JPH08175038A - Thermal transfer sheet - Google Patents

Abstract

(57) [Summary] (Corrected) [Purpose] To provide a thermal transfer sheet having a heat resistant slipping layer that does not cause variation in particle content depending on the manufacturing lot or the location of the coating film and that can prevent head wear, head debris, and sticking. To do. [Structure] The thermal transfer layer 3 is provided on one surface of the base material 2,
In the thermal transfer sheet 1 in which the heat resistant slipping layer 4 is provided on the surface opposite to the heat transferable layer 3, the heat resistant slipping layer 4 contains surface-treated particles.

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,
More specifically, by ensuring the dispersion stability of the particles in the coating liquid for the heat resistant slipping layer for forming the heat resistant slippery layer on the substrate, it is possible to improve the slipperiness and the heat release property between production lots. The present invention relates to a thermal transfer sheet which has no variation in heat resistance and does not suffer from thermal head wear, thermal head residue, sticking, printing wrinkles, and the like.

[0002]

2. Description of the Related Art Conventionally, as a thermal transfer sheet used for a thermal printer, a facsimile, etc., a sublimation type thermal transfer sheet in which a dye layer containing a heat transferable dye is provided on one surface of a base film, or it is melted by heating. A fused thermal transfer sheet using a molten ink layer containing a wax to be transferred and a coloring material is used. Such a conventional thermal transfer sheet has a thickness of 10 to 20 μm as a base film.
Dyes in which a dye is dispersed or dissolved in a binder resin on a base material film using a paper such as a capacitor paper or paraffin paper, or a plastic film such as polyester or cellophane having a thickness of about 3 to 10 μm. layer,
Alternatively, a molten ink layer using a wax in which a black pigment such as carbon black is kneaded is provided, and if necessary, a heat resistant slipping layer is provided on the back surface of the base film to improve slipperiness. Is. Then, from the back side of the substrate film, a predetermined portion is heated and pressed by a thermal head or the like according to the image information, and the dye or ink in the portion corresponding to the printing portion in the dye layer or the molten ink layer is transferred to the transfer material. Is being printed.

[0003]

When an image is formed with a thermal head using the thermal transfer sheet, the thermal head is heated to a high temperature when the substrate film is a thermoplastic resin film such as a polyester film.
There is a problem in that the thermal head is fused to the base material film, which hinders good running performance of the thermal head, resulting in damage and wrinkles on the thermal transfer sheet. In order to solve these problems, attempts to provide a heat resistant slipping layer on the back surface of the base sheet have been proposed so far. As such a heat resistant slipping layer, conventionally, a binder resin is added with an interfacial slipping agent such as a phosphoric acid ester as a lubricant, a silicone resin, silicone oil, wax or the like (JP-A-55-7).
467, JP-A-57-129789, etc.), talc or silica for further assisting lubricity and releasability, and preventing collapse or winding wrinkles or blocking during processing by winding.
An example is known in which particles such as calcium carbonate and Teflon are added (JP-A-58-171992). There is also a method of adding a cross-linking agent to cross-link the binder resin with heat, ultraviolet rays, electron beams or the like in order to impart heat resistance to the binder resin (JP-A-56-155794, etc.).

However, when particles are contained in the coating liquid for the heat resistant slipping layer, if the dispersion stability of the particles is poor, the particles will settle when the coating liquid is applied after being stored for a long period of time. The content rate of the particles inside sometimes changed. When the amount of particles in the coating film is too small due to the sedimentation of particles in the coating liquid, problems such as blocking and sticking occur. On the other hand, if the amount is too large, particles cause a problem such as a print wrinkle because the printing sensitivity is reduced, white spots on the printed surface are lost, and bleeding of the lubricant contained in the heat resistant slipping layer to the coating surface is hindered by particles.
When the content of particles in the heat resistant slipping layer varies depending on the place or lot, the performance as a thermal transfer sheet varies, and it is necessary to improve the dispersion stability of the particles. Also, if the printer is used for a long period of time and the cumulative number of prints increases, if particles are not properly fixed in the heat-resistant slipping layer coating, head debris will accumulate and the thermal head protective film will wear out. However, problems such as uneven density may occur.

[0005]

Means for Solving the Problems As a result of diligent studies on this point, the present inventor has found that by using a heat transfer sheet provided with a heat resistant slipping layer containing surface-treated particles, the above-mentioned production lot and coating film can be obtained. It has been found that there is no variation depending on the location of the head and that head wear, head debris, and sticking can be prevented. That is, the invention of claim 1 is a thermal transfer sheet having a heat transfer layer provided on one surface of a base material and a heat resistant slipping layer provided on the surface of the base material opposite to the heat transfer layer. It is a thermal transfer sheet characterized in that it contains surface-treated particles. According to a second aspect of the invention, the surface-treated particles are titanium compounds such as surfactants, carboxylic acids, amines, silane coupling agents, titanium coupling agents, aluminum compounds such as aluminum chelates, and zirco. It is characterized in that the particles are coated with at least one surface-treating agent selected from the group consisting of coupling agents such as aluminates, chromates, borates, stannates, isocyanates, β-diketone couplers, and phosphoric acid esters, The thermal transfer sheet according to claim 1.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. FIG. 1 is a longitudinal sectional view of a thermal transfer sheet showing an embodiment according to the present invention. The thermal transfer sheet 1 according to the present invention comprises at least the base film 2, the thermal transfer layer 3, and the heat resistant slipping layer 4 on the surface of the base film opposite to the surface on which the thermal transfer layer 3 is provided. The heat resistant slipping layer 4 is for preventing heat fusion with the thermal head and improving slipperiness.

(Substrate) As the substrate sheet used in the thermal transfer sheet 1 according to the present invention, the same material as that used in the conventionally known thermal transfer sheet can be used.
Other materials can be used and are not particularly limited. Specific examples of preferable materials include polyethylene terephthalate, polyethylene naphthalate, polyester films such as 1,4-polycyclohexylenedimethyl terephthalate, cellophane, cellulose derivatives such as cellulose acetate, polyethylene, polypropylene, polystyrene, polyphenylene sulfide, polycarbonate, Polyvinyl chloride, polyvinylidene chloride, nylon, polyimide,
Resins such as polyvinyl alcohol, fluororesins, chlorinated rubber, and ionomers. Further, it may be a composite of these resins and paper such as condenser paper and paraffin paper, non-woven fabric and the like. It is also preferable to provide an adhesive layer (primer layer) on one or both surfaces of the film, if necessary. The thickness of the base film 2 may be appropriately selected depending on the application and material so that the mechanical strength, thermal conductivity, etc. are appropriate, and generally, for example, 1.5 to 50.
It is about μm, preferably 2 to 10 μm.

(Thermal Transfer Layer) The thermal transfer layer 3 is not particularly limited as long as it is a thermal transfer layer according to a conventionally known method. For example, the thermal transfer layer in a sublimation type thermal transfer sheet is heated in a binder resin. It is a dispersion or solution of a migrating dye. As a binder resin, it has a suitable affinity for the dye, and the dye in the binder resin sublimates (transfers heat) by heating with a thermal head and transfers to the heat transfer material with good transferability. Even if the binder resin is used, the binder resin itself that does not transfer is used. Examples of the resin used as such a binder resin include ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose nitrate, cellulose acetate, cellulose-based resins such as acetic acid / butyrate cellulose, polyvinyl alcohol, Polyvinyl acetate, polyvinyl butyral,
Examples thereof include vinyl resins such as polyacrylamide and polyvinylpyrrolidone, polyesters and polyamides. The ratio of the dye contained in the thermal transfer layer 3 varies depending on the sublimation (melting) temperature of the dye, the dyeing property and the like.
The amount is preferably 30 parts by weight or more, more preferably 30 to 300 parts by weight, based on 00 parts by weight. If the amount of the dye is less than 30 parts by weight, the printing density and thermal sensitivity will be low, and if it exceeds 300 parts by weight, the storability and the adhesion of the thermal transfer layer 3 to the base film 2 will tend to be reduced.

The coloring material contained in the thermal transfer layer 3 is a dye which is melted, diffused or sublimated by heat and transferred to the material to be thermally transferred, and a disperse dye is particularly preferably used. The dye is selected in consideration of sublimation (melting) property, hue, light resistance, solubility in the binder resin, and the like. Examples of these dyes include diarylmethane-based, triarylmethane-based, thiazole-based, methine-based such as merocyanine, indoaniline,
Acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, azomethine typified by pyridone azomethine, xanthene, oxazine, dicyanostyrene, cyanomethylene typified by tricyanostyrene, thiazine, azine, acridine System, benzeneazo system, pyridone azo, thiophene azo, isothiazole azo, pyrrole azo, pyrazole azo, imidazole azo, thiadiazole azo, triazole azo, disazo and other azo systems, spiropyran system,
Examples thereof include indolinospyropyran type, fluorane type, rhodamine lactam type, naphthoquinone type, anthraquinone type and quinophthalone type. Specifically, the following dyes are used, for example.

CI (Color Index) Disperse Yellow
51,3,54,79,60,23,7,141,201,231 CI Disperse Blue 24,56,14,301,334,165,19,72,8
7,287,154,26,354 CI Disperse Red 135,146,59,1,73,60,167 CI Disperse Orange 149 CI Disperse Violet 4,13,26,36,56, 31 CI Solvent Yellow 56,14,16,29 CI Solvent Blue 70, 35,63,36,50,49, 111,105,97,1
1 CI Solvent Red 135,81,18,25,19,23,24,143,146,
182 CI Solvent Violet 13, CI Solvent Black 3, CI Solvent Green 3,

For example, as a cyan dye, Kayaset Blue 714 (Nippon Kayaku, Solvent Blue 63), Foron Brilliant Blue SR (Sand, Disperse Blue 354), Waxolin AP-FW (ICI, Solvent Blue 36). ), MS-REDG as magenta dye
(Mitsui Toatsu Co., Disperse Red 60), Macrolex Red Violet R (Bayer, Disperse Violet 26), Foron Brilliant Yellow S-6GL (Sand, Disperse Yellow 231) as a yellow dye, Macrolex Yellow 6G ( Disperse Yellow 201) manufactured by Bayer, and the skeletons shown below are also included. The thermal transfer layer 3 can be provided on the base film 2 by a known method. For example, a dye and a binder resin are dissolved or dispersed with a solvent to prepare an ink composition for a thermal transfer layer, which is provided on the base film 2 by a method appropriately selected from known printing methods or coating methods. Good. Further, if desired, any additive may be added to the ink composition for the thermal transfer layer. For example, organic fine particles such as polyethylene wax and inorganic fine particles may be contained in the dye layer in order to adjust coating suitability and prevent fusion with the image receiving sheet. The thickness of the dye layer is
A thickness of 0.2 to 5.0 μm, preferably 0.4 to 2.0 μm is suitable.

(Heat-resistant slip layer) In the present invention, the heat-resistant slip layer formed on the surface of the base material on which the dye layer is not provided is conventionally known except that it contains particles subjected to surface treatment. The same material as the object or other materials can be used without any particular limitation. As the binder resin used in the heat resistant slipping layer, known resins can be used, for example, polyester resin, polyacrylic ester resin, polyvinyl acetate resin, styrene acrylate resin, polyurethane resin, polyolefin resin. , Polystyrene resin, polyethylene resin, polypropylene resin, polyacrylate resin, polyacrylamide resin, polyvinyl chloride resin, polyvinyl butyral resin, polyvinyl acetoacetal resin, and other polyvinyl acetal resins, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose Cellulosic resins such as methyl cellulose, cellulose nitrate, cellulose acetate, acetic acid / cellulose butyrate, polyvinyl alcohol, polyvinyl pyro Vinyl resins such as Don include thermoplastic resins such as polyamide.

In order to increase the coating strength or heat resistance of the heat resistant slipping layer, it is desirable to use a reaction cured product of a thermoplastic resin having an active hydrogen group and an isocyanate. A particularly preferable resin as the resin used at that time is a thermoplastic resin containing a hydroxyl group, and among them, a polyvinyl acetal resin such as a polyvinyl butyral resin or a polyacetoacetal resin is particularly preferable. As the isocyanate curing agent, conventionally known ones can be used. For example, aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and other isocyanates, as an adduct of trimethylolpropane,
A prepolymerized product such as an isocyanurate ring can be used. The amount of polyisocyanate used is appropriately in the range of 5 to 200 parts by weight based on 100 parts by weight of the binder resin constituting the heat resistant slipping layer. The molar ratio of -NCO / -OH is 0.
The range of 8 to 2.0 is preferable. If the amount of the polyisocyanate used is too small, the crosslink density is low and the heat resistance becomes insufficient, resulting in print wrinkles and no sufficient effect.
On the other hand, if the amount of polyisocyanate used is too large, the shrinkage of the formed coating film becomes difficult to control, the curing time becomes long, unreacted isocyanate groups remain in the heat resistant slipping layer, and There is a problem that the number of crosslinking points with the thermoplastic resin having active hydrogen decreases by reacting with water.

By the way, a lubricant may be added to the heat resistant slipping layer in order to improve the slipping property. As the lubricant used here, various surfactants, silicone oils,
Examples thereof include silicone-modified resin, silicone resin, fluorine-modified resin, fluorine resin, wax, metal soap, and higher fatty acid amide. Of these, it is particularly preferable to add a phosphate ester surfactant. As the phosphoric acid ester-based surfactant to be used, 1) a long-chain alkyl phosphoric acid ester, for example, a saturated or unsaturated higher alcohol having 6 to 20 carbon atoms, preferably 12 to 18 carbon atoms, such as cetyl alcohol or stearyl. Alcohols, mono- and / or diesters of oleyl alcohol, etc. with phosphoric acid, 2) phosphoric acid esters, such as polyoxyalkylene alkyl ethers or polyoxyalkylene alkylaryl ethers, 3) alkylene oxide adducts of the saturated or unsaturated alcohols (usually Addition mole number 1-8) or carbon number 8-1
Nonionic or anionic phosphate-based surfactants such as phosphate mono- or diester salts of alkylphenols or alkylnaphthols (nonylphenol, dodecylphenol, diphenylphenol, etc.) having at least one, preferably 1-2, 2 alkyl groups Agents.

Further, although it is possible to use only the above phosphoric acid ester type surfactant, since the phosphoric acid ester type surfactant has 1 to 2 equivalents of acid radicals, the problem that the thermal head is corroded by the acid radicals. There is. There is also a problem that 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 corrosive wear of the thermal head increases. The above-mentioned drawbacks can be prevented by using an alkaline substance together with a phosphate ester type surfactant. That is, even if the phosphate ester type surfactant is decomposed by the heat from the thermal head to generate an acid radical, it is neutralized by the coexisting alkaline substance, so that the corrosion of the thermal head due to the generation of an acid group can be prevented. .

Examples of the above-mentioned alkaline substance include oxides of alkali metals or alkaline earth metals and / or organic amines. Preferred as an oxide or hydroxide of an alkali metal or an alkaline earth metal are, for example, magnesium hydroxide, magnesium oxide, hydrotalcite, aluminum hydroxide, aluminum silicate,
Examples thereof include magnesium silicate, magnesium carbonate, alumina hydroxide, and magnesium aluminum glycinate, and magnesium hydroxide is particularly preferable. Preferred as organic amines are, for example, mono, di or trimethylamine, mono, di or triethylamine,
Mono, di or tripropyl amine, mono, di or tributyl amine, mono, di or tripentyl amine, trihexyl amine, trioctyl amine, monodecyl amine, mono or didodecyl amine, mono tridecyl amine, mono tetradecyl amine , Monopentadecylamine, monohexadecylamine, monoheptadecylamine, monooctadecylamine, monoeicosylamine,
Monodocosylamine, mono-, di- or triethanolamine, mono- or dipropanolamine, monoisopropanolamine, N-methyl-nonylamine, N-methyl-
Examples thereof include decylamine and N-ethyl-palmitylamine. Particularly preferred amines are nonvolatile at room temperature and have a boiling point of 200 ° C or higher.

These amines stably exist in the heat resistant slipping layer, and when heat is applied to the heat resistant slipping layer from the thermal head, the amine becomes fluid and bleeds out to the surface to form a phosphate ester type surfactant. Alternatively, the acid radical generated in the decomposed product is easily neutralized to prevent corrosion of the thermal head, and at the same time, excellent lubricity is exhibited together with the phosphate ester type surfactant. As for the alkaline substance as described above, 0.1 mol of the alkaline substance is added to 1 mol of the phosphate ester surfactant.
It is desirable to use in the range of 10 to 10 moles. 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.

By the way, the present invention is characterized in that the heat resistant slipping layer contains particles which have been subjected to surface treatment. As the particles, one kind or a mixture of two or more kinds of conventionally known inorganic particles or organic particles can be used. Examples of the inorganic particles include talc, kaolin, clay minerals such as mica, calcium carbonate, carbonates such as magnesium carbonate,
Examples thereof include hydroxides such as aluminum hydroxide and magnesium hydroxide, sulfates such as calcium sulfate, oxides such as silica, graphite, slag, and boron nitride.
The organic particles include acrylic resin, Teflon resin,
Examples thereof include organic resins such as silicone resins, lauroyl resins, phenol resins, and acetal resins, or crosslinked resins obtained by reacting these with a crosslinking agent to crosslink them. The particles used in the present invention are preferably flaky and / or spherical, and the particle size is 5 μm or less, preferably 0.5 to 2 μm.

The surface treatment agent used in the present invention, for example, when the particles having a hydrophilic surface are dispersed in a hydrophobic resin or solvent, the surface treatment agent hydrophobizes the surface of the particles so that the surface treatment agent is compatible with the hydrophobic resin or solvent. This is to improve the dispersion stability of the particles in the coating liquid by making it easier. Examples of such surface treatment agents include surfactants, carboxylic acids, amines, silane coupling agents, titanium-based compounds such as titanium coupling agents, aluminum-based compounds such as aluminum chelates, zircoaluminates, chromates, and the like.
At least one selected from the group consisting of coupling agents such as borates and stannates, isocyanates, β-diketone couplers, and phosphoric acid esters can be used.

Among these, cationic surfactants, anionic surfactants, nonionic surfactants and the like can be used as the surfactant. The silane coupling agent is represented by the general formula YRSiX ₃ or YR (R ⁻ ) SiX ₂ . However, X is a hydrolyzable group bonded to a silicon atom, and is a chloro group, an alkoxy group,
Examples include acetoxy group. Y is an organic functional group that reacts with the organic matrix, and examples thereof include a vinyl group, a methacrylic group, an epoxy group, a mercapto group, and an amino group. Examples of R include H and hydrocarbons having 1 to 4 carbon atoms.

Titanium compounds include isopropyl triisostearoyl titanate and isopropyl tris-
Iso-dodecylbenzene-sulfonyl titanate, isopropyl tris-normal-dodecylbenzene-sulfonyl titanate, isopropyl-tris (dioctyl pyrophosphite) titanate, tetraisopropyl-bis (dioctyl phosphite) titanate, tetraoctyl-bis (dioctyl phosphite) Titanate, tetra (2,2-diaryloxymethyl-1-butyl) -bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate) -oxyacetate titanate, bis (dioctylpyrophosphate) -ethylene titanate, Isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl isostearoyl diacrylic titanate , Isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri (N- aminoethyl-aminoethyl) titanate, dicumyl phenyloxy acetate titanate, etc. diisostearoyl ethylene titanate and the like.

Examples of the aluminum compound include aluminum isopropylate, mono sec-butoxyaluminum diisopropylate, aluminum sec-butyrate,
Aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethylacetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum (isopropoxide) alkyl phosphate) (alkyl acetate), aluminum monoacetylacetonate bis ( Ethyl acetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate and the like.

The amount of these surface treatment agents used is 0.1 to 20% by weight, preferably 0.5 to 3 based on the particles.
Weight percent. Further, as the surface treatment method,
It is possible to adopt a method of treating the particles as they are or by adding a solution diluted with a suitable diluent and treating them with a mixer, or by treating the particles together with the particles in a proper solvent and then removing the solvent. . The particles as described above are preferably used in a proportion of 5 to 40 parts by weight with respect to 100 parts by weight of the binder resin, and if the addition amount is too small, the slipperiness is insufficient, while if the addition amount is too large, heat resistance is formed. The flexibility and film strength of the slipping layer are reduced. It should be noted that the surface treatment agent may be selected on the basis of the particle or the surface of the particle, whether the resin binder is hydrophilic or hydrophobic, or compatibility with the resin binder.

To provide the heat resistant slipping layer on the substrate sheet,
The above components are dissolved in a suitable solvent such as acetone, methyl ethyl ketone, toluene, xylene, and ethyl acetate to form a heat-resistant slip layer-forming ink, which is a conventional suitable printing method such as gravure coater, roll coater, and wire bar. It is formed on the base material sheet by the coating method. Then, the resin is dried by heating at a temperature of 30 ° C. to 80 ° C. and the resin having an active hydrogen group is reacted with isocyanates to form the heat resistant slipping layer. The heat resistant slipping layer has a thickness of 0.5 to 5 μm, preferably 1 to 2 μm. If this film thickness is less than 0.5 μm, the effect as a heat resistant slipping layer is not sufficient,
If it is thicker than m, the heat transfer from the thermal head to the dye layer is deteriorated and the printing density is lowered. When a heat resistant slipping layer is provided on the base material sheet, it is preferable to heat it in order to accelerate the reaction between the binder resin and the isocyanate, but in order to prevent the dye layer from being affected by heat, the heat resistant slipping layer is used. It is preferable to provide the dye layer after the functional layer is provided on the substrate sheet.

The transfer sheet of the present invention basically has the above-mentioned constitution, but further the adhesive force of each layer is provided between the dye layer and the base sheet or between the heat resistant slipping layer and the base sheet. You may provide a primer layer in order to improve.
Although a known primer layer can be used, when polyester is used as the base sheet, adhesion can be improved by providing a primer layer of acrylic resin, polyester resin, polyol and diisocyanate, for example. .

Further, if necessary, an antistatic agent may be added to at least one of the substrate, the heat resistant slipping layer and the thermal transfer layer. The antistatic agent used here is appropriately selected according to compatibility with the resin used for the base film, the dye layer or the heat resistant slipping layer, migration, thermal stability, processability, and other basic physical properties such as film strength. However, among them, the surfactant is inexpensive and excellent in processability, and the like. Surfactants used as antistatic agents include, for example, cationic antistatic agents such as primary amine salts, tertiary amines, quaternary ammonium compounds, and pyridine derivatives, and anionic antistatic agents include ricinolein. Sulfated oils such as acid sulfate soda salt, soaps such as fatty acid salt, sulfated ester oils such as lysyl cinnamate sulfate ester soda salt, sulfated amide oils such as sulfated ethyl oleate aniline, sulfate ester salts of olefins, Oleyl alcohol sulfate ester soda salt and other fatty alcohol sulfate salt, alkyl sulfate ester salt, fatty acid ethyl sulfonate, alkyl sulfonate, condensate of naphthalene sulfonic acid and formalin, succinate sulfonate, phosphate ester salt For nonionic antistatic agents, sorbitan Partial fatty acid ester of polyhydric alcohol such as fatty acid ester and fatty acid pentaerythritol, fatty alcohol, fatty acid, fatty amino, fatty acid amide, alkylphenol, alkylnaphthol, ethylene oxide adduct such as partial fatty acid ester of polyhydric alcohol, polyethylene Examples of glycols and amphoteric antistatic agents include carboxylic acid derivatives and imidazoline derivatives.

When the heat resistant slipping layer 4 is formed mainly of non-reactive silicone resin or the like, the antistatic agent may be selected without considering the influence of the reaction with the heat resistant slipping layer 4. . However, particularly when a binder resin composed of an isocyanate and an isocyanate-reactive resin is mainly used for the heat resistant slipping layer, when an antistatic agent containing an active hydrogen group is selected, the heat resistant slipping layer is formed. It is not preferable because it affects the reaction of isocyanate. In this respect, anionic surfactants are preferable. In particular, sodium alkane sulfonate has a high melting point, so when it is used as an antistatic agent, it has no stickiness on the surface and the softening temperature of the base film after kneading into the resin of the base film to form a film. It is particularly preferable because it does not decrease.

(Others) The thermal transfer sheet 1 may be a single sheet cut to a required size, may be continuous or may be wound, and may be a tape having a narrow width. Good. The material to be transferred used for forming an image using the thermal transfer sheet as described above is, for example, in the case of a sublimation type, as long as the recording surface has dye receptivity to the dye. But again,
In the case of paper, metal or glass synthetic resin having no dye receptivity, a dye receptive layer may be formed on at least one surface thereof.

As the material to be transferred which does not need to form a dye receiving layer, any material which has been conventionally used in this method can be used. Examples thereof include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride and polychlorinated resin. Halogenated polymers such as vinylidene, polyvinyl polymers such as polyvinyl acetate and polyacrylate, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, olefins such as ethylene and propylene, and other vinyls. Examples thereof include copolymer resins with monomers, ionomers, cellulosic resins such as cellulose acetate, fibers made of polycarbonate, polysulfone, polyimide and the like, woven fabrics, films, sheets, molded products and the like. Particularly preferred is a sheet or film made of polyester or a processed paper provided with a polyester layer. In addition, paper, metal, glass, or other non-dyeable transfer material,
A transfer material can be obtained by coating and drying the solution or dispersion of the dyeing resin as described above on the recording surface or laminating the resin film. Further, even with the transfer material having the above-mentioned dyeing property, a dye-receiving layer may be formed on the surface of the material having a more dyeing property in the same manner as the above paper.

The dye-receptive layer thus formed may be made of a single material or a plurality of materials, and may further contain various additives within a range not hindering the initial purpose. Good. The dye receiving layer as described above may have any thickness, but it is generally 3 to 50 .mu.m thick. Further, such a dye receiving layer is preferably a continuous coating,
A resin emulsion or resin dispersion may be used to form a discontinuous coating. The material to be transferred is basically as described above and can be used as it is, but the material to be transferred or the dye receiving layer thereof can contain an inorganic powder for preventing adhesion. By doing so, even if the temperature at the time of thermal transfer is further raised, the adhesion between the thermal transfer sheet and the transfer material can be prevented, and more excellent thermal transfer can be performed. Particularly preferred is finely divided silica. Further, a resin having a good releasability may be added instead of or in combination with the above-mentioned inorganic powder such as silica. Particularly preferable releasing polymer is a cured product of a silicone compound, for example, a cured product of an epoxy-modified silicone oil and an amino-modified silicone oil. Such a releasable polymer preferably accounts for about 05 to 30% by weight of the weight of the dye receiving layer. Further, the surface of the dye receiving layer of the transfer material to be used may be coated with the above-mentioned inorganic powder to enhance the anti-adhesion effect, or the releasable polymer having excellent releasability as described above. You may provide the mold release layer which consists of a mold release agent. Such a release layer exerts a sufficient effect with a thickness of about 0.01 to 5 μm, and can prevent the adhesion of the thermal transfer sheet to the dye receiving layer and further improve the dye receiving property.

[0031]

As described above, the thermal transfer sheet according to the present invention is characterized in that the heat-resistant slipping layer contains the particles subjected to the surface treatment. Therefore, the thermal stability of the thermal transfer sheet can be obtained, and therefore, there is no variation in performance such as slipperiness and thermal releasability between manufacturing lots, and thermal head wear, thermal head residue, sticking, and print wrinkles do not occur. . In addition, even if particles that are too hard and wear the thermal head as they are, by applying a surface treatment,
Since the wear resistance can be reduced, it is an effective means for the case where sticking has occurred when soft particles have been selected so far to prevent wear.

[0032]

EXAMPLES Next, the thermal transfer sheet according to the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, “part” or “%” is based on weight unless otherwise specified. [Reference Example 1] Surface treatment of particles (1) 2 kg of talc (manufactured by Nippon Talc, Microace L-1) as particles was put in a Henschel mixer, and the rotation speed was 60 r.
The temperature was set to pm and the temperature was 95 ° C., and preliminary drying was performed for 20 minutes. Then, 20 g of a silane coupling agent (manufactured by Nippon Unicar Co., Ltd., A-172) was dropped as a surface treatment agent, treated for about 10 minutes at a rotation speed of 1200 rpm and 80 ° C., and naturally cooled to treat the surface of talc. [Reference Example 2] Surface treatment of particles (2) In a Henschel mixer, kaolin clay (Tsuchiya Kaolin Industry, ASP-170): 2 kg Alkyl acetoacetate aluminum diisopropylate: 20 g (Ajinomoto, Planeact AL-M) Toluene: After adding 4 kg and stirring for 10 minutes, the kaolin clay was surface-treated by drying under reduced pressure at 100 ° C. for 2 hours. [Reference Example 3] Surface treatment of particles (3) In a Henschel mixer, calcium carbonate (manufactured by Shiraishi Industry Co., Ltd., Brilliant 1500): 2 kg Nonionic surfactant: 20 g (manufactured by Kawaken Fine Chemicals Co., KF-750) Ethyl acetate: 4 kg Was added, the mixture was stirred for 10 minutes, and dried under reduced pressure at 80 ° C. for 2 hours to surface-treat calcium carbonate. [Reference Example 4] Surface treatment of particles (4) 2 kg of high-purity alumina (Sumitomo Chemical Co., Ltd., AKP-20) was put into a Henschel mixer as particles, and the rotation speed was 60 rpm and the temperature was set to 95 ° C for 20 minutes. Was pre-dried. Thereafter, 20 g of aluminum (isopropoxide) (alkyl phosphate) (alkyl acetate) (Kawaken Fine Chemical Co., Ltd., aluminum chelate P-1) was dropped as a surface treatment agent, and the rotation speed was 1200.
The alumina was surface-treated by treating it at 80 ° C. for about 10 minutes at room temperature and naturally cooling it.

Example 1 Polyethylene terephthalate (manufactured by Diafoil Hoechst Co., Ltd.) as a base film
K203E4.5W, thickness 4.5 μm), and one side of which is coated with a coating solution for heat resistant slipping layer having the following composition using Miyabar # 5 when dried 1
The coating was applied so as to have a thickness of μm, dried, and further heat-aged in an oven at 60 ° C. for 2 days for curing treatment to form a heat resistant slipping layer. Coating liquid for heat resistant slipping layer Polyvinyl butyral 3.6 parts (Sekisui Chemical Co., Ltd. S-REC BX-1) Polyisocyanate 8.4 parts (Dainippon Ink and Chemicals Co., Ltd. Vernock D750) Phosphate ester-based surfactant Agent 2.8 parts (Prysurf A208S manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Talc surface-treated with [Reference Example 1] 0.6 parts Magnesium hydroxide 0.3 parts (Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts Next, on the surface of the base film opposite to the surface on which the heat resistant slipping layer is formed, the following dye layer forming ink is dried to a thickness of 1 μm.
To obtain the thermal transfer sheet of the present invention. Dye layer coating liquid C. I Solvent Blue 22 5.5 parts Polyvinyl acetoacetal resin 3.0 parts (Sekisui Chemical Co., Ltd., S-REC KS-5) Polyethylene wax 0.1 parts (BASF, AF31) Toluene 68.18 parts Methyl ethyl ketone 22. 54 copies

Example 2 A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for the heat resistant slipping layer having the following composition was used. Coating liquid for heat resistant slipping layer Polyvinyl butyral resin 2.0 parts (Sekisui Chemical Co., Ltd., S-REC BX-1) Acrylic polyol 8.0 parts (Soken Chemical Co., Ltd., Thermolac SU-100A) Polyisocyanate 5.0 parts (Bernock D750 manufactured by Dainippon Ink and Chemicals, Inc.) Silicone oil 0.7 parts (Painted 31 manufactured by Dow Corning Co., Ltd.) Kaolin clay surface-treated with [Reference Example 2] 0.1 parts Toluene 12 Part Methyl ethyl ketone 12 parts

Example 3 A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for the heat resistant slipping layer having the following composition was used. Coating liquid nitrocellulose resin for heat resistant slipping layer 23 parts (Asahi Kasei Co., Ltd., Cenoba BTH1 / 2) Polyisocyanate 3.4 parts (Asahi Kasei Co., Ltd., Duranate 22A-75CX) Sorbitan surfactant 2 3 parts (Nonion OP-85R manufactured by NOF CORPORATION) Calcium carbonate surface-treated with [Reference Example 3] 0.6 parts Toluene 35 parts Methyl ethyl ketone 35 parts

Example 4 A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for heat resistant slipping layer having the following composition was used. Coating liquid for heat resistant slipping layer Polyvinyl butyral 3.6 parts (Sekisui Chemical Co., Ltd. S-REC BX-1) Polyisocyanate 8.4 parts (Dainippon Ink and Chemicals Co., Ltd. Vernock D750) Phosphate ester-based surfactant Agent 2.8 parts (Prysurf A208S manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Alumina surface-treated with [Reference Example 4] 0.06 part Magnesium hydroxide 0.3 part (Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts

Comparative Example 1 A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for the heat resistant slipping layer used had the following composition. Coating liquid for heat resistant slipping layer Polyvinyl butyral 3.6 parts (Sekisui Chemical Co., Ltd. S-REC BX-1) Polyisocyanate 8.4 parts (Dainippon Ink and Chemicals Co., Ltd. Vernock D750) Phosphate ester-based surfactant Agent 2.8 parts (Daiichi Kogyo Seiyaku Co., Ltd. Prysurf A208S) Talc 0.6 part (Nippon Talc Co., Ltd. Microace L-1) Magnesium hydroxide 0.3 part (Kyowa Chemical Industry Co., Ltd.) Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts

(Comparative Example 2) A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for the heat resistant slipping layer used had the following composition. Coating liquid for heat resistant slipping layer Polyvinyl butyral resin 2.0 parts (Sekisui Chemical Co., Ltd., S-REC BX-1) Acrylic polyol 8.0 parts (Soken Chemical Co., Ltd., Thermolac SU-100A) Polyisocyanate 5.0 parts (Dainippon Ink and Chemicals Co., Ltd. Burnock D750) Silicone oil 0.7 parts (Dow Corning Co., Ltd. Painted 31) Kaolin clay 0.1 parts (Tsuchiya Kaolin Co., Ltd., ASP- 170) Toluene 12 parts Methyl ethyl ketone 12 parts

(Comparative Example 3) A thermal transfer sheet was obtained in the same manner as in Example 3 except that the coating solution for the heat resistant slipping layer having the following composition was used. Coating liquid nitrocellulose resin for heat resistant slipping layer 23 parts (Asahi Kasei Co., Ltd., Cenoba BTH1 / 2) Polyisocyanate 3.4 parts (Asahi Kasei Co., Ltd., Duranate 22A-75CX) Sorbitan surfactant 2 .3 parts (NONION OP-85R manufactured by NOF CORPORATION) Calcium carbonate (manufactured by Shiraishi Industry, Brilliant 1500) 0.6 parts Toluene 35 parts Methyl ethyl ketone 35 parts

(Comparative Example 4) A thermal transfer sheet was obtained in the same manner as in Example 1 except that the coating composition for heat resistant slipping layer having the following composition was used. Coating liquid for heat resistant slipping layer Polyvinyl butyral 3.6 parts (Sekisui Chemical Co., Ltd. S-REC BX-1) Polyisocyanate 8.4 parts (Dainippon Ink and Chemicals Co., Ltd. Vernock D750) Phosphate ester-based surfactant Agent 2.8 parts (Daiichi Kogyo Seiyaku Co., Ltd. Prysurf A208S) High-purity alumina (Sumitomo Chemical Co., Ltd.) 0.06 part Magnesium hydroxide 0.3 part (Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts

Table 1 shows the results of evaluation of dispersion stability and head residue and head wear as the running performance of the printer for the thermal transfer sheets of the above Examples and Comparative Examples. The evaluation method was as follows. (1) Dispersion stability After filling / sealing a petroleum can with the coating liquid for the heat resistant slipping layer, 25
After left standing in a room at 50 ° C RH for 3 months, the lid of the petroleum can was opened, and it was visually determined whether or not the particles had settled. (2) Head residue The dye layer side of the thermal transfer sheet and the material to be transferred formed as described below are superposed and solid printed using a commercially available video printer (VY-170 manufactured by Hitachi, Ltd.).
After repeating 000 screens, the surface of the thermal head was observed with a microscope to examine the presence or absence of head residue. The material to be transferred used for evaluating the performance in the printer was manufactured as follows. Synthetic paper (Yupo FPG150, manufactured by Oji Yuka Co., Ltd.) was used as a base material, and a coating liquid for a dye receiving layer having the following composition was applied on one side of this with a miya bar # 14 so that the coating amount when dried was 4 μm. At 130 ° C for 3
After being dried for a minute, a material to be transferred was prepared. Dye-Receptive Layer Coating Liquid Vinyl Chloride / Vinyl Acetate Copolymer Resin 20 parts (Denka Rack # 1000A manufactured by Denki Kagaku Co., Ltd.) Epoxy-modified silicone oil 3 parts (X-22-3000E manufactured by Shin-Etsu Chemical Co., Ltd.) Amino Modified silicone oil 3 parts (X-22-3050C manufactured by Shin-Etsu Chemical Co., Ltd.) Toluene 40 parts Methyl ethyl ketone 40 parts

(3) Head wear (2) Solid printing was performed using a printer of the same model as the head scrap, and 3000 screens were repeated, and then the surface of the thermal head was observed with a microscope to check for wear. Head wear ・ ・ ・ ○: No head wear △: Some head wear ×: Head wear is considerably advanced

[0043]

[Table 1]

[0044]

As described above, the thermal transfer sheet of the present invention is characterized in that the surface-treated particles are contained in the heat resistant slipping layer. Since the dispersion stability can be ensured, there is no variation in performance such as slipperiness and thermal releasability between manufacturing lots, and a thermal transfer sheet free from thermal head wear, thermal head residue, sticking, and print wrinkles can be obtained.

[Brief description of drawings]

FIG. 1 is a vertical cross-sectional view of a thermal transfer sheet according to the present invention.

[Explanation of symbols]

 1: Thermal transfer sheet 2: Base film 3: Thermal transfer layer 4: Heat resistant slipping layer

Claims (2)

[Claims] 1. A thermal transfer sheet having a heat transfer layer provided on one surface of a base material and a heat resistant slipping layer provided on the surface of the base material opposite to the heat transfer layer, wherein the heat resistant slipping layer is subjected to a surface treatment. A thermal transfer sheet containing the above particles. 2. The surface-treated particles include a surfactant, a carboxylic acid, an amine, a titanium compound such as a silane coupling agent and a titanium coupling agent, an aluminum compound such as an aluminum chelate, and zircoaluminate.
A particle which has been subjected to at least one surface-treating agent selected from the group consisting of a coupling agent such as chromate, borate, stannat, etc., an isocyanate, a β-diketone coupler, and a phosphoric acid ester. The thermal transfer sheet described.