JPH0890942A - Thermal transfer sheet - Google Patents

Abstract

PURPOSE: To provide a thermal transfer sheet having a heat resisting smooth layer which does not generate head residue and sticking and can prevent abrasion of a head. CONSTITUTION: In a thermal transfer sheet having a thermal transfer layer provided on one face of a base material and a particle-containing heat resisting smooth layer provided on an opposite face of the thermal transfer layer, the shot type abrasion degree of the particle included in the heat resisting smooth layer is set to 15-100mg.

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 used in a thermal recording system, and more particularly to a thermal transfer sheet free from abrasion, thermal head residue and sticking to a thermal head.

[0002]

2. Description of the Related Art Conventionally, as a thermal transfer sheet used for a thermal printer, a facsimile or the like, a sublimation type thermal transfer sheet having a dye layer containing a heat transferable dye on one surface of a substrate film, or melting by heating A fused thermal transfer sheet provided with a molten ink layer containing a wax to be transferred is used. Such a conventional thermal transfer sheet uses, as a base film, paper such as capacitor paper or paraffin paper having a thickness of about 10 to 20 μm, or plastic film such as polyester or cellophane having a thickness of about 3 to 10 μm. Provide a dye layer in which a dye is dispersed or dissolved in a binder resin on a base film, or a molten ink layer using a wax in which a black pigment such as carbon black is kneaded, and if necessary, On the back surface, a material provided with a heat resistant slipping layer was used for the purpose of improving slipperiness. Then, according to the image information from the back side of the base material film, by heating and pressurizing a predetermined portion with a thermal head or the like, the dye in the portion corresponding to the printing portion of the dye layer is transferred to the transfer material to print. Has been done.

[0003]

However, in the conventional thermal transfer sheet, the coating of the heat resistant slipping layer and the contained filler are scratched off by the thermal head while printing several thousand sheets. Alternatively, thermal fusion of the coating of the heat resistant slipping layer on the thermal head may lead to accumulation of head debris and abrasion of the protective film of the thermal head, resulting in defects such as uneven density. To prevent wear of the thermal head, use soft particles such as Mohs hardness 3
A method using the following particles is proposed in EP-A, 577051. However, when a natural mineral is used as the particles, the hardness may differ depending on the type and amount of impurities contained, even if the main components are the same. That is, the main component is
Even if the Mohs hardness is 3 or less, if the crystals containing the Mohs hardness of 3 or more are contained as impurities, it is not possible to prevent the wear of the thermal head. It turned out to be impossible to prevent. Further, when such soft particles are used, the particles are crushed by heat or pressure during printing, and the heat resistant slipping layer is thermally fused to the thermal head, which may cause so-called head residue or sticking. is there. Furthermore, even if a head residue occurs, if the particles contained in the heat resistant slipping layer are projected on the surface, the particles scrape off the head residue to prevent the accumulation of the head residue.
As described above, it was also found that when the soft particles having the abrasion resistance to the head were used, the particles were crushed by the heat and pressure at the time of printing and the head residue could not be scraped off.

[0004]

Means for Solving the Problems As a result of diligent studies on this point, the present inventor has provided a heat transfer layer on one surface of a base material, and a heat-resistant material containing particles on the surface of the base material opposite to the heat transfer layer. In a thermal transfer sheet provided with a slipping layer, by using a thermal transfer sheet characterized in that the abrasion resistance of particles contained in the heat resistant slipping layer is 15 to 100 mg,
It was found that the above-mentioned head wear, head residue, and sticking can be prevented. It was also found that the above problem can be solved by using a thermal transfer sheet characterized in that the particles to be used are a mixture of two or more kinds of particles having different levels of wear depending on the shot type.

[0005]

In the thermal transfer sheet of the present invention as described above, the particle diameter of the particles contained in the heat resistant slipping layer is 15 to 100 m.
By setting the value to g, the particles are not so soft that they are crushed by heat and pressure at the time of printing to cause head shavings. Since it has, it is possible to scrape off the head debris and prevent deposition.
On the other hand, by setting the upper limit of the shot type abrasion degree as described above, it is possible to prevent the thermal head from being abraded by particles, and it is possible to obtain a heat resistant slipping layer having abrasion resistance to the head.

[0006]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the thermal transfer sheet of the present invention will be described in more detail by the materials used and the forming method. First, as a preferable substrate used for the thermal transfer sheet of the present invention, for example, polyester films such as polyethylene terephthalate, polyethylene naphthalate, and 1,4-polycyclohexylene dimethyl terephthalate, cellophane, cellulose derivatives such as cellulose acetate, polyethylene, polypropylene. , Polystyrene, polyphenylene sulfide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, nylon, polyimide, polyvinyl alcohol, fluororesin, chlorinated rubber, ionomer and the like. 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 material may be appropriately selected depending on the application and material so that the mechanical strength, thermal conductivity and the like are appropriate, and generally, for example, about 1.5 to 50 μm, preferably 2 About 10 μm is suitable.

The thermal transfer layer 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 contains a heat transferable dye in a binder resin. It is dispersed or dissolved. It is preferable that the binder resin has an appropriate affinity for the dye, and that the dye in the binder resin sublimates (transfers heat) and is transferred to the heat transfer material by heating with a thermal head. Even if the binder resin is used, the binder resin itself that does not transfer is used. As the resin used as such a binder resin, for example, 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, Vinyl resins such as polyvinyl acetate, polyvinyl butyral, polyacrylamide, polyvinyl pyrrolidone, etc.
Examples thereof include polyester and polyamide.

The proportion of the dye contained in the thermal transfer layer varies depending on the sublimation (melting) temperature of the dye, the dyeability, etc., but is preferably 30 parts by weight or more based on 100 parts by weight of the binder resin. More preferably, it is 30 to 300 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 to the base film will tend to be lowered.

A dye which is melted, diffused or sublimated by heat contained in the thermal transfer layer and is transferred to the thermal transfer target, 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 type, triarylmethane type, thiazole type, methine type such as merocyanine, indoaniline, acetophenone azomethine, pyrazoloazomethine, imidazole azomethine, imidazoazomethine, and azomethine type represented by pyridone azomethine. , Xanthene-based, oxazine-based, dicyanostyrene, cyanomethylene-based represented by tricyanostyrene, thiazine-based, azine-based, acridine-based, benzeneazo-based, pyridoneazo, thiophenazo, isothiazoleazo, pyrroleazo, pyrazoleazo, imidazoleazo, Azo series such as thiadiazole azo, triazole azo and disazo, spiropyran series, indinospiropyran series, fluorane series, rhodamine lactam series, naphthoquinone series, anthraquino Systems include the quinophthalone like.

Specifically, for example, the following dyes are used. CI (Color Index) Disperse Yellow 51, 3, 54, 79, 6
0, 23, 7, 141 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 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 35)
4), Waxoline AP-FW (ICI, Solvent Blue 36), magenta dye MS-REDG (Mitsui Toatsu, Disperse Red 60), Macrolex Red Violet R (Bayer, Disperse Violet 26), No. 1 -Foron brilliant yellow S-6GL as dye (made by Sand, Disperse Yellow 231
), Macrolex Yellow 6G (manufactured by Bayer, Disperse Yellow 201), and those having the skeleton shown below.

To provide the thermal transfer layer on the substrate film,
It can be performed by a known method. For example, a dye and a binder resin may be dissolved or dispersed together with a solvent to prepare an ink composition for a thermal transfer layer, which may be provided on a substrate film 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 0.2-5.0μ
A thickness of m, preferably about 0.4 to 2.0 μm is suitable.

The present invention is characterized by having a heat resistant slipping layer containing particles on the surface of the above-mentioned substrate on which the thermal transfer layer is not provided. The heat resistant slipping layer may be made of the same material as a conventionally known material, or may be made of any other material and is not particularly limited. As the binder resin used in the present invention, 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,
And polyvinyl acetal resins such as polyvinyl acetoacetal resin, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose nitrate, cellulose acetate, cellulose resins such as acetic acid / cellulose butyrate, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Thermoplastic resins such as vinyl resins and polyamides can be used.

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 resin particularly preferable 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. Various types of isocyanate curing agents have been conventionally known, but it is preferable to use an aromatic isocyanate adduct. As the aromatic polyisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or 2,4-toluene diisocyanate and
Mixture of 2,6-toluene diisocyanate, 1,5 naphthalene diisocyanate, tolidine diisocyanate, p-
Phenylene diisocyanate, trans-cyclohexane 1,
4-diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate can be mentioned, especially 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or 2,4-toluene diisocyanate and 2 ,
A mixture of 6-toluene diisocyanate is preferred.

As these polyisocyanates, those which are adducted by a known method can be used.
Examples of the —OH agent used for forming an adduct include, for example,
Monomeric polyols such as trimethylolpropane,
Examples thereof include glycols, polyether polyols and polyester polyols. When a heat resistant slip layer is formed using an adduct of an aromatic isocyanate, a moderately hardened film is obtained compared to the case where an isocyanurate is used, so the lubricant added to the heat resistant slip layer easily bleeds. Therefore, there is an effect that good slipperiness is obtained and the running of the thermal head is improved. Further, by using an aromatic isocyanate, it is possible to prevent the dye from migrating to the opposing heat resistant slipping layer side when the transfer sheet is wound and stored. However, when another type of isocyanate, for example, an aliphatic isocyanate (hexamethylene diisocyanate) is used, there is a problem that when the transfer sheet is wound and stored, the dye migrates to the opposite heat resistant slipping layer side. The amount of polyisocyanate used is appropriately in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the binder resin forming the heat resistant layer. -N
The CO / -OH molar ratio is preferably in the range of 0.8 to 2.0.

If the amount of polyisocyanate used is too small, the crosslink density is low and the heat resistance is insufficient, so that printing wrinkles occur and sufficient effects cannot be obtained. 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 It reacts with water to cause problems such as a decrease in the number of crosslinking points with the thermoplastic resin having active hydrogen.

By the way, it is preferable to add a phosphate ester type surfactant to the heat resistant slipping layer in order to improve the slipping property. Examples of the phosphoric acid ester-based surfactant to be used include 1) long-chain alkyl phosphoric acid ester, for example, usually 6 carbon atoms.
To 20 and preferably 12 or 18 carbon atoms saturated or unsaturated higher alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol and the like and mono and / or diesters of phosphoric acid, 2) polyoxyalkylene alkyl ether or polyoxy Phosphoric acid esters such as alkylene alkyl aryl ethers, 3) alkylene oxide adducts of the saturated or unsaturated alcohols (usually 1 to 8 moles added) or 8 to 12 carbon atoms
Nonionic or anionic phosphate ester surfactants such as phosphoric acid mono- or diester salts of alkylphenols or alkylnaphthols (nonylphenol, dodecylphenol, diphenylphenol, etc.) having at least one, preferably 1-2, alkyl groups of Is mentioned.

Although only the above-mentioned phosphoric acid ester type surfactant may be used, since the phosphoric acid ester type surfactant has 1 to 2 equivalents of acid radicals, 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 becomes large, the phosphate ester is decomposed, the pH of the heat resistant slipping layer is further lowered, and the corrosive wear of the thermal head becomes severe. 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 to generate acid radicals by the heat from the thermal head, it is neutralized by the coexisting alkaline substance, so that the corrosion of the thermal head due to the generation of acid groups can be prevented. . Examples of the alkaline substance include oxides of alkali metals or alkaline earth metals, and / or organic amines. Preferred as oxides or hydroxides of alkali metals or alkaline earth metals 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 particularly preferred is magnesium hydroxide.

Preferred organic amines are, for example, mono, di or trimethylamine, mono, di or triethylamine, mono, di or tripropylamine, mono, di or tributylamine, mono, di or tripentylamine, trihexyl. Amine, 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 can be mentioned, particularly preferable amine is non-volatile at room temperature, It has a boiling point of 200 ° C. or higher. These amines exist stably in the heat resistant slipping layer, and when heat is applied from the thermal head to the heat resistant slipping layer, they become fluid and bleed out on the surface, and the phosphate ester surfactant or its decomposition is generated. It easily neutralizes acid radicals generated in the product to prevent corrosion of the thermal head, and at the same time, exhibits excellent lubricity with a 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.

In the present invention, the particles contained in the heat resistant slipping layer are characterized by having a shot abrasion degree of 15 to 100 mg, more preferably 20 to 40 mg. When the abrasion degree is lower than 15 mg, the particles are too soft and are crushed by heat and pressure during printing, resulting in head residue and sticking. When the abrasion degree is higher than 100 mg, the head abrasion resistance deteriorates. Further, by setting the shot type abrasion degree within the above range, since it has sufficient hardness, even if a head residue is generated, it can be scraped off and the accumulation can be prevented.

In the case of the present invention, the particles contained in the heat resistant slipping layer may have only one kind of particles having the above-mentioned characteristics so as to be in the above range, and the shot type abrasion degree may be used. It is also possible to use a mixture of two or more kinds of particles so that the value is within the range of 15 to 100 mg. In the case of mixing, as a result of mixing the particles, it is sufficient that the shot-type wear degree falls within the above range, and two or more kinds of particles having a wear degree within the above range are mixed with each other, or further, within the above range. It suffices to achieve a wear degree that falls within the above range by mixing particles having a wear degree with particles having a wear degree outside the above range. Incidentally, the shot type wear degree used in the present invention, the powder to be measured is put into a glass tube for measurement together with water and shots, and the amount of wear due to the wear of shots is measured by rotating a predetermined number of revolutions. This is a method of defining the degree of wear with this numerical value. However, the shot used here is a lead ball shot (2A) specified by the JIS standard.

Examples of particles having a shot wear degree of 15 to 100 mg include clay minerals such as talc and kaolin, carbonates such as calcium carbonate and magnesium carbonate, hydroxides such as aluminum hydroxide and magnesium hydroxide, and sulfuric acid. Sulfates such as calcium, oxides such as silica, inorganic fine particles such as graphite, glass stone and boron nitride, or acrylic resins, Teflon resins, silicone resins, lauroyl resins,
Phenol resin, acetal resin, polystyrene resin,
Examples thereof include organic resin fine particles made of nylon resin or the like, or crosslinked resin fine particles obtained by reacting these with a crosslinking agent.
However, it should be noted that some of the above-mentioned inorganic fine particles may have a shot type wear degree outside the above-mentioned range due to impurities or the like. 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.

Further, in the present invention, a lubricant such as wax, silicone oil, higher fatty acid amide, ester, interfacial lubricant, etc. may be added within a range not impairing the object of the present invention. In order to provide the heat resistant slipping layer on the base material sheet, the above components are acetone, methyl ethyl ketone,
Toluene, as a heat resistant slipping layer forming ink dissolved in a suitable solvent such as xylene, a gravure coater, a roll coater, a conventional suitable printing method such as a wire bar,
It is formed on the substrate sheet by the coating method. Then 30 ° C
The heat resistant slipping layer may be formed by heating the resin to a temperature of -80 ° C to dry the resin and reacting the resin having an active hydrogen group with isocyanates. The heat resistant slipping layer has a thickness of 0.5 to 5 μm, preferably 1 to 2 μm. When the film thickness is less than 0.5 μm, the effect as the heat resistant slipping layer is not sufficient, and when it is more than 5 μm, the heat transfer from the thermal head to the dye layer is deteriorated and the print density is lowered. There are drawbacks. 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 constitution as described above, and 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. . In addition, if necessary,
An antistatic agent may be added to at least one of the heat resistant slipping layer and the thermal transfer layer. The antistatic agent used here is appropriately selected according to the compatibility with the base film, the dye layer, or the resin used for heat-slip resistance, 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, pyridine derivatives, and anionic antistatic agents. As an agent,
Sulfated oils such as sodium ricinoleate sulfate, soaps such as fatty acid salts, sulfated ester oils such as sodium lysylate sulfate sulfates, sulfated amide oils such as sulfated ethylaniline oleate, sulfated salts of olefins Sulfate ester of fatty alcohol such as oleyl alcohol sulfate soda salt, alkyl sulfate salt, fatty acid ethyl sulfonate, alkyl sulfonate, condensate of naphthalene sulfonic acid and formalin, succinate sulfonate, phosphate ester Examples of salts and nonionic antistatic agents include partial fatty acid esters of polyhydric alcohols such as sorbitan monofatty acid ester and fatty acid pentaerythritol, fatty alcohol, fatty acid, fatty amino, fatty acid amide, alkylphenol, alkylnaphthol, and polyhydric alcohol. Ethylene oxide adducts such as partial fatty acid esters of the call, polyethylene glycol, as the amphoteric antistatic agent, carboxylic acid derivatives, imidazoline derivatives, and the like.

When the heat resistant slipping layer 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. 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, since sodium alkane sulfonate has a high melting point, when it is used as an antistatic agent, there is 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. From the fact that
Particularly preferred.

For example, in the case of a base film made of polyethylene terephthalate, which is a polyester film, after kneading fine particles into a resin, an unstretched film is first melt-extruded by a T-die method, and then this is subjected to a tenter system. A final biaxially stretched film is obtained by a sequential biaxial stretching machine. For polyethylene terephthalate,
It is extruded as a molten film from a T-die at a temperature of about 290 to 320 ° C. and rapidly cooled and solidified on a casting drum to give an unstretched film. At this time, an electrostatic contact method may be used to hold the film on the drum. The biaxial stretching is roughly classified into a sequential biaxial stretching method and a simultaneous biaxial stretching method, but the sequential biaxial stretching method is generally used in terms of efficiency and the like.
In the sequential biaxial stretching method, usually, the material is first stretched in the machine direction (longitudinal) and then in the width direction (lateral). First, the above unstretched film is heated to a temperature of 80 to 90 ° C. by a longitudinal stretching machine and stretched to about 2.5 to 4.5 times. Stretching is performed by utilizing the difference in speed between rolls. Next, with a tenter, 95-110 ℃
It is heated to the temperature of and is stretched 3 to 4 times. Next, in order to improve heat resistance by removing crystallization and residual strain, 180
Heat treatment is performed by applying hot air for 2 to 5 seconds at a temperature of to 260 ° C. When the film is transversely stretched after the above-mentioned longitudinal stretching and then longitudinally stretched again, or conversely, when the film is transversely stretched and then longitudinally stretched, a film having particularly high strength in the longitudinal direction can be obtained.

The thermal transfer sheet may be a single sheet cut to a required size, may be continuous or wound, and may be narrow tape. 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. However, in the case of paper, metal, glass, or synthetic resin having no dye-receptive property, a dye-receptive layer may be formed on at least one surface thereof. As the transferred material which does not need to form a dye receiving layer, any of those conventionally used in this method can be used, and examples thereof include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride and the like. Of halogenated polymers, vinyl polymers such as polyvinyl acetate and polyacrylic acid esters, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polystyrene resins, polyamide resins, olefins such as ethylene and propylene, and other vinyl monomers Examples thereof include copolymer resins, 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. Further, even for paper, metal, glass, or other non-dyeing transfer material, the solution or dispersion of the dyeing resin as described above is applied to the recording surface and dried, or By laminating a resin film, a material to be transferred can be obtained.
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 the range not impairing the initial purpose. . 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.
Although it can be used satisfactorily as it is, the transfer-receiving material or the dye-receiving layer thereof can contain an inorganic powder for tackiness prevention, which makes it possible to increase the temperature during thermal transfer. Adhesion between the thermal transfer sheet and the transfer target 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 0.5 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 at a thickness of about 0.01 to 5 μm, and prevents the thermal transfer sheet from sticking to the dye receiving layer,
The dye receptivity can be further improved.

[0030]

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. (Example 1) Polyethylene terephthalate (manufactured by Diafoil Hoechst Co., Ltd., K203E4.5W) as a base film,
(A thickness of 4.5 μm), one side of which is coated with a coating solution for a heat resistant slipping layer having the following composition so as to have a thickness of 1 μm when dried using Miyabar # 5, and further dried at 60 ° C. It was heat-aged in an oven for a day and then cured 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 (Daiichi Kogyo Seiyaku Co., Ltd. Prysurf A208S) Phosphate Na salt 0.9 parts (Toho Chemical Industry Co., Ltd. Phosphanol RD720) Talc (Nippon Talc) 0.6 parts ( Shot type abrasion degree = 15 mg) Magnesium hydroxide 0.3 part (Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts Next, on the surface opposite to the surface on which the heat resistant slipping layer of the base film is formed, The following dye layer forming ink has a thickness of 1μm when dried.
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 68.2 parts Methyl ethyl ketone 22. 5 copies

Example 2 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 surfactant Agent 2.8 parts (Daiichi Kogyo Seiyaku Co., Ltd. Prysurf A208S) Kaolin clay 0.6 part (ECC Japan Co., Ltd.) (Shotshot wear degree = 26.2 mg) Magnesium hydroxide 0.3 parts ( Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 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 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 (Prysurf A208S manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.9 part of phosphoric acid ester Na salt (Fosphanol RD720 manufactured by Toho Chemical Industry Co., Ltd.) 0.6 part talc (manufactured by Nippon Talc) ( Shot type wear degree = 51.6 mg) Magnesium hydroxide 0.3 part (Kyowa Chemical Industry Co., Ltd. Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 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 surfactant Agent 2.8 parts (Prysurf A208S manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Silica (manufactured by Tatsumori) 0.6 parts (shot type wear degree = 96.1 mg) Magnesium hydroxide 0.3 parts (Kyowa Chemical Industry ( Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts

Example 5 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 surfactant Agent 2.8 parts (Daiichi Kogyo Seiyaku Co., Ltd. Prysurf A208S) Talc (manufactured by Nippon Talc) 0.54 parts (shot type wear degree = 11 mg) Talc (manufactured by Nippon Talc) 0.04 parts (shot type wear Degree = 170 mg) 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 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.) Cross-linked acrylic resin particles 0.6 parts (Soken Chemical Co., Ltd. MR-7HG) (Shot-type abrasion degree = 10 mg) Magnesium hydroxide 0. 3 parts (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 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.) Silica (manufactured by Tatsumori) 0.6 parts (shot type wear degree = 178.2 mg) Magnesium hydroxide 0.3 parts (Kyowa Chemical Industry ( Kisuma 5A) Toluene 85 parts Methyl ethyl ketone 85 parts

(Comparative Example 3) 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.) Calcium carbonate (manufactured by Shiraishi Calcium) 0.6 parts (Shot-type abrasion degree = 150.7 mg) Magnesium hydroxide 0.3 parts (Kyowa Chemical Industry Co., Ltd. Kisuma 5A manufactured by Co., Ltd. Toluene 85 parts Methyl ethyl ketone 85 parts

With respect to the thermal transfer sheets of the above-mentioned Examples and Comparative Examples, the results of evaluation of shot-type wear degree and sticking, head residue, and head wear as running performance in the printer are shown in Table 1. The evaluation method was as follows. Shot type abrasion degree 5 g of particles are weighed and placed in a well-washed beaker. Add 45 cc of water to the beaker containing the particles and stir. Rinse the shot (Nikkosha Kogyo Co., Ltd., 2A tiger mark) thoroughly with water, and wipe off the moisture completely with a dry cloth. Accurately weigh 6 shots (A) with an analytical balance. Weigh the shot into a beaker of water and particles. This beaker is a shot-type wear tester (Osaka Kikai, NTL-318-
Type 02) and stir 37,500 times (about 5.5 hours). Remove the shot from the beaker, wash it thoroughly with water, and wipe it dry with a dry cloth. The weight (B) of these 6 shots is weighed on an analytical balance. (A) to (B)
The value obtained by subtracting is taken as the degree of wear. Sticking The dye layer side of the thermal transfer sheet and the transfer material formed as described below were overlaid, and a gradation pattern of 8 gradations was printed using a commercially available video printer (VY-170 manufactured by Hitachi, Ltd.). Occurrence of sticking was visually evaluated and evaluated according to the following criteria. Printing wrinkles ∘: No sticking occurs X: Sticking occurs Note that the material to be transferred used for evaluating the performance of the printer was prepared as follows. Synthetic paper (Yupo FPG150, manufactured by Oji Yuka Co., Ltd.) was used as a base material, and a coating solution for the 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. Then 13
A material to be transferred was prepared by drying at 0 ° C. for 3 minutes. 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

Head residue was printed in the same manner as sticking, and the surface of the thermal head was observed with a microscope to examine the presence or absence of head residue. Head cass ・ ・ ・ ○: No head shavings △: A little head shavings ×: A large amount of head shavings Head abrasion Head solid printing is performed using a printer of the same model as sticking, and this is repeated 3000 screens, then the thermal head surface Was observed under a microscope to check for wear. Head wear ∘: No head wear △: Some head wear ×: Head wear is considerably advanced

[0040]

[Table 1]

[0041]

EFFECTS OF THE INVENTION As in the present invention, when the particle diameter of the particles contained in the heat resistant slipping layer is set to 15 to 100 mg, the particles are too soft and are crushed by the heat and pressure of printing.
It can be prevented from causing a head residue, and in the above range, even if a head residue occurs, it can be scraped off because it has sufficient hardness. Further, by setting the upper limit to 100 mg, it is possible to provide a thermal transfer sheet that does not cause head wear.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nobuyuki Harada 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd.

Claims (4)

[Claims] 1. A heat transfer sheet having a heat transfer layer provided on one surface of a base material and a heat resistant slipping layer containing particles on the surface of the base material opposite to the heat transfer layer. A thermal transfer sheet having a shot abrasion degree of 15 to 100 mg. 2. The particles contained in the heat resistant slipping layer are a mixture of two or more kinds of particles having different shot-type abrasion degrees, and the mixture has a shot-type abrasion degree of 15 to 1 measured.
The thermal transfer sheet according to claim 1, wherein the thermal transfer sheet is 00 mg. 3. The particles are at least one selected from the group consisting of clay minerals, silica, calcium carbonate, magnesium carbonate, magnesium hydroxide, crosslinked acrylic resin particles, crosslinked polystyrene resin particles, and silicone resin particles.
The thermal transfer sheet according to claim 1, which is a seed. 4. The heat resistant slipping layer further contains a thermoplastic resin containing an active hydrogen group, polyisocyanate, and a phosphoric acid ester-based surfactant, according to claim 1. Thermal transfer sheet.