KR100559264B1 - Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them - Google Patents

Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them Download PDF

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KR100559264B1
KR100559264B1 KR1020040087422A KR20040087422A KR100559264B1 KR 100559264 B1 KR100559264 B1 KR 100559264B1 KR 1020040087422 A KR1020040087422 A KR 1020040087422A KR 20040087422 A KR20040087422 A KR 20040087422A KR 100559264 B1 KR100559264 B1 KR 100559264B1
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polyamic acid
liquid crystal
side chain
low polar
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이미혜
최중근
이윤정
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K19/00—Liquid crystal materials
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • 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
    • 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 저극성 폴리아믹산 수지를 함유하는 수직배향형 조성물 및 이를 이용한 액정 배향막과 액정 셀에 관한 것으로서, 더욱 상세하게는 지방족 고리계 산이무수물을 함유하는 산이무수물과 이미드 고리 함유 측쇄기를 갖는 방향족 디아민을 함유하는 방향족 디아민류를 용액 중합한 저극성의 폴리아믹산 수지와, 폴리아믹산 유도체를 적정 비율로 혼합하여, 내열성, 표면경도, 투명성 및 액정의 배향성이 우수한 신규의 폴리아믹산 혼합조성물과, 그리고 상기 폴리아믹산 조성물을 이용하여 낮은 표면 조도, 인쇄성, 내열성 및 투명성이 매우 우수한 액정 배향막 및 89 °이상의 선경사각 및 99% 이상의 전압보유율을 갖는 액정 셀에 관한 것이다.The present invention relates to a vertically oriented composition containing a low polar polyamic acid resin, and a liquid crystal alignment film and a liquid crystal cell using the same. A novel polyamic acid mixed composition having excellent heat resistance, surface hardness, transparency and liquid crystal orientation by mixing a low polar polyamic acid resin obtained by solution polymerization of aromatic diamines containing diamine and a polyamic acid derivative at an appropriate ratio, and It relates to a liquid crystal aligning film having excellent surface roughness, printability, heat resistance and transparency using the polyamic acid composition, and a liquid crystal cell having a pretilt angle of 89 ° or more and a voltage retention of 99% or more.

저극성 폴리아믹산, 폴리아믹산 유도체, 수직배향형, 액정 배향막, 혼합조성물Low polar polyamic acid, polyamic acid derivative, vertical alignment type, liquid crystal alignment film, mixed composition

Description

저극성 폴리아믹산 수지를 함유하는 수직배향형 조성물 및 이를 이용한 액정 배향막과 액정 셀{Composition of containing Polyamic acid blends and liquid crystal alignment layer and cell using them} Composition of containing polyamic acid blends and liquid crystal alignment layer and cell using them vertically aligned composition containing low polar polyamic acid resin             

도 1은 본 발명의 1-(3,5-디아미노페닐)-3-옥타데실-숙시닉이미드(DA-IM-18)의 1H-NMR 스펙트럼을 나타낸 것이다.1 shows the 1 H-NMR spectrum of 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18) of the present invention.

도 2는 본 발명의 제조예 15에 따라 제조된 PAA-1의 1H-NMR 스펙트럼을 나타낸 것이다.2 shows the 1 H-NMR spectrum of PAA-1 prepared according to Preparation Example 15 of the present invention.

도 3는 본 발명의 제조예 17에 따라 제조된 PAA-3의 1H-NMR 스펙트럼을 나타낸 것이다.Figure 3 shows the 1 H-NMR spectrum of PAA-3 prepared according to Preparation 17 of the present invention.

도 4는 본 발명의 실시예 1와 실시예 7 ∼ 10에 따라 제조된 BPAA-2와 BPAA-8 ∼ 11의 UV 스펙트럼과 비교예 2 ∼ 4에 따라 제조된 PAA-2 ∼ 3과 SPPA의 UV 스펙트럼을 나타낸 것이다.4 is a UV spectrum of BPAA-2 and BPAA-8 to 11 prepared according to Examples 1 and 7 to 10 of the present invention, and UV of PAA-2 to 3 and SPPA prepared according to Comparative Examples 2 to 4; The spectrum is shown.

본 발명은 저극성 폴리아믹산 수지를 함유하는 수직배향형 조성물 및 이를 이용한 액정 배향막과 액정 셀에 관한 것으로서, 더욱 상세하게는 지방족 고리계 산이무수물을 함유하는 산이무수물과 이미드 고리 함유 측쇄기를 갖는 방향족 디아민을 함유하는 방향족 디아민류를 용액 중합한 저극성의 폴리아믹산 수지와, 폴리아믹산 유도체를 적정 비율로 혼합하여, 내열성, 표면경도, 투명성 및 액정의 배향성이 우수한 신규의 폴리아믹산 혼합조성물과, 그리고 상기 폴리아믹산 조성물을 이용하여 낮은 표면 조도, 인쇄성, 내열성 및 투명성이 매우 우수한 액정 배향막 및 89 °이상의 선경사각 및 99% 이상의 전압보유율을 갖는 액정 셀에 관한 것이다.The present invention relates to a vertically oriented composition containing a low polar polyamic acid resin, and a liquid crystal alignment film and a liquid crystal cell using the same, and more particularly, aromatic having an acid dianhydride containing an aliphatic ring-based acid dianhydride and an imide ring-containing side chain group. A novel polyamic acid mixed composition having excellent heat resistance, surface hardness, transparency and liquid crystal orientation by mixing a low polar polyamic acid resin obtained by solution polymerization of aromatic diamines containing diamine with a polyamic acid derivative at an appropriate ratio, and It relates to a liquid crystal aligning film having excellent surface roughness, printability, heat resistance and transparency using the polyamic acid composition, and a liquid crystal cell having a pretilt angle of 89 ° or more and a voltage retention of 99% or more.

일반적으로 폴리이미드 수지라 함은 방향족 테트라카르복실산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합한 후, 이미드화하여 제조되는 고내열성 수지를 일컫는다. 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.

폴리이미드 수지는 사용된 단량체의 종류에 따라 여러 가지의 분자구조를 가질 수 있다. 일반적인 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. The polyimide resin may have various molecular structures depending on the type of monomer used. As a typical aromatic tetracarboxylic acid component, pyromellitic dianhydride (PMDA) or nonphthalic anhydride (BPDA) is used, and as aromatic diamine component, para-phenylenediamine ( p- PDA) and 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, It is produced by polycondensation polymerization using aromatic diamines such as 2-bisaminophenoxyphenylpropane (BAPP) and 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP).

대부분의 폴리이미드 수지는 불용 및 불융의 초고내열성 수지로서, (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 및 (6) 우수한 내약품성 등과 같은 특성을 가지고 있다. Most polyimide resins are insoluble and insoluble ultra-high heat resistant resins, which include (1) excellent thermal oxidation resistance, (2) high usable temperature, and (3) long-term temperature of about 260 ° C and short-term temperature of about 480 ° C. It has characteristics such as excellent heat resistance, (4) radiation resistance, (5) excellent low temperature property, and (6) excellent chemical resistance.

그러나, 폴리이미드 수지의 이러한 특성에도 불구하고 전하이동착체(charge transfer complex)의 형성에 기인한 가시광선 영역에서의 낮은 광투과도로 인하여 투명성이 요구되는 분야에의 적용이 매우 어렵다는 단점이 있다. 따라서, 다양한 종류의 주쇄형 지방족 폴리이미드계 수지들이 제조되어, 액정 배향막 등 우수한 광투과성이 요구되는 분야에 응용되고 있다. However, in spite of these characteristics of polyimide resin, there is a disadvantage in that it is very difficult to be applied to a field where transparency is required due to low light transmittance in the visible light region due to the formation of a charge transfer complex. Accordingly, various kinds of main chain aliphatic polyimide resins have been produced, and have been applied to fields requiring excellent light transmittance such as liquid crystal alignment films.

현재까지 개발된 지방족 고리기가 주쇄에 도입된 액정 배향막용 폴리이미드계 수지는 선경사각의 발현을 위해 긴 알킬 사슬기를 측쇄로 도입되어 사용되고 있으며, 용매에 용해되는 가용성 폴리이미드계 수지 및 폴리아믹산계 수지가 대표적이다. 그러나, 가용성 폴리이미드계 수지의 경우 용매에 대한 일반 유기 용제에 대한 용해성이 미흡하여 인쇄성이 양호하지 않은 단점이 있으며, 폴리아믹산계 배향막의 경우에는 높은 표면 극성으로 말미암아 전압보유율(VHR, voltage holding ratio)이 감소하는 단점이 있다. 뿐만 아니라, 다양한 구동 모드에 대응할 수 있는 배향막으로서의 응용을 위해서는 선경사각의 제어가 요구되고 있다.Polyimide-based resins for liquid crystal aligning films in which aliphatic ring groups have been introduced to the main chain have been introduced and used as side chains for the expression of pretilt angles. Soluble polyimide resins and polyamic acid resins dissolved in a solvent Is representative. However, in the case of soluble polyimide-based resins, there is a disadvantage in that printability is not good because of poor solubility in general organic solvents in solvents, and in the case of polyamic acid alignment layers, voltage holding ratio (VHR, voltage holding) is high. ratio is reduced. In addition, control of the pretilt angle is required for application as an alignment film that can cope with various driving modes.

이에, 본 발명의 발명자들은 종래의 폴리이미드계 수지를 이용하여 제조된 액정 배향막의 광투과성, 용해성 및 전압보유율의 저하 등의 문제를 해결하고자 연구 노력하였다. 그 결과, 유기 용제에 우수한 용해성을 가질 뿐만 아니라 저극성 측쇄를 갖는 폴리아믹산 수지와, 방향족 또는 지방족 고리계 폴리아믹산 유도체를 용액상태에서 일정 비율로 혼합한 조성물은 내열성, 투명성, 표면경도 및 수직배향성을 갖게 된다는 것을 알게되어 본 발명을 완성하게 되었다.Therefore, the inventors of the present invention have tried to solve the problems such as light transmittance, solubility and reduction of voltage retention of the liquid crystal alignment film prepared using a conventional polyimide resin. As a result, a composition in which a polyamic acid resin not only having excellent solubility in organic solvents but also having a low polar side chain and an aromatic or aliphatic ring-based polyamic acid derivative in a fixed ratio in a solution state is heat-resistant, transparent, surface hardness and vertically oriented. It was found that to have completed the present invention.

따라서, 본 발명은 우수한 내열성, 투명성, 표면경도 및 수직배향성을 갖는 수직배향형 조성물을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a vertically oriented composition having excellent heat resistance, transparency, surface hardness and vertical alignment.

또한, 본 발명은 상기한 수직배향형 조성물을 이용하여 낮은 표면조도, 유슈한 인쇄성, 내열성 및 투명성을 가지는 액정 배향막과, 우수한 선경사각 및 전압보유율을 가지는 액정 셀을 제공하는데 또 다른 목적이 있다.
Another object of the present invention is to provide a liquid crystal alignment layer having low surface roughness, excellent printability, heat resistance and transparency, and a liquid crystal cell having excellent pretilt angle and voltage retention rate by using the vertically oriented composition. .

본 발명은 다음 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 다음의 화학식 2로 표시되는 폴리아믹산 유도체가 혼합되어 이루어진 수직배향형 조성물에 그 특징이 있다.The present invention is characterized in a vertically oriented composition comprising a mixture of a low polar side chain-containing polyamic acid resin represented by the following formula (1) and a polyamic acid derivative represented by the following formula (2).

[화학식 1][Formula 1]

Figure 112004050101106-pat00001
Figure 112004050101106-pat00001

[화학식 2] [Formula 2]

Figure 112004050101106-pat00002
Figure 112004050101106-pat00002

상기 화학식 1 또는 2에서,In Chemical Formula 1 or 2,

Figure 112004050101106-pat00003
은
Figure 112004050101106-pat00004
,
Figure 112004050101106-pat00005
,
Figure 112004050101106-pat00006
,
Figure 112004050101106-pat00007
,
Figure 112004050101106-pat00008
,
Figure 112004050101106-pat00009
,
Figure 112004050101106-pat00010
,
Figure 112004050101106-pat00011
,
Figure 112004050101106-pat00012
,
Figure 112004050101106-pat00013
Figure 112004050101106-pat00014
중에서 선택된 1종 또는 2종 이상의 4가기로서, 반드시 구조식 (a), (b), (c), (d) 및 (e) 중에서 선택된 1종 또는 2종 이상의 지방족 고리계 4가기를 포함하며; 및
Figure 112004050101106-pat00003
silver
Figure 112004050101106-pat00004
,
Figure 112004050101106-pat00005
,
Figure 112004050101106-pat00006
,
Figure 112004050101106-pat00007
,
Figure 112004050101106-pat00008
,
Figure 112004050101106-pat00009
,
Figure 112004050101106-pat00010
,
Figure 112004050101106-pat00011
,
Figure 112004050101106-pat00012
,
Figure 112004050101106-pat00013
Figure 112004050101106-pat00014
One or two or more tetravalent groups selected from the group consisting of at least one aliphatic ring system tetravalent group selected from the structural formulas (a), (b), (c), (d) and (e); And

Figure 112004050101106-pat00015
및
Figure 112004050101106-pat00016
는 각각
Figure 112004050101106-pat00017
,
Figure 112004050101106-pat00018
,
Figure 112004050101106-pat00019
,
Figure 112004050101106-pat00020
,
Figure 112004050101106-pat00021
,
Figure 112004050101106-pat00022
,
Figure 112004050101106-pat00023
,
Figure 112004050101106-pat00024
,
Figure 112004050101106-pat00025
,
Figure 112004050101106-pat00026
,
Figure 112004050101106-pat00027
,
Figure 112004050101106-pat00028
(이때, n은 1 내지 30 범위의 자연수) 중에서 선택된 1종 이상의 2가기로서, 반드시 상기
Figure 112004050101106-pat00029
는 상기 구조식 (f)의 알킬숙시닉이미드 측쇄를 가지는 방향족 2가기를 포함하며;
Figure 112004050101106-pat00015
And
Figure 112004050101106-pat00016
Are each
Figure 112004050101106-pat00017
,
Figure 112004050101106-pat00018
,
Figure 112004050101106-pat00019
,
Figure 112004050101106-pat00020
,
Figure 112004050101106-pat00021
,
Figure 112004050101106-pat00022
,
Figure 112004050101106-pat00023
,
Figure 112004050101106-pat00024
,
Figure 112004050101106-pat00025
,
Figure 112004050101106-pat00026
,
Figure 112004050101106-pat00027
,
Figure 112004050101106-pat00028
Wherein n is a natural number in the range of 1 to 30.
Figure 112004050101106-pat00029
Comprises an aromatic divalent group having an alkylsuccinimide side chain of formula (f);

ℓ 및 m은 각각 1 내지 300 범위의 자연수를 나타낸다.L and m each represent a natural number ranging from 1 to 300.

또한, 본 발명은 상기 폴리아믹산 혼합조성물을 코팅하여 제조한 액정 배향막과 액정 셀에 또 다른 특징이 있다.In addition, the present invention has another feature in the liquid crystal alignment film and the liquid crystal cell prepared by coating the polyamic acid mixture composition.

이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.

본 발명은 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체를 적정비로 혼합한 수직배향형 조성물에 관한 것이다. 또한, 상기한 수직배향형 조성물을 코팅하여 우수한 내열성, 투명성, 표면경도, 높은 전압보유율 및 선경 사각성 등의 특성을 갖는 액정 배향막 또는 액정 셀 등에 관한 것이다.The present invention relates to a vertically oriented composition in which a low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 and a polyamic acid derivative represented by Chemical Formula 2 are mixed at an appropriate ratio. The present invention also relates to a liquid crystal alignment film or a liquid crystal cell having the characteristics such as excellent heat resistance, transparency, surface hardness, high voltage retention and wire diameter squareness by coating the vertically oriented composition.

상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체는 1 ∼ 99 중량% : 1 ∼ 99 중량% 혼합비 범위내에서 사용한다. The low polar side chain-containing polyamic acid resin represented by the general formula (1) and the polyamic acid derivative represented by the general formula (2) are used within a mixing ratio of 1 to 99% by weight: 1 to 99% by weight.

본 발명에 따른 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수 지와 상기 화학식 2로 표시되는 폴리아믹산 유도체는 방향족 테트라카르복실산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합하여 제조하며, 사용된 단량체의 종류에 따라 여러 분자구조를 가질 수 있다. 일반적으로 방향족 테트라카르복실산 단량체로는 피로멜리트산이무수물(PMDA), 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물(BPDA) 및 헥사플루오로이소프로필리덴디프탈산이무수물 등 중에서 선택 사용하고 있다. 그리고, 방향족 디아민 단량체로서는 일반적으로 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) 등 중에서 선택 사용하고 있다.The low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 and the polyamic acid derivative represented by Chemical Formula 2 according to the present invention are prepared by condensation polymerization of aromatic tetracarboxylic acid or its derivatives with aromatic diamine or aromatic diisocyanate, Depending on the type of monomer used, it may have several molecular structures. Generally, aromatic tetracarboxylic acid monomers include pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic dianhydride (BPDA) and hexafluoroisopropylidene diphthalic acid. It selects and uses from anhydrides. And, as the aromatic diamine monomer, generally 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-bisamino Phenoxybenzene (TPE-Q), 1,3-bisaminophenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), 2,2-bisaminophenoxyphenylhexafulo It is selected and used from roperopan (HFBAPP).

본 발명에 따른 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체는 상기한 일반적인 방향족 단량체 이외에도, 상기 구조식 (a) ∼ (e)로 표시되는 지방족 테트라카르복실산이무수물 단량체와 상기 구조식 (f)로 표시되는 알킬숙시닉이미드기가 치환된 방향족 디아민이 필수성분으로 포함된 디아민 단량체를 사용하여 제조된다.The low polar side chain-containing polyamic acid resin represented by the general formula (1) and the polyamic acid derivative represented by the general formula (2) according to the present invention are aliphatic tetracarboxyl represented by structural formulas (a) to (e) in addition to the general aromatic monomers described above. An acid dianhydride monomer and an aromatic diamine substituted with an alkyl succinimide group represented by the above formula (f) are prepared using a diamine monomer containing as an essential component.

즉, 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지는 산이무수물 단량체로서, 통상의 방향족 테트라카르복실산 단량체 이외에도 지방족 테트라카르복실산이무수물 단량체로서 1,2,3,4-시클로부탄 테트라카르복실산이무수물 [CBDA; (a)], 1,2,3,4-시클로펜탄 테트라카르복실산이무수물[CPDA; (b)], 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물[DOCDA; (c)], 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물[DOTDA; (d)], 및 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물[BODA; (e)] 중에서 선택된 1종 또는 2종 이상의 지방족 테트라카르복실산이무수물이 필수성분으로 포함한다. 이때, 상기 구조식 (a) ∼ (e)로 표시되는 지방족 테트라카르복실산이무수물은 전체 산이무수물 단량체의 사용량에 대하여 1 내지 99 몰% 범위로 사용한다.That is, the low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 is an acid dianhydride monomer, and 1,2,3,4-cyclobutane tetracarr as an aliphatic tetracarboxylic dianhydride monomer in addition to the usual aromatic tetracarboxylic acid monomer. Acid dianhydrides [CBDA; (a)], 1,2,3,4-cyclopentane tetracarboxylic dianhydride [CPDA; (b)], 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride [DOCDA; (c)], 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride [DOTDA; (d)], and bicyclooctene-2,3,5,6-tetracarboxylic dianhydride [BODA; (e)] one or two or more aliphatic tetracarboxylic dianhydride selected from among the essential components. At this time, the aliphatic tetracarboxylic dianhydride represented by the structural formulas (a) to (e) is used in the range of 1 to 99 mol% based on the total amount of the acid dianhydride monomers.

상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지의 경우 측쇄기로서 지방족 고리기와 함께 알킬숙시닉이미드기가 동시에 결합되어 있는 구조적 특징을 가지는 바, 이에 디아민 단량체로서는 통상의 방향족 디아민 단량체 이외에도 상기 구조식 (f)로 표시되는 알킬숙시닉이미드기가 치환된 방향족 디아민을 필수성분으로 포함시켜 중합하여 제조한다. 이때, 상기 구조식 (f)로 표시되는 방향족 디아민은 전체 디아민 단량체의 사용량에 대하여 1 내지 99 몰% 범위로 사용한다.The low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 has a structural feature in which an alkyl succinimide group is simultaneously bonded with an aliphatic ring group as a side chain, and as a diamine monomer, the above structural formula is used in addition to a conventional aromatic diamine monomer. It is prepared by including and polymerizing an aromatic diamine substituted with an alkylsuccinicimide group represented by (f) as an essential component. At this time, the aromatic diamine represented by the structural formula (f) is used in the range of 1 to 99 mol% based on the total amount of the diamine monomer.

이로써, 상기 (f)로 표시되는 방향족 디아민을 필수 단량체 성분으로 사용하여 제조된 신규한 혼합물은 저극성 알킬기가 치환된 숙시닉이미드 측쇄기가 도입된 폴리아믹사 수지와 혼합에 의하여 투명성, 인쇄성, 기계적 특성 및 상기 조성물을 이용하여 제조된 액정 셀의 전기 광학적 특성이 특히 개선된 것이다.Thus, the novel mixture prepared by using the aromatic diamine represented by the above (f) as an essential monomer component is prepared by transparency and printability, by mixing with a polyamic resin having a succinimide side chain group substituted with a low polar alkyl group. Mechanical properties and electro-optical properties of liquid crystal cells produced using the composition are particularly improved.

상기한 바와 같은 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지는 중량평균 분자량(Mw) 범위 5,000 ∼ 150,000 g/mol, 고유점도 범위 0.1 ∼ 1.5 dL/g, 유리전이온도 범위 150 ∼ 300 ℃의 특성을 가진다. 또한, 상기 화학식 1로 표시되는 가용성 폴리이미드 수지는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. As described above, the low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 has a weight average molecular weight (Mw) of 5,000 to 150,000 g / mol, an intrinsic viscosity of 0.1 to 1.5 dL / g, and a glass transition temperature of 150 to 300 ° C. Has the characteristics of In addition, the soluble polyimide resin represented by Formula 1 is aprotic polarity such as dimethylacetamide (DMAc), dimethylformamide (DMF), N -methyl-2-pyrrolidone (NMP), acetone, ethyl acetate Easily dissolved at room temperature with respect to organic solvents such as meta-cresol, including the solvent.

또한, 상기 화학식 2로 표시되는 폴리아믹산 유도체는 산이무수물 단량체로서 상기 구조식 (a) ∼ (e)로 표시되는 지방족 테트라카르복실산이무수물이 필수 단량체로 사용되어 기계적 특성을 향상시키고 내열성 저하를 최소로 하면서도 인쇄성이 개선된 폴리아믹산 유도체를 제조할 수가 있었다. 상기한 단량체의 조성으로 용액 중합하여 제조된 상기 화학식 2로 표시되는 폴리아믹산 유도체는 중량평균 분자량(Mw) 범위 10,000 ∼ 200,000 g/mol, 고유점도 범위 0.3 ∼ 2.0 dL/g, 유리전이온도 범위 200 ∼ 400 ℃, 이미드화 온도범위 200 ∼ 300 ℃의 특성을 가진다. 또한, 상기 화학식 2로 표시되는 폴리아믹산 유도체는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 아세톤, 에틸아세테이트와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로푸란(THF), 클로로포름과 같은 저비점 용매 및 감마-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. 또한, 이들의 혼합용매에 대해서도 높은 용해도를 나타낸다. In addition, the polyamic acid derivative represented by Chemical Formula 2 has an aliphatic tetracarboxylic dianhydride represented by the structural formulas (a) to (e) as an essential monomer as an acid dianhydride monomer to improve mechanical properties and minimize heat resistance reduction. At the same time, it was possible to prepare a polyamic acid derivative having improved printability. Polyamic acid derivative represented by the formula (2) prepared by solution polymerization in the composition of the monomer is a weight average molecular weight (Mw) range 10,000 ~ 200,000 g / mol, intrinsic viscosity range 0.3 ~ 2.0 dL / g, glass transition temperature range 200 It has the characteristic of -400 degreeC and imidation temperature range 200-300 degreeC. In addition, the polyamic acid derivative represented by Formula 2 is an aprotic polar solvent such as dimethylacetamide (DMAc), dimethylformamide (DMF), N -methyl-2-pyrrolidone (NMP), acetone, ethyl acetate In addition, the organic solvent such as meta-cresol has a characteristic that is easily dissolved at room temperature. 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. Moreover, high solubility is shown also about these mixed solvents.

한편, 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체를 당 분야에서 사용되는 통상적인 방법으로 코팅하여 액정 배향막 또는 액정 셀을 제조하여 전기 광학적 특성을 평가한 결과, 선경사각(pretilt angle)은 87.0 ∼ 89.9 °의 범위에 있었으며, 전압보유율(voltage holding ratio)은 98.0 ∼ 99.9%, 잔류 전압(residual-D.C)은 100 ∼ 400 mV 의 범위에 있었다. 상기와 같은 특성은 종래에 기존 폴리이미드 수지의 우수한 특성을 유지하면서도 용해성 및 액정 배향특성 등이 우수하게 나타나므로 각종 전기, 전자, 우주, 항공 등 첨단산업의 핵심 내열소재로 사용할 수 있다.Meanwhile, the low polar side chain-containing polyamic acid resin represented by Chemical Formula 1 and the polyamic acid derivative represented by Chemical Formula 2 are coated by a conventional method used in the art to prepare a liquid crystal alignment layer or a liquid crystal cell to evaluate electro-optical characteristics. As a result, the pretilt angle was in the range of 87.0 to 89.9 °, the voltage holding ratio was 98.0 to 99.9%, and the residual voltage was in the range of 100 to 400 mV. Such characteristics can be used as core heat-resistant materials of high-tech industries such as electric, electronics, space, aviation, etc., because they exhibit excellent solubility and liquid crystal alignment characteristics while maintaining excellent properties of conventional polyimide resins.

이와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 이에 한정되지 않고 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능하다.Such the present invention will be described in more detail based on the following examples, without being limited thereto, various modifications and changes are possible within the scope of the present invention.

제조예 1: 1-(3,5-디니트로페닐)-3-(1-헥센)-숙시닉이미드(DN-IM-6)의 제조Preparation Example 1 Preparation of 1- (3,5-dinitrophenyl) -3- (1-hexene) -succinicimide (DN-IM-6)

교반기, 질소주입장치가 부착된 250 mL의 반응기에 질소가스를 서서히 통과시키면서 3,5-디니트로아닐린 9.2 g(0.05 mole)을 반응용매인 아세틱산 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. While slowly passing nitrogen gas through a 250 mL reactor equipped with a stirrer and a nitrogen injection device, 9.2 g (0.05 mole) of 3,5-dinitroaniline was dissolved in 50 mL of acetic acid as a reaction solvent, and then passed through nitrogen gas. 9.1 g (0.05 mole) of 2-hexen-1-yl succinic anhydride was added and refluxed for 24 h. After the reaction solution was cooled to room temperature, a precipitated solid was obtained.

상기 수득된 고체를 메탄올에서 재결정하여, 12.7 g의 1-(3,5-디니트로펜닐)-3-(1-헥센)-숙시닉이미드(DN-IM-6)을 제조하였다(수율 73%).The obtained solid was recrystallized in methanol to prepare 12.7 g of 1- (3,5-dinitrofenyl) -3- (1-hexene) -succinimide (DN-IM-6) (yield 73 %).

제조예 2: 1-(3,5-디니트로페닐)-3-(1-옥텐)-숙시닉이미드(DN-IM-8)의 제조Preparation Example 2 Preparation of 1- (3,5-dinitrophenyl) -3- (1-octene) -succinicimide (DN-IM-8)

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 1과 동일하게 반응을 수행하여 1-(3,5-디니트로펜닐)-3-(1-옥텐)-숙시닉이미드(DN-IM-8)를 수득하였다. The reaction was carried out in the same manner as in Preparation Example 1, 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. -Dinitrofenyl) -3- (1-octene) -succinimide (DN-IM-8) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 13.1 g의 1-(3,5-디니트로펜닐)-3-(1-옥텐)-숙시닉이미드(DN-IM-8)을 제조하였다(수율 70%).The obtained solid was recrystallized in methanol to prepare 13.1 g of 1- (3,5-dinitrofenyl) -3- (1-octene) -succinimide (DN-IM-8) (yield 70 %).

제조예 3: 1-(3,5-디니트로페닐)-3-(1-데센)-숙시닉이미드(DN-IM-10)의 제조Preparation Example 3 Preparation of 1- (3,5-dinitrophenyl) -3- (1-decene) -succinicimide (DN-IM-10)

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 1과 동일하게 반응을 수행하여 1-(3,5-디니트로펜닐)-3-(1-데센)-숙시닉이미드(DN-IM-10)를 수득하였다. The reaction was carried out in the same manner as in Preparation Example 1, 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. -Dinitrofenyl) -3- (1-decene) -succinimide (DN-IM-10) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 14.5 g의 1-(3,5-디니트로펜닐)-3-(1-데센)-숙시닉이미드(DN-IM-10)을 제조하였다(수율 70%).The obtained solid was recrystallized in methanol to prepare 14.5 g of 1- (3,5-dinitrofenyl) -3- (1-decene) -succinimide (DN-IM-10) (yield 70) %).

제조예 4: 1-(3,5-디니트로페닐)-3-(1-도데센)-숙시닉이미드(DN-IM-12)의 제조Preparation Example 4 Preparation of 1- (3,5-dinitrophenyl) -3- (1-dodecene) -succinicimide (DN-IM-12)

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 1과 동일하게 반응을 수행하여 1- (3,5-디니트로펜닐)-3-(1-도데센)-숙시닉이미드(DN-IM-12)를 수득하였다. The reaction was carried out in the same manner as in Preparation Example 1, 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. 5-Dinitrofenyl) -3- (1-dodecene) -succinimide (DN-IM-12) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 14.0 g의 1-(3,5-디니트로펜닐)-3-(1-도데센)-숙시닉이미드(DN-IM-12)을 제조하였다(수율 65%).The obtained solid was recrystallized in methanol to prepare 14.0 g of 1- (3,5-dinitrofenyl) -3- (1-dodecene) -succinicimide (DN-IM-12) (yield) 65%).

제조예 5 : 1-(3,5-디니트로페닐)-3-(1-테트라데센)-숙시닉이미드(DN-IM-14)의 제조Preparation Example 5 Preparation of 1- (3,5-dinitrophenyl) -3- (1-tetradecene) -succinicimide (DN-IM-14)

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 1과 동일하게 수행하여 1-(3,5-디니트로펜닐)-3-(1-테트라데센)-숙시닉이미드(DN-IM-14)를 수득하였다.Except for using 14.7 g (0.05 mole) 2-tetradecen-1-yl succinic anhydride instead of 2-hexen-1-yl succinic anhydride was carried out in the same manner as in Preparation Example 1 1- (3,5- Dinitrofenyl) -3- (1-tetradecene) -succinimide (DN-IM-14) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 14.9 g의 1-(3,5-디니트로펜닐)-3-(1-테트라데센)-숙시닉이미드(DN-IM-14)을 제조하였다(수율 65%).The obtained solid was recrystallized in methanol to prepare 14.9 g of 1- (3,5-dinitrofenyl) -3- (1-tetradecene) -succinicimide (DN-IM-14) (yield) 65%).

제조예 6: 1-(3,5-디니트로페닐)-3-(1-헥사데센)-숙시닉이미드(DN-IM-16)의 제조Preparation Example 6 Preparation of 1- (3,5-dinitrophenyl) -3- (1-hexadecene) -succinicimide (DN-IM-16)

2-헥센-1-일 숙신산 무수물 대신 16.1 g(0.05 mole)의 2-헥사데센-1-일 숙신산 무수물을 사용하는 것을 제외하고는 상기 제조예 1과 동일하게 수행하여 1-(3,5-디니트로펜닐)-3-(1-헥사데센)-숙시닉이미드(DN-IM-16)를 수득하였다. Except for using 16.1 g (0.05 mole) 2-hexadecen-1-yl succinic anhydride instead of 2-hexen-1-yl succinic anhydride was carried out in the same manner as in Preparation Example 1 1- (3,5- Dinitrofenyl) -3- (1-hexadecene) -succinimide (DN-IM-16) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 15.4 g의 1-(3,5-디니트로펜닐)-3-(1-헥사데센)-숙시닉이미드(DN-IM-16)을 제조하였다(수율 63%).The obtained solid was recrystallized in methanol to prepare 15.4 g of 1- (3,5-dinitrofenyl) -3- (1-hexadecene) -succinicimide (DN-IM-16) (yield) 63%).

제조예 7: 1-(3,5-디니트로페닐)-3-(1-옥타데센)-숙시닉이미드(DN-IM-18)의 제조Preparation Example 7 Preparation of 1- (3,5-dinitrophenyl) -3- (1-octadecene) -succinicimide (DN-IM-18)

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 1과 동일하게 수행하여 1-(3,5-디니트로펜닐)-3-(1-옥타데센)-숙시닉이미드(DN-IM-18)를 수득하였다.Except for using 17.5 g (0.05 mole) 2-octadecen-1-yl succinic anhydride instead of 2-hexen-1-yl succinic anhydride was carried out in the same manner as in Preparation Example 1 1- (3,5- Dinitrofenyl) -3- (1-octadecene) -succinicimide (DN-IM-18) was obtained.

상기 수득된 고체를 메탄올에 재결정하여, 16.2 g의 1-(3,5-디니트로펜닐)-3-(1-옥타데센)-숙시닉이미드(DN-IM-18)을 제조하였다(수율 63%).The obtained solid was recrystallized in methanol to prepare 16.2 g of 1- (3,5-dinitrofenyl) -3- (1-octadecene) -succinicimide (DN-IM-18) (yield) 63%).

제조예 8 : 1-(3,5-디아미노페닐)-3-헥실-숙시닉이미드(DA-IM-6)의 제조Preparation Example 8 Preparation of 1- (3,5-diaminophenyl) -3-hexyl-succinicimide (DA-IM-6)

NMP와 에탄올(1/3 부피비) 100 mL에 DN-IM-6 6.9 g(0.02 mole)을 용해시킨 후, Pd/C(5%) 촉매(탄소입자의 표면에 금속 팔라듐을 5%의 양으로 도포한 촉매) 0.5 g과 함께 수소 반응기에 넣은 후, 60 ℃에서 2시간 동안 환원반응을 수행하였다. 반응혼합물을 여과한 후, 반응용매를 감압증류하였다. After dissolving 6.9 g (0.02 mole) of DN-IM-6 in 100 mL of NMP and ethanol (1/3 volume ratio), Pd / C (5%) catalyst (metal palladium on the surface of the carbon particles in an amount of 5%) After applying the catalyst) 0.5 g with a hydrogen reactor, a reduction reaction was carried out at 60 ℃ for 2 hours. After filtering the reaction mixture, the reaction solvent was distilled under reduced pressure.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 3.18 g의 1-(3,5-디아미노펜닐)-3-헥실-숙시닉이미드(DA-IM-6)을 제조하였다(수율 55%). The obtained solid was recrystallized in a hexane / ethyl acetate cosolvent to prepare 3.18 g of 1- (3,5-diaminophenyl) -3-hexyl-succinicimide (DA-IM-6) (yield 55 %).

제조예 9 : 1-(3,5-디아미노페닐)-3-옥실-숙시닉이미드(DA-IM-8)의 제조Preparation Example 9 Preparation of 1- (3,5-diaminophenyl) -3-oxyl-succinicimide (DA-IM-8)

DN-IM-6 대신 7.5 g(0.02 mole)의 DN-IM-8을 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-옥실-숙시닉이미드(DA-IM-8)를 수득하였다. 1- (3,5-diaminophenyl) -3-oxyl- in the same manner as in Preparation Example 8, except that 7.5 g (0.02 mole) of DN-IM-8 was used instead of DN-IM-6. Succinicimide (DA-IM-8) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 3.68 g의 1-(3,5-디아미노펜닐)-3-옥실-숙시닉이미드(DA-IM-8)을 제조하였다(수율 58%).The obtained solid was recrystallized in a hexane / ethyl acetate cosolvent to yield 3.68 g of 1- (3,5-diaminophenyl) -3-oxyl-succinicimide (DA-IM-8) (yield 58 %).

제조예 10 : 1-(3,5-디아미노페닐)-3-데실-숙시닉이미드(DA-IM-10)의 제조Preparation Example 10 Preparation of 1- (3,5-diaminophenyl) -3-decyl-succinicimide (DA-IM-10)

DN-IM-6 대신 8.1 g(0.02 mole)의 DN-IM-10을 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-데실-숙시닉이미드(DA-IM-10)를 수득하였다. 1- (3,5-diaminophenyl) -3-decyl- in the same manner as in Preparation Example 8, except that 8.1 g (0.02 mole) of DN-IM-10 was used instead of DN-IM-6. Succinicimide (DA-IM-10) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 4.15 g의 1-(3,5-디아미노펜닐)-3-데실-숙시닉이미드(DA-IM-10)을 제조하였다(수율 60%).The obtained solid was recrystallized in a hexane / ethyl acetate cosolvent to prepare 4.15 g of 1- (3,5-diaminophenyl) -3-decyl-succinicimide (DA-IM-10) (yield 60) %).

제조예 11 : 1-(3,5-디아미노페닐)-3-도데실-숙시닉이미드(DA-IM-12)의 제조Preparation Example 11 Preparation of 1- (3,5-diaminophenyl) -3-dodecyl-succinicimide (DA-IM-12)

DN-IM-6 대신 8.6 g(0.02 mole)의 DN-IM-12를 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-도데실-숙시닉이미드(DA-IM-12)를 수득하였다. 1- (3,5-diaminophenyl) -3-dodecyl in the same manner as in Preparation Example 8, except that 8.6 g (0.02 mole) of DN-IM-12 was used instead of DN-IM-6. -Succinicimide (DA-IM-12) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 4.48 g의 1-(3,5-디아미노펜닐)-3-도데실-숙시닉이미드(DA-IM-12)을 제조하였다(수율 60%). The obtained solid was recrystallized in hexane / ethyl acetate cosolvent to prepare 4.48 g of 1- (3,5-diaminophenyl) -3-dodecyl-succinicimide (DA-IM-12) (yield) 60%).

제조예 12 : 1-(3,5-디아미노페닐)-3-테트라데실-숙시닉이미드(DA-IM-14)의 제조Preparation Example 12 Preparation of 1- (3,5-diaminophenyl) -3-tetradecyl-succinicimide (DA-IM-14)

DN-IM-6 대신 9.2 g(0.02 mole)의 DN-IM-14를 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-테트라데실-숙시닉이미드(DA-IM-14)를 수득하였다. 1- (3,5-diaminophenyl) -3-tetradecyl was carried out in the same manner as in Preparation Example 8, except that 9.2 g (0.02 mole) of DN-IM-14 was used instead of DN-IM-6. -Succinicimide (DA-IM-14) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 5.6 g의 1-(3,5-디아미노펜닐)-3-테트라데실-숙시닉이미드(DA-IM-14)을 제조하였다(수율 70%). The obtained solid was recrystallized in hexane / ethyl acetate cosolvent to prepare 5.6 g of 1- (3,5-diaminophenyl) -3-tetradecyl-succinicimide (DA-IM-14) (yield) 70%).

제조예 13 : 1-(3,5-디아미노페닐)-3-헥사데실-숙시닉이미드(DA-IM-16)의 제조Preparation Example 13 Preparation of 1- (3,5-diaminophenyl) -3-hexadecyl-succinicimide (DA-IM-16)

DN-IM-6 대신 9.8 g(0.02 mole)의 DN-IM-16을 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-헥사데실-숙시닉이미드(DA-IM-16)를 수득하였다. 1- (3,5-diaminophenyl) -3-hexadecyl in the same manner as in Preparation Example 8, except that 9.8 g (0.02 mole) of DN-IM-16 was used instead of DN-IM-6. -Succinicimide (DA-IM-16) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 6.01 g의 1-(3,5-디아미노펜닐)-3-옥실-숙시닉이미드(DA-IM-16)을 제조하였다(수율 70%).The obtained solid was recrystallized in a hexane / ethyl acetate co-solvent to prepare 6.01 g of 1- (3,5-diaminophenyl) -3-oxyl-succinicimide (DA-IM-16) (yield 70 %).

제조예 14 : 1-(3,5-디아미노페닐)-3-옥타데실-숙시닉이미드(DA-IM-18)의 제조Preparation Example 14 Preparation of 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM-18)

DN-IM-6 대신 10.3 g(0.02 mole)의 DN-IM-18을 사용하는 것을 제외하고는 상기 제조예 8과 동일하게 수행하여 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18)를 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl was carried out in the same manner as in Preparation Example 8, except that 10.3 g (0.02 mole) of DN-IM-18 was used instead of DN-IM-6. -Succinicimide (DA-IM-18) was obtained.

상기 수득된 고체를 헥산/에틸아세테이트 공용매 중에서 재결정하여 6.87 g의 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18)을 제조하였다(수율 75%). The obtained solid was recrystallized in a hexane / ethyl acetate cosolvent to prepare 6.87 g of 1- (3,5-diaminophenyl) -3-octadecyl-succinimide (DA-IM-18) (yield) 75%).

상기 제조예 8 ∼ 14에서 제조한 저극성 알킬기가 치환된 숙시닉이미드 측쇄 기를 가지고 있는 디아민 단량체로서 DA-IM-6~18는 재결정후의 수율이 50 % 이상으로 제조가 가능함을 확인할 수 있었으며, 공기 중에서 매우 우수한 저장안정성을 나타내었다.As a diamine monomer having a succinimide side chain group substituted with the low polar alkyl group prepared in Preparation Examples 8 to 14, DA-IM-6-18 was able to be produced with a yield of 50% or more after recrystallization. Very good storage stability in air.

제조예 15. 저극성 측쇄 함유 폴리아믹산 수지(PAA-1)의 제조 Preparation Example 15 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin (PAA-1)

교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250 mL의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물 5.28 g(0.02 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액(PAA-1) 을 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM) while slowly passing nitrogen gas into a 250 mL reactor equipped with a stirrer, thermostat, nitrogen injector and cooler -18) 9.15 g (0.02 mole) was dissolved in the reaction solvent N-methyl-2-pyrrolidone, and then passed through nitrogen gas to give a solid 5- (2,5-dioxotetrahydrofuryl) -3-methyl 5.28 g (0.02 mole) of cyclohexane-1,2-dicarboxylic dianhydride was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-1).

제조예 16. 저극성 측쇄 함유 폴리아믹산 수지(PAA-2)의 제조 Preparation Example 16 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin (PAA-2)

교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250 mL의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 1,2,3,4-시클로부탄 테트라카르복실산이무수물 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하 여 폴리아믹산 용액(PAA-2) 을 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM) while slowly passing nitrogen gas into a 250 mL reactor equipped with a stirrer, thermostat, nitrogen injector and cooler -18) 9.15 g (0.02 mole) is dissolved in the reaction solvent N-methyl-2-pyrrolidone, and 3.92 g of 1,2,3,4-cyclobutane tetracarboxylic dianhydride in solid phase while passing through nitrogen gas. (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-2).

제조예 17. 폴리아믹산 (PAA-3)의 제조Preparation Example 17 Preparation of Polyamic Acid (PAA-3)

교반기, 질소주입장치가 부착된 500 mL의 반응기에 질소가스를 서서히 통과시키면서 메틸렌 디아닐린 19.8 g(0.1 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 1,2,3,4-시클로부탄 테트라카르복실산이무수물 19.6 g(0.1 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액(PAA-3)을 수득하였다.19.8 g (0.1 mole) of methylene dianiline was dissolved in the reaction solvent N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection device, and then passed through nitrogen gas. 19.6 g (0.1 mole) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride in solid phase was slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, while stirring for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-3).

제조예 18. 가용성 폴리이미드 수지(SPI)의 제조Preparation Example 18 Preparation of Soluble Polyimide Resin (SPI)

교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250 mL의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물 5.28 g(0.02 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM) while slowly passing nitrogen gas into a 250 mL reactor equipped with a stirrer, thermostat, nitrogen injector and cooler -18) 9.15 g (0.02 mole) was dissolved in the reaction solvent N-methyl-2-pyrrolidone, and then passed through nitrogen gas to give a solid 5- (2,5-dioxotetrahydrofuryl) -3-methyl 5.28 g (0.02 mole) of cyclohexane-1,2-dicarboxylic dianhydride was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution.

상기 폴리아믹산 용액에 아세틱산 무수물 6.12 g(0.06 mole)과 피리딘 0.1 g(0.1 mole)을 넣고 상온에서 24시간동안 교반시킨 후 120 ℃에서 3시간동안 교반 한 다음 메탄올에 여러 번 세척하여 가용성 폴리이미드 수지(SPI-1)를 수득하였다. 6.12 g (0.06 mole) of acetic anhydride and 0.1 g (0.1 mole) of pyridine were added to the polyamic acid solution. The mixture was stirred at room temperature for 24 hours, stirred at 120 ° C. for 3 hours, and then washed several times in methanol to obtain soluble polyimide. Resin (SPI-1) was obtained.

실시예 1 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-2)의 제조.Example 1: Preparation of low polar side chain containing polyamic acid resin and polyamic acid mixture (BPAA-2).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 1.973 g과 상기 제조예 17의 폴리아믹산 용액 50 g 을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injector, 1.973 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted. 80 g of methyl-2-pyrrolidone, 120 g of gamma -butyrolactone and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 2 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-3)의 제조.Example 2 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-3).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 4.166 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.4.166 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvent while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device. 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 3 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-4)의 제조.Example 3: Preparation of low polar side chain containing polyamic acid resin and polyamic acid mixture (BPAA-4).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 16.073 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.16.073 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvent while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection apparatus. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 4 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-5)의 제조.Example 4 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-5).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 37.503 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 37.503 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 5 : 저극성 측쇄 함유 폴리아믹산와 폴리아믹산 혼합물(BPAA-6)의 제조.Example 5 Preparation of Low Polar Side Chain Containing Polyamic Acid and Polyamic Acid Mixture (BPAA-6).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 87.5 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While diluting nitrogen gas slowly through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 87.5 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added thereto, and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 6 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-7)의 제조.Example 6: Preparation of low polar side chain containing polyamic acid resin and polyamic acid mixture (BPAA-7).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 15의 저극성 측쇄 함유 폴리아믹산 수지 용액 337.3 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 337.3 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 15 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 7 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-8)의 제조.Example 7 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-8).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 0.765 g 과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While diluting nitrogen gas slowly through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 0.765 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 8 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-9)의 제조.Example 8 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-9).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과 시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 1.974 g과, 상기 제조예 17의 폴리아믹산 용액 50 g 을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 1.974 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 9 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-10)의 제조.Example 9 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-10).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 4.166 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.4.166 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvent while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device. 80 g of N-methyl-2-pyrrolidone, 120 g of γ-butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 10 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-11)의 제조.Example 10 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-11).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 16.05 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.16.05 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvent while slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 11 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-12)의 제조.Example 11 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-12).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 37.503 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 37.503 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 12 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-13)의 제조.Example 12 Preparation of Low Polar Side Chain Containing Polyamic Acid Resin and Polyamic Acid Mixture (BPAA-13).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 87.5 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 87.5 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실시예 13 : 저극성 측쇄 함유 폴리아믹산 수지와 폴리아믹산 혼합물(BPAA-14)의 제조.Example 13: Preparation of low polar side chain containing polyamic acid resin and polyamic acid mixture (BPAA-14).

교반기, 질소주입장치가 부착된 1000 mL의 반응기에 질소가스를 서서히 통과 시키면서 상기 제조예 16의 저극성 측쇄 함유 폴리아믹산 수지 용액 337.3 g과, 상기 제조예 17의 폴리아믹산 용액 50 g을 희석용매인 N-메틸-2-피롤리돈 75 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.While slowly passing nitrogen gas through a 1000 mL reactor equipped with a stirrer and a nitrogen injection device, 337.3 g of the low polar side chain-containing polyamic acid resin solution of Preparation Example 16 and 50 g of the polyamic acid solution of Preparation Example 17 were diluted solvents. 75 g of N-methyl-2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

비교예 1. 저극성 측쇄 함유 폴리아믹산 수지(PAA-1)의 제조 Comparative Example 1. Preparation of low polar side chain-containing polyamic acid resin (PAA-1)

교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250 mL의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물 5.28 g(0.02 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액(PAA-1)을 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM) while slowly passing nitrogen gas into a 250 mL reactor equipped with a stirrer, thermostat, nitrogen injector and cooler -18) 9.15 g (0.02 mole) was dissolved in the reaction solvent N-methyl-2-pyrrolidone, and then passed through nitrogen gas to give a solid 5- (2,5-dioxotetrahydrofuryl) -3-methyl 5.28 g (0.02 mole) of cyclohexane-1,2-dicarboxylic dianhydride was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-1).

비교예 2. 저극성 측쇄 함유 폴리아믹산 수지(PAA-2)의 제조Comparative Example 2. Preparation of low polar side chain-containing polyamic acid resin (PAA-2)

교반기, 온도조절장치, 질소주입장치 및 냉각기를 부착한 250 mL의 반응기에 질소가스를 서서히 통화시키면서 1-(3,5-디아미노펜닐)-3-옥타데실-숙시닉이미드(DA-IM-18) 9.15 g(0.02 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 1,2,3,4-시클로부탄 테트라카르복실산이무수물 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 20 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 24시간 동안 교반하여 폴리아믹산 용액(PAA-2) 을 수득하였다. 1- (3,5-diaminophenyl) -3-octadecyl-succinicimide (DA-IM) while slowly passing nitrogen gas into a 250 mL reactor equipped with a stirrer, thermostat, nitrogen injector and cooler -18) 9.15 g (0.02 mole) is dissolved in the reaction solvent N-methyl-2-pyrrolidone, and 3.92 g of 1,2,3,4-cyclobutane tetracarboxylic dianhydride in solid phase while passing through nitrogen gas. (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 20% by weight, and stirred for 24 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-2).

비교예 3. 폴리아믹산 (PAA-3)의 제조Comparative Example 3. Preparation of Polyamic Acid (PAA-3)

교반기, 질소주입장치가 부착된 500 mL의 반응기에 질소가스를 서서히 통과시키면서 메틸렌 디아닐린 19.8 g(0.1 mole)을 반응용매 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 고체상의 1,2,3,4-시클로부탄 테트라카르복실산이무수물 19.6 g(0.1 mole)을 서서히 첨가하였다. 이때, 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액(PAA-3)을 수득하였다.19.8 g (0.1 mole) of methylene dianiline was dissolved in the reaction solvent N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection device, and then passed through nitrogen gas. 19.6 g (0.1 mole) of 1,2,3,4-cyclobutane tetracarboxylic dianhydride in solid phase was slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, while stirring for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution (PAA-3).

비교예 4. 가용성 폴리이미드 함유 폴리아믹산 (PAA-4)의 제조Comparative Example 4. Preparation of Soluble Polyimide-Containing Polyamic Acid (PAA-4)

교반기, 질소주입장치가 부착된 500 mL의 반응기에 질소가스를 서서히 통과시키면서 상기 제조예 17의 폴리아믹산 수지 50 g과, 상기 제조예 18의 가용성 폴리이미드 용액 0.395 g을 희석용매인 N-메틸-2-피롤리돈 80 g, γ-부틸로락톤 120 g, 2-n-부톡시에탄올 60 g에 넣고 24 시간동안 교반하여 25 cps의 점도를 갖는 용액을 제조하였다.50 g of the polyamic acid resin of Preparation Example 17 and 0.395 g of the soluble polyimide solution of Preparation Example 18 were slowly passed while passing nitrogen gas through a 500 mL reactor equipped with a stirrer and a nitrogen injection apparatus. 80 g of 2-pyrrolidone, 120 g of gamma -butyrolactone, and 60 g of 2-n-butoxyethanol were added and stirred for 24 hours to prepare a solution having a viscosity of 25 cps.

실험예 1Experimental Example 1

상기 실시예 1 ∼ 13 및 비교예 1 ∼ 4에 따라 제조된 용액을 ITO 유리판 위 에 0.05 ∼ 0.2 ㎛의 두께로 스핀 코팅한 후, 230 ℃의 온도에서 30 분 동안 열경화하여 얻은 폴리이미드 유도체 박막의 물성을 다음 표 1에 나타내었다.Polyimide derivative thin film obtained by spin coating the solution prepared according to Examples 1 to 13 and Comparative Examples 1 to 4 to a thickness of 0.05 to 0.2 μm on an ITO glass plate and then thermosetting at a temperature of 230 ° C. for 30 minutes. Physical properties of are shown in Table 1 below.

구 분division 성분 (중량%)Ingredient (wt%) 특성characteristic 조성물Composition PAA-1PAA-1 PAA-2PAA-2 PAA-3PAA-3 고유점도*) (dL/g)Intrinsic viscosity *) (dL / g) 표면장력 (dyne/cm)Surface tension (dyne / cm) 연필경도Pencil hardness 실 시 예Example 1One BPAA-2BPAA-2 55 9595 1.101.10 37.637.6 5H5H 22 BPAA-3BPAA-3 1010 9090 0.860.86 37.237.2 4H4H 33 BPAA-4BPAA-4 3030 7070 0.740.74 36.836.8 3H3H 44 BPAA-5BPAA-5 5050 5050 0.560.56 36.536.5 3H3H 55 BPAA-6BPAA-6 3030 7070 0.430.43 36.436.4 3H3H 66 BPAA-7BPAA-7 9090 1010 0.340.34 36.436.4 1H1H 77 BPAA-8BPAA-8 22 9898 1.381.38 37.637.6 5H5H 88 BPAA-9BPAA-9 55 9595 1.161.16 37.137.1 5H5H 99 BPAA-10BPAA-10 1010 9090 0.940.94 36.236.2 4H4H 1010 BPAA-11BPAA-11 3030 7070 0.860.86 36.336.3 4H4H 1111 BPAA-12BPAA-12 5050 5050 0.760.76 36.336.3 3H3H 1212 BPAA-13BPAA-13 3030 7070 0.580.58 36.336.3 3H3H 1313 BPAA-14BPAA-14 9090 1010 0.490.49 36.336.3 2H2H 비 교 예Comparative Example 1One PAA-1PAA-1 100100 0.150.15 36.436.4 1H1H 22 PAA-2PAA-2 100100 0.20.2 36.336.3 2H2H 33 PAA-3PAA-3 100100 1.501.50 47.547.5 5H5H 44 SPAASPAA SPI(5) : PAA-3 (95)SPI (5): PAA-3 (95) 1.261.26 36.636.6 1H1H *)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 저극성 측쇄함유 폴리아믹산 수지는 모두 밝은 호박색의 투명한 수지로, 0.49 ∼ 1.38 dL/g 범위의 고유점도를 가지는 것으로 확인되었으며, 상기 수지들은 용매주형에 의한 필름성형성 및 기계적 특성이 매우 우수한 것으로 나타났다. As shown in Table 1, all of the low polar side chain-containing polyamic acid resins according to the present invention are bright amber transparent resins, and have been found to have an intrinsic viscosity in the range of 0.49 to 1.38 dL / g. It was shown that the film forming and the mechanical properties by the very excellent.

또한, 본 발명에 따른 폴리이미드 박막의 연필경도는 1H ∼ 5H 범위로 평균 3H 이상으로 고르게 나타났으나, 비교예 1, 2 및 4는 현저히 저하되었다. 박막의 표면 장력은 이미드 고리 함유 고리계 측쇄기가 도입된 숙시닉이미드 측쇄기가 도입된 디아민의 함량이 증가함에 따라 감소하는 경향을 나타내었으며, 36.2 ∼ 37.2 dyne/cm의 고른값을 보여주었다.In addition, the pencil hardness of the polyimide thin film according to the present invention appeared evenly on the average 3H or more in the range of 1H to 5H, Comparative Examples 1, 2 and 4 were significantly reduced. The surface tension of the thin film tended to decrease as the content of the diamine introduced with the succinimide side chain group having the imide ring-containing ring side chain group was increased, and even values of 36.2 to 37.2 dyne / cm were shown.

실험예 2Experimental Example 2

상기 실시예 1 ∼ 13 및 비교예 1 ∼ 4에서 수득된 용액들의 상온에서의 용액 점도를 20 ∼ 40 cp로 유지시킨 뒤, 박막 코팅(코팅조건; 400 ∼ 4,000 rpm, 25초)하여 박막을 제조하였다. 그리고, 러빙(0.25 T)하여 액정셀을 제작한 후, 상기 제작된 액정셀의 특성을 측정하여, 그 결과를 다음 표 2에 나타내었다. After maintaining the solution viscosity at room temperature of 20 to 40 cp of the solutions obtained in Examples 1 to 13 and Comparative Examples 1 to 4, a thin film was coated (coating conditions; 400 to 4,000 rpm, 25 seconds) to prepare a thin film It was. Then, after rubbing (0.25 T) to form a liquid crystal cell, the characteristics of the produced liquid crystal cell were measured, and the results are shown in Table 2 below.

액정의 배향상태는 편광현미경을 사용하여 육안으로 관찰하였으며, 결정회전법(crystal rotation method)을 이용하여 각 액정셀의 선경사각(pretilt angles)을 측정하였고, DC bias 전압을 변화시켜가면서 액정패널의 전기용량을 측정한 C-V hysteresis 곡선의 커패시턴스 변화율이 20 %인 지점을 기준으로 하여, 동일 커패시턴스에서 전압차를 구해 잔류 전압(residual D.C)를 측정하였다.The alignment state of the liquid crystals was visually observed using a polarization microscope, the pretilt angles of each liquid crystal cell were measured using a crystal rotation method, and the DC bias voltage was changed while changing the DC bias voltage. Based on the capacitance change rate of the CV hysteresis curve measured at 20%, the voltage difference was calculated from the same capacitance, and the residual DC was measured.

구 분division 배향막Alignment film 선경사각 (°)Pretilt angle (°) VHR (%) (상온)VHR (%) (room temperature) R-D.C (mV)R-D.C (mV) 러빙 전Before rubbing 러빙 후After rubbing 실시예 1Example 1 BPAA-2BPAA-2 89.689.6 90.090.0 99.799.7 154154 실시예 2Example 2 BPAA-3BPAA-3 89.689.6 89.489.4 99.599.5 258258 실시예 3Example 3 BPAA-4BPAA-4 89.689.6 89.589.5 99.399.3 272272 실시예 4Example 4 BPAA-5BPAA-5 89.689.6 89.589.5 99.199.1 330330 실시예 5Example 5 BPAA-6BPAA-6 89.689.6 89.589.5 99.199.1 325325 실시예 6Example 6 BPAA-7BPAA-7 89.789.7 89.689.6 99.699.6 398398 실시예 7Example 7 BPAA-8BPAA-8 89.689.6 79.679.6 99.199.1 136136 실시예 8Example 8 BPAA-9BPAA-9 89.389.3 88.888.8 99.699.6 8989 실시예 9Example 9 BPAA-10BPAA-10 89.889.8 90.090.0 99.599.5 134134 실시예 10Example 10 BPAA-11BPAA-11 89.489.4 89.589.5 99.499.4 170170 실시예 11Example 11 BPAA-12BPAA-12 89.689.6 89.389.3 99.499.4 213213 실시예 12Example 12 BPAA-13BPAA-13 89.589.5 89.489.4 99.299.2 367367 실시예 13Example 13 BPAA-14BPAA-14 89.389.3 89.589.5 99.999.9 395395 비교예 1Comparative Example 1 PAA-1PAA-1 89.789.7 89.689.6 98.598.5 547547 비교예 2Comparative Example 2 PAA-2PAA-2 89.289.2 89.489.4 98.898.8 516516 비교예 3Comparative Example 3 PAA-3PAA-3 7.37.3 4.94.9 97.197.1 658658 비교예 4Comparative Example 4 SPAASPAA 90.090.0 70.370.3 97.597.5 260260

상기 표 2에 나타난 바와 같이, 실시예 1 ∼ 13으로부터 제조된 본 발명에 따른 저극성 측쇄를 가진 폴리아믹산이 함유된 폴리아믹산 혼합조성물을 이용하여 제조된 액정 셀은 매우 높은 선경사각, 전압보유율을 나타내었으며, 우수한 잔류 전압 특성을 보이고 있음을 알 수가 있었다. As shown in Table 2, the liquid crystal cell prepared using a polyamic acid mixed composition containing a polyamic acid having a low polar side chain according to the present invention prepared from Examples 1 to 13 has a very high pretilt angle and voltage retention. It can be seen that it shows excellent residual voltage characteristics.

선경사각은 90 °정도로서 저극성 측쇄 함유 폴리아믹산이 함유되지 않은 비교예 2에 비해 크게 증가하였으며, 러빙 후에도 평균 89 °이상의 높은 선경사각을 유지함으로써 가용성 폴리이미드 수지를 함유한 비교예 4의 경우에 비해 특성이 향상됨을 알 수가 있었다. 상온에서의 전압보유율은 99.1 ∼ 99.9% 범위를 나타내어 99% 이상으로 비교예 1 ∼ 4에 비해 우수하다는 확인할 수 있었으며, 특히, 것을 가용성 폴리이미드가 함유된 폴리아믹산 혼합조성물을 이용하여 제조된 비교예 4의 경우 보다 증가하는 결과를 나타내었다. 또한, 저극성 측쇄 갖는 폴리 아믹산을 함유한 폴리아믹산 혼합조성물은 액정 셀의 잔류 전압이 89 ∼ 395 mV까지 감소하는 결과를 보여주었다. 이는 비교예 1 ∼ 3에 비해 월등히 저하되는 경향을 보이는 것으로 이로부터 본 발명이 보다 우수하다는 것을 확인할 수 있었다. The pretilt angle was about 90 °, which was significantly increased compared to Comparative Example 2 without the low polar side chain-containing polyamic acid. It was found that the characteristics were improved. The voltage retention at room temperature was in the range of 99.1 to 99.9%, which was confirmed to be superior to Comparative Examples 1 to 4 at 99% or more. In particular, the comparative example prepared using a polyamic acid mixed composition containing soluble polyimide In case of 4, the result was increased. In addition, the polyamic acid mixed composition containing the polyamic acid having a low polar side chain showed a result that the residual voltage of the liquid crystal cell decreased to 89 to 395 mV. This shows a tendency to fall significantly compared with Comparative Examples 1-3, and from this, it was confirmed that this invention is more excellent.

따라서, 상기의 실험예 1 및 실험예 2의 결과를 종합해 볼 때, 본 발명에 따른 실시예 1 ∼ 13의 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체가 혼합되어 이루어진 폴리아믹산 혼합조성물은 수직배향형 TFT-TN 및 STN LCD용 액정 배향막 및 액정 셀로의 사용에 매우 적합한 특성을 나타낸다는 것을 확인할 수 있었다.Therefore, when combining the results of Experimental Example 1 and Experimental Example 2 described above, the low polar side chain-containing polyamic acid resin represented by Formula 1 of Examples 1 to 13 according to the present invention and the polya represented by Formula 2 It was confirmed that the polyamic acid mixed composition formed by mixing the mixed acid derivatives exhibits characteristics that are very suitable for use as a liquid crystal alignment film and a liquid crystal cell for vertical alignment TFT-TN and STN LCD.

상기한 바와 같이, 본 발명에 의해 광투과성, 내열성, 기계적 특성이 매우 우수할 뿐만 아니라 우수한 전기광학적 특성 및 높은 선경사각을 갖는 새로운 구조의 저극성 측쇄를 가진 폴리아믹산이 함유된 폴리아믹산 혼합조성물로서, 이들은 까다로운 전기광학적 특성이 요구되는 TFT-TN 및 STN LCD용 액정 배향막 및 각종 첨단 내열구조 재료로 유용하다. As described above, the present invention provides a polyamic acid mixed composition containing a polyamic acid having a low polar side chain having a novel structure having not only excellent light transmittance, heat resistance and mechanical properties but also excellent electro-optical properties and high pretilt angle. They are useful as liquid crystal alignment films for TFT-TN and STN LCDs and various advanced heat-resistant structural materials requiring demanding electro-optical properties.

Claims (13)

다음 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 다음 화학식 2로 표시되는 폴리아믹산 유도체가 혼합되어 이루어진 것임을 특징으로 하는 수직배향형 조성물.A vertically oriented composition comprising a mixture of a low polar side chain-containing polyamic acid resin represented by the following Chemical Formula 1 and a polyamic acid derivative represented by the following Chemical Formula 2. [화학식 1][Formula 1]
Figure 112004050101106-pat00030
Figure 112004050101106-pat00030
 [화학식 2] [Formula 2]
Figure 112004050101106-pat00031
Figure 112004050101106-pat00031
 상기 화학식 1 또는 2에서,In Chemical Formula 1 or 2,
Figure 112004050101106-pat00032
은
Figure 112004050101106-pat00033
,
Figure 112004050101106-pat00034
,
Figure 112004050101106-pat00035
,
Figure 112004050101106-pat00036
,
Figure 112004050101106-pat00037
,
Figure 112004050101106-pat00038
,
Figure 112004050101106-pat00039
,
Figure 112004050101106-pat00040
,
Figure 112004050101106-pat00041
,
Figure 112004050101106-pat00042
Figure 112004050101106-pat00043
중에서 선택된 1종 또는 2종 이상의 4가기로서, 반드시 구조식 (a), (b), (c), (d) 및 (e) 중에서 선택된 1종 또는 2종 이상의 지방족 고리계 4가기를 포함하며; 및
Figure 112004050101106-pat00032
silver
Figure 112004050101106-pat00033
,
Figure 112004050101106-pat00034
,
Figure 112004050101106-pat00035
,
Figure 112004050101106-pat00036
,
Figure 112004050101106-pat00037
,
Figure 112004050101106-pat00038
,
Figure 112004050101106-pat00039
,
Figure 112004050101106-pat00040
,
Figure 112004050101106-pat00041
,
Figure 112004050101106-pat00042
Figure 112004050101106-pat00043
One or two or more tetravalent groups selected from the group consisting of at least one aliphatic ring system tetravalent group selected from the structural formulas (a), (b), (c), (d) and (e); And
Figure 112004050101106-pat00044
및
Figure 112004050101106-pat00045
는 각각
Figure 112004050101106-pat00046
,
Figure 112004050101106-pat00047
,
Figure 112004050101106-pat00048
,
Figure 112004050101106-pat00049
,
Figure 112004050101106-pat00050
,
Figure 112004050101106-pat00051
,
Figure 112004050101106-pat00052
,
Figure 112004050101106-pat00053
,
Figure 112004050101106-pat00054
,
Figure 112004050101106-pat00055
,
Figure 112004050101106-pat00056
,
Figure 112004050101106-pat00057
(이때, n은 1 내지 30 범위의 자연수) 중에서 선택된 1종 이상의 2가기로서, 반드시 상기
Figure 112004050101106-pat00058
는 상기 구조식 (f)의 알킬숙시닉이미드 측쇄를 가지는 방향족 2가기를 포함하며;
Figure 112004050101106-pat00044
And
Figure 112004050101106-pat00045
Are each
Figure 112004050101106-pat00046
,
Figure 112004050101106-pat00047
,
Figure 112004050101106-pat00048
,
Figure 112004050101106-pat00049
,
Figure 112004050101106-pat00050
,
Figure 112004050101106-pat00051
,
Figure 112004050101106-pat00052
,
Figure 112004050101106-pat00053
,
Figure 112004050101106-pat00054
,
Figure 112004050101106-pat00055
,
Figure 112004050101106-pat00056
,
Figure 112004050101106-pat00057
Wherein n is a natural number in the range of 1 to 30.
Figure 112004050101106-pat00058
Comprises an aromatic divalent group having an alkylsuccinimide side chain of formula (f); ℓ 및 m은 각각 1 내지 300 범위의 자연수를 나타낸다.L and m each represent a natural number ranging from 1 to 300. 제 1 항에 있어서, 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지와 상기 화학식 2로 표시되는 폴리아믹산 유도체가 1 ∼ 99 중량% : 1 ∼ 99 중량% 혼합비로 함유된 것임을 특징으로 하는 수직배향형 조성물.According to claim 1, wherein the low polar side chain-containing polyamic acid resin represented by the formula (1) and the polyamic acid derivative represented by the formula (2) containing 1 to 99% by weight: 1 to 99% by weight mixed vertically Oriented Composition. 제 1 항에 있어서, 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지는 고유점도가 0.1 ∼ 1.5 dL/g 범위이며, 중량평균분자량이 5,000 ∼ 150,000 g/mol의 범위인 것임을 특징으로 하는 수직배향형 조성물.According to claim 1, wherein the low polar side chain-containing polyamic acid resin represented by the formula (1) is characterized in that the intrinsic viscosity is in the range of 0.1 to 1.5 dL / g, the weight average molecular weight is in the range of 5,000 to 150,000 g / mol Oriented Composition. 제 1 항에 있어서, 상기 화학식 2로 표시되는 폴리아믹산 유도체는 고유점도가 0.3 ∼ 2.0 dL/g 범위이며, 중량평균분자량 10,000 ∼ 200,000 g/mol의 범위인 것임을 특징으로 하는 수직배향형 조성물.The vertically oriented composition of claim 1, wherein the polyamic acid derivative represented by Chemical Formula 2 has an intrinsic viscosity ranging from 0.3 to 2.0 dL / g and a weight average molecular weight ranging from 10,000 to 200,000 g / mol. 제 1 항에 있어서, 상기 화학식 2로 표시되는 폴리아믹산 유도체의 이미드화 온도범위가 200 ∼ 300 ℃인 것임을 특징으로 하는 수직배향형 조성물.The vertically oriented composition of claim 1, wherein the imidation temperature range of the polyamic acid derivative represented by Chemical Formula 2 is 200 to 300 ° C. 제 1 항에 있어서, 상기 화학식 1로 표시되는 저극성 측쇄 함유 폴리아믹산 수지는 디메틸아세트아미드, 디메틸포름아미드, N-메틸-2-피롤리돈, 테트라히드로푸란, 클로로포름, 아세톤, 에틸아세테이트 및 감마-부티로락톤 중에서 선택된 용매에 대해 용해특성을 가지는 것임을 특징으로 하는 수직배향형 조성물.According to claim 1, wherein the low polar side chain-containing polyamic acid resin represented by Formula 1 is dimethylacetamide, dimethylformamide, N -methyl-2-pyrrolidone, tetrahydrofuran, chloroform, acetone, ethyl acetate and gamma -A vertically oriented composition, characterized in that it has dissolution characteristics with respect to a solvent selected from butyrolactone. 청구항 1 내지 청구항 6 중에서 선택된 어느 하나의 조성물을 코팅하여 제조한 것임을 특징으로 하는 액정 배향막.The liquid crystal aligning film which is manufactured by coating any composition selected from Claims 1-6. 제 7 항에 있어서, 상기 액정 배향막은 러빙 전 표면장력이 30 ∼ 40 dyne/cm 범위인 것임을 특징으로 하는 액정 배향막.The liquid crystal alignment layer of claim 7, wherein the liquid crystal alignment layer has a surface tension before rubbing in the range of 30 to 40 dyne / cm. 제 7 항에 있어서, 상기 액정 배향막은 막 표면의 연필경도가 1H ∼ 7H 범위인 것임을 특징으로 하는 액정 배향막.8. The liquid crystal aligning film according to claim 7, wherein the liquid crystal aligning film has a pencil hardness of 1H to 7H on the surface of the film. 청구항 1 내지 청구항 6 중에서 선택된 어느 하나의 조성물을 코팅하여 제조한 것임을 특징으로 하는 액정 셀.Liquid crystal cell characterized in that it is prepared by coating any one of the compositions selected from claim 1 to claim 6. 제 10 항에 있어서, 상기 액정 셀은 선경사각(pretilt angle)이 89 ∼ 90 °범위인 것임을 특징으로 하는 액정 셀.The liquid crystal cell of claim 10, wherein the liquid crystal cell has a pretilt angle in a range of 89 to 90 degrees. 제 10 항에 있어서, 상기 액정 셀은 상온 전압보유율이 99 ∼ 99.99 %의 범위인 것임을 특징으로 하는 액정 셀. The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a room temperature voltage retention of 99 to 99.99%. 제 10 항에 있어서, 상기 액정 셀은 상온 잔류 전압이 100 ∼ 400 mV 범위인 것임을 특징으로 하는 액정 셀. The liquid crystal cell according to claim 10, wherein the liquid crystal cell has a room temperature residual voltage in a range of 100 to 400 mV.
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KR20030042017A (en) * 2000-10-16 2003-05-27 닛산 가가쿠 고교 가부시키 가이샤 Aligning agent for liquid crystal for in-plane switching, liquid-crystal alignment film, and liquid-crystal display element
KR20040050166A (en) * 2002-12-09 2004-06-16 한국화학연구원 Polyimide derivatives with pendant imide group and method for preparing them

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KR100927704B1 (en) 2007-12-07 2009-11-18 제일모직주식회사 Liquid crystal aligning agent, Liquid crystal aligning film containing this, Liquid crystal display containing this

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