JPH01214475A - Thermal transfer recording film - Google Patents

Abstract

PURPOSE:To enhance adhesion to a base film and film-forming properties and prevent the repellence of an ink, by providing a thermal recording ink layer on one side of the base film, and providing an anti-sticking layer comprising a specified silicone graft polymer on the other side. CONSTITUTION:A thermal recording ink layer is provided on one side of a base film, and an anti-sticking layer comprising a silicone graft polymer is provided on the other side. The graft polymer is obtained by a method wherein a silicone macropolymer prepared by a condensation reaction of an acryl compound of formula (A) with a silicone of formula (B) is brought into radical copolymerization with other radical-polymerizable monomer. In formula (A), R is hydrogen or methyl, m is 0 or 1, l is an integer of 0-2 when m=0 and is 2 when m=1, and X is a 1-10C alkoxyl, acetoxyl or chlorine. In formula (B), (n) is a positive number, and each of R1 and R2 is a 1-10C monovalent saturated aliphatic hydrocarbon group, phenyl or monovalent halogenated hydrocarbon group. The silicone macromonomer unit in the silicone graft polymer comprises a condensation product of the silicone having a value of n in formula (B) of 100-600 with the acryl compound the amount of which is 1.3-3mol per mol of the silicone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermal transfer recording film,
More specifically, the present invention relates to a heat-sensitive transfer recording film having a heat-sensitive ink layer on one side of a substrate and a stick prevention layer on the other side.

[Conventional technology]

Thermal transfer recording films are used in printers, recorders, etc. of various office equipment that employ the thermal transfer recording method.

The thermal transfer recording method brings the recording paper, which is the material to be transferred, into contact with the thermal ink layer provided on the film, which serves as the base material.
The base film is selectively heated by a pulse signal from a thermal head on the opposite side of the ink layer. The ink layer heated through the film is transferred to the recording paper by melting or sublimation to form a recorded image.There is no noise during printing, the print has good heat resistance and chemical resistance, and has long shelf life. This is a recording method that has advantages such as superior performance.

In the heat-sensitive transfer recording film used in such a heat-sensitive transfer recording method, a part of the film melts due to the high temperature of the thermal head, and the molten resin sticks to the thermal head, resulting in poor film conveyance and characters. There is a problem of so-called sticking, which makes it difficult to transfer figures etc. to recording paper.To solve this problem, various types of anti-sticking layers are provided on the film surface that comes into contact with the thermal head, as shown below. This was commonly done. That is, there have been proposals to provide a metal layer such as aluminum, coat silicone, paraffin, etc., or use a thermosetting resin layer such as urethane, epoxy, melamine, or ethyl cellulose layer as a stick prevention layer.

However, all of these methods have insufficient stick prevention effects, and when thermosetting resins are used, they require heat treatment at high temperatures and for long periods of time to harden, resulting in poor workability and impractical use. There were problems such as a lack of Further, even if it has a stick prevention effect, there are problems such as poor adhesion to the base film, poor film forming properties, and corrosion of the thermal head.

As a means to solve this problem, the above-mentioned polydimethyl siloxane is produced by copolymerizing a silicone macromonomer in which a radically polymerizable polymer is bonded to one end of polydimethylsiloxane with an alkyl (meth)acrylic acid ester. It has been proposed to use a graft polymer having siloxane as a branch component as an anti-stick agent, and to provide an anti-stick layer made of the graft polymer (JP-A-62-30082 and JP-A-62-1575).
Publication No.). The above-mentioned graft polymer has good film-forming properties, and in the coated state, the branch components made of heat-resistant and lubricating polydimethylsiloxane face the surface, that is, the opposite side of the base film. Because the backbone component, which is mainly composed of monomer units such as (meth)acrylic acid alkyl esters that have adhesive properties, is oriented toward the substrate, it has excellent adhesion to the substrate and has the effect of suppressing sticking. It was said to be in good condition. ' However, conventional silicone macromonomers, especially those with the general formula HO (-8i-0→-H (n is a positive number; R, R2 are monovalent saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms) The silicone shown and the general formula % (R is a hydrogen atom or a methyl group; m is 0 or 1; t is m-
When = 0, it is an integer of θ to 2; when m-1, it is 2; p is 1.2 or 3; R3 is a methyl group, ethyl group, or phenyl group; It is an alkoxy group, an acetoxy group, or a chlorine atom. ) The silicone-based macromonomer obtained by condensing with the acrylic compound represented by () contains unreacted silicone, that is, silicone that does not have a radically polymerizable group, and therefore silicone manufactured using this as a raw material When a type graft polymer is used as an anti-stick agent, there are still problems as shown below.

That is, a thermal transfer recording film is usually manufactured by applying a stick preventive agent to a base film, winding up the carrier, and then unwinding it and applying a thermal ink to the other side. When the above-mentioned silicone-based graft polymer is used as an anti-stick agent, unreacted silicone migrates to the surface on which the thermal ink layer is to be provided during winding or storage of the wound roll.
In the process of applying the ink, ink repellency occurs and it is difficult to obtain a uniform ink layer, and the obtained thermal transfer recording film also undergoes a similar transition from the anti-stick layer to the thermal ink layer while being stored in a roll. occurs, and as a result, there is a problem in that the transfer print on the recording paper becomes unclear.

[Problem to be solved by the invention]

In the present invention, among the acrylic compounds represented by the general formula, an acrylic compound in which p in the general formula is 3, which is cheaper to manufacture than other acrylic compounds, that is, general formula (A) % formula % (R is a hydrogen atom or a methyl group; m is 0 or 1; t is m
= 0, it is an integer from 0 to 2, and m = 1, 2
and X has 1 to 10 carbon atoms. is an alkoxy group, acetoxy group or chlorine atom. ) A silicone-based macro obtained by condensing an acrylic compound represented by the formula (8) with a silicone represented by the general formula (8) (monovalent saturated aliphatic hydrocarbon, phenyl group, or halogenated hydrocarbon group) with a prime number of 1 to 10 When a silicone-based graft polymer obtained by copolymerizing a monomer with another radically polymerizable monomer is used as an anti-stick agent, the above-mentioned problem occurs due to unreacted silicone mixed in the graft polymer. This was an attempt to solve problems such as ink repellency.

(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that silicone Silica macromonomer is described as unfavorable because it causes gelation when radically copolymerized with other monomers: l-7HO+5i-0+-H (11 is a positive number; n R,, R2 is a monovalent saturated aliphatic hydrocarbon group with 1 to 10 carbon atoms, a phenyl group, or a halogenated hydrocarbon group) and an acrylic compound CH,,=C-C0C)+cH2 force ±ki CH2 square 5iX
3 (R is a hydrogen atom or a methyl group; m is O or 1; t is m
If = [], it is an integer from 0 to 2, and if m = 1, 2
and: X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) by setting the reaction molar ratio to an excess acrylic compound of 13 to 3 mol of acrylic compound per 1 mol of silicone, the content of unreacted silicone to which no acrylic compound has been added is made extremely small. We have discovered a very unique method for producing silicone macromonomers that allows for the production of silicone macromonomers that do not cause gelation during radical copolymerization with other monomers, and have filed a patent application. (Japanese Patent Application No. 62-60029) However, as a result of further studies, it was found that a silicone-based graft polymer produced using such a silicone-based macromonomer as a raw material has extremely good properties as a stick prevention layer in a thermal transfer recording film. The present inventors have discovered that the present invention is superior and have completed the present invention.

That is, the present invention has a heat-sensitive ink layer on one side of a film serving as a base material, and has a heat-sensitive ink layer on the other side with the following general formula (A
) from a silicone-based graft polymer obtained by radical copolymerization of a silicone-based macromonomer synthesized by a condensation reaction between an acrylic compound represented by the formula (B) and a silicone represented by the following general formula (B), with another radically polymerizable monomer. In a thermal transfer recording film provided with a stick prevention layer, the silicone macromonomer unit in the silicone graft polymer is a silicone in which n in the following general formula (B) is 100 to 600, and per mol thereof, the silicone macromonomer unit is This is a heat-sensitive transfer recording film characterized in that it is composed of a condensation reaction product with 1.6 to 3 moles of an acrylic compound.

General formula (A) % formula % (R is hydrogen atom or methyl group: m is 0 or 1: t is m=
In the case of Q, it is an integer of 0 to 2, and in the case of m=1, it is 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) General formula (B) A saturated aliphatic hydrocarbon group having a valence of 1 to 100, a phenyl group, or a halogenated hydrocarbon group having a valence of 1 to 100. ) Hereinafter, the present invention will be explained in more detail.

[Acrylic compound]

The acrylic compound used in the present invention has the general formula % (R is a hydrogen atom or a methyl group; m is 0 or 1; t is an integer from 0 to 2 when m20, and when m=1 , 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom), specifically γ-(meth)acryloyloxypropyltrimethoxysilane, γ -(meth)acryloyloxypropyltrichlorosilane, 3-(2-(meth)acryloyloxyethoxy)propyltrimethoxysilane, 3-(2-(meth)acryloyloxyethoxy)propyltricrosilane, 5-([meth) Acryloyloxy)pentyltrimethoxysilane, 5-((meth)
Examples include acryloyloxy)pentyltrichlorosilane.

Among these, γ-methacryloyloxypropyltrimethoxysilane is most preferred in terms of availability and low cost.

〔silicone〕

The silicone in the present invention has the general formula (B) R1 HO+5i-0+-H (n is 100 or more and 6[1[1 or less]; R,, R2 is a monovalent saturated aliphatic hydrocarbon having 1 to 10 carbon atoms) group, phenyl group, or halogenated hydrocarbon group), and such silicones include, for example, Toshiba Silicone's product names YF3800 and X.
There are F3905 etc.

Examples of the monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in the above general formula (B) include methyl group, ethyl group, decyl group, etc., and the -valent halogenated hydrocarbon group includes: Examples include 6,6°3-trifluoroglobyl group, 4,4.4-)lifluoro-3,3-difluorobutyl group, and 2-chloroethyl group. Particularly preferred as R1 and R2 is a methyl group.

A silicone macromonomer derived from a silicone with a large molecular weight in which the number of n in the silicone exceeds 600 decreases copolymerizability with a radically polymerizable monomer, causing a large amount of unpolymerized acrylic-modified silicone to remain; In a silicone-based macromonomer derived from silicone having a number of less than 100, radical polymerizable monomer Gelation occurs during copolymerization with

Silicones in which n is 200 to 500 are more preferred.

[Manufacture of silicone macromonomer] The silicone macromonomer in the present invention is a silicone macromonomer obtained by condensing the acrylic compound and the silicone in a range of 13 to 3 moles of the acrylic compound per mole of silicone. It is a monomer.

Most of the above condensation reactions follow the chemical reaction formula shown below, and as detailed below, the condensation reaction is carried out in an organic solvent inert to acrylic compounds and silicone, using catalysts as necessary. This can be done using .

If the molar ratio of the acrylic compound to the silicone is less than 1.3 mol per mol of silicone, the resulting silicone macromonomer will contain a large amount of unreacted silicone. In a thermal transfer recording film using a silicone-based graft polymer obtained from this as a raw material as an anti-stick agent, repellency of the ink occurs during application of the thermal ink.

Furthermore, when the amount of the acrylic compound exceeds 6 moles, the viscosity of the resulting silicone graft polymer increases significantly;
The anti-stick agent made of the graft polymer also has poor leveling properties, making it difficult to obtain a thin and uniform coating during coating.

The condensation reaction will be explained in more detail.

For example, when X in the acrylic compound represented by the general formula (B) is a chlorine atom, a solution of silicone represented by the general formula (B) and an acid acceptor dissolved in an appropriate solvent shown below at a concentration of 10 to 50% by weight is prepared. , an acrylic compound, or a solution of the same dissolved in a suitable solvent shown below at a concentration of 10 to 50% by weight is added dropwise at room temperature, and the reaction proceeds immediately and smoothly. After the reaction, the produced acid acceptor hydrochloride is filtered out, then washed with water depending on the case, and the solvent is evaporated to obtain the desired silicone macromonomer. Solvents that can be used in this reaction dissolve both reaction components,
A solvent that is inert to both reaction components under the reaction conditions is preferred, and examples of suitable solvents include diethyl ether, tetrahydrofuran, acetone, benzene, toluene, xylene, and mineral spirit. As the acid acceptor, known amines can be used, and for example, pyridine, triethylamine, aniline, etc. are preferably used. The amount of acid acceptor used is desirably about 1.2 times the molar amount of hydrochloric acid produced by the dehydrochlorination reaction.

X of the acrylic compound represented by general formula (8) has 1 carbon number
In the case of an alkoxy group of 1 to 10, it is a dealcoholization condensation reaction between a silicone represented by the general formula (B) and an acrylic compound. Although this reaction can be carried out without a catalyst, catalysts conventionally used in transesterification reactions are used to accelerate the reaction, such as sulfuric acid, p-toluenesulfonic acid, sodium hydroxide, potassium hydroxide, potassium acetate, and dibutyltin dilaurate. etc. can be used. A preferred catalyst includes p = toluenesulfonic acid. The amount of catalyst is desirably about 0.01 to 50% based on the total amount of silicone and acrylic compound.

The reaction temperature is preferably 50° to 150°C, and the reaction time is 1
~20 hours is preferred. Further, this reaction can be carried out without a solvent or with a solvent, and usable solvents include benzene, toluene, xylene, mineral spirit, and the like.

It is preferable to remove the used catalyst after the completion of the reaction, and any known method can be applied to remove it. However, when p"-)luenesulfonic acid is used as the catalyst, it is added to a basic ion exchange resin. The method of adsorption removal is easy to operate.

When X of the acrylic compound represented by the general formula (g) is an acetoxy group, the reaction is an acetic acid removal condensation reaction between the silicone represented by the general formula () and the acrylic compound. In this case, the same reaction operation as in the case where X is an alkoxy group can be used.

[Silicone-based graft polymer]

The silicone-based graft polymer in the present invention is obtained by radical copolymerization of the silicone-based macromonomer and a radically polymerizable monomer by a known polymerization method.
It is a silicone-based graft polymer that has silicone as a branch component and a polymer consisting of radically polymerizable monomer units as a backbone component. The radical copolymerization ratio of the silicone macromonomer and the radically polymerizable monomer is the total amount of the silicone macromonomer and the radically polymerizable monomer: 10
0 parts by weight, 2 to 90 parts of silicone macromonomer
mJi part, preferably 98 to 10 parts by weight of the radically polymerizable monomer, more preferably 5 to 60 parts by weight of the silicone macromonomer, and 95 to 40 parts by weight of the radically polymerizable monomer.
Parts by weight, particularly preferably 10 to 50 parts by weight of a silicone macromonomer and 90 to 90 parts by weight of a radically polymerizable monomer.
It is 50 parts by weight.

If f of the silicone macromonomer is less than 2Jii parts, the anti-stick effect will not be sufficient when used as an anti-stick agent, while if it exceeds 90% by weight, film forming properties will be poor and adhesion to the base film will be poor. Sexuality tends to deteriorate.

Examples of the radically polymerizable monomer include low molecular weight linear unsaturated hydrocarbons such as ethylene, propylene, and butylene; vinyl halides such as vinyl chloride and vinyl fluoride; organic acid nohinyl esters such as vinyl acetate; , styrene substitutes, vinyl aromatic carbon compounds such as vinylpyridine and vinylnaphthalene; acrylic acid, methacrylic acid, and derivatives of acrylic acid and methacrylic acid, including their alkyl esters, hydroxyalkyl esters, and amides; acrolein, acrylonitrile, N- N- such as vinylpyrrolidone and N-vinylcaprolactam
Vinyl compounds, vinylidene halides such as vinylidene fluoride and vinylidene chloride, unsaturated dicarboxylic acids such as maleic anhydride, maleic acid and fumaric acid, their alkyl esters, and CF3 (CF2)? (CH2)400CC=CH
2, CnF2n10, (CH2)200CCH-CH2(
Examples include acrylic monomers having a fluoroalkyl group represented by a specific formula such as (a mixture of n-4 to n-14), etc., and those having a carbon number of 1 to 1 are preferable because the obtained silicone graft polymer has excellent heat resistance. The main components of silicone-based graft polymers, such as methacrylic acid alkyl ester having four alkyl groups, styrene, and acrylonitrile, are mainly composed of the above-mentioned radically polymerizable monomer units. Compared to branch components made of silicone, they generally have inferior heat resistance and tend to flop when contacted by a heat-sensitive head. Preference is given to using monomers.

In addition, in order to impart heat resistance and adhesion to the base material to the polymer forming the backbone component, in addition to the above radically polymerizable monomers, we also use radically polymerizable monomers such as vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane. An organosilicon monomer may be used in combination in a small amount to the extent that gelation does not occur during the production of the silicone graft polymer.

As a method for radical copolymerization of a silicone macromonomer and a radically polymerizable monomer, known methods such as radiation irradiation and a method using a radical polymerization initiator can be used. It is preferable from the viewpoints of ease of polymerization and ease of controlling the molecular weight of the silicone graft polymer to be produced. Specifically, any method such as a solution polymerization method using a solvent, a bulk polymerization method, an emulsion polymerization method, etc. can be used.

As the radical polymerization initiator that can be used in the present invention, any of those used in general radical polymerization can be used, and an appropriate one may be selected depending on the polymerization method. Examples of inorganic radical polymerization initiators include ammonium persulfate, and examples of organic radical polymerization initiators include peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, and peroxyradical polymerization initiator. Examples include azo compounds such as esters and azobisisobutyronitrile, but in order to obtain a silicone graft polymer with a relatively clear structure, organic peroxides and azo compounds with low decomposition temperatures are used. are preferred, and azo compounds are particularly preferred.

In azo compounds, both nitrogen atoms in the azo bond are the sixth
is an azo compound bonded to a carbon atom and the remaining valency of the tertiary carbon atom is preferably satisfied by a nitrile, carboxyalkyl, cycloalkylene or alkyl group having 1 to 18 carbon atoms; Isobutyronitrile (hereinafter abbreviated as AIBN) is most preferred.

When copolymerizing by ultraviolet irradiation, a known sensitizer is used as a radical polymerization initiator, while when copolymerizing by electronic irradiation, it is not necessary to use a radical gold-forming initiator.

The amount of radical polymerization initiator is generally from 0.01 to 5% by weight, preferably from 0.1 to 2% by weight, based on the total weight of the polymerizable components.

The temperature of radical copolymerization is preferably higher than the decomposition temperature of the radical polymerization initiator, but if the reaction temperature is too high, undesirable reactions such as crosslinking reaction will occur, so the temperature is preferably as low as possible. Generally the temperature is 50-150°C, preferably 6
The temperature is 0 to 100°C.

Polymerization time is generally 6 to 100 hours, preferably 10 to 100 hours.
It is 25 hours.

The number average molecular weight of the silicone graft polymer produced by the above method was 25,000 to 100,000.

[Formation of anti-stick layer]

The anti-stick layer is formed on the base film by applying an organic solvent solution of the silicone-based graft polymer to polyethylene terephthalate, nylon, polycarbonate, polyethylene terephthalate, nylon, polycarbonate, polyethylene terephthalate, polycarbonate, polycarbonate, etc. using a method such as a gravure roll coater, a reverse mouth coater, or an air knife coating method. This can be done by coating the surface of paper and then heating and drying it.

The material for the base film is preferably polyethylene terephthalate (hereinafter abbreviated as PET) in terms of heat resistance and mechanical strength, and the thickness of the film is not particularly limited, but is usually 2 to 50 μm, preferably 6 to 10 μm. It is.

In forming the stick prevention layer, a polyvalent isocyanate compound or a melamine curing agent may be used together with the silicone graft polymer.

That is, if the silicone-based graft polymer used has a hydroxyl group or the like, the anti-stick layer formed can be crosslinked and cured by using the above-mentioned reactive compound in combination. Further, if the silicone-based graft polymer used has a hydrolyzable functional group bonded to a silicon atom, it may include, for example, dibutyltin dilaurate.

' In addition, as a stick preventive agent, together with the silicone graft polymer, it is possible to use, for example, acrylic resin, epoxy resin, unsaturated polyester resin, and especially A curable composition comprising a radically polymerizable component as a polymer precursor such as polyester polymethacrylate or polyester polyacrylate disclosed in JP-A-49-120889 can be blended.

The allowable blending amount of these resins is not constant depending on the type of resin to be blended, but in order to simultaneously exhibit excellent silicone properties and excellent adhesion to the substrate, it is necessary to combine the silicone graft polymer and these resins. It is desirable that the amount is 50% by weight or less.

In addition, talc, calcium carbonate, carbon black, silica powder, etc. are added to 1 to improve the heat resistance of the stick prevention layer, and fluororesin powder, etc. are added to improve the slipperiness of the resulting thermal transfer recording film. In order to prevent static electricity on the film, a known antistatic agent or the like may be added to the organic solvent solution of the silicone graft polymer to coat the base film.

The coating amount (solid content) of the silicone graft polymer on the film is 0.01 to 2 P/m from the viewpoint of flexibility, thermal transfer efficiency of the thermal head, cost, etc.
” is suitable, and more preferably 0.05 to 1 f/go.

[Thermal ink layer]

The heat-sensitive ink layer in the present invention can be formed by a known method using a heat-sensitive ink made of a thermoplastic resin, dye, pigment, etc. that has been conventionally used for forming a core layer in boat fishing.

Ethylene-acrylic ester copolymer, vinyl acetate-
Vinyl chloride copolymer, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, styrene-acrylic ester-acrylamide copolymer, styrene-butadiene copolymer, poly(meth)
Examples include alkyl acrylate, polyacrylonitrile, acrylonitrile-vinyl acetate copolymer, polyvinyl acetate, polyamide, and copolyester.

As the dye, oil-soluble dyes are preferred, such as oleosol fast blue EL (manufactured by Sumitomo Chemical Co., Ltd.) and oleosol first black BL (manufactured by Sumitomo Chemical Co., Ltd.).
, and Sumiplast Blue OR (manufactured by Sumitomo Chemical)
(Various oil-soluble dyes are commercially available, so it is possible to appropriately select and use them.

When a pigment is contained in the heat-sensitive ink layer, the pigment used may be either organic or inorganic, and the organic pigment may include:
Known organic pigments belonging to the azo dye series, anthraquinone series, indigoid series, cyanine series, etc. may be used, and examples of inorganic pigments include carbon black and the like.

Furthermore, appropriate amounts of various oils, various dispersants, plasticizers, stabilizers, etc. may be added to the heat-sensitive ink layer, if necessary.

The thermal ink can be coated on the base film by a coating method similar to that used in forming the anti-stick layer.

[Examples, reference examples and comparative examples]

EXAMPLES The present invention will be explained in more detail by giving Examples, Reference Examples, and Comparative Examples below.

The amount of unreacted silicone in the silicone graft polymer obtained by radical copolymerization of silicone macromonomers on each side was determined by the following method. Moreover, part and chi represent N11t part and east quantity chi, respectively.

Q Amount of unreacted silicone: Put 150 parts of toluene into a flask equipped with a stirrer, condenser, N2 inlet tube, and dropping funnel, and add 20 parts of silicone macromonomer and methyl methacrylate (hereinafter referred to as MM).
80 parts (abbreviated as A) and part AIBNI were placed in a dropping funnel, and after bubbling with toluene and N2, the temperature was raised to 80°, and the mixture in the dropping funnel was added dropwise over 2 hours to polymerize. After aging at this temperature for 1 hour, an additional portion of AIBNi was added and heated at the same temperature for an additional 2 hours.

The resulting solution was distilled under reduced pressure to obtain a white crystalline silicone graft polymer.

This graft polymer was powdered, and the powder 2017' and 1 ton of n-hexane were placed in an Erlenmeyer flask, and the mixture was left at room temperature for 24 hours to extract unreacted silicone. Next, filtration was performed, and the resulting filtrate was distilled under reduced pressure to remove n-hexane, yielding unreacted silicone oil as a residue. For silicone analysis in the graft polymer before extraction using unreacted silicone, approximately 0.21 g of the copolymer was accurately weighed in a platinum crucible, and then about 6 d of concentrated sulfuric acid was added thereto, and after thermal decomposition, The crucible was placed in an electric furnace and heated at 700° C. for 2 hours, and the silicone was determined as 5i02 by weighing.

Reference Examples 1 to 5 α, in a flask equipped with a stirrer, condenser, and thermometer.
ω-dihydroxypolydimethylsiliH3CH.

A mixed solution of 111i (G, 005 mol), p-toluenesulfonic acid 0.12y-1, toluene 74y-1 and methyl ethyl ketone (hereinafter abbreviated as MEK) 67
Heated at 0°C for 6 hours. After that, after cooling, add a basic anion exchange resin (t-21 manufactured by Organo ■) to this reaction solution.
50% of the solution was added and stirred at 40° C. for 2 hours to neutralize. The ion exchange resin is removed by filtration, the filtrate is distilled under reduced pressure,
When the solvent was removed, a colorless and transparent silicone macromonomer oil was obtained. As a result of gas chromatography analysis of the filtrate, γ-methacryloyloxypropyltrimethoxysilane was not detected, and the reaction rate was 100%.

Reference example 6 α,ω-dihydroxypolydimethylsilico-CH.

■、? (0,005 mol), γ~methacryloyloxypropyltrimethoxysilane 2.07 II (0,00
835 mol) (molar ratio -171,65), I) -) Reference Examples 1 to 4 except for using 0.20 F of luenesulfonic acid
In the same manner as above, a colorless and transparent silicone macromonomer oil was obtained. In addition, γ-methacrylic H3, P (0,003 mol), p-)luenesulfonic acid 0
．． 2I, toluene 116 &, MEK581/, γ-methacryloyloxypropyltrimethoxysilane 1.24
．． A silicone-based macromonomer was obtained in the same manner as in Reference Examples 1 to 4 except that 9 (0,005 mol) (molar ratio = 171.67) was used.

Reference Example 8 The results of the measurement in Reference Example-1 according to the above measurement method using 0.744.9 (0,003 mol) (molar ratio = 110.6) of γ-methacryloyloxypropyltrimethoxysilane are shown in Table- Table 2-2 A silicone macromonomer obtained under reaction conditions in which n in CH3 and the reaction molar ratio of silicone/acrylic compound are both within the range specified in the present invention can be used to prepare a silicone graft polymer. It was found that the amount of unreacted silicone in the graft polymer was extremely small.

100 parts of a 1/1 (weight ratio) solvent (hereinafter abbreviated as liquid A), silicone macromonomer iog shown in Table 6 in a dropping funnel, 42 parts of Shibutsu, and butyl methacrylate (hereinafter abbreviated as HMA). ), 6 parts of 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), and 5 parts of A I B N O (hereinafter abbreviated as liquid B), and after bubbling liquid A with N, 80 The mixture was heated to 0.degree. C., and then Solution B was added dropwise over 2 hours. After aging at the same temperature for 1 hour, 0.5 part of AIBN was added, and the temperature was maintained for an additional 2 hours to complete the polymerization.

The obtained reaction solution was diluted with MEK to a solid content of 15%, and a virum was cut out on a 6 μm thick PET film.
The five sheets were stacked so that the front and back sides were in contact alternately, sandwiched between two glass plates, and heated at 60℃ under a load of 40g/ld.
Heated for 4 hours.

After that, apply 50 parts of paraffin wax and 25 parts of carnauba wax to the side of the film that does not have the anti-stick layer.
Hot-melt coating was performed using a hot-melt ink consisting of 10 parts of ethylene-vinyl acetate copolymer, and 15 parts of carbon black to a thickness of 4.0 μm. The degree of ink repellency at that time is as shown in Table 6. When the ink was applied, no ink repelling was observed and the ink could be applied evenly. On the other hand, when the comparative example ink was applied,
Nosing and scratches occurred over the entire surface, and a uniform coating film could not be obtained.

The polymerization reaction solutions (silicone graft polymer solutions) obtained on each side described here were all in an emulsified state, but no separation or sedimentation was observed even when stored at room temperature for more than 6 months. Table 6 Regarding the thermal transfer recording sheets obtained in Example 4 and Example 6 above, the recording power of the thermal head was actually 1.0 mJ/sec, and the pulse width was 1.5 m5ec.
The anti-sticking property was evaluated by performing transfer printing on plain paper.No sticking occurred, good printing was obtained, and stable running performance was obtained.

The degree of repellency during ink application was examined in the same manner as in Example 4, except that 40 parts of toluene and 10 parts of isopropyl alcohol were uniformly mixed and dispersed in a ball mill for 24 hours, but no repellency was observed. It wasn't done.

Reference Examples 9 to 10 α,ω-dihydroxypolydimethylsilico-H3,9 (0,005 mol) and γ-methacryloyloxypropyltrimethoxysilane 2.48, F(0,0
A silicone-based macromonomer was obtained in the same manner as in Reference Examples 1 to 4 except that 1 mole) (mole ratio = 172) was used (Reference Example 9).

This silicone macromonomer has a number average molecular weight of 31. D[] was 0.

Equipment: High performance liquid chromatography (manufactured by Toyo Soda Kogyo, product name HLC-802UR) Column: Polystyrene gel (manufactured by Toyo Soda Kogyo, part names G4000H8 and G30)
00H8) Elution solvent: Tetrahydrofuran Efflux rate: 1. □ml/min Column temperature = 40°C Detector: R, I detector α,ω-dihydroxypolydimethylsilico-CH3,9 (0,005 mol) and γ-methacryloyloxyglobyltrimethoxysilane 0.992.9 (0, O
A silicone-based macromonomer was obtained in the same manner as in Reference Examples 1 to 4, except that O4 mol) (mole ratio = 110.8) was used (Reference Example 10).

The number average molecular weight of this silicone macromonomer was measured using the same method as in Reference Example 9, and was 5.700.

Example 7 and Comparative Example 4 All procedures were the same as Examples 1 to 5, except that 100 parts of toluene was used as the polymerization solvent, and 50 parts of silicone-based macro-septumer synthesized in Reference Example 9 and 50 parts of MMA were used as monomer components. A silicone-based graft polymer solution was obtained by the operation, and then, using the obtained silicone-based graft polymer solution, a thermal transfer recording film was produced in the same manner as in Examples 1 to 5 (Example 7).

In addition, a thermal transfer recording film was produced in the same manner as in Example 7 except that the silicone macromonomer synthesized in Reference Example 10 was used in place of the silicone macromonomer used in Example 7 (comparison). Example 4).

The same evaluation tests as those conducted on the thermal transfer recording films manufactured in Examples 4 and 4'5 and Example 6 were conducted on the thermal transfer recording films manufactured in Example 7 and Comparative Example 4, and the results were as follows: In the film of Example 7, there was no ink repellency at all, the transfer printing was good, and no sticking occurred and stable running properties were exhibited, whereas in the film of Comparative Example 4, there was no ink repellency at all. Ink repelling occurred, and if printing was continued for a long period of time, sticking occurred, making it impossible to obtain stable running performance.

Reference example 11 α,ω-dihydroxypolydimethylsilico-CH.

CI (3,9 (0,03 mol), p-)luenesulfonic acid 0.1
F,) Luene 46 & MEK23 II, γ-methacryloyloxyglobyltrimethoxysilane 7.44
Except for using F (0.05 mol) (molar ratio = 171), everything was the same as in Reference Examples 1 to 4, and an attempt was made to obtain a silicone-based graft polymer in the same manner as in Flow Sides 1 to 4, but 1 hour after the start of polymerization. Gelation occurred and the whole became pudding-like, making it impossible to obtain a graft polymer that could be used as an anti-stick agent.

Reference example 12 α,ω-dihydroxypolydimethylsilico-CH3 " CH.

i (0.03 mol), toluene 86 II, MEK4
A silicone-based macromonomer was obtained in the same manner as in Comparative Example 5 except for 3 g, p-)luenesulfonic acid, and rail for F'&. Thereafter, an attempt was made to obtain a silicone-based graft polymer in the same manner as in Example 1, but gelation occurred 2 hours after the start of polymerization, resulting in the entire polymer becoming pudding-like.

- is a graft polymer obtained by radical copolymerization of a silicone-based macromonomer having a radically polymerizable functional group at the end with another radically polymerizable monomer, so it cannot be manufactured by other manufacturing methods. Compared to silicone-based graft polymers, the content of the homopolymer is low, and the molecular weight and content of the branch components are well controlled. Therefore, according to the present invention, which uses this as a stain preventive agent, a thermal transfer recording film with good slip properties, no repelling phenomenon of thermal ink, excellent stick prevention, and long-term running stability can be obtained. It is possible to manufacture

Claims (1)

[Claims] 1. A film serving as a base material has a heat-sensitive ink layer on one side, and an acrylic compound represented by the following general formula (A) and an acrylic compound represented by the following general formula (B) on the other side. A heat-sensitive transfer recording film provided with a stick prevention layer made of a silicone-based graft polymer obtained by radical copolymerizing a silicone-based macromonomer synthesized by a condensation reaction with a silicone shown below with another radically polymerizable monomer, The silicone-based macromonomer unit in the silicone-based graft polymer is a silicone in which n in the following general formula (B) is 100 or more and 600 or less;
A heat-sensitive transfer recording film characterized in that it is composed of a condensation reaction product with 1.3 to 3 moles of the acrylic compound per mole thereof. General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R is a hydrogen atom or methyl group; m is 0 or 1; l is m=
When 0, it is an integer of 0 to 2; when m=1, it is 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) General formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (n is a positive number; R_1
, R_2 is a monovalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a phenyl group, or a monovalent halogenated hydrocarbon group. )