

Example 19 The following composition was refluxed for 6 hours to carry out copolymerization.

Butyl methacrylate 284 parts by weight Stearyl acrylate 162 parts by weight 2-Hydroxyethyl methacrylate 65 〃 Ethyl acetate 1100 〃 α, α'-Azobisisobutyronitrile 2 〃 Then 0.1 parts by weight of paramethoxyphenol was added to stop the reaction. 100 parts by weight of 2 hydroxyethyl acrylate and 2,4-toluene diisocyanate
Add 5 parts by weight of dibutyltin dilaurylate to 1 mol of the adduct and add 5 parts by weight of dry air at 80 ° C.
The reaction was carried out for a time to obtain a copolymer (M).

Separately after copolymerizing the following compositions in the same manner, methyl methacrylate 200 parts by weight butyl methacrylate 142 parts by weight 2-hydroxyethyl methacrylate 65 〃 ethyl acetate 1200 〃 α, α'-azobisisobutyronitrile 2 〃 0.1 After the reaction was stopped by adding 1 part by weight of paramethoxyphenol, 100 parts by weight of 2-hydroxyethyl acrylate and 1 mol to 1 mol of an adduct of 2,4-toluene diisocyanate were added, and 5 parts by weight of dibutyltin dilaurate was added. In addition, a copolymer (N) was obtained by reacting at 80 ° C. for 5 hours while sending dry air. Then copolymer (M) 10
0 parts by weight, 50 parts by weight of the copolymer (N) and 2.5 parts by weight of an ultraviolet sensitizer (Irgakiure 184, manufactured by Ciba Geigy) were uniformly dissolved to obtain an ultraviolet curable coating material. The coating material was cured in the same manner as in Example 10 except that it was passed through a UV lamp having an output of 80 KW / cm instead of an electron beam 10 cm below at a running speed of 10 m / min and then coated with a wax ink in the same manner. A heat-sensitive transfer sheet was obtained. When the obtained heat-sensitive transfer sheet was applied to a thermal printer in the same manner as in Example 1, it ran smoothly.

Example 20 The following composition was refluxed for 6 hours for copolymerization.

Methyl methacrylate 100 parts by weight Methacrylic acid 22 parts by weight Behenyl methacrylate 10 parts by weight α, α'-azobisisobutyronitrile 1 part by weight Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight Then, 0.05 parts by weight of hydroquinone is added to stop the reaction. Then, 28 parts by weight of glycidyl methacrylate and 1 part by weight of pyridine were added, and dry air was blown into
Copolymer (O) was obtained by reacting at 0 ° to 100 ° C for 8 hours. 100 parts by weight of the above copolymer (O) and 20 parts by weight of the copolymer (L) described in Example 18 were uniformly dissolved or dispersed to obtain a coating material.

The obtained coating material was coated on a polyester film 6μ (Toray "Lumirror") with a solid content of 2 by reverse roll coating.
After coating so as to be g / m ² , the solvent was dried, and then an electron beam was irradiated in the same manner as in Example 1 to cure the coating material. Then, a gravure ink containing a sublimable dye (Kayasettsu B, manufactured by Nippon Kayaku Co., Ltd.) was printed on the opposite side of the polyester film so that the solid content was 2 g / m ² to obtain a heat-sensitive transfer sheet.

The obtained heat-sensitive transfer sheet was superposed on a 75 kg base form paper coated with polybutylmethacrylate and applied to a thermal printer (manufactured by Matsushita Electric Industrial Co., Ltd.) to obtain stable running properties and clear red printed matter.

Example 21 The coating material obtained in the same manner as in Example 18 was applied to polyester film 6 μ (Toray “Lumirror”) to obtain a solid content of 1.5 g.
/ M ² was applied uniformly and the solvent was dried to obtain a wound state.

Then, while being wound, the coating material was cured by irradiating with 5 Mrad of γ ray.

A wax ink was applied to the opposite surface of the film in the same manner as in Example 10 to obtain a heat-sensitive transfer sheet. As a result of performing a printing test in the same manner as in Example 10, very stable running performance was obtained.

Example 22 The following composition was refluxed for 6 hours to carry out copolymerization.

Methyl methacrylate 320 parts by weight Stearyl methacrylate 267 parts by weight Glycidyl methacrylate 284 parts by weight Toluene 1290 〃 Methyl ethyl ketone 1290 〃 α, α'-azobisisobutyronitrile 2.5 〃 Then 0.2 parts by weight of hydroquinone is added to stop the reaction. After that, 158 parts by weight of acrylic acid and 10 parts by weight of pyridine were added, and the mixture was reacted at 90 ° to 100 ° C. for 8 hours while blowing in dry air to obtain a copolymer (P).

Separately, the following composition was polymerized in the same manner, and then methyl methacrylate 100 parts by weight glycidyl methacrylate 70 parts by weight ethyl acetate 600 parts by weight α, α′-azobisisobutyronitrile 1 part by weight 0.05 parts by weight of hydroquinone and 35 parts by weight of acrylic acid and 2.5 parts by weight of pyridine were added and reacted to obtain a copolymer (Q).

Copolymer (P), copolymer (Q) and trimethylolpropane triacrylate were blended in the following formulation and uniformly dissolved to obtain a coating material.

Copolymer (P) 40 parts by weight Copolymer (Q) 60 〃 Trimethylolpropane triacrylate 1 〃 The obtained coating material was applied to a polyester film by the same method as described in Example 10 and then cured. Ink was applied to the opposite surface of the film to obtain a heat-sensitive transfer sheet. This product has no problems such as staking and has good running performance.

Example 23 The following composition was refluxed for 6 hours to carry out copolymerization.

Butyl methacrylate 284 parts by weight Stearyl acrylate 162 parts by weight 2-Hydroxyethyl methacrylate 65 〃 Ethyl acetate 1100 〃 α, α'-Azobisisobutyronitrile 2 〃 Then 0.1 parts by weight of paramethoxyphenol was added to stop the reaction. 100 parts by weight of 2-hydroxyethyl acrylate and 1,4-toluene diisocyanate
A copolymer (R) was obtained by adding an adduct of 1 mol to 1 mol of dibutyltin dilaurylate and reacting at 80 ° C. for 5 hours while feeding dry air.

Separately, the following compositions were similarly copolymerized and then methyl methacrylate 200 parts by weight butyl methacrylate 142 〃 2-hydroxyethyl methacrylate 65 〃 ethyl acetate 1200 〃 α, α'-azobisisobutyronitrile 2 〃 0.1 After the reaction was stopped by adding 1 part by weight of paramethoxyphenol, 100 parts by weight of 2-hydroxyethyl acrylate and 1 mol to 1 mol of an adduct of 2,4-toluene diisocyanate were added, and 5 parts by weight of dibutyltin dilaurate was added. In addition, the reaction was carried out at 80 ° C. for 5 hours while sending dry air to obtain a copolymer (S). Next, the following composition was uniformly dissolved to obtain an ultraviolet curable coating material.

Copolymer (R) 100 parts by weight Copolymer (S) 50 parts by weight Dipentaerythritol hexaacrylate 10 parts by weight Ultraviolet sensitizer (Irgakiure 184, manufactured by Ciba-Geigy) 2.5 parts by weight The coating material is applied. A heat-sensitive transfer sheet was obtained in the same manner as in Example 10, except that an ultraviolet ray lamp having an output of 80 kW / cm instead of an electron beam was passed under 10 cm at a running speed of 10 m / min to cure, and then wax ink was applied. .
When the obtained heat-sensitive transfer sheet was applied to a thermal printer in the same manner as in Example 10, it ran smoothly.

Example 24 The following composition was refluxed for 6 hours for copolymerization.

Methyl methacrylate 100 parts by weight Methacrylic acid 22 parts by weight Behenyl methacrylate 10 parts by weight α, α'-azobisisobutyronitrile 1 part by weight Toluene 200 parts by weight Methyl ethyl ketone 200 parts by weight Then, 0.05 parts by weight of hydroquinone is added to stop the reaction. Then, 28 parts by weight of glycidyl methacrylate and 1 part by weight of pyridine were added, and dry air was blown into
A copolymer (T) was obtained by reacting at 0 ° to 100 ° C for 8 hours. The following composition was uniformly dissolved or dispersed to obtain a coating material.

Copolymer (T) 100 parts by weight Copolymer (Q) 20 parts by weight Pentaerythritol tetraacrylate 20 parts by weight The obtained coating material was applied to a polyester film by the same method as described in Example 20, and after curing. An ink was applied to the opposite surface to obtain a heat-sensitive transfer sheet. This product had a stable running property and a clear red printed matter was obtained.

Example 25 The coating material obtained in the same manner as in Example 22 was applied to a polyester film 6 μ (Toray “Lumirror”) to give a solid content of 1.5 g.
/ M ² was applied uniformly and the solvent was dried to obtain a wound state.

Then, while being wound, the coating material was cured by irradiating with 5 Mrad of γ ray.

A wax ink was applied to the opposite surface of the film in the same manner as in Example 10 to obtain a heat-sensitive transfer sheet. As a result of performing a printing test in the same manner as in Example 10, very stable running performance was obtained.

Claims (1)

[Claims] 1. A plastic film comprising, on one surface thereof, an acrylic acid ester or methacrylic acid ester of a higher alcohol having 12 or more carbon atoms, and a monomer of acrylic acid or methacrylic acid derivative having a thermosetting functional group. A heat-sensitive transfer sheet, characterized in that a layer formed by curing a polymer by heat or radical polymerization is formed, and a heat-sensitive transfer ink layer is formed on the opposite surface of the plastic film.