JPH08164679A - Thermosensible recording transfer material - Google Patents

Abstract

PURPOSE: To provide a novel thermosensible recording transfer material which has good heat resistance, film making and slipping properties and has a good back coat layer free from staining and abrasion of a thermal head. CONSTITUTION: In a thermosensible recording use transfer material in which a thermal transfer coloring material layer is placed on one side of a film type base material, a back coat layer of polysaccharide derivative reacted with organopolysiloxane or its cured product is placed on the other side of the base material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal recording transfer material, and more particularly to a thermal recording transfer material having an excellent back coat layer which prevents a base film from being fused to a thermal head.

[0002]

2. Description of the Related Art Conventionally, a sublimation type and a heat melting type have been known as a thermal recording transfer material. In the former, a dye layer consisting of a heat-sublimable dye and a heat-resistant binder resin is provided on a substrate such as a polyester film, and a thermal sublimation image is printed on the back surface of the dye by a thermal head onto a transfer substrate such as paper. The image is transferred to the image receiving layer provided in
A color material layer composed of a pigment or dye and a heat-meltable binder resin is formed, and a heat-meltable image formed by heat printing is transferred. Polyethylene terephthalate, such as polyester, has been conventionally used as a base material film for such a thermal recording transfer material, but since these are thermoplastic, the thermal head and base material film are fused during thermal printing. It may become impossible to run.

In order to solve this problem, it has been proposed to provide a back coat layer (back surface slippery layer), which is disclosed in JP-A-55-7467, JP-A-60-225777, and JP-A-62. -1575 gazette, Unexamined-Japanese-Patent No. 2-1453.
Japanese Patent Publication No. 95, Japanese Patent Application Laid-Open No. 3-61087, Japanese Patent Publication No. 4-
It is disclosed in Japanese Patent No. 17160. However, even though the thermal printer is improved and the performance is improved, the problem of contamination and wear of the thermal head occurs, especially in the case of the sublimation type that requires several times as much heat energy as the heat fusion type,
At present, the heat resistance of the thermal recording transfer material is not satisfactory. Also in the heat-melting type, improvement in heat resistance is expected due to high-speed printing, diversification of transfer target material, and the like.

On the other hand, Japanese Patent Laid-Open No. 5-85070 discloses that
A back coat layer composed of a resin or a cured product thereof in which an organopolysiloxane is graft-bonded is proposed,
It is characterized by excellent heat resistance, film-forming property, and slip property, and does not contaminate or wear the thermal head, but it does not satisfy heat resistance, slip property, and wear resistance at the same time.

[0005]

In the above-mentioned conventional techniques, it was pointed out that the slip property is insufficient or blocking occurs under severe thermal transfer conditions because all of them are based on a thermoplastic resin. . In addition, there is a method of crosslinking a hydroxyl group of a resin with an isocyanate to obtain a cured product for the purpose of increasing heat resistance, but even with this method, it was relatively difficult to sufficiently give a hydroxyl group to a resin to be crosslinked.

The present invention is intended to provide a novel transfer material for heat-sensitive recording using a polysaccharide derivative, which has not been used in the above-mentioned conventional techniques, in the back coat layer. That is, it is an object of the present invention to provide a novel thermal recording transfer material having a good back coat layer which is excellent in heat resistance, film forming property, slip property and the like and is free from contamination and abrasion of the thermal head.

[0007]

The transfer material for heat-sensitive recording according to claim 1 of the present invention is a transfer material for heat-sensitive recording in which a heat transferable color material layer is provided on one surface of a film-shaped substrate. A back coat layer made of a polysaccharide derivative obtained by reacting an organopolysiloxane or a cured product thereof is provided on the other surface of the film substrate.

The transfer material for heat-sensitive recording according to claim 2 of the present invention is the transfer material for heat-sensitive recording according to claim 1, in which the organopolysiloxane has the following general formula:

Embedded image (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, n is a number of 0 to 200, a is 0 or 1,
b represents 0, 1 or 2. ) Is represented.

The transfer material for heat-sensitive recording according to claim 3 of the present invention is the transfer material for heat-sensitive recording according to claim 2, in which the organopolysiloxane has the following general formula:

[Chemical 6] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ^{9 to} R ¹¹ are monovalent hydrocarbon group having 1 to 10 carbon atoms, or —OSiR ¹² R
A siloxy group represented by ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), b is 0,
Represents 1 or 2. ) Is represented.

The transfer material for heat-sensitive recording according to claim 4 of the present invention is the transfer material for heat-sensitive recording according to claim 2, in which the organopolysiloxane has the following general formula:

[Chemical 7] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Represents an integer of 0 to 5, and n represents a number of 0 to 200. ) Is represented.

The transfer material for heat-sensitive recording according to claim 5 of the present invention is the transfer material for heat-sensitive recording according to claim 2, in which the organopolysiloxane has the following general formula:

Embedded image (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, b is 0, 1 or 2. ) Is represented.

A heat-sensitive recording transfer material according to claim 6 of the present invention is the heat-sensitive recording transfer material according to any one of claims 1 to 5, wherein the polysaccharide derivative is a cellulose derivative, starch,
It is one or a mixture of two or more selected from dextrin and pullulan.

The transfer material for heat-sensitive recording according to claim 7 of the present invention is the transfer material for heat-sensitive recording according to claim 6, in which the cellulose derivative is methyl cellulose, ethyl cellulose, hydroxypropylmethyl cellulose, hydroxypropyl cellulose, It is selected from hydroxyethyl cellulose, hydroxyethyl methyl cellulose, acetyl cellulose and acetyl cellulose butyrate.

The heat-sensitive recording transfer material according to claim 8 of the present invention is the heat-sensitive recording transfer material according to any one of claims 1 to 7, wherein the cured product is a crosslinking reaction of a polysaccharide derivative with polyisocyanate. It is a cured product.

The present invention will be described in detail below.

(Film-like substrate) It is desirable to use a film-like substrate having a certain degree of heat resistance and strength and high dimensional stability as the transfer material for heat-sensitive recording. For example, plain paper; coated paper, processed paper such as laminated paper; resin films of polyester, polystyrene, polyolefin, polyamide, polysulfone, polycarbonate, polyvinyl alcohol, etc. are preferably used, and polyethylene terephthalate film is particularly preferable.
The thickness of the film substrate is 50 μm or less, preferably 3 to
The thickness is about 10 μm, and the form is not particularly limited, and it is often used in a continuous type such as a roll, but a single sheet type may be used.

(Backcoat Layer) The backcoat layer provided on one surface of the film-shaped substrate is a polysaccharide derivative obtained by reacting an organopolysiloxane or a cured product thereof.

The organopolysiloxane is preferably represented by the chemical formula [Chem. 9].

[0019]

[Chemical 9] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, n is 0 to 200 (preferably 0 to 6)
0), a is 0 or 1 and b is 0, 1 or 2. ) R ¹ is exemplified by an alkylene group such as a methylene group, an ethylene group, a propylene group and a butylene group, preferably an alkylene group having 1 to 6 carbon atoms, and particularly preferably a propylene group. R
^{2 to} R ¹⁴ are alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, aryl groups such as phenyl group, aralkyl groups such as benzyl group, vinyl group, allyl Substituted hydrocarbon groups such as alkenyl groups such as groups, chloromethyl groups, 3,3,3-trifluoropropyl groups and 2-cyanoethyl groups are exemplified, and alkyl groups having 1 to 4 carbon atoms are preferable.

Among [Chemical formula 9], those represented by [Chemical formula 10] to [Chemical formula 12] are more preferable.

[Chemical 10] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ^{9 to} R ¹¹ are monovalent hydrocarbon group having 1 to 10 carbon atoms, or —OSiR ¹² R
A siloxy group represented by ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), b is 0,
Represents 1 or 2. )

[0021]

[Chemical 11] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Represents an integer of 0 to 5, and n represents a number of 0 to 200. ) [Chemical Formula 12] is particularly preferable.

[Chemical 12] (P represents a number of 10 to 60.)

[0022]

[Chemical 13] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, b is 0, 1 or 2. )

As described above, Japanese Patent Laid-Open No. 5-85070 has already been used.
In the publication, a back coat layer composed of a resin or a cured product thereof in which an organopolysiloxane is graft-bonded is proposed, and it is excellent in heat resistance, film-forming property, slip property, and there is no contamination or wear of the thermal head. Although all of them are characterized, it has been pointed out that all of them are based on a thermoplastic resin, so that under severe heat transfer conditions, slip properties are insufficient and blocking occurs. Therefore, the present inventors have compared the backcoat layer using any of the resins exemplified in this publication with excellent heat resistance and coatability, excellent slip property, and contamination and wear of the thermal head. As a back coat layer that does not generate even the above, the inventors have come to propose a polysaccharide derivative obtained by reacting the organopolysiloxane represented by the above general formula or a cured product thereof. According to the present invention, a high siloxane modification rate can be achieved, and it is possible to sufficiently leave hydroxyl groups necessary for isocyanate crosslinking.

Examples of the polysaccharide derivative include methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl methyl cellulose,
Cellulose derivatives such as acetyl cellulose and acetyl cellulose butyrate, starch, one or a mixture of two or more selected from dextrin and pullulan are used, and among them, particularly preferred are ethyl cellulose, hydroxypropylmethyl cellulose, hydroxyethyl methyl cellulose, Acetyl cellulose.

The method of reacting these polysaccharide derivatives with an organopolysiloxane is not particularly limited, but for example, the method disclosed in JP-A-6-145201 can be used. According to this method, the modification ratio (silicone content) of the organopolysiloxane can be appropriately controlled according to the characteristics to be imparted to the back coat layer. The modification ratio of the organopolysiloxane is preferably 1 to 90% by weight, particularly preferably 20 to 80% by weight. If the modification ratio of the organopolysiloxane is too low, the lubricity tends to be insufficient, while if it is too high, the film formability tends to deteriorate.

In the present invention, for the purpose of imparting heat resistance, coatability and adhesion to the base film to the back coat layer,
It is desirable to crosslink and cure with polyisocyanate.
The polyisocyanate is not particularly limited as long as it has two or more isocyanate groups in one molecule, and examples thereof include Coronate (manufactured by Nippon Polyurethane Co.), Takenate (manufactured by Takeda Pharmaceutical Co., Ltd.), Desmodur (Bayer Co., Ltd.). The products sold under the product names such as (made) are listed.

The amount of polyisocyanate added is such that the polysaccharide derivative 10 grafted with an organopolysiloxane is used.
5 to 200 parts by weight, more preferably 5 to 0 parts by weight
0 to 200 parts by weight, particularly 100 to 200 parts by weight are preferred. The excess or unreacted portion of the isocyanate group may be deactivated by reacting with an amine or alcohol, or may be left as it is. Here, if the addition amount of the polyisocyanate is too small, the heat resistance becomes insufficient due to the low crosslinking density, and if the addition amount is too large, the shrinkage of the formed coating film becomes large or the curing time becomes long, etc. Causes inconvenience.

In the present invention, in forming a back coat layer from the above materials, higher fatty acid amide, higher fatty acid ester, silica fine powder, fluororesin powder, alkyl phosphate ester, etc. are used for the purpose of improving lubricity. An antistatic agent such as a lubricant or a surfactant and a conductive agent such as carbon black may be added.

As a method for forming the back coat layer, a known method can be used, and ordinary coating and drying are sufficient, and no special technique is required. However, when trying to obtain a cured product by adding polyisocyanate,
It is desirable to apply heat treatment after drying. The backcoat layer is preferably formed so as to have a thickness of 0.1 to 10 μm. If the backcoat layer is too thin, the function of the backcoat layer will be insufficient, and if it is too thick, heat conduction from the thermal head will be impaired. Will hinder it.

(Heat Transferable Coloring Material Layer) In the heat transferable coloring material layer formed on the other surface of the film-shaped substrate, a heat sublimable dye is used in the case of a sublimation type, and on the other hand, in the case of a heat melting type. A pigment or a dye may be contained, respectively. The heat sublimation dye is preferably a disperse dye, for example, MS Yellow 32, MS Red 28, MS Blue 50 (manufactured by Mitsui Toatsu Dyes Co., Ltd.), Kayaset Yellow AG, Kayaset Red B, Kayaset. Blue FR (manufactured by Nippon Kayaku Co., Ltd.) and the like can be mentioned. Examples of the pigment to be used in the heat-melting type include inorganic pigments such as titania, carbon black, zinc oxide, cadmium sulfide, and iron oxide; azo-based, anthraquinone-based, and phthalocyanine-based organic pigments, and the dye is an acid dye, Both direct dyes and disperse dyes can be used. As the binder resin, one which has heat resistance in the sublimation type and which does not prevent the dye transfer from the dye layer to the image receiving layer during heating, for example, a cellulose resin or a vinyl resin is selected. In the heat melting type, it is common to use a thermoplastic resin having a softening point of 50 to 150 ° C., for example, a polyolefin resin, an acrylic resin, rubbers or the like together with waxes having a melting point of 50 to 100 ° C.

Also in the heat transferable color material layer, various known additives can be added in the same manner as in the back coat layer, and a known method can be used as a forming method. The thickness of the heat transferable color material layer is 0.2-
It is preferably 5 μm, and 0.5 to 8 μm for the heat melting type.

[0032]

EXAMPLES Examples of the present invention will be described in detail below, but the present invention is not limited thereto. In the following, “part” or “%” is based on weight unless otherwise specified. In addition, except for the solvent, the solid content is calculated.

Reference Example 1 Hydroxypropylmethylcellulose having 1.12 hydroxyl groups per glucose unit, 1.88 methoxyl groups and 0.26 hydroxypropoxy groups was dried at 105 ° C. for 2 hours, and 100 g of 10 g was dried. Dissolved in dimethylformamide, heated to 80 ° C. with stirring, to which 14 g of tristrimethylsiloxysilylpropyl isocyanate was added.
Stir for 2 hours at ℃ to complete the reaction, the reaction solution to 200
The precipitate formed by reprecipitation with ml was filtered off, washed repeatedly with water, and dried to give 23 g of silicone-modified hydroxypropyl methylcellulose (silicon content 43.9%).
I got

Reference Example 2 Instead of hydroxypropyl cellulose in Reference Example 1, 100 g of acetyl cellulose having 0.96 hydroxyl groups and 2.04 acetyl groups per glucose unit was used, and tristrimethylsiloxysilylpropyl isocyanate was added thereto. When treated in the same manner as in Reference Example 1 except that 13 g was used, 21 g of silicone-modified acetyl cellulose (silicon content 40.
8%).

Example 1 A coating solution A having the following composition was applied to a polyethylene terephthalate film having a thickness of 4.5 μm.
Was coated with a gravure coater so that the thickness after drying was 1 μm, and dried (room temperature: 10 minutes, 100 ° C .: 1 minute) to form a heat sublimable dye layer. Coating liquid A-Thermal sublimation dye layer Blue disperse dye (MS Blue 50, manufactured by Mitsui Toatsu Dye Co., Ltd.) 62.5 parts Acetal resin (S-REC KS-5, manufactured by Sekisui Chemical Co., Ltd.) 37.5 parts Solvent (methyl ethyl ketone / Toluene = 1/3) Adjusted to a solid concentration of 10%

Next, on the other surface of the above film, a coating liquid B having the following composition was dried with a bar coater # 5 to a thickness of 2
Coated to a thickness of μm and dried (room temperature 10 minutes, 100 ° C
1 minute). Further, it was heat-treated at 60 ° C. for 48 hours to form a back coat layer to obtain a thermal recording transfer material. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 1 47.5 parts Polyisocyanate (Desmodur HL, Bayer) 52.5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

(Example 2) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 1 45.1 parts Polyisocyanate (Desmodur HL, Bayer) 49.9 parts Higher fatty acid amide (Pharmine D86, Kao) 5.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Adjusted solid concentration 5%

(Example 3) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-back coat layer Silicone-modified hydroxypropylmethyl cellulose of Reference Example 1 40.4 parts Polyisocyanate (Desmodur HL, Bayer) 44.6 parts Higher fatty acid amide (Pharmine D86, Kao) 15.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Adjusted solid concentration 5%

(Example 4) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 1 37.6 parts Polyisocyanate (Desmodur HL, Bayer) 62.4 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

(Example 5) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-back coat layer Silicone-modified hydroxypropylmethyl cellulose of Reference Example 1 95.0 parts Higher fatty acid amide (Pharmine D86, manufactured by Kao Corporation) 5.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

Example 6 A transfer material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified acetyl cellulose of Reference Example 2 32.7 parts Polyisocyanate (Desmodur HL, Bayer) 67.3 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjustment

Comparative Example 1 A transfer material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was not applied.

Comparative Example 2 A transfer material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Hydroxypropylmethylcellulose of Reference Example 1 47.5 parts Polyisocyanate (Desmodur HL, Bayer) 52.5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration adjusted to 5%

Comparative Example 3 A transfer material for heat-sensitive recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Hydroxypropylmethylcellulose of Reference Example 1 35.5 parts Polyisocyanate (Desmodur HL, Bayer) 49.5 parts Higher fatty acid amide (Pharmine D86, Kao) 15.0 parts Solvent ( Methyl ethyl ketone / toluene = 1/1) Adjusted to a solid concentration of 5%

(Reference Example 3) 10 g of hydroxypropylmethylcellulose having 1.11 hydroxyl groups per glucose unit, 1.89 methoxyl groups and 0.24 hydroxypropoxy groups dried at 105 ° C. for 2 hours and dibutyl 0.35 g of tin dilaurate was dissolved in 200 ml of dimethylformamide and the temperature was raised to 100 ° C. with stirring.

Embedded image 25.5 g of an isocyanate group-containing organopolysiloxane represented by is added, and the reaction is completed by reacting at 110 to 120 ° C. for 2 hours, and the reaction solution is reprecipitated with 600 ml of water, and the resulting precipitate is separated by filtration. After repeatedly washing with water and n-hexane, it was dried to give 24.9 g of silicone-modified hydroxypropylmethylcellulose (silicone content: 5
3.6%).

Reference Example 4 0.35 g of dibutyltin dilaurate in Reference Example 3 was 0.17 g, and the following general formula was used as an isocyanate group-containing organopolysiloxane.

[Chemical 15] Was treated in the same manner as in Reference Example 3 except that 43.4 g of the compound represented by
2.2%) was obtained.

Reference Example 5 Instead of hydroxypropylcellulose in Reference Example 3, 100 g of acetylcellulose having 0.62 hydroxyl groups and 2.38 acetyl groups per glucose unit was used, and dibutyltin dilaurate was added to 0.1%. The amount of the compound of the general formula

Embedded image When the same treatment as in Reference Example 3 was carried out except that 17.1 g of the compound represented by the formula (1) was used, 24.8 g of silicone-modified acetyl cellulose (silicon content 52.5%) was obtained.

(Example 7) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 3 47.5 parts Polyisocyanate (Desmodur HL, Bayer) 52.5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

(Example 8) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 3 45.1 parts Polyisocyanate (Desmodur HL, Bayer) 49.9 parts Higher fatty acid amide (Pharmine D86, Kao) 5.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Adjusted solid concentration 5%

(Example 9) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 3 40.4 parts Polyisocyanate (Desmodur HL, Bayer) 44.6 parts Higher fatty acid amide (Pharmine D86, Kao) 15.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Adjusted solid concentration 5%

(Example 10) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 3 37.6 parts Polyisocyanate (Desmodur HL, Bayer) 62.4 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

(Example 11) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-Backcoat layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 3 95.0 parts Higher fatty acid amide (Farmin D86, manufactured by Kao Corporation) 5.0 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

(Example 12) A coating material for thermal recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating Liquid B-Backcoat Layer Silicone-modified hydroxypropylmethylcellulose of Reference Example 4 47.5 parts Polyisocyanate (Desmodur HL, Bayer) 52.5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjusted to

Example 13 A transfer material for heat-sensitive recording was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating liquid B-back coat layer Silicone-modified acetyl cellulose of Reference Example 5 47.5 parts Polyisocyanate (Desmodur HL, Bayer) 52.5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Solid content concentration 5% Adjustment

Comparative Example 4 A thermal recording transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the following composition. Coating Liquid B- Backcoat Layer Hydroxypropylmethylcellulose of Reference Example 3 22.0 parts Polydimethylsiloxane (100 cs) 25.5 parts (Silicone content 53.6%) Polyisocyanate (Desmodur HL, Bayer) 52. 5 parts Solvent (methyl ethyl ketone / toluene = 1/1) Adjusted solid concentration 5%

The transfer material for heat-sensitive recording obtained above was brought into contact with an uncoated polyethylene terephthalate film and a back coat layer, and the dynamic friction coefficient between them was measured by a friction tester (load 200 g, traction speed 150 mm / min, Toyo Seiki). (Manufactured by the company). Further, a mounting test was conducted with a sublimation type thermal transfer printer, and thermal fusion between the thermal head and the thermal recording transfer material and head contamination were visually observed, and the results are shown in Table 1.

[0057]

[Table 1]

Reference Examples 6 to 8 Ten parts of each silicone-modified hydroxypropylmethylcellulose obtained in Reference Examples 1, 3 and 4 was dissolved in a mixed solvent of 100 parts of methyl ethyl ketone and 100 parts of toluene to prepare a silicone-modified cellulose. A solution was obtained.

Reference Example 9 The following general formula

[Chemical 17] And 150 parts of polydimethylsiloxane diol having an average molecular weight of about 1000 are added to 250 parts of methyl ethyl ketone, and the mixture is charged into a reactor equipped with a stirrer, a reflux condenser, a dropping funnel, and a gas introduction tube. It is. Cool the contents from the outside to bring the internal temperature to 0-5 ° C,
While maintaining this temperature, carbon dioxide gas was continuously flown through the gas inlet tube.

Next, a solution prepared by dissolving 39 parts of hydrogenated MDI (methylene-bis- (4-phenylisocyanate)) in 100 parts of methyl ethyl ketone was dropped into the reactor through a dropping funnel and reacted. After the dropping is completed, the internal temperature is gradually increased, and when the temperature reaches 50 ° C, it is 50 hours for 1 hour.
Stirring was continued at 0 ° C. to obtain a polyurethane resin solution having a siloxane bond.

Reference Example 10 50 parts of polyvinyl butyral (polymerization degree: 1700, hydroxyl group content: 33 mol%) was dissolved in 500 parts of an equal mixed solvent of methyl ethyl ketone and toluene, and then the following general formula was used.

Embedded image Polysiloxane compound represented by (molecular weight 3000) 1
0 part was gradually added dropwise and reacted at 60 ° C. for 5 hours to obtain a polyvinyl butyral resin solution containing a siloxane segment.

Reference Example 11 30 parts of hydroxypropylmethyl cellulose used in Reference Example 1, the following general formula

[Chemical 19] Siloxanediol represented by (average molecular weight 5600)
20 parts and 50 parts of polyisocyanate (trade name “Desmodur HL”, manufactured by Bayer) were dissolved in 900 parts of an equal mixed solvent of methyl ethyl ketone and toluene to obtain a polysiloxane-containing crosslinkable cellulose resin solution.

(Examples 14 to 16 and Comparative Examples 5 to 7) On a polyethylene terephthalate film having a thickness of 4.5 μm,
A back coat layer was formed using each of the resin solutions obtained in Reference Examples 3 to 6, and slip properties of these layers were evaluated.
The heat resistance and abrasion resistance were evaluated. Slip properties are from Example 1
Similar to 6, the coefficient of dynamic friction was evaluated. Heat resistance is DSC
It was evaluated by Tg (glass transition temperature) measured by (differential scanning calorimetry) (trade name "TA4000", manufactured by METTLER CORPORATION). Further, the abrasion resistance was evaluated by the presence or absence of contamination of the thermal head as in Examples 1 to 6. Table 2 shows the results.

[0064]

[Table 2]

Here, it is generally said that an excellent back coat layer needs to satisfy the following conditions. Slip properties: Dynamic friction coefficient ≤ 0.30 Heat resistance: Tg ≥ 80 ° C Friction resistance: No dirt adhered to the thermal head

As is clear from Table 2, Examples 14-1
No. 6 satisfies all the above conditions and is suitable as a back coat layer. On the other hand, Comparative Example 5 lacked heat resistance, Comparative Example 6 lacked in slip properties, and Comparative Example 7 lacked in wear resistance.

[0067]

As described above, the heat-sensitive recording transfer material of the present invention has a heat resistance, a film-forming property, and a heat resistance, a film-forming property, by forming a polysaccharide derivative grafted with an organopolysiloxane or a cured product thereof as a back coat layer. It is a novel transfer material for heat-sensitive recording having a good back coat layer which is excellent in slip properties and is free from contamination and abrasion of the thermal head.

Particularly when the organopolysiloxane is represented by any one of the following general formulas, the effect is great.

Embedded image (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, n is a number of 0 to 200, a is 0 or 1,
b represents 0, 1 or 2. )

[Chemical 21] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ^{9 to} R ¹¹ are monovalent hydrocarbon group having 1 to 10 carbon atoms, or —OSiR ¹² R
A siloxy group represented by ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), b is 0,
Represents 1 or 2. )

[Chemical formula 22] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Represents an integer of 0 to 5, and n represents a number of 0 to 200. )

[Chemical formula 23] (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, b is 0, 1 or 2. )

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akira Yamamoto 1 Hitomi, Osamu, Matsuida-cho, Usui-gun, Gunma 10 Silicon Research Institute for Electronic Materials, Shin-Etsu Chemical Co., Ltd. No. 28, Nishi-Fukushima, Mura-dai

Claims (8)

[Claims] 1. A transfer material for heat-sensitive recording comprising a heat transferable color material layer provided on one surface of a film base material, wherein a polysaccharide derivative obtained by reacting an organopolysiloxane on the other surface of the film base material, or A heat-sensitive recording material comprising a back coat layer made of the cured product. 2. The organopolysiloxane has the following general formula: (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, n is a number of 0 to 200, a is 0 or 1,
b represents 0, 1 or 2. ) The transfer material for heat-sensitive recording according to claim 1, which is represented by 3. The organopolysiloxane has the following general formula: (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, R ^{9 to} R ¹¹ are monovalent hydrocarbon group having 1 to 10 carbon atoms, or —OSiR ¹² R
A siloxy group represented by ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), b is 0,
Represents 1 or 2. 3. The transfer material for heat-sensitive recording according to claim 2, which is represented by 4. The organopolysiloxane has the following general formula: (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Represents an integer of 0 to 5, and n represents a number of 0 to 200. 3. The transfer material for heat-sensitive recording according to claim 2, which is represented by 5. The organopolysiloxane has the following general formula: (However, R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ^{2 to} R ⁸ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, R ⁹ to
R ¹¹ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or —OSi
A siloxy group represented by R ¹² R ¹³ R ¹⁴ (R ¹² , R ¹³ and R ¹⁴ represent a monovalent hydrocarbon group having 1 to 10 carbon atoms), m
Is an integer of 0 to 5, b is 0, 1 or 2. 3. The transfer material for heat-sensitive recording according to claim 2, which is represented by 6. The thermal recording transfer according to claim 1, wherein the polysaccharide derivative is one kind or a mixture of two or more kinds selected from a cellulose derivative, starch, dextrin and pullulan. Material. 7. The cellulose derivative is methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, hydroxyethylmethylcellulose,
The transfer material for heat-sensitive recording according to claim 6, which is selected from acetyl cellulose and acetyl cellulose butyrate. 8. The transfer material for heat-sensitive recording according to claim 1, wherein the cured product is a cured product obtained by crosslinking reaction of a polysaccharide derivative with polyisocyanate.