CN101798463B - High-performance polyimide film and preparation method thereof - Google Patents
High-performance polyimide film and preparation method thereof Download PDFInfo
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- CN101798463B CN101798463B CN 201010133049 CN201010133049A CN101798463B CN 101798463 B CN101798463 B CN 101798463B CN 201010133049 CN201010133049 CN 201010133049 CN 201010133049 A CN201010133049 A CN 201010133049A CN 101798463 B CN101798463 B CN 101798463B
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Abstract
The invention provides a polyimide film. Dianhydride reacts with diamine in solvent to prepare polyimide solution, and the polyimide solution is subjected to high temperature cyclodehydration to prepare the polyimide film, wherein the dianhydride and the diamine are in the molar ratio of 1 to 1; the polyimide solution contains an component A and a component B: in the solvent, the component A is polymerized from 3,3',4,4'-biphenyltetracarboxylic anhydride and p-phenylenediamine or from the 3,3',4,4'-biphenyltetracarboxylic anhydride, the p-phenylenediamine and 4,4'-bisaminophenoxyphenyl, the component B is polymerized from pyromellitic dianhydride and 4,4'-bisaminophenoxyphenyl or from the pyromellitic dianhydride, the 4,4'-bisaminophenoxyphenyl and the p-phenylenediamine; and the component A is not less than 20 percent of the total weight of the components A and B. The invention also provides a method for preparing the polyimide film. The polyimide film has the advantages of excellent thermal stability, low thermal shrinkage, low water absorption, excellent alkali resistance and hydrolyzing performance, high tensile strength and strong toughness.
Description
Technical field
The present invention relates to the technical field of polyimide film, particularly a kind of polyimide film and preparation method thereof, polyimide film of the present invention is applicable to the basement membrane of flex circuit application FPC and the basement membrane of TAB band.
Background technology
Polyimide is the aromatic heterocycle polymer compound that molecular structure contains the imide chain link, can be divided into equal benzene type PI, solubility Pi, polyamide-imide (PAI) and polyimide (PEI) four classes.
Polyimide is mainly synthetic by binary acid anhydride and diamine, and raw material sources are wide, synthesize also to be easier to.Dianhydride, diamines are various in style, and different combinations just can obtain the polyimide of different performance.By selecting monomer can make the film of various performances, be widely used in the basement membrane of FPC circuit card and TAB circuit card.
Polyimide can be by dianhydride and diamines at polar solvent, as dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAC), carry out low-temperature polycondensation earlier in N-Methyl pyrrolidone (NMP) or the THE/ methanol mixed solvent, obtain soluble polyamic acid, be dehydrated into ring about film forming or spinning post-heating to 300 ℃ and change polyimide into; Also can in polyamic acid, add acetic anhydride and tertiary amine catalyst, carry out the chemical dehydration cyclisation, obtain polyimide solution and powder.Diamines and dianhydride can also be at high boiling solvents, and as adding thermal polycondensation in the phenol solvent, a step obtains polyimide.In addition, can also obtain polyimide by dibasic ester and the diamine reaction of tetraprotic acid; Also can change poly-different imide earlier into by polyamic acid, and then be converted into polyimide.These methods all are that processing brings convenience, and the former is called the PMR method, can obtain low viscosity, height and measure solution admittedly, is adding the window that has man-hour one to have low melt viscosity, is specially adapted to the manufacturing of matrix material; The latter has then increased solvability, does not emit low molecular compound in the process that transforms.
The process of general synthesis of polyimides does not produce inorganic salt, for the preparation particularly advantageous of insulating material.
Basic employing single dianhydride/single diamines polymerization at present prepares polyimide film, because the each have their own characteristic of each monomer, so the product that makes after the copolymerization also has limitation.As: pyromellitic acid anhydride and 4, the polyimide film that makes after the copolymerization of 4 '-diaminodiphenyl oxide has excellent in flexibility, but poor heat stability; 3,3 ', 4, the polyimide film that makes after 4 '-xenyl tetracarboxylic acid dianhydride and the Ursol D polymerization has thermostability preferably, but the flexibility deficiency.
Summary of the invention
Technical problem to be solved by this invention is that the polyimide film that a kind of water-intake rate is low, the alkali resistance hydrolysis is good, percent thermal shrinkage is low, tensile strength is high will be provided, and preparation method thereof.
In order to solve above technical problem, the invention provides a kind of polyimide film, reacted in solvent by dianhydride and diamines and make polyamic acid solution, make polyimide film through the high temperature cyclodehydration, the mol ratio of dianhydride and diamines is 1:1; Polyamic acid solution comprises A component and B component,
Described A component: in solvent, by 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D copolymerization make, perhaps by 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D and 4, the copolymerization of 4 '-diaminodiphenyl oxide makes;
Described B component: in solvent, by pyromellitic acid anhydride and 4, the copolymerization of 4 '-diaminodiphenyl oxide makes, and perhaps, by pyromellitic acid anhydride and 4,4 '-diaminodiphenyl oxide and Ursol D copolymerization make;
Wherein, the A component is no less than 20% of A, B component gross weight.
Polyamic acid solution of the present invention also comprises antioxidant, this antioxidant is triphenyl phosphite or Triphenyl phosphate (TPP), its consumption is 0.01～0.4% of amount of solid by weight, wherein consumption be by weight amount of solid can be 0.01,0.08,0.18,0.28 or 0.4%.
Described solvent is N, dinethylformamide, or be N,N-dimethylacetamide, or be N-Methyl pyrrolidone, or aforesaid mixed solvent.
A kind of preparation method of polyimide film, this method comprises following step:
⑴ the preparation of A component: 70
0C is following with 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D or with Ursol D and 4, the copolymerization in solvent of 4 '-diaminodiphenyl oxide makes; Wherein, total monomer concentration is 5～35%(weight), total monomer concentration can for 5,20 or 35%(weight), reacted 4～30 hours, as 4,10,12,14,16,20 or 30 hours, the weight-average molecular weight of prepared polyamic acid was 3 * 10
4～1 * 10
5
⑵ the preparation of B component: 70
0C is following with pyromellitic acid anhydride and 4,4 '-diaminodiphenyl oxide or with 4, the copolymerization in solvent of 4 '-diaminodiphenyl oxide and Ursol D makes; Wherein total monomer concentration is 5～35%(weight), total monomer concentration can for 5,20 or 35%(weight), reacted 4～30 hours, as 4,10,12,13,14,16,20 or 30 hours, the weight-average molecular weight of prepared polyamic acid was 3 * 10
4～1 * 10
5
⑶ 70
0C is following, and wherein, the A component is no less than 20% of A, B component gross weight with A component and B component blend, and blended under agitation 2～20 hours as 2,6,10 or 20 hours, namely obtains by the compound uniform polyamic acid solution of hard and soft molecule;
⑷ the polyamic acid solution that step ⑶ obtains is 70
0C is following to be filtered, and vacuumizes froth breaking and is no less than 4 hours;
⑸ predrying film processed: polyamic acid solution is sent into hydrostomia mouth hydrostomia on steel band, with 80～200 with pressure
0C is as 80,150 or 200
0The C warm air drying is made the polyamic acid salivation film of quantity of solvent 20～40%;
⑹ imidization is finished in high temperature cyclodehydration, 80～200
0C is as 80,180,280,380 or 450
0Stretching under the C, take off residual solvent and carry out cyclodehydration, finish imidization, cuts edge in the cooling back, and high-performance polyimide film is made in rolling.
Superior effect of the present invention is: polyimide film of the present invention, and shrinking percentage is low, and thermal stability is good, and water-intake rate is low, and the alkali resistance hydrolysis property is good, tensile strength height, good toughness.
Embodiment
Below the invention will be further described with specific embodiment.
Embodiment 1:
A kind of polyimide film is reacted in solvent by dianhydride and diamines and to make polyamic acid solution, makes polyimide film through the high temperature cyclodehydration, and the mol ratio of dianhydride and diamines is 1:1; Polyamic acid solution comprises A component and B component, wherein:
⑴ the preparation of A component: 17
0With 3,3 ', 4 of 1mol, the Ursol D of 4 '-xenyl tetracarboxylic acid dianhydride and 1mol carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 12 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑵ the preparation of B component: 17
0With 4 of the Ursol D of the pyromellitic acid anhydride of 1mol and 0.25mol and 0.75mol, 4 '-diaminodiphenyl oxide carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 13 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑶ 20
0C carries out blend, 40～680 rev/mins of rotating speeds, blend 6 hours, temperature＜55 with A component and B component by weight 9:1
0C obtains the polyamic acid solution that mixes;
⑷ the polyamic acid solution that step ⑶ obtains at room temperature filters, and vacuumizes froth breaking＞4 hour; With pressure it is sent into hydrostomia mouth hydrostomia on steel band, with 80～200 then
0The C warm air drying becomes the polyamic acid salivation film; Send into the imines stove after peeling off, in 80～450
0Stretch under the C, take off residual solvent and carry out the high temperature cyclodehydration, finish imidization, the side cut rolling of cooling back namely obtains the polyimide film of good thermal stability.The percent thermal shrinkage of this polyimide film is 0.062%, and water-intake rate is 1.5%.
Embodiment 2:
A kind of polyimide film is reacted in solvent by dianhydride and diamines and to make polyamic acid solution, makes polyimide film through the high temperature cyclodehydration, and the mol ratio of dianhydride and diamines is 1:1; Polyamic acid solution comprises A component and B component, wherein:
⑴ the preparation of A component: 25
0With 3,3 ', 4 of 1mol, the Ursol D of 4 '-xenyl tetracarboxylic acid dianhydride and 1mol carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 12 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑵ the preparation of B component: 25
0With 4 of the pyromellitic acid anhydride of 1mol and 1mol, 4 '-diaminodiphenyl oxide carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 12 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑶ 25
0C is following to carry out blend, 40～680 rev/mins of rotating speeds, blend 6 hours, temperature＜55 with A component and B component by weight 1:1
0C obtains the polyamic acid solution that mixes;
⑷ the polyamic acid solution that step ⑶ obtains at room temperature filters, and vacuumizes froth breaking＞4 hour; With pressure it is sent into hydrostomia mouth hydrostomia on steel band, with 80～200 then
0The C warm air drying becomes the polyamic acid salivation film; Send into the imines stove after peeling off, in 80～450
0Stretch under the C, take off residual solvent and carry out the high temperature cyclodehydration, finish imidization, the side cut rolling of cooling back namely obtains the polyimide film of good thermal stability.The percent thermal shrinkage of this polyimide film is 0.16%, and water-intake rate is 2.1%.
Embodiment 3:
A kind of polyimide film is reacted in solvent by dianhydride and diamines and to make polyamic acid solution, makes polyimide film through the high temperature cyclodehydration, and the mol ratio of dianhydride and diamines is 1:1; Polyamic acid solution comprises A component and B component, wherein:
⑴ the preparation of A component: 14
0With 3,3 ', 4 of 1mol, the Ursol D of 4 '-xenyl tetracarboxylic acid dianhydride and 1mol carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 14 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑵ the preparation of B component: 14
0With 4 of the Ursol D of the pyromellitic acid anhydride of 1mol and 0.25mol and 0.75mol, 4 '-diaminodiphenyl oxide carries out copolymerization and makes in the N,N-dimethylacetamide solvent under the C;
Temperature of reaction＜55
0C, N,N-dimethylacetamide content are 80% of whole system weight, and the consumption of triphenyl phosphite is 0.08% of amount of solid by weight, react 10 hours; The weight-average molecular weight of the polyamic acid that obtains is 3 * 10
4～1 * 10
5
⑶ 17
0C is following to carry out blend with A component and B component by 28% and 72% weight ratio, 40～680 rev/mins of rotating speeds, blend 6 hours, temperature＜55
0C obtains by the compound uniform polyamic acid solution of hard and soft molecule;
⑷ the polyamic acid solution that step ⑶ obtains at room temperature filters, and vacuumizes froth breaking＞4 hour; With pressure it is sent into hydrostomia mouth hydrostomia on steel band, with 80～200 then
0The C warm air drying becomes the polyamic acid salivation film; Send into the imines stove after peeling off, in 80～450
0Stretch under the C, take off residual solvent and carry out the high temperature cyclodehydration, finish imidization, the side cut rolling of cooling back namely obtains the polyimide film of good thermal stability.The percent thermal shrinkage of this polyimide film is 0.21%, and water-intake rate is 2.51%.
Following table is that the Upilex-s type performance of the polyimide film of embodiments of the invention 1 and embodiment 3 preparations and the equal benzene type of standard GB/T13542.6-2006 PI-, Ube Industries Ltd. compares:
As shown in the table:
The Upilex-s product performance of the performance of present embodiment 1 and Ube Industries Ltd. are very approaching, its feature shows as: water-intake rate is low, the alkali resistance hydrolysis is good, percent thermal shrinkage is low, Heat stability is good, tensile strength height and good toughness, is particularly suitable for doing the material of high performance microelectronic.
The performance of present embodiment 3 is better than the equal benzene type of GB PI standard, and its mark sheet is fit to do conventional FPC basement membrane now in low, the good thermal stability of water-intake rate.
Claims (4)
1. polyimide film is reacted in solvent by dianhydride and diamines and to make polyamic acid solution, makes polyimide film through the high temperature cyclodehydration, and the mol ratio of dianhydride and diamines is 1:1; It is characterized in that: polyamic acid solution comprises A component and B component,
Described A component: in solvent, by 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D copolymerization make, perhaps by 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D and 4, the copolymerization of 4 '-diaminodiphenyl oxide makes; The wherein preparation of A component: 70
0C is following with 3,3 ', 4,4 '-xenyl tetracarboxylic acid dianhydride and Ursol D or with Ursol D and 4, the copolymerization in solvent of 4 '-diaminodiphenyl oxide makes; Wherein, total monomer concentration is 5～35%(weight), to react 4～30 hours, the weight-average molecular weight of prepared polyamic acid is 3 * 10
4～1 * 10
5
Described B component: in solvent, by pyromellitic acid anhydride and 4, the copolymerization of 4 '-diaminodiphenyl oxide makes, and perhaps by pyromellitic acid anhydride and 4,4 '-diaminodiphenyl oxide and Ursol D copolymerization make; The wherein preparation of B component: 70
0C is following with pyromellitic acid anhydride and 4,4 '-diaminodiphenyl oxide or with 4, the copolymerization in solvent of 4 '-diaminodiphenyl oxide and Ursol D makes; Wherein total monomer concentration is 5～35%(weight), to react 4～30 hours, prepared polyamic acid weight-average molecular weight is 3 * 10
4～1 * 10
5
With A component and B component 70
0Described polyimide film is made in the following blend of C, and wherein the A component is no less than 20% of A, B component gross weight.
2. by the described polyimide film of claim 1, it is characterized in that: also comprise antioxidant, this antioxidant is triphenyl phosphite or Triphenyl phosphate (TPP), and its consumption is 0.01～0.4% of amount of solid by weight.
3. by the described polyimide film of claim 1, it is characterized in that: described solvent is N, dinethylformamide, or be N,N-dimethylacetamide, or be N-Methyl pyrrolidone, or aforesaid mixed solvent.
4. by the preparation method of one of claim 1 to 3 described polyimide film, it is characterized in that this method comprises following step:
⑴ described A component and B component are 70
0The following blending and stirring of C 2～20 hours namely obtains by the compound uniform polyamic acid solution of hard and soft molecule;
⑵ the polyamic acid solution of above-mentioned acquisition is 70
0C is following to be filtered, and vacuumizes froth breaking and is no less than 4 hours;
⑶ predrying film processed: polyamic acid solution is sent into hydrostomia mouth hydrostomia on steel band, with 80～200 with pressure
0The C warm air drying is made the polyamic acid salivation film of quantity of solvent 20～40%;
⑷ imidization is finished in high temperature cyclodehydration, 80～450
0Stretching under the C, take off residual solvent and carry out cyclodehydration, finish imidization, cuts edge in the cooling back, and high-performance polyimide film is made in rolling.
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| CN101798463B true CN101798463B (en) | 2013-07-17 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102824857A (en) * | 2011-06-14 | 2012-12-19 | 北京航空航天大学 | Preparation method of gas separation carbon membrane |
| CN102732032B (en) * | 2012-07-13 | 2014-07-23 | 周天兴 | Corona-resistant polyimide film and process for preparing same |
| CN104211973B (en) * | 2014-04-01 | 2015-06-17 | 无锡顺铉新材料有限公司 | Polyimide film |
| CN106380843A (en) * | 2016-10-08 | 2017-02-08 | 扬中市橡胶塑料厂有限公司 | High-temperature-resistant polyimide composite material |
| KR102362385B1 (en) * | 2019-11-13 | 2022-02-15 | 피아이첨단소재 주식회사 | High Elastic and High Heat Resistant Polyimide Film and Manufacturing Method Thereof |
| CN111875797B (en) * | 2020-07-27 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Polyimide diaphragm and preparation method thereof |
| CN112552514B (en) * | 2020-12-10 | 2023-05-16 | 武汉柔显科技股份有限公司 | Polyimide precursor, polyimide film and preparation method of polyimide film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166308A (en) * | 1990-04-30 | 1992-11-24 | E. I. Du Pont De Nemours And Company | Copolyimide film with improved properties |
| CN101173096A (en) * | 2007-11-23 | 2008-05-07 | 上海固创化工新材料有限公司 | Method for producing polyimide seamless tubular shaped film |
-
2010
- 2010-03-26 CN CN 201010133049 patent/CN101798463B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166308A (en) * | 1990-04-30 | 1992-11-24 | E. I. Du Pont De Nemours And Company | Copolyimide film with improved properties |
| CN101173096A (en) * | 2007-11-23 | 2008-05-07 | 上海固创化工新材料有限公司 | Method for producing polyimide seamless tubular shaped film |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平5-78503A 1993.03.30 |
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