JP2000108527A - Thermal transfer image receiving sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal transfer image receiving sheet stably having an excellent antistatic performance. SOLUTION: The thermal transfer image receiving sheet comprising a dye receiving layer 2 provided at least on one surface of a base material sheet 1, and a layer containing an organic conductive material obtained by introducing a sulfonic acid group and/or its salt group to a compound having a terpene skeleton as an antistatic agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image receiving sheet, and more particularly to a novel thermal transfer image receiving sheet made of a specific material and having excellent antistatic properties.

[0002]

2. Description of the Related Art Various thermal transfer methods have been conventionally known. Among them, a sublimable dye is used as a recording agent, and this is carried on a base sheet such as paper or a plastic sheet to form a thermal transfer sheet. There have been proposed methods for forming various full-color images on a thermal transfer image-receiving sheet that can be dyed with a dye, for example, a thermal transfer image-receiving sheet provided with a dye-receiving layer on the surface of paper or a plastic film.

In this case, a thermal head of a printer is used as a heating means, and a large number of color dots of three or four colors are transferred to a thermal transfer image receiving sheet by heating for a very short time, and the multicolored dots are used to copy an original. Is reproduced. The image formed in this way is very clear because the coloring material used is a dye, and is excellent in transparency. It is possible to form a high-quality image which is similar to an image by offset printing or gravure printing, and is comparable to a full-color photographic image.

As the thermal transfer image receiving sheet used in the above-described sublimation type thermal transfer system, a plastic sheet, a laminated sheet of a plastic sheet and paper, a synthetic paper, and the like are used. In order to expand to general offices, it is required to use plain paper such as coated paper (art paper), cast coated paper, and PPC paper as a base sheet of a thermal transfer image receiving sheet.
The sublimation type thermal transfer system is also useful for forming an OHP image, and is capable of forming a high quality image excellent in transparency and the like.
There is also a demand for a thermal transfer image receiving sheet.

[0005]

The thermal transfer image-receiving sheet is composed of various materials constituting the thermal transfer image-receiving sheet, in particular, the above-mentioned various materials constituting the substrate sheet, which have a high surface resistivity. , The formation of a cushion layer, a dye receiving layer, a back layer (slip layer), etc., the winding and cutting of a thermal transfer image receiving sheet, the storage in a cassette, the packing of boxes, and the like, tend to cause electrification due to mutual friction. Furthermore, during use, there is a problem that the toner is easily charged at the time of contact with a paper feed roll or a thermal transfer sheet, or at the time of peeling off from the thermal transfer sheet after printing.

When the thermal transfer image-receiving sheet is charged, dust and the like tend to adhere to the surface thereof, and as a result, the thermal transfer sheet in contact with the thermal transfer image-receiving sheet may be bent, and the resolution of the formed image is reduced. There's a problem. In addition, the thermal transfer sheet is similarly charged, and the thermal transfer sheet and the thermal transfer image receiving sheet are stuck to each other, which causes a problem in the transportability of the thermal transfer sheet and the thermal transfer image receiving sheet. In the worst case, sparks may be generated when the thermal transfer sheet or the thermal transfer image-receiving sheet is replaced or inserted, or a shock may be given to the human body. Such a problem occurs not only in an opaque thermal transfer image receiving sheet mainly composed of a paper core material but also in a transparent thermal transfer image receiving sheet used for OHP or the like.

It is known to form an antistatic layer on the surface of a thermal transfer image-receiving sheet with a surfactant or the like in order to prevent the above-mentioned charging. However, in this case, the thermal transfer image-receiving sheet becomes sticky. Or the antistatic agent migrates to the back layer. In addition to these problems, there is a problem that the antistatic effect decreases with time. Further, as another method, there is a method of forming a conductive layer using a conductive material such as conductive carbon black or tin oxide and a binder, but these conductive agents have a color such as black. In many cases, the resulting thermal transfer image-receiving sheet has poor appearance.

As a method for solving the above problems, there has been proposed a method of forming an antistatic layer by using an acrylic resin having a quaternary ammonium base (Japanese Patent Laid-Open No. Hei 2 (1990) -1990).
However, these materials basically have poor adhesion to the base material and other resins, and the materials are considerably limited. In addition, there is a slight problem that the antistatic performance changes depending on the environment. Accordingly, it is an object of the present invention to provide a thermal transfer image receiving sheet having excellent antistatic performance stably.

[0009]

The above object is achieved by the present invention described below. That is, the present invention relates to a thermal transfer image-receiving sheet having a dye-receiving layer provided on at least one surface of a substrate sheet, wherein the thermal transfer image-receiving sheet comprises a compound having a terpene skeleton as an antistatic agent and a sulfonic acid group and / or a salt thereof. A heat transfer image-receiving sheet, comprising a layer containing an organic conductive material into which a group (a) is introduced. According to the present invention, by using a specific organic conductive material as an antistatic agent, it is possible to provide a thermal transfer image receiving sheet having excellent antistatic performance stably.

[0010]

Next, the present invention will be described in more detail with reference to preferred embodiments. The thermal transfer image-receiving sheet of the present invention is basically a thermal transfer image-receiving sheet having a dye-receiving layer provided on at least one surface of a base sheet, wherein the heat-transfer image-receiving sheet serves as an antistatic agent for the specific organic conductive material. Is characterized by having a layer containing Preferred embodiments of the thermal transfer image-receiving sheet of the present invention will be described with reference to the drawings. FIG. 1 shows an embodiment in which the dye-receiving layer 2 provided on the surface of the base sheet 1 contains the specific organic conductive material as an antistatic agent. This is an example in which an antistatic layer 3 containing the above-mentioned specific organic conductive material is provided between the dye receiving layer 2 and the dye receiving layer 2. The embodiment shown in FIG. A back surface layer (slip layer) 4 containing the specific organic conductive material as an antistatic agent on the surface;
FIG. 4 shows an embodiment in which an antistatic layer 5 containing the specific organic conductive material is provided between the back surface layer 4 and the base sheet 1.

Next, the present invention will be described in more detail with reference to preferred embodiments. A compound preferable as an organic conductive material used as an antistatic agent in the present invention is represented by the following general formula 1
The present invention is not limited to these compounds.

[0012]

[0013]

[0014]

[0015] (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.

Examples of the phenol used as a raw material for producing the organic conductive material represented by the above general formulas 1 to 4 include 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 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 method for reacting one molecule of terpene with 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, chlorosulfonic acid and the like. 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.

The basic compound used for producing the sulfonate of the compound represented by the general formulas 1 and 2 includes, for example, an inorganic base 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.

Preferred 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.

[0023]

[0024]

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 reactant 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 reacting a reaction product of one molecule of a terpene with two molecules of a phenol with an alkylsultone, the reaction is carried out without a catalyst in the presence of a basic compound. 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

[0030]

Next, a method for producing a compound in which a sulfonic acid group is introduced into the terpene-based aromatic compound represented by the aforementioned general formula 5 is usually carried out by converting a 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.

[0032]

The base sheet used in the present invention includes various transparent to opaque plastic films and sheets, and various types of paper, for example, high-quality paper, art paper, coated paper, cast-coated paper, wallpaper, backing paper, and synthetic resin. Or, paper such as emulsion-impregnated paper, synthetic rubber latex-impregnated paper, synthetic resin-containing paper, paperboard, etc. is suitable, and the thickness of these base sheets is optional, but is generally about 30 to 200 μm. is there.

A laminate formed by laminating a foamed resin sheet such as foamed polypropylene, foamed polyethylene, foamed polystyrene, or a synthetic paper made of foamed resin sheet on both sides of the above-mentioned material as a base sheet and cushion layers on both sides thereof is used as the base sheet. In particular, foamed polypropylene is preferable in consideration of various strengths, cushioning properties, and the like. The preferred thickness of these cushion layers is 30μ.
m to 80 μm.

Since the coating solution for the antistatic layer described later is also excellent in adhesiveness, a coating solution for the antistatic layer may be used as an adhesive for laminating the base sheet. Alternatively, the organic conductive material may be added to a normal adhesive layer.
It can be similarly used for a pressure-sensitive adhesive layer of a peelable substrate such as a seal type. When the substrate sheet as described above has a poor adhesion to the dye receiving layer formed on its surface, it is preferable to apply a primer treatment or a corona discharge treatment to its surface.

The dye receiving layer formed on the surface of the base sheet receives the sublimable dye transferred from the thermal transfer image receiving sheet and maintains the formed image.
As a binder resin for forming a dye receiving layer,
For example, polyolefin resins such as polypropylene, polyvinyl chloride, vinyl resins such as polyvinylidene chloride, vinyl resins such as polyvinyl acetate and polyacrylic ester, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, and polystyrene Resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, polycarbonates, and the like. Particularly preferred are vinyl resins. And polyester resins.

The dye receiving layer preferably contains a release agent in order to provide good releasability from the thermal transfer sheet. Preferred release agents include silicone oil, phosphate ester-based surfactants, fluorine-based surfactants, and the like, with silicone oil being preferred. As the silicone oil, epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified,
Modified silicone oils such as alkyl aralkyl polyether-modified, epoxy / polyether-modified, and polyether-modified are preferred.

One or more release agents are used. Also, the amount of the release agent added is the same as that of the binder resin 1.
1 to 20 parts by weight is preferable with respect to 00 parts by weight. If the addition amount is not satisfied, problems such as fusion of the thermal transfer sheet and the dye receiving layer or reduction in printing sensitivity may occur. The dye-receiving layer formed as described above may have any thickness, but generally has a thickness of 1 to 50 μm.
Further, such a dye receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating using a resin emulsion or a resin dispersion.

The dye-receiving layer in the thermal transfer image-receiving sheet of the present invention comprises, on at least one surface of the above-mentioned base sheet, necessary additives such as an antioxidant and an ultraviolet absorber to the binder resin as described above. The added product is dissolved in an appropriate organic solvent or a dispersion obtained by dispersing in an organic solvent or water is applied by a forming means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. And dried to form.

In the embodiment of the present invention shown in FIG. 1, the conductive organic material is contained in the dye receiving layer. As a method of adding the conductive organic material, an appropriate amount of the conductive organic material may be added to the coating solution for the dye receiving layer. The amount of the conductive organic material is about 0.1 to 30 parts by weight per 100 parts by weight of the binder resin. If the added amount of the conductive organic material is too small, the desired antistatic effect cannot be obtained, while if the added amount is too large, the cost increases, which is not preferable.

In the embodiment shown in FIG. 2, an antistatic layer containing the conductive organic material is formed between the base sheet and the dye receiving layer. In forming the antistatic layer, by selecting an appropriate binder, a function as a primer layer for improving the adhesion between the dye receiving layer and the base sheet can be exhibited. The antistatic layer containing the conductive organic material is a layer composed of the conductive organic material and a binder. If necessary, an intermediate layer may be formed between the receiving layer and the antistatic layer, between the substrate and the antistatic layer, and between the back layer and the antistatic layer.

Examples of the binder include polyester resins, polyurethane resins, polyacrylic resins, polyvinyl formal resins, epoxy resins, polyvinyl butyral resins, polyamide resins, polyether resins, polystyrene resins, Styrene-acrylic copolymer resins and the like can be mentioned.

The antistatic layer in FIG. 2 is formed mainly of the binder and the conductive organic material, and may be formed by dissolving or dissolving in an appropriate solvent such as acetone, methyl ethyl ketone, toluene, xylene and ethyl acetate. Dispersed or a solvent containing water, for example, a coating liquid in which the binder and the conductive organic material are dissolved or dispersed in a mixture of water and a water-soluble organic solvent such as methanol, ethanol, isopropyl alcohol, and normal propyl alcohol. Is prepared. 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 antistatic layer is about 2 to 50% by weight, preferably 3 to 20% by weight, about 0.1 to 30% by weight, preferably 0.1 to 30% by weight of the conductive organic material. Compositions consisting of 25 to 20% by weight and the balance of the solvent are preferred. The antistatic 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.
１10.0 g / m ² , preferably about 0.07 to 5.0 g
/ M ² and the coating amount is less than the above range,
The performance as an antistatic layer is insufficient, on the other hand, even if the coating amount exceeds the above range, the above performance is not necessarily improved in proportion to the thickness thereof, which is not preferable because it is economically disadvantageous. .

In the embodiment shown in FIG. 3, when the back layer is formed on the back surface of the base sheet, the conductive organic material is contained in the back layer. This back layer is for the purpose of improving the transportability of the thermal transfer image receiving sheet in the printer,
On the opposite surface of the dye receiving layer, for example, a layer having a thickness of about 1 to 5 g / m ² by adding a resin having excellent lubricity such as acrylic resin or acrylic silicone resin or suitable lubricating particles thereto. Form as The method and amount of the conductive organic material contained in the back layer are the same as in the case of forming the dye receiving layer.

In the embodiment shown in FIG. 4, an antistatic layer is formed between the base sheet and the back layer. The method of forming the antistatic layer is the same as the method of forming the antistatic layer formed between the dye receiving layer and the base sheet.

The thermal transfer sheet used when performing thermal transfer using the thermal transfer image-receiving sheet of the present invention as described above is a paper or polyester film provided with a dye layer containing a sublimable dye. Any thermal transfer sheet can be used as it is in the present invention.

As a means for applying thermal energy at the time of thermal transfer, any conventionally known applying means can be used.
By controlling the recording time with a recording device such as a thermal printer (for example, Video Printer VY-100 manufactured by Hitachi, Ltd.), 5 to 100 mJ / m
By applying heat energy of about m ² , the intended purpose can be sufficiently achieved.

[0050]

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 condenser, 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, 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 cooling tube, and then kept at 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 thermometer, a stirrer, a dropping funnel and a cooling tube equipped with a cooling tube 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] 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 cooling tube, 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 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 100 μm-thick PET film (Lumirror, manufactured by Toray Industries, Inc.) was used as a base sheet, and a dye receiving layer coating solution 1 having the following composition was dried on one surface thereof with a miller bar. The coating was dried at 5 g / m ² and dried to form a dye receiving layer. <Dye-receiving layer coating liquid 1> Solid content ratio 4.2 parts of the compound represented by the chemical formula 3 Polyester resin (Vylonal MD1245, manufactured by Toyobo Co., Ltd.) 20.1 parts Silicone (KM-764E, Shin-Etsu Chemical Co., Ltd.) )) 2.5 parts Catalyst (CAT-PM-4E, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts Water 36.5 parts IPA 36.5 parts

Next, a back layer coating solution 1 having the following composition was dried on the opposite side of the dye receiving layer formed above at a rate of 1.5 g / m 2
^The resultant was applied and dried so as to obtain No. ² , and a back layer was formed to obtain a thermal transfer image-receiving sheet of the present invention. <Backside layer coating liquid 1> Solid content ratio Acrylic resin (BR-85, manufactured by Mitsubishi Rayon Co., Ltd.) 19.8 parts Nylon filler (MW-330, manufactured by Shinto Paint Co., Ltd.) 0.6 parts MEK 39 .1 part Toluene 39.1 parts

Example 2 A transparent PET film (100 μm) was used as a base sheet, and an antistatic layer coating liquid 1 having the following composition was applied to one surface of the base sheet so as to be 0.5 g / m ² when dried. Thus, an antistatic layer was formed. <Antistatic layer coating liquid 1> Solid content ratio Compound represented by chemical formula 1 15.0 parts Polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) 5.0 parts Methyl ethyl ketone 80.0 parts

Next, a dye receiving layer coating solution 2 having the following composition was applied to the surface of the above antistatic layer so as to be 2.5 g / m ² when dried to form a dye receiving layer. <Dye receiving layer coating liquid 2> Solid content ratio Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo KK) 19.6 parts Silicone (X62-1212, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0 parts Catalyst (CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.2 parts MEK 39.1 parts Toluene 39.1 parts Next, the test was carried out on the surface of the base material sheet opposite to the dye receiving layer. The same backside layer as in Example 1 was formed to obtain a thermal transfer image-receiving sheet of the present invention which can be used as an OHP.

Example 3 An antistatic layer was formed by using the antistatic layer coating solution 1 of Example 2 under the back layer of Example 1, and the thermal transfer of the present invention was carried out in the same manner as in Example 2 except that An image receiving sheet was obtained. Example 4 A thermal transfer image-receiving sheet of the present invention was obtained in the same manner as in Example 1, except that the coating liquid for the back layer in Example 1 was replaced with the coating liquid 2 for the back layer having the following composition. Example 5 An antistatic layer was formed by using the antistatic layer coating liquid 1 of Example 2 under the back layer of Example 2, and the other Example 2
In the same manner as in the above, a thermal transfer image-receiving sheet of the present invention was obtained.

Example 6 A thermal transfer image-receiving sheet of the present invention was obtained in the same manner as in Example 2 except that coating liquid 2 having the following composition was used in place of the coating liquid for the back layer in Example 2. <Backside layer coating liquid 2> Solid content ratio Compound represented by chemical formula 4 25 parts Aromatic polyester resin (Finetex ES-850, manufactured by Dainippon Ink) 8.3 parts Silica (Sylysia 445, Fuji Silysia Chemical Ltd.) 0.5 parts water 38.7 parts IPA 45.0 parts

Example 7 A thermal transfer image-receiving sheet of the present invention was obtained in the same manner as in Example 3 except that the dye receiving layer coating liquid 2 of Example 2 was used in place of the ink of the receiving layer in Example 3. . Example 8 A thermal transfer image-receiving sheet of the present invention was obtained in the same manner as in Example 4 except that the dye receiving layer coating liquid 2 of Example 2 was used in place of the ink of the receiving layer in Example 4.

Examples of the heat transfer image-receiving sheet of the present invention will be described with reference to a seal type. Example 9 A 100 μm-thick PET film (W400, manufactured by Diafoil Hoechst Co., Ltd.) was used as a base material for a release sheet.
g / m ² was applied and dried to form a release layer. <Releasing layer coating liquid> Solid content ratio Silicone (KS-847H, Shin-Etsu Chemical Co., Ltd.) 20.0 parts Catalyst (CAT-PL-50T, Shin-Etsu Chemical Co., Ltd.) 0.4 parts MEK 39.8 parts Toluene 39.8 parts

Next, a 50 μm-thick foamed PET film (W900I, manufactured by Diafoil Hoechst Co., Ltd.) was used as a sheet substrate, and one side was coated with an adhesive layer coating solution having the following composition at a drying time of 7.0 g / day. m ² and dried by application to form an adhesive layer. <Coating solution for adhesive layer> Solid content ratio Acrylic adhesive (SK Dyne 1310, manufactured by Soken Chemical Co., Ltd.) 20.0 parts Curing agent (E-AX, manufactured by Soken Chemical Co., Ltd.) 0.2 parts Ethyl acetate 79.8 parts The release layer surface and the pressure-sensitive adhesive layer surface of each base material prepared as described above were adhered to each other to prepare a base material for sealing. Using this base sheet, a dye receiving layer and a back surface layer were formed in the same manner as in Example 4.

Comparative Example 1 A thermal transfer image-receiving sheet of Comparative Example was obtained in the same manner as in Example 1 except that the compound represented by the chemical formula 3 was not used. Comparative Example 2 A thermal transfer image-receiving sheet of Comparative Example was obtained in the same manner as in Example 2, except that the compound represented by Chemical Formula 1 was not used.

Comparative Example 3 A coating liquid 2 having the following composition was applied (0.01 g / m ² ) to the surface of the dye receiving layer and the back layer in Comparative Example 1, and dried to obtain a thermal transfer image-receiving sheet of Comparative Example. <Antistatic layer coating liquid 2> Solid content ratio Cationic surfactant (Staticide, manufactured by ACL) 0.2 part IPA 99.8 parts

Comparative Example 4 A coating liquid 3 having the following composition was used in Example 5 in place of the primer on the dye receiving layer side and the primer on the back side.
In the same manner as in Example 1, a thermal transfer image-receiving sheet of Comparative Example was obtained. <Antistatic layer coating liquid 3> Solid content ratio Conductive acrylic resin (Elecond PQ-50B, manufactured by Soken Chemical Co., Ltd.) 20.0 parts Methanol 80.0 parts The thermal transfer image receiving sheets of the above Examples and Comparative Examples were prepared. Table 10 shows the results of continuous printing of 10 sheets at a time using an A4 type sublimation transfer printer and evaluation of transportability and charging characteristics.

[0072]

[Table 1] Table 1-1: Evaluation results Note 1: No problem

[0073]

[Table 2] Table 1-2: Evaluation results Note 2: Jam occurred. Note 3: Dye receiving layer had poor adhesion.

[0074]

According to the present invention, as described above,
By using a sulfonated polyaniline as an antistatic agent, a thermal transfer image receiving sheet having excellent antistatic performance stably can be obtained. Further, since it is excellent in transparency, it can be used for a transparent substrate such as an OHP sheet.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a cross section of a thermal transfer image receiving sheet of the present invention.

FIG. 2 is a diagram schematically illustrating a cross section of the thermal transfer image receiving sheet of the present invention.

FIG. 3 is a diagram schematically illustrating a cross section of the thermal transfer image receiving sheet of the present invention.

FIG. 4 is a diagram schematically illustrating a cross section of the thermal transfer image receiving sheet of the present invention.

[Explanation of symbols]

 1: base material sheet 2: dye receiving layer 3: antistatic layer 4: back surface layer 5: antistatic layer

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masaho Yamazaki 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo F-term in Dai Nippon Printing Co., Ltd. (reference) 2H111 AA01 AA02 AA27 CA03 CA04 CA05 CA12 CA23 CA25 CA33 CA50

Claims (6)

[Claims] 1. A thermal transfer image-receiving sheet having a dye-receiving layer provided on at least one surface of a substrate sheet, wherein the thermal transfer image-receiving sheet comprises a compound having a terpene skeleton as an antistatic agent and a sulfonic acid group and / or a salt thereof. A thermal transfer image-receiving sheet comprising a layer containing an organic conductive material into which a group is introduced. 2. The thermal transfer image-receiving sheet according to claim 1, wherein the dye-receiving layer contains an organic conductive material obtained by introducing a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton as an antistatic agent. 3. An antistatic layer is provided between the base sheet and the dye receiving layer, and the antistatic layer has a terpene skeleton as the antistatic agent into which a sulfonic acid group and / or a salt thereof is introduced. The thermal transfer image-receiving sheet according to claim 1, comprising an organic conductive material. 4. A backside layer is provided on the backside of a substrate sheet provided with a dye-receiving layer, and the backside layer introduces a sulfonic acid group and / or a salt thereof into a compound having a terpene skeleton as an antistatic agent. The thermal transfer image-receiving sheet according to claim 1, comprising an organic conductive material. 5. A compound having a back surface layer provided on the back surface of a base sheet provided with a dye receiving layer, an antistatic layer provided between the back surface layer and the base sheet, and the antistatic layer having a terpene skeleton. The thermal transfer image-receiving sheet according to claim 1, further comprising an organic conductive material having a sulfonic acid group and / or a salt group thereof introduced therein. 6. The organic conductive material contains at least one of the compounds represented by the following general formulas 1 to 5.
The thermal transfer image-receiving 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. )