JPH05169862A - Resin composition and sheet for thermal transfer recording - Google Patents

Abstract

PURPOSE:To provide a sheet for thermal transfer recording, in which no thermal head adhers on a base film at the time of recording and a sticking sound with fusion and the adhesion of tailings onto the thermal head are also prevented and which excellently travels. CONSTITUTION:In a sheet for thermal transfer recording having a heat- transferring coloring material layer on one surface of a base film, a heat- resistant layer obtained by curing the reaction product (A) of silicone oil having a carboxylic group in a molecule and a compound having specific structure and a resin composition containing two functional or more of an unsaturated group-contained compound except the component (A) is formed onto the other surface of the film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition which is cured by irradiation with ultraviolet rays or electron beams and a sheet for thermal transfer recording using the same, and in particular, color recording and television images in OA terminals such as facsimiles, printers and copiers. The present invention relates to a thermal transfer recording sheet that can be advantageously used for color recording.

[0002]

2. Description of the Related Art Various methods such as electrophotography, ink jet, and heat-sensitive transfer recording have been studied for color recording. The heat-sensitive transfer recording method is easy to operate, 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 material is superposed on the ink application surface of the thermal transfer recording sheet coated with the ink containing the color material, and the back surface of the thermal transfer recording sheet is heated by the thermal head to color the color material in the thermal transfer recording sheet. Is recorded on the image receptor. 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. Therefore, when the heat resistance of the base film of the thermal transfer recording sheet is insufficient, The base film is fused to the thermal head, and this fusion causes the generation of a sound called a stick sound and the attachment 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 conventional base films (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
789). However, recently, in the recording method of the present method, due to the speeding up of recording, higher energy is applied to the thermal head than in the past, and therefore a large load is applied to the thermal transfer sheet, which is described in the above patent publication. It is difficult to obtain sufficient runnability of the thermal head with this method. In particular, the thermal transfer recording sheet of the sublimation type thermal transfer recording method using the sublimable dye requires higher energy at the time of recording as compared with the thermal transfer recording sheet of the melting type thermal transfer recording method using the thermal melting ink, The thermal transfer recording sheet won by the conventionally proposed method cannot obtain sufficient running performance of the thermal head.

[0004]

Means for Solving the Problems As a result of investigations by the present inventors to obtain a thermal transfer recording sheet having good running and workability of a thermal head, a resin containing a specific compound in a base film was obtained. It has been found that a thermal transfer recording sheet can be obtained in which the thermal head has very good running property even at high energy recording by providing a heat resistant layer made of a cured product of the composition, and has no curl.

That is, the present invention is: Silicone oil having a carboxyl group in the molecule and a compound represented by the formula (1)

[0006]

[Chemical 2]

(R is a hydrogen atom or a methyl group.)
1. A resin composition containing a reaction product (A) of (1) and a bifunctional or higher functional unsaturated group-containing compound (B) other than the component (A), A thermal transfer recording sheet having a heat transferable color material layer on one surface of a base film, wherein a heat resistant layer formed by curing the resin composition according to item 1 is provided on the other surface of the film. A thermal transfer recording sheet. Hereinafter, the present invention will be described in detail.

The reaction product (A) of the silicone oil having a carboxyl group in the molecule and the compound represented by the formula (1) used in the resin composition of the present invention is a silicone oil having a carboxyl group in the molecule. It can be obtained by reacting the compound represented by the formula (1). Silicone oil having a carboxyl group in the molecule (hereinafter simply referred to as silicone oil) can be easily obtained from the market. For example, X- manufactured by Shin-Etsu Chemical Co., Ltd.
22-162A (carboxyl group equivalent 920, viscosity (2
5 ° C.) 110 cps), X-22-162C (carboxyl group equivalent 2330, viscosity (25 ° C.) 207 cps), X-22
-3701E (carboxyl group equivalent 3800, viscosity 25
C) 3000 cps), X-22-3710 (carboxyl group equivalent 1250, viscosity (25 ° C.) 50 cps) and the like. Specific examples of the compound represented by the formula (1) include

[0009]

[Chemical 3]

[0010]

[Chemical 4]

The following can be mentioned. The reaction between the silicone oil and the compound represented by the formula (1) is carried out preferably by adding about 0.5 to 1.5 of the epoxy group of the compound represented by the formula (1) to 1 equivalent of the carboxyl group of the silicone oil.
The reaction is carried out at an equivalent ratio, particularly preferably in a ratio of about 0.8 to 1.1 equivalents, and a catalyst (eg, benzyldimethylamine, methyltriethylammonium chloride, triphenylstibine, triphenylphosphine) is added to accelerate the reaction during the reaction. Etc.) is preferably used, and the amount of the catalyst used is 0.1 to 10% by weight with respect to the reaction raw material mixture.
It is preferable to use in the range of. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, metoquinone, hydroquinone, phenothiazine, etc.),
The amount used is preferably in the range of 0.01 to 1% by weight with respect to the reaction raw material mixture. The reaction temperature is usually 6
It is 0 to 150 ° C. The reaction time is usually 5 to 60 hours.

In the resin composition of the present invention (2
The functional group-containing unsaturated group-containing compound (B) is used. Specifically, for example, 1,6-hexanediol di (meth)
Acrylate, tricyclodecane dimethylol di (meth) acrylate, dioxaglycol di (meth) acrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD R-6)
04), trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta and hexa (meth).
It is a reaction product of (meth) acrylic acid with a reactive monomer such as acrylate and ditrimethylolpropane tetra (meth) acrylate, an epoxy resin such as phenol novolac type epoxy resin, cresol novolac type epoxy resin and bisphenol A type epoxy resin. An epoxy (meth) acrylate etc. can be mentioned. The amount of the unsaturated group-containing compound (B) used is preferably 100 to 20,000 parts by weight, particularly preferably 500 to 10,000 parts by weight, based on 100 parts by weight of the reaction product (A). Furthermore,
If necessary, a solvent, a photopolymerization initiator, and monofunctional reactive monomer (for example, (meth) acrylic acid ester) polymers can be contained.

The solvent is, for example, an alcoholic solvent,
Various solvents such as Kent 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, benzyldimethyl ketal, benzyl diethyl ketal, 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 based on 100 parts by weight of the total weight of the reaction product (A) and the component (B). The resin composition used in the present invention is a reaction product (A), 2 other than the component (A)
It can be obtained by mixing and dissolving a functional or higher unsaturated group-containing compound (B), a solvent, a photopolymerization initiator, polymers and the like.

In order to improve the slipperiness of the heat-resistant layer formed by the cured film of the resin composition with respect to the thermal head and further 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 metals, metal oxides, and Examples thereof include fine particles of metal sulfide, 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, fluororesin, benzoguanamine resin, phenol resin, melamine resin, urea resin and the like. it can. 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. Lubricants and surfactants are difficult to distinguish and some are commonly used. Specific examples of lubricants include natural and synthetic waxes, fatty acids, fatty acid amides, higher fatty acid metal salts, and higher alcohols. , Fatty acid esters, silicone oil, phosphoric acid esters and the like. Examples of the surfactant include various anionic surfactants, various cationic surfactants, various nonionic surfactants, fluorine-based surfactants and silicone-based surfactants. 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.

Examples of the method of applying the resin composition used for forming the heat resistant layer include various methods such as a gravure coater, a reverse roll coater, a wire bar coater and an air doctor coat. 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 beams, 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 thermal 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 and polypropylene film. Among them, polyethylene terephthalate film is
The thickness of these base films is preferably 1 to 30 μm, and more preferably 2 to 15 μm from the viewpoints of mechanical strength, dimensional stability, heat resistance, price, 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, coating this ink on a base film, and drying it. In the case of a melt-type thermal transfer recording sheet, an ink is prepared by dissolving or dispersing a pigment such as a pigment or a dye in a heat-fusible substance using a solvent as needed, and using this ink as a base film. It can be applied 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. ..

As the binder resin, polycarbonate resin, polysulfone resin, polyvinyl butyral resin, polyacrylate resin, polyamide resin, polyaramid resin, polyimide resin, polyetherimide resin,
Examples include polyester resins, acrylonitrile-styrene resins and cellulosic 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 solvents such as cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, alcohol solvents such as isopropanol and methyl cellosolve, halogen solvents such as methylene chloride, trichloroethylene and chlorobenzene,
An ether solvent such as dioxane or tetrahydrofuran is 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 acid dyes containing a sulfonic acid group. , Basic dyes, metal complex dyes, oil-soluble dyes and the like 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 wax, montan wax, microcrystalline wax, wood wax, and oil-based synthetic wax.

As the solvent, the same solvents as in the case of the above-mentioned sublimation type thermal transfer recording sheet can be mentioned. 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 method of applying these inks can be carried out in the same manner as described for the application of the heat-resistant layer, and 0.1 to 5 μm is suitable for the applied coating film. Further, in the production of the recording sheet of the present invention, in order to improve the adhesion between each layer formed by the above coating and the base film, the surface of the base film is subjected to a corona treatment, or a polyester resin, a cellulose resin, An undercoating treatment with a resin such as polyvinyl alcohol, a urethane resin, or polyvinylidene chloride may be performed. 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 like a line printer. In addition, the recording paper (image-receiving body) for transfer recording using the thermal transfer recording sheet is usually a synthetic paper or the like resin and a resin (for example, saturated polyester resin).
Use the one coated with. The resin composition of the present invention is useful as a thermal transfer recording sheet, but is also useful as a release agent, an overcoat agent for thermal recording paper, various coating agents, and the like.

[0020]

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. Synthetic Example of Component (A) Synthetic Example 1 Carboxyl-modified silicone oil (X-22-162A, manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl group equivalent 9)
20) 500 parts, compound of the formula (2) (manufactured by Daicel Chemical Industries, Ltd., GK-200, epoxy group equivalent 195)
116.6 parts, methoquinone 0.3 parts and triphenylphosphine 2.2 parts were charged, and the temperature was raised to 95 ° C. and 95 ° C.
The reaction was carried out until the acid value (mgKOH / g) of the reaction solution became 1.0 or less. The viscosity of the product obtained (25
C.) was 1100 cps.

Synthesis Example 2 Carboxyl-modified silicone oil (X-22-162C, manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl group equivalent 2)
330) 500 parts, GK-200, 46 parts, methoquinone 0.2 parts and triphenylphosphine 1.9 parts were charged and reacted at 95 ° C., and the acid value (mgKOH / g) of the reaction solution was 1.0. The reaction was carried out until the following. The viscosity of the obtained product (25 ° C.) was 710 cps.

Synthetic Example 3 Carboxyl-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-3701E, carboxyl group equivalent 3800) 400 parts, GK-200 20.6 parts, metoquinone 0.2 parts and triphenylphosphine. Charge 1.5 parts of fins, react at 95 ℃, and acid value of the reaction solution (mgKOH / g)
Was carried out until was 1.0 or less. The viscosity (25 ° C.) of the obtained product was 3900 cps.

Synthesis Example 4 Carboxyl-modified silicone oil (X-223710, manufactured by Shin-Etsu Chemical Co., Ltd., carboxyl group equivalent 1)
250) 400 parts, GK-200 62.4 parts, methoquinone 0.2 parts and 1.6 parts were charged and reacted at 95 ° C until the acid value (mgKOH / g) of the reaction solution became 1.0 or less. The reaction was carried out. The viscosity of the obtained product (25 ° C) is 155.
It was cps.

Example 1 (b) Production of thermal transfer recording sheet A polyethylene terephthalate film (thickness: 4 μm) was used as a base film, and the resin composition of the present invention described below was applied to one surface of the polyethylene terephthalate film and dried. High-pressure mercury lamp (2
(kw, 80 w / cm ² ), a curing reaction was carried out by treating under a condition of a distance between the mercury lamp and the film of 80 mm and an irradiation time of 5 seconds to form a heat resistant layer having a thickness of about 2 μm.

Resin composition (1) Reaction product (A) obtained in Synthesis Example 1 5 parts (2) Dipentaerythritol penta and hexaacrylate mixture 45 parts (3) Acrylate polymer (Rohm & Haas Co., Paraloid A- 21) 50 parts (4) Ethyl acetate 300 parts (5) Methyl ethyl ketone 100 parts (6) Silica fine particles (Aerosil R972, Nippon Aerosil Co., Ltd.) 20 parts (7) Photopolymerization initiator (Irgacure 907, Ciba Geigy) 5)

On the back surface of the heat-resistant layer of the above film, an ink comprising 5 parts of sublimable dye (CI Solvent Blue 95), 10 parts of polysulfone resin, and 85 parts of chlorobenzel was applied and dried to a thickness of about 1 μm. A color material layer was formed 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 at 100 ° C. for 30 minutes in an oven to prepare an image receptor. (C) Transfer recording result The resin coated surface of the image receiving member of the color material layer of the recording sheet manufactured as described above is overlaid and the heat-resistant layer surface of the recording sheet is coated with 8
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, there was no sticking sound, the sheet traveled 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 6 Various resin compositions shown in Table 1 were used as the resin composition for forming the heat-resistant layer, and the same procedure as in Example 1 was carried out except that the heat-resistant layer having the thickness shown in Table 1 was formed. And various thermal transfer recording sheets were manufactured. Transfer recording was performed in the same manner as in Example 1 by using the various transfer recording sheets obtained and the image receiver manufactured 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 sticking noise, and good transfer recording was obtained. Also, the surface of the head after recording was observed, but no dust was observed. Further, 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 Example 1 1 3 Reaction product (A) obtained in Synthesis Example 1 in Example 1 was synthesized. 2 Same as Example 1 except that the reaction product (A) obtained in 2 was changed. 4 The reaction product (A) obtained in Synthesis Example 1 in Example 1 was changed to the reaction product (A) obtained in Synthesis Example 3. 2 Same as Example 1 except that changed 5 Same as 2 except that the reaction product (A) obtained in Synthesis Example 1 in Example 1 was changed to the reaction product (A) obtained in Synthesis Example 4 6 Same as Example 1 except that the mixture of dipentaerythritol penta and hexaacrylate in Example 1 was changed to KAYARA 2 D R-604 (manufactured by Nippon Kayaku Co., Ltd., diacrylate).

Comparative Example 1 In the resin composition for forming a heat-resistant layer, the same procedure as in Example 1 was carried out except that a mixture of dipentaerythritol penta and hexaacrylate was used in place of the reaction product (A) obtained in Synthesis Example 1 in Example 1. A heat resistant layer was similarly formed on the film, but after curing, the film curled with the heat resistant layer inside. Then, an image receptor was prepared in the same manner as in Example 1, and transfer recording was performed. As a result, the head and the sheet were fused, there was a stick sound, the sheet did not run smoothly, and good transfer recording was not obtained. It was

[0031]

INDUSTRIAL APPLICABILITY The resin composition of the present invention and the sheet for thermal transfer recording using the same do not cause the thermal head to be fused to the base film during recording, and further, the stick sound and the residue of the thermal head caused by the fusion do not occur. Since it runs satisfactorily without adhesion, transfer recording with good image quality can be obtained. Further, this recording sheet has no curl and is easy to handle.

Claims (2)

[Claims] 1. A silicone oil having a carboxyl group in the molecule and a compound represented by the formula (1): A resin composition comprising a reaction product (A) with (R is a hydrogen atom or a methyl group) and a bifunctional or higher functional unsaturated group-containing compound (B) other than the component (A). 2. A heat transfer recording sheet having a heat transferable color material layer on one surface of a base film, and a heat resistant layer formed by curing the resin composition according to claim 1 on the other surface of the film. A thermal transfer recording sheet characterized by the above.