JPH054463A - Sheet for heat transfer recording - Google Patents

Abstract

PURPOSE:To obtain a favorable running property for a thermal head even at the time of high energy recording by providing a heat resistant layer for which a resin composition containing a compound, which is expressed by a specified formula, is cured, on the other surface, for a sheet for heat transfer recording, for which a heat transferrable color material layer is provided on one surface of a base film. CONSTITUTION:For a sheet for heat transfer recording for which a heat transferrable color material layer is provided on one surface of a base film, a heat resistant layer for which a resin compound contain-containing a compound, which is expressed by a formula I, is cured is provided on the other surface of the base film. In the formula I, R indicates H or CH3, and the compound which is expressed by this formula I is obtained by making a compound which is expressed by a formula II and (metha)acrylic acid react. As the compound which is expressed by this formula I, in addition to a carboepoxy acrylate resin, e.g. a reactive monomer such as tricyclodecan(meth)acrylate, etc., and epoxy(metha)acrylate, etc., is used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording sheet, and more particularly to a thermal transfer recording which can be advantageously used for color recording in OA terminals such as facsimiles, printers and copying machines and for color recording of television images. For the sheet.

[0002]

Various methods such as electrophotography, ink jet, and thermal transfer recording have been studied for color recording. The thermal transfer recording method is easy to maintain, easy to operate, and easy to operate.
It is advantageous over other methods in that the device and consumables are inexpensive. In the thermal transfer recording method, the image receiving member is placed on the ink application surface of the thermal transfer recording sheet coated with ink containing a color material, and the back surface of the thermal transfer recording sheet is supported.
Recording is performed by heating with a round head to transfer the color material in the thermal transfer recording sheet to the image receiving body. Such methods include a melt-type transfer recording method using a heat-meltable ink and a sublimation type transfer recording method using an ink containing a sublimable dye.

[0003]

In this type of thermal transfer recording system, the thermal transfer recording sheet is heated to a high temperature by the thermal head, so that the heat resistance of the base film of the thermal transfer recording sheet is high. When insufficient, the base film is fused to the thermal head, and this fusion causes generation of a sound called a stick sound and adhesion of dust to the thermal head.
If the fusion becomes more remarkable, the thermal head cannot run and recording cannot be performed. Therefore, it has been proposed to provide a protective film of various heat-resistant resins in order to improve the heat resistance of the conventional base film (see, for example, Japanese Patent Laid-Open No. Sho 5).
No. 5-7467, JP-A-57-74195), and it has also been proposed to add heat-resistant fine particles, a lubricant, a surfactant, etc. to the above protective layer in order to further improve the running property. (For example, JP-A-55-146790)
JP-A-56-155794, JP-A-57-129
797 publication). However, recently, in the recording method of the present system, in order to increase the recording speed, higher energy is applied to the thermal head than in the past, and thus a heavy load is applied to the thermal transfer sheet, and the above-mentioned patent publications are disclosed. It is difficult to obtain sufficient running performance of the thermal head by the method described in (1). In particular, a thermal transfer recording sheet of a sublimation type thermal transfer recording system using a sublimable dye requires higher energy during recording than a thermal transfer recording sheet of a melting type thermal transfer recording system using a heat-meltable ink. Therefore, the thermal transfer recording sheet processed by the conventionally proposed method cannot obtain sufficient running performance of the thermal head. In order to improve these problems, it has been proposed that a protective film of a resin obtained by curing a specific polyfunctional acrylate is effective. (For example, JP-A-62-21
However, when the above-mentioned resin protective film is formed on a base film, the curl of the film is large due to shrinkage of the cured film, and it is difficult to handle when used as a thermal transfer recording sheet. There is a problem. From such a background, there is a demand for a thermal transfer recording sheet which has good running performance of the thermal head and has no curl and has good workability.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted studies on obtaining a sheet having good running and workability of a thermal head in a thermal transfer recording sheet. By providing the film with a heat-resistant layer made of a cured product of a resin composition containing a specific compound, a thermal transfer recording sheet having very good running performance of the thermal head even at high energy recording and having no curl can be obtained. The inventors have found that they can be obtained and reached the present invention.

That is, the present invention provides a thermal transfer recording sheet having a heat transferable color material layer on one surface of a base film, and the following formula (1) is provided on the other surface of the film.

[0006]

[Chemical 2]

A sheet for thermal transfer recording comprising a heat resistant layer formed by curing a resin composition containing a compound represented by the formula (wherein R is H or CH ₃ ). Regarding Hereinafter, the present invention will be described in detail. The compound represented by the formula (1) used for forming the heat-resistant layer of the present invention is a compound represented by the following formula (2):

[0008]

[Chemical 3]

It can be obtained by reacting (meth) acrylic acid. Further, the compound represented by the formula (1) can be easily obtained from the market. For example, Nippon Steel Chemical Co., Ltd., cardo epoxy acrylate resin,
ASF-400 (softening point 50 ° C.) and the like. In the resin composition used in the present invention, in addition to the compound represented by the formula (1), tricyclodecane (meth) acrylate,
Isobornyl (meth) acrylate, adamantyl (meth) acrylate, 1,6-hexanedioldiyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, tricyclodecane dimethyl di (meth) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta and hexa (meth) ) Reactive monomers such as acrylate, phenol novolac type epoxy resin, cresol
Epoxy (meth) acrylate which is a reaction product of epoxy resin such as novolac type epoxy resin and bisphenol A type epoxy resin and (meth) acrylic acid can be used. The amount of the reactive monomer or epoxy (meth) acrylate used is 100% of the compound represented by the formula (1).
The amount is preferably 0 to 500 parts by weight, and particularly preferably 0 to 200 parts by weight. Furthermore, if necessary, a solvent, a photopolymerization initiator, and polymers can be added.

The solvent is, for example, an alcohol-based solvent,
Various solvents such as ketone type, ester type, aromatic hydrocarbon type and halogenated hydrocarbon type can be used, and the amount of the solvent used can be arbitrarily selected. Further, as the photopolymerization initiator, benzophenone, benzyldimethylketane
, Benzyldiethylketanol, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, 2,4. 6-trimethylbenzoyldiphenylphosphine oxide, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholino-propan-1-one and the like can be used. The amount of these photopolymerization initiators used is preferably 0 to 10% by weight based on the components excluding volatile components in the resin composition. As the polymers, various (meth) acrylic acid ester (meth) acrylic polymers, silicon-modified (meth) acrylic polymers, urethane polymers and the like can be used. The amount of these polymers used is preferably 0 to 500 parts by weight with respect to 100 parts by weight of the compound represented by the formula (1).

The resin composition used in the present invention comprises the compound represented by the formula (1), the above-mentioned reactive monomer, epoxy (meth) acrylate, solvent, photopolymerization initiator, polymers and the like. It can be obtained by mixing and dissolving.

In order to improve the lubricity of the heat-resistant layer formed of the cured film of the resin composition with respect to the thermal head and to improve the running property of the thermal transfer recording sheet, a heat-resistant organic material,
Inorganic fine particles, various lubricants, surfactants and other additives can be contained in the cured film. By adding heat-resistant fine particles to roughen the surface of the cured film, the coefficient of friction between the thermal transfer recording sheet and the thermal head can be reduced. Examples of such fine particles include metal and metal. Examples thereof include fine particles of oxides, metal sulfides, carbon black, minerals, inorganic salts, inorganic pigments, organic pigments, organic polymers and the like. Specific examples thereof include fine particles of alumina, silica, titanium oxide, zinc oxide, magnesium oxide, calcium carbonate, graphite, molybdenum sulfide, silicone resin, fluorine resin, benzoguanamine resin, phenol resin, melamine resin, urea resin and the like. Can be mentioned. It is suitable that these particles have a particle size of 0.01 to 10 μm, and the addition amount thereof is 3 to 100 parts by weight per 100 parts by weight of the resin composition excluding volatile components. ..

By adding a lubricant or a surface active agent, the coefficient of friction between the thermal transfer recording sheet and the thermal head can be lowered, and the generation of static electricity can be prevented or eliminated. As the lubricant and the surfactant, those generally used in the past may be used. It is difficult to distinguish a lubricant from a surfactant and some are commonly used. Specific examples of the lubricant include natural and synthetic waxes, fatty acids, fatty acid amides, higher fatty acid metal salts, and higher alcohols. Examples thereof include fatty acids, fatty acid esters, silicone oil, and phosphoric acid esters. Examples of the surfactant include various anionic surfactants, various cationic surfactants, various nonionic surfactants, fluorochemical surfactants, silicone surfactants and the like. The amount of the lubricant and the surfactant added is appropriately 0.1 to 20% by weight based on 100 parts by weight of the component excluding volatile components in the resin composition.

The resin composition used for forming the heat-resistant layer may be applied by various methods such as gravure coater, reverse roll coater, wire bar coater and air doctor coat. There is a method. The heat-resistant layer obtained by curing the resin composition used in the present invention can be obtained by drying the (coating film) by an appropriate means to remove the solvent and then curing it by irradiation with radiation. Examples of the radiation include ultraviolet rays, electron glands, and γ rays. The heat-resistant layer formed on the base film usually has a thickness of 0.1.
The thickness is from 10 to 10 μm, preferably from 0.5 to 5 μm. Examples of the base film in the heat transfer sheet of the present invention include polyethylene terephthalate film, polyamide film, polyaramid film, polyimide film, polycarbonate film, polyphenylene sulfide film, polysulfone film, cellophane, triacetate film. , Polypropylene film, etc. Among them, polyethylene terephthalate film is
The thickness of these base films is preferably 1 to 30 .mu.m, more preferably 2 to 15 .mu.m from the viewpoints of mechanical strength, dimensional stability, heat resistance, cost and the like.

The color material layer in the thermal transfer recording sheet of the present invention may be formed by a usual method. For example, in the case of a sublimation type thermal transfer recording sheet, an ink is prepared by dissolving or dispersing a sublimable dye and a binder resin having good heat resistance in an appropriate solvent, and coating this ink on a base film. It may be dried, and in the case of a melt-type thermal transfer recording sheet, an ink is prepared by dissolving or dispersing a dye such as a pigment or a dye in a heat-meltable substance using a solvent as required. Then, this ink may be applied to a base film and dried. Examples of sublimable dyes used in the sublimation type thermal transfer recording sheet include nonionic dyes such as azo dyes, anthraquinone dyes, azomethine dyes, methine dyes, indoaniline dyes, naphthoquinone dyes, quinophthalone dyes and nitro dyes. Can be mentioned.

As the binder resin, polycarbonate is used.
Resin, polysulfone resin, polyvinyl butyral resin, polyacrylate resin, polyamide resin, polyaramid resin, polyimide resin, polyetherimide resin,
Examples include polyester resins, acrylonitrile-styrene resins and cellulose resins such as acetyl cellulose, methyl cellulose, ethyl cellulose and the like. As the solvent, toluene, an aromatic solvent such as xylene, methyl ethyl ketone, methyl isobutyl ketone,
Ketone-based solvents such as cyclohexanone, ester-based solvents such as ethyl acetate and butyl acetate, alcohol-based solvents such as isopropanol and methyl cellosolve, halogen-based solvents such as methylene chloride, trichloroethylene and chlorobenzene,
Ether-based solvents such as dioxane and tetrahydrofuran are used. Examples of the dye used in the melt-type thermal transfer recording sheet include inorganic pigments such as carbon black as pigments, various azo-based and condensed polycyclic organic pigments, and dyes such as sulfonic acid groups. Acid dyes, basic dyes, metal complex salt dyes, oil-soluble dyes, and the like containing are used. The melting point of the heat fusible substance is 40 to 1
A solid or semi-solid substance at 20 ° C. is preferable, and examples thereof include carnauba washes, montan wax, microcrystalline wax, wood wax, and oil-based synthetic wax.

As the solvent, the same solvents as in the case of the sublimation type thermal transfer recording sheet can be used. In each of the above inks, in addition to the above components, organic or inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an antiblocking agent, an antifoaming agent, an antioxidant, a viscosity modifier may be added, if necessary. Additives such as can be added. The coating method of these inks can be carried out by the same method as described for the coating of the heat resistant layer, and the coating film thickness is preferably 0.1 to 5 μm. In the production of the recording sheet of the present invention, the surface of the base film is subjected to corona treatment in order to improve the adhesiveness between each layer formed by the above coating and the base film, or A subbing coat treatment with a resin such as polyester resin, cellulose resin, polyvinyl alcohol, urethane resin or polyvinylidene chloride may be carried out. The thermal transfer recording sheet of the present invention can be used in any shape such as a typewriter-ribbon shape or a wide tape shape such as a line printer. The recording paper (image-receiving body) for transfer recording using the thermal transfer recording sheet is usually a resin such as a synthetic polyester resin (for example, saturated polyester resin).
Use the one coated with.

[0018]

EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the present invention. The parts described in the examples mean parts by weight. Example 1 (b) Production of thermal transfer recording sheet A polyethylene terephthalate film (thickness: 4 μm) was used as a base film, and the following resin composition was applied to one surface of the film and dried, High pressure mercury lamp (2KW, 80W /
cm ² ), the distance between the mercury lamp and the film is 80 mm, the irradiation time is 5 seconds, and the curing reaction is performed to obtain a thickness of about 2 μm.
m heat resistant layer was formed. Resin composition (1) 15 parts of compound represented by formula (3)

[0019]

[Chemical 4]

(Nippon Steel Chemical Co., Ltd., cardo epoxy acrylate resin, ASF-400) (2) Ethyl acetate 60 parts (3) Isopropyl alcohol 20 parts (4) Silica fine particles (Aerosil R972, Nippon Aerosil 3 parts (5) Photopolymerization initiator (IRGACURE-907, manufactured by Ciba-Geigy) 1 part (6) Silicone-based surfactant (NVC Silicone L7602, Nippon Unicar Co., Ltd.) )) 1 part A sublimation dye (C.
I. Solvent Blue 95) 5 parts, polysulfone resin 10
Part, and an ink consisting of 85 parts of chlorobenzene were applied and dried to form a coloring material layer having a thickness of about 1 .mu.m to prepare a thermal transfer recording sheet. This thermal transfer recording sheet is easy to handle without curling after forming the heat resistant layer and after forming the coloring material layer.

(B) Preparation of image receptor 10 parts of saturated polyester resin (trade name: TP-220, manufactured by Nippon Gosei Co., Ltd.), amino-modified silicone (trade name:
KF-393, manufactured by Shin-Etsu Chemical Co., Ltd., 0.5 part, methyl ethyl ketone 15 parts, xylene 15 parts, a synthetic paper (trade name: YUPO FPG150, manufactured by Oji Yuka Co., Ltd.)
Was coated with a wire bar and dried (dry film thickness: about 5 μm), and further heat-treated in an oven at 100 ° C. for 30 minutes to prepare an image receptor. (C) Transfer recording result The color material layer of the recording sheet manufactured as described above and the resin-coated surface of the image receiving member are overlapped with each other, and 8 is formed on the heat-resistant layer surface of the recording sheet.
A thermal head with a heating resistor density of dot / mm,
8 lines / mm by applying 4W / dot power for 10ms
Transfer recording was performed at a density of 50 cm. As a result, the head and the sheet were not fused to each other, there was no futic sound, the sheet ran smoothly, and good transfer recording was obtained.
Further, the surface of the head after recording was observed, but no dust was observed.

Examples 2 to 5 In the same manner as in Example 1 except that various resin compositions shown in Table 1 were used as the resin composition for forming the heat resistant layer and the heat resistant layer having the thickness shown in Table 1 was formed. And various thermal transfer recording sheets were manufactured. Transfer recording was carried out in the same manner as in Example 1, using the various transfer recording sheets obtained and the image receptor produced in the same manner as in Example 1. As a result, in both cases, the head and the sheet did not fuse, and the sheet ran smoothly without stick noise, and good transfer recording was obtained. Also, the surface of the head after recording was observed, but no dust was observed. Each sheet had no curl and was easy to handle.

Table 1 Examples Resin Composition for Forming Heat-Resistant Layer Thickness of Heat-Resistant Layer (μm) 2 Same as in Example 1 1 3 Change the amount of cardo epoxy acrylate resin ASF-400 in Example 1 to 15 10 parts to 10 parts, 5 parts of a mixture of dipentaerythritol pentapenta and hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) was used, and the other parts were the same as in Example 1 2 4 Example 3 Same as 15 15 The amount of cardo epoxy acrylate resin ASF-400 in Example 1 was changed from 15 parts to 7.5 parts, pentaerythritol tetra acrylate 2.5 parts and KAYARAD DPHA 5 parts were used. Is the same as in Example 1 2

Comparative Example 1 In the resin composition for forming a heat resistant layer, a heat resistant layer was formed on the film in the same manner as in Example 1 except that KAYARAD DPHA was used in place of the cardo epoxy acrylate resin in Example 1. Although formed, the film curled greatly after curing, with the heat-resistant layer inside.

[0025]

The thermal transfer recording sheet of the present invention does not cause the thermal head to be fused to the base film during recording, and further, stick sound and adhesion of dust from the thermal head are caused by the fusion. Since the vehicle travels satisfactorily without any trouble, it is possible to obtain transfer recording with good image quality. Also, this recording sheet is
It is easy to handle because there is no package.

Claims (1)

What is claimed is: 1. A thermal transfer recording sheet having a heat transferable color material layer on one surface of a base film, wherein the other surface of the film is represented by the following formula (1): 1] A sheet for thermal transfer recording, comprising a heat-resistant layer formed by curing a resin composition containing a compound represented by the formula (wherein R is H or CH ₃ ).