CN108117654B - Dimensionally stable polyimide film and preparation method thereof - Google Patents
Dimensionally stable polyimide film and preparation method thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The invention discloses a dimension stable polyimide film and a preparation method thereof. The preparation method comprises the following steps: 1) weighing aromatic diamine and aromatic dianhydride according to a proportion for later use; wherein: the aromatic diamine is composed of rigid aromatic diamine and ODA, wherein the rigid aromatic diamine accounts for 15-30% of the total molar amount of the aromatic diamine; the aromatic dianhydride is a combination of PMDA and BPDA, wherein the mole amount of the BPDA accounts for 0-40% of the total mole amount of the aromatic dianhydride; 2) putting rigid aromatic diamine and partial aromatic dianhydride into a polar aprotic solvent for reaction to obtain an ordered chain segment terminated by the rigid aromatic diamine; 3) adding ODA into the ordered chain segment, dissolving, adding the residual aromatic dianhydride for reaction to obtain an ordered copolymer polyamic acid resin solution induced by the ordered chain segment; 4) and (3) casting and thermal imidization are carried out on the obtained polyamic acid resin solution according to a conventional process to obtain the polyamic acid resin.
Description
Technical Field
The invention relates to a polyimide film, in particular to a dimension stable polyimide film and a preparation method thereof.
Background
With the rapid development of electronic products in the direction of thin, light, short and small, the market of flexible printed circuit boards is rapidly expanded, Polyimide (PI) films are used as important insulating base materials of flexible printed circuit boards, the demand is increased year by year, the requirement on dimensional stability is higher and higher, and the requirements are mainly reflected on the indexes of thermal expansion coefficient, elastic modulus, thermal shrinkage rate and water absorption rate, namely the thermal expansion coefficient of the PI films is required to be close to 18 ppm/DEG C of copper foil, the elastic modulus is 4.0-5.0 GPa, the thermal shrinkage rate is less than 0.05%, and the water absorption rate is less than 2.0%. At present, although China adopts a biaxial stretching process to prepare an electronic grade PI film, the obtained PI film has poor dimensional stability and cannot be used as a base material film for a high-end flexible copper-clad plate, so domestic flexible copper-clad plate manufacturers almost use imported products such as Japan and Korea.
Aiming at the current production situation of domestic high-end PI films, the development of the dimension stable polyimide film is concerned by domestic large enterprises, colleges and universities and research institutes. The invention patent with publication number CN 101358034A adopts PMDA, BPDA, ODA and PDA monomers to combine with each other to prepare three-component polyamide acid (PAA) resin, wherein the addition amount of PDA is more than or equal to 60 percent, the addition amount of BPDA is less than or equal to 10 percent, and then the three resins are blended to prepare the polyimide film with dimensional stability. The CTE of the film is 18 ppm/DEG C, the elastic modulus is 4.0GPa, the thermal shrinkage rate is 0.06%, the tensile strength is 300MPa, the elongation at break is 60%, the comprehensive performance is high, and the film is mainly applied to a Flexible Printed Circuit (FPC) to realize high performance of the FPC. As another patent of invention with publication No. CN 102558860A, besides adopting PMDA, BPDA, ODA and PDA monomers, benzimidazole diamine monomers are added, and a resin synthesis method of three-component copolymerization and re-blending is also adopted to obtain a PI film with CTE as low as 8 ppm/DEG C, elastic modulus of 6.8GPa and heat shrinkage rate of 0.01%. From the prior art of these patents, in order to improve the dimensional stability of the PI film, rigid structural monomers such as PMDA, BPDA, PDA, etc. are added, and the larger the amount of rigid monomer added, the higher the dimensional stability. However, research shows that when a PI film is prepared by a thermal imidization method, if the rigid main chain component is larger, the PAA film has more violent thermal degradation reaction at 150-200 ℃, the film making difficulty is larger, and even continuous production cannot be realized (the foundation and application of polyimide, compiled by Japan polyimide research institute, compiled by Shufu, Gentianli man, compiled in 2002, and compiled by P76, Hefefeng and Wu-faith text), so that continuous large-scale production of high-quality and size-stable polyimide films in China is restricted.
Disclosure of Invention
The invention aims to provide a polyimide film with stable size and a preparation method thereof. The method is simple and easy to operate, and the prepared polyimide film has a thermal expansion coefficient of less than or equal to 22 ppm/DEG C, an elastic modulus of more than or equal to 4.0GPa, a thermal shrinkage rate of less than or equal to 0.05 percent, a water absorption rate of less than 2.0 percent, a tensile strength of more than or equal to 200MPa and a breaking elongation of more than or equal to 50 percent.
The preparation method of the dimension stable polyimide film comprises the following steps:
1) weighing aromatic diamine and aromatic dianhydride according to a proportion for later use; wherein:
the aromatic diamine is composed of rigid aromatic diamine and 4,4 '-diaminodiphenyl ether (ODA), wherein the rigid aromatic diamine is one or the combination of more than two of 1, 4-diaminobenzene (PDA), 4' -Diaminobiphenyl (DBZ) and 2- (4-aminophenyl) -5-aminobenzoxazole (BZA), and accounts for 15-30% of the total molar amount of the aromatic diamine;
the aromatic dianhydride is a combination of pyromellitic dianhydride (PMDA) and 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride (BPDA), wherein the molar amount of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride accounts for 0-40% of the total molar amount of the aromatic dianhydride;
2) putting rigid aromatic diamine and partial aromatic dianhydride into a polar aprotic solvent for reaction to obtain an ordered chain segment terminated by the rigid aromatic diamine; wherein the molar ratio of the rigid aromatic diamine to the aromatic dianhydride is n: n-1, wherein n is 4-10;
3) adding 4, 4' -diaminodiphenyl ether into the ordered chain segment which is obtained in the step 2) and is terminated by the rigid aromatic diamine, adding the residual aromatic dianhydride for reaction after dissolving, and obtaining the ordered copolymerized polyamic acid resin solution induced by the ordered chain segment;
4) casting and thermal imidization are carried out on the polyamic acid resin solution obtained in the step 3) according to a conventional process to obtain the dimension stable type polyimide film.
In the step 1) of the preparation method, the molar ratio of the aromatic diamine to the aromatic dianhydride is the same as that in the prior art, and specifically is 0.9-1.1: 1, preferably 0.95-1.05: 1, more preferably 0.99 to 1.01: 1. in the step, the rigid aromatic diamine accounts for 20-30% of the total molar amount of the aromatic diamine, and the molar amount of the 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride accounts for 5-25% of the total molar amount of the aromatic dianhydride.
In steps 2) and 3) of the above preparation method, the reaction temperature and time are the same as those of the polycondensation reaction of the polyamic acid resin solution in the prior art, specifically, the reaction temperature may be 0 to 80 ℃, preferably 0 to 60 ℃, more preferably 0 to 50 ℃, and the total reaction time is usually 3 to 12 hours. When the aromatic dianhydride and the aromatic diamine are added to react, the addition in a batch manner is preferably adopted, so that the reaction can be more uniform and complete.
In the above preparation method, the polar aprotic solvent may be a conventional solvent in the prior art, and specifically may be one or a combination of any two or more selected from N, N-Dimethylacetamide (DMAC), N-Dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), N-diethylacetamide and N, N-diethylformamide. When the polar aprotic solvent is selected from the above-mentioned two or more kinds of combinations, the ratio therebetween may be any ratio. The amount of the polar aprotic solvent is the same as that in the prior art, and specifically, when the aromatic diamine, the aromatic dianhydride and the polar aprotic solvent react to form the polyamic acid resin solution, the solid content in the polyamic acid resin solution is controlled to be 10-30 w/w%, preferably 12-25 w/w%, and more preferably 15-21 w/w%.
The invention also comprises the dimension stable polyimide film prepared by the method.
Compared with the prior art, the invention is characterized in that:
1. firstly, synthesizing rigid short-chain segment molecules by using rigid aromatic diamine and rigid aromatic dianhydride, and then sequentially adding ODA and residual rigid aromatic dianhydride to prepare the regular copolymerized PAA resin; the subsequent ordered arrangement of molecular chain segments is induced by utilizing a local ordered structure formed by rigid short chain segment molecules, the generation of in-plane orientation is promoted, the inter-molecular chain stacking density is increased, the purposes of reducing the CTE (coefficient of thermal expansion) of the obtained film and improving the elastic modulus and the tensile strength are achieved, and good dimensional stability is reflected.
2. The molar quantity of the rigid aromatic diamine is reduced to be less than 30 percent of the total molar quantity of the diamine, the thermal degradation degree of a rigid chain segment at 150-200 ℃ in the thermal imidization preparation process can be reduced, the film making difficulty is effectively reduced, in addition, the preparation process does not need to be divided into 3 components for preparing PAA resin, and the preparation process is simple and easy to operate.
3. The film prepared by the method has the thermal expansion coefficient less than or equal to 22 ppm/DEG C, the elastic modulus more than or equal to 4.0GPa, the thermal shrinkage rate less than or equal to 0.05 percent, the water absorption rate less than 2.0 percent, the tensile strength more than or equal to 200MPa and the elongation at break more than or equal to 50 percent.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
15mol of BZA was added to 175kg of DMAc, and the mixture was stirred for 0.5 hour, and then 12.5mol of PMDA was added to react for 1 hour, and then 85mol of ODA was added to dissolve the mixture by stirring for 0.5 hour, and then 67.1mol of PMDA was added to react for 1 hour, and then 20mol of BPDA was added to react for 5 hours, thereby obtaining a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (160 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 420 ℃ to obtain the dimension stable PI film.
Example 2
To 175kg of DMAc was added 10mol of DBZ and 15mol of BZA, and the mixture was stirred for 0.5 hour, and then 12.5mol of PMDA and 8.3mol of BPDA were added to react for 1 hour, and then 75mol of ODA was added to dissolve it by stirring for 0.5 hour, and then 67.1mol of PMDA was added to react for 1 hour, and then 11.7mol of BPDA was added to react for 5 hours, thereby obtaining a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (162 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Example 3
To 136kg of DMAc were added 5mol of PDA, 10mol of DBZ and 15mol of BZA, and the mixture was stirred for 0.5 hour, then 16.7mol of PMDA and 8.3mol of BPDA were added, and the mixture was reacted for 1 hour, then 70mol of ODA was added, and the mixture was dissolved by stirring for 0.5 hour, then 62.9mol of PMDA was added, and the mixture was reacted for 1 hour, then 11.7mol of BPDA was added, and the reaction was carried out for 5 hours, whereby a polyamic acid resin solution was obtained. Defoaming polyamic acid resin, coating the resin on a steel belt by a scraper, heating (163 ℃) to remove a solvent to obtain a PAA film, and performing unidirectional stretching and thermal imidization at 450 ℃ to obtain a dimension stable PI film.
Example 4
Adding 25mol of BZA into 175kg of DMAc, stirring for 0.5h, adding 0.8mol of PMDA and 20mol of BPDA, reacting for 1h, adding 75mol of ODA, stirring to dissolve for 0.5h, adding 50mol of PMDA, reacting for 1h, finally adding 28.8mol of PMDA, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (168 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 470 ℃ to obtain the dimension stable PI film.
Example 5
30mol of BZA was added to 176kg of NMP, and stirred for 0.5 hour, 25mol of PMDA was added and reacted for 1 hour, 70mol of ODA was added and dissolved for 0.5 hour, 20mol of BPDA was added and reacted for 1 hour, and finally 54.6mol of PMDA was added and reacted for 5 hours to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (158 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 440 ℃ to obtain the dimension stable PI film.
Example 6
Adding 20mol of PDA into 166kg of DMAc and kg of NMP, stirring for 0.5h, adding 16.7mol of BPDA, reacting for 1h, adding 80mol of ODA, stirring to dissolve for 0.5h, adding 3.3mol of BPDA, reacting for 1h, adding 60mol of PMDA, reacting for 1h, adding 19.6mol of PMDA finally, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (161 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Example 7
Adding 20mol of PDA and 10mol of DBZ into 200kg of DMAc, stirring for 0.5h, adding 25mol of PMDA, reacting for 1h, adding 70mol of ODA, stirring for dissolving for 0.5h, adding 20mol of BPDA, reacting for 1h, adding 54.6mol of PMDA, and reacting for 5h to obtain the polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (165 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 430 ℃ to obtain the dimension stable PI film.
Example 8
Example 7 was repeated, except that the DMAc had a mass of 167kg, DBZ was not added, and 10mol of BZA were added.
Example 9
Example 7 was repeated, except that the DMAc mass was 162kg, only 30mol of PDA were added to the rigid aromatic diamine, and DBZ and BZA were not added.
Example 10
Adding 20mol of PDA and 7mol of BZA into 163kg of DMAc, stirring for 0.5h, adding 22.5mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 67.1mol of PMDA, reacting for 1h, finally adding 10mol of BPDA, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (165 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Example 11
Example 10 was repeated, except that the DMAc mass was 227kg, no BPDA was added and the PMDA addition amount was 99.6 mol.
Example 12
Example 10 was repeated, except that the solvent was 170kg DMF, the amount of PMDA added was 69.6mol, and the amount of BPDA added was 30 mol.
Example 13
Example 10 was repeated, except that the solvents were 120kg of DMAc and 53kg of DMF, the amount of PMDA added was 59.6mol, and the amount of BPDA added was 40 mol.
Example 14
Adding 20mol of PDA and 7mol of BZA into 166kg of DMAc, stirring for 0.5h, adding 20.3mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 59.3mol of PMDA, reacting for 1h, finally adding 20mol of BPDA, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (166 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Example 15
Adding 20mol of PDA and 7mol of BZA into 167kg of DMAc, stirring for 0.5h, adding 23.6mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 56.7mol of PMDA, reacting for 1h, finally adding 20mol of BPDA, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (166 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Example 16
Adding 20mol of PDA and 7mol of BZA into 166kg of DMAc, stirring for 0.5h, adding 24.3mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 55.3mol of PMDA, reacting for 1h, finally adding 20mol of BPDA, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (166 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the dimension stable PI film.
Comparative example 1
Adding 20mol of PDA and 7mol of BZA into 166kg of DMAc, stirring for 0.5h, adding 18mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 61.6mol of PMDA, reacting for 1h, adding 20mol of BPDA finally, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (165 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the PI film.
Comparative example 2
Adding 20mol of PDA and 7mol of BZA into 166kg of DMAc, stirring for 0.5h, adding 24.6mol of PMDA, reacting for 1h, adding 73mol of ODA, stirring for dissolving for 0.5h, adding 55mol of PMDA, reacting for 1h, adding 20mol of BPDA finally, and reacting for 5h to obtain a polyamic acid resin solution. Defoaming the polyamic acid resin solution, coating the resin on a steel belt by a scraper, heating (170 ℃) to remove the solvent to obtain a PAA film, and then performing unidirectional stretching and thermal imidization at 400 ℃ to obtain the PI film.
Comparative example 3
Example 9 was repeated, except that the amount of DMAc added was 160kg, the amount of PDA added was 33mol and the amount of ODA added was 67 mol.
The above examples and comparative proportioning data are collated as in table 1 below:
table 1:
the properties of the PI films prepared in the above examples and comparative examples are tested, and the results are shown in the following Table 2:
table 2:
Claims (5)
1. the preparation method of the dimension stable type polyimide film comprises the following steps:
1) weighing aromatic diamine and aromatic dianhydride according to a proportion for later use; wherein:
the aromatic diamine is composed of rigid aromatic diamine and 4,4 '-diaminodiphenyl ether, wherein the rigid aromatic diamine is one or the combination of more than two of 1, 4-diaminobenzene, 4' -diaminobiphenyl and 2- (4-aminophenyl) -5-aminobenzoxazole, and accounts for 15-30% of the total molar amount of the aromatic diamine;
the aromatic dianhydride is a combination of pyromellitic dianhydride and 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the molar weight of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride accounts for 0-40% of the total molar weight of the aromatic dianhydride;
2) putting rigid aromatic diamine and partial aromatic dianhydride into a polar aprotic solvent for reaction to obtain an ordered chain segment terminated by the rigid aromatic diamine; wherein the molar ratio of the rigid aromatic diamine to the aromatic dianhydride is n: n-1, wherein n is 4-10;
3) adding 4, 4' -diaminodiphenyl ether into the ordered chain segment which is obtained in the step 2) and is terminated by the rigid aromatic diamine, adding the residual aromatic dianhydride for reaction after dissolving, and obtaining the ordered copolymerized polyamic acid resin solution induced by the ordered chain segment;
4) casting and thermal imidization are carried out on the polyamic acid resin solution obtained in the step 3) according to a conventional process to obtain the dimension stable type polyimide film.
2. The method of claim 1, wherein: in the step 1), the molar ratio of the aromatic diamine to the aromatic dianhydride is 0.9-1.1: 1.
3. the method of claim 1, wherein: in the step 1), the rigid aromatic diamine accounts for 20-30% of the total molar amount of the aromatic diamine.
4. The method of claim 1, wherein: in the step 1), the molar amount of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride accounts for 5-25% of the total molar amount of the aromatic dianhydride.
5. A dimensionally stable polyimide film produced by the method of any one of claims 1 to 4.
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| CN109438702A (en) * | 2018-09-29 | 2019-03-08 | 苏州市新广益电子有限公司 | It is a kind of for the TPI film of FPC industry and its preparation and processing method |
| CN109824896B (en) * | 2019-03-12 | 2021-07-13 | 黄山金石木塑料科技有限公司 | High-temperature-resistant wear-resistant polyimide resin and preparation method and application thereof |
| CN110372896A (en) * | 2019-06-20 | 2019-10-25 | 重庆文理学院 | A kind of heat treatment process of low thermal expansion coefficient polyimide |
| CN110437615B (en) * | 2019-08-15 | 2021-12-10 | 无锡高拓新材料股份有限公司 | FPC (flexible printed circuit) base material polyimide film special for LED (light-emitting diode) and preparation method thereof |
| CN111363354A (en) * | 2020-03-27 | 2020-07-03 | 中天电子材料有限公司 | Polyimide colorless transparent film, preparation method thereof and optical PI film |
| CN114456381B (en) * | 2022-02-11 | 2023-06-20 | 无锡顺铉新材料有限公司 | Method for preparing polyimide film by unidirectional stretching |
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| CN104961893A (en) * | 2015-07-01 | 2015-10-07 | 杭州福斯特光伏材料股份有限公司 | High-dielectric-constant polyimide and preparation method thereof |
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| CN104961893A (en) * | 2015-07-01 | 2015-10-07 | 杭州福斯特光伏材料股份有限公司 | High-dielectric-constant polyimide and preparation method thereof |
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| Novel Poly(benzoxazole-etherimide) Copolymer for Two-Layer Flexible Copper-Clad Laminate;Zhuang Yongbing等;《JOURNAL OF MACROMOLECULAR SCIENCE PART B-PHYSICS》;20120830;第51卷(第11期);2157-2170 * |
| Poly(benzoxazole-amide-imide) copolymers for interlevel dielectrics: interchain hydrogen bonding, molecular arrangement and properties;Zhuang Yongbing等;《JOURNAL OF POLYMER RESEARCH》;20130521;第20卷(第6期);168 * |
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