JPH08239473A - Silicon copolymerized polyamide imide ester resin and thermal recording material comprising same - Google Patents

Abstract

PURPOSE: To obtain a silicon copolymer polyamide imide ester resin permanently excelling in slipperiness and adhesion, not deterioration in heat resistance and being soluble in a general-purpose low-boiling solvent. CONSTITUTION: This silicon copolymer polyamide imide ester resin has an inherent viscosity of 0.1dl/g or above, a glass transition temperature of 120 deg.C or above and a surface tension of a dry film of 35dyn/cm or below and is soluble in an alcoholic solvent. This resin is excellent in heat resistance, slipperiness, adhesion and solubility, and therefore it is used as a back-coating agent or a top-coating agent for a thermal recording material such as a thermal transfer ribbon or a thermochromic film when e.g. a polyester film is coated therewith.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel silicone copolymerized polyamideimide ester resin. More specifically, it has excellent heat resistance, slipperiness, and adhesion, and since it dissolves in low-boiling alcohol solvents, it is useful as a back coat material or top coat material for thermal transfer ribbons, direct thermal recording materials, thermochromism recording materials, etc. The present invention relates to a copolyamideimide ester resin and a heat-sensitive recording material using the same.

[0002]

2. Description of the Related Art Conventionally, polyamide-imide resins are heat resistant,
It has excellent mechanical properties, electrical insulation, and chemical resistance, so it is used as a molding material and insulating paint.
As it is soluble only in solvents with high hygroscopicity and high boiling points such as pyrrolidone, dimethylformamide, and dimethylacetamide, the storage stability of the polymer solution is poor, and it is difficult to dry, so it can be used as a coating material for plastic such as polyester film. Could not be applied. In addition, when slipperiness is required, it was used by blending organic lubricants such as silicon, higher fatty acid, and fluorine resin, and inorganic lubricants such as graphite and molybdenum disulfide, but in the case of organic lubricants, the lubricant stains There is a problem of lack of durability and set-off due to ejection, and in the case of an inorganic lubricant, there is a problem that cost is increased because a complicated process such as dispersion is required.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to provide a durable slip property and adhesion without impairing the heat resistance of polyamide-imide resin, which can be applied to a coating agent for plastic such as polyester film. An object of the present invention is to provide a silicone-copolymerized polyamideimide ester resin that is excellent in solubility and is soluble in a general-purpose low boiling point solvent, and a heat-sensitive recording material using the same.

[0004]

Therefore, the inventors of the present invention have arrived at the present invention as a result of earnest research on improvement of slipperiness, solubility and adhesion. That is, the present invention has a logarithmic viscosity of 0.
Silicon-copolymerized polyamideimide ester resin composition characterized by being dissolved in an alcoholic solvent having a glass transition temperature of 1 dl / g or more, a glass transition temperature of 120 ° C. or more and a surface tension of a dry coating film of 35 dyn / cm or less, and this resin composition The present invention relates to a heat-sensitive recording material coated on at least one side of a polyester film, and a preferred embodiment thereof is a silicon-copolymerized polyamideimide ester containing trimellitic anhydride and cyclohexanedicarboxylic acid as acid components, and an amine. The residue is 4,4′-dicyclohexylmethane and / or isophorone, and the silicon component is a hydroxyl group, a carboxyl group, an epoxy group,
What is claimed is: 1. A silicone-copolymerized polyamideimide ester, characterized in that a polyfunctional silicon compound containing at least one selected from an amino group, an acid anhydride group and an unsaturated group is copolymerized, and a polyamideimide The present invention relates to a silicone copolymer polyamide-imide ester resin, wherein polyester is a block copolymer, of which the polyamide-imide component is 30 to 95% by weight. Furthermore, the present invention relates to a method for producing a polyamideimide ester, which comprises adding a prepolymerized polyester resin and a silicon compound to a solution in which polyamideimide has been synthesized, and polymerizing the solution.

The silicone-copolymerized polyamideimide ester resin of the present invention can be polymerized by a solution polymerization method, a melt polymerization method or a combination thereof, but when a block copolymer which is a preferred embodiment of the present invention is obtained. For this, a method in which a polyester resin and a silicon compound which have been melt-polymerized in advance are added to a solution obtained by solution-polymerizing a polyamideimide resin component and then polymerized is preferable.

The polyamideimide component is synthesized from an acid component and an isocyanate (amine) by a usual method such as an isocyanate method or an acid chloride method in a polar solvent such as an amide solvent.

Examples of the acid component used in the synthesis of the silicone-copolymerized polyamideimide ester resin of the present invention include the following polyvalent carboxylic acids, acid chlorides and acid anhydrides, but the acid components are not necessarily limited thereto. As the acid anhydride, trimellitic acid anhydride, ethylene glycol bis-anhydro trimellitate, propylene glycol bis-anhydro trimellitate, 1,4 butanediol bis-anhydro trimellitate, hexamethylene glycol bis-anhydro trimellitate , Polyethylene glycol bis-anhydro trimellitate, polypropylene glycol bis-anhydro trimellitate, etc. alkylene glycol bis-anhydro trimellitate, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride 3, 3 ', 4, 4'diphenylsulfone tetracarboxylic acid anhydride, 3,3 ', 4,4' biphenyl tetracarboxylic acid anhydride, 4,4 'oxydiphthalic acid anhydride, etc. are mentioned.

The polycarboxylic acids are terephthalic acid, isophthalic acid, 4,4'-biphenyldicarboxylic acid,
4,4 'biphenyl ether dicarboxylic acid, 4,4' biphenyl sulfone dicarboxylic acid, 4,4 'benzophenone dicarboxylic acid, pyromellitic acid, trimellitic acid,
3,3 ', 4,4'benzophenone tetracarboxylic acid,
3,3 ', 4,4' biphenyl sulfone tetracarboxylic acid, 3,3 ', 4,4' biphenyl tetracarboxylic acid,
Adipic acid, sebacic acid, maleic acid, fumaric acid, dimer acid, stilbene dicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, 1,2 cyclohexanedicarboxylic acid, etc., and the acid chlorides include acid chlorides of the above polycarboxylic acids. .

As the isocyanate component, dicyclohexylmethane 4,4'diisocyanate, 1,3 bis (isocyanatomethyl) cyclohexane, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, diphenylmethane 4,4 'diisocyanate, 3 ,
3'dimethyldiphenylmethane diisocyanate, 3,
3'diethyldiphenylmethane 4,4'diisocyanate, 3,3'dichlorodiphenylmethane 4,4'diisocyanate 4,4'diisocyanate 3,3'dimethylbiphenyl, hexamethylene diisocyanate, isophorone diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate Etc.

As the amine component, 4,4'diaminodicyclohexylmethane, 1,3 cyclohexanebis (methylamine), orthochloroparaphenylenediamine, p-phenylenediamine, m-phenylenediamine, 4,4'diaminodiphenylether, 3,4 diaminodiphenyl ether, 4,4 ′ diaminodiphenylmethane, 3,4 diaminodiphenylmethane, 4,4 ′ diaminodiphenyl sulfone, 3, 4 ′ diaminodiphenyl sulfone, 4, 4 ′ diaminobenzophenone, 3,
4'diaminobenzophenone, 2,2 'bis (aminophenyl) propane, 2,4 tolylenediamine, 2,6 tolylenediamine, p-xylelylenediamine, m-xylylenediamine, isophoronediamine, hexamethylenediamine, etc. Can be mentioned.

These acid components and isocyanate (amine) components can be used either individually or as a mixture of two or more, but as the acid component, a mixture of trimellitic anhydride and cyclohexanedicarboxylic acid is preferable,
It is particularly preferable that the content of cyclohexanedicarboxylic acid is 20 mol% or more. Cyclohexanedicarboxylic acid mol%
Is less than 20, the solubility decreases, and it may be difficult to dissolve unless an amide solvent such as dimethylformamide, dimethylacetamide, N-methyl-2pyrrolidone or a high boiling point solvent such as γ-butyrolactone is used in combination with alcohol. .

As the isocyanate (amine) component, dicyclohexylmethane diisocyanate (diamine) and isophorone diisocyanate (diamine) alone or as a mixture are particularly preferable from the viewpoint of heat resistance and solubility.

The solvent used for the polymerization of the polyamide-imide component of the present invention is a high boiling polar solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylurea, dimethylsulfoxide, γ-butyrolactone or dimethylimidazolidinone, alone or Although a mixed solvent can be used, a single solvent or a mixed solvent of γ-butyrolactone and dimethylimidazolidinone is preferable from the viewpoint of transparency of the synthesized polyamideimide ester with less side reaction.

The polyamideimide component of the present invention is synthesized by stirring in the above solvent at 50 to 230 ° C., preferably 80 to 200 ° C. In order to accelerate the reaction, triethylamine, lutidine, picoline, undecene,
Amines such as triethylenediamine, alkali metal such as lithium methylate, sodium methylate, potassium butoxide, potassium fluoride and sodium fluoride, alkaline earth metal compound, or metal such as cobalt, titanium, tin and zinc. Alternatively, it may be carried out in the presence of a catalyst such as a metalloid compound.

A preferred embodiment of the silicone copolymerized polyamideimide ester of the present invention is a block copolymer. To obtain this, a polyamideimide resin solution synthesized as described above is added with a prepolymerized polyester resin and a silicone compound and polymerized. The method is preferred. Therefore, when synthesizing the polyamide-imide by the isocyanate method, it is necessary to prepare so that the isocyanate component becomes excessive.

The polyester component is polymerized from a dicarboxylic acid and a diol, and the composition thereof is not particularly limited, and any of aliphatic, alicyclic and aromatic singly and in combination can be used, and the polymerization method is also a melt polymerization method. Although it can be produced by a usual method such as a solution polymerization method, an inexpensive melt polymerization method is preferable.

The dicarboxylic acid component of the polyester component of the present invention includes terephthalic acid, isophthalic acid, orthophthalic acid, 2,6 naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4. 'Aromatic dicarboxylic acids such as benzophenone dicarboxylic acid, succinic acid, glutaric acid, adipic acid,
Aliphatic dicarboxylic acids such as sebacic acid, maleic acid, fumaric acid, dimer acid, dodecanedicarboxylic acid, azelaic acid, 1,2 cyclohexanedicarboxylic acid, 1,3 cyclohexanedicarboxylic acid, 1,4 cyclohexanedicarboxylic acid, etc. Examples thereof include dicarboxylic acids, and among these, a mixture of terephthalic acid and isophthalic acid is preferable from the viewpoint of polymerizability, cost and solubility. Further, a polyvalent carboxylic acid such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenylsulfonetetracarboxylic acid, or biphenyltetracarboxylic acid and its anhydride may be used in combination.

As the diol component, ethylene glycol, propylene glycol, neopentyl glycol, 1,4 butane diol, 1,5 pentane diol,
1,6 hexanediol, 1,9 nonanediol, 1,
Alkylene glycols such as 10-decanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tetramethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like can be mentioned. Among them, ethylene glycol, propylene glycol, neopentyl glycol, 1,4 butanediol and 1,6 hexanediol are preferably used alone or as a mixture of two or more thereof in view of polymerizability, cost and solubility. Further, a polyhydric polyol such as trimethylolethane, trimethylolpropane, glycerin and pentaerythritol may be used in combination.

Further, metal salts such as 5 sulfoisophthalic acid, 4 sulfonaphthalene 2,7 dicarboxylic acid, 5 [4 sulfophenoxy] isophthalic acid, or 2 sulfo 1,4 butane diol 2,5 dimethyl 3 sulfo 2,5 A dicarboxylic acid or diol containing a sulfonic acid metal base such as a metal salt such as hexanediol may be used in the range of 10 mol% or less of the total acid or the total diol component.

The silicone-copolymerized polyamideimide ester of the present invention is polymerized by adding the polyester resin and the silicon compound, and dissolving and reacting at the initial stage of the synthesis of the polyamideimide, during the synthesis, or at the completion of the synthesis. In order to obtain the block copolymer which is a preferred embodiment of the present invention, it is preferable to add it during the synthesis.

The ratio of the polyamideimide component to the polyester component in the silicone-copolymerized polyamideimide ester of the present invention is 30 to 95% by weight of the polyamideimide component,
The range of 50 to 90 is preferable. If the polyamide-imide component is less than 30% by weight, the heat resistance will be insufficient and 95
If it exceeds the weight percentage, the adhesion may not be improved.

In order to provide one of the objects of the present invention, which is excellent in durability and slipperiness without set-off, it is necessary to permanently maintain the surface tension of the coating film at 35 dyn / cm or less. When the surface tension exceeds 35 dyn / cm, for example, when it is applied to a back coat material for a thermal transfer ribbon, the coefficient of friction with the thermal head becomes large and a sticking phenomenon appears.

The silicon component to be used in the present invention is not particularly limited, but from the viewpoint of reactivity, it may be one containing a hydroxyl group, a carboxyl group, an epoxy group, an amino group, an acid anhydride group or an unsaturated group at the terminal or molecular chain. A functional silicon compound is preferable, and the content of the silicon component is not particularly limited,
Although it depends on the molecular weight of the silicon compound, it is usually 0.1 to 50% by weight, preferably 1 to 30% by weight. When the content of the silicon component is less than 0.1% by weight, the surface tension of the coating film is not sufficiently improved, and as a result, the friction coefficient is high and sticking easily occurs. On the other hand, if it exceeds 50% by weight, the heat resistance and the strength of the coating film are deteriorated, which may cause abrasion during abrasion and powder drop.

The silicone-copolymerized polyamideimide ester resin polymerized in this manner must be redissolved in a low boiling point solvent in order to be coated on a polyester film or the like. To dissolve in a low boiling point general-purpose solvent,
Polyamideimide ester solution polymerized under the above conditions is stirred into water, a ketone, an ester, or a hydrocarbon solvent, coagulated and washed, and a dried silicone copolymerized polyamideimide ester resin is used as a solvent mainly containing alcohol. It can be achieved by dissolving.

The alcohol used as the main solvent is not particularly limited, but low boiling point alcohols such as methanol, ethanol, 1 propanol, isopropyl alcohol, n-butanol and isobutanol are preferable.

The solvent used in combination with alcohol is not limited, and ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ether-based solvents such as tetrahydrofuran and dioxane, methyl acetate,
Examples thereof include ester solvents such as ethyl acetate and butyl acetate, and hydrocarbon solvents such as benzene, toluene and xylene. Tetrahydrofuran and toluene are preferable from the viewpoint of solubility, drying property and cost.

When the silicone copolymerized polyamideimide ester resin solution of the present invention is coated on a polyester film and applied to a back coat material of a thermal transfer ribbon or a top coat material of a thermochromism card, the silicone copolymerized polyamideimide ester resin solution Surfactants, dyes, pigments, fillers such as inorganic oxides and carbon powder, polyamide imides, polyesters, etc. within the range that does not impair the characteristics.
Other resins such as acrylic, epoxy, urethane, silicon, polyisocyanate, etc., and curing agents may be added.

[0028]

The silicone copolymerized polyamideimide ester resin of the present invention is excellent in slipperiness, heat resistance and adhesion.
Since it dissolves in a low boiling point alcohol solvent, it is useful as a back coat agent or top coat agent for coating materials for plastics such as polyester films, especially for heat-sensitive recording materials such as thermal transfer ribbons and thermochromism cards.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the examples. The characteristics shown in the examples were measured by the following methods.

1, logarithmic viscosity; 0.5 g of dry polymer to 1
The solution dissolved in 00 ml of NMP was measured at 25 ° C. using an Ubbelohde type viscous tube.

2. Glass transition temperature: Measured by a differential thermal analyzer at a temperature rising rate of 10 ° C./min.

3. Surface tension: Calculated from the contact angle between water and methylene iodide.

4, coefficient of friction; surface measuring machine type HEID
A soldering iron having a tip R of 1 mm was attached to ON-14S, and the dynamic friction coefficient at a load of 200 g and 250 ° C. was measured.

Example 1 In a reaction vessel, 72 g of trimellitic anhydride, 65 g of 1,4 cyclohexanedicarboxylic sun, 168 g of isophorone diisocyanate and 1 g of potassium fluoride together with 1,3 dimethyl 2 imidazolidinone have a polymer concentration of 50% by weight. As described above, the temperature was raised to 180 ° C. and the reaction was carried out for 1 hour. Then, while diluting the polymer concentration to 40% by weight, 15
Cooled to 0 ° C. Byron RV220 (polyester resin manufactured by Toyobo Co., Ltd.) 12 g and KF90 in a reaction vessel.
12 (Shin-Etsu Chemical Co., Ltd. diaminopolysiloxane) 2
4 g was added and the reaction was continued for another 3 hours. The obtained polymer solution was diluted with cooling so that the polymer concentration became 20% by weight, poured into water under stirring to be precipitated and dried. The polymer obtained has an inherent viscosity of 0.48 dl
/ G, the glass transition temperature was 227 ° C. This dry polymer was dissolved in a mixed solvent of an equal amount of ethyl alcohol and toluene so that the concentration became 8% by weight. Coated so that it becomes 0.5μ, 100 ℃
And dried for 1 minute to prepare a thermal transfer ribbon. The surface tension of the coated surface of this thermal transfer ribbon was 19 dyn / cm and the coefficient of friction was 0.06. Contamination of the head was not observed even after repeated printing.

Example 2 169 g of isophorone diisocyanate, Byron RV
Polymerization, dilution, precipitation and drying were carried out in the same manner as in Example 1 except that 220 g was changed to 24 g. The polymer obtained has an inherent viscosity of 0.41 dl / g and a glass transition temperature of 208 ° C.
Met. This polymer was dissolved in a mixed solvent of alcohol and tetrahydrofuran to a concentration of 8% by weight to prepare a thermal transfer ribbon by the same method as in Example 1. The surface tension of the coated surface of this thermal transfer ribbon is 20 dyn / cm,
The friction coefficient was 0.07, and the head was not contaminated even after repeated printing.

Example 3 177 g of isophorone diisocyanate, Byron RV
Polymerization, dilution, precipitation and drying were carried out in the same manner as in Example 1 except that 220 g was set to 144 g. The polymer obtained had an inherent viscosity of 0.38 dl / g and a glass transition temperature of 125 ° C.
Met. This polymer was dissolved in methyl alcohol and toluene to a concentration of 8% by weight to prepare a thermal transfer ribbon by the same method as in Example 1. The surface tension of the coated surface of this thermal transfer ribbon is 22 dyn / cm, and the friction coefficient is 0.
It was 08, and the head was not contaminated even after repeated printing.

Example 4 101 g of trimellitic anhydride, 32 g of 1,4 cyclohexanedicarboxylic acid, 85 g of isophorone diisocyanate, 91 g of dicyclohexylmethane 1,4 diisocyanate and 1 g of potassium fluoride were placed in a reaction vessel with 1,3 dimethyl 2 imidazolidinone. Polymerization, dilution, precipitation and drying were carried out under the same conditions as in Example 1 except that the polymer was charged so that the concentration was 50% by weight. The polymer obtained had an inherent viscosity of 0.44 dl / g and a glass transition temperature of 181 ° C. A thermal transfer ribbon was prepared in the same manner as in Example 1 from a solution prepared by dissolving this polymer in a mixed solvent of methyl alcohol and toluene in an amount of 8% by weight. The surface tension of the coated surface of this thermal transfer ribbon is 18 dyn / c.
m, the coefficient of friction was 0.06, and the head was not contaminated even after repeated printing.

Comparative Example 1 In Example 1, KF8 was used without adding Byron RV220.
A silicone copolymerized polyamideimide ester resin having 012 as 0.12 g was synthesized under the same conditions. The polymer obtained had an inherent viscosity of 0.55 dl / g and a glass transition temperature of 255 ° C. This polymer was dissolved in a mixed solvent of an equal amount of methyl alcohol and toluene. When this polymer solution was applied to a polyester film in the same manner as in Example 1 to prepare a thermal transfer ribbon, the surface tension of the coated surface was 39 dyn / cm. It was not improved, and all peeled off in the adhesion test by the cross-cut method.

Comparative Example 2 177 g of isophorone diisocyanate, Byron RV
Polymerization, dilution, precipitation and drying were carried out in the same manner as in Example 1 except that 220 was 168 g. The glass transition temperature of the obtained polymer was 93 ° C., which was insufficient in heat resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Keiichi Uno 2-1-1 Katata, Otsu City, Shiga Prefecture Toyobo Co., Ltd.

Claims (8)

[Claims] 1. A logarithmic viscosity of 0.1 dl / g or more, a glass transition temperature of 120 ° C. or more, and a surface tension of a dried coating film of 35 d.
A silicone-copolymerized polyamideimide ester resin composition which is soluble in an alcohol solvent having a concentration of yn / cm or less. 2. The silicone-copolymerized polyamideimide ester resin composition according to claim 1, which contains trimellitic anhydride and cyclohexanedicarboxylic acid as acid components. 3. The silicone-copolymerized polyamideimide ester resin composition according to claim 1, which contains a dicyclohexylmethane and / or an isophorone group as an amine residue. 4. A hydroxyl group, a carboxyl group, an epoxy group,
The polyfunctional silicon compound containing at least one selected from an amino group, an acid anhydride group, and an unsaturated group is copolymerized, and the silicone-copolymerized polyamide according to any one of claims 1 to 3. Imide ester resin composition. 5. The silicone copolymerized polyamideimide ester resin composition according to claim 1, wherein the polyamideimide and the polyester are block copolymers. 6. The silicone-copolymerized polyamideimide ester resin composition according to claim 1, wherein the polyamideimide component is 30 to 95% by weight. 7. The silicone-copolymerized polyamide according to any one of claims 1 to 6, wherein a polyester resin prepolymerized and a polyfunctional silicon compound are added to a solution prepared by synthesizing a polyamide-imide resin and polymerized. Method for producing imide ester resin. 8. A polyester film having a glass transition temperature of 120 ° C. or higher and an inherent viscosity of 0.1 on at least one side.
The surface tension of the dry coating film is 35 dyn / cm at dl / g or more.
A heat-sensitive recording material characterized by being coated with the following silicone-copolymerized polyamide-imide ester resin.