JPS61143195A - Thermal transfer sheet - Google Patents

Abstract

PURPOSE:To prevent a thermal transfer sheet from being welded to a thermal head, thereby prevent the sheet from becoming unable to be moved or being broken, by providing a heat-resistant protective layer on the back side of a base sheet provided with a thermally transferable ink layer on the face side thereof. CONSTITUTION:The heat-resistant protective layer in the thermal transfer sheet is constituted essentially of [A] a vinyl polymer comprising organopolysiloxane units bonded in a block form or a graft form, [B] a derivative obtained by modifying the polymer [A] or both of the polymers [A] and [B]. The heat- resistant protective layer is provided by coating the back side of the base sheet with a coating material comprising the vinyl polymer [A] or the like and drying, or by forming the vinyl polymer [A] or the like on the back side of the base sheet through a reaction.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a thermal transfer sheet used mainly when obtaining an image using a thermal head. Even when printing is performed under the high energy required to obtain density, the thermal head does not thermally fuse with the sheet, and the thermal transfer sheet becomes unable to run or breaks midway. To provide a heat-sensitive transfer sheet that does not cause such problems.

[Conventional technology and its drawbacks]

Various heat-sensitive transfer sheets are used in which a heat-melting wax layer in which pigments or dyes are dispersed or a heat-sensitive sublimation transfer layer in which a sublimable dye is contained in a binder are formed on a base sheet.

The base sheet in the heat-sensitive transfer sheet used for heat-sensitive recording includes condenser paper, polyester film, polypropylene film, and cellophane having a thickness of about 5 to 12 μm.

Although cellulose acetate film is used, polyester film is sometimes used because it has a uniform thickness, a smooth surface, and is easy to handle in the printer. Most common.

By the way, when thermal printing is performed using a thermal head from the back side of the sheet using a heat-sensitive transfer sheet in which the above-described heat-melting wax layer or heat-sensitive sublimation transfer layer is formed on the plastic film, it is difficult to obtain sufficient print density. When printing is performed under the high energy required for this purpose, the base sheet fuses with the thermal head, causing so-called sticking, which can cause the transfer sheet to become unable to run, or in severe cases. The base sheet will break from this sticking portion.

For this reason, a method of providing a heat-resistant protective layer on the back side of the base sheet has been proposed.
52. JP-A-57-74195), method of providing a heat-resistant resin layer such as silicone or epoxy (JP-A-55-74)
67), a method of providing a resin layer to which a solid or semi-solid surfactant is added at room temperature (Japanese Patent Application Laid-Open No. 57-129789)
Alternatively, there is a method of providing a layer containing a lubricating inorganic pigment in a heat-resistant resin (Japanese Unexamined Patent Publication No. 155794/1984).

However, those that provide a heat-resistant protective layer on the back side of the base sheet require expensive processes such as vapor deposition, and a large amount of thermal energy is required for thermosetting. Thermal heads require long-term aging, or have insufficient smoothness to allow the thermal head to run smoothly, or have lubricants such as surfactants added to the thermal head. It has disadvantages such as promoting the adhesion of dirt to the surface.

[Means for solving problems]

The heat-sensitive transfer sheet of the present invention has a structure in which a heat-resistant and protective layer is provided on the back side of a base sheet on which a heat-sensitive transferable ink layer is formed, and the heat-resistant and protective layer is composed of organopolysiloxane units. Vinyl polymer [A] bonded in block or graft form, or the polymer [A]
] is essentially composed of a modified derivative [B], or a combination of both types [A] and [B].

Since the heat-sensitive transfer sheet of the present invention having the above structure is characterized by its heat resistance and protective layer, the heat resistance and protective layer will be explained below.

The heat-resistant and protective layer in the heat-sensitive transfer sheet of the present invention is made of a vinyl polymer [A] in which the above-described organopolysiloxane units are bonded in a block or graft form.
, or a derivative [B] obtained by modifying the polymer [A], or a derivative [B] obtained by modifying the polymer [A], or a polymer consisting essentially of both of these polymers [A] and [B], such as the vinyl polymer [A], etc. A method of forming a heat-resistant, protective layer by coating the back side of a base sheet with a coating agent containing a coat ink and drying, and a composition in which the above-mentioned vinyl polymer [A] etc. is produced by post-treatment such as heating. By coating the back side of the base sheet with a coating agent containing a There is a method of forming a protective layer.

One of the methods for obtaining a vinyl polymer [A] in which organopolysiloxane units are bonded in a block or graft form is to include at least one siloxane unit represented by the general formula % (1) in the molecule. This is a method of polymerizing an organopolysiloxane having at least 1 or more radically polymerizable monomers.

The organopolysiloxane used to obtain the vinyl polymer [A] by this method is represented by the general formula (11) or general formula (2) as a siloxane unit bonded to the silicon atom. Any siloxane unit may be used as long as it has at least one siloxane unit, and there are no particular restrictions on its molecular structure or the bonding position of the siloxane unit represented by the above general formula (1) or general formula (2). The structure may be either a linear structure or a two-molecular chain structure.Also, this organopolysiloxane has a molecular chain terminal such as a triorganosilyl group such as a trimethylsilyl group, or a hydroxydimethylsilyl group. Examples of organic groups bonded to silicon atoms other than the siloxane units represented by the above general formula (1) or general formula (2) include hydroxydiorgatoalkyldiorganoglyl groups such as , an ethyl group, a zolopyl group, a phenyl group, a trifluorozolobyl group, etc. are preferably used.Furthermore, this organopolysiloxane has the general formula (1) or the general formula (
It goes without saying that there are no restrictions on the arrangement order of the siloxane units represented by 2) and other organosiloxane units, and all units of the organopolysiloxane are represented by the general formula (1) or the general formula (2). ) may be displayed.

The other component, the radically polymerizable monomer, used in the above method to obtain the vinyl polymer [A] is a monomer represented by the general formula, such as methyl methacrylate, methyl Acrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate,
Butyl methacrylate, inbutyl acrylate, inbutyl methacrylate, t-butyl acrylate, t-
butyl methacrylate, isoamyl acrylate, isoamyl methacrylate, cyclohexyl acrylate,
Cyclohexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, N-methylolacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,
2-hydroxyzorobyl acrylate, 2-hydroxyzorobyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxy-3-phenoxyzorobyl methacrylate, 2
-Hydroxy-3-phenoxyzorobyl acrylate, acrylic acid, methacrylic acid, acryloyloxyethyl monosuccinate, glycidyl methacrylate, 2-aziridinylethyl methacrylate, allyl 2-aziridinylzolopionate, acrylamide, methacrylamide, Dia7 Contains active hydrogen and a diincyanate such as tonacrylamide, dimethylamine ethyl methacrylate, diethylaminoethyl methacrylate, 2-acrylamido-2-methylpropanesulfonic acid, and an equimolar adduct of 2.4-toluene diisocyanate and 2-hydroxyethyl acrylate. In addition to adducts with radically polymerizable monomers, vinyl esters of fatty acids such as vinyl acetate and vinyl zolopionate, styrene, and α-methylstyrene.

Monomers such as vinyltoluene, maleic anhydride, itaconic acid, and mixtures of these monomers can be used.

Another method for obtaining the vinyl polymer [A] in which organopolysiloxane units are bonded in a block or graft form is to add the above-mentioned radically polymerizable monomer to mercazo, which is added as necessary. ethanol, mercaptopropionic acid.

Polymerize in the presence of a polymerization degree regulator such as dodecyl mercaptan to form hydroxyl and carboxyl groups.

After obtaining a vinyl polymer having a functional group such as an epoxy group, an isocyanate group, or an amino group, the vinyl polymer having this functional group is combined with a methyloxy group, a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or a mercapto group. This is a method in which the bonding reaction with a reactive organopolysiloxane comprising the like is carried out, if necessary, in the presence of a polyvalent incyanate compound, a polyvalent epoxy compound, etc.

In addition, the vinyl polymer [which is the reaction product of the vinyl polymer having the functional group obtained by polymerizing the radically polymerizable monomer described above and the reactive organopolysiloxane]
A] is substantially heat resistant.

In the case where the protective layer is constituted, if the bonding reaction between the two is performed, for example, by a post-treatment such as heating, the protective layer contains a vinyl polymer having a functional group and a reactive organopolysiloxane. The heat-resistant, protective layer in the heat-sensitive transfer sheet of the present invention can also be formed by coating the back surface of the base sheet with a coating agent and then subjecting it to a post-treatment such as heating.

Although there is no particular restriction on the ratio of the organopolysiloxane and the radically polymerizable monomer in the vinyl polymer [A] that substantially constitutes the heat-resistant and protective layer of the heat-sensitive transfer sheet of the present invention. , organopolysiloxane 1
00 parts by weight of radically polymerizable monomer 100,000 parts by weight
It has been confirmed that a wide range of proportions from 0 to 1 part by weight constitutes a heat-resistant, protective layer that satisfactorily achieves the objectives of the present invention.

Incidentally, each polymerization to obtain the vinyl polymer [A] may be carried out using a conventionally known polymerization method, for example, benzoyl peroxide or t-butyl hydroperoxide.

Solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, etc. using a polymerization initiator such as cumene hydroperoxide, α, α'-azodiine butyronitrile, etc. can be used.

In addition, when obtaining the vinyl polymer [A] by each of the above methods, a monomer having a quaternary ammonium base or a tertiary amino group may be selected and used as a component of the radically polymerizable monomer. By doing so, it is possible to construct a heat-resistant, protective layer that has both superior sliding properties and antistatic performance.

Furthermore, as a component of the radically polymerizable monomer when forming the vinyl polymer [A], a monomer having a functional group such as a hydroxyl group, a carboxyl group, an epoxy group, an aziridinyl group, or an incyanate group was used. In this case, it is possible to heat-cure the heat-resistant and protective layer by utilizing the functional groups in the vinyl polymer [A] that substantially constitutes the heat-resistant and protective layer. It can be used as a heat-resistant and protective layer that has excellent properties such as hardness and plasticizer resistance.

Incidentally, the formation of a heat-resistant, protective layer that is thermoset is (1
) Vinyl polymer having the thermosetting functional group [A
] is applied to the base sheet and then heated; (2) a coating agent containing two or more thermosetting polymers is applied to the base sheet and then heated; (3)
) A thermosetting crosslinking agent such as a polyincyanate group compound, a polyepoxy compound, a polyaziridinyl group compound, a polyamino compound, etc. is added to the coating agent, and the mixture is applied to the base sheet and cured. Depending on the situation, various catalysts such as dibutyltin laurylate, pyridine, etc. are added to the base sheet.

Methods such as curing can be used.

Further, the derivative CB) obtained by modifying the vinyl polymer [A] contains, for example, a hydroxyl group or a carboxyl group, as at least one component of the radically polymerizable monomer used to obtain the vinyl polymer [A].

The vinyl polymer [A] obtained using a monomer having a functional group selected from an epoxy group, an aziridinyl group, an incyanate group, etc. was modified by introducing a third component into the functional group. However, as a representative example of this derivative [B], a radically polymerizable unsaturated group is introduced into the carboxyl group of the vinyl polymer [A] by, for example, addition reaction with glycidyl methacrylate. By using the derivative CB), a protective layer can be obtained which is substantially composed of a polymer having a crosslinked structure introduced by irradiation with ionizing radiation, and the layer can be made scratch-resistant and stain-resistant. plus chemical resistance.

It can exhibit excellent properties such as solvent resistance.

The method for introducing a radically polymerizable unsaturated group into the vinyl polymer [A] is as follows: (1) When the functional group is a hydroxyl group, a monomer having a carboxyl group such as acrylic acid or methacrylic acid is subjected to a condensation reaction; +21 When the functional group is a carboxyl group or a sulfone group, a monomer having a hydroxyl group is subjected to a condensation reaction. (3) When the functional group is an epoxy group or an isocyanate group.

Alternatively, in the case of an aziridinyl group, a monomer having a hydroxyl group or a monomer having a carboxyl group is subjected to an addition reaction. (4) If the functional group is a hydroxyl group or a carboxyl group, a monomer having an epoxy group or a monomer having an aziridinyl group is added. Furthermore, methods such as adding an equimolar adduct of a diisocyanate compound and an acrylic acid ester monomer having a hydroxyl group are used; It is preferable to carry out the drying process at a low temperature while blowing dry air.

Further, the derivative C into which the radically polymerizable unsaturated group is introduced
In the case of the heat-resistant, protective layer B), ethylene glycol diacrylate,
Ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, trimethylolpropane triacrylate.

Trimethylolpropane trimethacrylate, trimethylolpropane diacrylate, trimethylolzolopane dimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexaacrylate Methacrylate, ethylene glycol diglycidyl ether diacrylate, ethylene glycol diglycidyl ether dimethacrylate, polyethylene glycol diglycidyl ether diacrylate, polyethylene glycol diglycidyl ether dimethacrylate, propylene glycol diglycidyl ether diacrylate,
Propylene glycol diglycidyl ether dimethacrylate, polyzolopylene glycol diglydyl ether diacrylate, polypropylene glycol diglydyl ether dimethacrylate, sorbitol tetraglydyle ether tetraacrylate, sorbitol tetraglydyle ether tetraacrylate, etc., as the derivatives CB.
) is preferably about 0.1 to 100% by weight.

Methods for introducing a crosslinked structure into the derivative [B] include a method of irradiating with ionizing radiation and a method of using a radical (1o) cal polymerization initiator, but from the viewpoint of completing curing in a short time, ionizing Radiological methods are preferred. As the ionizing radiation, electron beams, ultraviolet rays, gamma rays, etc. can be used, and in the case of electron beams and gamma rays, it is preferably about 1 to 20 Mrad, and in the case of ultraviolet irradiation, benzoquinone, benzine, benzoinmethyl, etc. are used as sensitizers. It is preferable to use benzoin ethers such as ethers, halogenated acetophenones, and biacyls that generate diradicals when irradiated with ultraviolet rays. In addition, in the method using a radical polymerization initiator, a polymerization initiator such as various peroxides such as benzoyl peroxide or α, α′-azobisisobutyronitrile is added to the derivative CB).
．． What is necessary is to add 1 to 1% by weight of twist and heat above the decomposition temperature.

The heat-resistant and protective layer in the heat-sensitive transfer sheet of the present invention, that is, the vinyl polymer [A] in which organopolycloxane units are bonded in a block or graft form, or a modified derivative of the polymer (A') [B] or a combination of both types of these [A], CB) The heat-resistant and protective layer is made of a vinyl polymer (A) or a combination of these polymers [A] and CB on the back surface of the base sheet. ), or a coating agent containing both of them, or a coating agent containing a component that produces the polymer [A] etc. by post-treatment such as heating, and drying. Alternatively, it can be easily obtained by performing a post-treatment such as heating if necessary.The coating agent for forming a heat-resistant and protective layer may be added with an appropriate solvent as necessary to adjust the coating suitability. However, in some cases, the reaction product solution obtained when obtaining the polymer [A] or derivative [B] is used as it is as a coating agent.In addition, this coating agent contains substances with storage stability. In order to improve the polymerization, it is preferable to add a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether.
] or derivative CB], or polymer [A] or derivative CB
) and, if necessary, additives such as radically polymerizable monomers and sensitizers. However, the heat-resistant and protective layer in the heat-sensitive transfer sheet of the present invention is made of the vinyl polymer [A], a modified derivative of the polymer [A] [B], or a warm mixture thereof [A]. , [B]
Therefore, the above-mentioned coating agent may optionally contain cellulose-based resins such as evapo-ethyl cellulose and nitrocellulose,
In addition to polymers such as polyester resins, polyurethane resins, rhodiester resins, rubber resins such as cyclized imes, and chlorinated polyolefin resins, coloring agents such as pigments and dyes may also be added as appropriate.

The method of forming a heat-resistant, protective layer on the back surface of the base sheet using the coating agent is the same as the conventional coating method of general coating agents, such as roll coating method, gravure coating method, screen coating method, fountain coating method. A base sheet made of a polystyrene film, a polysulfonate film, a polyvinyl alcohol film, a cellophane film, etc., using a coating method such as the following.

In particular, from the point of view of heat resistance, a solid content of 0.00.
A method is used in which the coating is coated in 1 to 4 coats and dried. It should be noted that the irradiation with ionizing radiation applied to the heat-resistant and protective layer as necessary may be performed subsequent to the application and drying process of the coating agent for forming the heat-resistant and protective layer, or the irradiation with the heat-sensitive transferable It may be performed after forming the ink layer.

The most typical example of the heat-sensitive transfer sheet of the present invention, which has a heat-resistant, protective layer on the back side of the base sheet having the above-mentioned structure, has a heat-resistant, protective layer on the back side of the base sheet. A so-called heat-sensitive transfer ink layer containing a material that is transferred by heating and transferred to an object, such as a heat-melting wax layer in which pigments or dyes are dispersed, or heat-sensitive sublimation in which a sublimable dye is added to a binder. The transfer layer etc. are formed according to a conventional method.

As the binder in the hot-melt wax layer, carnabala wax, paraffin wax, andwax or a suitable synthetic binder is used, and as the coloring material,
Dyes or pigments are used, and the coloring agent is usually a binder.
It is added in an amount corresponding to ~30 parts by weight.

The heat-sensitive sublimation transfer layer is composed of a sublimable dye contained in a binder resin, and has a thickness of about 0.2 to 5.0 microns. The dye in this heat-sensitive sublimation transfer layer is preferably a disperse dye, and this dye has a molecular weight of about 150 to 40.

It is desirable to have a molecular weight of about The dye is selected in consideration of thermal sublimation temperature, hue, weather resistance, stability in the binder resin, etc., and specific examples include the following.

Mikenton Polyester Yellow
-YL (manufactured by Mitsui Toatsu, C, 1, Dispers Ye
yellow-42), Kayaset Yellow-
G (Japanese bodywork, C, 1, Dispers Yellow
ow77), PTY-52 (manufactured by Mitsubishi Kasei, C, 1,5o
lvent Yellow14-1'), Mike
ton Polyester RedBSE (Mitsui Toatsu, C, I-Disperse Redll), Ka
yaset Red B (Japanese bodywork, C61, D
isperse Red B), PTR-54 (manufactured by Mitsubishi Kasei, C, I, Disperse Red 50
), Miketon Polyester Blue
FBL) (Mitsui Toatsu, C, 1, Disperse
Bule 56), PTB-67, (Mitsubishi Kasei, C, I, DisperseBIue241), Ka
yaset BIue906 (Japanese bodywork, C, 1
, 5olvent 112) etc.

Depending on the sublimation temperature of the dye and the magnitude of the covering power in the developed state, the dye is about 5-70% in the heat-sensitive sublimation transfer layer.
It is contained in an amount of about 10 to 60% by weight, preferably about 10 to 60% by weight. Further, as the binder resin, one is usually selected that has high heat resistance and does not prevent dye transfer when the resin is heated. For example, the following resins are used.

(1) Cellulose resins ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, hydroxyzorosol cellulose, methyl cellulose, cellulose acetate, cellulose acetate butyrate, etc.

(2) Vinyl resins such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinylpyrrolidone, polyester, and polyacrylamide.

〔Example〕

Hereinafter, the specific structure of the thermal transfer sheet of the present invention will be explained with reference to manufacturing examples, and the properties of the obtained thermal transfer sheet will also be explained.

Example 1 The following composition (1) was sealed in a reaction vessel equipped with a heating and stirring device and refluxed for 10 hours to carry out a polymerization reaction to obtain coating material [A].

Composition ill Methyl methacrylate 100 parts by weight Dimethylpolysiloxane (*1) 10 parts by weight Methyl ethyl ketone 300 parts by weight α,α'-Azobisisobutyronitrile 0.3 parts by weight Next, a polyester film with a thickness of 6 μm [Toshi The coating material [A] was coated on one side of the coating material [A
] was applied uniformly at a ratio of 1.5p (solid content>/m'') and dried to form a heat-resistant, protective layer.

Thereafter, on the other side of the polyester film, wax ink in which carpon platz and resin were dispersed was heated to 120°C and applied at a ratio of 39/nl by reverse roll coating to form a heat-sensitive transfer ink layer. was formed to obtain a heat-sensitive transfer sheet (a) which is an example of the present invention.

The wax surface of the obtained thermal transfer sheet (a) and 7
．． 5 When the paper was overlapped with PC9 base form paper and printed using a thermal printer [manufactured by NEC Corporation], there were no problems such as sticking, stable running performance was obtained, and thermal recording with sufficient print density was performed. .

For comparison, a composition for thermal transfer obtained by removing dimethylpolysiloxane from the composition (1) was used, and all other procedures were the same as in Example 1. When I used it to print with a thermal printer, the transfer sheet fused to the thermal head.
The seat did not run.

Example 2 The following composition (2) was refluxed for 10 hours in a reaction vessel.

Composition (2) Methyl methacrylate 30 parts by weight Dimethylaminoethyl methacrylate 324 parts by weight Acrylic acid 72 parts by weight Dimethylpolysiloxane (*2) 35 parts by weight Benzoyl peroxide 1 part by weight Toluene
100 parts by weight methyl ethyl ketone 250
Part by Weight Next, 1000 parts by weight of toluene, 150 parts by weight of allyl chloride, and 500 parts by weight of isozorobyl alcohol were added to the reaction solution, and the mixture was reacted at 80°C for 4 hours to obtain a reaction solution (a). .

On the other hand, a polymerization reaction was carried out using the following composition (3) to obtain a reaction solution (b).

Composition (3) Methyl methacrylate 100 parts by weight 2-aziridinylethyl methacrylate 20 parts by weight Benzoyl peroxide 1 part by weight Toluene
1000 parts by weight 100 parts by weight of methyl ethyl ketone Thereafter, the reaction solution (
b) 100 parts by weight and reaction solution (0) 1'5 (1
'ffi parts were mixed to obtain coating material CB).

The obtained coating material CB) was formulated in exactly the same manner as the coating material [A] in Example 1, and a heat-sensitive transferable ink layer was also formed in the same manner to reduce the charging voltage by half, which is an example product of the present invention. A thermal transfer sheet (b) with a period of 5 seconds was obtained.

When the obtained thermal transfer sheet [b] was subjected to thermal recording in the same manner as the thermal transfer sheet (a) in Example 1, stable running properties were obtained without any problems such as sticking. A thermosensitive recording with sufficient print density was obtained.

Example 3 A polymerization reaction of the following composition (4) was carried out for 10 hours in a reaction vessel.

Composition (4) Methyl methacrylate 300 parts by weight Dimethylaminoethyl methacrylate 314 parts by weight 2-hydroxymethacrylate 130 parts by weight Dimethylpolysiloxane (*3) 15 parts by weight α, α'-
Next, 1000 parts by weight of toluene, 250 parts by weight of allyl bromide, and 200 parts by weight of methyl alcohol were added to the above reaction solution, and The mixture was reacted for 4 hours to obtain a reaction solution.

Thereafter, 1.5 parts by weight of tolylene diisocyanate adduct [manufactured by Nippon Polyurethane ■: Coronate L] in terms of solid content was added to the reaction solution to form a coating material (C).
I got it.

The obtained coating material (C) was applied uniformly to one side of a 6 μm thick polyester film (Nilmirror, manufactured by Toshi ■) at a solid content of 14 μm, and after drying, it was rolled up and placed in an atmosphere of 40°C. A heat-resistant, protective layer was formed by aging and curing the mixture for 48 hours.

Thereafter, the following composition (51) was coated on the other side of the polyester film by a wire bar coating method and dried to form a heat-sensitive transferable ink layer with a thickness of 1.5 μm. A thermal transfer sheet (C) having a barrel charging voltage half-life of 5 seconds was obtained.

Composition (5) Disperse dye [manufactured by Nippon Kayaku ■: Kayaset Red B] 3 parts by weight Ethylhydroxyethyl cellulose 5 parts by weight Toluene 40 parts by weight Methyl ethyl ketone 40 parts by weight Dioxane
10 parts by weight On the other hand, the following composition (
6) was applied at a ratio of 4 g (solid content) A'' using a wire bar +36 and dried to form an ink receiving layer to obtain a thermal transfer sheet.

Composition (6) Polyester resin [manufactured by Toyobo ■: Byron 103] 8 parts by weight EVA polymer plasticizer [manufactured by Mitsui Polychemical ■: Elvaloy, 741P] 2 parts by weight amino-modified silicone oil [manufactured by Shin-Etsu Silicone ■: KF- 393) 0.125 parts by weight epoxy-modified silicone oil [manufactured by Shin-Etsu Silicone ■: X-22-343) 0, 125
Parts by weight Toluene 70 parts Methyl ethyl ketone 10M parts Cyclohexanone
20 parts by weight Thereafter, the heat-sensitive transfer sheet [C] and the heat-transfer sheet are superimposed so that their respective heat-sensitive transfer ink layers and ink-receiving layers are in contact with each other to form a heat-sensitive transfer sheet [C]. Heat resistance, thermal head applied from the protective layer side, output 1w/dot, pulse width: 0.3 to 4.5 msec.

When thermal recording was carried out under the conditions of 7 mm (dot density = 3 dots), there was no sticking phenomenon, no wrinkles, etc., the thermal transfer sheet [C] ran smoothly, and a clear red thermal recording was made. I got something.

Example 4 The following composition (7) was refluxed for 10 hours in a reaction vessel to perform a polymerization reaction, and then 0.1 part by weight of para-methoxyphenol was added to stop the reaction.

Composition (7) Methyl methacrylate 300 parts by weight Dimethylaminoethyl acrylate 314 parts by weight 2-hydroxyethyl methacrylate 130 parts by weight Dimethylpolysiloxane (*4) 3.5 parts by weight α, α'-
Azobisisobutyronitrile 2 parts by weight Toluene 1000 parts by weight Methyl ethyl ketone 250 parts Next, 100 parts by weight of an equimolar adduct of 2-hydroxyethyl acrylate and 2.4-4 luene diincyanate was added to the reaction solution. Then, 5 parts by weight of dibutyltin silaurylate was added, and the mixture was reacted for 5 hours at 80'O while blowing dry air.

Furthermore, 1000 parts by weight of toluene, 150 parts by weight of allyl chloride, and 2QO methyl alcohol were added to the reaction solution.
parts by weight and heated to 80'C! After reacting for 24 hours, the reaction solution was cooled to room temperature, and 15 parts by weight of trimethylolpropane triacrylate and an ultraviolet sensitizer (Irgacure 184, manufactured by Ciba Geigy) were added to the coating material. Obtained [D].

The obtained coating material (D) was coated on one side of a polyester film in the same manner as the coating material (C) in Example 3, and after drying, it was coated at 80 K W/lt under a nitrogen gas atmosphere.
A heat-resistant and protective layer was formed by passing the sample under a UV lamp having an output of n at a running speed of 10 m/min.

Thereafter, a heat-sensitive transferable ink layer having the same structure as the heat-sensitive transferable ink layer in Example 3 was formed on the other side of the polyester film, and the half-life of the charging voltage, which is an example product of the present invention, was formed. 20 seconds thermal transfer sheet (d
) was obtained.

When the obtained thermal transfer sheet [d] was thermally recorded in the same manner as the thermal transfer sheet (c) in Example 3, there was no sticking phenomenon, no wrinkles, etc. The thermal transfer sheet (d) ran smoothly and a clear red thermal recording was obtained.

Example 5 After refluxing the following composition (8) in a reaction vessel for 10 hours to cause a polymerization reaction, 0.3 parts by weight of hydroquinone was added to this reaction solution, and then 71 parts by weight of glycidyl methacrylate was added. Blow dry air while adding, 9
It was made to react at 0-100 degreeC for 8 hours.

Composition (8) Stearyl acrylate 324 parts by weight Dimethylaminoethyl methacrylate 314 parts by weight Acrylic acid 72 parts by weight Dimethylpolysiloxane (*5) 0.5 parts by weight α,α'-azobisisobutyronitrile 2 parts by weight Toluene
1000 parts by weight 250 parts by weight of methyl ethyl lactone Next, 1000 parts by weight of toluene and 15 parts by weight of allyl chloride were added to the reaction solution obtained above.
0 parts by weight, 200 parts by weight of methyl alcohol were added, and 8
The reaction was carried out at 08C for 4 hours to obtain a coating material (E).

The obtained coating material (E) was applied to a polyester film having a thickness of 6 μm that had been subjected to a corona discharge treatment at a ratio of 1 f (solid content W), and after drying, it was coated in a nitrogen gas atmosphere for 17 μm.
Heat resistant,
A protective layer was formed.

Next, on the other side of the polyester film, a heat-sensitive transfer ink layer having the same structure as the heat-sensitive transfer ink layer of the heat-sensitive transfer sheet (a) in Example 1 was formed, thereby forming an embodiment of the present invention. A heat-sensitive transfer sheet (e) having a charging voltage half-life of 10 seconds was obtained.

When the obtained thermal transfer sheet (e) was operated in the same manner as the thermal transfer sheet (a) in Example 1 and thermally recorded, stable running was obtained without any problems such as sticking. Sufficient thermal recording of print density was performed.

Example 6 Diethyltriamine (
Add 35 parts by weight of epoxy curing agent) to coating material (F).
I got it.

Composition (9) Glycidyl methacrylate, 426 parts by weight Methyl methacrylate 600 parts by weight Dimethylpolysiloxane (*1) 3 parts by weight α,α'-Azobisisobutyronitrile 2.5 parts by weight Methyl ethyl ketone
3000 parts by weight of the obtained coating material (F) was uniformly applied to one side of a 9μ thick polyester film [Nilmirror manufactured by Toshi ■] at a ratio of IP (solid content)/m', and after drying, it was rolled up. A heat-resistant protective layer was formed by aging and curing in an atmosphere at 40° C. for 48 hours.

Thereafter, a heat-sensitive transferable ink layer having the same structure as the heat-sensitive transferable ink layer in Example 3 was formed on the other side of the polyester film, and the half-life of the charging voltage, which is an example product of the present invention, was formed. 20 seconds thermal transfer sheet) (f
) was obtained.

When the obtained thermal transfer sheet (f) was subjected to thermal recording in the same manner as the thermal transfer sheet (c) in Example 3, there was no sticking phenomenon, no wrinkles, etc. The thermal transfer sheet (d) ran smoothly, and a clear red thermal recording was obtained.

The half-life of the charging voltage of the heat-sensitive transfer sheets obtained in each of the above examples was measured using a measuring device [Kawaguchi Electric Works M
Fix the sample on the rotating disk of Odel 5P-428 Engineering V Cutrostatic Paper Analyzer and set it at 1,0
The sample was rotated at 00 rpm, a voltage of 5 KV was applied, and a charge was applied to the sample for 30 seconds by corona discharge, and then the charged voltage of the sample was measured in an atmosphere of 25° C. and 50 SRH.

[Action and effect]

The heat-sensitive transfer sheet of the present invention comprises a vinyl polymer [A] in which organopolysiloxane units are bonded in a block or graft form, or the polymer [A] on the back side of a base sheet made of a plastic film. Modified derivative [B] or both polymers thereof [A], [B]
Since the heat-resistant and protective layer has sufficient heat resistance and lubricity, when performing heating printing with a thermal head, Even when printing operations (thermal recording) are carried out under the high energy required to obtain sufficient print density,
There is no possibility that the thermal head is thermally fused to the thermal transfer sheet, and there is no problem such as the thermal transfer sheet becoming unable to run or breaking on the way, and the process is carried out smoothly and satisfactorily. This has the function and effect of making it possible to perform heat-sensitive recording with a print density of a certain degree.

Claims (4)

[Claims] (1) In a heat-sensitive transfer sheet having a heat-sensitive transferable ink layer on the surface of a base sheet made of plastic film, a vinyl-based polymer having organopolysiloxane units bonded in a block or graft form on the back surface of the base sheet. Coalescence [A], a modified derivative of the polymer [A] [B], or both of these polymers [A], [B]
] A heat-sensitive transfer sheet characterized by comprising a heat-resistant and protective layer consisting essentially of. (2) The ratio of organopolysiloxane and vinyl polymer in the vinyl polymer [A] or the modified derivative of the polymer [A] [B] is 100:1,000,000 to 1 (weight ratio). A heat-sensitive transfer sheet according to claim 1. (3) Vinyl polymer [A], a modified derivative of the polymer [A] [B], or both of these polymers [
The heat-sensitive transfer sheet according to claim 1, wherein A] and [B] are polymers having a crosslinked structure. (4) Vinyl polymer [A], a modified derivative of the polymer [A] [B], or both of these polymers [
The thermal transfer sheet according to claim 1, wherein A] and [B] are (co)polymers of one or more monomers having a quaternary ammonium base or a tertiary amino group. .