KR101583845B1 - Co-polymerized polyamide-imide film and method of producing the co-polmerized polyamide-imide - Google Patents

Abstract

The copolymerized polyamide-imide film according to the present invention has a unit structure derived from TFDB (2,2'-bis trifluoromethyl-4,4'-biphenyl diamine), 6FDA (4,4 '- (hexa-fluoroisopropylidene) diphthalic anhydride ) And a unit structure derived from TPC (Terephthaloyl chloride: 1,4-benzenedicarbonyl chloride) are copolymerized.

Description

[0001] The present invention relates to a method for producing a co-polymerized polyamide-imide film and a co-polymerized polyamide-imide,

The present invention relates to a method for producing a copolymerized polyamide-imide film and a copolymerized polyamide-imide.

The polyimide film has excellent thermal and mechanical properties, and in recent years, as demand for high-temperature materials has increased, the use of polyimide films has been limited, but its use has been limited due to its high price.

Particularly, in recent years, there is a need for a polyimide film excellent in optical properties and excellent in thermal and mechanical properties in an electronic display or the like.

Accordingly, there is an increasing demand for polyimide films that are less expensive and have better thermal, mechanical, and optical properties. Therefore, attempts have been made to mix or copolymerize polyimide with polyimide, which is the main material of polyimide films.

However, copolymerized polyamide-imide films which simultaneously satisfy optical and mechanical properties as well as optical properties required in the market have not yet been provided.

The present invention is intended to provide a method for producing copolymerized polyamide-imide films and copolymerized polyamide-imides having excellent thermal, mechanical and optical properties.

The copolymerized polyamide-imide film according to the present invention has a unit structure derived from TFDB (2,2'-bis trifluoromethyl-4,4'-biphenyl diamine), 6FDA (4,4 '- (hexa-fluoroisopropylidene) diphthalic anhydride ) And a unit structure derived from TPC (Terephthaloyl chloride: 1,4-benzenedicarbonyl chloride) are copolymerized, and the copolymerized resin may have a weight average molecular weight of 10,000 to 400,000.

That is, the copolymerized polyamide-imide film according to the present invention contains a unit structure derived from TFDB and a unit structure derived from TPC as a polyamide component, and includes a unit structure derived from TFDB as a polyimide component and a 6FDA , Wherein the diamine unit structure of the polyamide component and the polyimide component is made common to the TFDB, whereby the high glass transition temperature and excellent optical properties of the polyimide component thus formed, And by simultaneously realizing the low thermal expansion coefficient and the high mechanical properties of the polyamide component thus formed, it is possible to produce a film that is transparent and excellent in heat resistance.

The polyamide component and the polyimide component are copolymerized with each other so that the excellent thermal and mechanical properties of the polyimide component and the excellent optical properties of the polyamide component are not separated and can be expressed as a single copolymer.

Wherein the copolymerized resin has a unit structure derived from TFDB: a unit structure derived from 6FDA: the unit structure derived from TPC is copolymerized in a molar ratio of 1: 0.2 to 0.8: 0.8 to 0.2, whereby a polyamide component and a polyimide component And more preferably, a unit structure derived from TFDB: a unit structure derived from 6FDA: a unit structure derived from TPC having a ratio of 1: 0.3 to 0.7: 0.3 to 0.7 , It is possible to optimize the optical property by the polyamide component and the thermal and mechanical properties by the polyimide component.

When the unit structure derived from TPC is less than 0.2, the degree of improvement in heat resistance is insufficient and it is difficult to exhibit the properties of the polyamide component. When the unit structure is higher than 0.8, control of the degree of polymerization during copolymerization is difficult, Materials may be difficult to manufacture. When the unit structure derived from TPC is in the range of 0.3 to 0.7, the physical properties of the polyamide component and the polyimide component are uniformly expressed so that they have appropriate thermal, mechanical and optical properties.

The method for producing the copolymerized polyamide-imide according to the present invention comprises a first polymerization step of causing TFDB and 6FDA to react with each other and a second polymerization step of causing the TPC to react with the polymer obtained through the first polymerization step, A polyamic acid manufacturing process for producing a mixed acid solution; And an imidization step of subjecting the polyamic acid solution prepared by the polyamic acid production step to a chemical imidization reaction in the presence of an imidization catalyst.

That is, in the method for producing the copolymerized polyamide-imide according to the present invention, the polyimide component is first polymerized by first performing a first polymerization step in which TFDB and 6FDA are subjected to a solution reaction in the step of producing polyamic acid, A second polymerization step of polymerizing the polyamide component to polymerize the polyimide component first, followed by copolymerizing the polyamide component.

When the polyamide is first polymerized, the viscosity may rise too rapidly, the subsequent reaction of the polyimide component may not occur uniformly, and the solution may become cloudy due to the lower solubility of the polyamide component relative to the polyimide component It is advantageous to polymerize the polyimide component first because it may cause phase separation with the solvent.

In the polyamic acid production process, the first polymerization step is a solution reaction with X mole% of 6FDA relative to 100 mole% of TFDB and the second polymerization step is a solution reaction of 100-X mole% of TPC (X is 20 to 80 ), And more preferably, X may be 30 to 70. [

Here, in the imidization step, the imidization catalyst may be a commonly used imidization catalyst, and pyridine and acetic anhydride may be used at the same time.

The copolymerized polyamide-imide film according to the present invention can be produced by using the copolymerized polyamide-imide prepared by the above-mentioned method for producing a copolymerized polyamide-imide of the present invention, can do.

The present invention provides a method for producing copolymerized polyamide-imide films and copolymerized polyamide-imides having excellent thermal, mechanical and optical properties.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph of GPC-RI analysis results for an embodiment of the present invention. FIG.

Hereinafter, the present invention will be described in detail with reference to specific examples for carrying out the present invention.

≪ Example 1 >

Preparation of copolymerized polyamide-imide

In a 1.5 L reactor equipped with a stirrer, a nitrogen inlet, a dropping funnel, a temperature controller and a condenser, 812 g of N, N-dimethylacetamide (DMAc) was charged while nitrogen was passed through the reactor. 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 캜. 71.08 g (0.16 mol) of 6FDA was added thereto, followed by dissolution and reaction with stirring for 1 hour. The temperature of the solution was maintained at 25 占 폚. Then, 8.1208 g (0.04 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15 wt%.

The polyamic acid solution was stirred at room temperature for 2 hours, and then 27.8 g of pyridine and 35.9 g of acetic anhydride were added thereto. The mixture was stirred for 30 minutes, then stirred at 80 ° C for 1 hour and cooled to room temperature. To precipitate the precipitated solid. The precipitated solid was pulverized by filtration and then dried at 100 DEG C under vacuum for 6 hours to obtain 128 g of a copolymerized polyamide-imide of solid powder.

The resultant copolymer polyamide-imide had a weight average molecular weight of 170,000, and the GPC-RI analysis results showed that the copolymer was synthesized as a single peak as shown in (4) of the graph of FIG.

Preparation of copolymerized polyamide-imide film

The copolymer solution of 128 g of the solid powder was dissolved in 512 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution. The resulting solution was applied to a stainless steel plate and cast to 700 μm And dried at 130 ° C for 30 minutes. The film was peeled off from the stainless steel plate and fixed to the frame with a pin. The frame with the film fixed therein was placed in a vacuum oven, slowly heated from 100 ° C to 300 ° C for 2 hours, cooled gradually and separated from the frame to obtain a polyimide film. Thereafter, as a final heat treatment step, heat treatment was performed again at 300 캜 for 30 minutes (thickness: 100 탆).

≪ Example 2 >

Preparation of copolymerized polyamide-imide

785 g of N, N-dimethylacetamide (DMAc) was charged in Example 1, the temperature of the reactor was adjusted to 25 ° C, and 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 ° C. 62.195 g (0.14 mol) of 6FDA was added thereto, followed by dissolving and reacting with stirring for 1 hour. The temperature of the solution was maintained at 25 占 폚. Then, 12.1812 g (0.06 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15% by weight.

The polyamic acid solution was stirred at room temperature for 8 hours, and then 25 g of pyridine and 32 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature and slowly added to a container containing 20 L of methanol Precipitated, and the precipitated solid was pulverized by filtration, and then dried at 100 DEG C under vacuum for 6 hours to obtain 124 g of solid content powder of copolymerized polyamide-imide.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 200,000.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 124 g of the solid powder was dissolved in 496 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

≪ Example 3 >

Preparation of copolymerized polyamide-imide

After 753 g of N, N-dimethylacetamide (DMAc) was charged in Example 1, the temperature of the reactor was adjusted to 25 캜, and 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 캜. 53.31 g (0.12 mol) of 6FDA was added thereto, and the mixture was stirred for 1 hour to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 16.2416 g (0.08 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15% by weight.

The polyamic acid solution was stirred at room temperature for 8 hours, 21 g of pyridine and 27 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature, and slowly added to a container containing 20 L of methanol Precipitated, and the precipitated solid was pulverized by filtration, and then dried at 100 DEG C under vacuum for 6 hours to obtain 120 g of a copolymer powdery polyamide-imide powder.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 251,000, and the GPC-RI analysis results showed that the copolymer was synthesized as a single peak as shown in (3) of the graph of FIG.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 120 g of the solid powder was dissolved in 480 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

<Example 4>

Preparation of copolymerized polyamide-imide

After 725 g of N, N-dimethylacetamide (DMAc) was charged in Example 1, the temperature of the reactor was adjusted to 25 캜, and 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 캜. 44.425 g (0.1 mol) of 6FDA was added thereto, and the mixture was stirred for 1 hour to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 20.3 g (0.10 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15 wt%.

The polyamic acid solution was stirred at room temperature for 8 hours, and 17.4 g of pyridine and 22.5 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature, and slowly added to a container containing 20 L of methanol And the precipitated solids were filtered to be pulverized and then dried at 100 DEG C under vacuum for 6 hours to obtain 115 g of a copolymer powder of polyamide-imide having a solid content.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 250,000.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 115 g of the solid powder was dissolved in 460 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

&Lt; Example 5 >

After 703 g of N, N-dimethylacetamide (DMAc) was charged in Example 1, the temperature of the reactor was adjusted to 25 占 폚, and 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 占 폚. 35.54 g (0.08 mol) of 6FDA was added thereto, and the mixture was stirred for 1 hour to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 24.36 g (0.12 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15 wt%.

The polyamic acid solution was stirred at room temperature for 8 hours, 14 g of pyridine and 18 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature, and slowly added to a container containing 20 L of methanol Precipitated. The precipitated solids were filtered and pulverized, and then dried at 100 DEG C under vacuum for 6 hours to obtain 111 g of a solid content powder of copolymerized polyamide-imide.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 253, 400, and the GPC-RI analysis result shows that the copolymer was synthesized as a single peak as shown in ( 2) of the graph of FIG.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 111 g of the solid powder was dissolved in 444 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

&Lt; Example 6 >

Preparation of copolymerized polyamide-imide

In Example 1, 675 g of N, N-dimethylacetamide (DMAc) was charged, and the temperature of the reactor was adjusted to 25 ° C. Then, 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 ° C. 26.655 g (0.06 mol) of 6FDA was added thereto, followed by dissolving and reacting with stirring for 1 hour. The temperature of the solution was maintained at 25 占 폚. 28.42 g (0.14 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15% by weight.

The polyamic acid solution was stirred at room temperature for 8 hours, and 11 g of pyridine and 13.5 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature, and slowly added to a vessel containing 20 L of methanol And the precipitated solids were filtered and pulverized, and then dried at 100 DEG C under vacuum for 6 hours to obtain 107 g of a solid content powder of copolymerized polyamide-imide.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 310,000, and the GPC-RI analysis results showed that the copolymer was synthesized as a single peak as shown in ( 1) of the graph of FIG.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 107 g of the solid powder was dissolved in 428 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

&Lt; Example 7 >

Preparation of copolymerized polyamide-imide

After 648 g of N, N-dimethylacetamide (DMAc) was charged in Example 1, the temperature of the reactor was adjusted to 25 캜, 64.046 g (0.2 mol) of TFDB was dissolved, and the solution was maintained at 25 캜. 17.77 g (0.04 mol) of 6FDA was added thereto, and the mixture was stirred for 1 hour to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 32.48 g (0.16 mol) of TPC was added to obtain a polyamic acid solution having a solid content of 15% by weight.

The polyamic acid solution was stirred at room temperature for 8 hours, and 21 g of pyridine and 27 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 1 hour, cooled to room temperature and slowly added to a vessel containing 20 L of methanol, The precipitated solids were filtered and pulverized, and then dried at 100 DEG C under vacuum for 6 hours to obtain 102 g of a solid content powder of copolymerized polyamide-imide.

The weight average molecular weight of the copolymer polyamide-imide thus obtained was 227,000.

Preparation of copolymerized polyamide-imide film

The copolymerized polyamide-imide of 102 g of the solid powder was dissolved in 408 g of N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution.

Then, a polyimide film was produced in the same manner as in Example 1 above.

&Lt; Comparative Example 1 &

Production of polyimide

 N, N-dimethylacetamide (DMAc), the temperature of the reactor was adjusted to 25 캜, and 64.046 g (0.2 mol) of TFDB was dissolved and the solution was maintained at 25 캜. 88.85 g (0.2 mol) of 6FDA was added thereto, and a polyamic acid solution having a solid content of 20 wt% was obtained.

The polyamic acid solution was stirred at room temperature for 8 hours, and 31.64 g of pyridine and 40.91 g of acetic anhydride were added. After stirring for 30 minutes, the mixture was stirred at 80 ° C for 2 hours, cooled to room temperature and slowly added to a container containing 20 L of methanol And precipitated solid components were filtered and pulverized, and then dried at 100 DEG C under vacuum for 6 hours to obtain 136 g of polyimide powder.

Production of polyimide film

496 g of the polyimide of the solid powder was dissolved in N, N-dimethylacetamide (DMAc) to obtain a 20 wt% solution. Then, a polyimide film was prepared in the same manner as in Example 1.

&Lt; Comparative Example 2 &

Preparation of polyamide

In Example 1, 1203 g of N, N-dimethylacetamide (DMAc) was charged with 2 L of the reactor size, the temperature of the reactor was adjusted to 25 ° C., 64.046 g (0.2 mol) of TFDB was dissolved, Lt; 0 &gt; C. 40.6 g (0.2 mol) of TPC was added thereto, and the mixture was stirred for 1 hour to dissolve and react. At this time, the temperature of the solution was maintained at 25 占 폚, and a polyamic acid solution having a solid content of 8 wt% was obtained. This was gradually added to a container containing 20 L of distilled water to precipitate. The precipitated solid was filtered and pulverized, and then dried at 100 ° C under vacuum for 6 hours to obtain 101 g of a solid powdery polyamide.

Preparation of polyamide film

101 g of the polyamide of the solid powder was dissolved in 1161 g of N, N-dimethylacetamide (DMAc) to obtain a 8 wt% solution. Then, a polyimide film was prepared in the same manner as in Example 1.

&Lt; Property evaluation method &

(1) Average transmittance

The films prepared in the Examples were measured for their average transmittance at 380 to 780 nm using a UV spectrometer (Kotikaminolta CM-3700d).

(2) Yellow Index (Y.I.)

The yellowing degree at 380 to 780 nm was measured according to the ASTM E313 standard using a UV spectrometer (Kotikaminolta CM-3700d).

(3) Coefficient of thermal expansion (CTE)

TMA (Perkin Elmer, Diamond TMA) was used to measure the thermal expansion coefficient at 50 ~ 260 ° C twice in accordance with the TMA-method, and the heating rate was 10 ° C / min and a load of 100mN. Except for the first value, the second value is suggested because the residual stress may remain in the film through the film formation and heat treatment, so the residual value is completely removed after the first run and the second value is presented as the experimental value .

(4) Thickness measurement

The thickness was measured with an Anritsu Electronic Micrometer and the deviation of the device was less than 0.5%.

Table 1 shows the results of evaluating the physical properties of Examples 1 to 7 and Comparative Examples 1 and 2.

Thickness
(탆) Average transmittance
(%) Y.I. CTE
(ppm / DEG C) Comparative Example 1 50 90.8 2.2 65 Example 1 50 90.3 2.4 58 Example 2 50 90.1 2.5 52 Example 3 50 89.8 2.8 47 Example 4 50 89.8 2.8 42 Example 5 50 89.6 3.0 37 Example 6 50 89.6 3.1 24 Example 7 50 89.5 4.2 24 Comparative Example 2 35 84 10 12

As a result of the physical property evaluation, it can be seen that the embodiments of the present invention increase the yellowing degree and decrease the average transmittance slightly in comparison with the polyimide film of Comparative Example 1, Due to the relatively easy formation of intermolecular and intramolecular charge transfer complexes. On the contrary, it can be confirmed that the coefficient of thermal expansion is significantly lowered because the polyamide component composed of TFDB and TPC is excellent in rigidity, so that the polyimide component having a relatively high thermal expansion coefficient is expected to be displayed by being kept untouched.

In the case of Example 7, the thermal expansion coefficient value hardly changes even though the content of the polyamide component is increased in comparison with that of Example 6. This is because the viscosity increases sharply as the polyamide component increases and the polymerization degree becomes difficult to control It is predicted that the reaction will not occur sufficiently.

Comparative Example 2, which is a polyamide film, exhibited the best thermal expansion coefficient, but it was difficult to handle during film formation due to poor optical properties and high viscosity during polymerization. When the viscosity was lowered to enable film formation, the concentration was too low, There is a limit in that the thickness can not be made thick. Nevertheless, when the thickness is increased, the optical transmittance and the yellowing degree are rapidly deteriorated, making it difficult to use.

Claims (6)

A unit structure derived from 2,2'-bis trifluoromethyl-4,4'-biphenyl diamine, a unit structure derived from 6FDA (4,4 '- (hexa-fluoroisopropylidene) diphthalic anhydride) and TPC (Terephthaloyl chloride; 1,4-benzenedicarbonyl chloride) is formed of a polyamic acid copolymerized in a molar ratio of 1: X: 1-X (provided that 0.2? X? 0.8)
A polyimide group in which a unit structure derived from TFDB and a unit structure derived from 6FDA are copolymerized in a molecular structure; And a polyamide group in which a unit structure derived from TFDB and a unit structure derived from TPC are copolymerized,
Wherein the yellowing degree (YI) of the film is not more than 4.2 and the coefficient of thermal expansion (CTE) is not more than 58 ppm / 占 폚.
delete The copolymer according to claim 1, wherein the copolymerized resin has a unit structure derived from TFDB: a unit structure derived from 6FDA: a unit structure derived from TPC having a molar ratio of 1: X: 1-X &Lt; / RTI &gt; is copolymerized with the polyamide-imide film. delete delete delete

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