WO2012081763A1 - Film en polyimide - Google Patents

Film en polyimide Download PDF

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Publication number
WO2012081763A1
WO2012081763A1 PCT/KR2010/009622 KR2010009622W WO2012081763A1 WO 2012081763 A1 WO2012081763 A1 WO 2012081763A1 KR 2010009622 W KR2010009622 W KR 2010009622W WO 2012081763 A1 WO2012081763 A1 WO 2012081763A1
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WO
WIPO (PCT)
Prior art keywords
mol
polyimide film
film
tetracarboxylic dianhydride
benzoic acid
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PCT/KR2010/009622
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English (en)
Korean (ko)
Inventor
이길남
원동영
안찬재
김성원
명범영
Original Assignee
에스케이씨코오롱피아이주식회사
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Publication of WO2012081763A1 publication Critical patent/WO2012081763A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a polyimide film excellent in dimensional stability and tear strength.
  • Polyimide films are widely used in electrical / electronic materials, aerospace / aviation and telecommunications because of their excellent mechanical and thermal dimensional stability and chemical stability.
  • the polyimide film has been widely used as a flexible printed circuit board material having a fine pattern, for example, a base film such as TAB or COF due to light and small size of the component.
  • TAB or COF technology is a kind of technology for sealing IC chip or LSI chip. Specifically, TAB or COF technology is used to make a conductive pattern on a flexible tape and seal it by mounting the chip on it. It is advantageous to reduce the thickness of the product.
  • a polyimide film As a base film for TAB or COF, high dimensional stability is required. This is because a dimensional change may occur due to heat shrinkage or a dimensional change may occur due to residual stress after an etching process in a TAB or COF manufacturing process for bonding a polyimide film in a heated state or a cooling process after a sputtering process. As a result of the dimensional change, a position error may occur during the process of bonding the IC or LSI chip to the TAB or COF.
  • the polyimide film undergoes a high temperature treatment process, expansion occurs due to heat, and a coefficient of thermal expansion (CTE) is measured. If the coefficient of thermal expansion is large, the polyimide film shrinks more than the semiconductor while cooling after the semiconductor bonding at a high temperature, which is not good to stress the bonding site.
  • CTE coefficient of thermal expansion
  • the present invention is to provide a polyimide film with improved dimensional stability and tear strength by the network structure of the polymer.
  • Polyimide film according to an embodiment of the present invention is an aromatic tetracarboxylic dianhydride component containing biphenyltetracarboxylic dianhydride or a functional derivative thereof, p-phenylenediamine, diaminodiphenyl ether and Obtained by imidizing a polyamic acid comprising an aromatic diamine component comprising diamino benzoic acid; Dimensional stability, measured according to IPC TM 650 2.2.4A, is 0.02% or less; Tear strength measured according to ASTM D 1004 standard may be more than 3.0kgf.
  • the aromatic diamine component may include at least 3 mol% of diamine benzoic acid in the total aromatic diamine component.
  • the biphenyl tetracarboxylic dianhydride or a functional derivative thereof may be 90 mol% or more of the total aromatic tetracarboxylic dianhydride component.
  • an aromatic tetracarboxylic dianhydride component comprising biphenyltetracarboxylic dianhydride; It can be obtained by imidizing the polyamic acid which becomes 100 mol% of 55-75 mol% of p-phenylenediamine, 20-40 mol% of diamino phenyl ether, and 3-5 mol% of diamine benzoic acid.
  • the imidization may be accompanied by chemical conversion by a conversion agent comprising an imidization catalyst and a dehydrating agent.
  • the present invention provides an aromatic tetracarboxylic dianhydride component comprising a biphenyltetracarboxylic dianhydride or a functional derivative thereof, and an aromatic diamine component containing p-phenylenediamine, diaminodiphenylether and diamino benzoic acid. It relates to the polyimide film obtained by imidating the polyamic acid derived from it, Especially a dimensional stability is 0.02% or less; It relates to a polyimide film having a tear strength of 3.0 kgf or more.
  • the dimensional stability is performed according to IPC TM 650 2.2.4A, and after 2 hours at the temperature of 200 °C to measure the MD (Mechanical Direction) / TD (Transverse Direction) dimensional change rate, the dimensional change rate is a three-dimensional measuring equipment Measure
  • the tear strength is in accordance with the ASTM D 1004 standard and measured in the MD / TD direction.
  • the cross head speed is 51mm / min.
  • the polyimide film is subjected to a wet process and a high temperature process in order to use a base film for TAB and COF.
  • the polyimide film may have a minute dimensional change due to moisture, heat, etc.
  • it is to provide a polyimide film with improved dimensional stability and tear strength by strengthening the interpolymer network.
  • a polyimide film having a tear strength of 3.5 kgf or more, while the dimensional stability defined as described above is 0.02% or less.
  • the polyimide film according to one embodiment of the present invention is applied to a flexible circuit board, particularly a base film for TAB or COF, which is a semiconductor mounted flexible circuit board, dimensional change or separation of an adhesive layer in a severe flexible circuit board manufacturing process, etc. May not occur.
  • the polyimide film according to one embodiment of the present invention may have a moisture absorption rate of 1.4% or less in particular.
  • the moisture absorption is measured by cutting a portion of the film in a chamber (Chamber) at 100% RH (relative humidity) atmosphere for 48 hours and then analyzing it by using a thermal gravimetric analysis.
  • the temperature can be calculated by analyzing the change in weight by heating the temperature from 35 ° C to 250 ° C at 10 ° C / min.
  • the polyimide film according to the embodiment of the present invention may preferably have a moisture absorption of 1.3% or less.
  • the method for satisfying the dimensional stability and tear strength within the above range is not limited, but the method contemplated by the present invention is biphenyltetracar as the aromatic tetracarboxylic dianhydride component used to prepare the polyamic acid.
  • a method containing an acid dianhydride or a functional derivative thereof, and containing p-phenylenediamine, diaminophenyl ether and diamino benzoic acid as an aromatic diamine component is mentioned.
  • the aromatic diamine component contains at least 3 mol% of diamine benzoic acid in the total aromatic diamine component, thereby improving dimensional stability and tear strength by strengthening the network structure of the polymer while allowing viscosity control.
  • the aromatic tetracarboxylic dianhydride component includes biphenyltetracarboxylic dianhydride or a functional derivative thereof in an amount of 90 mol% or more in the total aromatic tetracarboxylic dianhydride component to improve chemical resistance. You can.
  • the most preferred polyimide film is 100 mol% of an aromatic tetracarboxylic dianhydride component comprising biphenyltetracarboxylic dianhydride; It may be obtained by imidizing a polyamic acid consisting of 100 mol% of an aromatic diamine component comprising 55 to 75 mol% of p-phenylenediamine, 20 to 40 mol% of diaminodiphenyl ether, and 3 to 5 mol% of diamino benzoic acid. .
  • imidization may involve chemical conversion by a conversion agent comprising an imidization catalyst and a dehydrating agent.
  • composition and the film forming method are specifically described below, but are not limited thereto.
  • the aromatic tetracarboxylic dianhydride that can be used in the present invention is biphenyltetracarboxylic dianhydride or functional derivatives thereof, such as 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, pyromelli Benzophenonetetracarboxylic dianhydride or its functional derivative, such as 3,3 ', 4,4'-benzophenonetetracarboxylic anhydride or p-phenylene-bis trimellis thereof
  • an acid dianhydride etc. can be used, it is preferable to use biphenyl tetracarboxylic dianhydride in 90 mol% or more of all aromatic tetracarboxylic dianhydride as mentioned above.
  • a polyimide film containing an excess of biphenyltetracarboxylic dianhydride units has a high modulus of elasticity, low moisture absorption and excellent chemical resistance.
  • Diamines usable in the present invention include p-phenylene diamine, diaminophenyl ethers such as 4,4'-diaminophenyl ether, 3,4-diaminophenyl ether, 2,4-diaminophenyl ether, And diamino benzoic acid such as 3,5-diamino benzoic acid.
  • the proportion of p-phenylene diamine in the total diamine is at least 55 mol%, more preferably 55 to 75 mol% in the total aromatic diamine component.
  • p-phenylene diamine is a monomer having a linearity compared to diamino phenyl ether serves to lower the coefficient of thermal expansion of the film (Coefficient of thermal expansion).
  • the content of p-phenylene diamine is high, the flexibility of the film may be reduced and the film forming ability may be lost.
  • the content of diaminophenyl ether used in combination may be 40 mol% or less, preferably 20 to 40 mol% of the total aromatic diamine components.
  • diamino benzoic acid used in combination may be 3 mol% or more, preferably 3 to 5 mol% in the total aromatic diamine component.
  • Diamino benzoic acid can improve the physical properties such as dimensional stability, tear strength by strengthening the intermolecular network structure at the same time to control the viscosity.
  • the method for forming a polyimide film is not particularly noticeable to those skilled in the art, but provides an example;
  • the aromatic tetracarboxylic dianhydride and the aromatic diamine component are reacted with an organic solvent to obtain a polyamic acid solution.
  • the solvent is generally preferably an aprotic polar solvent (Aprotic solvent) as the amide solvent, for example, N, N'- dimethylformamide, N, N'- dimethylacetamide, N-methyl- Pyrrolidone etc. can be mentioned and can also be used in combination of 2 types as needed.
  • Aprotic solvent aprotic polar solvent
  • the input form of the monomer may be added in the form of powder, lump, and solution.
  • the monomer may be added in the form of powder, and the reaction may be performed in the form of a solution to control the polymerization viscosity.
  • the weight of the monomer added in the total polyamic acid solution in the state in which the equimolar amount of the aromatic diamine component and the aromatic tetracarboxylic dianhydride is added is called solid content, and the solid content is between 10-30%, preferably between 14-20%
  • the polymerization may be performed in the range of. In particular, it is preferable to proceed block polymerization.
  • the order of monomer addition may be controlled so that the polyamic acid as described above contains a large amount of a molecular chain whose terminal is an amine.
  • a filler may be added to the polyimide film to improve various properties such as sliding properties, thermal conductivity, conductivity, and corona resistance.
  • the type of filler may not be limited, preferred examples include silica, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
  • the particle size of the filler depends on the thickness or type of the film and may be a modified surface of the filler. 0.1-100 micrometers is preferable and, as for the average particle diameter of a filler, 0.1-3 micrometers is more preferable.
  • the addition amount of the filler is also not particularly limited and may vary depending on the film to be modified, the type and particle size of the particles, the particle surface, and the like.
  • the addition amount of the filler is preferably used in the range of 0.04 to 3% based on the solids content of the polymerized polyamic acid solution. If the amount of the filler is used in the above range, the physical properties of the polyimide film may be impaired. If the filler is used in the range below, the modification effect is hardly seen.
  • the dosing method can be added at the beginning of the reactants or after the reaction is over. Alternatively, in order to prevent contamination of the reactor, it may be added in a catalyst mixing step, and the addition method and timing are not particularly limited.
  • the obtained polyamic acid solution may be applied to the support by mixing with a converting agent, preferably an imidization catalyst and a dehydrating agent.
  • a converting agent preferably an imidization catalyst and a dehydrating agent.
  • the catalyst used may include tertiary amines, and anhydrides may be cited as the dehydrating agent.
  • anhydrous acid include acetic anhydride, and tertiary amines include isoquinoline, ⁇ -picolin, pyridine and the like.
  • the amount of anhydrous acid can be calculated by the molar ratio of o-carboxylic amide functional group in the polyamic acid solution, and it is preferable to use 1.0-5.0 molar ratio.
  • the amount of tertiary amine can be calculated by the molar ratio of o-carboxylic amide groups in the polyamic acid solution, and it is appropriate to add between 0.2 and 3.0 molar ratios.
  • the conversion agent may be used in the form of a mixture of anhydrous acid / amines or anhydrous acid / amine / solvent mixture.
  • the film applied on the support is gelled on the support by dry air and heat treatment.
  • the gelation temperature of the coated film is preferably 100 ⁇ 250 °C and may be used as a support, such as glass plate, aluminum foil, circulating stainless belt or stainless drum, but is not limited thereto.
  • the treatment time required for gelation depends on the temperature, the type of the support, the amount of the polyamic acid solution applied, and the mixing conditions of the conversion agent, and is not limited to a certain time, but is preferably performed within a range of 5 minutes to 30 minutes. It is good.
  • the gelled film is separated from the support and heat treated to complete drying and imidization.
  • Heat treatment temperature is between 100 ⁇ 600 °C and treatment time is between 1 ⁇ 30 minutes.
  • the gelled film proceeds by being fixed to a support during heat treatment.
  • Gel film can be fixed using a pin type frame or a clip type.
  • the residual volatile content of the film after heat treatment is 5% or less and preferably 3% or less.
  • the film is heat treated under a constant tension to remove residual stress in the film. Since the tension and temperature conditions are correlated with each other, the tension conditions may vary with temperature. Temperature is preferably maintained between 100 ⁇ 600 °C, the tension is preferably 50N or less, the time is preferably maintained for 1 minute to 1 hour.
  • diamino benzoic acid (DABA) solution was added and stirred.
  • the diamino benzoic acid solution was prepared at 5% concentration using DMF as a solvent.
  • the completed polyamic acid solution had a solid content of 15 wt% and a viscosity of 2,000 poise.
  • the molar ratio of the injected monomer is BPDA 100%, ODA 35%, PDA 62%, DABA 3%.
  • the film on which the film was fixed was placed in a vacuum oven, heated slowly from 100 ° C. to 350 ° C. for 30 minutes, and then slowly cooled to separate the film from the frame.
  • the thickness of the film finally obtained is 38 micrometers.
  • the polyimide film was prepared in the same manner as in Example 1, except that the polyimide film was prepared by varying the monomer composition ratio as shown in Table 1 during the polyamic acid polymerization.
  • N, N'-dimethylformamide (DMF) was added to the 2 L jacket reactor as a solvent.
  • the temperature was 35 degreeC
  • 20.6g of p-phenylenediamine (p-PDA), biphenyl tetracarboxylic dianhydride (BPDA), and pyromellitic dianhydride (PMDA) were added.
  • ODA diaminophenyl ether
  • p-phenylenediamine p-PDA was added.
  • block polymerization was carried out for 2 hours while maintaining the temperature at 40 °C.
  • diamino benzoic acid (DABA) solution was added and stirred.
  • the diamino benzoic acid solution was prepared at 5% concentration using DMF as a solvent.
  • the completed polyamic acid solution had a solid content of 15 wt% and a viscosity of 1,800 poise.
  • the molar ratio of the injected monomer is 95 mol% BPDA, 5 mol% PMDA, 35 mol% ODA, 62 mol% PDA, and 3 mol% DABA.
  • the film on which the film was fixed was placed in a vacuum oven, heated slowly from 100 ° C. to 350 ° C. for 30 minutes, and then slowly cooled to separate the film from the frame.
  • a polyimide film was prepared in the same manner as in Example 1, except that paraphenylenediamine (PPD) was used instead of diamino benzoic acid (DABA) in polyamic acid polymerization.
  • PPD paraphenylenediamine
  • DABA diamino benzoic acid
  • N, N'-dimethylformamide (DMF) was added to the 2L jacket reactor as a solvent.
  • the temperature was set to 30 ° C., and 23.1 g of p-phenylenediamine (p-PDA) and 24.2 g of diaminophenyl ether (ODA) were added. Then, the resultant was dissolved.
  • a paraphenylenediamine (PPD) solution was added to the mixture, followed by stirring.
  • the paraphenylenediamine (PPD) solution was prepared in 5% concentration using DMF as a solvent.
  • the reaction solution of the polyamic acid has a solid content of 15 wt% and a viscosity of 1800 poise.
  • the molar ratio of the injected monomer is 100% BPDA, 35% ODA, 65% PDA.
  • the polyamic acid solution was applied to a stainless plate, cast at 250 ⁇ m, dried for 10 minutes with hot air at 120 ° C., and the film was peeled off from the stainless plate to fix the pin to the frame.
  • the film on which the film was fixed was placed in a vacuum oven, heated slowly from 100 ° C. to 350 ° C. for 30 minutes, and then slowly cooled to separate the film from the frame.
  • Tensile modulus was averaged by testing three times in accordance with ASTM D 882 using a standard instron testing apparatus.
  • a portion of the finished film was cut into a width of 4 mm and a width of 30 mm, and the coefficient of thermal expansion was measured using a TA company thermal mechanical apparatus Q400.
  • the sample was hooked to a quartz hook and subjected to a force of 0.010 N and then heated at 10 ° C./min from 30 ° C. to 420 ° C. in a nitrogen atmosphere.
  • the coefficient of thermal expansion was obtained within the range of 50 ° C to 200 ° C.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6
  • Example 7 Comparative Example 1 Comparative Example 2
  • Tensile Modulus (GPa) 5.4 5.7 6.0 6.2 5.5 6.2 5.5 5.4 5.1
  • Coefficient of linear expansion ppm /
  • 14 13 10 9
  • 14 9 14 18 Tear strength (kgf) 3.0 3.1 3.0 3.1 3.5 3.2 3.1 2.8 2.7
  • the polyimide film obtained by Comparative Examples 1 to 2 was found to have a lower tensile modulus and tear strength and a higher coefficient of linear expansion than the polyimide film obtained by Examples 1 to 7.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film en polyimide, et concerne un film en polyimide qui présente une stabilité dimensionnelle et une résistance à la déchirure incroyables, et qui est utilisé comme film de base pour les produits nécessitant une grande fiabilité.
PCT/KR2010/009622 2010-12-16 2010-12-31 Film en polyimide WO2012081763A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2010-0129175 2010-12-16
KR1020100129175A KR101558621B1 (ko) 2010-12-16 2010-12-16 폴리이미드 필름

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WO2012081763A1 true WO2012081763A1 (fr) 2012-06-21

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107207747A (zh) * 2014-12-30 2017-09-26 韩国爱思开希可隆Pi股份有限公司 利用交联型水溶性热塑性聚酰胺酸的热熔接多层聚酰亚胺膜及其制备方法
EP3162838A4 (fr) * 2014-06-30 2018-04-25 Kolon Industries, Inc. Solution de poly(acide amique) résistant à la chaleur élevée et film de polyimide
CN111491988A (zh) * 2017-12-28 2020-08-04 韩国爱思开希可隆Pi股份有限公司 用于制备柔性铜箔层压板的聚酰亚胺薄膜及包含其的柔性铜箔层压板
CN113795537A (zh) * 2019-05-08 2021-12-14 聚酰亚胺先端材料有限公司 聚酰亚胺薄膜的制备方法及由该方法制备的聚酰亚胺薄膜

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EP3070113A4 (fr) * 2013-11-15 2017-07-26 IUCF-HYU (Industry-University Cooperation Foundation Hanyang University) Copolymère poly(benzoxazole-imide) thermiquement réarrangé ayant une structure réticulée, membrane de séparation de gaz le comprenant et son procédé de préparation
KR101668059B1 (ko) * 2014-12-30 2016-10-20 에스케이씨코오롱피아이 주식회사 가교형 수용성 열가소성 폴리아믹산 및 이의 제조방법
KR102147349B1 (ko) 2019-09-30 2020-08-25 에스케이이노베이션 주식회사 윈도우 커버 필름 및 이를 이용한 플렉서블 디스플레이 패널
KR102147299B1 (ko) 2019-09-30 2020-08-24 에스케이이노베이션 주식회사 윈도우 커버 필름 및 이를 포함하는 플렉서블 디스플레이 패널
KR102141891B1 (ko) * 2019-11-08 2020-08-07 피아이첨단소재 주식회사 연성동박적층판 제조용 폴리이미드 필름 및 이를 포함하는 연성동박적층판
CN114685787B (zh) * 2020-12-27 2024-03-08 上海市塑料研究所有限公司 一种具有协同交联结构的聚酰亚胺薄膜及其制备方法和应用

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WO2009019968A1 (fr) * 2007-08-03 2009-02-12 Kaneka Corporation Film de polyimide multicouche, stratifié et stratifié revêtu de métal
KR20100065350A (ko) * 2007-09-20 2010-06-16 우베 고산 가부시키가이샤 폴리이미드막의 제조방법, 및 폴리아민산 용액 조성물

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US20040063898A1 (en) * 2001-02-23 2004-04-01 Masaru Nishinaka Polymide film and process for producing the same
KR20070121727A (ko) * 2005-04-12 2007-12-27 가부시키가이샤 가네카 폴리이미드 필름
WO2009019968A1 (fr) * 2007-08-03 2009-02-12 Kaneka Corporation Film de polyimide multicouche, stratifié et stratifié revêtu de métal
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3162838A4 (fr) * 2014-06-30 2018-04-25 Kolon Industries, Inc. Solution de poly(acide amique) résistant à la chaleur élevée et film de polyimide
US10538665B2 (en) 2014-06-30 2020-01-21 Kolon Industries, Inc. High heat-resistant polyamic acid solution and polyimide film
CN107207747A (zh) * 2014-12-30 2017-09-26 韩国爱思开希可隆Pi股份有限公司 利用交联型水溶性热塑性聚酰胺酸的热熔接多层聚酰亚胺膜及其制备方法
CN107207747B (zh) * 2014-12-30 2020-06-02 韩国爱思开希可隆Pi股份有限公司 利用交联型水溶性热塑性聚酰胺酸的热熔接多层聚酰亚胺膜及其制备方法
CN111491988A (zh) * 2017-12-28 2020-08-04 韩国爱思开希可隆Pi股份有限公司 用于制备柔性铜箔层压板的聚酰亚胺薄膜及包含其的柔性铜箔层压板
CN111491988B (zh) * 2017-12-28 2023-02-17 聚酰亚胺先端材料有限公司 用于制备柔性铜箔层压板的聚酰亚胺薄膜及包含其的柔性铜箔层压板
CN113795537A (zh) * 2019-05-08 2021-12-14 聚酰亚胺先端材料有限公司 聚酰亚胺薄膜的制备方法及由该方法制备的聚酰亚胺薄膜

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