TWI512011B - Polyimide copolymer and its preparation and coating film - Google Patents

Description

Polyimine copolymer and preparation method and cover film thereof

The invention relates to a polyimine copolymer and a preparation method thereof, in particular to a polyamidene copolymer suitable for uniaxially extending film formation and a preparation method thereof.

With the development of electronic products with lighter weight and higher functionality, highly functional polyimide films play an important role in materials. Polyimine film has excellent heat resistance and chemical resistance, mechanical properties and electrical properties, and is therefore widely used in various industries such as electronics, motors, automobiles, aerospace and machinery. Polyimine film plays an important role in materials in the electronics industry, mainly used in the LCD liquid crystal display industry, IC semiconductor industry and flexible circuit board industry. Among them, the proportion of the use of polyimine film type is the largest.

At present, the production of polyimide films mostly uses biaxially stretched films or uniaxially stretched films, and the biaxial stretching or process modification measures provide better appearance and dimensional stability. In contrast, the general uniaxially stretched film process still cannot meet the above requirements. Furthermore, due to the optimization of the winding technology and the post-processing conditions and the shelf life of the finished product, even if the polyimide film is prepared by biaxial stretching, wrinkles and dimensional stability are still poor. In addition, when a polyimide film (PI) is applied to a cover film of a flexible circuit board, poor punching on the product is not conducive to subsequent processing.

Therefore, how to solve the above problems of the prior art is a technical problem that needs to be solved in the industry.

Accordingly, the present invention provides a polyamidene copolymer comprising at least a first type of diamine monomer and a second type of diamine monomer, and a first type of dianhydride monomer and a second type of dianhydride monomer. And a cyclization reaction, wherein the first type of diamine single system is selected from the group consisting of a compound having a biphenyl structure, at least one of a group consisting of p-phenylenediamine, o-phenylenediamine, and m-phenylenediamine. The second type of diamine monomer has at least two structures in which a phenyl group and a chain rotatory atom of the phenyl group are bonded, and the first type of dianhydride single system is selected from the following formula (3-1) To at least one of the compounds of the formula (3-7), the second type of dianhydride single system has a compound of the following formula (4):

In the above polyimine copolymer, the compound having a biphenyl structure is selected from at least one of the compounds represented by the following formulas (1-1) to (1-7):

In the above polyimine copolymer, the chain rotates an atomic carbon atom or an oxygen atom. For example, the second type of diamine monosystem is selected from at least one of the following compounds of the formula (2-1) to the formula (2-7):

The invention provides a method for preparing a polyamidene copolymer, comprising: at least a first type of diamine monomer and a second type of diamine monomer and a first type of dianhydride monomer and a first solvent in the presence of a polar solvent The second type of dianhydride monomer is subjected to copolymerization to obtain a polyaminic acid solution, wherein the first type of diamine single system is selected from the group consisting of a compound having a biphenyl structure, p-phenylenediamine, o-phenylenediamine, and At least one of the group consisting of phenylenediamine; the second type of diamine monomer having at least two structures of a phenyl group and a chain-rotating atom bonded to the phenyl group, and the first type of dianhydride monomer Is at least one selected from the group consisting of compounds of the formula (3-1) to the formula (3-7), the second type of dianhydride single system having the compound of the formula (4), and the first type of diamine monomer The molar ratio to the second type of diamine monomer is between 0.25 and 0.34, the molar ratio of the first type of dianhydride monomer and the second type of dianhydride monomer is between 0.10 and 0.177; and cyclizing the polyfluorene Amino acid to obtain the polyimine copolymer.

The present invention finds that the molecular chain rotation of the second type of diamine monomer enhances the rotatory of the molecular chain, and the polyamic acid prepared by the first type of dianhydride monomer and the second type of dianhydride monomer proposed by the present invention. The solution is particularly suitable for uniaxially stretched film forming to obtain a high modulus, dimensional stability and impact resistant cover film product.

The polyimine copolymer of the present invention is produced by copolymerization in the presence of a polar solvent, wherein the temperature of the copolymerization is between 25 and 60 ° C, and the polar solvent is selected from N, N dimethyl B. Group of guanamine (DMAc), N,N diethylethyl acetamide (DMF), dimethyl sulfoxide dimethyl sulfo (DMSO) and N-methyl-2-pyrrolidone (NMP) At least one solvent. Further, the temperature of the cyclized polyamic acid is between 180 ° C and 450 ° C. Usually, the polyphthalic acid is cyclized by a chemical cyclization method or a thermal cyclization method in the presence of an acid anhydride and a tertiary amine catalyst, wherein the anhydride-based carboxylic acid anhydride (Aliphatic carboxyloic acid anhydride) For example, the acid anhydride type catalyst is at least one acid anhydride selected from the group consisting of Acetic anhydride, Propionic anhydride, and n-Butylric anhydride. The tertiary amine catalyst is selected from the group consisting of pyridine, 2-picoline, 3-picoline, 4-picoline and dimethyl. At least one compound of the group consisting of lutidine. Further, the acid anhydride type catalyst has a molar number of 0.001 to 0.009, and the tertiary amine catalyst has a molar number of 0.001 to 0.009.

According to the process of the present invention, the polyamine acid solution has a solid content of 15 to 35 wt%, preferably 22 wt%. After the polyamic acid obtained by cyclization, static defoaming, coating, and post cure are carried out to produce a PI film.

The present invention provides a cover film comprising: a polyimide film having a thickness of 10 to 50 μm, a polyimine copolymer having any one of claims 1 to 4; and a thickness of 5 An adhesive layer of 75 μm is formed on the polyimide film, and the thickness of the cover film is 15 to 125 μm, wherein the material of the adhesive layer is selected from epoxy resin, acrylic tree One or more resins of esters, urethane-based resins, ruthenium-based rubber resins, poly-p-xylene resins, bismaleimide resins, and polyamidiene resins.

Example 1

After 1 mole of the diamine monomer ODA was dissolved in the DMAc solvent, 1 mole of the dianhydride monomer PMDA was added and added to the DMAc solvent to dissolve at room temperature for 8 hours. The copolymerization of the copolymerized polyamic acid (PAA) has a solid content of about 22% by weight. Further add PAA to acetic anhydride and 3-methylpyridine, mix and stir evenly, then let stand for defoaming, then uniformly coat with the appropriate scraper at the end of the coating machine and pull out the film with a uniaxial stretching machine to enter the oven. The film was baked in a stepwise stage (180 ° C → 260 ° C → 400 ° C) to form a film, wherein the film thickness was 25 μm.

The above copolymerized polyimide film having a molar ratio of ODA:PMDA=50:50 can be obtained by chemical cyclization or thermal cyclization, wherein the film thickness ranges from 25 μm.

As shown in Fig. 1, after applying the adhesive 12 to the polyimide film 11, the cover film 10 having a thickness of 50 μm was baked, and the cover film was baked at 160 ° C for 101 hours, and then aged at 60 ° C for 36 hours. It becomes a cover film 10 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

Example 2

After 0.02 mole of diamine monomer p-PDA was added to dissolve in DMAc solvent, 0.08 mole of diamine monomer ODA was added to dissolve in DMAc solvent. After completely dissolved, 0.005 mole of dianhydride monomer BPDA was added. In the DMAc solvent, after completely dissolved, 0.095 mole of the dianhydride monomer PMDA was added and dissolved at room temperature for 8 hours of copolymerization. The copolymerization of the copolymerized polyamic acid (PAA) has a solid content of about 22% by weight. Further add PAA to acetic anhydride and 3-methylpyridine, mix and stir evenly, then let stand for defoaming, then uniformly coat with the appropriate scraper at the end of the coating machine and pull out the film with a uniaxial stretching machine to enter the oven. The film was baked in a stepwise stage (180 ° C → 260 ° C → 400 ° C) to form a film, wherein the film thickness was 25 μm.

The above copolymerized polyimine film having a molar ratio of p-PDA:ODA:PMDA=5:95:100 can be obtained by chemical cyclization or thermal cyclization, wherein the film thickness ranges from 25 μm.

As shown in Fig. 1, after applying the adhesive 12 to the polyimide film 11, the cover film 10 having a thickness of 50 μm was baked, and the cover film was baked at 160 ° C for 101 hours, and then aged at 60 ° C for 36 hours. It becomes a cover film 10 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

Example 3

After 0.02 mole of p-PDA was dissolved in DMAc solvent, 0.08 mole of ODA was added to dissolve in DMAc solvent. After completely dissolved, 0.01 mole of BPDA was added to the DMAc solvent. After completely dissolved, 0.09 was added. The PMDA of mole was dissolved at room temperature for 8 hours of copolymerization. The copolymerization of the copolymerized polyamic acid (PAA) has a solid content of about 22% by weight. Further add PAA to acetic anhydride and 3-methylpyridine, mix and stir evenly, then let stand for defoaming, then uniformly coat with the appropriate scraper at the end of the coating machine and pull out the film with a uniaxial stretching machine to enter the oven. The segments are baked in a stepwise stage (180 ° C → 260 ° C → 400 ° C) to form a film.

From the above chemical cyclization method or thermal cyclization method, a copolymerized polyimine film having a molar ratio of p-PDA:ODA:BPDA:PMDA=20:80:10:90 can be obtained, wherein the film thickness is 25 μm. .

As shown in Fig. 1, after applying the adhesive 12 to the polyimide film 11, the cover film 10 having a thickness of 50 μm was baked, and the cover film was baked at 160 ° C for 101 hours, and then aged at 60 ° C for 36 hours. It becomes a cover film 10 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

Example 4

After adding 0.025 mole of p-PDA to DMAc solvent, add 0.075 mole ODA to dissolve in DMAc solvent. After completely dissolved, add 0.015 mole of BPDA to DMAc solvent. After completely dissolved, add 0.085 mole. The PMDA was dissolved at room temperature for 8 hours of copolymerization. The copolymerization of the copolymerized polyamic acid (PAA) has a solid content of about 22% by weight. Further add PAA to acetic anhydride and 3-methylpyridine, mix and stir evenly, then let stand for defoaming, then uniformly coat with the appropriate scraper at the end of the coating machine and pull out the film with a uniaxial stretching machine to enter the oven. The segments are baked in a stepwise stage (180 ° C → 260 ° C → 400 ° C) to form a film.

The aromatic copolymerized polyimine film having a molar ratio of p-PDA:ODA:BPDA:PMDA=25:75:15:85 can be obtained by chemical cyclization or thermal cyclization, wherein the film thickness is 25 microns.

As shown in Fig. 1, after applying the adhesive 12 to the polyimide film 11, the cover film 10 having a thickness of 50 μm was baked, and the cover film was baked at 160 ° C for 101 hours, and then aged at 60 ° C for 36 hours. It becomes a cover film 10 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

Example 5

After adding 0.03 mole of TFMB to the DMAc solvent, add 0.07 mole 3, 4 ODA to dissolve in DMAc solvent. After completely dissolved, add 0.02 mole of BPDA to the DMAc solvent. After completely dissolved, add 0.08 mole. The PMDA was dissolved at room temperature for 8 hours of copolymerization. The copolymerization of the copolymerized polyamic acid (PAA) has a solid content of about 22% by weight. Further add PAA to acetic anhydride and 3-methylpyridine, mix and stir evenly, then let stand for defoaming, then uniformly coat with the appropriate scraper at the end of the coating machine and pull out the film with a uniaxial stretching machine to enter the oven. The segments are baked in a stepwise stage (180 ° C → 260 ° C → 400 ° C) to form a film.

The above aromatic ring copolymerization method or thermal cyclization method can obtain an aromatic copolymerized polyimide film having a molar ratio of TFMB: 3, 4 ODA: BPDA: PMDA = 30: 70: 20: 80, wherein the film thickness is 25 microns.

As shown in Fig. 1, after applying the adhesive 12 to the polyimide film 11, the cover film 10 having a thickness of 50 μm was baked, and the cover film was baked at 160 ° C for 101 hours, and then aged at 60 ° C for 36 hours. It becomes a cover film 10 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

Comparative example

The polyimide film 21 of the Damai TH-025 specification has a thickness of 25 μm, and a coating agent 22 is applied to the polyimide film 21 on the coating machine to form a cover film 20 having a thickness of 50 μm. After the cover film was baked at ° C for 201 hours, it was aged at 60 ° C for 36 hours, and then became a cover film 20 of a flexible circuit board. Then, the punching machine (model MK-416AB) was used for the punching evaluation test, and the test results were observed whether there were problems such as abnormal burrs, tearing of the cover film, and dimensional stability of the PI which became the cover film after the product.

The PI films obtained in Examples 1 to 5 and Comparative Examples were subjected to the specifications of the American Society for Testing and Materials using a universal tensile machine (Shimazu AG-IS 1kN) for the elastic modulus of PI mechanical properties (Specification ASTM D882). The data results are listed in Table 1.

The MD and TD directions described in the cover film product respectively refer to the MD (Movement Direction) of the machine end, and the other refers to the TD (Transverse Direction) which is perpendicular to the production direction of the machine end. In addition, the film size stability performance is based on the flexible printed circuit board test specification IPC-TM650 2.2.4C test method.

As shown in Table 1, the polyimine films obtained in Examples 1 to 4 change the molecular chain structure polymerization according to the composition ratio of the diamine monomer to the dianhydride monomer in the formulation, especially the first type of diamine monomer. The molar ratio to the second type of diamine monomer is between 0.25 and 0.34, and the molar ratio of the first type of dianhydride monomer and the second type of dianhydride monomer is between 0.10 and 0.177, which is particularly useful for manufacturing. An aromatic copolymerized polyimide film is obtained, and the PI film of the copolymer improves the modulus of elasticity and dimensional stability.

The polyimine films obtained in Examples 1 to 5 and the comparative examples were applied to a coverlay, and a punching test was performed using a punching machine. The test results are shown in Table 2, and the power was turned on after the equipment inspection. Perform the adjustment of the height of the die or steel mold and the material test and fine-tune the stroke to confirm the stroke condition; then start the die-cutting. The data of the problems such as burrs and tear film after punching results are shown in Table 2. Wherein "X" indicates that the ease of use in operation is not satisfactory; "△" indicates that the ease of use in operation is barely applicable; "○" indicates that the ease of use in operation is ideal.

The following table shows the dimensional stability of the polyimide film (according to IPC-TM650 2.2.4C test method)

10, 20. . . Cover film

11, 21. . . Polyimine film

12, 22. . . Follower

Figure 1 is a cover film produced in Examples 1 to 5 of the present invention;

Figure 2 is a cover film produced in the comparative example.

10. . . Cover film

11. . . Polyimine film

12. . . Follower

Claims (8)

A polyamidiene copolymer by copolymerization and cyclization of at least a first type of diamine monomer and a second type of diamine monomer and a first type of dianhydride monomer and a second type of dianhydride monomer Obtaining the reaction, wherein the first type of diamine single system is selected from the group consisting of a compound having a biphenyl structure, at least one of a group consisting of p-phenylenediamine, o-phenylenediamine and m-phenylenediamine; The diamine monomer has at least two structures in which a phenyl group and a chain rotatory atom of the phenyl group are bonded, and the first type of dianhydride single system is selected from the following formulas (3-1) to (3-2) At least one of the compounds shown, the second type of dianhydride single system having a compound of the following formula (4), wherein the total amount of the first type of diamine monomer and the second type of diamine monomer is The molar ratio of the first type of dianhydride monomer to the second type of dianhydride monomer is 1:1, wherein the molar ratio of the first type of diamine monomer to the second type of diamine monomer Between 20:80 and 30:70, and the molar ratio of the first type of dianhydride monomer and the second type of dianhydride monomer is between 10:90 and 20:80: Wherein the compound having a biphenyl structure is selected from at least one of the compounds represented by the following formulas (1-1) to (1-7): The polyimine copolymer according to claim 1, wherein the chain rotates an atomic carbon atom or an oxygen atom. The polyamidene copolymer according to claim 1, wherein the second type of diamine single system is at least one selected from the group consisting of the compounds represented by the following formulas (2-1) to (2-7); By: A method for preparing a polyamidene copolymer, comprising: at least a first type of diamine monomer and a second type of diamine monomer, and a first type of dianhydride monomer and a second type of dianhydride in the presence of a polar solvent The monomer is subjected to a copolymerization reaction to obtain a polyaminic acid solution, wherein the first type of diamine single system is selected from the group consisting of a compound having a biphenyl structure, p-phenylenediamine, o-phenylenediamine, and m-phenylenediamine. Forming at least one of the group; the second type of diamine monomer has at least two structures in which a phenyl group and a chain rotatory atom of the phenyl group are bonded, and the first type of dianhydride single system is selected from the following At least one of the compounds of the formula (3-1) to the formula (3-2), the second type of dianhydride single system having a compound of the following formula (4), and the first type of diamine monomer and the first The molar ratio of the diamine monomer of the second type is between 0.25 and 0.34, the molar ratio of the first dianhydride monomer and the second dianhydride monomer is between 0.10 and 0.177; and the polyamic acid is cyclized. To obtain the polyamidiene copolymer Wherein the compound having a biphenyl structure is selected from at least one of the compounds represented by the following formulas (1-1) to (1-7): The method for producing a polyamidene copolymer according to claim 4, wherein the chain rotates an atomic carbon atom or an oxygen atom. The method for producing a polyamidene copolymer according to claim 4, wherein the second type of diamine single system is selected from the compounds of the following formulas (2-1) to (2-7); At least one: A cover film comprising: a polyimide film having a thickness of 10 to 50 μm, having a polyamidene copolymer according to any one of claims 1 to 3; An adhesive layer having a thickness of 15 to 75 μm is formed on the polyimide film, and the thickness of the cover film ranges from 25 to 125 μm. The cover film according to claim 7, wherein the material of the adhesive layer is selected from the group consisting of epoxy resin, acrylic resin, urethane resin, ruthenium rubber resin. One or more resins of polyparaxylene resin, bismaleimide resin and polyimine resin.