JPH0462879B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a thermal transfer recording film, and more specifically to a thermal transfer film having a thermal ink layer on one side of a substrate and a stick prevention layer on the other side. The present invention relates to a method of manufacturing a recording film. [Prior Art] 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 heat-sensitive ink layer provided on the film, which serves as the base material, and then uses a pulse signal from a thermal head on the opposite side of the ink layer to move the base film. Selective heating. 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 a 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 transport and characters. There is a problem of so-called staking, which makes it difficult to transfer figures etc. onto recording paper.To solve this problem, various stiction prevention layers such as those shown below are applied to the film surface that comes into contact with the thermal head. It was common practice to provide In other words, a metal layer such as aluminum is provided as a stick prevention layer,
Proposals included applying silicone, paraffin, etc., or using a thermosetting resin layer such as urethane, epoxy, or melamine, or an ethyl cellulose 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 energy. 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 such problems, silicone macromonomers having a radically polymerizable group bonded to one end of polydimethylsiloxane are copolymerized with (meth)acrylic acid alkyl esters, etc. It has been proposed to use a graft polymer containing polydimethylsiloxane as a branch component as a stick preventive agent, and to provide a stay preventive agent made of this graft polymer (Japanese Unexamined Patent Publication Nos. 62-30082 and 1982-1575). . 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. The main component, which is mainly composed of monomer units such as (meth)acrylic acid alkyl ester, which has adhesive properties, is oriented toward the substrate, so it has excellent adhesion to the substrate and suppresses sticking. The effects were also said to be good. However, conventional silicone macromonomers, especially the general formula

[Problem to be solved by the invention]

In the present invention, among the acrylic compounds represented by the above general formula, an acrylic compound whose manufacturing cost is lower than other compounds, and in which p in the above general formula is 3, that is, the general formula (A) (R is a hydrogen atom or a methyl group; m is 0 or 1;
l is an integer from 0 to 2 when m=0, and m=1
In the case of , it is 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) and the general formula (B)

[Means to solve the problem]

As a result of intensive studies to solve the above-mentioned problems, the present inventors discovered that the silicone macromonomer obtained in the past, for example, in JP-A-60-123518, etc. Silicones that are described as undesirable because they cause gelation during polymerization

[Formula] (n is a positive number; R ₁ and R ₂ are monovalent saturated aliphatic hydrocarbon groups with 1 to 10 carbon atoms, phenyl groups, or halogenated hydrocarbon groups)
and acrylic compound (R is a hydrogen atom or a methyl group; m is 0 or 1;
l is an integer from 0 to 2 when m=0, and m=1
In the case of , it is 2; 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 1.3 to 3 moles of acrylic compound per 1 mole of silicone, the content of unreacted silicone to which no acrylic compound has been added is made extremely small. They discovered a very unique method for producing silicone macromonomers that allows the silicone macromonomers to do the same thing, yet does not cause gelation during radical copolymerization with other monomers, and filed a patent application. (Japanese Patent Application No. 62-60029), but 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 properties that can be used as a stick prevention layer in a thermal transfer recording film. They have found that this is extremely 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 a heat-sensitive ink layer on the other side.
In a method for producing a thermal transfer recording film comprising a stick prevention layer made of a silicone graft polymer obtained by radical copolymerization of a silicone macromonomer with another radically polymerizable monomer, the silicone graft polymer is used as a raw material for synthesis of the silicone graft polymer. , a silicone-based macromonomer obtained by condensing an acrylic compound represented by the following general formula (A) and a silicone represented by the following general formula (B) at a ratio of 1.3 to 3 mol of the acrylic compound per 1 mol of the silicone. This is a method for producing a heat-sensitive transfer recording film, characterized by using the following. General formula (A) (R is a hydrogen atom or a methyl group; m is 0 or 1;
l is an integer from 0 to 2 when m=0, and m=1
In the case of , it is 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) General formula (B)

[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;
l is an integer from 0 to 2 when m=0, and m=1
In the case of , it is 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) Propyltrichlorosilane, 5-((meth)
Examples include acryloyloxy)pentyltrimethoxysilane, 5-((meth)acryloyloxy)pentyltrichlorosilane, and the like. Of these, γ-
Most preferred is methacryloyloxypropyltrimethoxysilane. [Silicone] The silicone in the present invention has the general formula (B)

[Manufacture of silicone macromonomer]

The silicone macromonomer in the present invention comprises the acrylic compound and the silicone,
1.3 to 3 acrylic compounds per mole of silicone
It is a silicone-based macromonomer obtained by condensation reaction in a molar range. 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 . The molar ratio of acrylic compound to silicone is acrylic compound per mole of silicone.
If the amount is less than 1.3 mol, the obtained silicone macromonomer will contain a large amount of unreacted silicone, so in thermal transfer recording films using silicone graft polymers obtained from this as a raw material as a stagnation prevention agent, thermal ink Ink repellency occurs during application. Furthermore, if the amount of the acrylic compound exceeds 3 moles, the viscosity of the resulting silicone graft polymer will increase significantly, and the stick inhibitor made of the graft polymer will have poor leveling properties, making it difficult to obtain a thin and uniform coating during coating. Become. The condensation reaction will be explained in more detail. For example, X of an acrylic compound represented by general formula (A)
When is a chlorine atom, add an acrylic compound or an acrylic compound to a solution of silicone represented by general formula (B) and an acid acceptor dissolved in an appropriate solvent shown below at a concentration of 10 to 50% by weight. When a solution dissolved in a solvent at a concentration of 10 to 50% by weight is added dropwise at room temperature, the reaction proceeds immediately and smoothly. After the reaction, the produced acid acceptor hydrochloride is filtered out, and then, if necessary, washed with water and the solvent is evaporated to obtain the desired silicone macromonomer. The solvent that can be used in this reaction is preferably a solvent that dissolves both reaction components and is inert to both reaction components under the reaction conditions. Suitable solvents include, for example, diethyl ether, tetrahydrofuran, acetone, benzene, toluene, xylene, mineral Examples include spirits. 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 preferably about 1.2 times the molar amount of hydrochloric acid produced by the dehydrochlorination reaction. When X of the acrylic compound represented by the general formula (A) is an alkoxy group having 1 to 10 carbon atoms, the reaction is a dealcoholization condensation reaction between the silicone represented by the general formula (B) and the 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 is p-toluenesulfonic acid. The amount of catalyst is desirably about 0.01 to 5% by weight based on the total amount of silicone and acrylic compound. The reaction temperature is preferably 50° to 150°C, and the reaction time is preferably 1 to 20 hours. Additionally, this reaction can be carried out without a solvent or with a solvent, and usable solvents include benzene, toluene, xylene,
Examples include mineral spirits. It is preferable to remove the used catalyst after the reaction is completed, and any known method can be applied to remove it. However, when p-toluenesulfonic acid is used as a catalyst, it can be removed by adsorption on a basic ion exchange resin. This method is easy to operate. Further, when X of the acrylic compound represented by the general formula (A) is an acetoxy group, the reaction is an acetic acid removal condensation reaction between the silicone represented by the general formula (B) 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 using a known polymerization method, and is made from radically polymerizable monomer units with silicone as a branch component. It is a silicone-based graft polymer whose main component is a polymer. The radical copolymerization ratio of the silicone macromonomer and the radically polymerizable monomer is 2 to 90 parts by weight of the silicone macromonomer and 98 parts by weight of the radically polymerizable monomer to 100 parts by weight of the total amount of the silicone macromonomer and the radically polymerizable monomer.
~10 parts by weight is preferred, more preferably 5 to 60 parts by weight of the silicone macromonomer and 95 to 40 parts by weight of the radically polymerizable monomer, particularly preferably 10 to 50 parts by weight of the silicone macromonomer and 90 parts by weight of the radically polymerizable monomer. ~50 parts by weight. If the amount of the silicone macromonomer is less than 2 parts by weight, the stick prevention effect will not be sufficient when used as a stick prevention agent, while if it exceeds 90% by weight, film forming properties will be poor and it may cause damage to the base film. Adhesion tends to deteriorate. The radically polymerizable monomers include low molecular weight linear saturated hydrocarbons such as ethylene, propylene, and butylene; vinyl halides such as vinyl chloride and vinyl fluoride; vinyl esters of organic acids such as vinyl acetate; styrene and styrene substituted acrylic acid, methacrylic acid, and derivatives of acrylic acid and methacrylic acid, including their alkyl esters, hydroxyalkyl esters, and amides; acrolein, acrylonitrile,
N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; 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 CnF ₂ n+ ₁ (CH ₂ ) ₂ OOCCH=CH ₂ (mixture of n=4 to 14), etc., and acrylic monomers having a fluoroalkyl group, etc., can be mentioned, and the obtained silicone graft polymer can be Preferred are methacrylic acid alkyl esters having an alkyl group having 1 to 4 carbon atoms, styrene, acrylonitrile, and the like because of their excellent heat resistance. The core component of silicone graft polymer is
Although it is a polymer mainly composed of the above-mentioned radically polymerizable monomer units, such polymers generally have inferior heat resistance compared to branched components made of silicone, and tend to become sticky when contacted with a heat-sensitive head. , the glass transition temperature of the polymer forming the backbone component is
It is preferable to use a radically polymerizable monomer that can be heated to 50°C or higher. 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. organosilicon monomer,
It may be used in combination in a small amount to the extent that gelation does not occur when producing a silicone-based 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-based 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 preferred. ,
Particularly preferred are azo compounds. In the azo compound, both nitrogen atoms of the azo bond are bonded to a tertiary carbon atom, and the remaining valence of the tertiary carbon atom is preferably a nitrile, carboxyalkyl, cycloalkylene or It is an azo compound which is satisfied by an alkyl group, and azobisisobutyronitrile (hereinafter abbreviated as AIBN) is the most preferred. When copolymerizing by ultraviolet irradiation, a known sensitizer is used as a radical polymerization initiator, while when copolymerizing by electron beam irradiation, there is no need to use a radical polymerization initiator. The amount of radical polymerization initiator is generally 0.01 to 5% by weight, preferably 0.1% by weight based on the total weight of the polymerizable components.
~2% by weight. The temperature of radical copolymerization is preferably higher than the dispersion 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 60-100°C. Polymerization time is generally 3 to 100 hours, preferably
10-25 hours. The number average molecular weight of the silicone graft polymer produced by the above method was 25,000 to 100,000. [Formation of the stick prevention layer] Formation of the stick prevention layer on the base film is as follows:
The organic solvent solution of the silicone-based graft polymer is coated with polyethylene terephthalate, polyethylene terephthalate,
Nylon, polycarbonate, polypropylene,
This can be carried out by coating the surface of a plastic film such as cellophane or paper such as condenser paper or cellophane paper, followed by heating and drying. The material for the base film is preferably polyethylene terephthalate (hereinafter abbreviated as PET) from the viewpoint of heat resistance and mechanical strength, and the thickness of the film is not particularly limited, but is usually 2 to 50 μm, preferably 3 to 10 μm. be. 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 stick prevention layer to be 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 can be crosslinked and cured using the functional group in the presence of a catalyst such as dibutyltin dilaurate. In addition, as a stick prevention agent, in addition to silicone graft polymers, acrylic resins, epoxy resins, unsaturated polyester resins, and 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, the total amount of the silicone graft polymer and these resins must be Desirably 50% by weight or less based on the inside. In addition, talc, calcium carbonate, carbon black, silica powder, etc. are added 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, a known antistatic agent or the like may be added to the organic solvent solution of the silicone graft polymer and coated on the base film. The coating amount (solid content) of the silicone graft polymer on the film is suitably 0.01 to 2 g/m ² in terms of flexibility, thermal transfer efficiency of the thermal head, cost, etc., and more preferably
It is 0.05-1 g/ ^m2 . [Thermal Ink Layer] The thermal ink layer in the present invention is formed by a known method using a thermal ink made of a thermoplastic resin, dye, pigment, etc. that has been conventionally generally used for forming the layer. be able to. Examples of thermoplastic resins include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic ester copolymer, vinyl acetate-vinyl chloride copolymer, styrene-acrylonitrile copolymer, and styrene-acrylonitrile-butadiene copolymer. Coalescence, styrene-acrylic acid ester-acrylamide copolymer, styrene-butadiene copolymer, poly(meth)alkyl acrylate, polyacrylonitrile, acrylonitrile-
Examples include vinyl acetate copolymers, polyvinyl acetates, polyamides and copolyesters. As the dye, oil-soluble dyes are preferred, such as oleosol first blue-EL (Sumitomo Chemical Co., Ltd.).
Co., Ltd.), Oleosol Fast Black BL (manufactured by Sumitomo Chemical Co., Ltd.), and Sumiblast Blue
Various oil-soluble dyes such as OR (manufactured by Sumitomo Chemical Co., Ltd.) are commercially available, and an appropriate one can be selected from them for use. When a pigment is contained in the heat-sensitive ink layer, the pigment used may be either organic or inorganic. Examples of the organic pigment include known organic pigments belonging to the azo dye type, anthraquinone type, indigoid type, cyanine type, etc. However, examples of inorganic pigments include carbon black and the like. Furthermore, in the thermal ink layer, if necessary,
Appropriate amounts of various oils, various dispersants, plasticizers, stabilizers, etc. may be added. 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] The present invention will be explained in more detail by referring to Examples, Reference Examples, and Comparative Examples below. In addition, the amount of unreacted silicone in the silicone-based graft polymer obtained by radical copolymerization of the silicone-based macromonomer in each example was determined by the following method. In addition, parts and % represent parts by weight and % by weight, respectively. Γ Amount of unreacted silicone: Put 150 parts of toluene into a flask equipped with a stirrer, condenser, _N2 inlet tube, and dropping funnel, add 20 parts of silicone macromonomer, 80 parts of methyl methacrylate (hereinafter abbreviated as MMA), and AIBN1.
After bubbling toluene with N ₂ , the mixture was heated to 80°, and the mixture in the dropping funnel was added dropwise over 2 hours for polymerization. After aging at this temperature for 1 hour, 1 part of AIBN was added and heated at the same temperature for an additional 2 hours. The obtained solution was distilled under reduced pressure,
A silicone-based graft polymer with white crystals was obtained. This graft polymer was powdered, and 20 g of the powder and 1 part 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 obtained filtrate was distilled under reduced pressure to remove n-hexane, and unreacted silicone oil was obtained as a residue. The amount determined by the following formula was used as a measure of the amount of unreacted silicone. Unreacted silicone [%] = Unreacted silicone [parts] / Graft polymer before extraction x 100 To analyze the silicone in the graft polymer before extraction, accurately weigh about 0.2 g of the copolymer in a platinum crucible,
Next, about 3 ml of concentrated sulfuric acid was added to this, 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 SiO ₂ by weighing. Reference Examples 1 to 5 α,ω-Dihydroxypolydimethylsilicone [

[Formula] n is 300 on average] 111 g (0.005 mol), p-toluenesulfonic acid 0.12 g,
74g of toluene, and methyl ethyl ketone (below
(abbreviated as MEK) was charged, and to this was added γ-methacryloyloxypropyltrimethoxysilane in the amount shown in the column of each reference example in Table 1. Next, this mixed solution was heated at 70°C for 3 hours. After cooling, 30 g of a basic anion exchange resin (A-21 manufactured by Organo Co., Ltd.) was added to the reaction solution, and the mixture was stirred at 40° C. for 2 hours to neutralize it. 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%.

[Table] Reference example 6 α,ω-dihydroxypolydimethyl silicone [

[Formula] n is 500 on average] 185 g (0.005 mol), γ-methacryloyloxypropyltrimethoxysilane 2.07 g (0.00835 mol) (molar ratio 1/1.65), p-toluenesulfonic acid 0.20 g
A colorless and transparent silicone-based macromonomer oil was obtained by operating in the same manner as in Reference Examples 1 to 4 except for using . The reaction rate of γ-methacryloyloxypropyltrimethoxysilane was 100%. Reference example 7 α,ω-dihydroxypolydimethyl silicone [

[Formula] has an average n of 782] 174 g (0.003 mol), p-toluenesulfonic acid 0.2 g, toluene 116 g, MEK 58 g, γ-methacryloyloxypropyltrimethoxysilane 1.24 g (0.005
A silicone-based macromonomer was obtained in the same manner as in Reference Examples 1 to 4 except that mol) (molar ratio = 1/1.67) was used. Reference Example 8 Reference Example 1 except that 0.744 g (0.003 mol) (mole ratio = 1/0.6) of γ-methacryloyloxypropyltrimethoxysilane was used in Reference Example-1.
A silicone macromonomer was obtained by operating in the same manner as in 4. Using the silicone macromonomers obtained in Reference Examples 1 to 8, the amount of unreacted silicone was measured according to the method described above, and the results are shown in Table 2.

【table】 Silicone according to Table-2

A silicone-based macromonomer obtained under reaction conditions in which n in [Formula] and the reaction molar ratio of silicone/acrylic compound are both within the range specified in the present invention is used to produce a silicone-based graft polymer. It was found that the amount of unreacted silicone in the graft polymer was extremely small. Examples 1 to 5 and Comparative Examples 1 to 3 Stirrer, condenser, thermometer, dropping funnel,
MEK/methyl isobutyl ketone (hereinafter abbreviated as MIBK) = 1/1 in a flask equipped with an N ₂ inlet tube.
(weight ratio) of solvent (hereinafter referred to as liquid A)
100 parts, 10 parts of silicone macromonomer shown in Table 3, 42 parts of MMA, 42 parts of butyl methacrylate (hereinafter abbreviated as BMA), 2-
Hydroxyethyl methacrylate (HEMA)
(hereinafter referred to as "Liquid B") and 0.5 parts of AIBN (hereinafter referred to as "Liquid B") were added, and Solution A was heated to 80° C. after bubbling with _N2 , and then Solution B was added dropwise over a period of 2 hours. After aging at the same temperature for 1 hour,
0.5 parts of AIBN was added and the temperature was maintained for an additional 2 hours to complete the polymerization. The resulting reaction solution was diluted with MEK to a solid content of 15%, coated on a 6 μm thick PET film using a bar coater, heated at 70°C for 30 seconds, dried, and the film thickness
A colorless and transparent silicone-based graft polymer coating film of 0.5 μm was provided. The thus obtained film provided with the stick prevention layer was cut out, five sheets were stacked so that the front and back sides were in contact with each other alternately, and sandwiched between two glass plates to give a film of 40 g/cm ²
The mixture was heated at 60°C for 24 hours under a load of . Then, on the side of the film that does not have a stick prevention layer,
Parafine wax 50 parts, carnauba wax 25 parts
10 parts of ethylene-vinyl acetate copolymer and 15 parts of carbon black to a thickness of 4.0 μm.
Hot melt coating was applied so that The degree of ink repellency at that time is as shown in Table 3, and Examples 1 to 5
When the above-mentioned ink was applied to the opposite side of the film provided with the anti-stick layer made of silicone-based graft polymer obtained in 1, no repelling of the ink was observed and it was possible to apply the ink uniformly. On the other hand, when the ink was applied to the opposite side of the film provided with the stick prevention layer obtained in Comparative Examples 2 and 3, repelling was observed partially. When the ink was applied to the opposite side, repelling occurred on almost the entire surface, and a uniform coating film could not be obtained. The polymerization reaction solutions (silicone graft polymer solutions) obtained in each of the examples 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. It was stable.

[Table] 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 msec.
The anti-staking property was evaluated by performing transfer printing on plain paper, but no staining occurred, good printing was obtained, and stable running performance was obtained. Example 6 As the composition of the ink, a disperse dye [Sumiplast
The same procedure as Example 4 was used except that 10 parts of Red FB (manufactured by Sumitomo Chemical Co., Ltd., sublimation type), 10 parts of hydroxyethyl cellulose, 40 parts of toluene and 10 parts of isopropyl alcohol were uniformly mixed and dispersed in a ball mill for 24 hours. Similarly, the degree of repellency during ink application was examined, but no repellency was observed at all. Reference examples 9-10 α,ω-dihydroxypolydimethylsilicone [

n of [Formula] is 250 on average] 92.5 g (0.005 mol) and γ-methacryloyloxypropyltrimethoxysilane 2.48 g (0.01 mol)
A silicone macromonomer was obtained in the same manner as in Reference Examples 1 to 4 except that (molar ratio = 1/2) was used (Reference Example 9). The average molecular weight of this silicone macromonomer was measured by gel permeation chromatography under the following conditions, and the number average molecular weight in terms of polystyrene was 31,000. Equipment: High performance liquid chromatography (product name: HLC-802UR, manufactured by Toyo Soda Industries, Ltd.) Column: Polystyrene gel (product names: G4000H8 and G3000H8, manufactured by Toyo Soda Industries, Ltd.) Elution solvent: Tetrahydrofuran Outflow rate: 1.0ml/ min Column temperature: 40℃ Detector: RI detector α,ω-dihydroxypolydimethylsilicone [

n of [Formula] is 30 on average] 11.1 g (0.005 mol) and γ-methacryloyloxypropyltrimethoxysilane 0.992 g (0.004 mol)
A silicone-based macromonomer was obtained in the same manner as in Reference Examples 1 to 4 except that (molar ratio 1/0.8) was used (Reference Example 10). The number average molecular weight of this silicone macromonomer was 5,700, as measured by the same method as in Reference Example 9. Example 7 and Comparative Example 4 All operations were the same as in Examples 1 to 5, except that 100 parts of toluene was used as the polymerization solvent, and 50 parts of the silicone macromonomer synthesized in Reference Example 9 and 50 parts of MMA were used as the monomer components. to obtain a silicone-based graft polymer solution, then using the obtained silicone-based graft polymer solution,
A thermal transfer recording film was produced in the same manner as 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). Example 7 With the above film, there was no ink repelling at all, the transfer printing was good, and there was no states king, showing stable running performance.
In the film of Comparative Example 4, ink repellency occurred in some areas, and when printing was continued for a long period of time, staking occurred, making it impossible to obtain stable running performance. Reference example 11 α,ω-dihydroxypolydimethyl silicone [

[Formula] n is 30 on average] 67.2 g (0.03 mol), p-toluenesulfonic acid 0.1 g, toluene
46g, MEK23g, γ-methacryloyloxypropyltrimethoxysilane 7.44g (0.03mol)
Silicone-based macromonomers were obtained in the same manner as in Reference Examples 1 to 4 except that (molar ratio = 1/1) was used. Hereinafter, an attempt was made to obtain a silicone-based graft polymer in the same manner as in Examples 1 to 4, but gelation occurred one hour after the start of polymerization and the whole became pudding-like, making it impossible to obtain a graft polymer that could be used as a stick preventer. I couldn't do it. Reference example 12 α,ω-dihydroxypolydimethyl silicone [

A silicone macromonomer was obtained in the same manner as in Comparative Example 5, except that 127 g (0.03 mol) of n in formula 57 on average, 86 g of toluene, 43 g of MEK, and 0.2 g of p-toluenesulfonic acid were used. 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. (c) Effects of the invention The silicone-based graft polymer in the present invention is a graft polymer obtained by radical copolymerization of a silicone-based macromonomer having a radically polymerizable functional group at the end and another radically polymerizable monomer. Therefore, compared to silicone-based graft polymers produced by other production methods, the homopolymer content is small, the molecular weight and content of branch components are well controlled, and moreover, it contains only a small amount of unreacted silicone. Furthermore, since the branch component is a graft polymer with a sufficiently large molecular weight, according to the present invention in which this graft polymer is used as a stick prevention agent, it has good slipperiness, there is no repelling phenomenon of heat-sensitive ink, and it is excellent in preventing sticks. It is possible to produce a thermal transfer recording film that has long running stability.

Claims (1)

[Scope of Claims] 1 Silicone obtained by radical copolymerization of a silicone macromonomer with another radically polymerizable monomer, which has a heat-sensitive ink layer on one side of a film serving as a base material, and on the other side. In the method for producing a thermal transfer recording film provided with a stick prevention layer made of a silicone-based graft polymer, as a synthetic raw material for the silicone-based graft polymer,
An acrylic compound represented by the following general formula (A) and a silicone represented by the following general formula (B) are combined into silicone 1
A method for producing a thermal transfer recording film, characterized in that a silicone macromonomer obtained by condensation reaction is used at a ratio of 1.3 to 3 moles of the acrylic compound per mole. General formula (A) (R is a hydrogen atom or a methyl group; m is 0 or 1;
l is an integer from 0 to 2 when m=0, and m=1
In the case of , it is 2; X is an alkoxy group having 1 to 10 carbon atoms, an acetoxy group, or a chlorine atom. ) General formula (B) (n is an integer from 100 to 600; R ₁ and R ₂ are carbon numbers from 1 to
10 monovalent saturated aliphatic hydrocarbon groups, phenyl groups or monovalent halogenated hydrocarbon groups. )