JPH0773952B2 - Sheet for thermal transfer recording - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the Invention (Field of Industrial Application) The present invention relates to a sublimation type thermal transfer recording sheet having a good thermal head running property.

(Prior Art) A thermal transfer recording sheet having a heat-fusible ink layer or a coloring material layer containing a sublimable dye formed on one surface of a base film is heated by a thermal head, and the hot-melt ink on the thermal transfer recording sheet is heated. Alternatively, a heat-sensitive transfer recording method in which a sublimable dye is transferred onto a recording paper for recording has been recently used for reasons such as excellent maintainability and operability of the apparatus, good stability of recorded matter, and easy color recording. Attention has been paid.

However, in such a thermal transfer recording method, since the transfer recording sheet is heated to a high temperature by the thermal head, the heat resistance of the base film of the thermal transfer recording sheet is not sufficient.
The base film is fused to the thermal head and the thermal head cannot run. Then, as a means for improving the running property of such a thermal head, a heat resistant protective layer made of a heat resistant resin is provided on the base film (JP-A-55-
7467), an anti-stick layer comprising an inorganic pigment having high lubricity and a thermosetting or high softening point resin material (JP-A-56-155794), silicon oxide or polyfunctional (meta). Proposals have been made such as providing an abrasion-resistant and heat-resistant protective layer consisting of a three-dimensional cross-linked layer of acrylates (JP-A-57-74195).

(Problems to be Solved by the Invention) Although the above-mentioned conventional method is effective in the case of a heat-meltable ink transfer type sheet, a thermal transfer recording sheet for transferring a sublimable dye (this is used in the present specification) In the case of a "sublimation type thermal transfer recording sheet"), since a larger amount of heat energy is required at the time of the transfer recording, the heat resistance of the sheet is not sufficient and the running property of the thermal head is sufficiently improved. I couldn't.

An object of the present invention is to provide a sublimation type thermal transfer recording sheet in which the thermal head has good running properties.

(B) Structure of the Invention (Means for Solving the Problems) The present inventors have conducted research to improve the running property of the thermal head in the sublimation type thermal transfer recording sheet, and as a result,
The object could be achieved by providing a heat resistant slipping layer made of a cured product of a specific compound on the surface of the recording sheet in contact with the thermal head of the base film.

That is, the present invention is a sublimation-type thermal transfer recording sheet having a coloring material layer containing a sublimable dye on one surface of a base film, the other surface of the general formula (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an acryloyl group or a methacryloyl group, and R ⁶ represents an acryloyl group,
A methacryloyl group, an alkyloyl group, or a hydroxyl group is shown. And a heat resistant slipping layer obtained by curing the compound represented by the formula (3).

The compound represented by the general formula (I) used for forming the heat resistant slipping layer of the present invention is a pale yellow transparent liquid or crystal and has various trade names (for example, Nippon Kayaku Co., Ltd. trade name KAYARAD D- 310, KAYARAD DPHA, etc.), the present invention can be carried out using such commercially available products. The compound represented by the general formula (I) used in the present invention may be a single compound corresponding to the general formula or a mixture of several compounds corresponding to the general formula. .

In order to form a heat resistant slipping layer obtained by curing the compound on the base film of a thermal transfer recording sheet using the compound represented by the general formula (I), a coating solution containing this compound is applied on the base film. Is applied, and after drying, it is cured by heating or irradiation with radiation.

In addition to the compound represented by the general formula (I), the coating solution may contain a solvent and a radical polymerization initiator, if necessary. Examples of the solvent include various solvents such as alcohols, ketones, esters, aromatic hydrocarbons and halogenated hydrocarbons. Examples of the polymerization initiator include benzoin ethers such as benzophenone, benzoin, benzoin methyl ether, and benzoin ethyl ether; benzyl ketals such as benzyl methyl ketal and benzyl ethyl ketal; azo compounds such as azobis-isobutyronitrile. And organic peroxides such as benzoyl peroxide, lauryl peroxide, di-t-butyl peroxide, dicumyl peroxide and cumene hydroperoxide. The amount of these polymerization initiators used is 0.01 with respect to the compound represented by the general formula (I).
~ 10% by weight.

In addition to the above additives, various additives can be added to the coating liquid. For example, it is possible to add stabilizers such as polymerization inhibitors and antioxidants, organic or inorganic fine particles for improving the lubricity of the heat resistant slipping layer, a heat-melting substance, a surfactant, an antistatic agent, etc. it can. further,
In some cases, other curable compounds, heat resistant resins and the like can be added within the range where the effects of the present invention are not impaired.

Examples of the coating method of the coating liquid include a method using a gravure coater, a reverse roll coater, a wire bar coater, and an air doctor coater described in "Coating Method" by Yuji Harazaki (1979, published by Maki Shoten). .

The coating film of the coating solution is dried by an appropriate means to remove the solvent, and then cured by a conventional method such as heating or irradiation with radiation. Examples of the radiation include ultraviolet rays, electron beams, γ rays and the like. As a specific example of curing, in the case of heat curing, it is about 30 seconds to 10 minutes at 50 to 150 ° C.,
Further, in the case of UV curing, irradiation is performed with a UV lamp of 80 W / cm for about 5 seconds to 1 minute from a distance of about 10 cm. Particularly preferred curing is curing with ultraviolet rays or electron beams.

The thickness of the heat resistant slipping layer formed on the base film in the present invention is usually 0.1 to 10 μm, preferably 0.5 to 5 μm.
m.

The base film in the thermal transfer sheet of the present invention, polyethylene terephthalate film, polyamide film, polyaramid film, polyimide film, polycarbonate film, polyphenylene sulfide film, polysulfone film, cellophane,
Examples thereof include triacetate film and polypropylene film. In particular, the polyethylene terephthalate film is most preferable from the viewpoint of mechanical strength, dimensional stability, heat resistance, cost and the like. The thickness of these base films is 1
-30 μm, preferably 2-15 μm.

The thermal transfer recording sheet of the present invention is provided with a coloring material layer containing a sublimable dye on one surface of the base film. The coloring material layer is formed by the sublimable dye and a binder having good heat resistance. It is carried out by applying an ink in which a resin and a resin are dissolved or dispersed in an appropriate solvent to a base film and drying the ink.

Examples of the sublimable dye include nonionic dyes such as azo dyes, anthraquinone dyes, azomethine dyes, methine dyes, indoaniline dyes, naphthoquinone dyes, quinophthalone dyes, and nitro dyes.

Examples of the binder resin include polycarbonate resins, polysulfone resins, polyvinyl butyral resins, cellulosic resins such as acetyl cellulose, methyl cellulose and ethyl cellulose.

Ink for forming the color material layer, in addition to a sublimable dye, a binder resin and a solvent, organic or inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an antiblocking agent, a defoaming agent, Antioxidants, viscosity modifiers and the like can be added. The method of applying the ink may be the same as the method of applying the coating solution for forming the heat resistant slipping layer, and the thickness of the color material layer obtained by applying the ink is preferably 0.1 to 5 μm. Is.

The base film for a sheet of the present invention, in order to improve the adhesiveness of the base film, its surface is a water-soluble polyester resin, a cellulosic resin, polyvinyl alcohol,
It can be treated with a resin such as urethane resin or polyvinylidene chloride.

To perform recording using the thermal transfer recording sheet of the present invention, the color material layer of the thermal transfer recording sheet is superposed on the recording paper, and the thermal transfer recording sheet is heated with an electric signal corresponding to image information. It is carried out by heating from the back of the color material layer of the sheet, and infrared rays, laser light or the like is used as the heating means.

(Examples, etc.) Hereinafter, examples and comparative examples will be described in detail.

Example 1 (a) Production of thermal transfer recording sheet: A biaxially stretched polyethylene terephthalate film (thickness) provided with a coloring material layer containing Solvent Blue 93 (trade name of CI company) as a sublimable dye on one surface as a base film. 6 μm) was used to form a heat resistant slipping layer on it, to prepare a thermal transfer recording sheet.

That is, on the surface where the color material layer of the film provided with the color material layer is not provided, KAYARAD DPHA (trade name of Nippon Kayaku Co., Ltd.) of a commercially available ultraviolet curable resin 16.4 parts (parts by weight, The same shall apply hereinafter), zinc stearate 0.83 part, benzophenone 0.67 part, Darocur 1173 (Merck company trade name) 0.33
Part, and 81.47 parts of methyl ethyl ketone are applied and dried, and then a high pressure mercury lamp with an energy of 80 W / cm is used, the distance between the mercury lamp and the film is 115 mm, and the irradiation time is 2
The resin was cured by treatment under the condition of 0 seconds to obtain a thermal transfer recording sheet having a heat resistant slipping layer having a thickness of about 2 μm.

The above-mentioned KAYARAD DPHA used in the above general formula (I) is a compound in which R ^{1 to} R ⁵ are acryloyl groups, R ⁶ is a hydroxyl group, and R ^{1 to} R ⁶ are acryloyl groups. It is a mixture with a compound.

(B) Manufacture of recording paper: A polypropylene-based synthetic paper having a thickness of 150 μm and an aqueous solution (solid content of 20%) of a commercially available water-soluble polyester resin (Nippon Gosei Kagaku Kogyo Co., Ltd., trade name XWR-950, Tg: 34 ° C.) ),
Apply using wire bar No. 3 (wet film thickness is 24μ
m), and dried with hot air with a dryer to form a dyeing layer having a thickness of about 5 μm. Furthermore, 1 g of a commercially available crosslinkable silicone resin (Shin-Etsu Chemical Co., Ltd., trade name KS-841, solid content 30%) and a commercially available silicone resin curing catalyst (Shin-Etsu Chemical Co., Ltd. trade name PL-8) 0.01 g and toluene 29g were mixed uniformly and applied using a wire bar No.1 (wet film thickness 6μm), dried with hot air with a dryer to form a silicone film, and then in an oven.
A recording paper was prepared by heating at 100 ° C for 30 minutes.

The wire bar is a stainless steel rod with a diameter of 1/4 inch and is wound with stainless wire of various thicknesses without any gap, and the gap allows a coating film having a constant thickness to be formed. It is a tool.

(C) Transfer recording result The coloring material layer of the recording sheet manufactured as described above and the resin coated surface of the recording paper are overlapped, and the heat resistant slipping layer surface of the recording sheet has a heating resistor density of 8 dot / mm. With a thermal head,
Transfer was performed by applying 0.4 W / dot power for 10 milliseconds.
As a result, the head and the sheet did not fuse, the head ran well, and good transfer recording was obtained.

Examples 2 to 6 Various coating liquids shown in Table 1 were used as coating liquids for forming the heat resistant lubricant layer, and various thermal transfer recording sheets were produced by the layer forming treatment method shown in Table 1. did.

Using each of the obtained thermal transfer recording sheets and the recording paper produced in Example 1, transfer was performed in the same manner as in Example 1. As a result, in both cases, the head and sheet did not fuse, the head ran well, and good transfer was obtained.

Comparative Example 1 A thermal transfer recording sheet was produced in the same manner as in Example 1 except that 16.7 parts of a commercially available resin (Hitachi Chemical Co., Ltd., trade name FA731A) having the following structural formula was used as the ultraviolet curable resin. When transfer recording was performed in the same manner as in Example 1 using the same recording paper as in Example 1, the head and the sheet were fused and the thermal head could not run.

Example 7 (a) Production of thermal transfer recording sheet: As a base film, a biaxially stretched polyethylene terephthalate film (thickness 6 μm) having a coloring material layer containing a sublimable dye provided on one side as in Example 1 was used. make use of,
A thermal transfer recording sheet was manufactured by the following method.

That is, the ultraviolet curable resin KAYARA is formed on the surface of the film on which the color material layer is not provided, on the side where the color material layer is not provided.
D DPHA (trade name of Nippon Kayaku Co., Ltd.) 4.2 parts, silicone surfactant KF-351 (trade name of Shin-Etsu Chemical Co., Ltd.)
0.08 parts, dimethylformamide 20 parts, methyl ethyl ketone 75.47 parts, benzophenone 0.167 parts, and Darocur 1173.
(Merck company brand name) Apply 0.083 parts of the coating solution,
After drying, a high pressure mercury lamp with energy of 80 W / cm was used to cure the resin by treating it under the conditions of a distance of 115 mm between the mercury lamp and the film and an irradiation time of 20 seconds, and a heat resistant slipping layer with a thickness of about 0.3 μ was formed. A thermal transfer recording sheet having the above was obtained.

(B) Production of recording paper: A recording paper was produced in the same manner as in Example 1.

(C) Transfer recording result: The color material layer surface of the recording sheet manufactured as described above and the resin coated surface of the recording paper were overlaid, and transfer was performed under the same conditions as in Example 1. As a result, the head ran well without being fused to the sheet, and good transfer recording was obtained.

Examples 8 to 10 Using the same coating solution as used in Example 7 and using the same layer forming treatment method, the heat-resistant slipping layer had a thickness of about 0.1 μm (Example 8) and about 10 μm, respectively. Thermal transfer recording sheets of 0.5 μ (Example 9) and about 1.0 μ (Example 10) were manufactured.

Transfer recording was performed in the same manner as in Example 7 except that each of the obtained sheets was used. In all cases, the head ran well without fusing to the sheet, and good transfer recording was obtained. .

(C) Effects of the Invention In the thermal transfer recording sheet of the present invention, the thermal head does not fuse to the base film even during recording using high energy, runs well, and good sublimation type thermal transfer recording is obtained.

Claims (1)

[Claims] 1. A sublimation-type thermal transfer recording sheet having a coloring material layer containing a sublimable dye on one surface of a base film, wherein the other surface of the film has a general formula. (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent an acryloyl group or a methacryloyl group, and R ⁶ represents an acryloyl group, a methacryloyl group, an alkyloyl group or a hydroxyl group.) A thermal transfer recording sheet comprising a heat resistant slipping layer obtained by curing the above.