JPH10292013A - Resin, heat-resistant coating material and thermal transfer sheet coated with the coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin which can form a film and has excellent heat resistance and flexibility by reacting a polyvinyl butyral resin with an isocyanato (meth)acrylic acid or a derivative thereof. SOLUTION: To a solution obtained by dissolving a polyvinyl butyral resin in a solvent such as a ketone, cellosolver or DMSO, an isocyanate (meth)acrylic acid or a derivative thereof is added dropwise under agitation in such an amount that the ratio of isocyanato groups is 0.1-5 mol, desirably 0.5-3 mol per mol of the hydroxyl groups of the resin to form urethane bonds resulting from the reaction between the isocyanato groups and the hydroxyl groups. (Meth) acryloyl groups are introduced through the urethane bonds into the polyvinyl butyral resin to obtain the title resin of the formula [wherein X is H or acetyl; Y is a (meth)acryloyl-containing group; (l) is 40-85; (m) is 0-10; (m) is 0-10; (n) is 15-50; and l+m+n is 100].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin, a heat-resistant paint and a thermal transfer sheet using the paint, and more particularly to a (meth) acryl-modified polyvinyl butyral resin capable of forming a film having both heat resistance and flexibility. The present invention relates to a heat-resistant paint containing the resin and a thermal transfer sheet using the paint.

[0002]

2. Description of the Related Art Conventionally, so-called plastic paints have been known for protecting the surfaces of various plastic films, sheets and resin molded articles. One use of plastic films is in thermal transfer sheets. Hereinafter, the present invention will be described with reference to a thermal transfer sheet as an example of the use of the resin and the paint of the present invention. As the thermal transfer sheet, a sublimation type thermal transfer sheet provided with a dye layer composed of a sublimable dye and a binder on one surface of a polyester film or the like, and an ink layer composed of a pigment and wax instead of the dye layer were provided. 2. Description of the Related Art A heat transfer type heat transfer sheet is known. These thermal transfer sheets are heated imagewise from the back by a thermal head, and the dye or ink layer of the dye layer is transferred to a material to be transferred to form an image.

[0003]

When an image is formed by a thermal head using the above-mentioned thermal transfer sheet, and when the base film is a thermoplastic film such as a polyester film, the thermal head heats the base film by the heat of the thermal head. And it is difficult to form an image. One solution to this problem is
Various proposals have been made to form a heat-resistant lubricating layer made of a heat-resistant material. A conventional excellent heat-resistant lubricating layer is a crosslinked and cured heat-resistant lubricating layer composed of a thermoplastic resin having a hydroxyl group and polyisocyanate.

The method of forming a heat-resistant lubricating layer using the above-mentioned polyisocyanate as a cross-linking agent has various properties such as heat resistance as compared with a heat-resistant lubricating layer formed of a normal heat-resistant thermoplastic resin. However, in the method using the polyisocyanate, aging treatment (for example, holding in a 60 ° C. oven for 5 days) is required in order to sufficiently crosslink with the polyisocyanate. However, there is a problem in securing a storage place for the thermal transfer sheet during aging. When a heat-resistant lubricating layer is formed using an ordinary ionizing radiation curable resin such as an ultraviolet ray and an electron beam (epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, etc.) When the crosslink density of the lubricating layer is low, heat resistance is inferior. On the other hand, when the crosslink density is high, the flexibility of the formed layer is inferior. Accordingly, an object of the present invention is to provide a resin capable of imparting excellent heat resistance, coating property, flexibility, slip property, running property of a thermal head, etc. to a plastic film used as a base material of a thermal transfer sheet or the like. An object of the present invention is to provide a heat-resistant paint containing a resin and a thermal transfer sheet using the paint.

[0005]

The above object is achieved by the present invention described below. That is, the present invention is a polyvinyl butyral resin having a (meth) acryloyl group, represented by the following structural formula, a heat-resistant paint containing the resin, and a thermal transfer sheet using the paint. (X in the above formula represents a hydrogen atom or an acetyl group, Y is a group having a (meth) acryloyl group, and when the total of l (m), m and n in the formula is 100, Is 40 to 85, m is an integer of 0 to 10, and n is an integer of 15 to 50.)

According to the present invention, it is possible to provide a plastic film or the like used as a base material of a thermal transfer sheet or the like with a coating having excellent heat resistance, coating property, flexibility, slip property, running property of a thermal head, and the like. The resin which can be provided can be provided. In particular, in the formation of the heat-resistant lubricating layer of the thermal transfer sheet, ionizing radiation such as ultraviolet rays or electron beams can be used as a means for curing the formed film, so that aging treatment after forming the layer is unnecessary, and the high crosslinking density is high. However, a heat-resistant lubricating layer having excellent flexibility and heat resistance can be formed.

[0007]

Next, the present invention will be described in more detail with reference to preferred embodiments. The (meth) acryl-modified polyvinyl butyral resin of the present invention is a resin in which a (meth) acryloyl group is further introduced into a molecule by utilizing a hydroxyl group remaining in the polyvinyl butyral resin,
It is represented by the following structural formula.

In the above formula, X represents a hydrogen atom or an acetyl group, and Y is a group having a (meth) acryloyl group. The (meth) acryloyl group is aromatic, aliphatic,
It may be bonded to a hydroxyl group of a polyvinyl butyral resin via a linking group such as an alicyclic group. Also, l in the formula
When the total of m and n is 100, l is 40 to 8
5, m is an integer of 0 to 10 and n is an integer of 15 to 50, and the total molecular weight is preferably about 30,000 to 200,000.
As described above, by utilizing the hydroxyl groups remaining in the conventional polyvinyl butyral resin, a (meth) acryl-modified polyvinyl butyral resin having a large number of (meth) acryloyl groups introduced into the molecule can be used, for example, to reduce the heat resistance of a thermal transfer sheet. In the case of forming a lubricating layer, ionizing radiation such as ultraviolet rays or electron beams can be used as a curing means, so that aging treatment after forming the layer is unnecessary, and flexibility and heat resistance are high despite high crosslink density. A heat-resistant lubricating layer having excellent heat resistance can be formed.

The above (meth) acryl-modified polyvinyl butyral resin is dissolved in a solvent capable of dissolving the polyvinyl butyral resin, for example, ketone, cellosolve, DMSO or the like, and the solution having an isocyanate group (meth) is stirred while stirring. By dropping and reacting acrylic acid or a derivative thereof, an isocyanate group reacts with a hydroxyl group of the polyvinyl butyral resin to generate a urethane bond,
A (meth) acryloyl group can be introduced into the resin via the urethane bond. The amount of the isocyanate group-containing (meth) acrylic acid compound used at this time is 0.1 to 5 isocyanate groups per mole of hydroxyl groups in a ratio of hydroxyl groups to isocyanate groups of the polyvinyl butyral resin.
Mole, preferably in the range of 0.5 to 3 moles.

As another production method, a polyvinyl butyral resin is dissolved in a solvent capable of dissolving, for example, ketone, cellosolve, DMSO, etc., and (meth) acrylic acid chloride or a derivative thereof is stirred while the solution is stirred. The acid chloride group reacts with the hydroxyl group of the polyvinyl butyral resin to form an ester bond, and a (meth) acryloyl group can be introduced into the resin via the ester bond. The amount of (meth) acrylic acid chloride or a derivative thereof used at this time is 0.1 to 5 moles, preferably 0 to 5 moles, per mole of hydroxyl group, based on the ratio of hydroxyl group to acid chloride group of the polyvinyl butyral resin. The amount is in the range of 0.5 to 3 mol.

Next, a production example of the above (meth) acryl-modified polyvinyl butyral resin will be described. Production Example 1 In a four-necked flask equipped with a thermometer, a stirrer, a dropping funnel and a cooling tube, 2.5 g of polyvinyl butyral resin (Eslec BX-1, manufactured by Sekisui Chemical), 97 g of methyl ethyl ketone and 0.03 g of dibutyltin dilaurate were placed. The mixture was charged and the internal temperature was adjusted to 50 ° C., followed by stirring. To this, 1.07 g of methacryloyloxyethyl isocyanate (Karenz MOI, Showa Denko) was added dropwise. After the dropwise addition, a heating reaction was performed at 50 ° C. to obtain a solution of methacryl-modified polybutyral resin-1 (solid content: about 3.55% by weight). The reaction was terminated by measuring the amount of isocyanate in the reaction solution by reverse titration analysis and confirming that the charged isocyanate had reacted at 90% or more.

Production Example 2 In the same manner as in Production Example 1, 2.5 g of polyvinyl butyral resin (ESLEK BX-1), 97 g of MEK and 0.68 g of triethylamine were charged into a reactor, and the mixture was stirred at an internal temperature of 60 ° C. Acrylic acid chloride (Tokyo Kasei)
After the completion of the reaction, the precipitated triethylamine hydrochloride was removed by a centrifugal separator, and a solution of acrylic-modified polyvinyl butyral resin-2 (solid content: about 3.51 wt. %).

Production Example 3 As in Production Example 1, a reactor was charged with 2.5 g of polyvinyl butyral resin (ESLEC BX-1) and 97 g of MEK, and the mixture was stirred at an internal temperature of 50 ° C. This is followed by methacryloyl isocyanate (MAI, Nippon Paint) 2.93
g was dropped, and a heating reaction was performed at 50 ° C. after dropping to obtain a solution of methacryl-modified polyvinyl butyral resin-3 (solid content: about 5.3% by weight).

Production Example 4 As in Production Example 1, 2.5 g of polyvinyl butyral resin (ESLEK BL-SH, Sekisui Chemical), MEK
97 g and dibutyltin dilaurate 0.03 g were charged, and the mixture was stirred at an internal temperature of 50 ° C. To this, 0.65 g of methacryloyloxyethyl isocyanate (Karenz MOI, manufactured by Showa Denko KK) was dropped, and after the dropping, a heating reaction was carried out at 50 ° C. to give a solution of methacryl-modified polyvinyl butyral resin-4 (solid content: about 3.14 wt. %).

The heat-resistant paint of the present invention is characterized in that the (meth) acryl-modified polyvinyl butyral resin of the present invention is used as a film-forming component and is dissolved in a suitable organic solvent. As the organic solvent to be used, any organic solvent that dissolves the above (meth) acryl-modified polyvinyl butyral resin may be used. However, in consideration of coating properties and drying properties, aromatic solvents such as toluene and xylene, acetone ,
Methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, methyl cellosolve, cellosolve organic solvents such as ethyl cellosolve, and the like,
Particularly, a mixed solvent composed of these solvents is preferably used. The solid content concentration of the (meth) acryl-modified polyvinyl butyral resin in the paint is not particularly limited, but is generally preferably about 1 to 20% by weight on a weight basis. The heat-resistant paint of the present invention can contain various additives according to its use. These additives are used for the purpose of imparting lubricity, antistatic property, further heat resistance and the like to the formed film. These additives will be described in more detail by taking the following application to a thermal transfer sheet as a typical example.

The above-mentioned method of using the (meth) acryl-modified polyvinyl butyral resin and the heat-resistant paint of the present invention will be described in more detail with reference to an example in which the method is applied to the formation of a heat-resistant lubricating layer of a thermal transfer sheet. As the base sheet used for the production of the thermal transfer sheet, any one may be used as long as it has a conventionally known degree of heat resistance and strength.
Paper having a thickness of 5 to 50 μm, preferably about 3 to 10 μm, various processed papers, polyester film, polystyrene film, polypropylene film, polysulfone film, aramid film, polycarbonate film,
Polyvinyl alcohol film, cellophane, etc.,
Particularly preferred is a polyester film. These base sheets may be of a single-wafer type or a continuous film, and are not particularly limited. Of these, polyethylene terephthalate film is particularly preferable, and it is also preferable to form a primer layer or an adhesive layer on one or both surfaces of the film, if necessary.

In the present invention, on the surface of the base film,
A heat-resistant lubricating layer comprising the (meth) acryl-modified polyvinyl butyral resin of the present invention is formed. When forming the heat-resistant layer, a primer layer or an adhesive layer can be formed in advance on the surface of the base film as necessary. or,
In the present invention, when forming a heat-resistant lubricating layer from the above materials, wax, higher fatty acid amide, surfactant, sulfate, phosphorus, Acid powders, fatty acid esters, heat release agents such as silyl isocyanate and lubricants or organic powders such as fluororesins, silica, clay, talc,
Inorganic particles such as calcium carbonate can be included. These various additives are used in an amount of about 0 to 100 parts by weight, preferably 0 to 30 parts by weight, per 100 parts by weight (solid content) of the (meth) acryl-modified polyvinyl butyral resin of the present invention.

Particularly preferred surfactants are solid ionic surfactants such as sodium stearyl sulfate, sodium lauryl sulfate, sodium myristyl sulfate, sodium stearate, sodium laurate, sodium myristate, sodium stearyl sulfonate. , Sodium lauryl sulfonate, anionic surfactants such as sodium dioctylsulfosuccinate, and cationic surfactants such as stearyltrimethylammonium chloride and laurylpyridinium chloride. There is no stickiness in the heat-resistant active layer, which prevents blocking and set-off due to stickiness, yet the surfactant bleeds out to the surface of the layer only when it comes into contact with the thermal head, effectively It can provide excellent sliding property on the surface. These surfactants are preferably used in an amount of about 3 to 100 parts by weight per 100 parts by weight (solid content) of the (meth) acryl-modified polyvinyl butyral resin of the present invention. Also, in order to prevent electrification of the finally obtained thermal transfer sheet, carbon black in the heat-resistant paint,
Metal oxides such as tin oxide and titanium oxide, various metal alkoxides, conductive fillers such as ITO powder and polyaniline,
By adding an organic conductive material such as polythiophene and polypyrrole, a heat-resistant lubricating layer having excellent antistatic properties can be formed. The addition amount is preferably in the range of about 10 to 100 parts by weight per 100 parts by weight (solid content) of the (meth) acryl-modified polyvinyl butyral resin of the present invention.

Further, in order to adjust the flexibility and crosslink density of the heat-resistant lubricating layer to be obtained, a usual thermoplastic resin or a (meth) acrylic or other monofunctional or polyfunctional monomer is contained in the heat-resistant paint. , Oligomers and the like can be used as a mixture. The amount used is preferably in the range of about 50 to 500 parts by weight per 100 parts by weight (solid content) of the (meth) acryl-modified polyvinyl butyral resin of the present invention. For example, monofunctional monomers include mono (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, and (meth) acryloyloxyethyl phthalate. Examples of the difunctional or higher functional monomer include, for example, polyol (meth) acrylate (epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate), polyester (meth) acrylate, epoxy (Meth) acrylate, urethane (meth) acrylate, other, polybutadiene, isocyanuric acid, hydantoin,
Melamine-based, phosphoric-acid-based, imide-based, phosphazene-based poly (meth) acrylates and other various monomers that are UV-curable or electron-beam-curable,
Oligomer or polymer is mentioned.

More specifically, examples of the bifunctional monomer or oligomer include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol. Di (meth) acrylate and the like; and trifunctional monomers, oligomers and polymers, for example, aliphatic tri (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate Examples of the tetrafunctional monomer or oligomer include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate. Examples of the pentafunctional or higher functional monomer or oligomer include, for example, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, and a polyfunctional (meth) having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton. Acrylate and the like. The number of functional groups of these polyfunctional monomers and oligomers is not particularly limited, but when the number of functional groups is smaller than 3, the heat resistance of the heat-resistant lubricating layer formed tends to decrease. Since the flexibility of the heat-resistant lubricating layer to be formed tends to decrease, a layer having 3 to 20 functions is particularly preferable.

The heat-resistant lubricating layer is prepared by dissolving or dispersing the above-mentioned materials in an appropriate solvent such as acetone, methyl ethyl ketone, toluene and xylene to prepare the heat-resistant paint of the present invention. It is formed by coating and drying by a conventional coating means such as a coater and a wire bar, and then performing a cross-linking film forming treatment by irradiating ionizing radiation such as ultraviolet rays and electron beams. As a coating amount, i.e. there is also a significant thickness of the heat-resistant slip layer, on a solids basis in the present invention 2.0 g / m ² or less, preferably a sufficient thickness of 0.1 to 1.0 g / m ² A heat-resistant lubricating layer having performance can be formed. Thickness 0.1
When the thickness is less than g / m ² , the performance as a heat-resistant lubricating layer is insufficient. On the other hand, when the thickness exceeds 2.0 g / m ² , the thermal conductivity from the thermal head to the coloring material layer decreases, which is not preferable. .

As a color material layer formed on one side of the base sheet, a layer containing a sublimable dye is formed in the case of a sublimation type thermal transfer sheet, while a layer containing a sublimable dye is formed in the case of a heat melting type thermal transfer sheet. Forms a wax ink layer colored with a pigment.
Hereinafter, the case of a sublimation type thermal transfer sheet will be described as a typical example, but the present invention is not limited to the sublimation type thermal transfer sheet. As the dye used in the dye layer, any dye conventionally used in a thermal transfer sheet can be effectively used in the present invention, and is not particularly limited. For example, some preferred dyes include MS Red as a red dye.
G, Macrolex Red VioletR, CeresRed 7B, Samaron
Red HBSL, Resolin Red F3BS, etc., and as a yellow dye, Holon Brilliant Yellow 6GL, P
TY-52, Macrolex Yellow 6G, etc., and as the blue dye, Kayaset Blue 714,
Waxolin Blue AP-FW, Holon Brilliant Blue SR, MS Blue 100 and the like.

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

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

The dye layer thus formed has a thickness of 0.2 to
It has a thickness of about 5.0 μm, preferably about 0.4 to 2.0 μm, and the sublimable dye in the dye layer accounts for 5 to 90% by weight, preferably 10 to 70% by weight of the weight of the dye layer. It is preferably present in an amount. The dye layer to be formed is formed by selecting one color from the above dyes when the desired image is a monocolor, and when the desired image is a full color image, for example, suitable cyan, magenta and Select yellow (and black if necessary),
A magenta and cyan (and, if necessary, black) dye layers are formed.

The image-receiving sheet used to form an image using the above-described thermal transfer sheet may be any image-receiving sheet as long as its recording surface has a dye-accepting property for the above-mentioned dye. In the case of paper, metal, glass, synthetic resin, or the like having no dye receptivity, a dye receiving layer may be formed on at least one surface thereof. In the case of the heat transfer type thermal transfer sheet, the material to be transferred is not particularly limited, and may be ordinary paper or plastic film. A known thermal transfer printer can be used as it is as a printer used when performing thermal transfer using the thermal transfer sheet and the image receiving sheet as described above, and is not particularly limited.

In the above description, the present invention has been described with reference to an example in which the heat-resistant lubricating layer is formed on the base material sheet via the primer layer. It may be added to the layer, to the heat-resistant lubricating layer, or to both, and in any case, the obtained thermal transfer sheet can be provided with excellent antistatic properties. Also, the base sheet is subjected to an easy adhesion treatment, or if the heat-resistant lubricating layer has good adhesion to the base material, the primer layer may not be necessary.
By adding the above-described antistatic agent to the heat-resistant lubricating layer as needed, the obtained thermal transfer sheet can be provided with excellent antistatic properties.

[0028]

Next, the present invention will be described more specifically with reference to examples and comparative examples. In the following description, parts and% are based on weight unless otherwise specified. Example 1 Ink for primer layer: sulfonated polyaniline (conductive agent, manufactured by Nitto Kagaku Kogyo, solid content 10% aqueous solution) 0.25 part (solid content) water-soluble polyester resin (Polyester WR-961, manufactured by Nippon Synthetic Chemical Industry) 4.75 parts (solid content) Phosphate ester surfactant (Plysurf 217E, manufactured by Daiichi Kogyo Seiyaku) 0.2 parts Water 44.8 parts Isopropyl alcohol 50.0 parts

The above ink was applied to a PET base sheet (6 μm).
m, manufactured by Diafoil Co., Ltd.), using a Miya Bar ^# 5 to apply a thickness of 0.1 μm (coating amount: 0.1 g / m ² ) when dry using a miller bar ^# 5, followed by hot air drying to form a primer layer. Formed. Ink for heat-resistant lubricating layer (heat-resistant paint): 80 parts of methacrylic-modified polyvinyl butyral resin solution in Production Example 1 (solid content: 2.84%) Phosphate ester (Plysurf A-208S: phosphate ester liquid which is liquid at ordinary temperature) Neon surfactant, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 1 part Solvent (MEK / toluene = 1/1) 19 parts

The above ink is applied on the surface of the primer layer so as to have a thickness of 1.0 μm when dried, followed by hot air drying,
An electron beam accelerated at 180 kv in a nitrogen gas atmosphere
Cross-linking and curing treatment was performed by irradiation with Mrad to form a heat-resistant lubricating layer. Next, the following ink for forming a dye layer was applied to the opposite surface of the heat-resistant lubricating layer by gravure printing so as to have a dry thickness of 1.0 g / m ² and dried to obtain a thermal transfer sheet of the present invention. Ink for forming dye layer: C.I. I. Solvent Blue 22 5.50 parts Acetoacetal resin 3.00 parts Methyl ethyl ketone 22.54 parts Toluene 68.18 parts

Evaluation Sample Preparation Example 1 The ink for a heat-resistant lubricating layer was applied on a 6-μm-thick PET film so that the thickness of the coating film after drying was 50 μm, dried with warm air, and then dried under a nitrogen gas atmosphere at 180 kV. The coating film was cured by irradiating 5 Mrad with the electron beam accelerated by the above method to obtain a sample for measuring the glass transition temperature (Tg) of the coating film and measuring the weight loss at 500 ° C. Evaluation Sample Production Example 2 The ink for a heat-resistant lubricating layer was applied on a 6-μm-thick PET film so that the thickness of a coating film after drying was 1.0 μm, and after drying with hot air, at 180 kV in a nitrogen gas atmosphere. Irradiate the accelerated electron beam for 5 Mrad to cure the coating,
The coating film was used as a sample for measuring heat resistance and a sample for measuring flexibility.

Example 2 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Heat-resistant lubricating layer ink: 80 parts of acrylic-modified polyvinyl butyral resin solution in Preparation Example 2 (solid content: 2.81%) Phosphate ester (Plysurf A-217E: phosphate ester surfactant solid at room temperature, first) 1 part Solvent (MEK / toluene = 1/1) 19 parts A sample for measuring the Tg, 500 ° C. weight loss, heat resistance and flexibility of the heat-resistant lubricating layer of the obtained thermal transfer sheet was prepared as described above. It was produced in the same manner as in Evaluation Sample Production Examples 1 and 2.

Example 3 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer: 80 parts of methacryl-modified polyvinyl butyral resin solution in Production Example 3 (solid content: 4.24%) Phosphate ester (Plysurf A-217E, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene) = 1/1) 19 parts A sample for measuring the Tg of the heat-resistant lubricating layer of the obtained thermal transfer sheet, the weight loss rate at 500 ° C., the heat resistance, and the flexibility was prepared in the same manner as in Evaluation Sample Preparation Examples 1 and 2. Produced.

Example 4 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer: 80 parts of methacryl-modified polyvinyl butyral resin solution in Production Example 4 (solid content: 2.52%) Phosphate ester (Plysurf A-217E, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene) = 1/1) 19 parts A sample for measuring the Tg of the heat-resistant lubricating layer of the obtained thermal transfer sheet, the weight loss rate at 500 ° C., the heat resistance, and the flexibility was prepared in the same manner as in Evaluation Sample Preparation Examples 1 and 2. Produced.

Comparative Example 1 The following two kinds of inks were used in place of the heat-resistant lubricating layer ink in Example 1, and the coating was cured by aging in a 60 ° C. oven for 5 days. In the same manner as described above, two types of thermal transfer sheets of Comparative Examples were obtained. Heat-resistant lubricating layer ink A: Polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical) 3 parts Polyisocyanate curing agent (Bernock D750, manufactured by Dainippon Ink) 7 parts (NCO / OH = 1.8) Solvent (MEK) / Toluene = 1/1) 90 parts

Ink B for heat-resistant lubricating layer: polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical) 3 parts Polyisocyanate curing agent (Bernock D750, manufactured by Dainippon Ink) 7 parts (NCO / OH = 1.8) Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene = 1/1) 89 parts Tg of heat-resistant lubricating layer of two kinds of obtained thermal transfer sheets, 50
Example of preparing the evaluation sample except that two kinds of samples (A and B) for measuring the weight loss rate, heat resistance and flexibility at 0 ° C. were subjected to aging of the coating film in a 60 ° C. oven for 5 days. It was produced in the same manner as 1 and 2.

Comparative Example 2 A thermal transfer sheet of Comparative Example was prepared in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1 and that the coating film was dried by heating. Obtained. Ink for heat-resistant lubricating layer: polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical) 3 parts Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene = 1/1) 96 parts A sample for measuring the Tg of the heat-resistant lubricating layer of the obtained heat-transferable sheet, the weight loss rate at 500 ° C., the heat resistance, and the flexibility was formed by heating and drying the coating film. It was produced in the same manner as in Example 2.

Comparative Example 3 A thermal transfer sheet of Comparative Example was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer: Urethane acrylate (NK Oligo U-4HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 3 parts Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene = 1/1) 96 parts) A sample for measuring the Tg of the heat-resistant lubricating layer of the obtained thermal transfer sheet, the weight loss rate at 500 ° C., the heat resistance, and the flexibility was prepared in the same manner as in Evaluation Sample Preparation Examples 1 and 2.

Comparative Example 4 A thermal transfer sheet of Comparative Example was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Heat-resistant lubricating layer ink: Urethane acrylate (NK Oligo U-15HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 3 parts Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 1 part Solvent (MEK / toluene = 1/1) 96 parts) Tg of heat-resistant lubricating layer of thermal transfer sheet obtained above, 50
Samples for measuring the 0 ° C. weight loss rate, heat resistance, and flexibility were prepared in the same manner as in Evaluation Sample Preparation Examples 1 and 2.

Evaluation Method Each of the evaluation samples of Examples 1 to 4 and Comparative Examples 1 to 4 was evaluated by the following method, and the results shown in Table 1 below were obtained. Glass transition temperature (Tg) measurement: Leovibron DDV-II-E
The peak temperature of tan8 was determined as Tg temperature (° C.) using P (Orientec). Measurement of weight loss rate at 500 ° C .: Thermal analysis system TGA7
Using a WO (manufactured by PERKIN ELMER), the rate of decrease at 500 ° C. at a rate of temperature increase of 10 ° C./min was measured. Heat resistance: fusing and wrinkling between the thermal head and the thermal transfer sheet were evaluated. Flexibility: Evaluation of wrinkles during running of the thermal head was evaluated. (If the coating film had no flexibility, small cracks would occur in the coating film, causing wrinkles during printing.)

Table 1 ：: good ×: bad

Example 5 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used instead of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer : methacryl-modified polyvinyl butyral resin in Production Example 1 2 parts Pentaerythritol triacrylate (A-TMM-3, manufactured by Shin-Nakamura Chemical) 8 parts Triacrylate phosphate (Biscoat 3PA, manufactured by Osaka Organic Chemical Industry) ) 0.9 parts Talc (Micro Ace P-3, manufactured by Nippon Talc) 0.42 parts Talc (Micro Ace L-1, manufactured by Nippon Talc) 0.18 parts Phosphate ester (Plysurf A-217E, Daiichi Kogyo) Pharmaceutical) 0.4 part Isopropyl alcohol 20 parts Methyl ethyl ketone 68.1 parts A sample for measuring the heat resistance and flexibility of the heat-resistant lubricating layer of the obtained thermal transfer sheet was prepared in the above Evaluation Sample Production Example 2.
It was produced in the same manner as described above.

Example 6 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used instead of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer : methacrylic-modified polyvinyl butyral resin in Production Example 1 2 parts 6-functional polyphosphazene (PPZ, manufactured by Idemitsu Kosan) 8.9 parts Talc (Microace P-3, manufactured by Nippon Talc) 0.42 Part Talc (Microace L-1, manufactured by Nippon Talc) 0.18 part Phosphate ester (Plysurf A-217E, manufactured by Daiichi Kogyo Seiyaku) 0.4 part Isopropyl alcohol 20 parts Methyl ethyl ketone 68.1 parts The obtained thermal transfer A sample for measuring the heat resistance and the flexibility of the heat-resistant lubricating layer of the sheet was prepared as the evaluation sample preparation example 2 described above.
It was produced in the same manner as described above.

Example 7 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer : methacryl-modified polyvinyl butyral resin in Production Example 1 2 parts Hexafunctional polyphosphazene (PPZ, manufactured by Idemitsu Kosan) 0.9 parts Polyester acrylate (M8060, manufactured by Toa Gosei) 8.0 parts Talc ( Microace P-3, manufactured by Nippon Talc) 0.42 parts Talc (microace L-1, manufactured by Nippon Talc) 0.18 parts Phosphate ester (Plysurf A-208S, manufactured by Daiichi Kogyo Seiyaku) 0.4 parts Isopropyl alcohol 20 parts Methyl ethyl ketone 68.1 parts A sample for measuring the heat resistance and the flexibility of the heat-resistant lubricating layer of the obtained thermal transfer sheet was prepared as in Evaluation Sample Production Example 2 described above.
It was produced in the same manner as described above.

Example 8 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer : methacryl-modified polyvinyl butyral resin in Production Example 1 2 parts Dipentaerythritol monohydroxypentaacrylate (SR339, manufactured by Sartomer) 8 parts Triacrylate phosphate (Biscoat 3PA, manufactured by Osaka Organic Chemical Industry) 0. 9 parts Talc (Micro Ace P-3, manufactured by Nippon Talc) 0.42 parts Talc (Micro Ace L-1, manufactured by Nippon Talc) 0.18 parts Phosphate ester (Plysurf A-217E, manufactured by Daiichi Kogyo Seiyaku) 0.4 part Isopropyl alcohol 20 parts Methyl ethyl ketone 68.1 parts A sample for measuring the heat resistance and flexibility of the heat-resistant lubricating layer of the obtained thermal transfer sheet was prepared as in Evaluation Sample Production Example 2 described above.
It was produced in the same manner as described above.

Example 9 A thermal transfer sheet of the present invention was obtained in the same manner as in Example 1 except that the following ink was used in place of the heat-resistant lubricating layer ink in Example 1. Ink for heat-resistant lubricating layer : methacryl-modified polyvinyl butyral resin in Production Example 1 3 parts Urethane acrylate (NK Oligo U-15HA, manufactured by Shin-Nakamura Chemical) 7 parts Triacrylate phosphate (Biscoat 3PA, manufactured by Osaka Organic Chemical Industry) 0 .9 parts Talc (Micro Ace P-3, manufactured by Nippon Talc) 0.42 parts Talc (Micro Ace L-1, manufactured by Nippon Talc) 0.18 parts Phosphate ester (Plysurf A-217E, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.2 part Isopropyl alcohol 20 parts Methyl ethyl ketone 68.3 parts A sample for measuring the heat resistance and flexibility of the heat-resistant lubricating layer of the obtained thermal transfer sheet was prepared in the above-mentioned evaluation sample production example 2.
It was produced in the same manner as described above.

Evaluation method Each of the evaluation samples of Examples 5 to 9 was evaluated in the same manner as in Examples 1 to 4,
The results described in Table 2 below were obtained. Table 2 ◎: Excellent ○: Good

[0048]

According to the present invention as described above, a resin capable of imparting excellent heat resistance, coating property, flexibility, slipping property, running property of a thermal head, etc. to a plastic film such as a thermal transfer sheet is provided. Can be provided. In particular, in the formation of the heat-resistant lubricating layer of the thermal transfer sheet, ionizing radiation such as ultraviolet rays or electron beams can be used as a means for curing the formed film, so that aging treatment after forming the layer is unnecessary, and the high crosslinking density is high. However, a heat-resistant lubricating layer having excellent flexibility and heat resistance can be formed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 129/14 B41M 5/26 G // B05D 7/24 302 101G (72) Inventor Masayuki Ando Ichigaya Kagamachi, Shinjuku-ku, Tokyo No. 1-1, Dai Nippon Printing Co., Ltd. (72) Norikatsu Ono 1-1-1, Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai-Nippon Printing Co., Ltd. (72) Shigeki Nakajo, Ichigaya, Shinjuku-ku, Tokyo 1-1, Kagacho Dai Nippon Printing Co., Ltd.

Claims (14)

[Claims] 1. A polyvinyl butyral resin having a (meth) acryloyl group, which is represented by the following structural formula. (X in the above formula represents a hydrogen atom or an acetyl group, Y is a group having a (meth) acryloyl group, and when the total of l (m), m and n in the formula is 100, Is 40 to 85, m is an integer of 0 to 10, and n is an integer of 15 to 50.) 2. The polyvinyl butyral resin according to claim 1, having a molecular weight of 30,000 to 200,000. 3. A heat-resistant paint comprising the resin according to claim 1 as a film-forming component. 4. A heat-resistant paint comprising the resin according to claim 1 and a surfactant as a film-forming component. 5. The surfactant according to claim 4, wherein the surfactant is solid at room temperature.
The heat-resistant paint according to the above. 6. The heat-resistant paint according to claim 4, wherein the surfactant is an ionic surfactant which is solid at room temperature. 7. The heat-resistant paint according to claim 4, which comprises a polyfunctional monomer and / or a polyfunctional oligomer. 8. The heat transfer sheet according to claim 1, wherein a heat transferable color material layer is formed on one surface of the base sheet and a heat resistant slip layer is formed on the other surface. A thermal transfer sheet comprising the resin of claim 1 as a film-forming component. 9. The heat-resistant lubricating layer contains a surfactant.
4. The thermal transfer sheet according to 1. 10. The thermal transfer sheet according to claim 9, wherein the surfactant is solid at room temperature. 11. The thermal transfer sheet according to claim 9, wherein the surfactant is an ionic surfactant which is solid at room temperature. 12. The heat-resistant lubricating layer is cross-linked by a polyfunctional monomer and / or a polyfunctional oligomer.
12. The thermal transfer sheet according to any one of 11). 13. The thermal transfer sheet according to claim 8, wherein the heat-resistant lubricating layer has a thickness of 0.1 to 2 μm. 14. The thermal transfer sheet according to claim 8, further comprising a primer layer containing an antistatic agent between the heat-resistant lubricating layer and the substrate.