KR101167341B1 - Colorless polyimide resin, and liquid crystal alignment layer and polyimide film using the same - Google Patents

Colorless polyimide resin, and liquid crystal alignment layer and polyimide film using the same Download PDF

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KR101167341B1
KR101167341B1 KR1020060129009A KR20060129009A KR101167341B1 KR 101167341 B1 KR101167341 B1 KR 101167341B1 KR 1020060129009 A KR1020060129009 A KR 1020060129009A KR 20060129009 A KR20060129009 A KR 20060129009A KR 101167341 B1 KR101167341 B1 KR 101167341B1
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fda
film
dds
polyimide
polyimide film
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KR1020060129009A
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KR20080055543A (en
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정학기
송상민
강충석
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코오롱인더스트리 주식회사
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Priority to KR1020060129009A priority Critical patent/KR101167341B1/en
Priority to JP2009541229A priority patent/JP4891411B2/en
Priority to PCT/KR2007/006514 priority patent/WO2008072916A1/en
Priority to US12/518,258 priority patent/US20100048861A1/en
Priority to PCT/KR2007/006512 priority patent/WO2008072914A1/en
Priority to TW96148310A priority patent/TWI376392B/en
Priority to TW96148315A priority patent/TWI376394B/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers

Abstract

본 발명은 무색의 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름에 관한 것으로, 방향족 디안하이드라이드로서 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(FDA)를 포함하고, 방향족 디아민으로서 화학식 1로 표시되는 디아민과 화학식 2로 표시되는 디아민을 포함하는 폴리이미드 수지를 제공함으로써, 무색투명하고, 기계적 물성 및 열안정성의 물성이 우수하여 반도체 절연막, TFT-LCD 절연막, 투명전극필름, 패시베이션막, 액정배향막, 광통신용 재료, 태양전지용 보호막, 플랙시블 디스플레이 기판 등의 다양한 분야에 사용가능한 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름을 제공할 수 있는 발명이다.The present invention relates to a colorless polyimide resin, a liquid crystal alignment film and a film using the same, and includes 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (FDA) as an aromatic dianhydride. By providing a polyimide resin comprising a diamine represented by the formula (1) and a diamine represented by the formula (2) as the aromatic diamine, it is colorless and transparent, excellent in mechanical properties and thermal stability physical properties, semiconductor insulating film, TFT-LCD insulating film, The present invention provides a polyimide resin, a liquid crystal alignment film and a film using the same, which can be used in various fields such as a transparent electrode film, a passivation film, a liquid crystal alignment film, an optical communication material, a solar cell protective film, and a flexible display substrate.

<화학식 1>&Lt; Formula 1 >

Figure 112006093227834-pat00001
Figure 112006093227834-pat00001

상기 식에서 R1은

Figure 112006093227834-pat00002
또는
Figure 112006093227834-pat00003
이다.In which R 1 is
Figure 112006093227834-pat00002
or
Figure 112006093227834-pat00003
to be.

<화학식 2><Formula 2>

Figure 112006093227834-pat00004
Figure 112006093227834-pat00004

상기 식에서 R2는

Figure 112006093227834-pat00005
,
Figure 112006093227834-pat00006
,
Figure 112006093227834-pat00007
,
Figure 112006093227834-pat00008
및
Figure 112006093227834-pat00009
중 선택된 구조이다.In which R 2 is
Figure 112006093227834-pat00005
,
Figure 112006093227834-pat00006
,
Figure 112006093227834-pat00007
,
Figure 112006093227834-pat00008
And
Figure 112006093227834-pat00009
Among the structures selected.

Description

무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름{Colorless polyimide resin, and liquid crystal alignment layer and polyimide film using the same}Colorless and transparent polyimide resin and liquid crystal alignment layer and film using same {Colorless polyimide resin, and liquid crystal alignment layer and polyimide film using the same}

도 1은 본 발명의 폴리이미드 수지를 이용하여 액정 배향막을 제조한 한 형태를 도시한 것이다.FIG. 1: shows one form which produced the liquid crystal aligning film using the polyimide resin of this invention.

*도면의 주요부호의 설명* Explanation of the main symbols in the drawings

1, 2 : 유리기판 3 : 배향막 1, 2: glass substrate 3: alignment film

4 : 액정분자 5 : 액정층4: liquid crystal molecule 5: liquid crystal layer

α : 선경사각(pretilt angle)α: pretilt angle

본 발명은 무색의 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름에 관한 것이다.The present invention relates to a colorless polyimide resin and a liquid crystal alignment film and a film using the same.

일반적으로 폴리이미드(PI) 수지라 함은 방향족 디안하이드라이드와 방향족 디아민 또는 방향족 디이소시아네이트를 용액중합하여 폴리아믹산 유도체를 제조한 후, 고온에서 폐환탈수시켜 이미드화하여 제조되는 고내열수지를 일컫는다. 폴리이미드 수지를 제조하기 위하여 방향족 디안하이드라이드 성분으로서 피로멜리트산이무수물(PMDA) 또는 비페닐테트라카르복실산이무수물(BPDA) 등을 사용하고 있고, 방향족 디아민 성분으로서는 옥시디아닐린(ODA), p-페닐렌 디아민(p-PDA), m-페닐렌 디아민(m-PDA), 메틸렌디아닐린(MDA), 비스아미노페닐헥사플루오로프로판(HFDA) 등을 사용하고 있다. In general, the polyimide (PI) resin refers to a high heat-resistant resin prepared by solution polymerization of an aromatic dianhydride and an aromatic diamine or an aromatic diisocyanate to prepare a polyamic acid derivative, and then imidization by cyclization of the ring at a high temperature. In order to prepare a polyimide resin, pyromellitic dianhydride (PMDA) or biphenyltetracarboxylic dianhydride (BPDA) or the like is used as an aromatic dianhydride component, and oxydianiline (ODA), p is used as an aromatic diamine component. -Phenylene diamine (p-PDA), m-phenylene diamine (m-PDA), methylenedianiline (MDA), bisaminophenylhexafluoropropane (HFDA) and the like are used.

폴리이미드 수지는 불용, 불융의 초고내열성 수지로서 내열산화성, 내열특성, 내방사선성, 저온특성, 내약품성 등에 우수한 특성을 가지고 있어, 자동차 재료, 항공소재, 우주선 소재 등의 내열 첨단소재 및 절연코팅제, 절연막, 반도체, TFT-LCD의 전극 보호막 등 전자재료에 광범위한 분야에 사용되고, 최근에는 광섬유나 액정 배향막 같은 표시재료 및 필름 내에 도전성 필러를 함유하거나 표면에 코팅하여 투명전극필름 등에도 이용되고 있다.Polyimide resin is an insoluble and insoluble ultra high heat resistant resin, and has excellent characteristics such as heat oxidation resistance, heat resistance, radiation resistance, low temperature property, chemical resistance, and so on. It is used in a wide range of fields for electronic materials such as insulating films, semiconductors, electrode protective films of TFT-LCDs, and recently, it has been used in transparent electrode films and the like by containing conductive fillers in the display materials and films such as optical fibers and liquid crystal alignment films or by coating the surfaces thereof.

그러나 폴리이미드 수지는 높은 방향족 고리 밀도로 인하여 갈색 또는 황색으로 착색되어 있어 가시광선 영역에서의 투과도가 낮고 노란색 계열의 색을 나타내어 광투과율을 낮게 하여 투명성이 요구되는 분야에 사용하기에는 곤란한 점이 있었다. However, polyimide resins are colored brown or yellow due to the high aromatic ring density, and thus have a low transmittance in the visible region and a yellow-based color, which makes it difficult to be used in applications requiring transparency due to low light transmittance.

이러한 점을 해결하기 위하여 단량체 및 용제를 고순도로 정제하여 중합을 하는 방법이 시도되었으나, 투과율의 개선은 크지 않았다.In order to solve this problem, a method of polymerizing the monomer and the solvent by high purity has been attempted, but the improvement of the transmittance is not large.

미국특허 제5053480호에는 방향족 디안하이드라이드 대신 지방족 고리계 디안하이드라이드 성분을 사용하는 방법이 기재되어 있는데, 정제방법에 비해서는 용액상이나 필름화하였을 경우 투명도 및 색상의 개선이 있었으나, 역시 투과도의 개선에 한계가 있어 높은 투과도는 만족하지 못하였으며, 또한 열 및 기계적 특성의 저하를 가져오는 결과를 나타내었다.U.S. Patent No. 553480 describes a method of using an aliphatic ring-based dianhydride component instead of an aromatic dianhydride, and compared to the purification method, there was an improvement in transparency and color when solution or film was formed, but also an improvement in permeability. There was a limit to the high permeability was not satisfactory, and also resulted in degradation of thermal and mechanical properties.

또한 미국특허 제4595548호, 제4603061호, 제4645824, 제4895972호, 제5218083호, 제5093453호, 제5218077호, 제5367046호, 제5338826호. 제5986036호, 제6232428호 및 대한민국 특허공개공보 제2003-0009437호에는 -O-, -SO2-, CH2- 등의 연결기와 p-위치가 아닌 m-위치로의 연결된 굽은 구조의 단량체이거나 -CF3 등의 치환기를 갖는 방향족 디안하이드라이드 이무수물과 방향족 디아민 단량체를 사용하여 열적 특성이 크게 저하되지 않는 한도에서 투과도 및 색상의 투명도를 향상시킨 신규 구조의 폴리이미드를 제조한 보고가 있으나, 기계적 특성, 황변도 및 가시광선 투과도는 반도체 절연막, TFT-LCD 절연막, 전극 보호막, 플랙시블 디스플레이용 기재층으로 사용하기는 부족한 결과를 보였다.See also U.S. Pat.Nos. 4,595,548,4603061, 4,464,824,4895972, 52,18083, 5,345,3, 52,18077, 53,670, 46,337. No. 5986036, 6262328 and Korean Patent Publication No. 2003-0009437 are monomers having a curved structure connected to a linking group, such as -O-, -SO 2- , CH 2 -and the m-position rather than the p-position A report has been made of a novel polyimide structure having improved transmittance and color transparency using aromatic dianhydride dianhydrides having substituents such as -CF 3 and aromatic diamine monomers, without increasing the thermal properties significantly. Mechanical properties, yellowness and visible light transmittance have been insufficient to be used as a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a base layer for flexible displays.

따라서 본 발명은 무색투명하면서 기계적 물성 및 열안정성의 물성이 우수한 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름을 제공하는 데 그 목적이 있다.Accordingly, an object of the present invention is to provide a polyimide resin having a colorless transparency and excellent mechanical properties and thermal stability, and a liquid crystal alignment film and a film using the same.

상기의 목적을 달성하기 위한 본 발명은 방향족 디안하이드라이드로서 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(FDA)를 포함하고, 방향족 디아민으로서 화학식 1로 표시되는 디아민과 화학식 2로 표시되는 디아민을 포함하는 폴리이미드 수지를 제공한다. The present invention for achieving the above object includes 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (FDA) as aromatic dianhydride, represented by the formula (1) as aromatic diamine It provides a polyimide resin comprising a diamine and a diamine represented by the formula (2).

<화학식 1>&Lt; Formula 1 >

Figure 112006093227834-pat00010
Figure 112006093227834-pat00010

상기 식에서 R1은

Figure 112006093227834-pat00011
또는
Figure 112006093227834-pat00012
이다.Where R 1 is
Figure 112006093227834-pat00011
or
Figure 112006093227834-pat00012
to be.

<화학식 2><Formula 2>

Figure 112006093227834-pat00013
Figure 112006093227834-pat00013

상기 식에서 R2는

Figure 112006093227834-pat00014
,
Figure 112006093227834-pat00015
,
Figure 112006093227834-pat00016
,
Figure 112006093227834-pat00017
및
Figure 112006093227834-pat00018
중 선택된 구조이다.In which R 2 is
Figure 112006093227834-pat00014
,
Figure 112006093227834-pat00015
,
Figure 112006093227834-pat00016
,
Figure 112006093227834-pat00017
And
Figure 112006093227834-pat00018
Among the structures selected.

본 발명은 상기 방향족 디안하이드라이드로서 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트라하이드로나프탈렌-1,2-디카르복실릭 안하이드라이드(TDA)를 더 포함하는 것을 특징으로 한다.The present invention provides 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride as the aromatic dianhydride. It further comprises (TDA).

아울러 본 발명은 폴리이미드 수지를 포함하는 액정 배향막을 제공한다.Moreover, this invention provides the liquid crystal aligning film containing polyimide resin.

상기 액정 배향막은 선경사각(Pretilt Angle)이 0~2°인 것임을 특징으로 한다.The liquid crystal alignment layer is characterized in that the pretilt angle (Pretilt Angle) is 0 ~ 2 °.

또한 본 발명은 상기의 폴리이미드 수지를 포함하는 무색투명한 폴리이미드 필름을 제공한다.The present invention also provides a colorless and transparent polyimide film containing the polyimide resin.

상기 폴리이미드 필름은 필름 두께 50~100㎛를 기준으로 UV분광계로 측정시 380~780㎚에서의 평균 투과도가 85% 이상이고, 551~780㎚에서의 평균 투과도가 88% 이상인 것을 특징으로 한다.The polyimide film has an average transmittance of 85% or more at 380 to 780 nm and an average transmittance at 551 to 780 nm of 88% or more, as measured by a UV spectrometer, based on a film thickness of 50 to 100 μm.

상기 폴리이미드 필름은 필름 두께 50~100㎛를 기준으로 UV분광계로 측정시 550㎚에서 투과도가 88% 이상, 500㎚에서 투과도가 85% 이상, 420㎚에서 투과도가 50% 이상인 것을 특징으로 한다.The polyimide film has a transmittance of 88% or more at 550 nm, a transmittance of 85% or more at 500 nm, and a transmittance of 50% or more at 420 nm when measured with a UV spectrometer based on a film thickness of 50 to 100 μm.

상기 폴리이미드 필름은 필름 두께 50~100㎛를 기준으로 황변도가 15 이하인 것을 특징으로 한다.The polyimide film has a yellowing degree of 15 or less based on a film thickness of 50 to 100 μm.

상기 폴리이미드 필름은 1GHz에서의 유전율이 3.0 이하인 것을 특징으로 한다.The polyimide film is characterized by a dielectric constant of 3.0 or less at 1 GHz.

상기 폴리이미드 필름은 50~200℃에서의 평균 선팽창 계수(CTE)가 50ppm 이하인 것을 특징으로 한다.The polyimide film has an average linear expansion coefficient (CTE) of 50 ppm or less at 50 to 200 ° C.

상기 폴리이미드 필름은 탄성률은 3.0GPa 이상인 것을 특징으로 한다.The polyimide film has an elastic modulus of 3.0 GPa or more.

상기 폴리이미드 필름은 UV분광계로 투과도를 측정시 50% 차단파장(cut off wavelength)이 400㎚ 이하인 것을 특징으로 한다.The polyimide film has a 50% cut off wavelength of 400 nm or less when measuring transmittance with a UV spectrometer.

이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명의 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름은 디아민 성분과 디안하이드라이드 성분을 공중합하여 이루어진 것으로, 특히 무색투명한 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름이다. The polyimide resin and the liquid crystal aligning film and film using the same of the present invention are made by copolymerizing a diamine component and a dianhydride component, and are particularly colorless and transparent polyimide resins and liquid crystal aligning films and films using the same.

이를 위하여 사용되는 방향족 디안하이드라이드는 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(FDA)를 필수적으로 포함한다. The aromatic dianhydrides used for this purpose essentially comprise 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (FDA).

이 외 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트라하이드로나프 탈렌-1,2-디카르복실릭안하이드라이드(TDA)를 더 포함할 수 있다. 이 때 상기 FDA 성분은 전체 디안하이드라이드 성분 중 1~99몰%의 범위로 사용하는 것이 바람직하며, 더욱 좋게는 10~90몰%의 범위로 사용하는 것이 바람직하다.In addition, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthylene-1,2-dicarboxylic anhydride (TDA) may further be included. Can be. At this time, the FDA component is preferably used in the range of 1 to 99 mol% of the total dianhydride component, and more preferably in the range of 10 to 90 mol%.

이로써 투명하고 가시광선의 투과도가 높고, UV흡수율과 황변도가 낮으며, 높은 점도를 갖는 폴리아믹산의 제조가 가능할 수 있다. As a result, it may be possible to prepare a polyamic acid that is transparent and has high transmittance of visible light, low UV absorption and yellowing, and high viscosity.

한편, 본 발명에서 사용되는 방향족 디아민으로서 화학식 1로 표시되는 디아민과 화학식 2로 표시되는 디아민을 필수적으로 포함한다.On the other hand, the aromatic diamine used in the present invention essentially includes a diamine represented by the formula (1) and a diamine represented by the formula (2).

<화학식 1>&Lt; Formula 1 >

Figure 112006093227834-pat00019
Figure 112006093227834-pat00019

상기 식에서 R1은

Figure 112006093227834-pat00020
또는
Figure 112006093227834-pat00021
이다.In which R 1 is
Figure 112006093227834-pat00020
or
Figure 112006093227834-pat00021
to be.

<화학식 2><Formula 2>

Figure 112006093227834-pat00022
Figure 112006093227834-pat00022

상기 식에서 R2는

Figure 112006093227834-pat00023
,
Figure 112006093227834-pat00024
,
Figure 112006093227834-pat00025
,
Figure 112006093227834-pat00026
및
Figure 112006093227834-pat00027
중 선택된 구조이다.In which R 2 is
Figure 112006093227834-pat00023
,
Figure 112006093227834-pat00024
,
Figure 112006093227834-pat00025
,
Figure 112006093227834-pat00026
And
Figure 112006093227834-pat00027
Among the structures selected.

이 때 상기 화학식 1로 표시되는 디아민 성분을 전체 디아민 성분 중 10~90몰%의 범위로 사용하는 것이 바람직하며, 더욱 좋게는 20~80몰%의 범위인 것이 바람직하다. 이로써 높은 투과도와 투명도를 가질 수 있으며, 전기적 특성, 열적 특성 및 기계적 특성이 개선될 수 있다.At this time, it is preferable to use the diamine component represented by the said Formula (1) in the range of 10-90 mol% among all the diamine components, More preferably, it is the range of 20-80 mol%. This may have a high transmittance and transparency, electrical properties, thermal properties and mechanical properties can be improved.

이상의 디안하이드라이드 성분과 디아민 성분은 등몰량이 되도록 하여 유기용매 중에 용해하여 반응시키고 폴리아믹산 용액을 제조한다. The dianhydride component and the diamine component described above are dissolved in an organic solvent in an equimolar amount to react to prepare a polyamic acid solution.

반응시의 조건은 특별히 한정되지 않지만 반응 온도는 -20~80℃가 바람직하고, 반응시간은 2~48시간이 바람직하다. 또한 반응시 아르곤이나 질소 등의 불활성 분위기인 것이 보다 바람직하다.Although the conditions at the time of reaction are not specifically limited, The reaction temperature is preferably -20 to 80 ° C, and the reaction time is preferably 2 to 48 hours. Moreover, it is more preferable that it is inert atmosphere, such as argon and nitrogen, at the time of reaction.

상기한 단량체들의 용액 중합반응을 위한 유기용매는 폴리아믹산을 용해하는 용매이면 특별히 한정되지 않는다. 공지된 반응용매로서 m-크레졸, N-메틸-2-피롤리돈(NMP), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 디메틸설폭사이 드(DMSO), 아세톤, 디에틸아세테이트 중에서 선택된 하나 이상의 극성용매를 사용한다. 이외에도 테트라하이드로퓨란(THF), 클로로포름과 같은 저비점 용액 또는 γ-부티로락톤과 같은 저흡수성 용매를 사용할 수 있다.The organic solvent for the solution polymerization of the monomers described above is not particularly limited as long as it is a solvent in which the polyamic acid is dissolved. As a known reaction solvent, m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), acetone, diethyl acetate Use at least one polar solvent selected. In addition, low boiling point solutions such as tetrahydrofuran (THF), chloroform or low absorbing solvents such as γ-butyrolactone may be used.

유기용매의 함량에 대하여 특별히 한정되지는 않으나, 적절한 폴리아믹산 용액의 분자량과 점도를 얻기 위하여 유기용매의 함량은 전체 폴리아믹산 용액 중 50~95중량%가 바람직하고, 더욱 좋게는 70~90중량%인 것이 보다 바람직하다. The content of the organic solvent is not particularly limited, but in order to obtain an appropriate molecular weight and viscosity of the polyamic acid solution, the content of the organic solvent is preferably 50 to 95% by weight of the total polyamic acid solution, and more preferably 70 to 90% by weight. It is more preferable that is.

이와 같이 제조된 폴리아믹산 용액을 이미드화하여 제조된 폴리이미드 수지는 유리전이온도가 200~350℃인 것이 바람직하다.The polyimide resin prepared by imidating the polyamic acid solution thus prepared is preferably a glass transition temperature of 200 ~ 350 ℃.

상기한 단량체들로 인해 제조된 폴리아믹산을 액정 배향막으로 사용시에는 유리기판(일반적으로 ITO Glass)위에 스핀 코팅 또는 롤 코팅 한 후 80℃/5분, 250℃/20분 열경화 공정을 거쳐서 용제를 제거함과 동시에 폴리이미드화를 진행하여 유리기판 위에 박막(보통 100~1000nm 정도)을 형성키게 되는데, 이때 코팅성, 표면 평탄성 등의 개선 및 공정 적용성을 위해 제조된 폴리아믹산 용액을 적절한 코팅용액의 점도인 10 ~ 50cps로 희석하여 사용하며, 이때 희석을 위해 사용되는 용제는 중합용으로 사용된 용제로 제한되는 것은 아니다. 공지된 희석용매로는 N-메틸-2-피롤리돈(NMP), 디메틸포름아미드(DMF), 디메틸아세트아미드(DMAc), 또는 γ-부티로락톤과, 2-n-부톡시에탄올 등이 있으며, 이들 중에서 선택된 하나 이상의 극성용매를 단독 또는 혼합하여 사용 한다. When using polyamic acid prepared by the above monomers as a liquid crystal alignment film, spin coating or roll coating on a glass substrate (usually ITO Glass), followed by 80 ° C./5 minutes, 250 ° C./20 minutes thermal curing process. At the same time, polyimide is removed to form a thin film (usually about 100 ~ 1000 nm) on the glass substrate. At this time, the polyamic acid solution prepared for improvement of coating property, surface flatness, and process applicability may be Dilute to a viscosity of 10 ~ 50cps, where the solvent used for dilution is not limited to the solvent used for polymerization. Known diluents include N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethylacetamide (DMAc), or γ-butyrolactone, 2-n-butoxyethanol, and the like. One or more polar solvents selected from these are used alone or in combination.

또한 이때 상기한 단량체들로 인해 제조된 폴리아믹산을 액정 배향막으로 사용시에는 아래에 열거한 코팅액의 제조법 중에서 선택된 한가지 이상의 방법에 따라 제조한다. In addition, when using the polyamic acid prepared by the above-described monomers as a liquid crystal alignment film, it is prepared according to one or more methods selected from the methods of preparing a coating solution listed below.

1. 폴리아믹산 용액 사용 1. Using polyamic acid solution

2. 중합된 폴리아믹산을 열 및/또는 화학적 경화를 통해 폴리이미드화 한 후 침전법을 이용하여 수지화하여 다시 유기용매에 녹여 용액(즉 코팅액)화 하여 사용2. The polymerized polyamic acid is polyimidized by heat and / or chemical curing, then resinized using precipitation method, dissolved in organic solvent, and then converted into a solution (ie, coating solution).

3. 2.와 같이 중합된 폴리아믹산을 열 및/또는 화학적 경화를 통해 폴리이미드화 한 후 (수지화 하지 않고) 코팅액으로 사용 3. Use polyamic acid polymerized as 2. in polyimide through thermal and / or chemical curing and then as a coating solution (without resination).

4. 1.의 형태와 2. 또는 3.의 형태의 용액을 혼합하여 코팅액으로 사용 4. Mix the solution in the form of 1. and 2. or 3. and use it as coating liquid.

5. 1.의 폴리아믹산 용액에 2.의 방법으로 제조된 수지를 첨가(용해)하여 코팅액으로 사용 5. Add (dissolve) the resin prepared by the method of 2. to the polyamic acid solution of 1.

또한 상기의 방법으로 제조된 코팅액들은 코팅공정 직전에 Pore 사이즈가 0.1 ~ 5㎛ 의 갖는 범위 내에서 선택한 미립자(Particle) 및 이온 필터를 사용해 2단계 이상의 여과를 거쳐서 사용한다.In addition, the coating liquids prepared by the above method are used through two or more steps of filtration using a particle and an ion filter selected in the range having a pore size of 0.1 to 5 μm immediately before the coating process.

본 발명의 폴리이미드 수지는 액정 배향막으로 사용할 경우 안정된 선경사각(Pretilt angle)을 갖는다. 선경사각이란 액정에 전압을 가하여 액정을 일정방향으로 배열시킬 때, 전압에 대한 응답속도를 빠르게 해주기 위하여 미리 약간 액정 을 세워두는 각을 말하는 것으로, 본 발명의 폴리이미드수지를 포함하는 액정 배향막은 0~2°의 안정된 선경사각을 나타내므로, 2°미만의 선경사각을 요구하는 IPS(In-Plane Switching)모드용 배향막으로 적용이 가능하게 된다. The polyimide resin of the present invention has a stable pretilt angle when used as a liquid crystal alignment film. The pretilt angle refers to an angle in which the liquid crystal is set up in advance in order to increase the response speed to the voltage when the liquid crystals are arranged in a predetermined direction by applying a voltage to the liquid crystal. The liquid crystal alignment layer including the polyimide resin of the present invention is 0 Since it exhibits a stable pretilt angle of ˜2 °, it can be applied as an alignment film for IPS (In-Plane Switching) mode requiring a pretilt angle of less than 2 °.

아울러 폴리아믹산 용액을 이용하여 폴리이미드 필름으로 제조시, 폴리이미드 필름의 접동성, 열전도성, 도전성, 내코로나성과 같은 여러 가지 특성을 개선시킬 목적으로 폴리아믹산 용액에 충전제를 첨가할 수 있다. 충전제로는 특별히 한정되지 않지만, 바람직한 구체예로는 실리카, 산화티탄, 층상실리카, 카본나노튜브, 알루미나, 질화규소, 질화붕소, 인산수소칼슘, 인산칼슘, 운모 등을 들 수 있다. In addition, when preparing a polyimide film using a polyamic acid solution, a filler may be added to the polyamic acid solution for the purpose of improving various properties such as the sliding property, thermal conductivity, conductivity, and corona resistance of the polyimide film. Although it does not specifically limit as a filler, As a preferable specific example, a silica, titanium oxide, layered silica, carbon nanotube, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, etc. are mentioned.

상기 충전제의 입경은 개질하여야 할 필름의 특성과 첨가하는 충전제의 종류에 따라서 변동될 수 있는 것으로, 특별히 한정되지 않으나, 일반적으로는 평균 입경이 0.001~50㎛인 것이 바람직하고, 0.005~25㎛인 것이 보다 바람직하며, 더욱 바람직하게는 0.01~10㎛인 것이 좋다. 이 경우 폴리이미드 필름의 개질효과가 나타나기 쉽고, 폴리이미드 필름에 있어서 양호한 표면성, 도전성 및 기계적 특성을 얻을 수 있다.The particle diameter of the filler may vary depending on the characteristics of the film to be modified and the type of filler to be added, but is not particularly limited, but in general, the average particle diameter is preferably 0.001-50 μm, and preferably 0.005-25 μm. It is more preferable, More preferably, it is good that it is 0.01-10 micrometers. In this case, the modification effect of a polyimide film tends to appear, and favorable surface property, electroconductivity, and a mechanical characteristic can be acquired in a polyimide film.

또한 상기 충전제의 첨가량에 대해서도 개질해야 할 필름 특성이나 충전제 입경 등에 따라 변동할 수 있는 것으로 특별히 한정되는 것은 아니다. 일반적으로 충전제의 첨가량은 폴리아믹산 용액 100중량부에 대하여 0.001~20중량부인 것이 바람직하고, 더욱 바람직하게는 0.01~10중량부인 것이 좋다.Moreover, it does not specifically limit as it can fluctuate also with the film characteristic to be modified, filler particle diameter, etc. about the addition amount of the said filler. Generally, it is preferable that the addition amount of a filler is 0.001-20 weight part with respect to 100 weight part of polyamic-acid solutions, More preferably, it is 0.01-10 weight part.

충전제의 첨가 방법은 특별히 한정되는 것은 아니지만, 예를 들면, 중합 전 또는 중합 후에 폴리아믹산 용액에 첨가하는 방법, 폴리아믹산 중합 완료 후 3본롤 등을 사용하여 충전제를 혼련하는 방법, 충전제를 포함하는 분산액을 준비하여 이것을 폴리아믹산 용액에 혼합하는 방법 등을 들 수 있다.The addition method of a filler is not specifically limited, For example, the method of adding to a polyamic-acid solution before superposition | polymerization or after superposition | polymerization, the method of kneading a filler using 3 rolls etc. after completion | finish of polyamic acid polymerization, the dispersion liquid containing filler The method of preparing and mixing this into a polyamic-acid solution, etc. are mentioned.

상기 수득된 폴리아믹산 용액으로부터 폴리이미드 필름을 제조하는 방법은 특별히 한정되는 것이 아니고, 종래부터 공지된 방법을 사용할 수 있다. 폴리아믹산 용액의 이미드화시키는 방법으로는 열 이미드화법과 화학 이미드화법을 들 수 있는데, 화학적 이미드화법을 사용하는 것이 보다 바람직하다. 화학 이미드화법은 폴리아믹산 용액에 아세트산무수물 등의 산무수물로 대표되는 탈수제와 이소퀴놀린, β-피콜린, 피리딘 등의 3급 아민류 등으로 대표되는 이미드화 촉매를 적용시키는 방법이다. 화학 이미드화법에 열 이미드화법을 병용할 수 있으며, 가열 조건은 폴리아믹산 용액의 종류, 필름의 두께 등에 의하여 변동될 수 있다.The method of manufacturing a polyimide film from the obtained polyamic-acid solution is not specifically limited, A conventionally well-known method can be used. As a method of imidating a polyamic-acid solution, a thermal imidation method and a chemical imidation method are mentioned, It is more preferable to use a chemical imidation method. The chemical imidization method is a method of applying an imidization catalyst represented by a dehydrating agent represented by acid anhydrides such as acetic anhydride and tertiary amines such as isoquinoline, β-picolin and pyridine to the polyamic acid solution. The thermal imidation method may be used in combination with the chemical imidization method, and the heating conditions may vary depending on the type of the polyamic acid solution, the thickness of the film, and the like.

폴리아믹산 용액을 지지체상에서 80~200℃, 바람직하게는 100~180℃에서 가열하여 탈수제 및 이미드화 촉매를 활성화함으로써 부분적으로 경화 및 건조한 후 겔 상태의 폴리아믹산 필름을 지지체로부터 박리하여 얻고, 상기 겔 상태의 필름을 200~400℃에서 5~400초간 가열하여 폴리이미드 필름을 얻는다. The polyamic acid solution was heated at 80-200 ° C. on the support, preferably 100-180 ° C. to activate the dehydrating agent and the imidization catalyst, thereby partially curing and drying the polyamic acid film in a gel state to obtain a peeled from the support, and the gel The film of a state is heated at 200-400 degreeC for 5 to 400 second, and a polyimide film is obtained.

얻어지는 폴리이미드 필름의 두께는 특별히 한정되는 것은 아니지만, 10~250㎛의 범위인 것이 바람직하고, 보다 바람직하게는 25~150㎛인 것이 좋다.Although the thickness of the polyimide film obtained is not specifically limited, It is preferable that it is the range of 10-250 micrometers, More preferably, it is 25-150 micrometers.

본 발명에서 제조된 폴리이미드 필름은 필름 두께 50~100㎛를 기준으로 UV분 광계로 투과도 측정시 550㎚에서 투과도가 88% 이상, 500㎚에서 투과도가 85% 이상, 420㎚에서 투과도가 50% 이상인 것이 바람직하다. 더 나아가 380~780㎚에서의 평균 투과도가 85% 이상이며, 551~780㎚에서 평균 투과도가 88% 이상인 것이 바람직하다.The polyimide film prepared in the present invention has a transmittance of 88% or more at 550 nm, a transmittance of at least 85% at 500 nm, and a transmittance of 50% at 420 nm when measuring transmittance with a UV spectrophotometer based on a film thickness of 50 to 100 μm. It is preferable that it is above. Furthermore, it is preferable that the average transmittance at 380-780 nm is 85% or more, and the average transmittance at 551-780 nm is 88% or more.

또한 필름 두께 50~100㎛를 기준으로 황변도가 15 이하인 것이 바람직하다.Moreover, it is preferable that yellowing degree is 15 or less based on film thickness of 50-100 micrometers.

상기의 투과도 및 황변도를 만족하는 본 발명의 폴리이미드 필름은 기존의 폴리이미드 필름이 갖는 노란색으로 인하여 사용이 제한되었던 보호막 또는 TFT-LCD 등에서의 확산판 및 코팅막, 예컨대 TFT-LCD에서 Interlayer, Gate Insulator 및 액정 배향막 등 투명성이 요구되는 분야에 사용이 가능하며, 액정배향막으로 상기의 투명 폴리이미드를 적용시 개구율 증가에 기여하여 고대비비의 TFT-LCD의 제조가 가능하다. 또한, 플렉시블 디스플레이 기판(Flexible Display substrate)용으로 사용이 가능하다.The polyimide film of the present invention that satisfies the above-mentioned transmittance and yellowing degree is used for diffusion plates and coating films in protective films or TFT-LCDs, which are limited in use due to the yellow color of existing polyimide films, such as in interlayers and gates in TFT-LCDs. It can be used in fields requiring transparency such as insulator and liquid crystal alignment film, and it is possible to manufacture high-contrast TFT-LCD by contributing to increase of aperture ratio when applying transparent polyimide as liquid crystal alignment film. It can also be used for flexible display substrates.

또한 본 발명의 폴리이미드 필름은 1GHz에서의 유전율이 3.0 이하인 것이 바람직하며, 이로부터 반도체에서의 패시베이션(passivation) 막으로의 사용이 가능해진다.In addition, the polyimide film of the present invention preferably has a dielectric constant of 3.0 or less at 1 GHz, which makes it possible to use a passivation film in a semiconductor.

한편, 본 발명의 폴리이미드 필름은 50~200℃에서의 평균 선팽창 계수(CTE)가 50ppm 이하인 것이 바람직한데, 50ppm 초과일 경우 필름 상에 박막 트랜지스터(TFT)를 올리는 공정(TFT ARRAY)에서 폴리이미드 필름을 사용하는 경우, 공정 온 도 변화에 따라 필름이 수축/팽창을 하기 때문에 전극 도핑공정에서 얼라인먼트(Allignment)가 맞지 않으며, 또한 필름이 수평(평탄화)성을 유지 하지 못해서 휨 현상이 발생되는 문제가 있다. 따라서 CTE값이 작을수록 정밀한 TFT 공정이 가능하다.Meanwhile, the polyimide film of the present invention preferably has an average linear expansion coefficient (CTE) of 50 ppm or less at 50 to 200 ° C., and when the polyimide film is more than 50 ppm, the polyimide in the process of raising a thin film transistor (TFT) on the film (TFT ARRAY) In case of using film, alignment does not match during electrode doping process because the film shrinks / expands according to process temperature change, and the film does not maintain horizontality (flattening), resulting in warpage. There is. Therefore, the smaller the CTE value, the more precise TFT processing is possible.

아울러 본 발명의 폴리이미드 필름은 탄성률이 3.0GPa 이상인 것이 바람직한데, 이 경우 플랙시블 디스플레이 기판을 위한 롤투롤(Roll to Roll) 제조공정에의 적용이 더욱 용이하다. 폴리이미드 필름을 플랙시블 디스플레이(Flexible display) 및 FCCL용 기판 필름으로 사용시 롤투롤 공정을 거치게 되며, 이때 필름은 롤과 롤사이에서 감김과 풀림에 따른 장력을 받게 되는 바, 탄성률이 3.0GPa 미만의 값을 갖는 필름을 사용하는 경우 필름의 파단이 발생하기 때문이다.In addition, the polyimide film of the present invention preferably has an elastic modulus of 3.0 GPa or more. In this case, the polyimide film may be more easily applied to a roll-to-roll manufacturing process for a flexible display substrate. When the polyimide film is used as a flexible display and a substrate film for FCCL, it undergoes a roll-to-roll process, and the film is subjected to tension between winding and unrolling between rolls, and has an elastic modulus of less than 3.0 GPa. This is because breakage of the film occurs when a film having a value is used.

그리고 본 발명의 폴리이미드 필름은 UV분광계로 투과도 측정시 50% 차단파장(cut off wavelength)이 400㎚ 이하인 것이 바람직하다. 따라서 본 발명의 폴리이미드 필름은 태양전지(Solar cell) 등의 표면 보호막으로도 사용이 가능하다.The polyimide film of the present invention preferably has a 50% cut off wavelength of 400 nm or less when measuring transmittance with a UV spectrometer. Therefore, the polyimide film of the present invention can be used as a surface protective film such as a solar cell.

이하, 본 발명을 실시예를 통하여 보다 상세히 설명하나, 본 발명의 범위가 하기 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples.

<실시예 1> &Lt; Example 1 >

반응기로써 교반기, 질소주입장치, 적하깔때기, 온도조절기 및 냉각기를 부착한 100㎖ 3-Neck 둥근바닥 플라스크에 질소를 통과시키면서 N,N-디메틸아세타아미드(DMAc) 35.26648g을 채운 후, 반응기의 온도를 0℃로 낮춘 후 4-BDAF 3.62922g(0.007mol)을 용해하여 이 용액을 0℃로 유지하였다. 4-BDAF가 완전히 용해된 후 3-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시키고, 여기에 6-FDA 4.4425g(0.01mol)을 첨가하고, 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이 후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액점도 2400cps의 폴리아믹산 용액을 얻었다.After the reactor was filled with 35.26648 g of N, N-dimethylacetaamide (DMAc) while passing nitrogen through a 100 ml 3-Neck round bottom flask equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a cooler, After the temperature was lowered to 0 ° C., 3.62922 g (0.007 mol) of 4-BDAF was dissolved to maintain the solution at 0 ° C. After 4-BDAF is completely dissolved, 0.7449g (0.003mol) of 3-DDS is added to dissolve completely, and 4.4425g (0.01mol) of 6-FDA is added thereto and stirred for 1 hour to completely dissolve 6-FDA. I was. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the solution viscosity at 23 degreeC was obtained the polyamic-acid solution of 2400 cps.

반응이 종료된 후 수득된 폴리아믹산 용액을 유리판에서 Doctor blade를 이용하여 두께 500㎛~1000㎛로 캐스팅한 후 진공오븐에서 40℃에서 1시간, 60℃에서 2시간 건조하여 Self standing film을 얻은 후 고온 퍼니스 오븐에서 5℃/min의 승온속도로 80℃에서 3시간, 100℃에서 1시간, 200℃에서 1시간, 300℃에서 30분 가열하여 두께 50㎛ 및 100㎛인 폴리이미드 필름을 얻었다. After completion of the reaction, the polyamic acid solution obtained was cast to a thickness of 500㎛ ~ 1000㎛ by using a doctor blade on a glass plate and dried in a vacuum oven for 1 hour at 40 ℃, 2 hours at 60 ℃ to obtain a self standing film A polyimide film having a thickness of 50 μm and 100 μm was obtained by heating at 80 ° C. for 3 hours at 100 ° C., 1 hour at 100 ° C., 1 hour at 200 ° C., and 30 minutes at 300 ° C. in a high temperature furnace oven.

<실시예 2><Example 2>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 33.1052g에 4-BDAF 2.5923g(0.005mol)을 용해시키고, 3-DDS 1.2415g(0.005mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하여 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2100cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.5923 g (0.005 mol) of 4-BDAF was dissolved in 33.1052 g of N, N-dimethylacetamide (DMAc), and 1.2415 g (0.005 mol) of 3-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2100 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 3> <Example 3>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 30.94392g에 4-BDAF 1.55538g(0.003mol)을 용해시키고, 3-DDS 1.7381g(0.007mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1900cps인 폴리아믹산 용액을 얻었다. In Example 1, 4-BDAF 1.55538 g (0.003 mol) was dissolved in 30.94392 g of N, N-dimethylacetaamide (DMAc), and 3-DDS 1.7381 g (0.007 mol) was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1900 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 4> <Example 4>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 35.26648g에 4-BDAF 3.62922g(0.007mol)을 용해시키고, 4-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2300cps인 폴리아믹산 용액을 얻었다. In Example 1, 3.62922g (0.007mol) of 4-BDAF was dissolved in 35.26648g of N, N-dimethylacetaamide (DMAc), and 0.7449g (0.003mol) of 4-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2300 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 5> <Example 5>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 33.1052g에 4-BDAF 2.5923g(0.005mol)을 용해시키고, 4-DDS 1.2415g(0.005mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하여 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2000cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.5923 g (0.005 mol) of 4-BDAF was dissolved in 33.1052 g of N, N-dimethylacetamide (DMAc), and 1.2415 g (0.005 mol) of 4-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2000 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 6> <Example 6>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 30.94392g에 4-BDAF 1.55538g(0.003mol)을 용해시키고, 4-DDS 1.7381g(0.007mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1900cps인 폴리아믹산 용액을 얻었다. In Example 1, 4-BDAF 1.55538 g (0.003 mol) was dissolved in 30.94392 g of N, N-dimethylacetaamide (DMAc), and 4-DDS 1.7381 g (0.007 mol) was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1900 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 7> &Lt; Example 7 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.93484g에 APB-133 2.04631g(0.007mol)을 용해시키고, 3-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2200cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.04631 g (0.007 mol) of APB-133 was dissolved in 28.93484 g of N, N-dimethylacetaamide (DMAc), and 0.7449 g (0.003 mol) of 3-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2200 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 8> &Lt; Example 8 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.5826g에 APB-133 1,46165g(0.005mol)을 용해시키고, 3-DDS 1.2415g(0.005mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하여 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1900cps인 폴리아믹산 용액을 얻었다. In Example 1, 1,46165 g (0.005 mol) of APB-133 was dissolved in 28.5826 g of N, N-dimethylacetaamide (DMAc), and 1.2415 g (0.005 mol) of 3-DDS was completely dissolved. 4.4425 g (0.01 mol) of 6-FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1900 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 9> &Lt; Example 9 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.23036g에 APB-133 0.87699g(0.003mol)을 용해시키고, 3-DDS 1.7381g(0.007mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1800cps인 폴리아믹산 용액을 얻었다. In Example 1, 0.87699 g (0.003 mol) of APB-133 was dissolved in 28.23036 g of N, N-dimethylacetamide (DMAc), and dissolved completely by adding 1.7381 g (0.007 mol) of 3-DDS. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1800 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 10> &Lt; Example 10 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.93484g에 APB-133 3.62922g(0.007mol)을 용해시키고, 4-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2200cps인 폴리아믹산 용액을 얻었다. In Example 1, 3.62922 g (0.007 mol) of APB-133 was dissolved in 28.93484 g of N, N-dimethylacetaamide (DMAc), and 0.7449 g (0.003 mol) of 4-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2200 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 11> <Example 11>

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.5826g에 APB-133 2.5923g(0.005mol)을 용해시키고, 4-DDS 1.2415g(0.005mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하여 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2000cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.5923 g (0.005 mol) of APB-133 was dissolved in 28.5826 g of N, N-dimethylacetamide (DMAc), and 1.2415 g (0.005 mol) of 4-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2000 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 12> &Lt; Example 12 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 28.23036g에 APB-133 1.55538g(0.003mol)을 용해시키고, 4-DDS 1.7381g(0.007mol)을 투입하여 완전히 용해시킨 후, 6-FDA 4.4425g(0.01mol)을 첨가하고 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1900cps인 폴리아믹산 용액을 얻었다. In Example 1, 1.55538g (0.003mol) of APB-133 was dissolved in 28.23036g of N, N-dimethylacetaamide (DMAc), and 1.7381g (0.007mol) of 4-DDS was completely dissolved. 4.4425 g (0.01 mol) of -FDA was added and stirred for 1 hour to completely dissolve 6-FDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1900 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 13>&Lt; Example 13 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 33.5386g에 4-BDAF 3.62922g(0.007mol)을 용해시키고, 3-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 3.1097g(0.007mol)을 투입한 후 TDA 0.90078g(0.003mol)을 투입하여 1시간동안 교반하여 6-FDA 및 TDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2200cps인 폴리아믹산 용액을 얻었다. In Example 1, 3.62922g (0.007mol) of 4-BDAF was dissolved in 33.5386g of N, N-dimethylacetaamide (DMAc), and 0.7449g (0.003mol) of 3-DDS was completely dissolved. -FDA 3.1097g (0.007mol) was added, then 0.90078g (0.003mol) of TDA was added and stirred for 1 hour to completely dissolve 6-FDA and TDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2200 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 14>&Lt; Example 14 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 33.5386g에 4-BDAF 3.62922g(0.007mol)을 용해시키고, 4-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 3.1097g(0.007mol)을 투입한 후 TDA 0.90078g(0.003mol)을 투입하여 1시간동안 교반하여 6-FDA 및 TDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2100cps인 폴리아믹산 용액을 얻었다. In Example 1, 3.62922g (0.007mol) of 4-BDAF was dissolved in 33.5386g of N, N-dimethylacetamide (DMAc), and 0.7449g (0.003mol) of 4-DDS was completely dissolved. -FDA 3.1097g (0.007mol) was added, then 0.90078g (0.003mol) of TDA was added and stirred for 1 hour to completely dissolve 6-FDA and TDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2100 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 15>&Lt; Example 15 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 27.20696g에 APB-133 2.04631g(0.007mol)을 용해시키고, 3-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 3.10975g(0.007mol)을 투입한 후 TDA 0.90078g(0.003mol)을 투입하여 1시간동안 교반하여 6-FDA 및 TDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1900cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.04631 g (0.007 mol) of APB-133 was dissolved in 27.20696 g of N, N-dimethylacetaamide (DMAc), and 0.7449 g (0.003 mol) of 3-DDS was completely dissolved. -FDA 3.10975g (0.007mol) was added and TDA 0.90078g (0.003mol) was added and stirred for 1 hour to completely dissolve 6-FDA and TDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1900 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<실시예 16>&Lt; Example 16 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 27.20696g에 APB-133 2.04631g(0.007mol)을 용해시키고, 4-DDS 0.7449g(0.003mol)을 투입하여 완전히 용해시킨 후, 6-FDA 3.10975g(0.007mol)을 투입한 후 TDA 0.90078g(0.003mol)을 투입하여 1시간동안 교반하여 6-FDA 및 TDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1950cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.04631 g (0.007 mol) of APB-133 was dissolved in 27.20696 g of N, N-dimethylacetaamide (DMAc), and 0.7449 g (0.003 mol) of 4-DDS was completely dissolved. -FDA 3.10975g (0.007mol) was added and TDA 0.90078g (0.003mol) was added and stirred for 1 hour to completely dissolve 6-FDA and TDA. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1950 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Example 1.

<비교예 1>&Lt; Comparative Example 1 &

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 38.5084g에 4-BDAF 5.1846g(0.01mol)을 용해시키고, 6-FDA 4.4425g(0.01mol)을 투입한 후 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1300cps인 폴리아믹산 용액을 얻었다. In Example 1, 5.1846 g (0.01 mol) of 4-BDAF was dissolved in 38.5084 g of N, N-dimethylacetaamide (DMAc), and 4.4425 g (0.01 mol) of 6-FDA was added thereto, followed by stirring for 1 hour. 6-FDA was completely dissolved. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1300 cps was obtained.

이후 상기 실시예 1과 동일한 방법으로 폴리이미드 필름을 제조하였으며, 두께가 25㎛, 50㎛ 및 100㎛인 폴리이미드 필름을 얻었다.Thereafter, a polyimide film was prepared in the same manner as in Example 1, and a polyimide film having a thickness of 25 μm, 50 μm, and 100 μm was obtained.

<비교예 2>Comparative Example 2

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 29.4632g에 APB-133 2.9233g(0.01mol)을 용해시키고, 6-FDA 4.4425g(0.01mol)을 투입한 후 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1200cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.9233 g (0.01 mol) of APB-133 was dissolved in 29.4632 g of N, N-dimethylacetaamide (DMAc), and 4.4425 g (0.01 mol) of 6-FDA was added thereto, followed by stirring for 1 hour. 6-FDA was completely dissolved. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1200 cps was obtained.

이후 상기 비교예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Comparative Example 1.

<비교예 3>&Lt; Comparative Example 3 &

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 27.702g에 3-DDS 2.4830g(0.01mol)을 용해시키고, 6-FDA 4.4425g(0.01mol)을 투입한 후 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1300cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.4830 g (0.01 mol) of 3-DDS was dissolved in 27.702 g of N, N-dimethylacetaamide (DMAc), and 4.4425 g (0.01 mol) of 6-FDA was added thereto, followed by stirring for 1 hour. 6-FDA was completely dissolved. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1300 cps was obtained.

이후 상기 비교예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Comparative Example 1.

<비교예 4>&Lt; Comparative Example 4 &

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 27.702g에 4-DDS 2.4830g(0.01mol)을 용해하고, 6-FDA 4.4425g(0.01mol)을 투입한 후 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1400cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.4830 g (0.01 mol) of 4-DDS was dissolved in 27.702 g of N, N-dimethylacetamide (DMAc), and 4.4425 g (0.01 mol) of 6-FDA was added thereto, followed by stirring for 1 hour. 6-FDA was completely dissolved. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1400 cps was obtained.

이후 상기 비교예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Comparative Example 1.

<비교예 5>&Lt; Comparative Example 5 &

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 25.7796g에 ODA 2.0024g(0.01mol)을 용해시키고, 6-FDA 4.4425g(0.01mol)을 투입한 후 1시간동안 교반하여 6-FDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 1600cps인 폴리아믹산 용액을 얻었다. In Example 1, 2.025 g (0.01 mol) of ODA was dissolved in 25.7796 g of N, N-dimethylacetaamide (DMAc), 4.4425 g (0.01 mol) of 6-FDA was added thereto, followed by stirring for 1 hour. The FDA was completely dissolved. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 1600 cps was obtained.

이후 상기 비교예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Comparative Example 1.

<비교예 6>&Lt; Comparative Example 6 >

상기 실시예 1에서 N,N-디메틸아세타아미드(DMAc) 16.7344g에 ODA 2.0024g(0.01mol)을 용해시키고, PMDA 2.1812g(0.01mol)을 투입한 후 1시간동안 교반하여 PMDA를 완전히 용해시켰다. 이 때 고형분의 농도는 20중량%였으며, 이후 용액을 상온으로 방치하여 8시간 교반하였다. 이 때 23℃에서의 용액 점도가 2500poise인 폴리아믹산 용액을 얻었다. In Example 1, 2.0024 g (0.01 mol) of ODA was dissolved in 16.7344 g of N, N-dimethylacetaamide (DMAc), and 2.1812 g (0.01 mol) of PMDA was added thereto, followed by stirring for 1 hour to completely dissolve PMDA. I was. At this time, the concentration of the solid was 20% by weight, after which the solution was left at room temperature and stirred for 8 hours. At this time, the polyamic-acid solution whose solution viscosity in 23 degreeC is 2500 poise was obtained.

이후 상기 비교예 1과 동일한 방법으로 폴리이미드 필름을 제조하였다.Thereafter, a polyimide film was prepared in the same manner as in Comparative Example 1.

상기 실시예 및 비교예에서 제조된 폴리이미드 필름의 물성을 다음과 같이 측정하여 하기 표 1 내지 표 5에 나타내었다. The physical properties of the polyimide films prepared in Examples and Comparative Examples were measured as follows, and are shown in Tables 1 to 5 below.

(1) 투과도 및 50% 차단파장(1) Permeability and 50% blocking wavelength

실시예에서 제조된 필름을 UV분광계(Varian사, Cary100)를 이용하여 가시광선 투과도 및 50% 차단파장을 측정하였다.In the film prepared in Example, the visible light transmittance and 50% blocking wavelength were measured using a UV spectrometer (Varian, Cary 100).

(2) 황변도(2) yellowing degree

ASTM E313규격으로 황변도를 측정하였다.Yellowing degree was measured by ASTM E313 standard.

(3) 탄성율(3) elastic modulus

Instron사의 Universal Testing Machine Model 1000을 사용하여 JIS K 6301에 의거하여 측정하였다. The measurement was performed according to JIS K 6301 using Instron's Universal Testing Machine Model 1000.

(4) 유리전이온도(Tg)(4) Glass transition temperature (Tg)

시차주사열량계(DSC, TA Instrument사, Q200)를 이용하여 유리전이온도를 측 정하였다.Differential scanning calorimetry (DSC, TA Instrument, Q200) was used to measure the glass transition temperature.

(5) 선팽창계수(CTE)(5) coefficient of linear expansion (CTE)

TMA(TA Instrument사, Q400)를 이용하여 TMA-Method에 따라 50~200℃ 에서의 선팽창계수를 측정하였다.The coefficient of linear expansion at 50-200 ° C. was measured using TMA (TA Instrument, Q400) according to TMA-Method.

(6) 유전율(6) permittivity

ASTM D-150규격에 따라 유전율을 측정하였다.Permittivity was measured according to ASTM D-150 standard.

(7) 선경사각(Pretilt Angle)(7) Pretilt Angle

실시예 및 비교예의 폴리아믹산 용액을 희석 용제를 사용하여 용액점도를 10~50cps로 희석한 후, 2㎛, 0.45㎛, 0.2㎛ 의 Particle 및 이온 필터를 사용하여 여과하고, 유리기판(ITO Glass)에 코팅(코팅조건 : 스핀코팅, 400~4,000rpm, 10~40초)한 후, 80℃/5분, 250℃/20분 열경화 공정을 거쳐서 용제를 제거함과 동시에 하고 폴리이미드화를 진행하여 유리기판 위에 박막(보통 100~1000nm 정도)을 형성시킨다. 이 코팅된 유리기판(1, 2)을 상하판으로 하고, 유리기판(1, 2)사이의 공간에 액정분자(4)를 주입하여 액정층(5)을 포함하는 액정셀을 제작(도 1 참조)하여, 결 정회전법(Crystal Rotation Method)을 통하여 각 액정셀의 선경사각(pretilt angle)을 측정하였으며, 그 결과는 표 5와 같다.After diluting the solution viscosity of the polyamic acid solution of Examples and Comparative Examples to 10 ~ 50cps using a diluting solvent, and then filtered by using a particle and ion filter of 2㎛, 0.45㎛, 0.2㎛, ITO Glass After coating on (coating condition: spin coating, 400 ~ 4,000rpm, 10 ~ 40sec), the solvent is removed at the same time by 80 ℃ / 5min, 250 ℃ / 20min heat curing process and polyimide A thin film (usually about 100 ~ 1000nm) is formed on the glass substrate. The coated glass substrates 1 and 2 are used as upper and lower plates, and the liquid crystal molecules 4 are injected into the spaces between the glass substrates 1 and 2 to produce a liquid crystal cell including the liquid crystal layer 5 (FIG. 1). The pretilt angle of each liquid crystal cell was measured by the crystal rotation method, and the results are shown in Table 5.

구분division 조성Furtherance 몰비율Molar ratio 두께
(㎛)thickness
(Μm) 투과도Permeability 380㎚
~780㎚380 nm
780 nm 551㎚
~780㎚551 nm
780 nm 550㎚550 nm 500㎚500 nm 420㎚420 nm 실시예Example 1One 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:7:310: 7: 3 5050 85.785.7 88.388.3 88.288.2 87.487.4 64.064.0 22 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:5:510: 5: 5 5050 86.186.1 88.788.7 88.688.6 88.088.0 65.165.1 33 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:3:710: 3: 7 5050 86.586.5 88.988.9 88.988.9 88.588.5 65.765.7 44 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:7:310: 7: 3 5050 85.785.7 88.488.4 88.288.2 87.587.5 64.564.5 55 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:5:510: 5: 5 5050 86.286.2 88.788.7 88.688.6 88.388.3 65.265.2 66 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:3:710: 3: 7 5050 86.486.4 88.988.9 88.988.9 88.388.3 66.266.2 77 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:7:310: 7: 3 5050 85.885.8 88.988.9 88.888.8 88.288.2 77.477.4 88 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:5:510: 5: 5 5050 86.086.0 90.090.0 89.889.8 89.489.4 77.577.5 99 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:3:710: 3: 7 5050 86.586.5 90.590.5 90.590.5 90.190.1 78.078.0 1010 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:7:310: 7: 3 5050 86.086.0 88.588.5 88.388.3 88.088.0 77.477.4 1111 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:5:510: 5: 5 5050 86.386.3 89.989.9 89.789.7 89.189.1 78.078.0 1212 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:3:710: 3: 7 5050 86.786.7 90.690.6 90.590.5 90.090.0 78.578.5 1313 6-FDA/TDA/4-BDAF/3-DDS6-FDA / TDA / 4-BDAF / 3-DDS 7:3:7:37: 3: 7: 3 5050 85.685.6 88.988.9 88.788.7 86.486.4 63.163.1 1414 6-FDA/TDA/4-BDAF/4-DDS6-FDA / TDA / 4-BDAF / 4-DDS 7:3:7:37: 3: 7: 3 5050 85.785.7 89.089.0 88.888.8 87.487.4 63.863.8 1515 6-FDA/TDA/APB-133/3-DDS6-FDA / TDA / APB-133 / 3-DDS 7:3:7:37: 3: 7: 3 5050 87.387.3 89.689.6 89.489.4 89.089.0 75.475.4 1616 6-FDA/TDA/APB-133/4-DDS6-FDA / TDA / APB-133 / 4-DDS 7:3:7:37: 3: 7: 3 5050 86.886.8 88.988.9 88.788.7 88.288.2 75.875.8 실시예Example 1One 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:7:310: 7: 3 100100 85.085.0 88.488.4 88.088.0 86.086.0 60.460.4 22 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:5:510: 5: 5 100100 85.585.5 88.588.5 88.288.2 86.586.5 61.061.0 33 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:3:710: 3: 7 100100 85.985.9 88.688.6 88.488.4 87.287.2 61.661.6 44 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:7:310: 7: 3 100100 85.185.1 88.488.4 88.088.0 86.286.2 60.360.3 55 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:5:510: 5: 5 100100 85.685.6 88.688.6 88.388.3 86.886.8 61.161.1 66 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:3:710: 3: 7 100100 86.086.0 88.888.8 88.588.5 86.986.9 62.062.0 77 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:7:310: 7: 3 100100 85.385.3 88.788.7 88.388.3 87.687.6 73.373.3 88 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:5:510: 5: 5 100100 85.685.6 89.689.6 89.289.2 87.887.8 73.573.5 99 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:3:710: 3: 7 100100 86.186.1 89.989.9 89.689.6 88.488.4 74.074.0 1010 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:7:310: 7: 3 100100 85.485.4 88.688.6 88.188.1 86.686.6 73.473.4 1111 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:5:510: 5: 5 100100 85.685.6 89.789.7 89.189.1 87.687.6 74.274.2 1212 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:3:710: 3: 7 100100 86.186.1 90.190.1 89.789.7 88.588.5 74.374.3 1313 6-FDA/TDA/4-BDAF/3-DDS6-FDA / TDA / 4-BDAF / 3-DDS 7:3:7:37: 3: 7: 3 100100 85.185.1 88.388.3 88.288.2 85.585.5 59.859.8 1414 6-FDA/TDA/4-BDAF/4-DDS6-FDA / TDA / 4-BDAF / 4-DDS 7:3:7:37: 3: 7: 3 100100 85.285.2 88.688.6 88.488.4 86.086.0 60.260.2 1515 6-FDA/TDA/APB-133/3-DDS6-FDA / TDA / APB-133 / 3-DDS 7:3:7:37: 3: 7: 3 100100 86.886.8 89.989.9 89.889.8 87.587.5 70.170.1 1616 6-FDA/TDA/APB-133/4-DDS6-FDA / TDA / APB-133 / 4-DDS 7:3:7:37: 3: 7: 3 100100 86.086.0 88.788.7 88.388.3 86.786.7 70.370.3

구분division 조성Furtherance 몰비율Molar ratio 두께
(㎛)thickness
(Μm) 황변도Yellowing degree 50% 차단파장
(㎚)50% blocking wavelength
(Nm) 탄성율
(GPa)Modulus
(GPa) Tg
(℃)Tg
(℃) CTE
(ppm/℃)CTE
(ppm / ℃) 유전율
/1GHzpermittivity
/ 1 GHz 실시예Example 1One 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:7:310: 7: 3 5050 7.67.6 396396 3.23.2 265265 49.749.7 2.62.6 22 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:5:510: 5: 5 5050 7.37.3 388388 3.43.4 267267 48.648.6 2.82.8 33 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:3:710: 3: 7 5050 6.96.9 384384 3.53.5 270270 48.248.2 2.82.8 44 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:7:310: 7: 3 5050 7.47.4 396396 3.23.2 267267 49.649.6 2.62.6 55 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:5:510: 5: 5 5050 7.17.1 388388 3.43.4 287287 48.148.1 2.82.8 66 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:3:710: 3: 7 5050 6.76.7 384384 3.53.5 295295 46.246.2 2.82.8 77 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:7:310: 7: 3 5050 4.74.7 390390 3.23.2 216216 46.446.4 2.762.76 88 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:5:510: 5: 5 5050 4.54.5 386386 3.43.4 232232 46.046.0 2.852.85 99 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:3:710: 3: 7 5050 4.14.1 384384 3.53.5 255255 45.445.4 2.882.88 1010 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:7:310: 7: 3 5050 4.64.6 386386 3.23.2 221221 46.246.2 2.82.8 1111 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:5:510: 5: 5 5050 4.34.3 384384 3.43.4 253253 44.944.9 2.882.88 1212 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:3:710: 3: 7 5050 3.93.9 384384 3.53.5 274274 43.743.7 2.912.91 1313 6-FDA/TDA/4-BDAF/3-DDS6-FDA / TDA / 4-BDAF / 3-DDS 7:3:7:37: 3: 7: 3 5050 6.76.7 394394 3.053.05 234234 48.848.8 2.602.60 1414 6-FDA/TDA/4-BDAF/4-DDS6-FDA / TDA / 4-BDAF / 4-DDS 7:3:7:37: 3: 7: 3 5050 6.56.5 394394 3.093.09 241241 47.947.9 2.612.61 1515 6-FDA/TDA/APB-133/3-DDS6-FDA / TDA / APB-133 / 3-DDS 7:3:7:37: 3: 7: 3 5050 4.64.6 388388 3.03.0 212212 46.746.7 2.702.70 1616 6-FDA/TDA/APB-133/4-DDS6-FDA / TDA / APB-133 / 4-DDS 7:3:7:37: 3: 7: 3 5050 4.44.4 396396 3.03.0 260260 46.446.4 2.702.70 실시예Example 1One 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:7:310: 7: 3 100100 8.58.5 399399 3.243.24 -- 48.748.7 -- 22 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:5:510: 5: 5 100100 8.28.2 392392 3.453.45 -- 47.747.7 -- 33 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:3:710: 3: 7 100100 7.77.7 389389 3.563.56 -- 47.347.3 -- 44 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:7:310: 7: 3 100100 8.28.2 398398 3.263.26 -- 48.548.5 -- 55 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:5:510: 5: 5 100100 7.97.9 391391 3.453.45 -- 47.047.0 -- 66 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:3:710: 3: 7 100100 7.57.5 388388 3.563.56 -- 45.345.3 -- 77 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:7:310: 7: 3 100100 5.65.6 394394 3.283.28 -- 45.545.5 -- 88 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:5:510: 5: 5 100100 5.35.3 389389 3.473.47 -- 45.145.1 -- 99 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:3:710: 3: 7 100100 5.05.0 388388 3.563.56 -- 44.344.3 -- 1010 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:7:310: 7: 3 100100 5.75.7 390390 3.273.27 -- 45.345.3 -- 1111 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:5:510: 5: 5 100100 5.25.2 388388 3.463.46 -- 44.044.0 -- 1212 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:3:710: 3: 7 100100 5.05.0 388388 3.543.54 -- 43.143.1 -- 1313 6-FDA/TDA/4-BDAF/3-DDS6-FDA / TDA / 4-BDAF / 3-DDS 7:3:7:37: 3: 7: 3 100100 7.57.5 397397 3.093.09 -- 47.947.9 -- 1414 6-FDA/TDA/4-BDAF/4-DDS6-FDA / TDA / 4-BDAF / 4-DDS 7:3:7:37: 3: 7: 3 100100 7.57.5 396396 3.143.14 -- 47.147.1 -- 1515 6-FDA/TDA/APB-133/3-DDS6-FDA / TDA / APB-133 / 3-DDS 7:3:7:37: 3: 7: 3 100100 5.85.8 393393 3.123.12 -- 46.046.0 -- 1616 6-FDA/TDA/APB-133/4-DDS6-FDA / TDA / APB-133 / 4-DDS 7:3:7:37: 3: 7: 3 100100 5.75.7 398398 3.173.17 -- 45.645.6 --

구분division 조성Furtherance 몰비율Molar ratio 두께
(㎛)thickness
(Μm) 투과도Permeability 380㎚
~780㎚380 nm
780 nm 551㎚
~780㎚551 nm
780 nm 550㎚550 nm 500㎚500 nm 420㎚420 nm 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 2525 82.882.8 90.090.0 87.287.2 86.086.0 63.163.1 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 2525 84.484.4 89.389.3 87.887.8 86.086.0 77.377.3 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 2525 84.384.3 88.688.6 89.789.7 88.688.6 66.566.5 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 2525 84.684.6 89.489.4 90.590.5 90.090.0 72.572.5 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 2525 84.984.9 89.889.8 90.090.0 87.687.6 77.177.1 66 PMDA/ODAPMDA / ODA 10:1010:10 2525 56.656.6 85.285.2 7373 35.035.0 0.050.05 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 5050 82.282.2 89.789.7 86.886.8 85.185.1 60.060.0 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 5050 83.883.8 88.888.8 87.287.2 84.884.8 73.273.2 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 5050 83.783.7 88.288.2 89.189.1 87.687.6 63.163.1 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 5050 83.983.9 89.189.1 90.090.0 89.189.1 69.469.4 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 5050 84.384.3 89.389.3 89.289.2 86.386.3 73.873.8 66 PMDA/ODAPMDA / ODA 10:1010:10 5050 56.056.0 84.584.5 69.269.2 33.133.1 00 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 100100 81.681.6 89.289.2 86.386.3 84.384.3 51.251.2 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 100100 83.183.1 88.188.1 86.786.7 84.384.3 63.363.3 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 100100 83.183.1 87.887.8 88.588.5 87.087.0 53.553.5 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 100100 83.283.2 88.888.8 89.589.5 88.688.6 58.658.6 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 100100 83.583.5 88.788.7 88.888.8 85.485.4 62.162.1 66 PMDA/ODAPMDA / ODA 10:1010:10 100100 -- -- -- -- --

구분division 조성Furtherance 몰비율Molar ratio 두께
(㎛)thickness
(Μm) 황변도Yellowing degree 50% 차단파장
(㎚)50% blocking wavelength
(Nm) 탄성율
(GPa)Modulus
(GPa) Tg
(℃)Tg
(℃) CTE
(ppm/℃)CTE
(ppm / ℃) 유전율
/1GHzpermittivity
/ 1 GHz 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 2525 9.79.7 411411 3.03.0 263263 52.352.3 2.52.5 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 2525 5.55.5 395395 3.053.05 206206 47.147.1 2.72.7 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 2525 1.821.82 388388 3.13.1 270270 4747 3.03.0 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 2525 1.681.68 382382 3.13.1 310310 4646 3.13.1 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 2525 5.295.29 396396 3.03.0 244244 4141 2.732.73 66 PMDA/ODAPMDA / ODA 10:1010:10 2525 91.791.7 514514 3.03.0 없음none 2626 3.33.3 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 5050 11.211.2 413413 3.063.06 -- 51.151.1 -- 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 5050 6.96.9 398398 3.113.11 -- 46.046.0 -- 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 5050 2.952.95 392392 3.163.16 -- 45.345.3 -- 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 5050 2.812.81 386386 3.173.17 -- 45.145.1 -- 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 5050 6.466.46 399399 3.053.05 -- 39.639.6 -- 66 PMDA/ODAPMDA / ODA 10:1010:10 5050 -- -- 3.123.12 -- 25.025.0 -- 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 100100 23.423.4 415415 3.093.09 -- 48.848.8 -- 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 100100 14.214.2 401401 3.143.14 -- 44.544.5 -- 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 100100 4.544.54 396396 3.203.20 -- 44.944.9 -- 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 100100 4.264.26 390390 3.223.22 -- 44.644.6 -- 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 100100 14.2614.26 405405 3.133.13 -- 39.139.1 -- 66 PMDA/ODAPMDA / ODA 10:1010:10 100100 -- -- -- -- -- --

구분division 조성Furtherance 몰비율Molar ratio 선경사각(°)Pretilt angle (°) 실시예Example 1One 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:7:310: 7: 3 1.81.8 22 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:5:510: 5: 5 1.71.7 33 6-FDA/4-BDAF/3-DDS6-FDA / 4-BDAF / 3-DDS 10:3:710: 3: 7 1.71.7 44 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:7:310: 7: 3 1.71.7 55 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:5:510: 5: 5 1.61.6 66 6-FDA/4-BDAF/4-DDS6-FDA / 4-BDAF / 4-DDS 10:3:710: 3: 7 1.51.5 77 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:7:310: 7: 3 1.81.8 88 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:5:510: 5: 5 1.61.6 99 6-FDA/APB-133/3-DDS6-FDA / APB-133 / 3-DDS 10:3:710: 3: 7 1.61.6 1010 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:7:310: 7: 3 1.81.8 1111 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:5:510: 5: 5 1.61.6 1212 6-FDA/APB-133/4-DDS6-FDA / APB-133 / 4-DDS 10:3:710: 3: 7 1.51.5 1313 6-FDA/TDA/4-BDAF/3-DDS6-FDA / TDA / 4-BDAF / 3-DDS 7:3:7:37: 3: 7: 3 1.51.5 1414 6-FDA/TDA/4-BDAF/4-DDS6-FDA / TDA / 4-BDAF / 4-DDS 7:3:7:37: 3: 7: 3 1.51.5 1515 6-FDA/TDA/APB-133/3-DDS6-FDA / TDA / APB-133 / 3-DDS 7:3:7:37: 3: 7: 3 1.41.4 1616 6-FDA/TDA/APB-133/4-DDS6-FDA / TDA / APB-133 / 4-DDS 7:3:7:37: 3: 7: 3 1.41.4 비교예Comparative example 1One 6-FDA/4-BDAF6-FDA / 4-BDAF 10:1010:10 3.53.5 22 6-FDA/APB-1336-FDA / APB-133 10:1010:10 3.23.2 33 6-FDA/3-DDS6-FDA / 3-DDS 10:1010:10 3.13.1 44 6-FDA/4-DDS6-FDA / 4-DDS 10:1010:10 3.13.1 55 6-FDA/3,3'-ODA6-FDA / 3,3'-ODA 10:1010:10 2.72.7 66 PMDA/ODAPMDA / ODA 10:1010:10 1.21.2

상기 투과도 및 황변도등의 물성평가 결과, 본 발명의 실시예에 의하여 제조된 폴리이미드 필름은 50㎛ 및 100㎛의 두께에도 불구하고 투과도가 가시광선 영역인 550㎚에서 88% 이상이고, 500㎚에서 85% 이상이며, 420㎚에서 50%이상인 것을 볼 수 있다. 또한 380~780㎚에서의 평균 투과도가 85% 이상이고, 551~780㎚에서의 평균 투과도가 88% 이상이며, 전반적으로 황변도가 낮은 것을 볼 수 있으며, 이로써 본 발명의 폴리이미드 필름이 투명성이 우수한 것을 알 수 있다. As a result of evaluation of physical properties such as transmittance and yellowing degree, the polyimide film prepared according to the embodiment of the present invention has a transmittance of 88% or more at 550 nm in the visible light region despite the thickness of 50 μm and 100 μm, and 500 nm 85% or more, and 50% or more can be seen at 420nm. In addition, it can be seen that the average transmittance at 380 to 780 nm is 85% or more, the average transmittance at 551 to 780 nm is 88% or more, and the overall yellowing is low, whereby the polyimide film of the present invention has transparency It can be seen that it is excellent.

비교예의 경우, 두께와 상관없이 가시광선 영역인 380~780㎚에서의 평균 투과도가 85% 이상인 경우가 없었으며, 특히 비교예 6의 경우에는 90㎛ 이상의 두께로 필름화가 불가능하였다.In the case of the comparative example, the average transmittance in the visible ray region of 380 to 780 nm was not more than 85% regardless of the thickness, and especially in the case of Comparative Example 6, film formation was not possible with a thickness of 90 μm or more.

그리고 본 발명의 실시예에 의하여 제조된 폴리이미드 필름은 투과도가 50%가 되는 파장이 400㎚ 이하로써 우수한 가시광선 투과도를 갖는 무색의 투명한 폴리이미드 필름으로 태양전지 등 표면 보호막으로 사용 가능하고, 평균 선팽창 계수가 50ppm 이하로 치수안정성이 우수하고, 탄성률이 3.0GPa이상으로 롤투롤(Roll to Roll) 공정에도 적용 가능한 필름 특성을 가지며, 플렉서블 디스플레이등의 기판소재 및 능동 구동형 디스플레이 소자 제작을 위한 TFT공정에 적용이 가능하다. 또한 유전율이 3.0 이하이므로 반도체 패시베이션막으로 사용할 수 있다. In addition, the polyimide film prepared according to the embodiment of the present invention is a colorless transparent polyimide film having excellent visible light transmittance with a wavelength of 400 nm or less, the transmittance of which is 50%, and can be used as a surface protective film such as a solar cell. Linear expansion coefficient is 50ppm or less, excellent dimensional stability, elastic modulus is 3.0GPa or more, has film characteristics applicable to roll-to-roll process, TFT for manufacturing substrate materials and flexible display devices Applicable to the process. Moreover, since the dielectric constant is 3.0 or less, it can be used as a semiconductor passivation film.

한편 본 발명의 폴리이미드 수지로 제조한 액정 배향막의 선경사각은 모두 2° 이하이므로 IPS 모드용 배향막으로도 사용할 수 있다. On the other hand, since all the pretilt angles of the liquid crystal aligning film manufactured from the polyimide resin of this invention are 2 degrees or less, it can be used also as an oriented film for IPS modes.

이상에서 설명한 바와 같이 본 발명은 무색투명하고, 기계적 물성 및 열안정성의 물성이 우수하여 반도체 절연막, TFT-LCD 절연막, 패시베이션막, 액정배향막, 광통신용 재료, 태양전지용 보호막, 플랙시블 디스플레이 기판 등의 다양한 분야에 사용가능한 폴리이미드 수지와 이를 이용한 액정 배향막 및 필름을 제공할 수 있다.As described above, the present invention is colorless and transparent, and has excellent mechanical and thermal stability properties such as semiconductor insulating film, TFT-LCD insulating film, passivation film, liquid crystal alignment film, optical communication material, solar cell protective film, flexible display substrate, etc. A polyimide resin usable in various fields and a liquid crystal alignment film and a film using the same can be provided.

Claims (12)

방향족 디안하이드라이드로서 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(FDA) 및 4-(2,5-디옥소테트라하이드로푸란-3-일)-1,2,3,4-테트 라하이드로나프탈렌-1,2-디카르복실릭 안하이드라이드(TDA)를 포함하고, 방향족 디아민으로서 화학식 1로 표시되는 디아민과 화학식 2로 표시되는 디아민을 포함하는 폴리이미드 수지.2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (FDA) and 4- (2,5-dioxotetrahydrofuran-3-yl) -1 as aromatic dianhydride, Polyimide comprising 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride (TDA) and comprising a diamine represented by the formula (1) and a diamine represented by the formula (2) as an aromatic diamine Suzy. <화학식 1>&Lt; Formula 1 >
Figure 112012012223210-pat00028
Figure 112012012223210-pat00028
 상기 식에서 R1은
Figure 112012012223210-pat00030
이다.In which R 1 is
Figure 112012012223210-pat00030
to be. <화학식 2><Formula 2>
Figure 112012012223210-pat00031
Figure 112012012223210-pat00031
 상기 식에서 R2는
Figure 112012012223210-pat00032
,
Figure 112012012223210-pat00033
,
Figure 112012012223210-pat00034
및
Figure 112012012223210-pat00036
중 선택된 구조이다.In which R 2 is
Figure 112012012223210-pat00032
,
Figure 112012012223210-pat00033
,
Figure 112012012223210-pat00034
And
Figure 112012012223210-pat00036
Among the structures selected. 삭제delete 제 1 항의 폴리이미드 수지를 포함하는 액정 배향막.The liquid crystal aligning film containing the polyimide resin of Claim 1. 제 3 항에 있어서,The method of claim 3, wherein 선경사각(Pretilt Angle)은 0~2°인 것임을 특징으로 하는 액정 배향막.Pretilt angle (Pretilt Angle) is a liquid crystal alignment film, characterized in that 0 to 2 °. 제 1 항의 폴리이미드 수지를 포함하는 무색투명한 폴리이미드 필름.A colorless transparent polyimide film comprising the polyimide resin of claim 1. 제 5 항에 있어서,6. The method of claim 5, 필름 두께 50~100㎛를 기준으로 UV분광계로 투과도 측정시 380~780㎚에서의 평균 투과도가 85% 이상이고, 551~780㎚에서의 평균 투과도가 88% 이상인 것을 특 징으로 하는 폴리이미드 필름.A polyimide film, characterized in that the average transmittance at 380 to 780 nm is 85% or more, and the average transmittance at 551 to 780 nm is 88% or more when the transmittance is measured with a UV spectrometer based on a film thickness of 50 to 100 μm. 제 5 항에 있어서,6. The method of claim 5, 필름 두께 50~100㎛를 기준으로 UV분광계로 투과도 측정시 550㎚에서 투과도가 88% 이상, 500㎚에서 투과도가 85% 이상, 420㎚에서 투과도가 50% 이상인 것을 특징으로 하는 폴리이미드 필름.A polyimide film having a transmittance of 88% or more at 550 nm, a transmittance of 85% or more at 500 nm, and a transmittance of 50% or more at 420 nm based on a film thickness of 50 to 100 μm when measured by UV spectrophotometer. 제 5 항에 있어서,6. The method of claim 5, 필름 두께 50~100㎛를 기준으로 황변도가 15이하인 것을 특징으로 하는 폴리이미드 필름.A polyimide film having a yellowing degree of 15 or less based on a film thickness of 50 to 100 µm. 제 5 항에 있어서,6. The method of claim 5, 1GHz에서의 유전율이 3.0 이하인 것을 특징으로 하는 폴리이미드 필름.The dielectric constant at 1GHz is 3.0 or less, The polyimide film characterized by the above-mentioned. 제 5 항에 있어서,6. The method of claim 5, 50~200℃에서의 평균 선팽창 계수(CTE)가 50ppm 이하인 것을 특징으로 하는 폴리이미드 필름.The average linear expansion coefficient (CTE) in 50-200 degreeC is 50 ppm or less, The polyimide film characterized by the above-mentioned. 제 5 항에 있어서,6. The method of claim 5, 탄성률은 3.0GPa 이상인 것을 특징으로 하는 폴리이미드 필름.Elastic modulus is 3.0 GPa or more, The polyimide film characterized by the above-mentioned. 제 5 항에 있어서,6. The method of claim 5, UV에 의한 50% 차단파장(cut off wavelength)이 400㎚ 이하인 것을 특징으로 하는 폴리이미드 필름.50% cut off wavelength by UV is 400nm or less.
KR1020060129009A 2006-12-15 2006-12-15 Colorless polyimide resin, and liquid crystal alignment layer and polyimide film using the same KR101167341B1 (en)

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PCT/KR2007/006514 WO2008072916A1 (en) 2006-12-15 2007-12-13 Polyimide film
US12/518,258 US20100048861A1 (en) 2006-12-15 2007-12-13 Polyimide resin and liquid crystal alignment layer and polyimide film using the same
PCT/KR2007/006512 WO2008072914A1 (en) 2006-12-15 2007-12-13 Polyimide resin and liquid crystal alignment layer and polyimide film using the same
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