TWI674284B - Polyimine film manufacturing method (1) - Google Patents

Abstract

The invention is a method for manufacturing a polyimide film, which includes providing a polyamidic acid copolymer, which must contain at least a semi-aromatic polyamidic acid, the semi-aromatic polyamidic acid is passed through 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and aromatic ring diamine; the polyamidoacid copolymer is added with a dehydrating agent, an ortho-position-free pyridine catalyst and an acid; and The polyfluorinated acid copolymer is subjected to fluorinated imidization by a chemical cyclization method to form a polyfluorinated imine film.

Description

Method for manufacturing polyimide film (1)

The present invention relates to a method for manufacturing a polyfluoreneimide film, and particularly to a method that has better mechanical characteristics and is more convenient to manufacture.

The production of polyimide film is obtained by performing polyimide reaction of the polyimide precursor of polyimide, and the methods of the polyimide reaction are divided into chemical cyclization and thermal cyclization; thermal Cyclization is the imidization of polyfluorene precursors at high temperatures, while chemical cyclization is the use of dehydrating agents and catalysts to allow the polyamidate precursors to achieve partial imidization at lower temperatures After that, it is baked at a high temperature to make the amidine imidization more complete. Thermal cyclization requires more baking time in production, and under long-term baking, it will also cause the mechanical properties of the polyimide film to decrease and the color to yellow. The chemical cyclization method has a fast production time and can maintain good mechanical properties, so it is a better choice to use the chemical cyclization method in mass production.

Polyimide film containing 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) component can have good optical characteristics and thermal stability. Therefore, it is often used as a liquid crystal alignment treatment agent for liquid crystal elements and semiconductor elements. , Or used in protective films, insulating films, and optical waveguide materials for optical communications. Patent No. US5053480A mentions the use of a reaction between CBDA and diamine to form a polyfluorinated acid, which can be cyclized by a thermal closed-loop method to produce a polyfluoreneimide film with good optical penetration and heat resistance. Patent No. US6489431B1 uses CBDA and then a diamine with hexafluoropropylene, which can be cyclized by a thermal closed-loop method to produce a polyfluorene imine film with better optical properties. The above articles all use the thermal closed-loop method for film formation, but because the thermal closed-loop method takes a lot of baking time, and the mechanical properties of the resulting polyimide film are worse than the chemical cyclization film-forming method, so Many research scholars have attempted to form films by chemical cyclization, but Hasegawa High Perform. Polym. 2001, 13, S93-S106 mentions that the use of a poly (amino acid) with a CBDA component through chemical cyclization may cause solubility problems and cause precipitation. So far, in the field of chemical cyclization film formation technology, no product based on such dianhydride has been found.

Therefore, the present invention provides a method for making a polyimide film having a 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) component using a chemical cyclization method, and the method produced by the method Polyimide film can have better mechanical properties.

The present invention is a method for manufacturing polyimide film, which includes: providing a polyamidic acid copolymer, which must contain at least a semi-aromatic polyamidic acid, the semi-aromatic polyamidic acid is , 2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) and aromatic cyclic diamine are obtained by adding the polyamidic acid copolymer to a dehydrating agent, an ortho-position-free pyridine catalyst and an acid, to The polyfluorinated acid copolymer is subjected to a fluorinated imidization reaction by a chemical cyclization method to prepare a polyfluorinated imine film.

FIG. 1 is a flowchart of a method for manufacturing a polyfluoreneimide film according to the present invention.

Please refer to FIG. 1. The present invention is a method for manufacturing a polyimide film, which includes: providing a polyamidic acid copolymer (S1), which must contain at least a semi-aromatic polyamidic acid, the semi-aromatic Group polyamino acids are obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) with aromatic ring diamines; the polyamino acid copolymer is added with a dehydrating agent and has no ortho substituents The pyridine-based catalyst and the acid (S2) are used to perform a polyimide reaction (S3) by a polyamidate copolymer by a chemical cyclization method to form a polyamidoimide film.

The semi-aromatic polyamidic acid is obtained by reacting 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) with an aromatic ring diamine. The aromatic ring diamine may be p-phenylenediamine ( PDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis [4- (4-aminophenoxyphenyl)] propane (BAPP), 2,2'-bis (tris Fluoromethyl) diaminobiphenyl (TFMB), 3,5-diaminobenzoic acid (35DABA), 4,4'-diaminobenzidine aniline (44DABA), 5 (6) -amino-1- (4 -Aminophenyl) -1,3,3-trimethylindane (TMDA), 4,4'-bis (4-aminophenoxy) diphenylhydrazone (BAPS), 4,4'-bis (4 -Aminophenoxy) biphenyl (BAPB), 1,4-bis (4-aminophenoxy) benzene (TPEQ), 2,2'-bis (trifluoromethyl) -4,4'-diamino Phenyl ether (6FODA), 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane (HFBAPP), 9,9- Bis (4-aminophenyl) fluorene (BAFL), 2- (4-aminophenyl) -5-aminobenzoxazole (5BPOA), m-phenylenediamine ( m PDA), 4,4'-diamino Diphenylhydrazone (44DDS), 2,2-bis (4-aminophenyl) hexafluoropropane (Bis-A-AF), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane ( 6FAP), 4,4 '-[1,4-phenylbis (oxy)] bis [3- (trifluoromethyl) aniline] (FAPB). The composition of the polyamidic acid copolymer may be a semi-aromatic polyamidic acid and an aromatic polyamidic acid. The aromatic polyamino acid is obtained by reacting an aromatic diamine with an aromatic dianhydride.

The polyamino acid copolymer may further include an aromatic polyamino acid, which is obtained by reacting an aromatic diamine with an aromatic dianhydride.

This aromatic diamine contains 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFMB), 2,2'-bis [4- (4-aminophenoxyphenyl)] propane (BAPP ), 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane (HFBAPP), 5 (6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane (TMDA), p-phenylenediamine (PDA), 4,4'-bis (4-aminophenoxy) biphenyl (BAPB) 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA), 4,4'-bis (4-aminophenoxy) diphenylhydrazone (BAPS), 9 , 9-bis (4-aminophenyl) fluorene (BAFL), 4,4'-diaminodiphenylhydrazone (44DDS), 4,4'-diaminodiphenyl ether (ODA), 4,4'-di Aminophenidamine (44DABA), 2,2-bis (4-aminophenyl) hexafluoropropane (Bis-A-AF), m-phenylenediamine (mPDA), 2,2-bis (3-amino- 4-hydroxyphenyl) hexafluoropropane (6FAP), 3,5-diaminobenzoic acid (35DABA), 2- (4-aminophenyl) -5-aminobenzoxazole (5BPOA), 1,4- Bis (4-aminophenoxy) benzene (TPEQ), 4,4 '-[1,4-phenylbis (oxy)] bis [3- (trifluoromethyl) aniline] (FAPB). The aromatic dianhydride contains 1,2,4,5-benzenetetracarboxylic anhydride (PMDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxygen Diphthalic anhydride (ODPA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3,4,4-diphenylphosphonium tetracarboxylic dianhydride ( (DSDA), 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride (α-BPDA), 4,4-hexafluoroisopropylphthalic anhydride (6FDA), 4,4'-(4 , 4'-Isopropyldiphenoxy) diphthalic anhydride (BPADA).

The polyfluorenic acid copolymer uses a chemical cyclization method to perform amidation reaction, adding a dehydrating agent, an ortho-substituted pyridine catalyst and an acid, of which ortho-substituted pyridine The catalysts can be pyridine, 3-methylpyridine, 4-methylpyridine, isophenylpyridine, and phenylpyridine. The acid is an organic acid and may be acetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid, terephthalic acid, terephthalic acid, or phthalic acid. Wherein, if the number of moles added to the acid needs to be greater than or equal to the number of moles added to the pyridine catalyst having no ortho substituents.

Examples

<Detection method>

Chroma b *: Measured according to ASTM E313 using Nippon Denshoku company model NE-4000.

<Example 1>

Manufacture of polyamic acid copolymer

53.645 grams of 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.1675 moles, 0.75 mole ratio of total diamine moles) was added to 412.5 grams of N, N-dimethylethyl Ammonium amine (DMAc), after it is completely dissolved, add 26.282 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, 0.134 moles, accounting for 60% of the total anhydride moles), stir the reaction for six hours and The temperature was continuously maintained at 25 ° C to form a semi-aromatic polyamidic acid solution. After six hours, add the above-mentioned semi-aromatic polyamidic acid solution to 17.882 g of 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.0558 mole) and stir until completely dissolved, and then add 38.698 g 4,4-hexafluoroisopropyl phthalic anhydride (6FDA, 0.1074 mol), stirred for a certain period of time to dissolve and react, and the temperature of the solution was maintained at 25 ° C, and finally a polymer with a solid content of 25% was obtained. Amidine copolymer.

Polyimide film production

Take out 54.4 g of the polyamino acid copolymer and dilute the solid content to 17% using N, N-dimethylacetamide (DMAc), and then add 8 ml of acetic acid (0.14 mol) sequentially. , 4.3 ml of 3-methylpyridine (0.044 mol) and 12.5 ml of acetic anhydride, the solution was applied to a glass plate after uniform stirring, and then applied with a doctor blade with a gap of 900 μm. The coated samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

The polyimide film prepared as described above is a polyimide film having a lower chroma b * of 1.5.

<Example 2>

Manufacture of polyamic acid copolymer

Add 18.606 grams of 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFMB, 0.0581 moles) and add 90 grams of N, N-dimethylacetamide (DMAc). 11.394 grams of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, 0.0581 mole) was added, and the temperature was controlled to 25 ° C during the addition. The reaction was stirred for twenty-four hours and the temperature was continuously maintained at 25 ° C. Polyamine solution with a solids content of 25%.

Production of polyimide film

Take out 20.2 grams of the above polyamic acid copolymer, and use N, N-dimethylacetamide (DMAc) to dilute the solid content to 15.8%, and then add 1.2 grams (0.02 moles) of acetic acid and 0.9 g of 3-methylpyridine (0.0097 mol), add 2.0 g of acetic anhydride after homogeneous stirring, apply the solution to a glass plate, and then apply with a doctor blade with a gap of 400 μm. The coated samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

The polyimide produced as described above can form a film and has a lower chroma b * of 0.9.

<Example 3>

Preparation of poly (amino acid) copolymer

18.948 grams of 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA, 0.0564 mole) was added to 90 grams of N, N-dimethylacetamide ( DMAc), after all dissolution, add 11.052 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA, 0.0564 moles), control the temperature to 25 ° C during the addition, stir the reaction for 24 hours and the temperature continues The temperature was maintained at 25 ° C., and finally a polyamino acid copolymer having a solid content of 25% was obtained.

Production of polyimide film

Take out 20.2 g of the polyamino acid copolymer, and dilute the solid content to 15.8% using N, N-dimethylacetamide (DMAc), and then add 1.1 g of acetic acid (0.018 moles) and 0.9 g of 3-methylpyridine (0.0097 mol), add 1.9 g of acetic anhydride after homogeneous stirring, apply the solution to a glass plate, and then apply with a doctor blade with a gap of 600 μm. Finish coating The finished samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

The transparent polyfluorene imide produced above can form a film and has a lower chroma b * of 1.0.

<Comparative example 1>

Preparation of Polyamic Acid Copolymer

The manufacturing method is the same as in Example 1.

Production of polyimide film

Take out 54.4 grams of the copolymerized polyamidic acid solution, and use N, N-dimethylacetamide (DMAc) to dilute the solid content to 17%. After applying the solution to the glass plate, use a doctor blade with a gap of 900 μm Perform coating. The coated samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

The transparent polyfluorene imide produced above can form a film and has a higher chroma b * of 3.6.

<Comparative example 2>

Preparation of Polyamic Acid Copolymer

The manufacturing method is the same as in Example 2.

Production of polyimide film

20.2 g was taken out of the above polyamic acid copolymer, and the solid content was diluted to 15.8% using N, N-dimethylacetamide (DMAc). After applying the solution to a glass plate, a doctor blade with a gap of 400 μm was used. Perform coating. The coated samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

The above-mentioned production method cannot form a film.

<Comparative example 3>

Preparation of poly (amino acid) copolymer

The manufacturing method is the same as in Example 3.

Production of polyimide film

54.4 g was taken out of the above polyamic acid copolymer, and N, N-dimethylacetamide (DMAc) was used to dilute the solid content to 17%, and then 4.3 ml of 3-methylpyridine and 12.5 ml of acetic anhydride quickly gels after stirring, so it cannot form a film.

<Comparative Example 4>

Preparation of poly (amino acid) copolymer

The manufacturing method is the same as in Example 3.

Production of polyimide film

20.2 g was taken out of the above polyamic acid copolymer, and the solid content was diluted to 15.8% using N, N-dimethylacetamide (DMAc), and the solution was applied to a glass plate using a doctor blade with a gap of 600 μm Perform coating. The coated samples were placed in an oven at 50 ° C for 20 minutes, and then slowly heated to 170 ° C for 20 minutes, and then the oven was heated to 260 ° C for 20 minutes as the final treatment.

Polyimide film with chroma b * of 3.8 can be made.

X: Film formation is impossible; ○: Film formation is possible

The content of the specific embodiments described above is used to describe the present invention in detail. However, these embodiments are only used for illustration and are not intended to limit the present invention. Those skilled in the art will understand that the present invention is directed to the scope of the present invention without departing from the scope defined by the appended claims. Various changes or modifications made are part of the present invention.

Claims (6)

A method for manufacturing a polyimide film, comprising: providing a polyamidic acid copolymer, which must include at least a semi-aromatic polyamidic acid, the semi-aromatic polyamidic acid being passed through 1,2,3 , 4-Cyclobutanetetracarboxylic dianhydride (CBDA) and aromatic cyclic diamine; the polyacrylic acid copolymer is added with a dehydrating agent, ortho-substituted pyridine catalyst and acid; and The amino acid copolymer is subjected to a fluorene imidization reaction by a chemical cyclization method to form a polyfluorene film. According to the method for manufacturing a polyfluorene imine film described in item 1 of the scope of patent application, the aromatic ring diamine may be p-phenylenediamine (PDA), 4,4'-diaminodiphenyl ether (ODA), 2,2'-bis [4- (4-aminophenoxyphenyl)] propane (BAPP), 2,2'-bis (trifluoromethyl) diaminobiphenyl (TFMB), 3,5-bis Aminobenzoic acid (35DABA), 4,4'-diaminobenzidine (44DABA), 5 (6) -amino-1- (4-aminophenyl) -1,3,3-trimethylindane (TMDA), 4,4'-bis (4-aminophenoxy) diphenylhydrazone (BAPS), 4,4'-bis (4-aminophenoxy) biphenyl (BAPB), 1,4-bis (4-aminophenoxy) benzene (TPEQ), 2,2'-bis (trifluoromethyl) -4,4'-diaminophenyl ether (6FODA), 2,2-bis [4- (4 -Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane (HFBAPP), 9,9-bis (4-aminophenyl) fluorene (BAFL), 2- (4 -Aminophenyl) -5-aminobenzoxazole (5BPOA), m-phenylenediamine (mPDA), 4,4'-diaminodiphenylhydrazone (44DDS), 2,2-bis (4-aminophenyl) ) Hexafluoropropane (Bis-A-AF), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), 4,4 '-[1,4-phenylbis (oxygen) )] Bis [3- (trifluoromethyl) aniline] (FAPB). The method for manufacturing a polyimide film according to item 1 of the scope of the patent application, wherein the polyamidic acid copolymer may further include an aromatic polyamidic acid, and the aromatic polyamidic acid is an aromatic Diamine and aromatic dianhydride. The method for manufacturing a polyfluorene imide film according to item 1 of the scope of patent application, wherein the ortho-position-free pyridine-based catalyst may be pyridine, 3-methylpyridine, 4-methylpyridine, or isophenylhydrazone Pyridine, phenylpyridine. The method for producing a polyimide film according to item 1 of the scope of the patent application, wherein the acid is an organic acid, and may be acetic acid, propionic acid, butyric acid, oxalic acid, benzoic acid, terephthalic acid, and phthalic acid. acid. According to the method for manufacturing a polyfluoreneimide film described in item 1 of the scope of the patent application, the number of moles added to the acid must be greater than or equal to the number of moles added to the ortho-position-free pyridine-based catalyst.