JPS62184883A - Anti-thermal-sticking agent for thermal transfer material - Google Patents

Abstract

PURPOSE:To obtain an excellent title agent, by using a composition comprising as essential constituents a compound having at least one polymerizable unsaturated group in its molecule and an organopolysiloxane having a specified reactive group in its molecule. CONSTITUTION:An anti-thermal-sticking agent for a thermal transfer comprises, as essential constituents,(A) a compound having at least one polymerizable unsaturated group in its molecule and (B) an organopolysiloxane of average composition formula I and/or a partially hydrolyzed co-condensate of an organopolysiloxane with a silicon-containing compound of general formula II. Component (B) is used in an amount of 0.01-1000 pts.wt. per 100 pts.wt. of component (A), the amount being in such a range that the two component are compatible with each other at room temperature. The agent is uniform in an unhardened liquid state. When a coated film of the agent is formed, phase separation of the two components occurs efficiently due to the difference in hardened form between the two components, and a perfect silicone resin film layer is formed at the surface of the coated film, whereby high degrees of lubricity and heat resistance are developed on the surface.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a novel thermal stick prevention agent for thermal transfer materials. More specifically, in a heat-sensitive transfer body comprising a base film and a heat-transferable ink layer provided on one surface of the film, a heat stick prevention layer is provided on the other surface of the base film, so that the ink is applied from a heating head. 16 Thermal stick prevention agent for thermal transfer material that prevents part of the base film from melting and adhering to the heating head due to heat pulses, and also provides lubricity for smooth heating head movement and paper feeding. Regarding.

(Prior Art) In recent years, facsimile machines and printers have frequently used a thermosensitive recording method in which a thermosensitive coloring layer is provided on a base material, in which two components that develop color when heated are dispersed. However, this method has drawbacks such as poor storage stability, easy falsification after recording, and poor solvent resistance. A transfer type thermal recording system is known as a method for improving these drawbacks.

This method prints on a receiving sheet (for example, plain paper) by passing a thermal transfer material through it and applying heat pulses from a heating head. Those provided with a thermally transferable ink layer such as a containing layer are generally used.

As the base film of the heat-sensitive transfer member, a plastic film is suitable from the viewpoints of film thickness, strength, and moisture resistance, and a polyester film or the like is used.

(Problems to be Solved by the Invention) Recently, there has been a desire to improve printing performance and printing speed in transfer-type thermal recording methods, such as reducing the thickness of the base film or increasing the amount of heat applied to the heating head. However, with these methods, the heat load applied to the base film becomes large, causing the base film to melt and
This creates a problem that hinders the running of the heating head. Such a phenomenon is generally called a thermal sticking phenomenon.

Various attempts have been proposed to improve this thermal stick phenomenon. For example, JP-A-55-7467 proposes a method of coating one side of a base film with a heat-resistant resin such as silicone resin or epoxy resin, but these require heat curing treatment at 100°C or higher for several hours. In addition, silicone resins have poor adhesion to the base film, and epoxy resins have poor lubricity on the coating surface, so a high degree of heat stick prevention effect cannot be expected. Furthermore, JP-A-56-155794 discloses a composition consisting of a heat-resistant polymer and fine inorganic powder such as silica or talc, but it has the disadvantage that heat-curing treatment takes a long time, and inorganic The powder tends to roughen the surface, leaving problems with the running performance of the heating head. Further, JP-A No. 60-15193 proposed a composition consisting of colloidal particles of silica and alumina and an organic binder such as polyvinyl alcohol, and JP-A No. 60-151096 proposed a cured resin composition containing a liquid lubricating substance. However, the former is still insufficient in terms of the heat resistance of the composition itself and the slipperiness of the coating surface, and the latter causes the thermal transfer ink layer to be contaminated with liquid lubricant when the thermal transfer material is wound up. However, the following problems remain.

The present invention solves the above-mentioned conventional problems, and its object is to provide an excellent thermal stick prevention agent for thermal transfer materials.

(Means and effects for solving the problem) As a result of intensive research into heat stick preventive agents, the present inventors have found a compound having at least one polymerizable unsaturated group in the molecule and a specific compound in the molecule. The inventors have discovered that a composition comprising an organopolysiloxane having a reactive group as an essential component can solve the conventional problems, and have completed the present invention.

That is, the present invention provides (A) a compound having at least one polymerizable unsaturated group in the molecule; and (B) an average composition formula % formula % (wherein R1 has no polymerizable unsaturated group and the number of carbon atoms is 1-1
0 substituted or unsubstituted 11i1i hydrocarbon groups,
X is a monovalent reactive group selected from HlOH and OR2 (where R2 is a hydrocarbon group having 1 to 6 carbon atoms), and a and b are each 0.5≦a≦2 .0, O,
OO1≦b≦”+, o Te exists, and a+b is 1.2
There is ≦a+b≦2.5te. ] and/or the organopolysiloxane with the general formula R3C-8i -Ya-c (wherein R3 is hydrogen or a substituted or unsubstituted compound having 1 to 10 carbon atoms having no polymerizable unsaturated group) a substituted monovalent hydrocarbon group, Y is a hydrolyzable group,
C is either 0.1.2.

) is composed of a hydrolyzed co-condensate with a silicon-containing compound represented by ] as an essential component, and the blending ratio of component (A) and component (B) is 10% of component (A).
The present invention relates to a thermal stick preventive agent for a thermal transfer material, in which the amount of component (B) is 0.01 to 1,000 parts by weight based on 0 weight parts, and the ratio is in a range where they are compatible with each other at room temperature.

The thermal stick preventive agent for thermal transfer materials of the present invention is uniform in an uncured liquid state, and due to the difference in curing form during coating formation, both components phase separate efficiently, and the coating surface is By forming a complete silicone resin coating layer, the surface exhibits high lubricity and heat resistance, but even more surprisingly, the coating obtained from this thermal stick prevention agent for thermal transfer materials Although both components are completely separated at the air-side interface and the base film-side interface, the image components are compatible to some extent and no clear interface can be seen despite JI, so for example, if the two are separated separately. The peeling phenomenon of both components 1, which occurs in coatings that are coated and cured and then overcoated, does not occur at all. Therefore, by applying the thermal stick prevention agent for thermal transfer material of the present invention to the back surface of the thermal transfer material base film, the thermal sticking phenomenon is significantly improved, and troubles such as contamination of the heating head during running do not occur at all. It has characteristics.

An application example of the thermal stick prevention agent for thermal transfer materials of the present invention is shown in FIG. 1, in which a thermal transfer ink layer 2 is provided on one surface of a base film 1, Another example is a thermal transfer body provided with a thermal stick prevention layer 3 containing the thermal stick prevention agent of the present invention as a main component.

Component (A), which is one of the essential components constituting the thermal stick prevention agent for thermal transfer materials of the present invention, is a compound (hereinafter referred to as a compound) having at least one polymerizable unsaturated group in the molecule.
A). ), and can be easily cured to form a film by irradiation with radiation such as ultraviolet rays or electron beams, or by heating.

Of the compounds (A) that can be used, at least 2
Compounds having (meth)acryloyl groups release OA
This is preferable because it is easy to form a cured film by irradiation with radiation, and the heat resistance of the resulting film can be further improved. Examples of the compound having at least two (meth)acryloyl groups include ethylene glycol di(meth)acrylic acid ester, propanediol-1
, 3-di(meth)acrylic ester, trimethylolpropane tri(meth)acrylic ester, pentaerythritol tri- or tetra(meth)acrylic ester, and (meth)acrylic acid. polyesters of (meth)acrylic acid and condensates of polyols such as diethylene glycol, dipropylene glycol, dipentaerythritol, etc.; polyesters of (meth)acrylic acid; Meth)acrylate: Examples include epoxy acrylate obtained from the reaction of polyglycidyl ether of polyol and (meth)acrylic acid, and one type or a mixture of two or more types selected from these groups can be used. .

Compounds (A) other than the aforementioned compounds having at least two (meth)acryloyl groups that can constitute component (A) include, for example, (meth)acrylic acid; methyl, ethyl, propyl, butyl (meth)acrylic acid; , octyl, 2-
Ester of (meth)acrylic acid such as ethylhexyl, stearyl or cyclohexyl ester with linear or branched aliphatic alcohol or alicyclic alcohol having 1 to 18 carbon atoms: ethylene glycol (meth)acrylic acid ester, propane Monoesters of polyols having 1 to 10 carbon atoms, such as diol (meth)acrylic acid esters, and (meth)acrylic acid; condensates of polyols, such as diethylene glycol, dipropylene glycol, dipentaerythritol, etc., and (meth)acrylic acid. monoester; (meth)acrylamide, N-methylol (
(meth)acrylamide or derivatives thereof, such as meth)acrylamide, diacetone (meth)acrylamide, etc.;
Glycidyl (meth)acrylate: Glycidyl (meth)acrylate and a saturated aliphatic monocarboxylic acid or dicarboxylic acid having 2 to 18 carbon atoms, or an ethylenically unsaturated monocarboxylic acid or dicarboxylic acid having 3 to 10 carbon atoms. Reaction product with acid: Unsaturated dibasic acid or its anhydride such as maleic acid, fumaric acid, itaconic acid, etc.; Unsaturated dibasic acid or its anhydride and linear or branched chain having 1 to 18 carbon atoms mono- or diesters with aliphatic alcohols or alicyclic alcohols; aromatic vinyl or divinyl compounds such as styrene, α-methylstyrene, divinylbenzene, etc.; vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, etc.; ) Esters of allyl alcohol or (meth)allyl alcohol and aliphatic monocarboxylic acids having 1 to 18 carbon atoms; mono- or diesters of (meth)allyl alcohol and dicarboxylic acids such as maleic acid, phthalic acid, adipic acid, etc. Mono- or polyethers of (meth)allylic alcohol and polyols such as ethylene glycol, 1,2-propanediol, glycerin, etc.; Maleic acid, fumaric acid, itaconic acid, glutaconic acid or anhydrides thereof and ethylene glycol, 1 ．．
2-propanediol, diethylene glycol, glycerin, hexanetriol, trimethylolpropane,
Unsaturated polyesters obtained from reaction with polyols such as pentaerythritol; vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxy Polymerizable unsaturated group-containing silane compounds such as propyltriethoxysilane, γ-(meth)acryloxypropyldimethoxymethylsilane, etc. can be mentioned, and 1 selected from these groups.
Seeds or mixtures of two or more types can be used.

Component (B), which is another essential component constituting the thermal stick prevention agent for thermal transfer materials of the present invention, is an organopolysiloxane represented by the above average compositional formula (hereinafter referred to as polysiloxane (B1)). ), polysiloxane (B
1) and a silicon-containing compound represented by the above general formula (hereinafter, this will be referred to as silicon-containing compound 0).

) (hereinafter referred to as co-condensed polysiloxane (B2)) or polysiloxane (B2)
1) and a co-condensed polysiloxane (B2), which can be cured at room temperature or under heating conditions to form a film, but cannot copolymerize with compound (A). It does not contain any polymerizable unsaturated groups in its molecule. If the molecule contains a polymerizable unsaturated group, phase separation from compound (A) during film formation will be insufficient, resulting in poor thermal sticking prevention effect.

As the polysiloxane (B1) that can be used in the present invention,
There are no particular restrictions on the organopolysiloxane as long as it is represented by the above average compositional formula, such as silanol dimethylpolysiloxane at both ends, silanol methylphenylborisiloxane at both ends silanol at both ends diphenylpolysiloxane-dimethylpolysiloxane block copolymer, dimethyl methoxy groups at both ends Polysiloxane methylhydrodiene polysiloxane l-13 -8i -CH3 H3 and the like can be mentioned. Furthermore, it is not limited to those having a linear structure as described above, but various organopolysiloxanes having, for example, a branched structure or a lattice structure can be used.

The co-condensed polysiloxane (B2) that can be used in the present invention is:
It is a partially hydrolyzed co-condensate of the silicon-containing compound ω represented by the above general formula and polysiloxane (81), for example, in the absence of a solvent or in compound (A) or other organic solvent, to 01 mol of the silicon-containing compound. It is obtained by adding 0.5 mol or more of water to the polysiloxane (B1) and hydrolyzing it in the presence of polysiloxane (B1) and an acid at room temperature or under heating conditions.

The silicon-containing compound 0 that can be used to obtain the co-condensed polysiloxane (B2) is a silicon-containing compound that has two or more hydrolyzable groups in the molecule and does not have a polymerizable unsaturated group. Without particular limitation, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane; methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, ethyltrimethoxysilane, etc. Alkyltrialkoxysilane; Dialkyldialkoxysilane such as dimethyldimethoxysilane, dimethyljethoxysilane, etc.: γ-glycidoxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, 3.3.3-trichloropropyltrimethoxy Examples include substituted alkyl polyalkoxysilanes such as silane; alkyl acyloxysilanes such as methyltriacetoxysilane and dimethyldiacetoxysilane; and hydrosilane compounds such as trimethoxysilane and triethoxysilane. Alternatively, a mixture of two or more types can be used.

In this way, a silicon-containing compound ω is co-condensed with polysiloxane (B1) to prepare a co-condensed polysiloxane (B2), and this is used as component (8) to prevent thermal stickiness for a thermal transfer material. In some cases, the compatibility of the agent in a liquid state can be improved, and the curing of component (B) after film formation can be accelerated.

The amount of component (B) composed of polysiloxane (B1) and/or co-condensed polysiloxane (B2) used is 0.01 parts by weight per 100 parts by weight of component (A) composed of compound (A). -1000 parts by weight, and more preferably in the range of 0.05 to 100 parts by weight, considering the balance between the thermal sticking preventive effect of the obtained thermal transfer material anti-sticking agent and the adhesion to the base film. be. If it is less than 0.01 part by weight, the surface rSlI slipperiness of the obtained thermal stick preventive agent for a thermal transfer material will be reduced, and a sufficient thermal sticking preventive effect cannot be expected;
If the amount exceeds 1,000 parts by weight, the adhesion to the base film will be poor.

In addition, it is essential that the thermal stick preventive agent for thermal transfer materials of the present invention be compatible in an uncured liquid state;
When mixing component A) and component (B), it is necessary to select a combination that is compatible with each other at room temperature. This can be achieved by combining substances with similar solubility coefficients, but if it is necessary to mix substances with significantly different solubility F/I' coefficients and which are difficult to mix with each other, it is possible to achieve compatibility with an appropriate solvent. It can be dissolved. The solvent used is preferably a solvent in which both components can be dissolved, and suitable solvents include monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexyl alcohol, benzyl alcohol, etc.; ethylene glycol; Propylene glycol, 1,4
- Polyhydric alcohols such as butanediol, glycerin, etc.; Aromatic hydrocarbons such as benzene, toluene, etc.; Saturated hydrocarbons such as hexane, petroleum ether, cyclohexane, etc.; Ketones such as acetone, methyl ethyl ketone, etc.; ethyl acetate, butyl acetate, etc. Solvents such as esters and the like can be mentioned, and one or a mixture of two or more of these can be used.

In the thermal stick preventive agent for thermal transfer materials of the present invention, since the compound of component (A) and the compound of component (8) have different curing forms, they phase-separate efficiently in the process of forming a film.
By orienting the cured film of the compound of component (B) to the air side interface, the cured film of the compound of component (A) has excellent adhesion to the base film and the cured film of the compound of component (B) has an excellent surface surface. A film with lubricity can be obtained. Furthermore, since the cured coatings of the compounds of component (A) and component (8) both have a high degree of heat resistance, they exhibit excellent characteristics as a heat stick preventive agent. The compound of component (A) can be cured by irradiation with radiation such as ultraviolet rays or electron beams, or by heating. When curing by ultraviolet irradiation, it is desirable to add a photosensitizer to shorten the curing time. The photosensitizer that can be used here may be any known one conventionally added to photocurable resins, such as acenaphthene, pyrene, acridone, acedraquinone, benzophenone, α-naphthoquinone, p-nitroaniline, Examples include 2-nitrofluon, triphenylamine, triethylamine, benzoin, α-hydroxymethylbenzoin, benzoin ethyl ether, benzoin isopropyl ether, and the like. When curing by heating, it is desirable to add an azo compound or an organic peroxide as a polymerization initiator. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2'2'-azobis-2,4-dimethylvaleronitrile, 1-azobis-1-cyclohexanecarbonitrile, dimethyl-2-2' - Azobisisobutyrate, etc. can be mentioned. Examples of the organic peroxide include benzyl peroxide, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. Also, N, N
-Dimethylaniline, N,N-dimethyl-p-toluidine, triethylamine, diethyltriamine, triethyltetramine, thiourea, ethylenethiourea, acetylthiourea, tetramethylthiourea, organic acid salts or inorganic acids such as iron, cobalt, manganese, vanadium, etc. It can be used in combination with known accelerators such as acid salts. Furthermore, in order to further shorten the curing time, a method of curing in an inert gas atmosphere can also be adopted.

Although it is usually desirable to heat the compound of component (B) to 80° C. or higher, it can be carried out at a lower temperature by adding a conventionally known integrated catalyst to the curing of the reactive silicone compound. Catalysts that can be used include, for example, metal salts of carboxylic acids such as alkyl titanates, organosilicon titanates, dibutyltin laurate, dibutyltin maleate, tin octylate, tin acetate, zinc octylate and zinc acetate: tetramethyl Examples include quaternary ammonium salts such as ammonium acetate and trimethylhexylammonium chloride, as well as acidic and basic catalysts, and one type or a mixture of two or more types selected from these can be used. .

The thermal stick preventive agent for thermal transfer materials of the present invention may optionally contain a partial hydrolysis condensate of an organic silicon-containing compound having two or more hydrolyzable groups in the molecule. The anti-stick agent can be used within a range in which the anti-stick agent is uniformly compatible with the liquid state.

In order to obtain the partially hydrolyzed condensate which can be used as necessary, for example, in addition to the silicon-containing compound ω, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltributoxysilane, vinyltris(β-methoxyethoxy)silane, allyl Triethoxysilane, trimethoxysilylpropylallylamine, γ-(meth)acryloxypropyltrimethoxysilane, γ-(meth)acryloxypropyltriethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, γ-(meth)acryloxypropylmethyldimethoxysilane, ) Acryloxypropylmethyljethoxysilane, γ-(meth)
Acryloxypropyltris (β-methoxyethoxy)
Silane, N-8-(N-vinylbenzylamino)ethyl-γ-7minopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 2
-Styrylethyltrimethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane, (meth)acryloxyethyldimethyl (
3-trimethoxysilylpropyl) ammonium chloride, γ-glycidoxypropyltrimethoxysilane,
organic silicon-containing compounds such as vinyltriacetoxysilane,
The condensation may be carried out by the same method as that used to obtain the co-condensed polysiloxane (B2). By using the partially hydrolyzed condensate, the compatibility of the resulting thermal stick preventive agent for thermal transfer materials in a liquid state can be improved, and the curing can be accelerated.
The effect of preventing thermal sticking of the resulting cured film may be improved in some cases.

The thickness of the heat stick prevention layer is preferably 0.1 to 5 microns. The thermal stick prevention layer can be coated by a conventionally known method using the thermal stick prevention agent for thermal transfer materials of the present invention. In addition, when forming the heat stick prevention layer, heat-resistant particles such as surfactants, titanium oxide, iron oxide, zirconium oxide, antimony oxide, silicon oxide, carbon black, amine resins such as melamine resin and benzoguanamine resin, and fluorine resins are used. You are also free to use it.

As the base film, conventionally used ones can be used.
Examples include polyester film, polycarbonate film, cellulose acetate film, polypropylene film, and cellophane.

The heat transferable ink layer is a conventionally used heat-melting ink layer or a heat-sublimable dye-containing layer, and is formed by coating or printing using a conventionally known method.

(Effects of the Invention) The thermal stick prevention agent for thermal transfer materials of the present invention is easy to process and exhibits good adhesion to the base film, and has excellent heat resistance, slipperiness, and thermal stick prevention ability. The present invention provides a heat-sensitive transfer member with good printing performance by forming a heat stick prevention layer.

(Examples) The present invention will be specifically described below with reference to Examples, but the present invention is not limited in any way by these. In addition, all parts and percentages in the examples indicate parts by weight and 1.5% by weight.

Reference Example 1 A 75% toluene solution of an addition reaction product of 70 parts of ethyl acetate, 1 mole of trimethylolpropane, and 3 moles of tolylene diisocyanate was placed in a flask equipped with a stirrer, an air inlet tube, a dropping funnel, a thermometer, and a reflux condenser. (trade name: Coronate, manufactured by Nippon Polyurethane Industry ■) and 0.1 part of dibutyltin dilaurate were charged, and the temperature was adjusted to 40° C. while blowing air. There, 48 parts of hydroxyethyl acrylate and 0.0 parts of hydroquinone, which had been prepared in advance, were added.
The two-part mixture was added dropwise at 40° C. over a period of 2 hours. Next, the reaction was carried out at 80°C for 12 hours, and after confirming that the specific absorption (2300α-1) of the NGO group had disappeared in the infrared absorption spectrum, the solution was cooled for 5 minutes and a 60% solution of urethane acrylate (1) was prepared. I got it.

Reference Example 2 60 parts of ethyl alcohol, 200 parts of tetraethoxysilane, and 70 parts of methyltriethoxysilane were placed in a flask equipped with a stirrer, a dropping funnel, a thermometer, and a reflux condenser, and the mixture was stirred to bring the liquid temperature to 20 to 25°C. It was adjusted to There 0
．． After 50 parts of 0.1N aqueous hydrochloric acid solution was added dropwise over 30 minutes, stirring was continued for 2 hours. Thereafter, the mixture was left to ripen at room temperature for 24 hours to obtain a partially hydrolyzed condensate (1) of an organic silicon-containing compound.

Reference Example 3 The same method as in Reference Example 2 was followed except that the raw materials charged into the flask were 20 parts of ethyl alcohol, 40 parts of ethyl acetate, 180 parts of tetraethoxysilane, and 60 parts of γ-glycidoxypropyltrimethoxysilane. A partially hydrolyzed condensate (2) of a silicon compound was obtained.

Reference Example 4 Into a flask equipped with a stirrer, dropping funnel, thermometer and U reflux condenser were added 20 parts of ethyl alcohol, 50 parts of ethyl acetate, 80 parts of tetraethoxysilane, 60 parts of methyltriethoxysilane and a compound having a molecular weight of about 2500. 160 parts of methylhydrodiene polysiloxane was charged, and the liquid temperature was raised to 75° C. while stirring. 25 parts of a 0.01N aqueous hydrochloric acid solution was added dropwise thereto over 1 hour, and stirring was further continued at 75°C for 3 hours. The solution was cooled to the invasion temperature and left to mature for 24 hours to obtain a solution of a partially hydrolyzed cocondensate of the organopolysiloxane and the silicon-containing compound (hereinafter referred to as cocondensed polysiloxane (1)).

Example 1 In a flask equipped with a stirrer and a reflux condenser, 16 parts of ethyl acetate as a solvent, 30 parts of trimethylolpropane triacrylate and 70 parts of pentaerythritol tetraacrylate as a compound (A), and a molecular weight of about 650 as an organopolysiloxane were added. Two parts of both-terminated silanol dimethylborisoloxane and one part of methylhydrodiene polysiloxane having a molecular weight of about 2500 were charged and stirred to form a homogeneous solution. Then, 3 parts of benzoin ethyl ether and 0.0 parts of dibutyltin dilaurate were added as a curing catalyst.
1 part was added and stirred for 2 hours to obtain the thermal stick inhibitor (1) of the present invention (approximately 85% non-volatile).

This heat stick preventive agent (1) was applied to one side of a 6μ thick polyethylene terephthalate base film using a bar coater, and a 80W/cIR metal halide lamp (
Manufactured by Eye Graphics, uses MO3-L31 lamp)
After setting the distance between the coating film and the metal halide lamp to 15 CIR and irradiating the film for 1 minute, the film was heated in a hot air dryer at 100° C. for 3 minutes to form a heat stick prevention layer with a thickness of 1.5 μm. Next, the other side of the base film is coated with a thickness of 2 μm.
A heat-transferable ink layer was provided to obtain a heat-sensitive transfer member (1).

Examples 2 to 5 Thermal transfer members (2) to (5) were obtained in the same manner as in Example 1, except that the raw materials used for preparing the thermal stick inhibitor were as shown in Table 1.

Comparative Examples 1 to 2 A comparative thermal transfer material ( 1
) to (2) were obtained.

Comparative Example 3 A comparative thermal transfer material (3 ) was obtained.

Comparative Example 4 In a flask equipped with a stirrer, an air inlet tube, a thermometer, and a reflux condenser, 100 parts of both-terminated silanol dimethylpolysiloxane having a molecular weight of about 650, 40 parts of γ-methacryloxypropyltrimethoxysilane, and para-toluenesulfonic acid were added. 1
．． 5 parts and 0.2 parts of hydroquinone were charged, and the liquid temperature was heated to 120°C under a stream of air. The reaction was carried out at 120°C for 5 hours while removing the methanol by-produced from the condensation reaction of both-terminated silanol dimethylpolysiloxane and γ-methacryloxypropyltrimethoxysilane, and the amount of by-produced methanol was the same as that at the completion of the synthesis reaction. After confirming that the theoretical amount had been reached, it was cooled. Add 50% distilled water to the cooled product.
Add 0 parts, shake well, wash with water, leave to stand in a separatory funnel, separate the lower aqueous layer, add calcium chloride in oil form, leave to stand for 24 hours to dehydrate, then remove calcium chloride. Then, a comparison organopolysiloxane having a polymerizable unsaturated group in the molecule (hereinafter referred to as unsaturated group-containing dimethylpolysiloxane (1)) was obtained.

The unsaturated group-containing dimethylpolysiloxane (1
) 30 parts, trimethylolpropane triacrylate 3
0 parts, 70 parts of pentaerythritol tetraacrylate, and 23 parts of ethyl acetate were charged and stirred to obtain a uniform solution. Next, 4 parts of benzoin ethyl ether and 0.1 part of dibutyltin dilaurate were added thereto as a curing catalyst, and the mixture was stirred for 2 hours.
) was obtained.

Using this comparative heat stick inhibitor (4), Example 1
A comparative thermal transfer member (4) was obtained in the same manner as described above.

Example 6 Into the same flask used in Example 1 was added ethyl acetate.
parts, 30 parts of trimethylolpropane triacrylate,
70 parts of pentaerythritol tetraacrylate, 2 parts of both-end silanol dimethyl polysiloxane having a molecular weight of about 650, and 1 part of methylhydrodiene polysiloxane having a molecular weight of about 2500 were charged and stirred to form a uniform solution. Next, 1 part of benzoyl peroxide and 0.1 part of dibutyltin dilaurate were added thereto as a curing catalyst, and the mixture was stirred for 2 hours to form a thermal stick inhibitor of the present invention (6
) (nonvolatility promise 85%) was obtained.

This thermal stick prevention agent (6) was applied to one side of a polyethylene terephthalate base film with a thickness of 6μ using a bar coater, and heated in a hot air dryer at 130°C for 10 minutes to form a thermal stick with a thickness of 1.5μ. A prevention layer was formed.

Next, a heat-transferable ink layer having a thickness of 2 μm was provided on the other surface of the base film to obtain a heat-sensitive transfer member (6).

Example 7 A thermal transfer member (7) was obtained in the same manner as in Example 6, except that the raw materials used in the preparation of the thermal stick inhibitor were as shown in Table 2.

Comparative Examples 5 to 7 In Example 6, compound (A) and organopolysiloxane were excluded from the scope of the present invention as shown in Table 2,
Unsaturated group-containing dimethylpolysiloxane obtained in Comparative Example 4 (
Following the same method except using 1) instead,
Comparative thermal transfer members (5) to (7) were obtained.

Example 8 and Comparative Example 8 Thermal transfer bodies (1) to (7) obtained in Examples 1 to 7 and Comparative Examples 1 to 7 and comparative thermal transfer bodies (1) to (7)
For each, a thermal transfer test was conducted on recording paper using a thermal head printing test device (manufactured by Matsushita Electronic Components 1). The test conditions were an applied voltage of 20 V and a printing speed of 2
It was milliseconds.

The presence or absence of a thermal stick phenomenon during the thermal transfer test was evaluated by observing the running state of the thermal head. The contamination state of the thermal head after the thermal transfer test was also investigated. These results are shown in Table 3.

Table 3 (Note 1) Melted polyester film adheres (Note 2)
) Peeled heat stick prevention layer adheres (Note 3) Oily substance adheres

[Brief explanation of drawings]

FIG. 1 is a diagram (a sectional view of a thermal transfer body) showing an application example of the thermal stick prevention agent for a thermal transfer body of the present invention. 1. Base film 2, thermal transfer ink layer 3, thermal stick prevention layer

Claims (1)

[Claims] 1. (A) A compound having at least one polymerizable unsaturated group in the molecule; and (B) an average composition formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 is Number of carbon atoms without polymerizable unsaturated group is 1 or more
10 substituted or unsubstituted monovalent hydrocarbon groups, X is H, OH, OR^2 (where R
^2 is a hydrocarbon group having 1 to 6 carbon atoms. ), where a and b are each 0
．． 5≦a≦2.0, 0.001≦b≦1.0, and a+b is 1.2≦a+b≦2.5. ] and/or the organopolysiloxane with the general formula R^3_c-Si-Y_4_-_c [wherein R^3 is hydrogen or has 1 to 10 carbon atoms without a polymerizable unsaturated group] is a substituted or unsubstituted monovalent hydrocarbon group, Y is a hydrolyzable group, and c is any one of 0, 1, and 2. It consists of a partially hydrolyzed co-condensate with a silicon-containing compound represented by ] as an essential component, and the blending ratio of component (A) and component (B) is 10% of component (A).
A thermal stick prevention agent for a thermal transfer material, in which the amount of component (B) is 0.01 to 1000 parts by weight relative to 0 parts by weight, and the ratio is in a range that they are compatible with each other at room temperature. 2. Claims in which (A) the compound having at least one polymerizable unsaturated group in the molecule contains as an essential component a compound having at least two (meth)acryloyl groups in the molecule The thermal stick prevention agent for thermal transfer materials according to item 1.