JP2000103178A - Thermal transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermal transfer sheet having heat resistance, coating properties, slip properties and the like in addition to antistatic properties and corrosion preventive properties, and also provided with thermal head-traveling properties and good antistatic properties (and a heat-resistant lubricant layer) preventing the accumulation of refuses in a thermal head and the wear of the thermal head. SOLUTION: A heat melting ink layer 2 is formed on one face of a base sheet 1, and a heat-resistant lubricant layer 3 is formed on the other face of a thermal transfer sheet, and a primer layer 4 is formed between the base sheet 1 and the heat-resistant lubricant layer 3, and the primer layer 4 contains an organic electroconductive material formed of a compound of terpene skeleton into which a sulfonic group and/or a group of its salt is introduced.

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 particularly to a novel thermal transfer sheet made of a specific material and having excellent antistatic properties.

[0002]

2. Description of the Related Art Conventionally, as a thermal transfer sheet, there has been known a thermal transfer sheet in which a heat-fusible ink layer comprising a coloring agent such as a pigment and a binder such as a wax is provided on one surface of a polyester film or the like. These thermal transfer sheets are heated imagewise from the back by a thermal head,
The image is formed by transferring the ink layer to a material to be transferred.

[0003]

When an image is formed by a thermal head using the above-mentioned thermal transfer sheet, and when the base film is a thermoplastic film such as a polyester film, the surface specific resistance of the surface contacted by the thermal head is determined. because there high as 10 ¹⁴ or more, static electricity is generated at the time of image formation, it is liable to charge.

When the thermal transfer sheet is charged, dust and the like tend to adhere to the surface thereof. As a result, dust and the like adhere to the thermal head, and there is a problem that the resolution of the formed image is reduced. Further, similarly, the transfer material such as paper is charged, which causes a problem in the transportability of the transfer material. In the worst case, sparks may be generated when a thermal transfer roll or a material to be transferred is replaced or inserted, or a shock may be given to the human body.

As a method for solving such a problem, it is known to form an antistatic layer on the back surface of the thermal transfer sheet. When the antistatic layer is formed with a surfactant or the like, the thermal transfer sheet becomes sticky, or when the thermal transfer sheet is wound into a roll, the antistatic agent migrates to the heat-meltable ink layer, or conversely. There is a problem that the ink moves to the back surface. In addition to these problems, there is a problem that the antistatic effect of the antistatic layer decreases with time.

As another method, there is a method of forming a conductive layer using a conductive agent such as conductive carbon black and a binder. However, in this case, a thermal head is severely abraded, and a thermal transfer sheet other than black is used. In such a case, there is a problem that not only the entire color becomes black and the appearance is inferior, but also it becomes difficult to detect the detection mark formed on the thermal transfer sheet.

As a method for solving the above problems, there has been proposed a method of forming an antistatic layer with an acrylic resin having a quaternary ammonium salt group (Japanese Patent Laid-Open No. Hei 2 (Kokai)).
182491), but the anion of the quaternary ammonium base is usually a chloride ion or a bromide ion,
Another problem arises in that the halogen head is significantly corroded by these halogen ions.

As another problem, since the thermal head is heated to a high temperature, the thermal head is fused to the base film, and the good running property of the thermal head is hindered.
There is a problem that the thermal transfer sheet is damaged or wrinkled. Such a problem cannot be solved by the heat-resistant lubricating layer composed of the acrylic resin having a quaternary ammonium base.

As a method for solving these problems, a method is known in which a back layer made of a heat-resistant resin is formed on the contact surface of the thermal head. It is difficult to form a thin coating to a degree that is not so large. Further, even if the thermal head can be formed, the slip property of the thermal head is insufficient, and the running property of the thermal head cannot be satisfied.

On the other hand, it is also known to form a slip layer using silicone oil or silicone wax. However, these silicone oils or waxes have low film strength, are scraped off by a running thermal head, and residue is deposited on the thermal head. Therefore, there is a problem that good printability cannot be obtained. Accordingly, an object of the present invention is to provide a thermal head having excellent heat resistance, coating properties, slip properties, etc. in addition to antistatic properties and corrosion prevention properties, good thermal head runnability, and accumulation of scum on the thermal head. An object of the present invention is to provide a thermal transfer sheet having a good antistatic property (and a heat-resistant lubricating layer) which does not cause abrasion.

[0011]

The above object is achieved by the present invention described below. That is, the present invention provides a heat transfer sheet in which a heat-fusible ink layer is formed on one surface of a base sheet and a heat-resistant slip layer is formed on the other surface. A primer layer is formed between
A thermal transfer sheet characterized in that the primer layer contains, as an antistatic agent, an organic conductive material obtained by introducing a sulfonic acid group and / or a salt group thereof into a compound having a terpene skeleton, and a thermal transfer sheet having another structure. It is.

A heat transfer sheet having a heat-resistant lubricating layer which is excellent in antistatic properties and does not corrode a thermal head by containing a specific organic conductive material in a primer layer between a base film and a heat-resistant lubricating layer of a thermal transfer sheet. A sheet is provided.

In a further preferred embodiment, the heat-resistant lubricating layer is formed from a reaction product of a thermoplastic resin having a hydroxyl group such as polyvinyl butyral and a polyisocyanate.
Provided is a thermal transfer sheet having a good antistatic property and a heat-resistant lubricating layer that is excellent in film properties, slip properties, etc., has good running properties of a thermal head, and does not accumulate residues on the thermal head or wear the thermal head. be able to.

[0014]

Next, the present invention will be described in more detail with reference to preferred embodiments. FIG. 1 is a diagram schematically illustrating a first embodiment of the present invention. As shown in the drawing, in one example of the thermal transfer sheet of the present invention, a heat-fusible ink layer 2 is formed on one surface of a base sheet 1, and a heat-resistant lubricating layer 3 is formed on the other surface via a primer layer 4. A thermal transfer sheet formed, wherein the primer layer contains, as an antistatic agent, an organic conductive material obtained by introducing a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton.

FIGS. 2 to 4 schematically illustrate another embodiment of the present invention. When the primer layer is not formed (or does not need to be formed) in the example shown in FIG. The conductive material can be added to the heat-resistant lubricating layer 3 (FIG. 2). When a release layer and / or a mat layer 5 is formed between the base film 1 and the hot-melt ink layer 2 as shown in FIG. 3, these layers 5 include the organic conductive material. Can be done. As shown in FIG. 4, when an adhesive layer or a surface layer 6 is formed on the surface of the hot-melt ink layer 2, the organic conductive material can be included in these layers 6. Hereinafter, the first embodiment will be described as a representative example.

As the base sheet used in the thermal transfer sheet of the present invention, any base sheet having a certain degree of heat resistance and strength known in the art may be used.
Paper having a thickness of about 50 μm, preferably about 3 to 10 μm;
Various processed papers, polyester films, polystyrene films, polypropylene films, polysulfone films, aramid films, polycarbonate films, polyvinyl alcohol films, cellophane, and the like, with polyester films being particularly preferred. These base sheets may be of a single-wafer type or a continuous film, and are not particularly limited. Of these, polyethylene terephthalate film is particularly preferable, and it is also preferable to form a primer layer or an adhesive layer on one or both surfaces of the film, if necessary.

The antistatic primer layer formed on one side of the base sheet is a compound having a binder having good adhesion to both the base film and the heat-resistant lubricating layer and a compound having a terpene skeleton as an antistatic agent. A sulfonic acid group and / or
Alternatively, it is formed mainly of an organic conductive material into which a salt group is introduced. As the binder, any of conventionally known binder resins can be used.For example, polyester resins, polyurethane resins, polyacrylate resins, polyvinyl formal resins, polyvinyl butyral resins, epoxy resins, polyamide resins, Solvents or water-soluble resins such as polystyrene resins, styrene-acryl copolymer resins, chlorinated polypropylene resins, and polyether resins are exemplified. The binder resin is used after being dissolved in a solvent or as an aqueous emulsion (aqueous dispersion). These binder resins are desirably selected and used in consideration of the adhesion to a molded article to be antistatic. In particular, polyester resins are preferred for polyethylene terephthalate films and sheets.

Preferred compounds as the organic conductive material used as the antistatic agent in the present invention are compounds represented by the following formulas 1 to 5, but the present invention is not limited thereto.

[0019]

[0020]

[0021]

[0022] (X ₁ , X ₂ , X ₃ and X ₄ in the above formula are the same or different,
It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. Ya, Yb and Yc are the same or different and represent a proton (H ⁺ ) or a positive ion of a basic compound, and n is 0
Represents an integer of １５15. The organic conductive material as described above can be obtained from Yashara Chemical Co., Ltd. and used in the present invention, or can be manufactured and used as follows.

As the terpene compound as a raw material for producing the organic conductive material, a monoterpene compound having 10 carbon atoms is generally used. The monoterpene compound may be a monocyclic terpene compound or a bicyclic terpene compound. Specifically, for example, α-pinene, β-pinene, dipentene, limonene, α-pherandrene, β-pherandrene, α-terpinene, γ-terpinene, terpinolene, 1,8-cineole, 1,4- Examples include, but are not limited to, cineol, α-terpineol, β-terpineol, γ-terpineol, paramentadienes, and the like. These monoterpene compounds are generally raw materials that can be industrially obtained as components of plant essential oils and rosins.

Examples of the phenols used as a raw material for producing the organic conductive materials represented by the general formulas 1 to 4 include phenol or a phenol compound having a substituted alkyl group and / or hydroxyl group having 1 to 5 carbon atoms. No. Specifically, examples of the phenol compound to which an alkyl group having 1 to 5 carbon atoms is added include o-cresol, p-cresol, m-cresol, 2,6-xylenol,
4-xylenol, propylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p
-Butylphenol, 2,3-xylenol, 2,4-
Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,6-xylenol, compounds such as p-phenylphenol,
It is not limited to these compounds. In addition, the phenol compounds substituted with hydroxyl groups include catechol, resorcinol,
Examples include compounds such as hydroquinone and pyrogallol, but are not limited to these compounds.

Examples of the alkyl sultone used as a raw material for producing the compounds having the organic conductivity represented by the general formulas 3 and 4 include 1,3-propane sultone and 1,4-butane sultone. But
It is not limited to these compounds. The above alkyl sultones have 0 to 15 carbon atoms, preferably 1 to 8 carbon atoms. Compounds represented by the above-mentioned general formulas 1 and 2 in which one molecule of terpene is reacted with two molecules of phenol and further a sulfonic acid group is introduced, for example, are obtained by reacting a monoterpene compound with a phenol and further sulfonating the compound. Can be manufactured. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound.

The reaction between one molecule of terpene and two molecules of phenols is, for example, using 0.5 to 20 moles, preferably 2 to 12 moles of phenols per mole of monoterpene, in the presence of an acidic catalyst. At a temperature of 40-160 ° C.
The reaction is carried out for 10 to 10 hours. Examples of the acidic catalyst used in this case include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or a complex thereof, a cation exchange resin, a heteropolyacid, and activated clay. In this reaction, a reaction solvent need not be used, but a solvent such as an aromatic hydrocarbon, an alcohol, or an ether can also be used.

The sulfonation of the reaction product of one molecule of terpene and two molecules of phenols is usually carried out by reacting with a sulfonating agent such as sulfuric acid, sulfuric anhydride, fuming sulfuric acid and chlorosulfonic acid. Can be. The reaction temperature for the sulfonation is usually from -50 to 150C, preferably from 0 to 100C. When the reaction temperature is lower than −50 ° C., the reaction rate is low, and when it exceeds 150 ° C., side reactions such as resinification become remarkable, which is not preferable. or,
A solvent may not be used in the sulfonation reaction, but usually a lower alcohol such as methanol or a chlorine-based solvent such as dichloroethane or ethylene dichloride is used. The target substance can be obtained by directly collecting the solvent and concentrating and purifying the obtained sulfonated product.However, since the sulfonating agent usually remains in the reaction product, a recrystallization method using a solvent or a dialysis membrane is used. By performing purification, a highly pure sulfonated product can be obtained.

Examples of the basic compound used for producing the sulfonate of the compound represented by the general formulas 1 and 2 include, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and ammonia. , Pyridine,
Examples include, but are not limited to, organic bases such as triethylamine and tetramethylammonium hydroxide.

Preferable specific examples of the organic conductive materials represented by the general formulas 1 and 2 include, for example, JP-A-8-198.
No. 791 which is a sulfonated terpene diphenol compound represented by the following chemical formula 1 and a compound of the following chemical formula 2 which is an analog thereof.

[0030]

[0031]

Next, two molecules of phenol are added to one terpene molecule.
Production of the compounds represented by the above general formulas 3 and 4 obtained by reacting a molecule and further reacting an alkyl sultone is
As in the case of the compound represented by the chemical formula 1, the reaction can be carried out by reacting a monoterpene compound with a phenol and then reacting an alkylsultone.
Further, the sulfonate is produced by subjecting the above-mentioned reaction product with the alkyl sultone to an acid-base reaction with the above-mentioned basic compound.

The reaction between one molecule of a terpene and two molecules of a phenol is carried out in the same manner as in the case of the compounds represented by the above general formulas 1 and 2. One molecule of terpene and phenols 2
The reaction between the reactant with the molecule and the alkyl sultone can be usually carried out by reacting the alkyl sultone in the presence of a catalyst. As the catalyst, for example, lithium hydride, sodium hydride, potassium hydride and the like can be used. In that case, the reaction is usually carried out using a solvent such as dimethylacetamide. The reaction temperature with the alkyl sultone is usually from 0 to
Performed at 150 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate is low, and when the reaction temperature is higher than 150 ° C., side reactions become remarkable, which is not preferable.

The obtained reaction product is dissolved in purified water, purified by a dialysis membrane, and the catalyst is removed to obtain a compound having a sulfonic acid group at the end. As the dialysis membrane used at that time, for example, cellulose ester or the like is used, but is not limited thereto. Examples of the basic compound used for producing the sulfonate of the reaction product with the obtained alkyl sultones include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia, pyridine and triethylamine. And organic bases such as tetramethylammonium hydroxide, but are not limited thereto.

As another method for producing this sulfonate, when a reaction product of one molecule of a terpene and two molecules of a phenol is reacted with an alkylsultone, the reaction is carried out in the presence of a basic compound without a catalyst. In this way, a target substance having a terminal sulfonate can be obtained. Further, the sulfonic acid salt is subjected to ion exchange with sulfuric acid or hydrochloric acid, dissolved in purified water, and purified by a dialysis membrane, whereby the terminal can be converted into a compound having a sulfonic acid group.

Preferred specific examples of the organic conductive material represented by the general formula 3 include, for example, JP-A-8-1987.
No. 91, a compound of the following chemical formula 3 obtained by reacting 1,3-propanesultone with a terpene diphenol compound. A preferred specific example of the organic conductive material represented by the general formula 4 is a compound represented by the following chemical formula 3.
A compound of the following chemical formula 4, which is an analog of the compound of

[0037]

[0038]

Next, a method for producing a compound in which a sulfonic acid group is introduced into the terpene-based aromatic compound represented by the above general formula 5 is usually carried out by converting the terpene-based aromatic compound into sulfuric acid, sulfuric anhydride,
The reaction can be carried out using a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid. The sulfonate is produced by further subjecting the sulfonated product to an acid-base reaction with a basic compound. The method of sulfonation and the method of producing the sulfonate can be carried out in the same manner as in the compound of the above-mentioned general formula 1. Preferred examples of the compound represented by Formula 5 are shown in Chemical Formula 5 below.

[0040]

The primer layer in the present invention is formed by using the above binder and the above organic conductive material as main components.
Examples of the formation method include dissolving or dispersing in an appropriate solvent such as methyl ethyl ketone, acetone, toluene, and xylene, and a solvent containing water, for example, water and a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol. To prepare a coating solution in which the binder and the organic conductive material are dissolved.
An optional additive such as a surfactant for improving the wettability of the base sheet during coating and an antifoaming agent for suppressing bubbles can be added to the coating liquid.

The composition of the coating solution for the primer layer is such that the binder resin is about 2 to 30% by weight, preferably 3 to 15% by weight, and the organic conductive material is about 0.1 to 30% by weight, preferably 0.25% by weight. Compositions comprising up to 15% by weight and the balance of solvent are preferred. The primer layer is formed by applying and drying the above-mentioned coating solution on one surface of the substrate sheet by a conventional coating method such as a gravure coater, a roll coater, and a wire bar.

The coating amount was about 0.02 as a solid content of the coating liquid.
１．０1.0 g / m ² , preferably about 0.07-0.2 g / m ²
in the range of m ^2, the coating amount is less than the above range, an insufficient performance as a primer layer and an antistatic layer, whereas, even coating amount exceeds the above range, in proportion to its thickness This does not mean that the above performance is improved, which is not only economically disadvantageous but also unfavorably lowers the thermal conductivity from the thermal head to the sublimable dye layer.

In the present invention, a heat-resistant lubricating layer is formed from a thermoplastic resin on the surface of the above-mentioned primer layer (antistatic layer). As the thermoplastic resin, polyester resin, polyacrylate resin, polyvinyl acetate resin, styrene acrylate resin, polyurethane resin, polyolefin resin, polystyrene resin, polyvinyl chloride resin, polyether resin , Thermoplastic resins such as polyvinyl acetal resins such as polyamide resins, polycarbonate resins, polyethylene resins, polypropylene resins, polyacrylate resins, polyacrylamide resins, polyvinyl chloride resins, polyvinyl butyral resins, and polyvinyl acetoacetal resins, or silicones thereof. Modified products and the like are used, and among these, particularly preferred resins are polyvinyl acetal resins such as polyvinyl butyral resins and polyacetoacetal resins, and silicone modified products thereof. A resin having a hydroxyl group which reacts with a cyanate group.

In a preferred embodiment of the present invention, it is preferable to use a polyisocyanate as a crosslinking agent in order to impart heat resistance, coating properties and adhesion to the primer layer to the heat-resistant lubricating layer. As these polyisocyanates, any of the conventionally known polyisocyanates used in the synthesis of paints, adhesives, polyurethanes and the like may be used. These polyisocyanate compounds include, for example, Takenate (manufactured by Takeda Pharmaceutical), Vernock (manufactured by Dainippon Ink and Chemicals), Coronate (manufactured by Nippon Polyurethane), Duranate (manufactured by Asahi Kasei Kogyo), DisModule (manufactured by Bayer)
And can be used in the present invention.

The amount of the polyisocyanate added is 5 to 2 parts by weight per 100 parts by weight of the resin binder constituting the heat-resistant lubricating layer.
A range of 00 parts by weight is suitable. The ratio of NCO / OH is preferably in the range of about 0.8 to 2.0. If the content of the polyisocyanate is too small, the crosslinking density is low and the heat resistance is insufficient. On the other hand, if the content is too large, the shrinkage of the formed coating film cannot be controlled, the curing time is prolonged, and the unreacted NCO group is heat-resistant. It acts in the negative layer, such as remaining in the conductive layer and reacting with moisture in the air.

In the present invention, when a heat-resistant lubricating layer is formed from the above-mentioned materials, a heat-releasing type of wax, higher fatty acid amide, ester, surfactant or the like is used for the purpose of improving the slip property of the heat-resistant lubricating layer. An organic powder such as an agent, a lubricant or a fluororesin, and inorganic particles such as silica, clay, talc, and calcium carbonate can be included.

To form the heat-resistant lubricating layer, the above-mentioned materials are dissolved or dispersed in a suitable solvent such as acetone, methyl ethyl ketone, toluene, xylene or the like to prepare a coating solution, and this coating solution is gravure-coated. Coater, roll coater,
It is formed by coating and drying by a conventional coating means such as a wire bar, and then performing a crosslinking treatment by a heat treatment. The coating amount, that is, the thickness of the heat-resistant lubricating layer is also important, and in the present invention, the solid content is 2.0 g / m ² or less,
Preferably, a heat-resistant lubricating layer having sufficient performance can be formed at a thickness of 0.1 to 1.0 g / m ² .

In the present invention, on the other surface of the base film,
If necessary, a heat-fusible ink layer is formed via a release layer and / or a mat layer. The hot-melt ink comprises a colorant and a vehicle, and may further contain various additives as necessary. As the coloring agent, among organic or inorganic pigments or dyes, those having good characteristics as a recording material, for example, having a sufficient coloring density, light,
Those which do not discolor by heat, temperature, etc. are preferred. Further, a substance which is colorless when not heated but develops a color when heated, or a substance which develops a color when it comes into contact with a substance applied to a transfer-receiving body may be used. Cyan, magenta, yellow,
In addition to the black-forming colorants, various other colorants can also be used.

The ink layer to be formed is formed by selecting one color from the above colorants when the desired image is a monocolor, and when the desired image is a full color image,
For example, by selecting appropriate cyan, magenta, and yellow (and, if necessary, black) colorants, yellow,
An ink layer of magenta and cyan (and black if necessary) is formed.

As the vehicle, a mixture containing wax as a main component and other derivatives of wax, such as drying oil, resin, mineral oil, cellulose and rubber, is used. Representative examples of the wax include microcrystalline wax, carnauba wax, and paraffin wax. Furthermore,
Various waxes such as Fischer-Tropsch wax, various low molecular weight polyethylene, wood wax, beeswax, spermaceti, Ibota wax, wool wax, shellac wax, candelilla wax, petrolatum, partially modified wax, fatty acid ester, and fatty acid amide are used. In addition, a heat conductive substance can be added to the heat fusible ink in order to provide the heat fusible ink layer with good heat conductivity and melt transferability. These substances include carbonaceous substances such as carbon black, aluminum, copper, tin oxide, molybdenum dioxide and the like.

As a method for forming a hot-melt ink layer on the surface of a substrate film (or the surface of a release layer and / or a mat layer), a hot-melt coat, a hot lacquer coat, a gravure coat, a gravure reverse coat, Examples of the method include a method of applying the above ink by roll coating and other various means. The thickness of the ink layer to be formed should be determined so as to balance the required density with the heat sensitivity, and is in the range of 0.1 to 30 μm, preferably 1 to 20 μm.
m.

In the example shown in FIG.
A release layer and / or a mat layer 5 is formed between the ink and the heat-meltable ink layer 2. The release layer promotes good release of the ink layer at the time of printing, and has a melting point or a softening point which is somewhat lower than that of the vehicle constituting the ink layer. It is formed to a thickness of 0 μm.
Suitable materials for the release layer can be readily selected from among the vehicles for the ink layer. Such a release layer also serves as a protective layer for an image formed after printing.

The mat layer is for imparting a matting effect to a printed image, and is formed by dispersing an inorganic pigment as a matting agent, for example, silica or calcium carbonate, in an appropriate resin solution. The ink can be formed to a thickness of about 0.05 to 1.0 μm by a gravure printing method or the like, for example. In one embodiment of the present invention, the organic conductive material can be included in the above layer instead of or in addition to the primer.

Further, in the present invention, an adhesive layer or a surface layer can be formed on the surface of the ink layer. The adhesive layer improves the adhesiveness to the transfer paper at the time of transfer and promotes the transferability of the ink layer. As a material forming the adhesive layer, a thermoplastic resin having a relatively low melting point, for example, ethylene /
A hot melt adhesive such as a vinyl acetate copolymer is preferably used. The surface layer, for example, when printing on rough paper, fills the unevenness of the rough paper to promote uniform printing. The material used to form the surface layer is the same as the wax used in the above-described ink layer. In one embodiment of the present invention, the organic conductive material can be included in the above layer instead of or in addition to the primer.

A known thermal transfer printer can be used as it is, without any particular limitation, as a printer used for performing thermal transfer using the above-mentioned thermal transfer sheet and various kinds of paper or a suitable recording paper such as a plastic film.
In the above description, the present invention has been described with reference to an example in which the heat-resistant lubricating layer is mainly formed on the base material sheet via the primer layer. When the adhesion of the heat-resistant lubricating layer to the substrate sheet is good, as shown in FIG. 2, the organic conductive material, which is an antistatic agent, is added to the primer layer by the same method as described above. It is also possible to add antistatic properties to the heat-resistant lubricating layer by adding to the heat-resistant layer.

[0057]

Now, the present invention will be described in further detail with reference to Synthesis Examples, Examples and Comparative Examples. In the following, parts and percentages are by weight unless otherwise specified. Synthesis Example 1 [Synthesis Example of Compound Represented by Chemical Formula 1] Phenol 564 g in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser.
And after charging 34 g of a strongly acidic cation exchange resin,
While maintaining the temperature at ° C., 136 g of α-pinene was added dropwise over 4 hours, and then reacted by stirring for 2 hours. Next, the cation exchange resin was removed from the mixture by filtration, and the obtained reaction solution was washed twice with distilled water.
The mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of Hg to distill off residual phenol and by-products to obtain a pale yellow resin. This pale yellow resinous material was purified by repeating recrystallization using a solvent (toluene) to obtain 32 g of a white crystal of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 32 g of the above white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube, and then kept at a temperature of 5 ° C. Sulfuric anhydride 15.8g
Was added dropwise over 1 hour, and then reacted by stirring for 4 hours.
The reaction product was concentrated to dryness at 40 ° C. under a reduced pressure of 10 mmHg to obtain 45 g of yellow-brown crystals. The obtained crystal was subjected to structural analysis by nuclear magnetic resonance spectrum analysis (NMR) and mass spectrum analysis (MS), and as a result, was identified to be a compound represented by Chemical Formula 1. The obtained crystals had a purity of 93% by weight as determined by high performance liquid chromatography analysis (HPLC).

Synthesis Example 2 [Synthesis Example of Compound Represented by Chemical Formula 2] A pale yellow resinous material was obtained in the same manner as in Synthesis Example 1, and then recrystallized with a solvent (toluene), and the mother liquor was concentrated. To obtain a resinous material. The resinous material was further purified by recrystallization with a solvent (chloroform) to obtain 28 g of a white crystal of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 28 g of the above-mentioned white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube. Chlorosulfonic acid (20.2 g) was added dropwise over 30 minutes, and then stirred for 4 hours to react. The reaction was performed under reduced pressure of 10 mmHg at 50 ° C.
And dried to give 39.6 g of yellow-brown crystals. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 2. The obtained crystals had a purity of 92% by HPLC analysis.
% By weight.

Synthesis Example 3 [Synthesis Example of Compound Represented by Chemical Formula 3] A thermometer, a stirrer, a dropping funnel and a cooling tube equipped with a cooling pipe were prepared.
A 0 ml four-necked flask was charged with 32 g of a white crystal of a terpene diphenol compound obtained in the same manner as in Synthesis Example 1, 130 g of acetonitrile, and 69.8 g of a 25% by weight aqueous solution of tetramethylammonium hydroxide. While maintaining the temperature, 23.7 g of 1,3-propanesultone was added dropwise over 1 hour, and the mixture was stirred and reacted for 2 hours. The reaction product was concentrated to dryness at 70 ° C. under a reduced pressure of 50 mmHg to obtain 67.2 g of white crystals. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 3. The obtained crystals had a purity of 96% by weight according to HPLC analysis.

Synthesis Example 4 [Synthesis Example of Compound Represented by Chemical Formula 4] In the same manner as in Synthesis Example 3, except that 32 g of a white crystal of a terpene diphenol compound obtained in the same manner as in Synthesis Example 2 was used. By operation, 66.8 g of white crystals were obtained. The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a compound represented by Chemical Formula 4. The obtained crystals had a purity of 94% by weight according to HPLC analysis.

Synthesis Example 5 [Synthesis Example of Compound Represented by Chemical Formula 5] A 50 equipped with a thermometer, a stirrer, a dropping funnel and a cooling pipe
After charging 200 g of methanol and 40 g of paracymene into a 0 ml four-necked flask, 23.2 g of sulfuric anhydride was added dropwise over 1 hour while maintaining the temperature at 5 ° C.
The mixture was stirred for an hour to react. The reaction product was concentrated to dryness at 50 ° C. under a reduced pressure of 10 mmHg to give a black-brown viscous body.
5 g were obtained. NMR analysis and MS
As a result of structural analysis by analysis, it was identified as paracymensulfonic acid. The obtained viscous body is H
Purity was 95% by weight by PLC.

Synthesis Example 6 Synthesis Example of Mixture of Compounds Represented by Chemical Formulas 1 and 2 564 g of phenol was placed in a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser.
And after charging 34 g of a strongly acidic cation exchange resin,
While maintaining the temperature at ° C., 136 g of d-limonene was added dropwise over 4 hours, and then the mixture was stirred and reacted for 2 hours.
Next, the cation exchange resin was removed from the mixture by filtration, and the obtained reaction solution was washed twice with distilled water.
The mixture was kept at 250 ° C. for 30 minutes under a reduced pressure of Hg to distill off residual phenol and by-products to obtain a pale yellow resin. The pale yellow resinous material was further distilled by thin-film distillation to obtain 85 g of slightly yellow crystals of a terpene diphenol compound.

Next, 200 g of ethylene dichloride and 32 g of the above white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube. Sulfuric anhydride 15.8g
Was added dropwise over 1 hour, followed by stirring for 4 hours to cause a reaction.
The reaction product was concentrated to dryness at 40 ° C. under a reduced pressure of 10 mmHg to obtain 116 g of tan crystals. NM
As a result of structural analysis by R analysis and MS analysis, it was identified as a mixture of the compounds represented by Chemical Formula 1 and Chemical Formula 2. The obtained crystals had a purity of 87 by HPLC analysis.
In weight%, the composition ratio of the compound of Formula 1 to the compound of Formula 2 was 66:34.

Synthesis Example 7 [Synthesis Example of Mixture of Compounds Represented by Chemical Formulas 3 and 4] Synthesis Example 3 was repeated except that 85 g of white crystals of a terpene diphenol compound obtained in the same manner as in Synthesis Example 6 were used. The same operation as in Example 3 was performed to obtain 177 g of white crystals.
The obtained crystal was subjected to structural analysis by NMR analysis and MS analysis, and as a result, was identified to be a mixture of the compounds represented by Chemical Formulas 3 and 4. The composition ratio of the compound of Formula 3 to the compound of Formula 4 was 66:34.

Example 1 A coating liquid A for a primer layer having the following composition was applied to a 6 μm thick polyethylene terephthalate film as a substrate film so as to be about 0.1 g / m ² when dried, and dried. A coating liquid A for a heat-resistant lubricating layer having the following composition was applied and dried so as to be about 1.0 g / m ² when dried. Further, a curing treatment was performed by heating in an oven at 60 ° C. for 5 days to form a heat-resistant lubricating layer. Next, on the other surface of the base film, a coating liquid A for a hot-melt ink layer having the following composition is heated at a temperature of 100 ° C., and the coating amount is about 4 g / m ² by a roll coating method using hot melt. Thus, a thermal transfer ink layer was formed to prepare a thermal transfer sheet of Example 1 of the present invention.

Coating solution A for primer layer (antistatic layer): 7.5 parts of compound represented by chemical formula 1 Polyester resin (Vylon 200, manufactured by Toyobo Co., Ltd.) 2.5 parts Methyl ethyl ketone 90 parts Coating for heat-resistant lubricating layer Liquid A: Polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical) 5.07 parts Polyisocyanate curing agent (Bernock D750, manufactured by Dainippon Ink) 29.46 parts Oily polyol resin (Olester C1066, manufactured by Mitsui Toatsu Chemicals) 1.48 parts Magnesium hydroxide (Kisuma 5A, manufactured by Kyowa Chemical) 0.36 parts Talc (manufactured by Nippon Talc, Microace L-1) 0.2 parts Talc (manufactured by Nippon Talc, Microace P-3) 0. 7 parts Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 4.22 parts Methyl ethyl ketone 29.255 parts Toluene 29.25 5 copies

Coating liquid A for hot-melt ink layer: carbon black (Diablack G, manufactured by Mitsubishi Kasei) 15 parts Ethylene / vinyl acetate copolymer (EVA Flex 310, manufactured by Mitsui Polychemicals) 8 parts Paraffin wax (paraffin) 150F, made by Nippon Seisaku) 50 parts Carnauba wax 25 parts

Example 2 A thermal transfer sheet of Example 2 was obtained in the same manner as in Example 1 except that the following coating liquid B was used in place of the coating liquid A for forming a primer layer of Example 1. Coating solution B for primer layer (antistatic layer): 7.5 parts of compound represented by chemical formula 2 Polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) 2.5 parts Methyl ethyl ketone 90 parts

Example 3 A thermal transfer sheet of Example 3 was obtained in the same manner as in Example 1 except that the following coating liquid C was used in place of the coating liquid A for forming a primer layer of Example 1. Coating solution C for primer layer (antistatic layer): 7.5 parts of compound represented by chemical formula 3 : Aromatic polyester emulsion resin (Finetex ES-850, manufactured by Dainippon Ink) 8.3 parts Water 39.2 parts Isopropyl alcohol 45 parts

Example 4 A thermal transfer sheet of Example 4 was obtained in the same manner as in Example 1 except that the following coating liquid D was used in place of the coating liquid A for forming a primer layer of Example 1. Coating solution D for primer layer (antistatic layer): 7.5 parts of compound represented by chemical formula 4 : Aromatic polyester emulsion resin (Finetex ES-850, manufactured by Dainippon Ink) 8.3 parts Water 39.2 parts Isopropyl alcohol 45 parts

Example 5 A thermal transfer sheet of Example 5 was obtained in the same manner as in Example 1 except that the following coating liquid E was used in place of the coating liquid A for forming a primer layer of Example 1. Coating solution E for primer layer (antistatic layer): Compound represented by chemical formula 5 2.5 parts Polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) 7.5 parts Methyl ethyl ketone 90 parts

Example 6 A mat layer (2.0 μm thick) was formed between the base film and the hot-melt ink layer using the following coating liquid A without forming the primer layer in Example 1. A thermal transfer sheet of Example 6 was obtained in the same manner as in Example 1, except for the above. Coating solution A for forming mat layer: Compound represented by chemical formula 1 7.0 parts CAP (482-05, manufactured by Kodak) 4.0 parts PET (UE3200, Tg65 ° C, manufactured by Unitika) 3.0 parts Colored carbon ( Seast S, 66mμ, manufactured by Tokai Electrode) 8.0 parts Soybean lecithin (lecithin, manufactured by Ajinomoto) 0.2 parts Crystalline cellulose (KC Floc W400, manufactured by Sanyo Kokusaku Pulp) 3.0 parts Solvent (MEK / toluene = 1/1) ) 74.8 parts

Example 7 Example 7 was repeated except that the primer layer was not formed and the adhesive layer (1.0 μm thick) was formed on the surface of the hot-melt ink layer using the following coating solution A. A thermal transfer sheet of Example 7 was obtained in the same manner as in Example 1. Coating solution A for adhesive layer: Compound represented by chemical formula 1 4.0 parts Ethylene / vinyl acetate copolymer (Evaflex 410) 16.0 parts Toluene 80.0 parts

Comparative Example 1 A thermal transfer sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that the following coating liquid F was used instead of the coating liquid A for forming a primer layer of Example 1. Coating solution F for primer layer (antistatic layer): polyester resin (manufactured by The Inktec, D anchor revised 3) 1 part methyl ethyl ketone 6 parts 1,4-dioxane 3 parts

Comparative Example 2 A thermal transfer sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the following coating liquid G was used instead of the coating liquid A for forming a primer layer of Example 1. Coating solution G for primer layer (antistatic layer): Antistatic agent (TB-34, manufactured by Matsumoto Yushi) 1 part Acrylic resin (manufactured by Mitsubishi Rayon, BR-85) 5 parts Methyl ethyl ketone / toluene = 1: 1 mixed solvent 96 Department

Comparative Example 3 A thermal transfer sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the following coating liquid H was used instead of the coating liquid A for forming a primer layer of Example 1. Coating solution H for primer layer (antistatic layer): carbon black (furnace CB950, manufactured by Mitsubishi Chemical) 1 part Water-soluble polyester resin (Nippon Synthetic Chemical Industry, Polyester WR-961) 4 parts water 55.5 parts isopropyl Alcohol 40 parts Comparative Example 4 The polyethylene terephthalate film itself used in Example 1.

The above-mentioned thermal transfer sheet is superimposed on a conventionally used heat-receiving sheet, and is transferred under the following transfer conditions using a transfer recording apparatus. The results of examining the surface resistance and coloring are shown in Table 1 below. Transfer conditions : pulse width: 1 ms Recording cycle: 2.0 ms / line Recording energy: 3.0 J / cm ²

Table 1

Evaluation method: generation of fusion and wrinkles—by visual observation. Surface resistance ‥‥ The surface resistance per cm ^{2 under} the conditions described in Table 1 is shown using a high resistivity meter (Hiresta IP, manufactured by Mitsubishi Yuka). Adhesiveness ‥‥ Mending tape (Sumitomo 3M, width 18m
m) was applied to the surface of the heat-resistant lubricating layer, and the degree of separation of the heat-resistant lubricating layer and the antistatic layer when peeled off instantaneously was examined. ○: No peeling △: Partial peeling ×: Complete peeling Coloring △ Visual observation

[0082]

According to the present invention as described above, a specific organic conductive material is contained in a primer layer between a base film of a thermal transfer sheet and a heat-resistant lubricating layer, thereby providing excellent antistatic properties and thermal resistance. A thermal transfer sheet having a heat-resistant lubricating layer that does not corrode the head is provided. In particular, the above-mentioned organic conductive material has low temperature dependency in its antistatic property, high transparency, and has a sufficient effect with a small amount of addition, and is used to form an antistatic layer inside the heat-resistant lubricating layer. Therefore, there is no problem that the thermal transfer sheet becomes sticky or that the antistatic agent migrates to the ink layer and conversely the ink layer migrates to the back surface when the thermal transfer sheet is wound in a roll. Also, since it is not necessary to add a conductive agent such as conductive carbon black to the heat-resistant lubricating layer, the wear of the thermal head, in the case of a thermal transfer sheet other than black, the whole is visible and formed on the thermal transfer sheet. There is no problem that the detection of the detected detection mark becomes difficult. Further, since there is no need for halogen ions to be present in the heat-resistant lubricating layer, corrosion of the thermal head does not occur.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a layer configuration of a thermal transfer sheet of the present invention.

FIG. 2 is a diagram schematically illustrating a layer configuration of a thermal transfer sheet of the present invention.

FIG. 3 is a diagram schematically showing a layer configuration of the thermal transfer sheet of the present invention.

FIG. 4 is a diagram schematically illustrating a layer configuration of the thermal transfer sheet of the present invention.

[Explanation of symbols]

 1: base film 2: hot-melt ink layer 3: heat-resistant lubricating layer 4: primer layer 5: release layer and / or mat layer 6: adhesive layer or surface layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tomoyuki Izuhara 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. (reference) 2H111 AA01 AA15 AA26 AA33 BA02 BA03 BA04 BA07 BA08 BA09 BA55 BA64 BA65 BA73 BA76

Claims (5)

[Claims] 1. A thermal transfer sheet having a heat-fusible ink layer formed on one side of a base sheet and a heat-resistant lubricating layer formed on the other side. A thermal transfer sheet comprising a primer layer formed therebetween, and the primer layer containing, as an antistatic agent, an organic conductive material obtained by introducing a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton. . 2. A heat transfer sheet comprising a base sheet having a heat-meltable ink layer formed on one surface and a heat-resistant lubricating layer formed on the other surface, wherein the heat-resistant lubricating layer is used as an antistatic agent. The compound having a terpene skeleton has a sulfonic acid group and / or
Or a thermal transfer sheet containing an organic conductive material into which a salt group is introduced. 3. A thermal transfer sheet having a heat-fusible ink layer formed on one surface of a substrate sheet via a release layer and / or a mat layer, wherein the release layer and / or the mat layer serves as an antistatic agent. And a compound having a terpene skeleton containing an organic conductive material in which a sulfonic acid group and / or a salt group thereof is introduced. 4. A thermal transfer sheet comprising a base sheet having a heat-meltable ink layer formed on one surface thereof and an adhesive layer and / or a surface layer formed on the surface thereof, wherein the adhesive layer and / or the surface layer A thermal transfer sheet comprising, as an antistatic agent, an organic conductive material obtained by introducing a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton. 5. The organic conductive material contains at least one of the compounds represented by the following general formulas 1 to 5.
The thermal transfer sheet according to any one of the above. (X ₁ , X ₂ , X ₃ and X ₄ in the above formula are the same or different,
It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a hydroxyl group. Ya, Yb and Yc are the same or different and represent a proton (H ⁺ ) or a positive ion of a basic compound;
Represents an integer of １５15. )