KR101230078B1 - Polyamide-imide film and method for preparing the same - Google Patents

Abstract

The present invention provides a polyamideimide-imide film comprising a polymer matrix represented by the following Chemical Formula 1, which is excellent in heat resistance and inexpensive as compared with a polyimide film. In addition, according to the method for producing a polyamideimide-imide mixed film provided in one embodiment of the present invention, a film containing a polymer containing a polyamideimide unit as a matrix may be excellently produced.

Formula 1

또는

이고, PAI는

또는

로, 여기서 n은 10 내지 200의 정수이고, m은 5 내지 50의 정수이고 PI는

이며 n+m은 10 내지 250의 정수이고 l은 5 내지 200의 정수이다.Where A is

or

And PAI is

or

Where n is an integer from 10 to 200, m is an integer from 5 to 50 and PI is

N + m is an integer from 10 to 250 and l is an integer from 5 to 200.

Description

Polyamide-imide film and method for preparing the same

The present invention relates to a polyamideimide-imide film and a method for producing the same, and more particularly, to a polyamideimide-imide film having improved thermal stability and a method for easily producing the same.

Polyimide films have excellent thermal and mechanical properties, but their use has been limited due to their high cost. Moreover, as the demand for high-temperature materials is not only used for electronic materials but also for heavy equipment, construction, aviation, and other industries, supply demand for films having cheaper and superior heat resistance characteristics is increasing.

The present invention seeks to provide a polyamideimide-imide film having excellent mechanical properties and heat resistance.

The present invention also provides a polyamideimide-imide film which is excellent in mechanical properties and excellent in heat resistance and yet inexpensive as compared to a conventional polyimide film.

Another embodiment of the present invention is to provide a method for producing a film having a good film forming properties by a solution film forming technology from a polyamideimide resin.

In view of this, in one embodiment of the present invention provides a polyamideimide-imide film comprising a polymer matrix represented by the following formula (1).

Formula 1

또는

이고, PAI는

또는

로, 여기서 n은 10 내지 200의 정수 이고, m은 5 내지 50의 정수이고 PI는

이며 n+m은 10 내지 250의 정수이고 l은 5 내지 200의 정수이다.Where A is

or

And PAI is

or

Where n is an integer from 10 to 200, m is an integer from 5 to 50 and PI is

N + m is an integer from 10 to 250 and l is an integer from 5 to 200.

In terms of thermal stability, the film of the present invention preferably has a glass transition temperature of 290 ° C or higher.

In the polyamideimide film of the present invention, the polyamideimide polymer may have a weight average molecular weight of 10,000 to 300,000 g / mol.

In another embodiment of the present invention, after trimellitic anhydride and at least one diisocyanate compound selected from diphenylmethane diisocyanate and toluene diisocyanate are reacted at 30 to 100 ° C. for 1 to 2 hours in the presence of a solvent , Pyromellitic anhydride was added and reacted at 120 to 140 ° C. for 1 to 4 hours and carbon dioxide was discharged as a by-product to prepare a polyamideimide solution at the anhydride end. 4,4-methyleneanilide and pyromelli Process of reacting the acid anhydride at 5 to 50 ° C. for 4 to 8 hours in the presence of a solvent to prepare an amine-terminated polyimide precursor solution A polyamideimide solution at the anhydride end and a polyimide precursor solution at the amine end are mixed and polymerized. Removing a polyamideimide solution containing a polyimide precursor Step of applying a polyamideimide solution containing the obtained polyimide precursor on a support, a polymer matrix represented by the formula (1) comprising a step of obtaining a film having a self-supporting drying and peeling and heat treatment from the support It provides a method for producing a polyamideimide-imide film comprising a.

According to the production method of the present invention, it is possible to induce a chemical bond between the anhydride end of the polyamideimide and the end of the polyimide precursor to exhibit higher miscibility and excellent mechanical strength. In addition, the polyamide-imide containing polyimide precursor is advantageous in that the resulting aqueous by-products by imidation of the polyamide-imide containing the polyimide precursor serve as a lubricating layer, thereby increasing the peeling properties with the support and having high film-forming properties. The method may further include mixing a chemical imidating agent before applying the mid solution onto the support.

In this manufacturing method, the polyamide-imide polymer solution may be 10 to 35% by weight solid content.

 In the method for producing a polyamideimide film according to an embodiment of the present invention, the polyimide precursor solution may be 10 to 35% by weight solid content.

In particular, in mixing the anhydride-terminated polyamideimide solution with the amine-terminated polyimide precursor solution, an anhydride-terminated polyamideimide solution is used in an amount of 50 to 95% by weight based on the solids content of the total mixture, The mid precursor solution may be used at 5 to 50% by weight.

Meanwhile, in the above embodiment, the chemical imidating agent may include a dehydrating agent and an imidization catalyst.

In the method for producing a film according to an embodiment of the present invention, the drying may be performed at 100 to 160 ℃.

In the method for producing a film according to an embodiment of the present invention, the heat treatment process may be carried out in a temperature range of 200 to 400 ℃.

In consideration of the film forming properties and the thermal and mechanical properties of the mixed film, the solution viscosity of the polyamideimide solution including the polyimide precursor may be 10,000 to 300,000 cP.

In addition, in consideration of the heat resistance and thermal expansion properties, the pyromellitic anhydride may be used in an amount of 5 to 20 mol% based on the total molar amount of the acid anhydride in preparing the polyamide-imide polymer solution.

In addition, in terms of controlling the polyamideimide terminal to an anhydride, the total amount of trimellitic anhydride and pyromellitic anhydride and diphenylmethane diisocyanate may be 1: 0.70 to 1: 0.95 molar ratio in the preparation of the polyamideimide solution.

According to one embodiment of the present invention, a polyamideimide film having improved thermal properties may be manufactured and used effectively in a product field that has been applied as a conventional polyimide film, and also has excellent film forming properties in manufacturing a polyamideimide film. The method is useful in that the polyamideimide film can be mass-produced in an easier manner by providing the method.

Hereinafter, the present invention will be described in detail.

Polyamideimide-imide film according to an embodiment of the present invention is to include a polymer matrix represented by the following formula (1).

Formula 1

또는

이고, PAI는

또는

로, 여기서 n은 10 내지 200의 정수이고, m은 5 내지 50의 정수이고 PI는

이며 n+m은 10 내지 250의 정수이고 l은 5 내지 200의 정수이다. Where A is

or

And PAI is

or

Where n is an integer from 10 to 200, m is an integer from 5 to 50 and PI is

N + m is an integer from 10 to 250 and l is an integer from 5 to 200.

These polymer matrices are acid anhydrides such as amide groups and imide groups (represented by repeating unit n) by reaction of trimellitic anhydride and diisocyanate, and imide groups by reaction of pyromellitic anhydride and diisocyanate (m repeating unit m). Bar), by adjusting the content of the acid anhydride can adjust the ratio of the imide group as a whole, thereby ensuring sufficient thermal stability.

For example, when the acid anhydride and diisocyanate content are close to equimolar, a film having improved thermal stability may be provided, but there is a concern that the miscibility with the mixed polyimide precursor is inhibited and the viscosity of the polyamideimide solution becomes too high. have.

If the viscosity is too high, it is difficult to complete the polymerization process, but may also be a problem in performing the subsequent film forming process.

In this regard, in the polyamideimide film according to the embodiment of the present invention, n in the general formula (1) is preferably 10 to 200, more preferably 50 to 150, and most preferably 80 to 100. It may be Accordingly, in Formula 1, m is preferably 5 to 50, more preferably 10 to 40, and most preferably 15 to 30.

In addition, the polyimide unit represented by the repeating unit l is considered to give excellent film forming characteristics through the formation of a gel film during the drying process, which may be 5 to 200, more preferably 50 to 150, and most preferably Is 80 to 100.

The polymer represented by Formula 1 of the present invention may have a weight average molecular weight of 100,000 to 300,000 g / mol may be preferable when considering the mechanical strength of the film.

The film including such a polymer matrix may be obtained by preparing a polyamideimide polymer and then forming the same by solution casting. However, in consideration of the film forming property, a method according to a preferred embodiment is an anhydrous polyamide solution. To prepare a polyamideimide solution containing a polyimide precursor by mixing a amine-terminated polyimide precursor to induce a chemical bond in the matrix, and then imidize it on a support.

Specifically, after trimellitic anhydride and trimellitic anhydride and at least one diisocyanate compound selected from diphenylmethane diisocyanate and toluene diisocyanate are reacted for 1 to 2 hours at 30 to 100 ° C. in the presence of a solvent. , Pyromellitic anhydride was added and reacted at 120 to 140 ° C. for 1 to 4 hours and carbon dioxide was discharged as a by-product to prepare a polyamideimide solution at the anhydride end. 4,4-methyleneanilide and pyromelli Process of reacting the acid anhydride at 5 to 50 ° C. for 4 to 8 hours in the presence of a solvent to prepare an amine-terminated polyimide precursor solution A polyamideimide solution at the anhydride end and a polyimide precursor solution at the amine end are mixed and polymerized. Polyamideimide Solution Including Polyimide Precursor Process of preparing a process of applying a polyamideimide solution containing the obtained polyimide precursor on a support, and a step of obtaining a film having a self-supporting drying and peeling from the support and heat treatment A polyamideimide-imide film comprising a polymer matrix can be prepared.

In the case of forming a film from a polyamideimide polymer by a solution casting method, the polymer solution is heated on a support under constant temperature conditions for a predetermined time, and then the film is peeled off from the support to obtain a partially dried polyamideimide film. The final film can be obtained. At this time, in order to obtain a film having high productivity and uniform mechanical properties, it is important that the dried viscous polymer solution is self-supporting and peels off smoothly from the support. It has to be dried to less than ~ 20wt%, which leads to a long drying residence time on the support, and on the contrary, when excessive drying, the adhesion to the support is greatly increased, which makes it difficult to peel off. The difficulty of such a film forming has a problem that the film productivity can be lowered and the physical properties also become uneven.

In this regard, in one embodiment of the present invention, the polyamideimide solution is mixed with a polyimide precursor (commonly referred to as a polyamic acid or a polyamic acid) and cast to form an anhydride end of the polyamideimide and an amine end of the polyimide precursor. By inducing the chemical bonds of the higher miscibility and excellent heat resistance and mechanical strength to enable the production of a film. Furthermore, when chemical imidation is used in combination, the water-based by-products generated by the imidization of the polyimide precursor serve as a lubricating layer to increase the support and the peeling property to produce a polyamideimide-imide mixed film having excellent film forming properties. have.

In the description above and below, the term "chemical imidation" will be understood by those skilled in the art to use a dehydrating agent and a catalyst together in carrying out imidization from a polyimide precursor.

Specifically, step by step in the step, first, in the process of preparing a polyamideimide solution having an anhydride terminal, it is arranged that the pyromellitic anhydride reacts with trimellitic anhydride and the diisocyanate compound and then sequentially added Through structural control, packing between molecular chains can be made more smooth, and anhydride terminal control can be facilitated, thereby increasing the compatibility of polymer mixtures and enabling chemical bonding, which can be advantageous in improving the mechanical and heat resistance properties of the final mixed film. . At this time, the diisocyanate compound reacting with the pyromellitic anhydride is not particularly limited, but methylene diisocyanate, toluene diisocyanate and the like can be cited in consideration of price and ease of purchase.

In the preparation of the polyamideimide polymer, the isocyanate method is used to prepare the final polyamide-imide polymer through the decarbonation reaction, so that no water is generated during the reaction, so that the polymer is hydrolyzed. It may be advantageous in terms of prevention.

It is preferable to use a polar solvent as a solvent in the process of preparing a polyamideimide solution, and for example, N-methyl-2-pyrrolidone, dimethylacetamide, N, N-dimethylformamide, or the like can be used. It is preferable to use N-methyl-2-pyrrolidone as a solvent.

In the process for producing a polyamideimide solution by such an isocyanate method, the reaction temperature is advantageously reacted at 30 to 100 ° C. for 1 to 2 hours to react the trimellitic anhydride and the diisocyanate compound. In the reaction after the anhydride is added, it may be advantageous to react at 120 to 140 ° C. for 1 to 4 hours.

The ratio of trimellitic anhydride and pyromellitic anhydride used as the acid anhydride and the pyromellitic anhydride in the raw monomer may be 80:20 to 95: 5 molar ratio in terms of securing heat resistance, and also improves the storage stability and film forming properties of the resin. When considered, the ratio of isocyanate, which is a reactant of trimellitic anhydride and pyromellitic dianhydride, is preferably used in a ratio of 1: 0.70 to 1: 0.95, and more preferably 1: 0.80 to 1: 0.90. Do. When the molar ratio is close to 1: 1, it is difficult to prepare a polyamideimide having an appropriate amount of anhydride ends, and when the molar ratio is lower than 1: 0.7, it is difficult to obtain a high molecular weight polyamideimide polymer, which lowers heat resistance and mechanical properties. have.

The polyamideimide polymer solution obtained may be advantageous in terms of increasing productivity at a solid content concentration of 15 to 30% by weight.

The polyamideimide polymer obtained as described above may have a weight average molecular weight of about 1,000 to 100,000 g / mol in terms of improving heat resistance while maintaining an appropriate viscosity for film formation.

On the other hand, the polyimide precursor used together to form the polyamideimide solution is not particularly limited, and any one may be rigid or partially rigid. Preferably, when the polyimide precursor is at the reactive amine end, it is possible to chemically bond with the polyamideimide having an anhydride end to prepare a tough film having high compatibility and miscibility.

As an example, the preferred polyimide precursor may be a two-component system composed of 4,4-methylenedianilide having a structure similar to pyromellitic anhydride and diphenylmethane diisocyanate. However, the present invention is not limited thereto, and amines may include ODA, PPD, ODPA, etc. in addition to 4,4-methyleneanilide.In addition to pyromellitic anhydride, BPDA, BPADA, ODPA, 6-FDA, etc. may be used. It may be a polyimide precursor consisting of two or more components.

The process of obtaining such a bicomponent polyimide precursor is not specifically limited, The method of making it react for 4 to 8 hours at 5-50 degreeC in presence of a solvent is mentioned.

The solvent contained in the polyimide precursor solution may be any solvent capable of dissolving the polyamideimide polymer described above while dissolving the polyimide precursor. Examples thereof include N, N-dimethylformamide and N, N-dimethylacetamide. And N-methyl-2-pyrrolidone.

The polyimide precursor solution may be advantageous in terms of increasing productivity at a solid concentration of 10 to 35% by weight.

By obtaining the polyamideimide polymer solution at the anhydride end and the polyimide precursor at the amine end by the above-described method, and mixing them, a reaction between both polymer ends occurs to prepare a polyamideimide including the polyimide precursor.

When mixing, an anhydride-terminated polyamideimide solution may be used in an amount of 20 to 80% by weight based on the total solid content of the mixture, and an amine-terminated polyimide precursor may be used in an amount of 80 to 20% by weight, in particular, an amine-terminated polyimide precursor Since it is added in consideration of the film forming properties, increasing the content is not intended to be intended and may be contrary to the object to provide a low-temperature heat-resistant film intended in the present invention.

At this time, the mixed solution may be advantageous when the solution viscosity is 10,000 to 300,000 cP considering the smooth polymer mixed solution discharge and the flatness of the solution.

As described above, when only the polyamide-imide polymer solution is softly coated and dried on a support, a gel film cannot be formed, thereby obtaining a self-supporting film by drying for a long time, and thus, a long residence time is required in the support. When more dried, there was a problem that the polyamide-imide film and the support are not peeled off.

However, when the chemical imidating agent is used in combination with the polyamideimide and the polyimide precursor solution, the imidization proceeds on the support to form a gel self-supporting film in spite of the high residual solvent amount. By the operation, a liquid lubricating layer is formed on the interface between the polymer urine and the support, thereby solving various problems such as film cutting, surface defects, and physical property irregularities generated when the film is peeled from the support.

In this regard, after mixing and polymerizing the polyamideimide solution at the anhydride end and the polyimide solution at the amine end, it is preferable to further add a solution containing a chemical imidating agent to the flexible coating on the support.

Here, the chemical imidating agent is a combination called a dehydrating agent, a catalyst, and a diluting solvent composition. Specific examples thereof include a dehydrating agent represented by an acid anhydride such as acetic anhydride, and tertiary amines such as isoquinoline, β-picolin, and pyridine. Typical imidation catalyst and dilution solvent combinations, such as NMP, DMF, and DAMc, are mentioned. The acid anhydride and the imidization catalyst may be added in an amount of 1 to 5 times the polyimide equivalent ratio, and in consideration of the film forming property, it is preferable to add 1 to 3 times more preferably 1 to 1.5.

When a polyamideimide polymer solution and a polyimide precursor solution including a chemical imidizing agent are mixed, cast on a support, and dried, a gel film having self-supportability can be obtained despite a high residual solvent amount. Drying may be performed at 100 to 160 ° C. in consideration of the boiling point of the solvent and the production rate.

The dried self-supporting film may be peeled from the support, and then heat-treated to imidize the remaining amic acid of the polyimide precursor to prepare the polyamideimide film of the present invention.

Finally, the heat treatment process is heated for 3 to 30 minutes at a temperature of 200 to 600 ℃ in consideration of the glass transition temperature of the film to dry the dehydration ring-closed. At this time, if the temperature is higher or longer than the above temperature, the film may be deteriorated to cause a problem. On the contrary, if the temperature is lower than this temperature or the time is short, imidization may not be sufficiently performed, and thus the film may be easily broken. The average thickness of the polyamideimide film including the polyimide group prepared as described above may range from 5 to 125 μm.

Meanwhile, the polyamideimide film according to one embodiment of the present invention obtained has a glass transition temperature of 290 ° C. or more in terms of thermal stability, and in view of the thermal stability, a polyimide film has been applied to conventional polyimide films, in particular, an insulating tape and a flexible copper clad laminate. It is expected that the polyamideimide film of the present invention can be applied to fields such as electric and electronics.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only and the scope of the present invention is not limited to these examples.

Example 1

(1) Preparation of Anhydride-terminated Polyamideimide Solution

One liter of the reactor is charged with nitrogen gas, and then 51.428 g (0.268 mol) of trimellitic anhydride and 200 g of N-methyl-2-pyrrolidone are added to the reactor. Then, 79.448 g (0.3029 mol) of 4,4'-methylenediphenyl diisocyanate was dissolved in 200 g of N-methyl-2-pyrrolidone while stirring the reactor at a rotational speed of about 200 RPM, and slowly added to the reactor over 1 hour. Add and stir for about 30 minutes at a rate of 200 RPM. After slowly increasing the temperature to 80 ° C. over 30 minutes, the solution was further stirred for 30 minutes, and then 10.303 g (0.047 mol) of pyromellitic anhydride and 222 g of N-methyl-2-pyrrolidone were sequentially added thereto. Stir for 30 minutes, then increase the temperature back to 140 ° C. over about 30 minutes. Thereafter, the solution was stirred while rotating at a speed of 100 RPM for about 30 minutes while maintaining the temperature of the solution at 140 ° C, and the temperature of the reaction solution was gradually lowered to 40 ° C to obtain a polyamideimide solution having a solid content of 18.5% anhydride. Prepared.

This is summarized in the following scheme.

(2) Preparation of Amine Terminal Polyimide Precursor Solution

One liter of the reactor is charged with nitrogen gas and then 68.066 g (0.343 mol) of 4,4-methyleneanilide and 300 g of N, N-dimethylformamide are added to the reactor. Then, the reactor was dissolved while stirring at a rotational speed of about 200 RPM, and then sequentially charged into 71.835 g (0.329 mol) of pyromellitic anhydride and 317 g of N, N-dimethylformamide and then polymerized with stirring at a rotational speed of 200 RPM at 40 ° C. To prepare a polyimide precursor solution having a solid content of 18.5%.

This is summarized in the following scheme.

(3) polyamideimide solution and polyimide precursor mixing and polymerization

100 g of the polyamideimide solution (solid content 18.5%) obtained from the above (1) at room temperature was prepared so that the polyimide precursor solution (solid content 18.5%) obtained in the above (2) was 100: 50 by weight based on the solid content. . Substantially mixed to produce a polymerization reaction to obtain a polyamideimide (solution viscosity 186,000 cP) comprising the following polyimide precursor.

이고 PAA는

이다.Where PAI is

And PAA is

to be.

(4) production

100 g of a polyamideimide solution containing such a polyimide precursor was mixed with N, N-dimethylformamide diluent, acetic anhydride as a dehydrating agent, and 35 g of a catalyst including isoquinoline as an imidization catalyst.

The mixed solution was discharged from the die, cast on a support, and dried at 120 to 160 degrees for about 4 minutes to obtain a gel self-supporting film having a residual solvent content of 40 to 50 wt%.

The film on the obtained gel was peeled off, dried at a temperature range of 200 to 300 degrees, and heat treated at a range of 300 to 400 degrees to prepare a polyamide imide mixed film (weight average molecular weight of 20,000 g / mol of polyamideimide-imide polymer). .

Example 2

A film was prepared in the same manner as in Example 1, except that in (1), the molar ratio of trimellitic anhydride and pyromellitic anhydride was changed to 1: 0.07 to prepare a polyamideimide polymer solution.

Example 3

A film was prepared in the same manner as in Example 1 except that (3), except for the process of mixing the dehydrating agent and the catalyst, the mixed solution was discharged from the die and cast onto the support for 10 minutes at 120 to 160 degrees. Drying was performed to obtain a self-supporting film having a residual solvent content of 10 to 20 wt%.

The obtained film was peeled off, dried at a temperature range of 200 to 300 degrees, and heat treated at a range of 300 to 400 degrees to prepare a polyamide imide mixed film.

Example 4

(1) Preparation of Anhydride-terminated Polyamideimide Solution

One liter of reactor is charged with nitrogen gas, and then 65.308 g (0.340 mol) of trimellitic anhydride and 200 g of N-methyl-2-pyrrolidone are added to the reactor. Then, while stirring the reactor at a rotational speed of about 200 RPM, 61.846 g (0.386 mol) of 2,4'-toluene isocyanate was dissolved in 200 g of N-methyl-2-pyrrolidone and slowly added to the reactor over 1 hour, and 200 RPM Stir for about 30 minutes at a speed of. After slowly increasing the temperature to 80 ° C. over 30 minutes, the solution was further stirred for 30 minutes, and then 13.100 g (0.060 mol) of pyromellitic anhydride and 220 g of N-methyl-2-pyrrolidone were sequentially added thereto. Stir for 30 minutes, then increase the temperature back to 140 ° C. over about 30 minutes. Thereafter, the solution was stirred while rotating at a speed of 100 RPM for about 30 minutes while maintaining the temperature of the solution at 140 ° C, and the temperature of the reaction solution was gradually lowered to 40 ° C to obtain a polyamideimide solution having a solid content of 18.5% anhydride. Prepared.

This is summarized in the following scheme.

(2) Preparation of Amine Terminal Polyimide Precursor Solution

    An amine terminated polyimide precursor solution was prepared in the same manner as in Example 1-2.

(3) polyamideimide solution and polyimide precursor mixing and polymerization

100 g of the polyamideimide solution (solid content 18.5%) obtained from the above (1) at room temperature was prepared so that the polyimide precursor solution (solid content 18.5%) obtained in the above (2) was 100: 50 by weight based on the solid content. . Substantially mixed to polymerize to obtain a polyamideimide solution (solution viscosity 126,000 cP) comprising the following polyimide precursor.

(4) Production

In the same manner as in Example 1-2, a polyamideimide-imide film (weight average molecular weight 20,000 g / mol of polyamide imide-imide) was prepared.

Example 5

A film was prepared in the same manner as in Example 1 except that (3), except for the process of mixing the dehydrating agent and the catalyst, the mixed solution was discharged from the die and cast onto the support for 10 minutes at 120 to 160 degrees. Drying was performed to obtain a self-supporting film having a residual solvent content of 10 to 20 wt%.

The obtained film was peeled off, dried at a temperature range of 200 to 300 degrees, and heat treated at a range of 300 to 400 degrees to prepare a polyamide imide mixed film.

Experimental Example

For the films obtained in Examples 1 to 3, the film forming properties and the thicknesses of the final obtained films were measured, and the mechanical and thermal properties were evaluated, and the results are shown in Table 1 below.

The specific measuring method is as follows.

(1) film forming characteristics

    Oven residence time measurement for the formation of self supporting green film.

    Measure Green Solvent Residue.

    Peeling Characteristics with Support

 (2) film thickness

     Device: KG601B Electric Micro Meter (Anritsu)

 (3) strength

     Device: UTM (Instron)

     Method: ASTM D882

 (4) Glass transition temperature

     Device: DSC-2940 (TA)

      Temperature Profile: 20 ~ 350 ℃

      Heating rate: 10 ℃ / min

      Load: 3g

 (5) coefficient of thermal expansion (CTE)

      Device: TMA-2940 (TA)

      Method: ASTM D696-98

      Temperature Profile: 20 ~ 400 ℃

      Heating rate: 10 ℃ / min

      Sample size: 5 X 20mm

Oven
Residence time Residue
Solvent
(wt%) Support
Exfoliation
characteristic thickness
(μ) The tensile strength
(Mpa) Elongation
(%) Modulus
(Gpa) Tg
(℃) CTE (ppm / ℃) 100-200 ℃ 200-300 ℃ Example
One 4 minutes 45 Great 25 15 15 3.5 300 43 50 2 5 minutes 47 Great 25 13 13 3.2 290 53 63 3 10 minutes 21 usually 25 15 10 3.3 295 44 55 4 4 minutes 46 Great 25 23 22 5.2 298 25 29 5 11 minutes 18 usually 25 24 12 5.0 300 30 33

From the result of Table 1, it can be seen that a robust film with easy film forming characteristics can be produced.

Although the exemplary embodiments of the present invention have been exemplified above, the present invention is not limited to the above-described specific preferred embodiments, and the present invention may be used without departing from the gist of the present invention as claimed in the claims. Various modifications can be made by those skilled in the art, and such changes are within the scope of the claims.

Claims (14)

A polyamideimide-imide film comprising a polymer matrix represented by the following Chemical Formula 1. Formula 1

Where A is

or

And PAI is

or

Where n is an integer from 10 to 200, m is an integer from 5 to 50 and PI is

N + m is an integer from 10 to 250 and l is an integer from 5 to 200. The polyamideimide-imide film according to claim 1, wherein the glass transition temperature is 290 ° C or higher. The polyamideimide-imide film of claim 1, wherein the polymer represented by Chemical Formula 1 has a weight average molecular weight of 10,000 to 300,000. After trimellitic anhydride and at least one diisocyanate compound selected from diphenylmethane diisocyanate and toluene diisocyanate are reacted at 30 to 100 ° C. for 1 to 2 hours in the presence of a solvent, pyromellitic anhydride is added and Reaction for 1 to 4 hours at 120 to 140 ℃ and then discharge the carbon dioxide as a by-product, to prepare a polyamideimide solution of the anhydride terminal Separately, 4,4-methyleneanilide and pyromellitic anhydride are reacted at 5 to 50 ° C. for 4 to 8 hours in the presence of a solvent to prepare an amine-terminated polyimide precursor solution. A process of preparing a polyamideimide solution containing a polyimide precursor by mixing and polymerizing a polyamideimide solution at the anhydride end and a polyimide precursor solution at the amine end. Process of apply | coating the polyamideimide solution containing the obtained polyimide precursor on a support body Drying to obtain a film having self-support and Method for producing a polyamideimide-imide film comprising a polymer matrix represented by the following formula (1) including a step of peeling off the support and heat treatment. Formula 1

Where A is

or

And PAI is

or

Where n is an integer from 10 to 200, m is an integer from 5 to 50 and PI is

N + m is an integer from 10 to 250 and l is an integer from 5 to 200. The method for producing a polyamideimide-imide film according to claim 4, further comprising a step of mixing a chemical imidating agent before applying the polyamideimide solution containing the polyimide precursor onto the support. The method for producing a polyamideimide-imide film according to claim 4, wherein the polyamideimide solution has a solid content of 10 to 35% by weight. The method for producing a polyamideimide-imide film according to claim 4, wherein the polyimide precursor solution has a solid concentration of 10 to 35% by weight. The method according to claim 4, wherein in mixing the anhydride-terminated polyamideimide solution with the amine-terminated polyimide precursor solution, an anhydride-terminated polyamideimide solution is used at 50 to 95% by weight based on the solids content of the total mixture. A method for producing a polyamideimide-imide film using 5 to 50% by weight of an amine-terminated polyimide precursor solution. 6. The method of claim 5, wherein the chemical imidating agent comprises a dehydrating agent and an imidization catalyst. The method of claim 4, wherein the drying is performed at 100 to 160 ° C. 6. The method of claim 4, wherein the heat treatment process is performed at a temperature in the range of 200 to 400 ° C. 6. The method of claim 7, wherein the polyamideimide solution comprising the polyimide precursor has a solution viscosity of 10,000 to 300,000 cP. The method for producing a polyamideimide-imide film according to claim 4, wherein the pyromellitic anhydride is used in an amount of 5 to 20 mol% based on the total molar amount of the acid anhydride in the preparation of the polyamideimide solution. The method for preparing a polyamideimide-imide film according to claim 4, wherein the total amount of trimellitic anhydride and pyromellitic anhydride and diphenylmethane diisocyanate are 1: 0.70 to 1: 0.95 molar ratio when the polyamideimide solution is prepared. .