KR100611467B1 - Novel Diamine with pendant imide group and LC Alignment layer Prepared by Using the Same - Google Patents

Novel Diamine with pendant imide group and LC Alignment layer Prepared by Using the Same Download PDF

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KR100611467B1
KR100611467B1 KR1020030083487A KR20030083487A KR100611467B1 KR 100611467 B1 KR100611467 B1 KR 100611467B1 KR 1020030083487 A KR1020030083487 A KR 1020030083487A KR 20030083487 A KR20030083487 A KR 20030083487A KR 100611467 B1 KR100611467 B1 KR 100611467B1
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dianhydride
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polyamic acid
cyclobutane
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KR20050049759A (en
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이무영
오재민
이범진
오준석
권오범
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제일모직주식회사
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    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
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    • 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
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    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films

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Abstract

본 발명은 이미드기를 포함하는 기능성 디아민 및 이를 이용하여 제조된 액정배향막에 관한 것으로, 보다 상세하게는 헤테로 방향족 고리와 환형 이미드기를 포함하는 신규한 기능성 디아민 화합물을 제공하고, 이를 이용하여 폴리아믹산 및 폴리이미드를 제조함으로서, 내열성, 표면강도와 같은 기계적 특성이 우수하고, 액정과의 상호작용이 뛰어나 액정배향성이 우수한 액정배향막을 제공한다.The present invention relates to a functional diamine containing an imide group and a liquid crystal alignment film prepared using the same, and more particularly, to provide a novel functional diamine compound including a heteroaromatic ring and a cyclic imide group, and using the polyamic acid And by producing a polyimide, to provide a liquid crystal alignment film excellent in mechanical properties such as heat resistance, surface strength, excellent interaction with the liquid crystal and excellent liquid crystal orientation.

액정 배향막, 폴리아믹산, 폴리이미드, 배향성, 표면장력, 선경사각Liquid crystal aligning film, polyamic acid, polyimide, orientation, surface tension, pretilt angle

Description

이미드기를 포함하는 기능성 디아민 및 이를 이용하여 제조된 액정배향막 {Novel Diamine with pendant imide group and LC Alignment layer Prepared by Using the Same} Functional diamine containing an imide group and a liquid crystal alignment film prepared using the same {Novel Diamine with pendant imide group and LC Alignment layer Prepared by Using the Same}             

도 1은 본 발명의 제조예 10에서 제조된 3,5-디아미노페녹시-(3-(1-도데센)-숙시닉이미드)-2,6-피리미딘 (DAPIPM-12)의 제조)의 1H-NMR 스펙트럼이다.1 is a preparation of 3,5-diaminophenoxy- (3- (1-dodecene) -succinimide) -2,6-pyrimidine (DAPIPM-12) prepared in Preparation Example 10 of the present invention. ) Is the 1 H-NMR spectrum of.

도 2는 본 발명의 실시예 1에서 제조된 DPTAA-1의 1H-NMR 스펙트럼이다.2 is a 1 H-NMR spectrum of DPTAA-1 prepared in Example 1 of the present invention.

도 3는 본 발명의 실시예 1에서 제조된 DPTAAI-1의 DSC 곡선이다.3 is a DSC curve of DPTAAI-1 prepared in Example 1 of the present invention.

도 4는 본 발명의 실시예 9에서 제조된 CPTAA-3의 1H-NMR 스펙트럼이다4 is a 1 H-NMR spectrum of CPTAA-3 prepared in Example 9 of the present invention.

본 발명은 이미드기를 포함하는 기능성 디아민 및 이를 이용하여 제조된 액정배향막에 관한 것으로, 보다 상세하게는 이미드 고리를 포함하는 새로운 구조의 기능성 디아민을 제공하고, 이를 이용하여 내열성, 표면강도와 같은 기계적 특성이 우수하고, 액정과의 상호작용이 뛰어나 액정배향성이 우수한 액정배향막을 제공한다.The present invention relates to a functional diamine containing an imide group and a liquid crystal alignment film prepared using the same, and more particularly, to provide a functional diamine having a new structure including an imide ring, and using the same as heat resistance and surface strength. Provided is a liquid crystal alignment film excellent in mechanical properties, excellent in interaction with liquid crystals, and excellent in liquid crystal alignment.

일반적으로 폴리이미드 수지라 함은 방향족 테트라카르복실산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합한 후, 이미드화하여 제조되는 고내열성 수지를 일컫는다. 폴리이미드 수지는 사용된 단량체의 종류에 따라 여러가지의 분자구조를 가질 수 있으며, 일반적으로 방향족 테트라카르복실산 성분으로서는 피로멜리트산이무수물(PMDA) 또는 비프탈산무수물(BPDA)를 사용하고 있고, 방향족 디아민 성분으로서는 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민 (m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP), 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP) 등의 방향족 디아민을 사용하여 축중합시켜 제조하고 있다. In general, the polyimide resin refers to a high heat resistant resin prepared by condensation polymerization of an aromatic tetracarboxylic acid or a derivative thereof with an aromatic diamine or an aromatic diisocyanate, followed by imidization. The polyimide resin may have various molecular structures according to the type of monomers used, and in general, aromatic tetracarboxylic acid components use pyromellitic dianhydride (PMDA) or nonphthalic anhydride (BPDA). As the diamine component, para-phenylenediamine ( p- PDA), meta-phenylenediamine ( m- PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2 -Bisaminophenylhexafluoropropane (HFDA), metabisaminophenoxydiphenylsulfone ( m- BAPS), parabisaminophenoxydiphenylsulfone ( p- BAPS), 1,4-bisaminophenoxybenzene (TPE -Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP) It manufactures by polycondensation using aromatic diamines, such as these.

대부분의 폴리이미드 수지는 불용, 불융의 초고내열성 수지로서 다음과 같은 특성을 가지고 있다: (1) 뛰어난 내열산화성, (2) 높은 사용가능온도, (3) 약 260 ℃의 장기 사용 가능온도와 약 480 ℃의 단기 사용 가능온도를 나타내는 우수한 내열특성, (4) 내방사선성, (5) 우수한 저온특성, (6) 우수한 내약품성 등.Most polyimide resins are insoluble and insoluble ultra-high heat resistant resins, which have the following characteristics: (1) excellent thermal oxidation resistance, (2) high usable temperature, and (3) long service life of about 260 ° C. Excellent heat resistance, (4) radiation resistance, (5) good low temperature, (6) good chemical resistance, etc.

그러나 상기와 같이 방향족 산이무수물 및 디아민 만을 사용할 경우 열안정성, 내약품성, 기계적 성질 등은 우수한 반면 전하이동착제(charge transfer complex)에 의해 투명성 및 용해성이 저하되고, 또한 전기 광학 특성이 저하되는 문제점이 있다. 이를 해결하기 위해 지방족 고리형 산이무수물 단량체 혹은 지방족 고리형 디아민을 도입하여 상기 문제를 개선하려는 시도가 있었고(일본 특허공개 11-84391), 액정의 선경사각 증가와 안정성을 위하여 측쇄를 갖는 기능성 디아민 또는 측쇄를 갖는 기능성 산이무수물 등이 도입되고 있다(일본 특허공개 06-136122). However, when only aromatic acid dianhydride and diamine are used as described above, thermal stability, chemical resistance, mechanical properties, etc. are excellent, but transparency and solubility are degraded by charge transfer complex, and electro-optical properties are deteriorated. have. In order to solve this problem, there have been attempts to improve the problem by introducing an aliphatic cyclic acid dianhydride monomer or an aliphatic cyclic diamine (Japanese Patent Laid-Open No. 11-84391), and a functional diamine having a side chain for increasing the pretilt angle and stability of liquid crystal. Functional acid dianhydrides and the like having side chains are introduced (Japanese Patent Laid-Open No. 06-136122).

그러나 최근 액정 표시소자 시장의 성장에 따라 고품질의 표시소자에 대한 요구가 지속적으로 높아지고 있고, 액정 표시소자 생산사에서는 대면적화가 급속히 진행되면서 생산성이 높은 배향막에 대한 요구가 커지고 있다. 따라서 LCD생산공정에서 불량률이 적으며, 전기광학 특성이 우수하고, 신뢰성이 높으며, 액정의 퍼짐성이 우수한 배향막의 개발이 요구되고 있다.However, with the recent growth of the liquid crystal display device market, the demand for high quality display devices continues to increase, and as liquid crystal display device manufacturers are rapidly becoming larger in area, the demand for highly productive alignment films is increasing. Accordingly, there is a demand for the development of an alignment film having a low defect rate, excellent electro-optical characteristics, high reliability, and excellent spreadability of liquid crystals in an LCD production process.

본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로, 측쇄로 이미드기를 가지는 새로운 구조의 디아민 화합물을 제공하고, 이를 이용하여 내열성, 표면강도와 같은 기계적 특성이 우수하고, 액정과의 상호작용이 뛰어나 액정배향성이 우수한 액정배향막을 제공함을 목적으로 한다.The present invention is to solve the problems of the prior art as described above, to provide a diamine compound having a new structure having an imide group as a side chain, by using this excellent mechanical properties such as heat resistance, surface strength, and mutually with the liquid crystal An object of the present invention is to provide a liquid crystal alignment film excellent in liquid crystal alignment.

즉, 본 발명은 하기 화학식 1로 표시되는 디아민 화합물에 관한 것이다. That is, the present invention relates to a diamine compound represented by the following formula (1).                         

[화학식 1][Formula 1]

Figure 112003044260171-pat00001
Figure 112003044260171-pat00001

(상기 식에서(In the above formula

A는 단일결합 또는 -O-, -COO-, -OCO-, -NHCO-, -CONH- 이고, A is a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-,

B는

Figure 112003044260171-pat00002
또는
Figure 112003044260171-pat00003
이며,B is
Figure 112003044260171-pat00002
or
Figure 112003044260171-pat00003
Is,

C는

Figure 112003044260171-pat00004
,
Figure 112003044260171-pat00005
,
Figure 112003044260171-pat00006
,
Figure 112003044260171-pat00007
또는
Figure 112003044260171-pat00008
이고,C is
Figure 112003044260171-pat00004
,
Figure 112003044260171-pat00005
,
Figure 112003044260171-pat00006
,
Figure 112003044260171-pat00007
or
Figure 112003044260171-pat00008
ego,

이때 D는 이때 D는 탄소수 1 내지 30의 선형, 가지형 또는 고리형 알킬기, 또는 하나 이상의 불포화 결합을 포함하고 있는 탄소수 6 내지 40의 선형, 가지형 또는 고리형 알킬기이며, 상기 D에는 1 내지 10의 할로겐기가 치환될 수 있고, 또한 D가 2개 존재하는 경우 2개의 D는 서로 연결되어 단일환 또는 복소환 구조의 지방족 또는 방향족 고리를 형성할 수 있으며,Wherein D is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a linear, branched or cyclic alkyl group having 6 to 40 carbon atoms including at least one unsaturated bond, wherein D is 1 to 10 May be substituted, and when two D's are present, the two Ds may be linked to each other to form an aliphatic or aromatic ring having a monocyclic or heterocyclic structure,

Z는 -H, -CH3, -Cl, -Br, -F, -CN, 혹은 -CF3이다.)Z is -H, -CH 3 , -Cl, -Br, -F, -CN, or -CF 3. )

본 발명의 다른 측면은 상기 디아민 화합물, 방향족 고리형 산이무수물 및 지방족 고리형 산이무수물과 여기에 방향족 고리형 디아민을 포함시켜 공중합하여 제조된 폴리아믹산에 관한 것이다.Another aspect of the present invention relates to a polyamic acid prepared by copolymerizing the diamine compound, the aromatic cyclic acid dianhydride and the aliphatic cyclic acid dianhydride with the aromatic cyclic diamine.

본 발명의 또 다른 측면은 상기 폴리아믹산을 부분적으로 또는 전체적으로 이미드화시켜 얻어진 폴리이미드에 관한 것이다.Another aspect of the invention relates to a polyimide obtained by partially or wholly imidating the polyamic acid.

본 발명의 또 다른 측면은 상기 폴리아믹산 또는 폴리이미드를 코팅, 건조, 경화하여 얻어진 액정 배향막에 관한 것이다.
Another aspect of the present invention relates to a liquid crystal alignment film obtained by coating, drying, and curing the polyamic acid or polyimide.

이하에서 본 발명을 보다 상세하게 설명한다.The present invention will be described in more detail below.

본 발명에서 새롭게 제공되는 기능성 디아민은 하기 화학식 1과 같은 구조를 가진다.Functional diamine newly provided in the present invention has a structure as shown in the following formula (1).

Figure 112003044260171-pat00009
Figure 112003044260171-pat00009

(상기 식에서(In the above formula

A는 단일결합 또는 -O-, -COO-, -OCO-, -NHCO-, -CONH- 이고, A is a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-,

B는

Figure 112003044260171-pat00010
또는
Figure 112003044260171-pat00011
이며,B is
Figure 112003044260171-pat00010
or
Figure 112003044260171-pat00011
Is,

C는

Figure 112003044260171-pat00012
,
Figure 112003044260171-pat00013
,
Figure 112003044260171-pat00014
,
Figure 112003044260171-pat00015
또는
Figure 112003044260171-pat00016
이고,C is
Figure 112003044260171-pat00012
,
Figure 112003044260171-pat00013
,
Figure 112003044260171-pat00014
,
Figure 112003044260171-pat00015
or
Figure 112003044260171-pat00016
ego,

이때 D는 이때 D는 탄소수 1 내지 30의 선형, 가지형 또는 고리형 알킬기, 또는 하나 이상의 불포화 결합을 포함하고 있는 탄소수 6 내지 40의 선형, 가지형 또는 고리형 알킬기이며, 상기 D에는 1 내지 10의 할로겐기가 치환될 수 있고, 또한 D가 2개 존재하는 경우 2개의 D는 서로 연결되어 단일환 또는 복소환 구조의 지방족 또는 방향족 고리를 형성할 수 있으며, Wherein D is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a linear, branched or cyclic alkyl group having 6 to 40 carbon atoms including at least one unsaturated bond, wherein D is 1 to 10 May be substituted, and when two D's are present, the two Ds may be linked to each other to form an aliphatic or aromatic ring having a monocyclic or heterocyclic structure,

Z는 -H, -CH3, -Cl, -Br, -F, -CN, 혹은 -CF3이다.)Z is -H, -CH 3 , -Cl, -Br, -F, -CN, or -CF 3. )

삭제delete

본 발명에서는 상기 기능성 디아민, 방향족 고리형 산이무수물 및 지방족 고리형 산이무수물과 여기에 방향족 고리형 디아민을 포함시켜 공중합하여 폴리아믹산을 제조한다.In the present invention, a polyamic acid is prepared by copolymerization of the functional diamine, aromatic cyclic acid dianhydride and aliphatic cyclic acid dianhydride, and aromatic cyclic diamine.

상기 폴리아믹산에 포함되는 기능성 디아민과 방향족 고리형 디아민의 몰비는 100:0∼0.1:99.1, 바람직하게는 100:0∼80.0:20.0의 범위이다.The molar ratio of the functional diamine and the aromatic cyclic diamine contained in the polyamic acid is in the range of 100: 0 to 0.1: 99.1, preferably 100: 0 to 80.0: 20.0.

또한 방향족 고리형 산이무수물과 지방족 고리형 산이무수물의 몰비는 10:90∼90:10, 바람직하게는 10:90∼50:50 범위이다. 만일 방향족 고리형 산이무수물이 10 몰% 미만일 경우에는 배향막의 기계적 특성 및 내열성 등이 낮아지게 되고, 90 몰% 초과일 경우에는 전압보전율과 같은 전기광특성이 저하하게 된다.The molar ratio of aromatic cyclic acid dianhydride and aliphatic cyclic acid dianhydride is in the range of 10:90 to 90:10, preferably 10:90 to 50:50. If the aromatic cyclic acid dianhydride is less than 10 mol%, the mechanical properties and heat resistance of the alignment layer are lowered, and if it is more than 90 mol%, the electro-optical properties such as voltage retention are lowered.

본 발명에 의해 제공되는 폴리아믹산은 보다 구체적으로 하기 화학식 2의 구조를 가진다.Polyamic acid provided by the present invention more specifically has the structure of formula (2).

Figure 112003044260171-pat00017
Figure 112003044260171-pat00017

(상기 식에서 (In the above formula

Figure 112003044260171-pat00018
는 하기 화학식 3으로 표시되는 작용기로 이루어진 군에서 선택된 작용기, 및 하기 화학식 4로 표시되는 작용기로 이루어진 군으로부터 선택된 작용기를 나타내며, 이때 화학식 3으로 표시되는 작용기와 화학식 4로 표시되는 작용기의 10:90 내지 80:20이고,
Figure 112003044260171-pat00018
Represents a functional group selected from the group consisting of functional groups represented by Formula 3, and a functional group selected from the group consisting of functional groups represented by Formula 4, wherein 10:90 of the functional group represented by Formula 3 and functional group represented by Formula 4 To 80:20,

Figure 112005076214357-pat00019
는 하기 화학식 5로 표시되는 작용기로 이루어진 군에서 선택된 작용기, 및 하기 화학식 6으로 표시되는 작용기로 이루어진 군에서 선택된 작용기를 나타내고, 이때 화학식 5로 표시되는 작용기와 화학식 6으로 표시되는 작용기의 비는 100:0 내지 0.1:99.9이다.)
Figure 112005076214357-pat00019
Represents a functional group selected from the group consisting of functional groups represented by Formula 5, and a functional group selected from the group consisting of functional groups represented by Formula 6, wherein the ratio of the functional group represented by Formula 5 and the functional group represented by Formula 6 is 100 : 0 to 0.1: 99.9.)

Figure 112003044260171-pat00020
Figure 112003044260171-pat00020

Figure 112003044260171-pat00021
Figure 112003044260171-pat00021

Figure 112003044260171-pat00022
Figure 112003044260171-pat00022

Figure 112003044260171-pat00023
Figure 112003044260171-pat00023

본 발명의 폴리아믹산 제조시 사용되는 방향족 고리형 산이무수물로는 구체적으로 피로멜리트산이무수물, 벤조페논테트라카르복실산 이무수물, 옥시디프탈산이무수물, 비프탈산이무수물, 헥사플루오로이소프로필리덴디프탈산이무수물 등을 예로 들 수 있으나, 이에 한정하는 것은 아니다.Aromatic cyclic acid dianhydrides used in the production of the polyamic acid of the present invention specifically include pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride, hexafluoroisopropyl. Dendiphthalic dianhydride, and the like, but is not limited thereto.

지방족 고리형 산이무수물로는 구체적으로 1,2,3,4-시클로부탄 테트라카르복 실산 이무수물, 1,2,3,4-시클로펜탄 테트라카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-3-시클로헥센-1,2-디카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-4-시클로헥센-1,2-디카르복실산이무수물, 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산 이무수물, 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물, 2,3,5-트리카르복실시클로펜틸아세틱 액시드 디안하이드라이드, 1,2,3,4-테드라메틸-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디메틸-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-메틸-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2,3,4-테드라플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디플루오르-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디메틸-3,4-디플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1-메틸-3-플루오르-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-메틸-4-플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물 등을 예로 들 수 있으나, 이에 한정되는 것은 아니다.As the aliphatic cyclic acid dianhydride, specifically 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 5- (2,5-di Oxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dica Le dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-4-cyclohexene-1,2-dicarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuryl 3-yl) -tetralin-1,2-dicarboxylic dianhydride, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl Acetic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetradranic dianhydride, 1,2-dimethyl-1,2,3, 4-cyclobutane tedracarboxylic dianhydride, 1-methyl-1,2,3,4-cyclobutane tedracarboxylic dianhydride, 1,2,3,4-ted Fluorine-1,2,3,4-cyclobutane tetradranic dianhydride, 1,2-difluoro-1,2,3,4-cyclobutane tetradracarboxylic dianhydride, 1-fluor-1 , 2,3,4-cyclobutane tetradranic dianhydride, 1,2-dimethyl-3,4-difluoro-1,2,3,4-cyclobutane tetradracarboxylic dianhydride, 1- Methyl-3-fluoro-1,2,3,4-cyclobutane tetradranic dianhydride, 1-methyl-4-fluor-1,2,3,4-cyclobutane tetradranic dianhydride, etc. For example, but is not limited thereto.

방향족 디아민으로는 구체적으로 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민(m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP) 및 2,2-비스아미노페 녹시페닐헥사풀루오로프로판(HFBAPP) 등을 예로 들 수 있으나, 이에 한정되는 것은 아니다.Aromatic diamines specifically include para-phenylenediamine ( p- PDA), meta-phenylenediamine ( m- PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2-bisaminophenylhexafluoropropane (HFDA), metabisaminophenoxydiphenylsulfone ( m- BAPS), parabisaminophenoxydiphenylsulfone ( p- BAPS), 1,4-bisaminophenoxy Benzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP) and the like, but is not limited thereto.

본 발명의 폴리아믹산은 지방족 고리형 산이무수물 단량체가 적절한 비율로 포함됨으로서, 기계적 특성과 내열성의 저하를 최소로 하면서도 인쇄성이 개선되며, 본 발명에서 신규로 제시된 화학식 1로 표시되는 디아민 단량체가 포함됨으로서 우수한 내열성, 광투과성 및 액정 배향력을 나타내고, 1∼90°까지 원하는 크기로 선경사각을 구현할 수 있다.The polyamic acid of the present invention includes aliphatic cyclic acid dianhydride monomers in an appropriate ratio, thereby improving printability while minimizing a decrease in mechanical properties and heat resistance, and including a diamine monomer represented by Formula 1 newly proposed in the present invention. As a result, excellent heat resistance, light transmittance, and liquid crystal alignment force can be exhibited, and a pretilt angle can be realized at a desired size from 1 to 90 °.

또한 본 발명에서는 상기와 같은 본 발명의 폴리아믹산을 아세틱 안하이드라이드/피리딘 혼합용매하에서 25℃∼150℃의 온도에서 2∼24시간동안 화학적 이미드화를 시키던지, 톨루엔 혹은 자일렌/N-메틸피롤리돈 혼합용매하에서 120℃℃∼200℃의 온도에서 2∼14시간 공비를 이용한 이미드화를 시키던지, 메티크레졸 용매를 사용하여 200℃이상에서 고온 이미드화 방법을 사용하여 부분적으로 또는 전체적으로 이미 이미드화시켜 폴리이미드를 제공한다.In the present invention, the polyamic acid of the present invention as described above is subjected to chemical imidization at a temperature of 25 ° C. to 150 ° C. under acetic anhydride / pyridine mixed solvent for 2 to 24 hours, or toluene or xylene / N-. Imidation using azeotropes for 2 to 14 hours at a temperature of 120 ° C. to 200 ° C. under a methylpyrrolidone mixed solvent, or partly or entirely using a high temperature imidization method at 200 ° C. or higher using a meticcresol solvent. Already imidized to give polyimide.

상기한 바와 같은 본 발명에 따른 폴리아믹산 및 그로부터 유도된 폴리이미드는 기존에 제조된 바 없는 신규한 물질로서, 이미드기 함유 측쇄기의 도입에 의하여 투명성과 기계적 특성이 우수하고, 헤테로 방향족기 도입으로 상기 물질의 적용에 의하여 제조된 액정 셀의 전기 광학적 특성 및 액정 배향력이 특히 개선된 신규한 고분자이다.The polyamic acid and the polyimide derived therefrom according to the present invention as described above is a novel material that has not been produced in the past, and has excellent transparency and mechanical properties by introducing an imide group-containing side chain group, It is a novel polymer in which the electro-optical properties and liquid-crystal orientation of liquid crystal cells produced by the application of the material are particularly improved.

이와 같은 본 발명의 폴리아믹산 및 그로부터 유도된 폴리이미드는 중량평균 분자량(Mw)이 10,000 내지 250,000 g/mol이고, 고유점도 범위가 0.3 내지 2.0 dL/g 이며, 유리전이온도가 200 내지 400 ℃이고, 선경사각(pretilt angle)은 기능성 디아민의 함량에 따라 1 ~ 90° 범위의 특성을 가진다. 이때 상기 폴리아믹산의 중합도가 너무 낮으면 도막의 막강도가 충분하지 않고, 중합도가 너무 높으면 도막 형성시 공정성이 나빠지는 문제점이 있다.The polyamic acid and polyimide derived therefrom have a weight average molecular weight (Mw) of 10,000 to 250,000 g / mol, an intrinsic viscosity range of 0.3 to 2.0 dL / g, and a glass transition temperature of 200 to 400 ° C. The pretilt angle has a characteristic in the range of 1 to 90 ° depending on the content of the functional diamine. At this time, if the degree of polymerization of the polyamic acid is too low, the film strength of the coating film is not sufficient, if the degree of polymerization is too high, there is a problem that the processability during coating film deterioration.

본 발명의 액정배향막은 본 발명에 의한 폴리아믹산, 또는 이를 이미드화하여 얻어진 폴리이미드를 고형분 함량이 0.5∼40 중량%, 바람직하게는 1∼20 중량%, 더욱 바람직하게는 2∼10 중량%가 되는 범위로 용매에 용해시켜 코팅액 조성물을 제조하고, 이를 코팅, 건조, 경화시켜 얻어진다.The liquid crystal aligning film of the present invention has a solid content of 0.5 to 40% by weight, preferably 1 to 20% by weight, more preferably 2 to 10% by weight of the polyamic acid according to the present invention or the polyimide obtained by imidizing the same. It is obtained by dissolving in a solvent to the extent that it becomes a coating liquid composition, and coating, drying and hardening it.

본 발명에 따른 폴리아믹산 및 그로부터 유도된 폴리이미드는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 디메틸 설폭사이드, N-메틸 카프로락탐, 디메틸 술폰, 헥사메틸 설폭사이드, 테트라 메틸 요소, 피리딘, 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로퓨란(THF), 클로로포름과 같은 저비점 용매 및 감마-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. The polyamic acid and polyimide derived therefrom are dimethylacetamide (DMAc), dimethylformamide (DMF), N -methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, N-methyl caprolactam, It has the property of easily dissolving at room temperature for organic solvents such as meta-cresol, including aprotic polar solvents such as dimethyl sulfone, hexamethyl sulfoxide, tetra methyl urea, pyridine, acetone, ethyl acetate. In particular, low solubility solvents such as tetrahydrofuran (THF), chloroform and low absorption solvents such as gamma-butyrolactone exhibit high solubility of 10% by weight or more at room temperature.

한편, 본 발명에 의한 폴리아믹산, 그로부터 유도된 폴리이미드를 직접 용해하지 않는 용매의 경우에도, 폴리아믹산 등을 석출시키지 않는 범위에서 상기 용매와 혼합하는 것이 가능하다. 이러한 목적으로 사용가능한 용매의 예로는 에틸 셀로솔브, 부틸 셀로솔브, 에틸 갈비 톨, 부틸 갈비 톨, 에틸 갈비 톨 아세테이트, 에틸렌 글리콜, 1-메톡시 2-프로판올, 1-에톡시 2-프로판올, 1-부톡시 2-프로판올, 1-페녹시 2-프로판올, 프로필렌 글리콜 아세테이트, 프로필렌 글리콜 디아세테이트, 프로필렌 글리콜 1-모노메틸 에테르 2-아세테이트, 프로필렌 글리콜 1-에틸 에테르 2-아세테이트, 디프로필렌 글리콜, 디프로필렌 글리콜 모노메틸 에테르, 2-(2-에톡시 프로폭시) 프로판올, 유산 메틸 에스테르, 유산 에틸 에스테르, 유산 n-프로필 에스테르, 유산 n-브틸 에스테르, 유산 이소 아밀 에스테르 등이 있다. On the other hand, even in the case of a solvent which does not directly dissolve the polyamic acid and the polyimide derived therefrom, the polyamic acid and the polyimide derived therefrom can be mixed with the solvent within a range in which no polyamic acid or the like is precipitated. Examples of solvents usable for this purpose include ethyl cellosolve, butyl cellosolve, ethyl galbitol, butyl galbitol, ethyl galbitol acetate, ethylene glycol, 1-methoxy 2-propanol, 1-ethoxy 2-propanol, 1 Butoxy 2-propanol, 1-phenoxy 2-propanol, propylene glycol acetate, propylene glycol diacetate, propylene glycol 1-monomethyl ether 2-acetate, propylene glycol 1-ethyl ether 2-acetate, dipropylene glycol, di Propylene glycol monomethyl ether, 2- (2-ethoxy propoxy) propanol, lactic methyl ester, lactic ethyl ester, lactic n-propyl ester, lactic n-butyl ester, lactic iso amyl ester and the like.

이때, 액정 배향막과 기판의 밀착성을 더욱 향상시키는 목적으로 커플링제 등의 첨가제를 추가로 첨가할 수 있다. 구체적으로, 3-아미노 프로필 트리 메톡시 실란, 3-아미노 프로필 트리 에톡시 실란, 3-아미노 프로필 메틸 디에톡시 실란, 2-아미노 프로필 트리 에톡시 실란, N-(2-아미노 에틸)-3-아미노 프로필 트리 메톡시 실란, N-(2-아미노 에틸)-3-아미노 프로필 메틸 디메톡시 실란 등 관능성 실란 함유 화합물이나, 트리메틸올프로판 트리글리시딜 에테르, 트리페닐올메탄 트리글리시딜 에테르, 트리스(2,3-에폭시프로필) 아이소시안우레이트, 1,1,1-트리스 (파라-히드록시페닐)에탄 글리시딜 에테르 같은 에폭시기를 함유하는 화합물들을 첨가하는 것이 가능하다. 이들 커플링제의 사용 비율은 수지 고형분 100중량에 대하여 30 중량부 이하, 바람직하게는 0.01∼20 중량부이다.At this time, additives, such as a coupling agent, can be further added in order to further improve the adhesiveness of a liquid crystal aligning film and a board | substrate. Specifically, 3-amino propyl trimethoxy silane, 3-amino propyl triethoxy silane, 3-amino propyl methyl diethoxy silane, 2-amino propyl triethoxy silane, N- (2-amino ethyl) -3- Functional silane containing compounds, such as amino propyl trimethoxy silane and N- (2-amino ethyl) -3-amino propyl methyl dimethoxy silane, trimethylolpropane triglycidyl ether, triphenylolmethane triglycidyl ether, and tris It is possible to add compounds containing epoxy groups such as (2,3-epoxypropyl) isocyanurate, 1,1,1-tris (para-hydroxyphenyl) ethane glycidyl ether. The use ratio of these coupling agents is 30 weight part or less with respect to 100 weight of resin solid content, Preferably it is 0.01-20 weight part.

본 발명에 있어서 액정 배향제의 도포 방법은, 스핀코팅법, 인쇄법, 롤 코터법 등을 사용할 수 있으나 이들로 한정되는 것은 아니다. 본 발명에 있어 액정 배향막 형성을 위한 경화온도는 100∼350℃, 바람직하게는 150∼300℃이고, 더욱 바람직하게는 180∼250℃이다. 폴리이미드 전구체인 폴리아믹산으로부터 폴리이미드로의 변화율은 경화 온도에 의존하지만, 본 발명에 있어서 액정배향제는 반드시 100% 이미드화시킬 필요는 없다.In the present invention, the coating method of the liquid crystal aligning agent may be spin coating, printing, roll coating, or the like, but is not limited thereto. In this invention, the hardening temperature for liquid crystal aligning film formation is 100-350 degreeC, Preferably it is 150-300 degreeC, More preferably, it is 180-250 degreeC. Although the rate of change from polyamic acid, which is a polyimide precursor, to polyimide depends on the curing temperature, in the present invention, the liquid crystal aligning agent does not necessarily need to be imidized 100%.

본 발명에 따른 폴리아믹산 유도체는 기존 폴리이미드 수지의 특성을 유지하면서도 용해성 및 액정배향특성 등이 우수하게 나타나므로 각종 전기, 전자, 우주, 항공 등 첨단산업의 핵심 내열소재로 사용할 수 있다.The polyamic acid derivative according to the present invention can be used as a core heat-resistant material of high-tech industries such as various electric, electronic, aerospace and aviation because it shows excellent solubility and liquid crystal alignment characteristics while maintaining the properties of the existing polyimide resin.

이하에서 실시예를 통하여 본 발명을 보다 상세하게 설명하고자 하나, 하기의 실시예는 설명의 목적을 위한 것으로 본 발명을 제한하고자 하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

제조예 1: 3,5-디클로로-(3-(1-헥센)-숙시닉이미드)-트리아진의 제조Preparation Example 1 Preparation of 3,5-dichloro- (3- (1-hexene) -succinicimide) -triazine

교반기, 질소주입장치가 부착된 250 mL의 반응기에 질소가스를 서서히 통과시키면서 2-아미노-4,6-디클로로트리아진 9.2 g(0.산 50 mL에 용해시킨 후, 질소가스를 통과시키면서 2-헥센-1-일 숙신산 무수물 9.1 g(0.05 mole)을 넣고, 24시간 동안 환류시켰다. 반응용액을 상온으로 냉각시킨 후, 석출된 고체를 얻었다. 수득된 고체를 메탄올에서 재결정하여, 12.2 g의 3,5-디클로로-(3-(1-헥센)-숙시닉이미드)-트리아진을 제조하였다(수율 70%).9.2 g of 2-amino-4,6-dichlorotriazine (dissolved in 50 mL of acid) after slowly passing nitrogen gas through a 250 mL reactor equipped with a stirrer and a nitrogen injector. 9.1 g (0.05 mole) of hexen-1-yl succinic anhydride was added and refluxed for 24 hours After cooling the reaction solution to room temperature, a precipitated solid was obtained, and the obtained solid was recrystallized from methanol to obtain 12.2 g of 3 , 5-Dichloro- (3- (1-hexene) -succinimide) -triazine was prepared (yield 70%).

제조예 2: 3,5-디니트로페녹시-(3-(1-헥센)-숙시닉이미드)-트리아진의 제조Preparation Example 2 Preparation of 3,5-dinitrophenoxy- (3- (1-hexene) -succinicimide) -triazine

제조예 1에서 얻어진 반응물 9.7g을 클로로포름 100ml에 용해시키고, 4-니트로페놀 21.62g, 수산화나트륨 6.22g과 테트라암모늄브로마이드 2.4g의 수용액에 첨가한 후 환류하며 24시간 동안 반응시켰다. 반응종결 후 수용액층은 분리해 내고 남아있는 클로로포름 층은 1N 농도의 수용액으로 추출한 후 초순수로 여러회 세척하고, 마그네슘설페이트를 이용하여 건조하였다. 남아있는 클로로포름은 감압 증류하여 반응물을 고체화하고 무수 에탄올로 재결정하여 흰색의 3,5-디니트로페녹시-(3-(1-헥센)-숙시닉이미드)-트리아진을 제조하였다. 9.7 g of the reaction product obtained in Preparation Example 1 was dissolved in 100 ml of chloroform, and added to an aqueous solution of 21.62 g of 4-nitrophenol, 6.22 g of sodium hydroxide, and 2.4 g of tetraammonium bromide, followed by reflux for 24 hours. After completion of the reaction, the aqueous layer was separated, and the remaining chloroform layer was extracted with an aqueous solution of 1N concentration, washed several times with ultrapure water, and dried using magnesium sulfate. The remaining chloroform was distilled under reduced pressure to solidify the reaction and recrystallized with anhydrous ethanol to give white 3,5-dinitrophenoxy- (3- (1-hexene) -succinimide) -triazine.

제조예 3 : 3,5-디아미노페녹시-(3-(1-헥센)-숙시닉이미드)-트리아진(DAPIT-6)의 제조Preparation Example 3 Preparation of 3,5-diaminophenoxy- (3- (1-hexene) -succinimide) -triazine (DAPIT-6)

제조예 2에서 얻어진 3,5-디니트로페녹시-(3-(1-헥센)-숙시닉이미드)-트리아진 14.5g을 THF 300ml에 넣고 Pd/C 1.4g을 첨가한 후 수소를 50psi 압력으로 가압 제공하며 온도를 60℃로 승온하고 12시간 동안 반응을 수행하였다. 반응이 종결된 후 셀라이트(cellite)를 이용, 여과하여 팔라듐을 제거하고 감압 증류하여 고체를 수득하였다. 생성된 화합물을 다시 무수 에탄올로 재결정을 하여 순수한 3,5-디아미노페녹시-(3-(1-헥센)-숙시닉이미드)-트리아진(DAPIT-6)을 제조 하였다. 최종 수율은 약40%였다. 14.5 g of 3,5-dinitrophenoxy- (3- (1-hexene) -succinic imide) -triazine obtained in Preparation Example 2 was added to 300 ml of THF, and 1.4 g of Pd / C was added. The pressure was provided under pressure and the temperature was raised to 60 ° C. and the reaction was carried out for 12 hours. After the reaction was terminated, filtered through celite to remove palladium and distilled under reduced pressure to obtain a solid. The resultant compound was recrystallized with anhydrous ethanol to prepare pure 3,5-diaminophenoxy- (3- (1-hexene) -succinimide) -triazine (DAPIT-6). The final yield was about 40%.

제조예 4: 3,5-디아미노페녹시-(3-(1-옥텐)-숙시닉이미드)-트리아진(DAPIT-8)의 제조Preparation Example 4 Preparation of 3,5-diaminophenoxy- (3- (1-octene) -succinimide) -triazine (DAPIT-8)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 10.5 g(0.05 mole)의 2-옥텐-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1 내지 제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-옥텐)-숙시닉이미드)-트리아 진(DAPIT-8)을 수득하였다. 최종 수율은 약 37%였다.The reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 10.5 g (0.05 mole) of 2-octen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride in Preparation Example 1. This gave 3,5-diaminophenoxy- (3- (1-octene) -succinimide) -triazine (DAPIT-8). The final yield was about 37%.

제조예 5: 3,5-디아미노페녹시-(3-(1-데센)-숙시닉이미드)-트리아진(DAPIT-10)의 제조Preparation Example 5 Preparation of 3,5-diaminophenoxy- (3- (1-decene) -succinicimide) -triazine (DAPIT-10)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 11.9 g(0.05 mole)의 2-데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1 내지 제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-데센)-숙시닉이미드)-트리아진(DAPIT-10)를 수득하였다. 최종 수율은 약 36%였다.The reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 11.9 g (0.05 mole) of 2-decen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride in Preparation Example 1. This gave 3,5-diaminophenoxy- (3- (1-decene) -succinimide) -triazine (DAPIT-10). The final yield was about 36%.

제조예 6: 3,5-디아미노페녹시-(3-(1-도데센)-숙시닉이미드)-트리아진(DAPIT-12)의 제조Preparation Example 6 Preparation of 3,5-diaminophenoxy- (3- (1-dodecene) -succinimide) -triazine (DAPIT-12)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 13.3 g(0.05 mole)의 2-도데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시- (3-(1-데센)-숙시닉이미드)-트리아진 (DAPIT-12)를 수득하였다. 최종 수율은 약 35%였다.Reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 13.3 g (0.05 mole) of 2-dodecen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride in Preparation Example 1. Was carried out to give 3,5-diaminophenoxy- (3- (1-decene) -succinimide) -triazine (DAPIT-12). The final yield was about 35%.

제조예 7: 3,5-디아미노페녹시-(3-(1-테트라데센)-숙시닉이미드)-트리아진(DAPIT-14)의 제조Preparation Example 7 Preparation of 3,5-diaminophenoxy- (3- (1-tetradecene) -succinicimide) -triazine (DAPIT-14)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 14.7 g(0.05 mole)의 2-테트라데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-테트라데센)-숙시닉이미드)-트리아진(DAPIT-14)를 수득하였다. 최종 수율은 약 34%였다.Reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 14.7 g (0.05 mole) of 2-tetradecen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride in Preparation Example 1. Was carried out to give 3,5-diaminophenoxy- (3- (1-tetradecene) -succinimide) -triazine (DAPIT-14). The final yield was about 34%.

제조예 8: 3,5-디아미노페녹시-(3-(1-헥사데센)-숙시닉이미드)-트리아진(DAPIT-16)의 제조Preparation Example 8 Preparation of 3,5-diaminophenoxy- (3- (1-hexadecene) -succinicimide) -triazine (DAPIT-16)

제조예 1에서 22-헥센-1-일 숙신산 무수물 대신 16.1 g(0.05 mole)의 2-헥사데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-헥사데센)-숙시닉이미드)-트리아진(DAPIT-16)를 수득하였다. 최종 수율은 약 34%였다.Reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 16.1 g (0.05 mole) of 2-hexadecen-1-yl succinic anhydride was used instead of 22-hexen-1-yl succinic anhydride in Preparation Example 1. Was carried out to give 3,5-diaminophenoxy- (3- (1-hexadecene) -succinimide) -triazine (DAPIT-16). The final yield was about 34%.

제조예 9: 3,5-디아미노페녹시-(3-(1-옥타데센)-숙시닉이미드)-트리아진(DAPIT-18)의 제조Preparation Example 9 Preparation of 3,5-diaminophenoxy- (3- (1-octadecene) -succinicimide) -triazine (DAPIT-18)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 17.5 g(0.05 mole)의 2-옥타데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-옥타데센)-숙시닉이미드)-트리아진(DAPIT-18)를 수득하였다. 최종 수율은 약 32%였다.Reaction was carried out in the same manner as in Preparation Examples 1 to 3, except that 17.5 g (0.05 mole) of 2-octadecen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride in Preparation Example 1. Was carried out to give 3,5-diaminophenoxy- (3- (1-octadecene) -succinimide) -triazine (DAPIT-18). The final yield was about 32%.

제조예 10: 3,5-디아미노페녹시-(3-(1-도데센)-숙시닉이미드)-2,6-피리미딘 (DAPIPM-12)의 제조Preparation Example 10 Preparation of 3,5-diaminophenoxy- (3- (1-dodecene) -succinimide) -2,6-pyrimidine (DAPIPM-12)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 13.3 g(0.05 mole)의 2-도데 센-1-일 숙신산 무수물을 사용하고, 2-아미노-4,6-디클로로트리아진 대신 8.2 g(0.05 mole)의 2-아미노-4,6-디클로로피리미딘을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 3,5-디아미노페녹시-(3-(1-도데 센)-숙시닉이미드)-2,6-피리미딘(DAPIPM-12)를 수득하였다. 최종 수율은 약 35%였다. 도 1에 상기 DAPIPM-12의 1H-NMR 스펙트럼을 나타내었다.In Preparation Example 1, 13.3 g (0.05 mole) of 2-dodecen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride, and 8.2 g (instead of 2-amino-4,6-dichlorotriazine) The reaction was carried out in the same manner as in Production Examples 1 to 3, except that 0.05 mole) of 2-amino-4,6-dichloropyrimidine was used to prepare 3,5-diaminophenoxy- (3- ( 1-dodecene) -succinimide) -2,6-pyrimidine (DAPIPM-12) was obtained. The final yield was about 35%. Figure 1 shows the 1 H-NMR spectrum of the DAPIPM-12.

제조예 11: 4,6-디아미노페녹시-(3-(1-옥타데센)-숙시닉이미드)-2-피리딘 (DAPIP-18)의 제조Preparation Example 11 Preparation of 4,6-diaminophenoxy- (3- (1-octadecene) -succinimide) -2-pyridine (DAPIP-18)

제조예 1에서 2-헥센-1-일 숙신산 무수물 대신 13.3 g(0.05 mole)의 2-옥타데센-1-일 숙신산 무수물을 사용하고, 2-아미노-4,6-디클로로트리아진 대신 8.2 g(0.05 mole)의 2-아미노-3,5-디클로로피리딘을 사용하는 것을 제외하고는 상기 제조예 1~제조예 3과 동일하게 반응을 수행하여 4,6-디아미노페녹시-(3-(1-옥타데 센)-숙시닉이미드)-2-피리딘(DAPIP-18)를 수득하였다. 최종 수율은 약 29%였다.In Preparation Example 1, 13.3 g (0.05 mole) of 2-octadecen-1-yl succinic anhydride was used instead of 2-hexen-1-yl succinic anhydride, and 8.2 g (instead of 2-amino-4,6-dichlorotriazine) The reaction was carried out in the same manner as in Production Example 1 to Production Example 3, except that 0.05 mole) of 2-amino-3,5-dichloropyridine was used, to obtain 4,6-diaminophenoxy- (3- (1 -Octadecene) -succinimide) -2-pyridine (DAPIP-18) was obtained. The final yield was about 29%.

실시예 1Example 1

교반기, 온도조절장치, 질소주입장치, 적하깔대기 및 냉각기를 부착한 50 mL의 반응기에 질소가스를 서서히 통과시키면서 메틸렌 디아닐린 18.8 g(0.095 mole)과 2.65 g(0.005 mole)의 DAPIT-16을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 디옥소테트라히드로퓨릴-3-메틸시클로헥산-1,2- 디카르복실산이무수물(DOCDA) 13.2 g(0.05 mole)과 피로멜리트산이무수물 10.9 g(0.05 mole)의 혼합물을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 10 중량%로 고정하였으며, 반응온도를 10 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액(DPTAA-1)을 얻었다. 도 2는 상기 DPTAA-1의 1H-NMR 스펙트럼을 나타내고, 도 3는 DSC 곡선을 나타낸다.Methylene dianiline 18.8 g (0.095 mole) and 2.65 g (0.005 mole) DAPIT-16 are reacted slowly with nitrogen gas through a 50 mL reactor equipped with a stirrer, temperature controller, nitrogen injector, dropping funnel and cooler. 13.2 g (0.05) of dioxotetrahydrofuryl-3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA) in solid form while dissolved in solvent N -methyl-2-pyrrolidone and passed through nitrogen gas mole) and 10.9 g (0.05 mole) of pyromellitic dianhydride were added slowly. At this time, the solid content (solid content) was fixed to 10% by weight, and stirred for 24 hours while maintaining the reaction temperature below 10 ℃ to obtain a polyamic acid solution (DPTAA-1). FIG. 2 shows the 1 H-NMR spectrum of DPTAA-1, and FIG. 3 shows the DSC curve.

실시예 2Example 2

메틸렌 디아닐린 17.8 g(0.09 mole)과 4.3 g(0.01 mole)의 DAPIT-16을 사용하는 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아믹산 수지(DPTAA-2)를 얻었다.Except for using 17.8 g (0.09 mole) and 4.3 g (0.01 mole) of DAPIT-16 methylene dianiline was carried out in the same manner as in Example 1 to obtain a polyamic acid resin (DPTAA-2).

실시예 3Example 3

메틸렌 디아닐린 9.9 g(0.05 mole)과 21.48 g(0.05 mole)의 DAPIT-16을 사용하는 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아믹산 수지(DPTAA-3)를 얻었다.Except for using 9.9 g (0.05 mole) and 21.48 g (0.05 mole) of DAPIT-16 methylene dianiline was carried out in the same manner as in Example 1 to obtain a polyamic acid resin (DPTAA-3).

실시예 4Example 4

메틸렌 디아닐린 1.98 g(0.01 mole)과 38.7 g(0.09mole)의 DAPIT-16을 사용하는 것을 제외하고는 상기 실시예 2과 동일하게 수행하여 폴리아믹산 수지(DPTAA- 4)를 얻었다.A polyamic acid resin (DPTAA-4) was obtained in the same manner as in Example 2, except that 1.98 g (0.01 mole) of methylene dianiline and 38.7 g (0.09 mole) of DAPIT-16 were used.

실시예 5Example 5

DAPIT-16 대신 21.48 g(0.05 mole)의 DAPIT-6를 사용하는 것을 제외하고는 상기 실시예 3와 동일하게 수행하여 폴리아믹산 수지(DPTAA-5)를 얻었다.A polyamic acid resin (DPTAA-5) was obtained in the same manner as in Example 3 except that 21.48 g (0.05 mole) of DAPIT-6 was used instead of DAPIT-16.

실시예 6Example 6

DAPIT-16 대신 4.4 g(0.01 mole))의 DAPIT-18를 사용하는 것을 제외하고는 상기 실시예 1와 동일하게 수행하여 폴리아믹산 수지(DPTAA-6)를 얻었다.A polyamic acid resin (DPTAA-6) was obtained in the same manner as in Example 1 except that 4.4 g (0.01 mole) of DAPIT-18 was used instead of DAPIT-16.

실시예 7Example 7

DOCDA 대신 9.8 g(0.05 mole)의 1,2,3,4-시클로부탄테트라카르복실산이무수물(CBDA)을 사용하고, 반응용매로서 NMP와 γ-부티로락톤(5/5 부피비)을 사용하는 것을 제외하고는 상기 실시예 1과 동일하게 수행하여 폴리아믹산 수지(CPTAA-1)를 얻었다.9.8 g (0.05 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is used instead of DOCDA, and NMP and γ-butyrolactone (5/5 by volume) are used as the reaction solvent. Except that was carried out in the same manner as in Example 1 to obtain a polyamic acid resin (CPTAA-1).

실시예 8Example 8

DOCDA 대신 9.8 g(0.05 mole)의 CBDA를 사용하는 것을 제외하고는 상기 실시예 2와 동일하게 수행하여 폴리아믹산 수지(CPTAA-2)를 얻었다.A polyamic acid resin (CPTAA-2) was obtained in the same manner as in Example 2, except that 9.8 g (0.05 mole) of CBDA was used instead of DOCDA.

실시예 9Example 9

DOCDA 대신 9.8 g(0.05 mole)의 CBDA를 사용하는 것을 제외하고는 상기 실시예 3과 동일하게 수행하여 폴리아믹산 수지(CPTAA-3)를 얻었다. 도 4에 상기 CPTAA-3의 1H-NMR 스펙트럼을 나타내었다.A polyamic acid resin (CPTAA-3) was obtained in the same manner as in Example 3 except that 9.8 g (0.05 mole) of CBDA was used instead of DOCDA. Figure 4 shows the 1 H-NMR spectrum of the CPTAA-3.

실시예 10Example 10

DAPIT-16 대신 4.3 g(0.01 mole)의 DAPIPM-12를 사용하는 것을 제외하고는 상기 실시예 2와 동일하게 수행하여 폴리아믹산 수지(DPMAA-1)를 얻었다.A polyamic acid resin (DPMAA-1) was obtained in the same manner as in Example 2 except that 4.3 g (0.01 mole) of DAPIPM-12 was used instead of DAPIT-16.

실시예 11Example 11

DAPIT-16 대신 2.4 g(0.005 mole)의 DAPIP-18를 사용하는 것을 제외하고는 상기 실시예 1와 동일하게 수행하여 폴리아믹산 수지(DPPAA-1)를 얻었다.Polyamic acid resin (DPPAA-1) was obtained in the same manner as in Example 1 except that 2.4 g (0.005 mole) of DAPIP-18 was used instead of DAPIT-16.

비교예 1Comparative Example 1

디아민 단량체로서 19.8 g(0.1 mole)의 메틸렌 디아닐린만을 사용하는 것을 제외하고는 상기 실시예 2와 동일하게 수행하여 폴리아믹산 용액(DPTAA-0)을 얻었다.A polyamic acid solution (DPTAA-0) was obtained in the same manner as in Example 2, except that only 19.8 g (0.1 mole) of methylene dianiline was used as the diamine monomer.

비교예 2Comparative Example 2

디아민 단량체로서 19.8 g(0.1 mole)의 메틸렌 디아닐린만을 사용하는 것을 제외하고는 상기 실시예 7과 동일하게 수행하여 폴리아믹산 용액(CPTAA-0)을 얻었다.A polyamic acid solution (CPTAA-0) was obtained in the same manner as in Example 7 except that only 19.8 g (0.1 mole) of methylene dianiline was used as the diamine monomer.

상기 실시예 1 내지 11 및 비교예 1 내지 2에 따라 제조된 폴리아믹산 용액은 모두 밝은 호박색의 투명한 수지였다. 상기 폴리아믹산 용액의 고유점도를 측정하고, 이를 ITO 유리판 위에 0.05 ∼ 0.2 ㎛의 두께로 스핀 코팅한 후, 230 ℃의 온도에서 30 분동안 열경화하여 얻은 폴리이미드 박막의 물성에서 유리전이온도, 표면장력, 연필경도를 측정하여 이를 다음 표 1에 나타내었다.The polyamic acid solutions prepared according to Examples 1 to 11 and Comparative Examples 1 to 2 were all bright amber transparent resins. The intrinsic viscosity of the polyamic acid solution was measured, spin-coated to a thickness of 0.05 to 0.2 μm on an ITO glass plate, and thermally cured for 30 minutes at a temperature of 230 ° C. in the physical properties of the polyimide thin film. Tension and pencil hardness were measured and shown in Table 1 below.

배향막Alignment film 고유점도* (dL/g)Intrinsic viscosity * (dL / g) 유리전이온도 (℃)Glass transition temperature (℃) 표면장력 (dyne/cm)Surface tension (dyne / cm) 연필경도Pencil hardness 실시예 1Example 1 DPTAA-1DPTAA-1 0.980.98 335335 4646 4H4H 실시예 2Example 2 DPTAA-2DPTAA-2 0.940.94 331331 4545 4H4H 실시예 3Example 3 DPTAA-3DPTAA-3 0.720.72 318318 4343 3H3H 실시예 4Example 4 DPTAA-4DPTAA-4 0.850.85 305305 3939 3H3H 실시예 5Example 5 DPTAA-5DPTAA-5 1.021.02 345345 4848 5H5H 실시예 6Example 6 DPTAA-6DPTAA-6 0.850.85 325325 4444 3H3H 실시예 7Example 7 CPTAA-1CPTAA-1 0.920.92 270270 3434 5H5H 실시예 8Example 8 CPTAA-2CPTAA-2 0.870.87 265265 3232 4H4H 실시예 9Example 9 CPTAA-3CPTAA-3 0.910.91 260260 3030 4H4H 실시예 10Example 10 DPMAA-1DPMAA-1 0.690.69 329329 4242 3H3H 실시예 11Example 11 DPPAA-1DPPAA-1 0.710.71 315315 4040 3H3H 비교예 1Comparative Example 1 DPTAA-0DPTAA-0 1.151.15 330 330 50 50 BB 비교예 2Comparative Example 2 CPTAA-0CPTAA-0 1.301.30 275 275 41 41 HBHB *)NMP을 용매로 하여 0.5 g/dL의 농도로 30 ℃에서 측정. *) Measured at 30 ° C. at a concentration of 0.5 g / dL using NMP as a solvent.

상기 표 1에서 나타난 바와 같이, 본 발명에 따른 폴리아믹산 용액은 0.3 ~ 1.5 dL/g의 고유점도를 가지는 것으로 확인되었으며, 용매주형에 의한 필름성형성 및 기계적 특성이 매우 우수한 것으로 나타났다.As shown in Table 1, the polyamic acid solution according to the present invention was confirmed to have an intrinsic viscosity of 0.3 ~ 1.5 dL / g, it was shown that the film formation and mechanical properties by the solvent casting very excellent.

또한, 상기 표 1에서 나타난 바와 같이, 이미드 고리 함유 고리계 측쇄기가 도입된 본 발명에 따른 폴리아믹산 유도체들로부터 제조된 폴리이미드 박막의 연필경도는 3H∼5H 정도로서, 이들이 도입되지 않은 비교예 1 및 2의 폴리이미드에 비해 표면경도가 현저히 개선되었다. 폴리이미드 박막의 표면 장력은 이미드 고리 함유 고리계 측쇄기가 도입된 단량체의 함량이 증가함에 따라 감소하는 경향을 나타내었으며, CBDA가 단량체로 사용된 실시예 7 내지 9는 DOCDA가 사용된 실시예 1 내지 6보다 낮은 값을 보여주었다.In addition, as shown in Table 1, the pencil hardness of the polyimide thin film prepared from the polyamic acid derivatives according to the present invention introduced with an imide ring-containing ring-based side chain group is about 3H to 5H, Comparative Example 1 Compared with the polyimide of 2 and 2, the surface hardness was significantly improved. The surface tension of the polyimide thin film showed a tendency to decrease as the content of the monomer into which the imide ring-containing ring-based side chain group was introduced increased. Values lower than 6 were shown.

한편, 상기 실시예 1 내지 11 및 비교예 1, 2에서 수득된 본 발명에 따른 폴리아믹산 용액들을 감마-부티로락톤에 희석시켜, 상온에서의 용액점도를 20 ∼ 40 cps로 유지시킨 뒤, 400 ∼ 4,000 rpm 속도로, 25초간, ITO 유리기판에 코팅하여 박막을 형성하고, 80℃에서 5분간 건조한 후 220℃에서 15분동안 이미드화시켜 액정배향막을 형성하였다. 이를 이용하여 액정셀을 제작하고 그 특성들을 측정하여 다음 표 2에 나타내었다. Meanwhile, the polyamic acid solutions according to the present invention obtained in Examples 1 to 11 and Comparative Examples 1 and 2 were diluted with gamma-butyrolactone to maintain a solution viscosity at room temperature of 20 to 40 cps, followed by 400 25 seconds, coated on an ITO glass substrate at a speed of 4,000 rpm to form a thin film, dried for 5 minutes at 80 ℃ and imidized at 220 ℃ for 15 minutes to form a liquid crystal alignment film. Using this, a liquid crystal cell was fabricated and its properties are shown in Table 2 below.

구 분division 배향막Alignment film 선경사각 (°)Pretilt angle (°) VHR(%) (상온)VHR (%) (room temperature) 잔류DC(mV) (상온)Residual DC (mV) (room temperature) 실시예 1Example 1 DPTAA-1DPTAA-1 6.16.1 99.899.8 4545 실시예 2Example 2 DPTAA-2DPTAA-2 89.089.0 99.599.5 5757 실시예 3Example 3 DPTAA-3DPTAA-3 89.889.8 99.599.5 6969 실시예 4Example 4 DPTAA-4DPTAA-4 89.989.9 99.799.7 8080 실시예 5Example 5 DPTAA-5DPTAA-5 4.54.5 99.399.3 6565 실시예 6Example 6 DPTAA-6DPTAA-6 89.589.5 99.599.5 7171 실시예 7Example 7 CPTAA-1CPTAA-1 6.56.5 99.699.6 8585 실시예 8Example 8 CPTAA-2CPTAA-2 88.088.0 99.699.6 8989 실시예 9Example 9 CPTAA-3CPTAA-3 88.088.0 99.499.4 9595 실시예 10Example 10 DPMAA-1DPMAA-1 6.56.5 99.499.4 7777 실시예 11Example 11 DPPAA-1DPPAA-1 6.06.0 99.599.5 9494 비교예 1Comparative Example 1 DPTAA-0DPTAA-0 2.02.0 9898 225225 비교예 2Comparative Example 2 CPTAA-0CPTAA-0 2.52.5 9999 300300

[물성측정방법][Measurement of physical properties]

1. 선경사각 : 결정회전법(crystal rotation method)을 이용하여 측정하였다.1. Pretilt angle was measured by the crystal rotation method.

2. VHR(%) : 액정 평가 셀을 제작하여, 25℃(상온)에 30분 동안 방치하여 평가 셀의 온도를 유지시킨다. 그리고 평가 셀에 게이트 전압(1V)을 69㎲동안 인가하고 16.7ms 프레임 주기 동안 인가된 전압의 변화 정도를 측정한다. 2. VHR (%): A liquid crystal evaluation cell was produced and left at 25 ° C (room temperature) for 30 minutes to maintain the temperature of the evaluation cell. The gate voltage (1V) is applied to the evaluation cell for 69 mA and the degree of change of the applied voltage during the 16.7 ms frame period is measured.

3. 잔류DC(mV): 액정 평가 셀을 제작하여, -10V에서 10V까지 전압을 반복적으로 인가한다. 그리고 전압에 따른 평가셀의 카파시던스를 측정하면 히스테리시스 곡선이 발생한다. 이때 발생한 첫번째 곡선과 두번째 곡선사이의 전압차로부터 잔류 DC를 측정한다. 3. Residual DC (mV): A liquid crystal evaluation cell was fabricated and voltage was repeatedly applied from -10V to 10V. The hysteresis curve is generated by measuring the capacitance of the evaluation cell according to the voltage. The residual DC is measured from the voltage difference between the first and second curves.

상기 표 2로부터, 본 발명에 따른 폴리아믹산을 이용하여 제조된 액정 셀은 선경사각이 4 ~ 89.9°정도로서 본 발명에 의한 신규한 기능성 디아민의 함량에 따라 용이하게 조절가능함을 알 수 있다. 또한 비교예에 비해 VHR 및 잔류DC 특성도 매우 우수함을 알 수 있다.From Table 2, it can be seen that the liquid crystal cell prepared using the polyamic acid according to the present invention can be easily adjusted according to the content of the novel functional diamine according to the present invention with a pretilt angle of about 4 to 89.9 °. In addition, it can be seen that the VHR and residual DC characteristics are also very good compared to the comparative example.

본 발명에 의해 제공되는 폴리아믹산은 내열성과 기계적 특성이 매우 우수할 뿐만 아니라 우수한 광투과성 및 안정한 선경사각을 나타내어, 까다로운 전기광학적 특성이 요구되는 STN LCD용 액정배향막으로 유용하게 적용할 수 있으며, 그 이외에 각종 첨단 내열 소재로도 유용하게 적용할 수 있다.The polyamic acid provided by the present invention not only has excellent heat resistance and mechanical properties but also shows excellent light transmittance and stable pretilt angle, and thus can be usefully applied as a liquid crystal aligning film for STN LCD, which requires demanding electro-optic properties. In addition, it can be usefully applied to various advanced heat-resistant materials.

Claims (8)

하기 화학식 1로 표시되는 디아민 화합물.Diamine compound represented by following formula (1). [화학식 1][Formula 1]
Figure 712006001505692-pat00024
Figure 712006001505692-pat00024
 (상기 식에서(In the above formula A는 단일결합 또는 -O-, -COO-, -OCO-, -NHCO-, -CONH- 이고, A is a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, B는
Figure 712006001505692-pat00025
또는
Figure 712006001505692-pat00026
이며,B is
Figure 712006001505692-pat00025
or
Figure 712006001505692-pat00026
Is, C는
Figure 712006001505692-pat00027
,
Figure 712006001505692-pat00028
,
Figure 712006001505692-pat00029
,
Figure 712006001505692-pat00030
또는
Figure 712006001505692-pat00031
이고,C is
Figure 712006001505692-pat00027
,
Figure 712006001505692-pat00028
,
Figure 712006001505692-pat00029
,
Figure 712006001505692-pat00030
or
Figure 712006001505692-pat00031
ego, 이때 D는 탄소수 1 내지 30의 선형, 가지형 또는 고리형 알킬기, 또는 하나 이상의 불포화 결합을 포함하고 있는 탄소수 6 내지 40의 선형, 가지형 또는 고리형 알킬기이며,Wherein D is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, or a linear, branched or cyclic alkyl group having 6 to 40 carbon atoms containing at least one unsaturated bond, Z는 -H, -CH3, -Cl, -Br, -F, -CN, 혹은 -CF3이다.)Z is -H, -CH 3 , -Cl, -Br, -F, -CN, or -CF 3. ) (i) 상기 청구항 제 1항의 디아민 화합물, (ii) 피로멜리트산이무수물, 벤조페논테트라카르복실산 이무수물, 옥시디프탈산이무수물, 비프탈산이무수물, 헥사플루오로이소프로필리덴디프탈산이무수물로 구성된 군으로부터 선택된 하나 이상의 방향족 고리형 산이무수물 및 (iii) 1,2,3,4-시클로부탄 테트라카르복실산 이무수물, 1,2,3,4-시클로펜탄 테트라카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-3-시클로헥센-1,2-디카르복실산이무수물, 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸-4-시클로헥센-1,2-디카르복실산이무수물, 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산 이무수물, 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물, 2,3,5-트리카르복실시클로펜틸아세틱 액시드 디안하이드라이드, 1,2,3,4-테드라메틸-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디메틸-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-메틸-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2,3,4-테드라플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디플루오르-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1,2-디메틸-3,4-디플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물, 1-메틸-3-플루오르-1,2,3,4- 시클로부탄 테드라카르복실산 이무수물, 1-메틸-4-플루오르-1,2,3,4-시클로부탄 테드라카르복실산 이무수물로 구성된 군으로부터 선택된 하나 이상의 지방족 고리형 산이무수물과 (iv) 여기에 파라-페닐렌디아민(p-PDA), 메타-페닐렌디아민 (m-PDA), 4,4-옥시디아닐린(ODA), 4,4-메틸렌디아닐린(MDA), 2,2-비스아미노페닐헥사풀루오로프로판(HFDA), 메타비스아미노페녹시디페닐설폰(m-BAPS), 파라비스아미노페녹시디페닐설폰(p-BAPS), 1,4-비스아미노페녹시벤젠(TPE-Q), 1,3-비스아미노페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP), 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP)으로 구성된 군으로부터 선택된 하나 이상의 방향족 고리형 디아민을 포함시켜 공중합하여 제조된 폴리아믹산.(i) the diamine compound of claim 1, (ii) pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, oxydiphthalic dianhydride, non-phthalic dianhydride, hexafluoroisopropylidene diphthalic dianhydride At least one aromatic cyclic acid dianhydride selected from the group consisting of (iii) 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 5 -(2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclo Hexene-1,2-dicarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-4-cyclohexene-1,2-dicarboxylic dianhydride, 4- (2, 5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 2,3, 5-tricarboxyl Pentylacetic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tedracarboxylic dianhydride, 1,2-dimethyl-1,2,3 , 4-cyclobutane tetradranic dianhydride, 1-methyl-1,2,3,4-cyclobutane tetradracarboxylic dianhydride, 1,2,3,4-tetrafluoro-1,2 , 3,4-cyclobutane tetradranic dianhydride, 1,2-difluoro-1,2,3,4-cyclobutane tetradracarboxylic dianhydride, 1-fluoro-1,2,3, 4-cyclobutane tedracarboxylic dianhydride, 1,2-dimethyl-3,4-difluoro-1,2,3,4-cyclobutane tedracarboxylic dianhydride, 1-methyl-3-fluoro One selected from the group consisting of -1,2,3,4-cyclobutane tedracarboxylic dianhydride, 1-methyl-4-fluor-1,2,3,4-cyclobutane tedracarboxylic dianhydride Above aliphatic cyclic acid dianhydride and (iv) para-phenylenediamine ( p- PDA), meta-phenylenediamine ( m- PDA), 4,4-oxydianiline (ODA), 4,4-methylenedianiline (MDA), 2,2-bisaminophenylhexafuluropropane (HFDA), metabisaminophenoxydiphenylsulfone ( m- BAPS) , Parabisaminophenoxydiphenylsulfone ( p- BAPS), 1,4-bisaminophenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisamino A polyamic acid prepared by copolymerizing one or more aromatic cyclic diamines selected from the group consisting of phenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafulopropane (HFBAPP). 제 2항에 있어서, 상기 폴리아믹산에 포함된 전체 디아민 단량체 중 상기 기능성 디아민과 상기 방향족 고리형 디아민의 몰비가 100:0∼0.1:99.9이고, 전체 산이무수물 단량체 중 상기 방향족 고리형 산이무수물과 상기 지방족 고리형 산이무수물의 몰비가 10:90∼80:20인 것을 특징으로 하는 폴리아믹산.The molar ratio of the functional diamine and the aromatic cyclic diamine in the total diamine monomers contained in the polyamic acid is 100: 0 to 0.1: 99.9, and the aromatic cyclic acid dianhydride and the A polyamic acid, wherein the molar ratio of aliphatic cyclic acid dianhydride is 10:90 to 80:20. 제 2항에 있어서, 상기 폴리아믹산이 하기 화학식 2로 표시되는 것을 특징으로 하는 폴리아믹산.The polyamic acid according to claim 2, wherein the polyamic acid is represented by the following Chemical Formula 2. [화학식 2][Formula 2]
Figure 112005076214357-pat00032
Figure 112005076214357-pat00032
 (상기 식에서 (In the above formula
Figure 112005076214357-pat00033
는 하기 화학식 3으로 표시되는 작용기로 이루어진 군에서 선택된 작용기, 및 하기 화학식 4로 표시되는 작용기로 이루어진 군으로부터 선택된 작용기를 나타내며, 이때 화학식 3으로 표시되는 작용기와 화학식 4로 표시되는 작용기의 10:90 내지 80:20이고,
Figure 112005076214357-pat00033
Represents a functional group selected from the group consisting of functional groups represented by Formula 3, and a functional group selected from the group consisting of functional groups represented by Formula 4, wherein 10:90 of the functional group represented by Formula 3 and functional group represented by Formula 4 To 80:20,
Figure 112005076214357-pat00034
는 하기 화학식 5로 표시되는 작용기로 이루어진 군에서 선택된 작용기, 및 하기 화학식 6으로 표시되는 작용기로 이루어진 군에서 선택된 작용기를 나타내고, 이때 화학식 5로 표시되는 작용기와 화학식 6으로 표시되는 작용기의 비는 100:0 내지 0.1:99.9이다.)
Figure 112005076214357-pat00034
Represents a functional group selected from the group consisting of functional groups represented by Formula 5, and a functional group selected from the group consisting of functional groups represented by Formula 6, wherein the ratio of the functional group represented by Formula 5 and the functional group represented by Formula 6 is 100 : 0 to 0.1: 99.9.) [화학식 3][Formula 3]
Figure 112005076214357-pat00035
Figure 112005076214357-pat00035
 [화학식 4][Formula 4]
Figure 112005076214357-pat00036
Figure 112005076214357-pat00036
 [화학식 5][Formula 5]
Figure 112005076214357-pat00037
Figure 112005076214357-pat00037
 [화학식 6][Formula 6]
Figure 112005076214357-pat00038
Figure 112005076214357-pat00038
 제2항에 있어서, 상기 폴리아믹산의 평균 분자량이 10,000∼300,000g/mol인 것을 특징으로 하는 폴리아믹산.The polyamic acid according to claim 2, wherein the polyamic acid has an average molecular weight of 10,000 to 300,000 g / mol. 제2항에 의한 폴리아믹산을 부분적으로 또는 전체적으로 이미드화시켜 얻어진 폴리이미드.A polyimide obtained by imidating the polyamic acid according to claim 2 in part or in whole. 제2항에 의한 폴리아믹산 또는 제6항에 의한 폴리이미드를 코팅, 건조, 경화하여 얻어진 액정 배향막.The liquid crystal aligning film obtained by coating, drying, and hardening the polyamic acid of Claim 2 or the polyimide of Claim 6. 제7항에 의한 액정 배향막을 포함하는 액정 표시 소자.The liquid crystal display element containing the liquid crystal aligning film of Claim 7.
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US10606128B2 (en) 2015-10-02 2020-03-31 Lg Chem, Ltd. Method for preparing photoalignment layer

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US10606128B2 (en) 2015-10-02 2020-03-31 Lg Chem, Ltd. Method for preparing photoalignment layer

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