JPH09295465A - Thermal transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermal transfer sheet which is excellent in adhesiveness and has a charge preventive effect by a method wherein the charge priventive layer composed of an organic polymer having an ether group to which a metallic salt is coordinated, the metallic salt, and binder resin is provided between at least a base material sheet and a heat resistant lubricant layer 4 or the base material sheet and a thermal transferrable colorant layer 3 in the thermal transfer sheet. SOLUTION: In a thermal transfer sheet 1 wherein a thermal transfer colorant layer 3 is provided to one side face of a base material sheet, and a heat resistant lubricant layer 4 is formed on the other face, a charge preventive layer 5 composed of an organic polymer having ether bond, metallic salt, and binder resin is provided between at least the base material sheet and the heat resistant lubricant layer 4 or the base material sheet and the thermal transferrable colorant layer 3. For a method of forming the charge preventive layer 5, polyester resin is dissolved or dispersed in organic solvent or water selected so as to meet coating adaptability, and ink is coated and dried by, for example, a means of a gravure printing method or the like to form the charge preventive layer 5. Thereby, the thermal transfer sheet 1 which is excellent in adhesiveness and has a charge preventive effect is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer sheet, and more specifically, an organic polymer having an ether bond between at least one of a base material sheet and a heat resistant slipping layer or between a base material sheet and a heat transferable coloring material layer. The present invention relates to a thermal transfer sheet in which an antistatic layer composed of a metal salt and a binder resin is formed to prevent peeling noise or abnormal transfer during printing that occurs due to charging of the thermal transfer sheet.

[0002]

2. Description of the Related Art Conventionally, as a heat transfer sheet, a plastic film such as a polyester film is used as a base film, and a heat transfer color material layer composed of a heat-sensitive sublimable dye and a binder resin is formed on one surface of the base film. The sublimation type thermal transfer sheet provided and a thermal transferable colorant layer made of a heat-meltable composition containing a colorant instead of the thermal transferable colorant layer (hereinafter, these are collectively referred to as a thermal transferable colorant layer) are provided. A heat-melting type heat transfer sheet is known. These thermal transfer sheets are heated imagewise from the back side by a thermal head to sublimate the dye or transfer the thermal transferable color material layer to form an image.

Further, in these thermal transfer sheets, as described above, high-temperature heating printing is performed by the thermal head from the back side substrate side of the thermal transferable color material layer, so that running stability of the thermal transfer sheet is improved. Alternatively, it is known to provide a heat-resistant slip layer having heat resistance and releasability on the back surface of the thermal transfer sheet in order to prevent fusion of the base material to the thermal head. Further, when a conventional thermal transfer sheet is apt to be charged as a base material film such as a plastic film, it becomes difficult to separate the transfer medium from the thermal transfer sheet due to static electricity during printing. As a result, a large peeling noise may be generated, paper may be jammed in the printer, and the thermal head may be destroyed by static electricity. Therefore, in order to prevent the heat transfer sheet from being charged, various antistatic agents are added to the heat transferable color material layer or the heat resistant slipping layer, or the heat transferable color material layer or the heat resistant slipping layer and the base material. It has been proposed to provide an antistatic layer between and.

[0004]

In order to solve the above-mentioned problems, conventionally, conductive fine particles have been added as an antistatic agent to the heat transferable coloring material layer or heat resistant slipping layer of a heat transfer sheet. It was However, these methods required a considerable amount of addition to obtain the desired performance. Therefore, the performances of the heat transferable color material layer and the heat resistant slipping layer are impaired. Further, it has been practiced to use a resin containing an ion in its side chain as an antistatic agent. The antistatic layer formed by these methods has a large antistatic ability depending on the humidity at the time of printing. Therefore, the desired antistatic ability may not be obtained depending on the conditions of use.

[0005]

The inventors of the present invention have made diligent efforts in view of the above-mentioned problems, and as a result, have a heat transferable color material layer on one surface of a base sheet and a heat-resistant lubricity on the other surface. In a thermal transfer sheet in which a layer is formed, an antistatic agent composed of an organic polymer having an ether bond, a metal salt and a binder resin at least between the base material sheet and the heat resistant slipping layer or between the base material sheet and the heat transferable color material layer The above problem could be solved by providing the layer. According to the present invention, an antistatic layer composed of an organic polymer having an ether group in which a metal salt is coordinated, a metal salt and a binder resin is provided at least between the heat resistant slipping layer or the heat transferable coloring material layer of the heat transfer sheet. By providing the heat transfer sheet, it is possible to provide a heat transfer sheet in which the film is not charged during storage and printing.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to FIG. 1 as a preferred embodiment. The base film 2 constituting the thermal transfer sheet 1 of the present invention may be any one as long as it has a conventionally known degree of heat resistance and strength, for example, 0.5 to 50 μm, preferably about 3 to 10 μm. Thickness of polyethylene terephthalate film, 1,4-polycyclohexylene dimethylene terephthalate film, polyethylene naphthalate film, polyphenylene sulfide film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane , Cellulose derivatives such as cellulose citrate, polyethylene film, polyvinyl chloride film, nylon film, polyimide film, ionomer film, etc., capacitors It may be a paper such as paper or paraffin paper, a non-woven fabric or the like, or a composite of paper or non-woven fabric and a resin.

The heat resistant slipping layer 4 formed on one surface of the film is usually composed of a binder resin, a lubricant, a filler and the like. As the binder resin, one that has heat resistance and does not exhibit heat fusion property when heated is used, and for example, urethane resin, melanin resin, epoxy resin, silicone resin and the like can be used. Above all, a resin as a reaction product of an isocyanate and an active hydrogen-containing thermoplastic resin having active hydrogen is preferable.

As the active hydrogen-containing thermoplastic resin, known thermoplastic resins having active hydrogen can be used. For example, polyester resin, polyurethane resin, polyvinyl acid phosphide resin, polyacrylamide resin, polyvinyl butyral resin, polyvinyl aceto A thermoplastic resin such as a polyvinyl acetal resin such as an acetal resin may be used. Among these, a particularly preferable resin is a thermoplastic resin having active hydrogen as a hydroxyl group, and among them, a polyvinyl acetal resin such as a polyvinyl butyral resin or a polyvinyl acetoacetal resin is particularly preferable.

As the isocyanate, various conventionally known polyisocyanates can be used. Among them, the polyisocyanate of an aromatic polyisocyanate adduct is preferable. Those isocyanate compounds are compounds having two or more isocyanate groups, and any of the isocyanate compounds used in branching related to conventional polyurethane resins can be used,
For example, TDI (toluene diisocyanate), MDI
(Diphenylmethane diisocyanate), NDI (1,
5-naphthalene diisocyanate), TODI (trizine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), p-phenylene diisocyanate, XDI (xylylene diisocyanate), hydrogenated HDI, hydrogenated MDI,
LDI (lysine diisocyanate), TMXDI (tetramethyl xylene diisocyanate), lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene Examples thereof include triisocyanate, bicycloheptane triisocyanate, and TMDI (trimethylhexamethylene diisocyanate), but any other isocyanate group can be used, and the present invention is not limited to these. In fact, Takenate (manufactured by Takeda Pharmaceutical), Barnock (manufactured by Dainippon Ink and Chemicals),
Coronate (manufactured by Nippon Polyurethane), Duranate (manufactured by Asahi Kasei Kogyo), Dismodur (manufactured by Bayer) and the like can be used in the present invention.

The amount of isocyanate added depends on the heat resistant slipping layer 4
5 to 280 per 100 parts by weight of the binder resin that constitutes the
A range of parts by weight is appropriate. In the NCO / OH ratio of 0.
A range of about 6 to 2.0 is preferable. If the amount of isocyanate used is too small, the crosslinking density is low and the heat resistance is insufficient,
On the other hand, if the amount is too large, the shrinkage of the formed coating film cannot be controlled,
In addition to lengthening the curing time, when unreacted NCO groups remain in the heat resistant slipping layer, it reacts with moisture in the air, reacts with the binder resin and dye of the transferable color material layer, and acts negatively. I have something to do.

In addition, instead of or in combination with the above-mentioned isocyanate, a monomer having an unsaturated bond or a monomer having an unsaturated bond is added for the purpose of imparting heat resistance, coating property and adhesion to the base film to the heat resistant slipping layer 4. An oligomer can be used together. When a monomer or oligomer having an unsaturated bond is used as a crosslinking agent, the curing method is electron beam or UV.
Irradiation curing may be used, but when the amount of filler added is large, curing by electron beam irradiation is desirable. Examples of the monomer or oligomer having an unsaturated bond include tetraethylene glycol di (meth) acrylate [(meth)
Acrylate means both acrylate and methacrylate. The same shall apply hereinafter], difunctional monomers such as divinylbenzene and diallyl phthalate, trifunctional monomers such as triallyl isocyanurate and trimethylolpropane tri (meth) arylate, tetramethylolmethanetetra (meth) arylate, trimethoxyethoxy. Examples thereof include vinyl silane and the like, monomers having 5 or more functional groups, and oligomers and macromers composed of these monomers.

As the lubricant to be added to the heat resistant slipping layer 4 in order to improve the slipperiness, various conventionally known lubricants can be used, but it is preferable to add a phosphate ester type surfactant among them. As the phosphate ester-based surfactant,
1) Long-chain alkyl phosphates, for example, usually having carbon atoms
Saturated or unsaturated higher alcohols having 6 to 20, preferably 12 to 18 carbon atoms, for example, phosphoric acid monoester salts or diester salts of alcohols such as cetyl alcohol, stearyl alcohol and oleyl alcohol. 2) Phosphoric acid monoester salts or diester salts of polyoxyalkylene alkyl ether or polyoxyalkylene alkyl allyl ether. 3) Alkylene oxide adduct of the saturated or unsaturated higher alcohol (usually 1 to 8 moles added), or an alkylphenol or alkyl having at least 1, preferably 1 to 2 alkyl groups having 8 to 12 carbon atoms. Anionic phosphoric acid ester-based surfactants such as phosphoric acid monoester salts such as naphthol (nonylphenol, dodecylphenol, diphenylphenol, etc.), diester salts and the like can be mentioned.

Although only the above-mentioned phosphate ester type surfactant may be used, the phosphate ester type surfactant is 1 to
Since it has 2 equivalents of acid groups, there is a problem that the thermal head is corroded by the acid groups. Further, when the amount of heat from the thermal head increases, the phosphoric acid ester decomposes, the pH of the heat resistant slipping layer further decreases, and the corrosion and wear of the thermal head becomes severe. The above drawbacks can be prevented by using an alkaline substance in combination with a phosphate ester surfactant. That is, even if the phosphate ester type surface activity is decomposed by the heat from the thermal head to generate an acid group, it is neutralized by the coexisting alkaline substance, so that the corrosion of the thermal head due to the generation of the acid group can be prevented. . The addition amount of the phosphate ester-based surfactant is 50 to 100 parts by weight of the binder resin.
The range of 120 parts by weight is preferable, and when it is over 50 parts by weight, sufficient slipperiness cannot be obtained, and conversely, when it exceeds 120 parts by weight, dye stainability increases.

Examples of the alkaline substance include oxides or hydroxides of alkali metals or alkaline earth metals, or organic amines. Preferred as the oxide or hydroxide of an alkali metal or alkaline earth metal are, for example, magnesium hydroxide, magnesium oxide, hydrotalcite, aluminum hydroxide,
Aluminum silicate, magnesium silicate, magnesium carbonate, alumina hydroxide, magnesium aluminum glycinate and the like can be mentioned, and magnesium hydroxide is particularly preferable. Preferred as the organic amine are, for example, mono-, di- or tripropylamine, mono,
Di or tributylamine, mono, di or tripentylamine, trihexylamine, trioctylamine, monodecylamine, mono or didodecylamine, monotridecylamine, monotetradecylamine monopentadecylamine, monohexadecylamine, Monoheptadecylamine, monooctadecylamine, monoeicosylamine, monodocosylamine, mono-, di- or triethanolamine, mono- or dipropanolamine monoisopropanolamine, N-methyl-nonylamine, N-methyl-decylamine, N -Ethyl-palmitylamine and the like are mentioned, and particularly preferable organic amines are nonvolatile at room temperature and have a boiling point of 200 ° C or higher. These organic amines exist stably in the heat resistant slipping layer, and when heat is applied from the thermal head to the heat resistant slipping layer 4, the organic amine becomes fluid and bleeds out to the surface to form a phosphate ester surfactant or The acid group generated in the decomposed product is easily neutralized to prevent corrosion of the thermal head, and at the same time, it exhibits excellent activity together with the phosphate ester type surfactant. As for the alkaline substance as described above, it is desirable to use the alkaline substance in the range of 0.1 to 10 mol with respect to 1 mol of the phosphate ester surfactant. If the amount of the alkaline substance is too small, the neutralization is insufficient, so that the sufficient effect cannot be obtained. On the other hand, if the amount of the alkaline substance is too large, the particular effect is not improved.

Further, in the present invention, it is desirable to use an inorganic or organic filler in order to improve the processability of the transfer sheet, stabilize the print running property, and impart the cleaning property of the thermal head. When selecting the filler, it is necessary that the heat resistant slipping layer 4 has a particle size and a shape sufficient to form an uneven shape on the surface, and the thermal head is less worn. Suitable fillers for use include, for example, talc, kaolin, clay, calcium carbonate, magnesium hydroxide, magnesium carbonate, magnesium oxide, precipitated barium sulfate, inorganic fillers such as hydrotalcite silica, acrylic resin, benzoguanamine resin And organic fillers made of silicone, Teflon, etc., and preferably those having a cracking property, such as talc, kaolin, and clay, and having a relatively low hardness but having a cleaning property for a thermal head. Specifically, in the case of talc, the shot type abrasion degree is preferably 15 to 200 mg. When the abrasion degree is low, head slag is likely to occur, and when it is high, the thermal head protective layer is significantly abraded.

Next, as a method for forming the ripening-resistant layer 4, the above materials are dissolved or dispersed in a solvent such as acetone, methyl ethyl ketone, toluene, xylene, or the like selected so as to suit the coating suitability. A method of forming a coating liquid by applying the coating liquid, coating the coating liquid with a conventional coating means such as a gravure coater, a roll coater, and a wire bar, and drying and solidifying the coating liquid can be used. As a coating amount, i.e. the thickness of the heat-resistant lubricating layer may have 3.0 mg / m ² or less on a solids basis, heat preferably with sufficient performance at a thickness of 0.1 to 1.0 mg / m ² The slipping layer 4 can be formed. Incidentally, when using a heat-resistant slip layer coating solution containing an isocyanate as a cross-linking agent, since the coating solution is applied and unreacted isocyanate groups often remain in the layer even after drying, In order to complete the reaction, it is preferable to perform heat aging treatment.

In the case of a sublimation type maturing transfer sheet, a layer containing a sublimable dye is formed as the heat transferable coloring material layer 3 formed on the other surface of the base film, while the heat melting type maturing layer is formed. In the case of a transfer sheet, a heat-melting heat-transferable coloring material layer colored with a pigment or the like is formed. The case of a sublimation type thermal transfer sheet will be mainly described below as a representative example, but the present invention is not limited to the sublimation type thermal transfer sheet. As the dye used in the sublimation type thermal transfer color material layer 3, any dye conventionally used in known thermal transfer sheets can be used in the invention and is not particularly limited. For example, some preferred dyes include magenta dyes such as MSRedG,
MacroRedVioledR, CeresRed7
B, SamaronRedHBSL, ResolinR
edF3BS and the like, and as the yellow dye, holon brilliant yellow 6GL, PTY-5
2, Macrolex Yellow 6G and the like, and as the blue dye, Kayaset Blue 714, Waxoimble-AP-FW, Holon Brilliant Blue SR, M
S blue 100 etc. are mentioned.

Preferred binder resins for carrying the above dyes are exemplified by the following: Cellulose resins such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl resins. Vinyl-based resins such as alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetoacetal, and polyvinylpyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane-based resins, polyamide-based resins,
Examples thereof include polyester resins. Among them, cellulose resins, vinyl resins, acrylic resins, urethane resins, polyester resins and the like are preferable from the viewpoint of heat resistance and dye migration.

The heat transferable color material layer 3 is obtained by adding an additive such as a release agent or inorganic fine particles to the dye and the binder as described above on one surface of the base film, if necessary. Of toluene, ethyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexanone, DM
A dispersion dissolved in a suitable organic solvent such as F or dispersed in an organic solvent or water is applied by a means such as a gravure printing method, a screen printing method, a reverse roll coating printing method using a gravure plate, and the like. It can be formed by drying. The heat transferable color material layer thus formed is 0.2 to 5.0 μm, preferably 0.4 to 2.0 μm.
It is preferable that the sublimable dye has a thickness of about 5 to 90% by weight, preferably 10 to 70% by weight based on the weight of the heat transferable color material layer. Is. When the desired image is a monocolor, the heat transferable color material layer to be formed is formed by selecting one color from the dyes,
When the desired image is a full-color image, for example, appropriate cyan, magenta, and yellow (and black, if necessary) are selected, and yellow, magenta, and cyan (and black, if necessary) are selected. A heat transferable color material layer is formed.

The image-receiving sheet used to form an image using the thermal transfer sheet as described above may be any image-receiving sheet as long as its recording surface has dye receptivity to the above-mentioned dye, and In the case of paper, metal, glass, synthetic resin or the like having no dye-accepting property, the dye-accepting layer may be formed on at least one surface thereof. In the case of a heat-melting type heat transfer sheet, the material to be transferred is not particularly limited and may be ordinary paper or plastic film. As the above-mentioned thermal transfer sheet and a printer used when performing thermal transfer using the above-mentioned sheet, a known thermal transfer printer can be used as it is and is not particularly limited.

Next, the antistatic agent which is a feature of the present invention will be described. The material functioning as an antistatic agent in the present invention is composed of an organic polymer having an ether bond group and a metal salt coordinated with the organic polymer, and the organic polymer having an ether bond group has at least one ether bond per molecule. A conjugate having two or more groups having one or at least one ether-bonding group per molecule is preferable. Further, it is necessary that the product is obtained by reacting the terminal hydroxyl group of the substance having an ether bond group with various crosslinking agents. Preferred crosslinking agents include polyisocyanates, melanin resins, urea resins and the like. The organic polymer having an ether bond used in the present invention preferably has 2 or 3 carbon atoms in terms of ether bond, and particularly has 2 carbon atoms.
Of polyethylene glycol is preferred. The molecular weight of the polyethylene glycol group is 1000 to 1000.
00 is preferable, and 2000 to 50000 is particularly preferable. Further, although polypropylene glycol type ones can be used, usable metal salts are limited as compared with polyethylene glycol type ones. For this reason, it is effective to use the polypropylene glycol type by copolymerizing it with the polyethylene glycol type.

The metal salt coordinated to the ether group of the organic polymer having an ether bond includes lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt,
It is preferably a zinc salt or a copper salt, and examples of counter ions thereof include halogen, organic acid, nitric acid, trifluoromethanesulfonic acid, and perchloric acid. Most preferred of these is the smallest lithium salt in the ionic state. The amount used is 1/5 to 1 for 1 ether group.
/ 100 mol is preferable, and 1/10 to 1/50 mol is most preferable. Further, only the organic polymer having an ether bond group and the metal salt coordinated thereto as an antistatic agent do not have sufficient adhesiveness to the substrate 1, and it is necessary to add a binder resin as a binder. Preferred examples of these binder resins include ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose resins such as cellulose acetate butyrate, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl. Examples include vinyl resins such as acetoacetal and polyvinylpyrrolidone, acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide, polyurethane resins, polyamide resins, polyester resins and the like. A resin is preferable because it has excellent film forming properties as an antistatic layer.

The antistatic layer 5 is formed by dissolving or dispersing the above-mentioned materials in an organic solvent or water selected to suit the coating suitability, and using an ink, for example, a gravure printing method, a screen printing method or a gravure plate. It can be formed by coating and drying by means such as the reverse roll coating printing method used. The antistatic layer thus formed has a thickness of 0.01 to 5.0 μm, preferably 0.05 to 5.0 μm.
It is preferable to apply it to a thickness of about 2.0 μm. This can be provided at least on the heat resistant slipping layer side and the heat transferable color material layer side of the substrate film, and the configuration provided on the heat transfer colorant layer side is shown in FIG. Further, it may be provided on both sides of the base film, and in that case, the same metal salt may be used on both sides of the film, but the type may be changed. FIG. 3 shows the configuration. Furthermore, in order to further improve the adhesiveness between the antistatic layer 5 and the base sheet 2,
A binder resin layer 6 may be provided as a primer layer, and one configuration example showing it is shown in FIG. Examples of the binder resin used include ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate, cellulose-based resins such as cellulose acetate butyrate, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetoacetal, polyvinyl pyrrolidone, etc. Vinyl resin, poly (meth) acrylate,
Examples thereof include acrylic resins such as poly (meth) acrylamide, polyurethane-based resins, polyamide-based resins, polyester-based resins and the like. Among these, polyester resins are preferable because of their excellent adhesion to the substrate. Binder resin layer 6
The method of forming, the above material is dissolved or dispersed in an organic solvent or water selected to suit the coating suitability, the ink, for example, gravure printing method, screen printing method, reverse roll coating printing method using a gravure plate It can be formed by coating and drying by such means. The antistatic layer thus formed has a thickness of 0.01 to 5.0 μm.
m, preferably about 0.05 to 2.0 μm.

The material to be transferred used for forming an image using the thermal transfer sheet as described above is not particularly limited in the case of a heat-melting type thermal transfer sheet, and may be plain paper or plastic film. Good. In the case of a sublimation type thermal transfer sheet, any recording surface may be used as long as it has a dye receptive property to the above dye,
In the case of paper, metal, glass, or synthetic resin having no dye-accepting property, a dye-accepting layer may be formed on at least one surface thereof. A known thermal transfer printer can be used as it is, and is not particularly limited, as a printer used when performing thermal transfer using the thermal transfer sheet and the material to be transferred.

[0025]

[Examples] Specific examples will be described below. In the following description, parts and% are based on weight unless otherwise specified. (Example 1) A PET (polyethylene terephthalate) film having a thickness of 6.0 μm was used as a base material and the following antistatic layer liquid A was used.
Is applied and dried to give a coating amount of about 0.1 g / m ² , and the heat-resistant slipping layer liquid A is dried thereon to about 1.0 g / m 2.
A coating amount of ² was applied and dried, and the mixture was heat-aged and cured to form a ripening-resistant layer. On the back side, the following thermal transferable color material layer ink A is dried to about 1.0.
The thermal transfer sheet of the present invention was obtained by applying a coating amount of g / m ² and drying to form a thermal transfer color material layer. <Liquid A for heat resistant slipping layer> Polyvinyl butyral resin 1.60 parts by weight (S-Rex BX-1, manufactured by Sekisui Chemical Co., Ltd.) Polyisocyanate 8.46 parts by weight (Barnock D750-45, Dainippon Ink and Chemicals Inc. stock) Company made) Phosphate ester type interfacial lubricant 1.36 parts by weight (Prysurf A208S, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Talc 0.32 parts by weight (Microace L-1, manufactured by Nippon Talc) Methyl ethyl ketone 38.43 parts by weight Parts Toluene 38.43 parts by weight <Thermal transfer color material layer ink A> MS-RED-G 2.00 parts by weight (Disperse Red 60, manufactured by Mitsui Toatsu Chemicals, Inc.) Macrolex Red Violet R 1.50 parts by weight ( Disperse Violet 26, Bayer company) Polyvinyl acetoacetal resin 3.50 parts by weight (D Rex KS-5, manufactured by Sekisui Chemical Co., Ltd.) Methyl ethyl ketone 46.50 parts by weight Toluene 46.50 parts by weight <antistatic layer liquid A> Polyethylene glycol # 20000 4.0 parts by weight (MERCK-Schuchardt) Polyisocyanate 0 0.6 parts by weight (Coronate 2030, manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.3 parts by weight of lithium nitrate (manufactured by Kanto Chemical Co., Inc.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (LP-035, Nippon Synthetic Chemical Industry Co., Ltd.) (Industrial Co., Ltd.)

(Example 2) 6.0 μm PE as a base material
The following antistatic layer liquid B was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² , and dried, and a heat-resistant slipping layer liquid A was dried to about 1.0 g on the upper layer. Coated and dried to a coating amount of / m ² ,
Further, it was heat-aged and cured to form a heat resistant slipping layer. The thermal transfer color material layer ink A is applied to the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried, and dried to form a thermal transfer color material layer to obtain the thermal transfer sheet of the present invention. It was <Antistatic Layer Liquid B> Polyethylene glycol # 20000 4.0 parts by weight (manufactured by MERCK-Schuchardt) Polyisocyanate 0.6 parts by weight (Coronate 2030, manufactured by Nippon Polyurethane Industry Co., Ltd.) Lithium trifluoromethanesulfonate 0.3 parts by weight Part (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (LP-035, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

(Example 3) 6.0 μm PE as a base material
The following antistatic layer liquid C is applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² and dried, and the heat-resistant slipping layer liquid A is dried thereon to about 1.0 g. Coated and dried to a coating amount of / m ² ,
Further, it was heat-aged and cured to form a heat resistant slipping layer. The thermal transfer color material layer ink A is applied to the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried, and dried to form a thermal transfer color material layer to obtain the thermal transfer sheet of the present invention. It was <Antistatic Layer Liquid C> Polyethylene glycol # 60000 4.0 parts by weight (Kanto Chemical Co., Inc.) Polyisocyanate 0.6 parts by weight (Coronate 2030, Nippon Polyurethane Industry Co., Ltd.) Lithium trifluoromethanesulfonate 0.3 parts by weight Part (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (LP-035, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)

Example 4 PE of 6.0 μm as a base material
The following antistatic layer liquid D was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² and dried, and a heat-resistant slipping layer liquid A was dried thereon to about 1.0 g. Coated and dried to a coating amount of / m ² ,
Further, it was heat-aged and cured to form a heat resistant slipping layer. The thermal transfer sheet of the present invention is formed by applying a mature transferable color material layer ink A on the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried and forming a thermal transferable color material layer. Obtained. <Antistatic Layer Liquid D> Polyethylene glycol # 2000 4.0 parts by weight (Kanto Chemical Co., Inc.) Polyisocyanate 0.6 parts by weight (Coronate 2030, Nippon Polyurethane Industry Co., Ltd.) Lithium trifluoromethanesulfonate 0.3 parts by weight Part (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (Adcoat 335A, manufactured by Toyo Morton)

(Example 5) 6.0 μm PE as a base material
The following antistatic layer liquid E was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² , and dried, and a heat-resistant slipping layer liquid A was dried thereon to about 1.0 g. Coated and dried to a coating amount of / m ² ,
Further, it was heat-aged and cured to form a ripening-resistant layer. The thermal transfer color material layer ink A is applied to the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried, and dried to form a thermal transfer color material layer to obtain the thermal transfer sheet of the present invention. It was <Antistatic Layer Liquid E> Polyethylene glycol # 60000 4.0 parts by weight (Kanto Chemical Co., Inc.) Polyisocyanate 0.6 parts by weight (Coronate 2030, Nippon Polyurethane Industry Co., Ltd.) Magnesium trifluoromethanesulfonate 0.3 parts by weight Part (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (Adcoat 335A, manufactured by Toyo Morton)

Example 6 6.0 μm PE as a base material
A T (polyethylene terephthalate) film was coated with the following heat-resistant slipping layer liquid A so that the coating amount was about 1.0 g / m ² when dried, and then heat-aged to cure and heat-treat. A slippery layer was formed. The antistatic layer liquid C was applied to the back surface thereof so as to have a coating amount of about 0.1 g / m ² when dried, and dried to form a thermal transferable color material layer, thereby obtaining a thermal transfer sheet of the present invention.

Example 7 PE having a thickness of 6.0 μm as a base material
The antistatic layer liquid E is applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² when dried, and the heat-resistant slipping layer liquid F is dried thereon to about 1.0 g. Coated and dried to a coating amount of / m ² ,
Further, it was heat-aged and cured to form a heat resistant slipping layer. About 0.1 g / m ² of antistatic layer liquid C is applied to the back surface.
To obtain a heat transferable colorant layer ink, and the thermal transferable colorant layer ink A is applied to the upper layer so as to have a coating amount of about 1.0 g / m ² when dried to form a heat transferable colorant layer. By forming, a thermal transfer sheet of the present invention was obtained.

(Example 8) 6.0 μm PE as a base material
The following antistatic layer liquid F was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.1 g / m ² when dried, and the heat-resistant slipping layer liquid A was dried on the upper layer to about 1 g. The heat-resistant slipping layer was formed by coating and drying so as to have a coating amount of 0.0 g / m ² , and further aging by heating for curing treatment. The thermal transfer color material layer ink A is applied to the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried, and dried to form a thermal transfer color material layer to obtain the thermal transfer sheet of the present invention. It was <Antistatic Layer Liquid F> Polyethylene glycol modified resin 4.0 parts by weight (Adeka Polyether AM-505, manufactured by Asahi Denka Co., Ltd.) Polyisocyanate 0.6 parts by weight (Coronate 2030, manufactured by Nippon Polyurethane Industry Co., Ltd.) Trifluoromethane Lithium sulfonate 0.3 parts by weight (manufactured by Tokyo Chemical Industry Co., Ltd.) Methyl ethyl ketone 80.0 parts by weight Polyester resin 2.0 parts by weight (Adcoat 335A, manufactured by Toyo Morton)

(Comparative Example 1) PE of 6.0 μm as a base material
The following primer layer liquid A was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.3 g / m ² when dried, and the heat resistant slipping layer liquid A was dried on the upper layer to about 1. The heat-resistant slipping layer was formed by coating and drying so that the coating amount was 0 g / m ² , and further aging by heating for curing treatment. The thermal transfer color material layer ink A is applied to the back surface thereof so as to have a coating amount of about 1.0 g / m ² when dried, and dried to form a thermal transfer color material layer to obtain the thermal transfer sheet of the present invention. It was <Primer layer liquid A> Polyester resin 10.00 parts by weight (LP-035, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Methyl ethyl ketone 90.00 parts by weight

Comparative Example 2 PE of 6.0 μm as a base material
The following primer layer liquid B was applied to a T (polyethylene terephthalate) film so as to have a coating amount of about 0.3 g / m ² when dried, and the heat resistant slipping layer liquid A was dried on the upper layer to about 1. The heat-resistant slipping layer was formed by coating and drying so that the coating amount was 0 g / m ² , and further aging by heating for curing treatment. The heat transferable color material layer ink of the present invention is applied to the back surface thereof to form a heat transferable color material layer by applying and drying the following heat transferable color material layer ink A to a coating amount of about 1.0 g / m ² when dried. Got <Primer layer liquid B> Polyethylene glycol # 20000 4.0 parts by weight (manufactured by MERCK-Schuchardt) Polyisocyanate 0.6 parts by weight (Coronate 2030, manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.3 parts by weight lithium nitrate (Kanto Kagaku) Stock company) Methyl ethyl ketone 80.0 parts by weight

(Evaluation Method 1) (Adhesiveness) An antistatic layer and a heat resistant slipping layer were applied to a substrate, dried, and heat-cured at 60 ° C., and then a mending tape (manufactured by Sumitomo 3M Limited). , Scotch810m
(m width) was rubbed 3 times with a thumb, and the peeled state of the antistatic layer or the maturing slip resistant layer when peeled off was evaluated as follows. ○: No peeling ×: Peeling

(Evaluation Method 2) (Charge Attenuation) STATIC HONESTMETER
(H0110: SHISEDO ERECTROSTAT
IC, LTD. ) Was applied to the film surface under an environment of 25 ° C. and 40% RH, and the time (half-dead period) required to attenuate 3 KV to 1.5 KV was measured.

(Evaluation method 3) (Surface resistivity) High resistivity meter (MCP-HT250: Hi
2 using Desra IP, manufactured by Mitsubishi Chemical Corporation.
The surface resistivity per unit area was measured under the environment of 5 ° C. and 30% RH.

(Evaluation Results) Table 1 shows the evaluation results of the above Examples and Comparative Examples. (Below margin)

[0039]

[Table 1]

As described above, the adhesion was excellent in all the examples. In each of the examples, a thermal transfer sheet having appropriate charge decay and surface resistivity, that is, an excellent antistatic ability was obtained. On the other hand, in the comparative example, the charge decay ability was poor, that is, it was very difficult to discharge after the film was charged and it was difficult to remove the charge.

[0041]

EFFECT OF THE INVENTION From at least the base sheet and the heat resistant slipping layer, or between the base sheet and the heat transferable color material layer, an organic polymer having a plurality of ether bonds coordinated to a metal salt and a polyester resin are used. By providing such an antistatic layer, it is possible to provide a thermal transfer sheet having good adhesiveness and an antistatic effect.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a thermal transfer sheet of the present invention.

FIG. 2 is a cross-sectional view showing another example of the thermal transfer sheet of the present invention.

FIG. 3 is a cross-sectional view showing another example of the thermal transfer sheet of the present invention.

FIG. 4 is a cross-sectional view showing another example of the thermal transfer sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermal transfer sheet 2 Base film 3 Thermal transferable color material layer 4 Heat resistant slipping layer 5 Antistatic layer 6 Binder resin layer

Claims (8)

[Claims] 1. A thermal transfer sheet having a heat transferable coloring material layer on one surface of a base sheet and a heat resistant slipping layer formed on the other surface, wherein the base material sheet, the heat resistant slipping layer, and the base material. An antistatic layer comprising an organic polymer having an ether bond, a metal salt, and a binder resin is provided between at least one of the material sheet and the heat transferable color material layer. 2. The thermal transfer sheet according to claim 1, wherein the metal salt is any one of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt and copper salt. 3. The thermal transfer sheet according to claim 1, wherein the counter ion of the metal salt is any one of halogen, organic acid, nitric acid, trifluoromethanesulfonic acid, and perchloric acid. 4. An organic polymer having an ether bond, which is a reaction product of an organic polymer having at least one ether bond per unit molecule, and a compound which is the polymer and has a chemical bond at the terminal. 2. The method according to claim 1, wherein
4. The thermal transfer sheet according to 1. 5. The thermal transfer sheet according to claim 1, wherein the organic polymer having an ether group is crosslinked. 6. The binder resin used in the antistatic layer comprises:
The thermal transfer sheet according to claim 1, which is a polyester resin. 7. The thermal transfer sheet according to claim 1, wherein a binder resin layer is provided between the base sheet and the antistatic layer to improve the adhesiveness between the base sheet and the antistatic layer. . 8. The heat transfer sheet according to claim 1, wherein the heat transferable color material layer is either a heat sublimable dye heat transferable color material layer or a heat fusible ink layer.