JP3259809B2 - Thermal transfer material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer material, and more particularly to a thermal transfer material capable of forming a color image on a recording sheet in accordance with a heat signal given from a thermal head.

[0002]

2. Description of the Related Art Conventionally, as a transfer material for thermal recording (hereinafter simply referred to as a heat-sensitive transfer material), a sublimation transfer material and a hot-melt transfer material are known. In the former, a dye layer composed of a heat sublimable dye and a heat-resistant binder resin is provided on a base material such as a polyester film, and the image of the heat sublimable dye is transferred to paper or the like by thermal printing from the back side with a thermal head. The latter is to transfer to the image receiving layer provided on the base material, the latter is to melt the coloring material layer composed of the pigment or dye and the heat-fusible binder resin by thermal printing with a thermal head and transfer this to the image receiving layer. is there.

[0003] As a substrate film of such a thermal transfer material, polyesters such as polyethylene terephthalate have conventionally been used, but since these are thermoplastic, the thermal head and the substrate film are fused during thermal printing. There is a disadvantage that the thermal head may not be able to run. In order to solve this drawback, it has been proposed to provide a back coat layer (backside slip layer) (JP-A-55-7467 and JP-A-60-225777).
JP-A-62-1575, JP-A-2-1453
No. 9).

[0004] However, despite the improvement in the performance of the thermal printer, the problem that the thermal head is contaminated or worn occurs, and in particular, the thermal energy several times that in the case of using a hot-melt transfer material is generated. In the case of a required sublimation type transfer material, there is a disadvantage that the heat resistance of the thermal transfer material is insufficient. Further, even in the case of a hot-melt transfer material, there is a disadvantage that the heat resistance of the back coat layer is insufficient in order to sufficiently cope with high-speed printing and diversification of a substrate to be transferred.

On the other hand, JP-A-5-85070 discloses that
There has been proposed a back coat layer comprising a resin to which an organopolysiloxane is graft-bonded or a cured product thereof. This back coat layer is excellent in heat resistance, film properties and slip properties, and can reduce contamination and abrasion of the thermal head, but has not been able to sufficiently satisfy the requirements. On the other hand, in the case of the silicone / polyester copolymer, its heat resistance is insufficient,
Until now, it could not be used as a back coat layer (heat-resistant lubricating layer) of a thermal transfer material.

[0006]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned drawbacks. As a result, the present inventors have found that a polyester-silicone copolymer having a polyester portion containing a dicarboxylic acid derivative having a naphthalene ring is obtained. When the coalescing resin was used for the back coat layer of the thermal transfer material, it was found that extremely good results could be obtained, and the present invention was reached. Accordingly, a first object of the present invention is to provide a thermal transfer material having excellent slip properties and heat resistance. A second object of the present invention is to provide a thermal transfer material capable of reducing contamination and wear of a thermal head.

[0007]

The above objects of the present invention are to provide: (1) a support; (2) a dye layer provided on one surface of the support and comprising at least a heat sublimable dye and a binder resin. Or a color material layer comprising at least a pigment and / or a dye and a heat-fusible binder resin; and (3) a back coat layer provided on the other surface of the support;
A heat-sensitive transfer material comprising the back coat layer,
This is achieved by a heat-sensitive transfer material characterized by containing a polyester-silicone copolymer having a polyester portion having a naphthalene ring and a dimethylpolysiloxane portion and having a glass transition point of 60 ° C. or higher. Was.

The heat-sensitive transfer material of the present invention comprises a support on one surface of which at least a dye layer comprising a thermosublimable dye and a binder resin, or a color comprising at least a pigment and / or a dye and a heat-fusible binder resin. A backcoat layer comprising a polyester-silicone copolymer or a cured product thereof having a glass transition point of 60 ° C. or higher is formed on the other surface of the support. It is provided.

The support in the heat-sensitive transfer material of the present invention is not particularly limited as long as it has a certain degree of heat resistance and strength and high dimensional stability. It is a processed paper such as a coated paper or a laminated paper, a resin film or a sheet of polyester, polystyrene, polyolefin, polyamide, polysulfone, polycarbonate, polyvinyl alcohol or the like, and a polyethylene terephthalate film or sheet is particularly preferable. Further, the thickness may be 50 μm or less,
In particular, it is preferably about 3 to 10 μm.

In the case of a sublimation type thermal transfer material, the color material layer provided on the support comprises at least a heat sublimation dye and a heat resistant binder resin. The above-mentioned thermal sublimation dye can be appropriately selected from known dyes, and is particularly preferably a disperse dye. Such disperse dyes include, for example, MS Yellow 32, MS Red 28, MS Blue 5
0 (the above are trade names of Mitsui Toatsu Dye Co., Ltd.), Kayaset Yellow AG, Kayaset Red B, and Kayaset Blue FR (the above are trade names of Nippon Kayaku Co., Ltd.).

The binder resin forming the color material layer is
Any material that has heat resistance and does not hinder the transfer of the dye from the dye layer to the image receiving layer during heating may be used. Examples of such a binder resin include a polyolefin-based resin, and a vinyl-based resin is particularly preferable.
It should be noted that various known additives can be added to the color material layer. The thickness of the color material layer is preferably from 0.2 to 5 μm, and the formation method thereof may be appropriately according to a known method.

On the other hand, in the case of a hot-melt transfer material, the color material layer provided on the support comprises at least a dye and / or a pigment and a hot-melt binder resin. The dye / pigment contained in the color material layer can be appropriately selected from known ones. Preferred pigments include inorganic pigments such as titania, carbon black, zinc oxide, cadmium sulfide, and iron oxide, and organic pigments such as azo, anthraquinone, and phthalocyanine. As the dye, any dye such as an acid dye, a direct dye and a disperse dye can be used. These dyes / pigments may be used alone or in combination of two or more.

The binder resin contained in the coloring material layer may be a thermoplastic resin having a softening point of 50 ° C. to 150 ° C., for example, a polyolefin resin, an acrylic resin,
It is common to use rubbers and the like together with waxes having a melting point of 50 ° C to 100 ° C. The thickness of the hot-melt type color material layer is preferably 0.5 μm to 0.8 μm.

In the present invention, the binder resin of the back coat layer provided on the other surface of the support, which is different from the surface provided with the color material layer, has a glass transition point of 60 ° C. or higher, preferably 60 to 200 ° C. , More preferably 60 to 100
A polyester-silicone copolymer containing a naphthalene ring at a temperature of ° C is used. When the glass transition point is lower than 60 ° C., thermal fusion occurs between the thermal head and the transfer material.
The polyester portion in the polyester-silicone copolymer is preferably obtained by polycondensation of a polyhydric carboxylic acid and / or a derivative thereof with a polyhydric alcohol, and has a naphthalene ring in its skeleton. Features. It can be easily synthesized by using a polycarboxylic acid having a naphthalene ring and / or a derivative thereof.

In the present invention, it is particularly preferable to use naphthalenedicarboxylic acid and / or a derivative thereof represented by the following formula (4).

Embedded image R ^{1 in} Formula 4 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. Specific examples of such a naphthalenedicarboxylic acid and / or a derivative thereof include compounds represented by the following chemical formulas (5) and (6).

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The polyvalent carboxylic acid and / or its derivative used for synthesizing the polyester portion of the polyester-silicone copolymer of the present invention contains at least 20 mol% of naphthalenedicarboxylic acid and / or its derivative. Is preferable, and it is particularly preferable to contain 30 mol% or more.
It is preferable from the viewpoint of increasing the glass transition point of the finally obtained polyester-silicone copolymer. If it is less than 20 mol%, the glass transition point of the finally obtained polyester-silicone copolymer will be low, and the heat resistance will be poor.

Examples of polycarboxylic acids or derivatives thereof other than naphthalenedicarboxylic acid or derivatives thereof include phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid and sebacic acid. And dicarboxylic acids such as azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate and dimethyl adipate.

In particular, the main component is preferably an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid and terephthalic acid, or a derivative thereof. In the present invention, a small amount of 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, an anhydride thereof, or a lower alkyl ester thereof is used so as not to form a gel. You may.

The polyhydric alcohol used in the present invention includes ethylene glycol, propylene glycol,
4-butanediol, 1,3-butanediol, 2,3
-Butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,
3-diol, hydrogenated bisphenol A, 2,2-di (4-hydroxyethoxyphenyl) propane, 2,2
Diol compounds such as -di (4-hydroxypropoxyphenyl) propane are exemplified as preferred.

In the present invention, a small amount of a triol compound or a tetraol compound such as glycerin, trimethylolethane, trimethylolpropane, or pentaerythritol may be used to such an extent that a gel is not formed. The polyester moiety in the polyester-silicone copolymer of the present invention is obtained by reacting the above-mentioned polyvalent carboxylic acid and / or derivative thereof with a polyhydric alcohol at 150 to 300 ° C. in an inert gas atmosphere, or if necessary. It can be produced by a usual method for producing polyester in which condensation polymerization is carried out under reduced pressure.

In producing the polyester of the present invention,
Catalysts that promote the esterification reaction include tetrabutyl zirconate, zirconium naphthenate, tetrabutyl titanate, tetraoctyl titanate, tetraphenyl tin, dibutyl tin dichloride, dibutyl tin dilaurate, dibutyl tin oxide, zinc acetate, calcium acetate, and antimony oxide A commonly used catalyst such as stannous oxalate or the like can be used.

The polyester moiety in the present invention is GP
C, the weight average molecular weight in terms of polystyrene is 2,0
It is preferably in the range of 00 to 100,000. When the weight average molecular weight is less than 2,000, the glass transition point becomes low, and the film forming property when used in the back coat layer becomes poor. On the other hand, if it exceeds 100,000, the solubility in a solvent is reduced.

The dimethylpolysiloxane used for producing the polyester-silicone copolymer in the present invention is preferably represented by the following formula (7) or (8) from the viewpoints of mold release and slipperiness.

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Embedded image In the formula, n is a natural number of 3 to 100, and R ² is a carbon number of 1 to 1.
4 is a monovalent hydrocarbon group, and A represents an organic group bonded to the polyester.

It is particularly preferable that n is a natural number of 6 to 50. When n is less than 3, the releasability and slipperiness become insufficient, and when it exceeds 100, the glass transition point of the polyester-silicone copolymer becomes low, and the solubility in a solvent is lowered. Specific examples of R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Examples include an isobutyl group and a tertiary butyl group.

The following two methods are representative of the method for obtaining the polyester-silicone copolymer of the present invention. The first method is a method of reacting a hydroxyl group contained in a polyester with a dimethylpolysiloxane containing an isocyanate group represented by the following chemical formulas (9), (10), (11) and (12) (JP-A-4-36325, JP-A-6-36325). -25
No. 6661).

[0026]

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Embedded image R ³ in the formula is a divalent organic group, L is a natural number of 0 to 50, m
Is an integer of 2 to 3, and n and R ² have the same meanings as shown in the above formulas (7) and (8). In this reaction, a solvent is not particularly required, but since the polyester is solid at ordinary temperature and the polyester and the isocyanate group-containing organopolysiloxane are not compatible before the reaction, the reaction is performed in order to make the reaction rate uniform. Preferably, a solvent is used.

The solvent used in this case includes esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; ketones such as acetone, MEK, MIBK, diisobutyl ketone and cyclohexanone; and aromatics such as benzene, toluene and xylene. Examples thereof include hydrocarbons, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane. These solvents can be used alone or in combination of two or more.

In the above reaction, if necessary, an organotin compound such as dibutyltin dilaurate, dibutyltin dioctate, tin dioctate; triethylamine, N-ethylmorpholine, N, N, N ', N'-tetramethyl-1 , 3
-Butanediamine, 1,4-diazabicyclo (2,2,
2) Octane, 1,8-diazabicyclo (5,4,0)
A catalyst usually used as a catalyst for producing polyurethane, such as a tertiary amine compound such as undecene-7, alone or
A mixture of more than one species can be used.

In order to complete the reaction in a short time, the above catalyst is used in an amount of 0.01 to 5% by weight, preferably 0.05 to 2% by weight, based on the weight of the isocyanate group-containing organopolysiloxane.
Is preferably used. Reaction temperature is 50-1
At 00C, a reaction time of 1 to 20 hours is sufficient.

In the second method, the above-mentioned polyvalent carboxylic acid and / or
Or a dimethylpolysiloxane represented by the following formula (13) and / or (14) having a functional group capable of forming two ester bonds in one molecule when polycondensing a derivative thereof with a polyhydric alcohol. This is a method of performing co-condensation polymerization using the compound.

[0031]

Embedded image X in the formula is a monovalent organic group having a functional group capable of forming two ester bonds, n and R ² are the same as those shown in Chemical formula 7, and have 1 to 4 carbon atoms. Represents a monovalent hydrocarbon group.

Embedded image Y in the formula is a monovalent organic group having a functional group capable of forming one ester bond. And n is the above formula
And represents a natural number of 3 to 100.

X in the above formula is not particularly limited as long as it is a monovalent organic group having a functional group capable of forming two ester bonds. Suitable functional groups include a group, a carboxylic anhydride, an epoxy group and the like. Specific examples of preferred functional groups include the following chemical formulas 15, 16, 16, 17,
And groups represented by the following chemical formulas (8), (19) and (20).

[0033]

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Embedded image In the formula, n and R ² have the same meanings as shown in the above formula (7).

The Y in Chemical Formula 14 is not particularly limited as long as it is a monovalent organic group having a functional group capable of forming one ester bond. Is a preferred functional group.
Specific examples of preferable functional groups include the following chemical formulas (21) and (2).
And groups represented by Chemical Formulas 2 and 23 and 24.

[0035]

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Embedded image The modification rate of dimethylpolysiloxane is preferably from 1 to 90% by weight, particularly preferably from 5 to 60% by weight. If the modification ratio of dimethylpolysiloxane is too small, the lubricity tends to be insufficient, and if it is too large, the film properties tend to decrease.

Comparing the above-mentioned chemical formulas 13 and 14, as is known in the silicone industry, a chemical formula 13-type dimethylpolysiloxane having a functional group only at one end is produced by a special anionic polymerization. On the other hand, dimethylpolysiloxane of formula (14) can be produced by ordinary polymerization of silicone, so that it is inexpensive. Therefore, a polyester resin using dimethylpolysiloxane of formula 14 is particularly preferable because it is more advantageous in cost.

The polyester obtained as described above
Dilute the silicone copolymer as is with a solvent and apply,
A back coat layer may be used, but when the back coat layer is to be further improved in heat resistance, coating properties, and adhesion to a support, it is preferable to crosslink and cure using a polyisocyanate. In this case, the polyisocyanate can be appropriately selected from those having two or more isocyanate groups in one molecule, and specific examples thereof include, for example, coronate (manufactured by Nippon Polyurethane Co., Ltd.) and takenate ( Takeda Pharmaceutical Co., Ltd.) and Death Module (Bayer Co., Ltd.).

The amount of the polyisocyanate added is 5 to 2 parts per 100 parts by weight of the polyester-silicone copolymer.
It is preferably 00 parts by weight. The excess or unreacted portion of the isocyanate group may be deactivated by reacting with an amine or alcohol, or may be left as it is. If the amount of the polyisocyanate is less than 5 parts by weight, the heat resistance becomes insufficient because the crosslinking density is low, and if it exceeds 200 parts by weight, the formed coating film shrinks greatly and the curing time is long. In some cases, such inconveniences may occur.

In the present invention, in order to improve the lubricity of the back coat layer, a lubricant such as a higher fatty amide, a higher fatty acid ester, a silica fine powder, a fluororesin powder, an alkyl phosphate ester, etc. An antistatic agent such as an agent or a conductive agent such as carbon black may be added.

The back coat layer can be formed by a known method, ordinary coating and drying are sufficient, and no special technique is required. However, when a cured product is to be obtained by adding a polyisocyanate, it is desirable to perform a heat treatment after drying. Further, it is preferable to form the back coat layer so that the thickness is 0.1 to 10 μm. If it is too thin, the function as a back coat layer will be insufficient, while if it is too thick, heat conduction from the thermal head will be hindered.

In the heat-sensitive transfer material of the present invention, a back coat layer is applied to one surface of a support, dried and, if necessary, heat-treated, and then the above-mentioned color material layer is applied to the other surface of the support.・
It can be easily manufactured by drying. Before providing the back coat layer, the color material layer may be provided first. As the support at the time of manufacture, a sheet-shaped support wound in a roll shape is used, and a product obtained by cutting the support may be any of a sheet type, a roll shape, and a tape shape.

[0042]

The heat-sensitive transfer material of the present invention has a polyester having a high glass transition point and lubricity on its back surface which is in contact with a thermal head and having excellent adhesion to a support.
Because it has a back layer containing a silicone copolymer,
Not only can fusion with the thermal head be prevented, but also thermal head contamination and wear can be reduced, and durability is excellent.

[0043]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Synthesis Example 1: Polyester having naphthalene ring
In a 1-liter glass flask equipped with a Terl synthesis stirrer, thermometer, condenser, ester adapter and pressure reducing device, 73.8 g (0.3 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester and dimethyl terephthalate were placed. 1
35.8 g (0.7 mol), 2,4-di (4-hydroxypropoxyphenyl) propane 206.4 g (0.6
Mol), 124.0 g (2.0 mol) of ethylene glycol, and 0.27 g of tetrabutyl titanate, and heated with a mantle heater under a stream of nitrogen to give 160 g.
The methanol removal reaction was performed at -170 ° C for 6 hours. At this time, methanol distilled off with the ester adapter was 62.
1 g.

Next, after the temperature was raised to 220 ° C. over 1 hour, a deethylene glycol reaction was carried out at 220 to 240 ° C. under a reduced pressure of 20 mmHg for 3 hours. The amount of ethylene glycol distilled off was 84.2 g. After completion of the reaction, the obtained polymer was cooled to room temperature, and a light brown transparent solid 35 was obtained.
5.6 g were obtained. The weight average molecular weight of the obtained polyester in terms of polystyrene by GPC was 15,400,
The glass transition point determined by SC (differential thermal analyzer) was 76 ° C., and the softening point by ring and ball method was 121 ° C. The hydroxyl value measured according to JIS K0070 is 2
3.5 mgKOH / g.

Further, the monomer composition was analyzed by alkali hydrolysis. As a result, the monomer composition was a dicarboxylic acid having a molar ratio shown in the following chemical formula 25 and a diol having a molar ratio shown in the chemical formula 26.

[25]

[26]

Synthesis Example 2: Polyester having naphthalene ring
Synthesis of ter The same as Synthesis Example 1 except that 244.0 g (1.0 mol) of 2,6-naphthalenedicarboxylic acid dimethyl ester used in Synthesis Example 1 was used and dimethyl terephthalate was not used. The reaction was performed. 6 methanol
1.5 g and 65.8 g of ethylene glycol were distilled off.
361.4 g of a light brown transparent solid were obtained. The polyester has a weight average molecular weight of 8,520 and a glass transition point of 8
5 ° C., softening point 128 ° C., and hydroxyl value 32.7 mg
KOH / g. The monomer composition was naphthalenedicarboxylic acid and a diol having the ratio shown in the following formula.

[27]

Synthesis Example 3: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer A reaction was carried out in exactly the same manner as in Synthesis Example 1 except that 111.4 g (0.12 mol) of an epoxy group-containing dimethylpolysiloxane represented by the following formula was further added. 62.0 g of methanol and 71.2 g of ethylene glycol were distilled off to obtain 386.9 g of a light brown translucent solid.

The weight average molecular weight is 20,000, the glass transition point is 66 ° C., the softening point is 115 ° C., and the hydroxyl value is 25.7 m.
gKOH / g.

The composition of the corresponding monomer is shown below.
The dicarboxylic acid had a molar ratio of 9 and the diol had a molar ratio of 30.

[29]

The amount of dimethylpolysiloxane was determined by atomic absorption spectroscopy.
9.9% by weight was dimethylpolysiloxane.

Synthesis Example 4: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer A reaction was carried out in exactly the same manner as in Synthesis Example 2 except that 121.0 g (0.1 mol) of a dihydroxy group-containing dimethylpolysiloxane represented by the following formula was further added. 60.8 g of methanol and 80.8 g of ethylene glycol were distilled off to obtain 492.7 g of a light brown translucent solid.

The weight average molecular weight is 18,600, the glass transition point is 72 ° C., the softening point is 121 ° C., and the hydroxyl value is 26.3 m.
gKOH / g.

The corresponding monomer compositions were naphthalenedicarboxylic acid and a diol having the molar ratio shown in Chemical formula 32.

The amount of dimethylpolysiloxane was determined by atomic absorption spectrometry.
8.3% by weight was dimethylpolysiloxane.

Comparative Synthesis Example 1 2,6- in Synthesis Example 1
Reduce the amount of naphthalenedicarboxylic acid dimethyl ester to 2
The reaction was carried out in exactly the same manner as in Synthesis Example 1 except that the amount of dimethyl terephthalate used was changed to 174.6 g (0.9 mol) to 4.4 g (0.1 mol).
2 g and 81.2 g of ethylene glycol were distilled off.
2.9 g of a light brown translucent solid were obtained.

The weight average molecular weight is 17,500, the glass transition point is 50 ° C., the softening point is 104 ° C., and the hydroxyl value is 2
It was 8.4 mgKOH / g. The compositions of the corresponding monomers were a dicarboxylic acid having a molar ratio shown in the following chemical formula 33 and a diol having a molar ratio shown in the chemical formula 34.

[33]

The amount of dimethylpolysiloxane was determined by atomic absorption spectrometry.
0.2% by weight was dimethylpolysiloxane.

Synthesis Example 5: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer In a 1-liter glass flask equipped with a stirrer, a thermometer and a condenser, 156.9 g of the polyester obtained in Synthesis Example 1 and 300 g of toluene were charged and dissolved at 60 ° C. Next, 43.1 g of an isocyanate group-containing dimethylpolysiloxane represented by the following formula 35 and 0.2 g of dibutyltin dilaurate were added, and the mixture was heated to 70 ° C. under a nitrogen stream.
For 5 hours.

[35]

When the IR spectrum analysis of the reaction solution was carried out, the result was 2260 cm 2 due to NCO observed before the reaction.
^-1 absorption had disappeared. From this reaction solution, the solvent toluene was removed by stripping to obtain 196.3 g of a light brown translucent solid. The weight average molecular weight of the obtained solid was 17,600, the glass transition point was 65 ° C, and the softening point was 11
At 8 ° C, the hydroxyl value was 10.1 mgKOH / g. When dimethylpolysiloxane was quantified by atomic absorption analysis, 16.5% in the obtained polymer was determined.
% By weight was dimethylpolysiloxane.

Synthesis Example 6: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer 156.9 g of the polyester used in Synthesis Example 5 was added to 115.5 g of the polyester obtained in Synthesis Example 2 and 43.1 of an isocyanate group-containing dimethylpolysiloxane represented by Chemical Formula 35.
The reaction was carried out in exactly the same manner as in Synthesis Example 5, except that g was replaced with 84.5 g of an isocyanate group-containing dimethylpolysiloxane represented by the following formula.
3.1 g were obtained.

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The weight average molecular weight of the obtained solid was 10,3.
The glass transition point was 68 ° C, the softening point was 119 ° C, and the hydroxyl value was 9.8 mgKOH / g. Further, when dimethylpolysiloxane was quantified by atomic absorption analysis, 40.3% by weight of the obtained polymer was dimethylpolysiloxane.

Synthesis Example 7: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer Instead of the epoxy group-containing dimethylpolysiloxane represented by Chemical Formula 28 used in Synthesis Example 3, 111.4 g of hydroxy group-containing dimethylpolysiloxane represented by Chemical Formula 37 below was used. Otherwise, the reaction was carried out in exactly the same manner as in Synthesis Example 3 to obtain 383.1 g of a light brown translucent solid.

Embedded image The obtained solid has a weight average molecular weight of 22,000, a glass transition point of 64 ° C, a softening point of 116 ° C, and a hydroxyl value of 2 ° C.
It was 4.8 mgKOH / g. When dimethylpolysiloxane was quantified by atomic absorption analysis, 20.1% by weight of the obtained polymer was dimethylpolysiloxane.

Synthesis Example 8: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer Instead of the epoxy group-containing dimethylpolysiloxane represented by Chemical Formula 28 used in Synthesis Example 3, 50.7 g of hydroxy group-containing dimethylpolysiloxane represented by Chemical Formula 38 below was used. Otherwise, the reaction was carried out in exactly the same manner as in Synthesis Example 3 to obtain 330.2 g of a light brown translucent solid.

Embedded image The weight average molecular weight of the obtained solid was 24,300, the glass transition point was 62 ° C, the softening point was 118 ° C, and the hydroxyl value was 2
2.3 mgKOH / g. Further, when dimethylpolysiloxane was quantified by atomic absorption analysis, 10.8% by weight of the obtained polymer was dimethylpolysiloxane.

Synthesis Example 9: Polyester having naphthalene ring
Synthesis of Ter-Silicone Copolymer In place of the dimethylpolysiloxane represented by Chemical Formula 37 used in Synthesis Example 6, 84.5 g of dimethylpolysiloxane containing an isocyanate group represented by Chemical Formula 39 below was used. The reaction was carried out in exactly the same manner as in Example 6 to obtain a polyester-silicone copolymer resin solution.

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Comparative Synthesis Example 2 153.1 g of the polyester synthesized in Comparative Synthesis Example 1 was reacted with 43.1 g of an isocyanate group-containing dimethylpolysiloxane represented by the above formula to obtain 191.7 g of a light brown translucent solid. The weight average molecular weight of the obtained solid was 23,500, the glass transition point was 40 ° C, and the softening point was 92 ° C. Further, when dimethylpolysiloxane was quantified by atomic absorption analysis, dimethylpolysiloxane was 16.2% by weight in the obtained polymer.

Example 1 A coating liquid A having a composition shown in Table 1 below was coated on a 4.5 μm thick polyethylene terephthalate film using a gravure coater so that the thickness after drying was 1 μm. The resultant was dried (at room temperature for 10 minutes and at 100 ° C. for 1 minute) to form a heat sublimable dye layer.

[Table 1] 青色 Blue disperse dye (MS Blue 50, Mitsui Toatsu) 62.5 parts of acetal resin (S-LEC KS-5, trade name of Sekisui Chemical Co., Ltd.) 37.5 parts Solvent (methyl ethyl ketone / toluene / = 1/3) Solid content concentration Adjusted to 10% ───────────────────────────────────

Next, a coating solution B having the composition shown in Table 2 below was applied to the other surface of the film using a bar coater # 5 so that the thickness after drying was 2 μm. After drying (room temperature: 10 minutes, 100 ° C .: 1 minute), heat treatment was performed at 60 ° C. for 48 hours to form a back coat layer, thereby obtaining a thermal transfer material.

２ Silicone polyester copolymer of Synthesis Example 3 73. 5 parts Polyisocyanate (Desmodur HL, trade name, manufactured by Bayer K.K.) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ─────────────────────────

Embodiment 2 FIG. A heat-sensitive transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 3 below.

３ Silicone polyester copolymer of Synthesis Example 3 68. 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Higher fatty acid amide (Pharmin D86, trade name of Kao Corporation) 5.0 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration 5% Adjustment ───────────────────────────────────

Embodiment 3 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 4 below.

４ Silicone polyester copolymer of Synthesis Example 3 58. 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Higher fatty acid amide (Pharmin D86) 15.0 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to a solid content concentration of 5% ───────────────────────────

Embodiment 4 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 5 below.

Table 5: Silicone polyester copolymer of Synthesis Example 3 5 parts Polyisocyanate (Desmodur HL) 52.5 parts ───────────────────────────────────

Embodiment 5 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 6 below.

Table 6: Silicone polyester copolymer of Synthesis Example 8 0 parts Higher fatty acid amide (Pharmin D86) 5.0 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ────────────────

Embodiment 6 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 7 below.

Table 7: Silicone polyester copolymer of Synthesis Example 4 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ─────────────────── ────────────────

Embodiment 7 FIG. A thermal transfer material was obtained in the same manner as in Example 1, except that the coating liquid B in Example 1 was changed to the composition shown in Table 8 below.

Table 8: Silicone polyester copolymer of Synthesis Example 5 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ─────────────────── ────────────────

Embodiment 8 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 9 below.

Table 9: Silicone polyester copolymer of Synthesis Example 6 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration adjusted to 5% ─────────────────── ────────────────

Embodiment 9 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 10 below.

Table 10: Silicone polyester copolymer of Synthesis Example 7 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration adjusted to 5% ─────────────────── ────────────────

Embodiment 10 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 11 below.

Table 11: Silicone polyester copolymer of Synthesis Example 8 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration adjusted to 5% ─────────────────── ────────────────

Embodiment 11 FIG. A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 12 below.

Table 12: Silicone polyester copolymer of Synthesis Example 9 0 parts Higher fatty acid amide (Pharmin D86) 5.0 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ────────────────

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

Comparative Example 2 A heat-sensitive transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 13 below.

Table 13: Silicone polyester copolymer of Synthesis Example 1 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration adjusted to 5% ─────────────────── ────────────────

Comparative Example 3 A thermal transfer material was obtained in the same manner as in Example 1 except that the coating liquid B in Example 1 was changed to the composition shown in Table 14 below.

Table 14: Silicone polyester copolymer of Synthesis Example 2 5 parts Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Solid content concentration adjusted to 5% ─────────────────── ────────────────

The uncoated polyethylene terephthalate film and the back coat layer were brought into contact with the heat-sensitive transfer material obtained above, and the coefficient of kinetic friction between them was measured using a friction tester (200 g load, 150 mm / min traction speed, Toyo Seiki Co., Ltd. )
Was used for the measurement. Further, a mounting experiment was performed using a sublimation type thermal printer, and the occurrence of thermal fusion between the thermal head and the transfer material for thermal recording and head contamination were visually observed. The results are as shown in Table 15 below.

[Table 15]

Reference Example 1 The coating liquid B in Example 1 was changed to the composition shown in Table 16 and Table 17 below, and
In the same manner as described above, the adhesion of the obtained thermal transfer material to PET was measured.

[Table 16] 73.5 parts of silicone-modified polyvinyl butyral resin (dimethyl Polysiloxane 10% by weight) Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to a solid content concentration of 5% ────────────────────

[0079]

[Table 17] 73.5 parts of silicone-modified acrylic resin (dimethyl poly Siloxane 10% by weight) Polyisocyanate (Desmodur HL) 26.5 parts Solvent (methyl ethyl ketone / toluene / = 1/1) Adjusted to solid content concentration 5% ───────────────────

The silicone-modified acrylic resin contained in Table 17 has a weight ratio of MMA / EA / HEMA / methacrylic dimethyl polysiloxane at one end (degree of polymerization: 30) of 70/10/10/10. As a result of evaluating the adhesion of the back coat layer to the polyethylene terephthalate of Tables 16 and 17 and Example 10 by sufficiently measuring the hand, the back coat layer shown in Tables 16 and 17 shows a portion. Although film floating was observed, no film floating was observed in the case of the back coat layer of Example 10, confirming that the adhesion was good.

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────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ichiro Ono 1-10, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Inside the Silicone Electronics Materials Research Laboratory, Shin-Etsu Chemical Co., Ltd. (56) References JP-A-3-3 147894 (JP, A) JP-A-2-239973 (JP, A) JP-A-64-1586 (JP, A) JP-A-6-219059 (JP, A) JP-A-6-171248 (JP, A) JP-A-5-330246 (JP, A) JP-A-5-286271 (JP, A) JP-A-2-92589 (JP, A) JP-A-1-190489 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (4)

(57) [Claims] (1) a support; (2) a dye layer comprising at least a thermosublimable dye and a binder resin provided on one surface of the support, or at least a pigment and / or a dye and a heat-fusible material A color material layer comprising a binder resin; and (3) a back coat layer provided on the other surface of the support;
A heat-sensitive transfer material comprising the back coat layer,
A heat-sensitive transfer material comprising a copolymer having a polyester portion having a naphthalene ring and a dimethylpolysiloxane portion and having a glass transition point of 60 ° C. or higher. 2. The thermal transfer material according to claim 1, wherein the polyester-silicone copolymer is cured by a crosslinking agent. 3. The polyester portion of the polyester-silicone copolymer is obtained by polycondensation of a polycarboxylic acid and / or a derivative thereof with a polyhydric alcohol, and the polycarboxylic acid and / or 3. The heat-sensitive transfer material according to claim 1, wherein at least 20 mol% of the derivative component is naphthalenedicarboxylic acid represented by the following chemical formula 1 and / or a derivative thereof. Embedded image In the formula, R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. 4. The polyester-silicone copolymer has a dimethylpolysiloxane moiety represented by the following chemical formula (2) and / or chemical formula (3).
The thermal transfer material according to any one of claims 1 to 3, which has the structural formula: Embedded image Embedded image In the formula, n is a natural number of 3 to 100, and R ² is a carbon number of 1 to 1.
4 is a monovalent hydrocarbon group, and A represents an organic group bonded to the polyester.