JPH08244369A - Heat transfer ribbon and manufacture thereof - Google Patents

Abstract

PURPOSE: To provide a heat resistant heat transfer ribbon in which a high speed printing and many times printing can be performed and a method for manufacturing the same. CONSTITUTION: A heat transfer ribbon comprises polyamideimide resin having a glass transition temperature of at least 120 deg.C and containing isophorone residue and 2-10C aliphatic dicarboxylic acid and soluble in alcohol solvent and coating at least one side of a polyester film. Accordingly, the melting or adherence of the film due to the heat of a thermal head can be prevented, and the ribbon can deal with the acceleration of a printing speed and many times printing.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermal transfer ribbon and a method for manufacturing the same. More specifically, the present invention relates to a thermal transfer ribbon capable of high-speed printing and multiple printing by coating a polyamideimide resin on at least one side of a polyester film, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, the thermal transfer recording method has been widely used in word processors, printers and the like. In the thermal transfer recording method, a heat-melting or heat-sublimable ink layer is coated on a ribbon base material, the coated surface of the ribbon and the image receiving paper are superposed, and the non-coated surface of the ribbon is heated by a thermal head to melt the heat The heat- or heat-sublimable ink is transferred to the image receiving paper. The heat generated from the thermal head melts or sublimes the ink through the support, but it is necessary that the support such as a plastic film does not melt. However, due to the high printing speed, the high temperature of the thermal head, the multiple printing, etc., the pressure and heat quantity applied to the plastic film increase, which hinders normal operation. Such a phenomenon is generally called a stick phenomenon. Conventionally, in order to improve this stick phenomenon, a polyacetal resin, polyester, polyurethane, acrylic resin or the like in which inorganic particles are dispersed on the non-ink layer surface of the thermal transfer ribbon is used. However, there is a problem that the heat resistance is not sufficient for higher printing speed, higher temperature of the thermal head, and multiple printing.

[0003]

There is a strong demand for high heat resistance of the back coat agent of the thermal transfer ribbon in order to cope with high printing speed of a printer or the like, high temperature of thermal head, and multi-time printing.

[0004]

Means for Solving the Problems In order to solve these problems, the inventors of the present invention have earnestly studied and arrived at the present invention. That is, the present invention provides a polyamide which has a glass transition temperature of 120 ° C. or higher on at least one side of a polyester film, contains an isophorone residue and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, and is soluble in an alcohol solvent. The present invention relates to a thermal transfer ribbon characterized by being coated with an imide resin, and the polyamide-imide resin has a hydroxyl group, a carboxyl group, an epoxy group, an amino group,
The thermal transfer ribbon, which is copolymerized or modified with a polyfunctional silicon compound containing an acid anhydride group, wherein the aliphatic dicarboxylic acid having 2 to 10 carbon atoms is adipic acid and / or azelaine. The thermal transfer ribbon characterized by being an acid, and further the thermal transfer ribbon characterized by being a polyamide-imide resin in which a part of the aliphatic dicarboxylic acid is replaced with an aromatic polycarboxylic acid. And the aromatic polyvalent carboxylic acid is trimellitic acid or / and pyromellitic acid, and 3 to 70 mol% of all acid components is a copolymerized polyamideimide. It is about. Furthermore, the present invention coats a polyamideimide resin after stretching the polyester film in one direction,
The present invention also relates to a method for producing the thermal transfer ribbon, which is characterized in that it is stretched in a perpendicular direction and heat-fixed.

A conventionally known polyester film can be used as the polyester film in the present invention.

The polyamideimide resin used in the present invention can be produced by any method such as a melt polymerization method and a solution polymerization method. In the case of the solution polymerization method, it can be polymerized by a usual method such as an acid chloride method, a direct polymerization method, an isocyanate method, but in the industrially advantageous isocyanate method, one or more diisocyanates containing isophorone diisocyanate as an essential component are used. And a dicarboxylic acid, and / or one or more aromatic polycarboxylic acid in an organic solvent
Obtained by reacting with each other at a temperature of ℃ or below.

The organic polar solvent used in the reaction includes ethers such as diethylene glycol dimethyl ether and diethylene glycol diethyl ether, ketones such as cyclohexanone and methyl ethyl ketone, esters such as γ-butyrolactone and cellosolve acetate, and N-methyl-
Examples thereof include amides such as 2-pyrrolidone, dimethylimidazolidinone and dimethylacetamide, aromatic hydrocarbons such as xylene and toluene, and these are preferably used alone or as a mixture.

The reaction temperature is preferably 50 to 200 ° C., and the reaction is a catalyst for the reaction of isocyanate with an active hydrogen compound, for example, tertiary amines such as triethylamine, lutidine, picoline, undecene, triethylenediamine, sodium methylate, sodium. It may be carried out in the presence of an alkali metal such as ethylate, potassium butoxide, sodium fluoride or potassium fluoride, an alkaline earth metal compound, or a metal such as cobalt, titanium, tin or zinc, or a metalloid compound.

A characteristic of the polyamide-imide resin used in the present invention is that it has a glass transition temperature of 120 ° C. or higher and is soluble in an alcohol solvent having a low boiling point. This is achieved by using an isophorone residue and one or more aliphatic dicarboxylic acids having 2 to 10 carbon atoms as essential components. In particular, the aliphatic dicarboxylic acid is adipic acid and / or azelaic acid. Good results are obtained when the aromatic polycarboxylic acid is trimellitic anhydride or pyromellitic anhydride.

When obtaining the polyamide-imide resin used in the present invention, it is necessary to use an aliphatic dicarboxylic acid having 2 to 10 carbon atoms as an acid component.
Other aliphatic dicarboxylic acids, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, etc. 1
One kind or a mixture of two or more kinds may be copolymerized. Further, an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid may be copolymerized.

As the aromatic polycarboxylic acid, tricarboxylic acids such as trimellitic acid and naphthalene-1,2,4-tricarboxylic acid and their anhydrides,

Or / and pyromellitic acid, benzophenone-3,3 ', 4,4'-tetracarboxylic acid, diphenyl ether-3,3', 4,4'-tetracarboxylic acid,
Benzene-1,2,3,4-tetracarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, biphenyl-2,2', 3,3'-tetracarboxylic acid, naphthalene-2, 3,6,7-Tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-
1,4,5,8-Tetracarboxylic acid, decahydronaphthalene-1,4,5,8-tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic acid, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid, 2,3,6,7-Tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid, Phenanthrene-1,3,9,10-tetracarboxylic acid, Berylene-3,4,9,10-tetracarboxylic acid Acid, bis (2,3
-Dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane, 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-
Dicarboxyphenyl) ethane, 2,2-bis (2,3
-Tetracarboxy such as dicarboxyphenyl) propane, 2,3-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether Although it is necessary to use one or more of acids and their anhydrides, isophthalic acid, 5-tert
-Butyl-1,3-benzenedicarboxylic acid, terephthalic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylmethane-2,4'-dicarboxylic acid, diphenylmethane-3,4'-dicarboxylic acid, diphenylmethane-
3,3'-dicarboxylic acid, 1,2-diphenylethane-
4,4'-dicarboxylic acid, 1,2-diphenylethane-
2,4'-dicarboxylic acid, 1,2-diphenylethane-
3,4'-dicarboxylic acid, 1,2-diphenylethane-
3,3′-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) propane, 2,2-bis (3-carboxyphenyl) propane, 2- (2-carboxyphenyl)
-2- (4-carboxyphenyl) propane, 2- (3
-Carboxyphenyl) -2- (4-carboxyphenyl) propane, diphenyl ether-4,4-dicarboxylic acid, diphenyl ether-2,4-dicarboxylic acid, diphenyl ether-3,4-dicarboxylic acid, diphenyl ether-3,3-dicarboxylic acid , Diphenyl sulfide-4,4-dicarboxylic acid, diphenyl sulfide-
2,4-dicarboxylic acid, diphenyl sulfide-3,4
-Dicarboxylic acid, diphenyl sulfide-3,3-dicarboxylic acid, diphenyl sulfone-4,4-dicarboxylic acid, diphenyl sulfone-2,4-dicarboxylic acid, diphenyl sulfone-3,4-dicarboxylic acid, diphenyl sulfone-3,3 -Dicarboxylic acid, benzophenone-4,
4-dicarboxylic acid, benzophenone-2,4-dicarboxylic acid, benzophenone-3,4-dicarboxylic acid, benzophenone-3,3-dicarboxylic acid, 1,1,3-trimethyl-5-carboxy-3- (p-carboxy Aroma such as phenyl) indane, pyridine-2,6-dicarboxylic acid, bis [(4-carboxy) phthalimide] -4,4′-diphenyl ether, bis [(4-carboxy) phthalimide] -α, α′-meta-xylene A group dicarboxylic acid may be copolymerized.

These aromatic polycarboxylic acids are used within the range in which the effects of the present invention can be achieved, but usually 3 to 70 mol%, preferably 5 to 30 mol% of the total acid components.
Used in the range of. The ratio of aromatic polycarboxylic acid is 3
If it is less than mol%, the glass transition temperature is lowered to 70 mol.
When it is more than%, it becomes difficult to dissolve in a polar solvent such as alcohol.

As the amine component of the polyamideimide resin used in the present invention, it is necessary to use isophoronediamine, but it is also possible to copolymerize one or more of the following diamines or diisocyanates. .

Specifically, hexamethylenediamine, tetramethylenediamine, 4,4-diaminocyclohexyl, 4,4-diaminodicyclohexylmethane, 1,3
-Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, p-phenylenediamine, m-phenylenediamine, 4,4-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4-diaminodiphenylmethane, 3,3-diaminodiphenylmethane, 2,4-dimethylmetaphenylenediamine, 5-nitrometaphenylenediamine, 5-
Chlorometaphenylenediamine, 4,4-diaminodiphenylhexafluoropropane, 3,3-diaminodiphenylhexafluoropropane, 4,4-diaminodiphenylsulfone, 3,3-diaminodiphenylsulfone, 4,4-diaminodiphenylsulfide, 3 , 3
-Diaminodiphenyl sulfide, 4,4-diaminobenzophenone, 3,3-diaminobenzophenone, 3,
4-diaminobiphenyl, 3,3-diaminobiphenyl, isopropylidenedianiline, 3,3-diaminodiphenylpropane, 2,4-tolylenediamine, 3,3
-Diaminobenzanilide, 4,4-diaminobenzanilide, o-tolidine, 1,4-naphthalenediamine,
1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,7-naphthalenediamine, 2,2-bis (4
-Aminophenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4- [1,3-phenylenebis (1-methylethylidene)] bisaniline,
4,4- [1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,3- [1,3-phenylenebis (1-methylethylidene)] bisaniline, 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl]
Propane, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, Bis [4- (3-aminophenoxy) phenyl] sulfone,
4,4-bis (3-aminophenoxy) biphenyl,
4,4-bis (4-aminophenoxy) biphenyl and the like can be mentioned.

The diamine or diisocyanate which may be copolymerized is used in a range not deteriorating the properties of the polyamideimide of the present invention, but usually 70% of all diamine components.
It is at most mol%, preferably at most 40 mol%.

In the present invention, a polyfunctional silicone compound containing a hydroxyl group, a carboxyl group, an epoxy group, an amino group, or an acid anhydride group at the terminal or in the molecular chain is copolymerized or modified to prevent set-off and blocking. You can

The amount of copolymerization or modification of the silicon compound is 0.1 to 50% by weight, preferably 1 to 30% by weight. When the silicon compound is 0.1% by weight or less, the friction coefficient is high and sticking is likely to occur. On the other hand, if it is 50% by weight or more, the heat resistance and the strength of the film are lowered, and problems such as head contamination occur.

The copolymerization or modification of the silicon compound may be carried out at the same time as the synthesis of the polyamide-imide resin or after the synthesis of the polyamide-imide resin.

The optimum value of the molecular weight of the polyamide-imide of the present invention is 0.1 dl / g or more, preferably 0.2 dl / g or more in N-methyl-2-pyrrolidone as measured by an Ubbelohde viscosity tube at 30 ° C. Is.

The solvent used in the polyamide-imide solution of the present invention can be dissolved in a solvent such as dimethylformamide, dimethylacetamide, phenol, cresol, methylene chloride or benzyl alcohol, which is a solvent for ordinary polyamideimide having heat resistance. In addition, it is also soluble in alcohol-based organic solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and xylenol, which cannot be dissolved by conventional heat-resistant polyamide-imide polymers. Further, the above alcohol solvent and tetrahydrofuran, diglyme, ether organic solvents such as dioxane, cyclohexanone, cyclopentanone, ketone organic solvents such as methyl isobutyl ketone, ethyl acetate, ester organic solvents such as methyl acetate, toluene and the like. Although it is soluble in a mixed solvent with an aromatic hydrocarbon organic solvent or the like, a solvent having a relatively low boiling point and high volatility is preferable.

The polyamide-imide resin composition used in the present invention further includes inorganic particles such as titanium oxide, barium sulfate, calcium sulfate, calcium carbonate, alumina and silicon oxide, surfactants, dispersants, antistatic agents and leveling agents. ,
A defoaming agent, a cross-linking agent such as an epoxy resin, a phenol resin, a melamine resin and a polyfunctional isocyanate, and a polyester or an acrylic resin can be added.

The coating method in the present invention may be any known method as long as it can be applied thinly, and a method using a reverse kiss coater, a fountain nozzle coater or the like can be used.

The heat-resistant thermal transfer ribbon of the present invention can be obtained by coating a polyamide-imide resin solution on at least one side of a biaxially stretched polyester film and drying the polyester film, which is coated after the polyester film is stretched in one direction. Alternatively, it can be obtained by a method of further stretching in a perpendicular direction and heat-setting. The latter is preferable in terms of productivity and cost.

The following examples are given to explain the present invention in more detail, but of course the present invention is in no way limited by the examples.

The measurement in this example was carried out by the following method. 1. Logarithmic viscosity: 0.5 in N-methyl-2-pyrrolidone
It was measured using an Ubbelohde viscosity tube at a concentration of g / dl at 30 ° C. 2. Glass transition temperature: Measured at a temperature rising rate of 10 ° C./min using TMA. 3. Dynamic friction coefficient: Using a surface measuring device HEIDON-14S, the friction coefficient with a stainless steel plate of 20 × 20 mm was measured at room temperature and a load of 200 g.

Example 1 0.9 mol of azelaic acid, 0.1 mol of pyromellitic anhydride, 0.5 mol of isophorone diisocyanate, 0.5 mol of 4,4-dicyclohexyl diisocyanate were placed in a reaction vessel.
Mol, potassium fluoride 0.02 mol, and γ-butyrolactone 350 ml, and the mixture is stirred at 150 ° C.
After reacting for 3 hours at room temperature, KF8012 (amino group-containing dimethylsiloxane manufactured by Shin-Etsu Silicone) was used as a monomer of 15
Weight% was added, and the mixture was further reacted at 150 ° C. for 3 hours. Then diluted with N-methyl-2-pyrrolidone and reprecipitated with water,
It was dried to obtain polyamideimide powder. The obtained polymer is dissolved in a mixed solvent of methanol and toluene so that the solid content concentration becomes 5%, and coated on a polyester film having a thickness of 4.5 μm so that the film thickness becomes 0.5 μm, It was dried at 100 ° C. for 1 minute.

Example 2 A polyamideimide resin was synthesized in the same procedure as in Example 1 except that trimellitic anhydride was used instead of pyromellitic anhydride in Example 1 to obtain a coated film.

Example 3 Using isophoronediamine in place of isophoronediisocyanate and 4,4-dicyclohexyldiamine in place of 4,4-dicyclohexyldiisocyanate in Example 2, heating to 260 ° C., melting and stirring for 3 hours, A polyamide-imide resin was synthesized. The obtained polymer was dissolved and coated in the same manner as in Example 1 to obtain a coated film.

Example 4 An unstretched polyester film having a thickness of 65 μm was stretched 4 times in one direction at 90 ° C. with a simple biaxial stretching machine (manufactured by TM Long Co.), and then the polyamideimide resin synthesized in Example 1 was used. The coating film was prepared by dissolving and coating in a mixed solvent of methanol and toluene so as to be 10% by weight, stretching at 90 ° C. in the perpendicular direction 3.5 times, and heat-treating at 230 ° C. for 15 seconds.

Comparative Example 1 Polyamideimide resin was synthesized in the same procedure as in Example 1 except that undecanedioic acid was used instead of azelaic acid in Example 1 to obtain a coated film, which had a very large dynamic friction coefficient. It was not practical as a thermal transfer ribbon.

Comparative Example 2 A polyamideimide resin was synthesized in the same procedure as in Example 1 except that KF8012 was changed to 0.05% by weight to obtain a coated film.

Comparative Example 3 A polyamide-imide resin was synthesized in the same procedure as in Example 1 except that KF8012 was changed to 60% by weight to obtain a coated film.

Comparative Example 4 A polyamideimide resin was synthesized by the same procedure as in Example 1 except that azelaic acid was 0.2 mol and pyromellitic acid was 0.8 mol in Example 1. The obtained polyamide-imide resin did not dissolve in methanol.

The logarithmic viscosity and glass transition temperature of the polyamide-imide resins obtained in Examples 1 to 4 and Comparative Examples 1 to 3 and the dynamic friction coefficient of the coating film obtained by coating these resins are measured. It shows in Table 1.

[0036]

[Table 1]

[0037]

The heat-resistant thermal transfer ribbon of the present invention can prevent the polyester film from melting and adhering to the thermal head even if the amount of heat of the thermal head is increased, and can cope with the increase in printing speed. It is possible.

Continued Front Page (72) Inventor Tomoharu Kurita 1-1-1, Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (6)

[Claims] 1. A polyester film having a glass transition temperature of 120 ° C. or higher, containing an isophorone residue and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms, and soluble in an alcohol solvent. A thermal transfer ribbon characterized by being coated with a polyamide-imide resin. 2. The thermal transfer according to claim 1, wherein the polyamide-imide resin is copolymerized or modified with a polyfunctional silicon compound containing a hydroxyl group, a carboxyl group, an epoxy group, an amino group and an acid anhydride group. ribbon. 3. The aliphatic dicarboxylic acid is adipic acid or /
And azelaic acid, The thermal transfer ribbon according to claim 1 or 2. 4. The thermal transfer ribbon according to claim 1, wherein the aliphatic dicarboxylic acid is a polyamideimide resin in which a part of the aromatic dicarboxylic acid is replaced with an aromatic polycarboxylic acid. 5. The aromatic polycarboxylic acid is trimellitic acid and / or pyromellitic acid, and 3 to 3 of all the acid components are used.
The thermal transfer ribbon according to any one of claims 1 to 4, wherein 70 mol% is a copolymerized polyamideimide. 6. The thermal transfer ribbon according to claim 1, wherein the polyester film is stretched in one direction, then coated with a polyamide-imide resin, and further stretched in a perpendicular direction and heat-fixed. Production method.