JP2000103175A - Thermal transfer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermal transfer sheet provided with heat resistance, coating properties, slip properties and the like in addition to antistatic properties and corrosion prevention properties, and also provided with excellent thermal- head-traveling properties and good antistatic properties (and a heat-resistant lubricant layer) without accumulation of refuses in a thermal head and wear of the thermal head. SOLUTION: A thermal transfer coloring matter layer is formed on one face of a base sheet, and a heat-resistant lubricant layer is formed on the other face through a primer layer on a thermal transfer layer, and the primer layer contains an organic conductive 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. Related Background Art Hitherto, as a thermal transfer sheet, a sublimation type thermal transfer sheet in which a dye layer comprising a sublimable dye and a binder is provided on one surface of a polyester film or the like is known. These thermal transfer sheets are heated imagewise from the back side by a thermal head, and transfer the dye of the dye layer to a material to be transferred to form an image.

[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 of a surfactant or the like, the thermal transfer sheet becomes sticky, or when the thermal transfer sheet is wound in a roll, the antistatic agent migrates to the color material layer, and conversely, the color material There is a problem that shifts to the back. 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 thermal transfer sheet in which a sublimable dye layer is formed on one surface of a base sheet and a heat-resistant lubricating layer is formed on the other surface via a primer layer. A thermal transfer sheet comprising, as an agent, an organic conductive material obtained by introducing a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton.

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. The substrate sheet used in the thermal transfer sheet of the present invention may be any one having conventionally known heat resistance and strength, for example, 0.5 to 50 μm, preferably 3 to 10 μm.
m paper, various processed papers, polyester film, polystyrene film, polypropylene film,
Polysulfone film, aramid film, polycarbonate film, polyvinyl alcohol film, cellophane, etc., and particularly preferred are polyester films. 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 substrate sheet is a compound having a binder having good adhesiveness to both the substrate 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, a polyester resin is desirable for a polyethylene terephthalate film or sheet.

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

[0017]

[0018]

[0019] (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. 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.

The phenol used as a raw material for producing the organic conductive material represented by the above general formulas 1 to 4 includes phenol or a phenol compound having an alkyl group having 1 to 5 carbon atoms and / or a hydroxyl group substituted. 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 organic conductive compounds represented by the above-mentioned general formulas 3 and 4 include, for example, 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 method of one molecule of terpene with two molecules of phenol is, for example, using 0.5 to 20 moles, preferably 2 to 12 moles of phenol 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 a reaction product of one molecule of a terpene and two molecules of a phenol 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.

[0027]

[0028]

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 terpene and two molecules of phenols 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

[0034]

Next, the 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.

[0036]

The primer layer in the present invention is formed with 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 15% by weight, preferably 0.25% by weight. Compositions consisting of -10% 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 solution.
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 for the purpose of imparting 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 based on 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 agent such as wax, higher fatty acid amide, ester, surfactant and 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.

In order to form a heat-resistant lubricating layer, the above-mentioned materials are dissolved or dispersed in an appropriate 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 .

As the dye for the colorant layer formed on one surface of the base sheet, any dye conventionally used in a thermal transfer sheet can be effectively used in the present invention and is not particularly limited. For example, some preferred dyes include MS RedG, Macrolex Red Violet as red dyes.
R, CeresRed 7B, Samaron Red HBSL, Resolin Red F3BS
And the like, and as the yellow dye, Holon Brilliant Yellow 6GL, PTY-52, Macrolex Yellow 6G
And blue dyes include Kayaset Blue 714, Waxolin Blue AP-FW, Holon Brilliant Blue SR, MS Blue 100 and the like.

Preferred examples of the binder resin for supporting the dye as described above include cellulose resins such as ethylcellulose, hydroxyethylcellulose, ethylhydroxycellulose, hydroxypropylcellulose, methylcellulose, cellulose acetate and cellulose acetate butyrate; Vinyl resins such as alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, and polyvinyl pyrrolidone; acrylic resins such as poly (meth) acrylate and poly (meth) acrylamide; polyurethane resins; polyamide resins; and polyester resins. Among them, cellulose-based, vinyl-based, acrylic-based, polyurethane-based and polyester-based resins are preferred from the viewpoints of heat resistance, dye transferability, and the like. A.

The dye layer is prepared by dissolving the above-mentioned dye and binder and, if necessary, additives such as a releasing agent on one surface of the base sheet in an appropriate organic solvent. Or a dispersion dispersed in an organic solvent or water,
For example, it can be formed by applying and drying by a forming means such as a gravure printing method, a screen printing method, and a reverse roll coating method using a gravure plate.

The dye layer thus formed has a thickness of 0.2 to
It has a thickness of about 5.0 μm, preferably about 0.4 to 2.0 μm, and the sublimable dye in the dye layer accounts for 5 to 90% by weight, preferably 10 to 70% by weight of the weight of the dye layer. It is preferably present in an amount.

When the desired image is monocolor, the dye layer to be formed is formed by selecting one color from the above dyes,
When the desired image is a full-color image, for example, appropriate cyan, magenta and yellow (and black if necessary) are selected, and yellow, magenta and cyan (and black if necessary) are selected. Form a dye layer.

The image-receiving sheet used to form an image using the above-described thermal transfer sheet may be any image-receiving sheet as long as its recording surface has a dye-accepting property for the dye. In the case of paper, metal, glass, synthetic resin, or the like having no dye receptivity, a dye receiving layer may be formed on at least one surface thereof.

A known thermal transfer printer can be used as it is as a printer used for performing thermal transfer using the above-mentioned thermal transfer sheet and the above-mentioned image receiving sheet, and is not particularly limited.

In the above description, the present invention has been described by exemplifying an example in which the heat-resistant lubricating layer is formed on the base material sheet via the primer layer, but the base material sheet is subjected to the easy adhesion treatment. Or, when the adhesion of the heat-resistant lubricating layer to the substrate sheet is good, the organic conductive material as an antistatic agent is added to the heat-resistant lubricating layer in the same manner as when added to the primer layer. It is also possible to impart antistatic properties to the heat-resistant lubricating layer.

[0053]

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 substance 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 white crystals were charged into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, and then maintained at a temperature of 35 ° C. 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 50 equipped with a thermometer, a stirrer, a dropping funnel and a cooling pipe.
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 terpene diphenol compound white crystal 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] In a 1-liter four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser, 564 g of phenol was added.
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 condenser, and then kept at a temperature of 5 ° C. 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 is the same as Synthesis Example 6, except that 85 g of terpene diphenol compound white crystals obtained in the same manner as in Synthesis Example 6 are 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 primer layer coating solution A having the following composition was applied to a 6 μm-thick polyethylene terephthalate film as a base 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. On the other surface of the base film, a coating liquid A for a thermal transfer color material layer having the following composition is applied and dried so as to be about 1.0 g / m ² when dried to form a thermal transfer color material layer. A thermal transfer sheet of Example 1 was produced.

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 solution A for transfer color material layer: MS-RED-G (manufactured by Mitsui Toatsu Chemical, CI Disperse Red 60) 2.00 parts Macrolex Red Violet R (manufactured by Bayer AG, C.I. I. Disperse Violet 26) 1.50 parts Polyvinyl acetal resin (manufactured by Sekisui Chemical, Eslek KS-5) 3.50 parts Methyl ethyl ketone 46.50 parts Toluene 46.50 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 instead 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

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 in place 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 thermal transfer sheet is superimposed on a conventionally used thermal transfer sheet, and the image is transferred using a transfer recording apparatus under the following transfer conditions to fuse the thermal head with the thermal transfer sheet, generate wrinkles, adherence, and the like. 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

[0074]

[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

[0076]

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, the thermal transfer sheet becomes sticky, or when the thermal transfer sheet is wound into a roll, the antistatic agent migrates to the color material layer,
On the contrary, there is no problem that the color material shifts to the back surface. 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.

Claims (7)

[Claims] 1. A thermal transfer sheet comprising a substrate sheet having a sublimable dye layer formed on one surface and a heat-resistant lubricating layer formed on the other surface via a primer layer, wherein the primer layer is an antistatic agent. A thermal transfer sheet comprising a compound having a terpene skeleton and an organic conductive material having a sulfonic acid group and / or a salt thereof introduced therein. 2. The thermal transfer sheet according to claim 1, wherein the organic conductive material contains at least one compound represented by the following general formulas 1 to 5. (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. ) 3. The thermal transfer sheet according to claim 1, wherein the primer layer contains a polyester resin as a binder. 4. The primer layer has a thickness of 0.05 to 0.5.
The thermal transfer sheet according to claim 1, which has a thickness of μm. 5. The thermal transfer sheet according to claim 1, wherein the heat-resistant lubricating layer comprises a reaction product of a thermoplastic resin and a polyisocyanate. 6. The thermal transfer sheet according to claim 1, wherein the thickness of the heat-resistant lubricating layer is 0.1 to 2 μm. 7. A thermal transfer sheet comprising a substrate sheet having a sublimable dye 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.
A thermal transfer sheet comprising a compound having a terpene skeleton and an organic conductive material in which a sulfonic acid group and / or a salt group thereof is introduced.