CN114231029B - Cross-linked high-transparency polyimide film and preparation method thereof - Google Patents
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Abstract
The invention belongs to the technical field of functional polymer materials, and in particular relates to a cross-linked high-transparency polyimide film and a preparation method thereof, wherein the cross-linked high-transparency polyimide film is prepared by polycondensation reaction of novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-amino-benzamide) cyclohexane and aromatic dianhydride monomer, and an amide group, an alicyclic structure and a fluorine-containing group are introduced into a cross-linked polyimide molecular chain. The cross-linked high-transparency polyimide film prepared by the invention has the characteristics of high transparency, low expansion, low dielectric property, low expansion and high heat resistance, the light transmittance at 400nm is more than 85%, the yellowness index is less than 2, the thermal expansion coefficient is reduced to be below 20 ppm/DEG C, the dielectric constant is less than 3, the glass transition temperature is more than 300 ℃, and the cross-linked high-transparency polyimide film has wide application in the photoelectric fields of electronic microelectronics and the like. The invention has simple preparation process, excellent processing performance and simple film forming process, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a cross-linked high-transparency polyimide film and a preparation method thereof.
Background
The polyimide has the characteristics of high temperature resistance, high strength, corrosion resistance, radiation resistance, wear resistance and the like, and the comprehensive performance is positioned at the top end of a material pyramid, so that the polyimide is called as a polymer material king and a hand for solving the problem, and is widely applied to the fields of electronics, microelectronics, aerospace, photoelectricity and the like. With the continuous expansion of the market of intelligent electronic products and the development of flat panel display technology, the ultrathin, ultralight, foldable and crimpable flexible display technology will become the standard configuration of new generation electronic products. The performance requirements of the optoelectronic device on the polymer material, besides transparency and heat resistance, also need to have good dimensional stability, flexibility, dielectric properties, excellent solvent resistance, and simple film forming process. Polyimide can meet the high temperature resistance requirement in the processing process of photoelectric devices, is superior to other transparent high polymer materials such as polyethylene terephthalate, polycarbonate, polyacrylate, polyether sulfone and the like, and becomes the first choice in polymer materials, so polyimide films with high transparency, low dielectric property, low expansion and good heat resistance are increasingly demanded.
The traditional aromatic polyimide is generally prepared by condensation polymerization of diamine and dianhydride, and because conjugated units exist in molecules, charge transfer complexes are extremely easy to generate, most of common polyimide films are brown yellow, the light transmittance in the visible light range is low, the dielectric constant is about 3.4, the thermal expansion coefficient of the common polyimide is more than 40 ppm/DEG C, curling and warping can occur between the common polyimide and a matrix in the high-temperature preparation process, and the performance mutual balance of the common polyimide films is difficult to realize, so that the application of the common polyimide films in photoelectric devices is severely limited.
Because of the hyperbranched property of the crosslinked polymer material, the side group of the one-dimensional material is maximized, the intermolecular gap can be improved to the greatest extent, meanwhile, the crosslinked structure can limit the movement of molecular chains, the dielectric constant is reduced, and the thermal expansion coefficient can be reduced, but the crosslinked polyimide reaction solution is easy to form a gel polymer, so that a solution processing method cannot be adopted to prepare the polyimide film. In addition, the attraction strength of the functional group of the anhydride or the amine for synthesizing the polyimide to electrons and the steric hindrance play a role in determining the comprehensive performance of the polyimide, and the polarity and the relative position of an electron donor and an electron acceptor on a polyimide molecular chain can influence the comprehensive stability of the polyimide. Starting from the molecular structure design of polyimide, alicyclic structure, fluorine-containing substituent, large steric hindrance side group, twisted non-coplanar surface and the like are introduced to reduce or avoid conjugated units, reduce or eliminate the occurrence of intramolecular and intermolecular charge transfer, improve the light transmittance and transparency of the polyimide film, but greatly reduce the heat resistance and improve the thermal expansion coefficient. The introduction of amide groups, imidazole, oxazole and other nitrogen-containing heterocyclic structures into the PI molecular chain can reduce the thermal expansion coefficient of polyimide, but has certain defects in other properties, so that the improvement of the comprehensive properties of the film is limited, and the application of the photoelectric device cannot be satisfied. For polyimide, designing and synthesizing a polyimide of a new structure to achieve the reconciliation of various properties is critical, and thus, a great deal of research has been conducted.
Patent CN111218000a discloses a novel network type polyimide resin and a preparation method thereof, which takes triamine compounds such as 1,3, 5-tri (4-aminophenyl) benzene and various dianhydrides (6 fda, pmda, BPDA and the like) as reaction raw materials, controls the gelation phenomenon to occur through a low-temperature synthesis method, prepares a polyimide film with a network structure through thermal imidization, can be used for gas separation, has good gas selectivity and gas permeability, and has not been studied in the field of electronic microelectronic devices.
Patent CN112625278A reports a low dielectric polyimide film and a preparation method thereof, wherein biphenyl tetracarboxylic dianhydride (BPDA) and 1, 4-bis (4-amino-2-trifluoromethyl phenoxy) benzene (6 FAPB) are used as monomers, tris (4-aminophenyl) amine (TPA) is used as a cross-linking agent, and a film with a dielectric constant of 1.76-2.80, a glass transition temperature (Tg) is not significantly reduced, and light transmittance and thermal expansion coefficient are not reported.
Patent US20200369832A1 discloses a crosslinked polyimide, a film and a preparation method thereof, 4, 40-diamino-400-N-carbazolyl triphenylamine, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride and a p-xylene diamine crosslinking agent are introduced, and the polyimide film prepared in the way has low dielectric constant and high transmittance, the dielectric constant is 1.5-2, the light transmittance is 80-99%, but the thermal expansion coefficient is not reported.
Han Zhou et al used a triamine monomer 1,3, 5-tris (4-aminophenoxy) benzene (TAPOB) to react with 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) and p-Phenylenediamine (PDA) monomers to produce a series of crosslinked polyimide films by thermal imidization, which had excellent dielectric and mechanical properties, and in addition, as the proportion of the triamine monomer TAPOB was increased, the thermal expansion coefficient was significantly reduced, and the light transmittance was not studied by thermal imidization.
Disclosure of Invention
The invention aims to avoid mutual balance between different functional groups and multiple performances brought by specific structures, and provides a cross-linked high-transparency polyimide film which has good light transmittance, low expansion coefficient, excellent heat resistance and dielectric property, and simultaneously provides a preparation method thereof, which is simple, convenient and easy to implement, energy-saving and environment-friendly, and a film forming process is simple.
The cross-linked high-transparency polyimide film is prepared by polycondensation reaction of novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzene amide) cyclohexane and aromatic dianhydride monomer, and amide groups, alicyclic structures and fluorine-containing groups are introduced into a cross-linked polyimide molecular chain.
The novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzene amide) cyclohexane is synthesized by taking (1S, 3S, 5S) -cyclohexane-1, 3, 5-triamine and 2-trifluoromethyl-4-aminobenzene acyl chloride as raw materials. The branched structure improves the intermolecular gap to the greatest extent, enlarges the free volume fraction, and reduces the dielectric constant; the alicyclic structure and the fluorine-containing group can effectively inhibit the formation of intermolecular and intramolecular charge transfer complexes, and greatly improve the optical transparency; the cross-linked structure can limit molecular chain movement, improve polymer rigidity and reduce thermal expansion coefficient; the amido group can keep the excellent heat resistance and dimensional stability of polyimide, thus realizing the harmony of various properties, obtaining the cross-linked polyimide with high transparency, low dielectric, low expansion and high heat resistance, and the existence of fluorine-containing groups simultaneously ensures the solubility of polyimide.
The structural formula of the novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzamide) cyclohexane is as follows:
the aromatic dianhydride monomer is one of hexafluorodianhydride (6 FDA), 1,2,4, 5-cyclohexane tetracarboxylic dianhydride (HPMDA), cyclobutane tetracarboxylic dianhydride (CBDA), dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride (HBPDA) or CpODA, and has the following structural formula:
the preparation method of the cross-linked high-transparency polyimide film comprises the following steps:
(1) Under the protection of nitrogen, adding novel alicyclic structure-containing triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzene amide) cyclohexane into an organic solvent, adding aromatic dianhydride in batches after complete dissolution, and obtaining polyamic acid (PAA) solution through polycondensation reaction;
(2) Adding a catalyst and a dehydrating agent into the polyamic acid solution to perform chemical imidization to obtain a polyimide solution;
(3) Casting the polyimide solution on a super flat culture dish, and then placing the super flat culture dish in an oven to dry and remove the solvent to obtain the cross-linked high-transparency polyimide film.
Wherein:
in the step (1), the molar ratio of the triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-amino-benzamide) cyclohexane to the aromatic dianhydride is 2:2.7-3.3, the polycondensation reaction temperature is 0-60 ℃, and the solid content of the polyamide acid solution is 5-30wt%. The organic solvent is N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), N-dimethylformamide (DMF or Tetrahydrofuran (THF)).
The catalyst in the step (2) is tertiary amine (such as but not limited to trimethylamine, triethylamine, tripropylamine, pyridine, diazabicycloundecane, diazabicyclooctane and dimethylaminopyridine, preferably triethylamine), the dehydrating agent is anhydride (such as but not limited to acetic anhydride and propionic anhydride), the molar ratio of the dehydrating agent to the catalyst is 1-2:1, and the molar ratio of the dehydrating agent to the polyamic acid is 1-6:1. The chemical imidization temperature of the polyamic acid is 10-80 ℃.
The casting film forming time in the step (3) is 12-48 h, and the film forming temperature is 60-250 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention synthesizes the cross-linked polyimide by designing the new-structure triamine monomer and introducing the amide structure, the alicyclic structure and the fluorine-containing group into the polyimide main chain, thereby endowing the polyimide material with the new structure with excellent optical transparency and dielectric property, maintaining the excellent heat resistance and dimensional stability of the polyimide, and having low thermal expansion coefficient and good solubility.
(2) The cross-linked high-transparency polyimide film prepared by the invention has the characteristics of high transparency, low expansion, low dielectric property, low expansion and high heat resistance, the light transmittance at 400nm is more than 85%, the yellowness index is less than 2, the thermal expansion coefficient is reduced to be below 20 ppm/DEG C, the dielectric constant is less than 3, the glass transition temperature is more than 300 ℃, and the cross-linked high-transparency polyimide film has wide application in the photoelectric fields of electronic microelectronics and the like.
(3) The invention has simple preparation process, excellent processing performance and simple film forming process, and is suitable for industrial production.
Detailed Description
The invention is further illustrated below with reference to examples. It should be noted that the following examples are only for illustrating the present invention and are not intended to limit the technical solutions described in the present invention, and therefore all technical solutions and modifications thereof without departing from the spirit and scope of the present invention are included in the scope of the claims of the present invention.
The triamine monomer 1,3, 5-tris (2-trifluoromethyl-4-aminobenzamide) cyclohexane used in the following examples was synthesized by substitution reaction using (1 s,3s,5 s) -cyclohexane-1, 3, 5-triamine and 2-trifluoromethyl-4-aminobenzoyl chloride as raw materials.
Example 1
The crosslinked highly transparent polyimide film was prepared as follows:
under the protection of nitrogen, adding 6.54g of 1,3, 5-tris (2-trifluoromethyl-4-aminobenzamide) cyclohexane and 74.82g of DMAc into a four-neck flask, adding 6.6636g of dianhydride monomer 6FDA in batches after complete dissolution, stirring for 6 hours at 25 ℃, and obtaining a polyamide acid solution through polycondensation reaction; adding 3.0357g of triethylamine serving as a catalyst and 3.0627g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 25 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in a 100 ℃ oven for drying for 24 hours to obtain the cross-linked high-transparency polyimide film.
Example 2
The high-transparency low-expansion polyimide film is prepared according to the following method:
under the protection of nitrogen, 6.54g of 1,3, 5-tri (2-trifluoromethyl-4-amino-benzamide) cyclohexane and 40.06g of DMAc are added into a four-neck flask, 3.4746g of dianhydride monomer HPMDA is added in batches after complete dissolution, and the mixture is stirred for 6 hours at 25 ℃ to obtain a polyamide acid solution through polycondensation reaction; adding 2.0238g of triethylamine serving as a catalyst and 2.0418g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 30 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in a 100 ℃ oven for drying for 24 hours to obtain the cross-linked high-transparency polyimide film.
Example 3
The high-transparency low-expansion polyimide film is prepared according to the following method:
under the protection of nitrogen, 6.54g of 1,3, 5-tris (2-trifluoromethyl-4-aminobenzamide) cyclohexane and 37.53g of DMAc are added into a four-neck flask, 2.8436g of dianhydride monomer CBDA is added in batches after complete dissolution, and the mixture is stirred for 6 hours at 25 ℃ to obtain a polyamide acid solution through polycondensation reaction; adding 4.0476g of triethylamine serving as a catalyst and 4.0836g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 50 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in a baking oven at 150 ℃ for drying for 20 hours to obtain the cross-linked high-transparency polyimide film.
Example 4
The high-transparency low-expansion polyimide film is prepared according to the following method:
under the protection of nitrogen, 6.54g of 1,3, 5-tris (2-trifluoromethyl-4-aminobenzamide) cyclohexane and 63.10g of DMAc are added into a four-neck flask, 4.5947g of dianhydride monomer HBPDA is added in batches after complete dissolution, and stirred for 6 hours at 25 ℃ to obtain a polyamide acid solution through polycondensation reaction; adding 3.5417g of triethylamine serving as a catalyst and 3.5732g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 60 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in a baking oven at 150 ℃ for drying for 20 hours to obtain the cross-linked high-transparency polyimide film.
Example 5
The high-transparency low-expansion polyimide film is prepared according to the following method:
under the protection of nitrogen, 6.54g of 1,3, 5-tris (2-trifluoromethyl-4-aminobenzamide) cyclohexane and 48.45g of DMAc are added into a four-neck flask, 5.5735g of dianhydride monomer CpODA is added in batches after complete dissolution, and stirred for 6 hours at 25 ℃ to obtain a polyamide acid solution through polycondensation reaction; adding 3.0357g of triethylamine serving as a catalyst and 3.0627g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 50 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then placing the ultra-flat glass in a 180 ℃ oven for drying for 12 hours to obtain the cross-linked high-transparency polyimide film.
Comparative example 1
The polyimide film was prepared as follows:
under the protection of nitrogen, adding 3.4089g of 4,4' -diaminobenzidine and 57.08g of DMAc into a four-neck flask, adding 6.6636g of dianhydride monomer 6FDA in batches after complete dissolution, stirring for 6 hours at 25 ℃, and obtaining a polyamide acid solution through polycondensation reaction; adding 4.5536g of triethylamine serving as a catalyst and 4.5941g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 65 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then drying the ultra-flat glass in an oven at 150 ℃ for 18 hours to obtain the polyimide film.
Comparative example 2
The polyimide film was prepared as follows:
under the protection of nitrogen, 4.8035g of TFMB and 37.78g of DMAc are added into a four-neck flask, 4.6406g of dianhydride monomer HBPDA is added in batches after complete dissolution, and stirred for 6 hours at 25 ℃ to obtain a polyamic acid solution through polycondensation reaction; adding 4.5536g of triethylamine serving as a catalyst and 4.5941g of acetic anhydride serving as a dehydrating agent into the polyamic acid solution to perform chemical imidization, and stirring at 80 ℃ for 10 hours to obtain a polyimide solution; and casting the obtained polyimide solution on ultra-flat glass, and then drying the ultra-flat glass in an oven at 180 ℃ for 12 hours to obtain the polyimide film.
The polyimide films prepared in examples 1 to 5 and comparative examples 1 to 2 were subjected to performance test, and the test results are shown in Table 1.
TABLE 1 Performance test results of polyimide films prepared in examples 1-5 and comparative examples 1-2
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (6)
1. A cross-linked high-transparency polyimide film is characterized in that: the aromatic diamine is prepared by polycondensation reaction of a triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzamide) cyclohexane and an aromatic dianhydride monomer, wherein the triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzamide) cyclohexane has the following structural formula:
the triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzene amide) cyclohexane is synthesized by taking (1S, 3S, 5S) -cyclohexane-1, 3, 5-triamine and 2-trifluoromethyl-4-aminobenzene acyl chloride as raw materials;
the aromatic dianhydride monomer is one of hexafluorodianhydride, 1,2,4, 5-cyclohexane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, dicyclohexyl-3, 4,3',4' -tetracarboxylic dianhydride or CpODA;
the preparation method of the crosslinked high-transparency polyimide film comprises the following steps:
(1) Adding a triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-aminobenzene amide) cyclohexane into a solvent, dissolving, adding aromatic dianhydride, and carrying out polycondensation reaction to obtain a polyamide acid solution;
(2) Adding a catalyst and a dehydrating agent into the polyamic acid solution to perform chemical imidization to obtain a polyimide solution;
(3) Casting and drying the polyimide solution to obtain a cross-linked high-transparency polyimide film;
in the step (1), the molar ratio of the triamine monomer 1,3, 5-tri (2-trifluoromethyl-4-amino-benzamide) cyclohexane to the aromatic dianhydride is 2:2.7-3.3.
2. The crosslinked highly transparent polyimide film according to claim 1, wherein: the solvent in the step (1) is N, N-dimethylacetamide, N-methylpyrrolidone, N-dimethylformamide or tetrahydrofuran.
3. The crosslinked highly transparent polyimide film according to claim 1, wherein: the polycondensation reaction temperature in the step (1) is 0-60 ℃, and the solid content of the polyamic acid solution is 5-30wt%.
4. The crosslinked highly transparent polyimide film according to claim 1, wherein: in the step (2), the catalyst is tertiary amine, the dehydrating agent is anhydride, the molar ratio of the dehydrating agent to the catalyst is 1-2:1, and the molar ratio of the dehydrating agent to the polyamide acid is 1-6:1.
5. The crosslinked highly transparent polyimide film according to claim 1, wherein: the chemical imidization temperature of the polyamic acid in the step (2) is 10-80 ℃.
6. The crosslinked highly transparent polyimide film according to claim 1, wherein: the casting film forming time in the step (3) is 12-48 h, and the film forming temperature is 60-250 ℃.
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Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000063518A (en) * | 1998-08-18 | 2000-02-29 | Mitsui Chemicals Inc | Low-dielectric polyimide containing crosslinkable group and its production |
JP2005336244A (en) * | 2004-05-25 | 2005-12-08 | Nissan Chem Ind Ltd | Polyimide having combination of low dielectric constant, low coefficient of linear thermal expansion, high transparency and high glass transition temperature, and its precursor |
JP2014114328A (en) * | 2012-12-06 | 2014-06-26 | Hitachi Chemical Co Ltd | Heat-resistant polyimide resin and seamless tubular body, coating film, coating film plate, and heat-resistant coating material using the same |
JP2014210896A (en) * | 2013-04-22 | 2014-11-13 | 住友ベークライト株式会社 | Polyimide resin and polyimide film |
WO2017069165A1 (en) * | 2015-10-19 | 2017-04-27 | 宇部興産株式会社 | Polyimide precursor, polyimide having crosslinked structure, and production method therefor |
CN108822296A (en) * | 2018-06-28 | 2018-11-16 | 上海交通大学 | A kind of all aromatic transparent polyimide film and preparation method thereof |
CN108864426A (en) * | 2018-06-12 | 2018-11-23 | 中国科学院化学研究所 | A kind of super-low expansion fluorinated polyimide film and the preparation method and application thereof |
CN109134858A (en) * | 2018-07-27 | 2019-01-04 | 深圳瑞华泰薄膜科技有限公司 | A kind of transparent polyimide film and preparation method thereof |
CN110734559A (en) * | 2018-07-18 | 2020-01-31 | 北京化工大学 | Cross-linked polyimide film and preparation method and application thereof |
CN111116912A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin |
CN111117241A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
CN111218000A (en) * | 2020-03-11 | 2020-06-02 | 天津理工大学 | Novel network type polyimide resin, preparation method thereof and application of resin film |
WO2020138645A1 (en) * | 2018-12-28 | 2020-07-02 | 주식회사 두산 | Polyamic acid composition and transparent polyimide film using same |
CN112457493A (en) * | 2020-11-30 | 2021-03-09 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
CN112625278A (en) * | 2020-12-08 | 2021-04-09 | 北京科技大学 | Low-dielectric polyimide film and preparation method thereof |
WO2021189723A1 (en) * | 2020-03-27 | 2021-09-30 | 中天电子材料有限公司 | Polyimide colorless transparent thin film, preparation method therefor, and optical pi film |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE602004031098D1 (en) * | 2003-03-28 | 2011-03-03 | Pi R & D Co Ltd | NETWORKED POLYAMIDE, COMPOSITION, AND METHOD OF PREPARING THEREOF |
AT517146A2 (en) * | 2015-05-13 | 2016-11-15 | Technische Universität Wien | Process for the preparation of crystalline polyimides |
CN111212867A (en) * | 2017-10-11 | 2020-05-29 | 株式会社钟化 | Polyimide resin and method for producing same, polyimide solution, and polyimide film and method for producing same |
US10428181B2 (en) * | 2017-10-11 | 2019-10-01 | Ohio Aerospace Institute | Porous cross-linked partially aliphatic polyimide networks |
US11525038B2 (en) * | 2019-05-21 | 2022-12-13 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Crosslinked polymide, polymide film and method for preparing thereof, organic light emitting diode device |
-
2021
- 2021-12-29 CN CN202111636483.0A patent/CN114231029B/en active Active
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000063518A (en) * | 1998-08-18 | 2000-02-29 | Mitsui Chemicals Inc | Low-dielectric polyimide containing crosslinkable group and its production |
JP2005336244A (en) * | 2004-05-25 | 2005-12-08 | Nissan Chem Ind Ltd | Polyimide having combination of low dielectric constant, low coefficient of linear thermal expansion, high transparency and high glass transition temperature, and its precursor |
JP2014114328A (en) * | 2012-12-06 | 2014-06-26 | Hitachi Chemical Co Ltd | Heat-resistant polyimide resin and seamless tubular body, coating film, coating film plate, and heat-resistant coating material using the same |
JP2014210896A (en) * | 2013-04-22 | 2014-11-13 | 住友ベークライト株式会社 | Polyimide resin and polyimide film |
WO2017069165A1 (en) * | 2015-10-19 | 2017-04-27 | 宇部興産株式会社 | Polyimide precursor, polyimide having crosslinked structure, and production method therefor |
CN108864426A (en) * | 2018-06-12 | 2018-11-23 | 中国科学院化学研究所 | A kind of super-low expansion fluorinated polyimide film and the preparation method and application thereof |
CN108822296A (en) * | 2018-06-28 | 2018-11-16 | 上海交通大学 | A kind of all aromatic transparent polyimide film and preparation method thereof |
CN110734559A (en) * | 2018-07-18 | 2020-01-31 | 北京化工大学 | Cross-linked polyimide film and preparation method and application thereof |
CN109134858A (en) * | 2018-07-27 | 2019-01-04 | 深圳瑞华泰薄膜科技有限公司 | A kind of transparent polyimide film and preparation method thereof |
WO2020138645A1 (en) * | 2018-12-28 | 2020-07-02 | 주식회사 두산 | Polyamic acid composition and transparent polyimide film using same |
CN111116912A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | Polyimide resin, preparation method thereof and method for preparing polyimide film/cross-linked polyimide film by using polyimide resin |
CN111117241A (en) * | 2019-12-31 | 2020-05-08 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
CN111218000A (en) * | 2020-03-11 | 2020-06-02 | 天津理工大学 | Novel network type polyimide resin, preparation method thereof and application of resin film |
WO2021189723A1 (en) * | 2020-03-27 | 2021-09-30 | 中天电子材料有限公司 | Polyimide colorless transparent thin film, preparation method therefor, and optical pi film |
CN112457493A (en) * | 2020-11-30 | 2021-03-09 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
CN112625278A (en) * | 2020-12-08 | 2021-04-09 | 北京科技大学 | Low-dielectric polyimide film and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
一种新型含氟聚酰亚胺聚合物的合成及性能研究;李昶红 等;衡阳师范学院学报;第45-49页 * |
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