KR100837788B1 - Aromatic diamines with a photoreactive aromatic side group, polyamic acid photo-alignment layers with them and method for preparing liquid crystal cells - Google Patents

Aromatic diamines with a photoreactive aromatic side group, polyamic acid photo-alignment layers with them and method for preparing liquid crystal cells Download PDF

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KR100837788B1
KR100837788B1 KR1020070057624A KR20070057624A KR100837788B1 KR 100837788 B1 KR100837788 B1 KR 100837788B1 KR 1020070057624 A KR1020070057624 A KR 1020070057624A KR 20070057624 A KR20070057624 A KR 20070057624A KR 100837788 B1 KR100837788 B1 KR 100837788B1
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polyamic acid
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liquid crystal
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이미혜
안택
박희진
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한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/32—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and esterified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety

Abstract

A novel aromatic diamine compound, a poly(amic acid) using the compound, a light alignment layer using the poly(amic acid), and a liquid crystal cell containing the light alignment layer are provided to improve heat resistance, transparency, surface hardness and voltage holding ratio and to reduce surface roughness. An aromatic diamine compound is represented by the formula 1, wherein a is an integer of 1-10; b is an integer of 0-10; A is a group represented by the formula A if b is an integer of 1-10; R1, R2, R3, R4 and R5 are independently a C1-C10 alkyl substituted or unsubstituted with a halogen atom, a cyano group, a nitro group, a carboxyl acid group or an aminocarbonyl group; and A is a group represented by the formula B if b is 0.

Description

광반응형 방향족 고리 측쇄기를 갖는 폴리아믹산 광배향막의 제조방법 및 이를 이용한 액정 셀{Aromatic diamines with a photoreactive aromatic side group, polyamic acid photo-alignment layers with them and method for preparing liquid crystal cells}Aromatic diamines with a photoreactive aromatic side group, polyamic acid photo-alignment layers with them and method for preparing liquid crystal cells}

도 1은 제조예 1에 따라 제조된 DA-1의 1H NMR 스펙트럼이다.1 is a 1 H NMR spectrum of DA-1 prepared according to Preparation Example 1. FIG.

도 2은 제조예 2에 따라 제조된 DA-2의 1H NMR 스펙트럼이다.2 is a 1 H NMR spectrum of DA-2 prepared according to Preparation Example 2. FIG.

도 3은 제조예 3에 따라 제조된 DA-3의 1H NMR 스펙트럼이다.3 is a 1 H NMR spectrum of DA-3 prepared according to Preparation Example 3. FIG.

도 4은 제조예 4에 따라 제조된 DA-4의 1H NMR 스펙트럼이다.4 is a 1 H NMR spectrum of DA-4 prepared according to Preparation Example 4. FIG.

도 5은 제조예 5에 따라 제조된 CBDA의 1H NMR 스펙트럼이다.5 is a 1 H NMR spectrum of CBDA prepared according to Preparation Example 5. FIG.

도 6은 제조예 6에 따라 제조된 DM-CBDA의 1H NMR 스펙트럼이다.6 is a 1 H NMR spectrum of DM-CBDA prepared according to Preparation Example 6. FIG.

도 7은 실시예 1에 따라 제조된 PAA-1의 1H NMR 스펙트럼이다.7 is a 1 H NMR spectrum of PAA-1 prepared according to Example 1. FIG.

본 발명은 광반응형 방향족 고리 측쇄기를 갖는 폴리아믹산 광배향막 및 그의 제조방법에 관한 것으로서, 보다 상세하게는 지방족 고리계 산이무수물을 적정비율 이상 포함하는 산이무수물과 광반응형 방향족 고리 측쇄기를 갖는 방향족 디아민을 적정비율 이상 포함하는 방향족 디아민류를 용액 중합함으로써, 용제에 우수한 용해성을 갖는 폴리아믹산을 제조하였으며, 이에 편광자외선을 조사하여 러빙공정을 거치지 않고 액정을 배향시키는 것을 특징으로 한다.The present invention relates to a polyamic acid photoalignment film having a photoreactive aromatic ring side group and a method for preparing the same, and more particularly to an aromatic having an acid dianhydride and a photoreactive aromatic ring side chain containing an aliphatic ring acid dianhydride in an appropriate ratio or more. By solution polymerization of aromatic diamines containing a diamine or more in an appropriate ratio, a polyamic acid having excellent solubility in a solvent was prepared, and the liquid crystal is oriented without irradiating polarized ultraviolet rays to the liquid crystal without undergoing a rubbing process.

편광자외선을 조사하여 제조된 본 발명의 폴리아믹산 광배향막은 가시광선 영역에서의 우수한 투명성, 우수한 인쇄성, 내열성, 표면경도 및 액정 배향성이 뛰어나며, 특히 낮은 광량을 사용하여 광배향성 우수하며, 선경사각 및 우수한 전압보유율을 가지는 특징이 있다.The polyamic acid photoalignment film of the present invention prepared by irradiating polarized ultraviolet rays has excellent transparency, excellent printability, heat resistance, surface hardness, and liquid crystal orientation in the visible light region, and excellent light alignment by using a low amount of light. And excellent voltage retention.

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)을 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-비스아미노 페녹시벤젠(TPE-R), 2,2-비스아미노페녹시페닐프로판(BAPP), 및 2,2-비스아미노페녹시페닐헥사풀루오로프로판(HFBAPP)등의 방향족 디아민을 사용하여 축중합으로 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-bisamino phenoxybenzene (TPE-R), 2,2-bisaminophenoxyphenylpropane (BAPP), and 2,2-bisaminophenoxyphenylhexafuluropropane (HFBAPP It is manufactured by polycondensation polymerization using aromatic diamine such as).

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 등이다.Most polyimide resins are insoluble and insoluble ultra high heat resistant resins and have the following properties; (1) excellent thermal oxidation resistance, (2) high usable temperature, (3) excellent heat resistance indicating long term usable temperature of about 260 ° C and short term available temperature of about 480 ° C, (4) radiation resistance, (5 ) Excellent low temperature property, (6) Good chemical resistance.

그러나 폴리이미드 수지는 상기한 바와 같은 특성을 가지고 있음에도 불구하고, 전하이동착체(charge transfer complex)의 형성에 기인한 가시광선 영역에서의 낮은 광투과도로 인하여 투명성이 요구되는 분야에의 적용이 매우 어렵다는 단점이 있다. However, although polyimide resins have the characteristics described above, they are difficult to be applied to fields requiring transparency due to low light transmittance in the visible region due to the formation of charge transfer complexes. There are disadvantages.

따라서 다양한 종류의 주쇄형 지방족 폴리이미드계 수지들이 제조되어, 액정배향막 등 우수한 광투과성이 요구되는 분야에 응용되고 있다. 특히 러빙공정을 거치지 않는 광배향막의 경우 배향 공정 중 분진 혹은 정전기 발생 등의 문제를 해결할 수 있기 때문에 개발이 특히 요구되는 분야이다. Therefore, various kinds of main chain aliphatic polyimide-based resins have been prepared, and have been applied to fields requiring excellent light transmittance such as liquid crystal alignment films. In particular, in the case of the photo-alignment film that does not go through the rubbing process, it is a field in which development is particularly required because it can solve problems such as dust or static electricity during the alignment process.

그러나 현재까지 개발된 지방족 고리계 광배향막의 경우 액정을 배향시키기 위해 요구되는 조사 자외광의 파장이나 조사광량이 높기 때문에 배향막 공정시간 및 에너지 소모가 늘어나는 측면을 보인다.However, in the case of the aliphatic ring-oriented photoalignment films developed to date, the process time and energy consumption of the alignment film are increased due to the high wavelength or the amount of irradiation light required for the alignment of the liquid crystal.

이에 본 발명자들은 상기와 같은 문제점을 해결하기 위하여, 300 nm 이상의 장파장 및 200 mJ/cm2이하의 낮은 광량에서 우수한 광배향성을 갖는 방향족 디아민을 분자설계한 후 제조하였으며, 상기 방향족 디아민을 포함하는 폴리아믹산 수지를 이용하여 얻어진 박막에 편광자외선을 조사하여 뛰어난 액정배향성, 우수한 전압보유율(VHR, voltage holding ratio), 4H 이상의 높은 표면경도 및 0.01~2.0o 범위의 낮은 선경사각을 갖는 신규 광배향막을 개발하여 본 발명을 완성하였다.In order to solve the above problems, the present inventors prepared and prepared an aromatic diamine having excellent optical orientation at a long wavelength of 300 nm or more and a low light quantity of 200 mJ / cm 2 or less, and a polya including the aromatic diamine. Development of a novel optical alignment film having excellent liquid crystal orientation, excellent voltage holding ratio (VHR), high surface hardness of more than 4H and low pretilt angle in the range of 0.01 ~ 2.0 o The present invention was completed.

즉, 본 발명에 도입된 폴리아믹산은 지방족 고리계 산이무수물인 트리카르복시시클로펜틸아세트산 무수물(TCA-AH), 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA), 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물(DOTDA), 1,2,3,4-시클로부탄 테트라카르복실산이무수물(CBDA), 1,3-디메틸-1,2,3,4-시클로부탄 테트라카르복실산이무수물(DM-CBDA), 1,2,3,4-시클로펜탄 테트라카르복실산이무수물(CPDA), 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물(BODA)과 피로멜리트산이무수물, 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물 및 헥사플루오로이소프로필리덴디프탈산이무수물 등의 테트라카르복실산 이무수물의 혼합물과 광반응형 방향족 고리 측쇄를 갖는 방향족 디아민 및 방향족 디아민의 혼합물로부터 제조되었으며, 제조된 폴리아믹산 수지를 박막화 한 후 편광자외선을 조사함으로써 우수한 내열성, 투명성, 표면경도, 높은 전압보유율 및 낮은 선경사각을 갖는 신규 액정 광배향막을 개발하여 본 발명을 완성하였다.That is, the polyamic acid introduced into the present invention is an aliphatic ring acid dianhydride tricarboxycyclopentyl acetic anhydride (TCA-AH), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1, 2-dicarboxylic dianhydride (DOCDA), 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride (DOTDA), 1,2, 3,4-cyclobutane tetracarboxylic dianhydride (CBDA), 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride (DM-CBDA), 1,2,3,4- Cyclopentane tetracarboxylic dianhydride (CPDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA), pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, oxydiphthalic acid Aromatic diamines having photoreactive aromatic ring side chains with a mixture of tetracarboxylic dianhydrides such as anhydrides, nonphthalic dianhydrides and hexafluoroisopropylidenediphthalic dianhydrides; and Completed the present invention by developing a novel liquid crystal photo-alignment film having excellent heat resistance, transparency, surface hardness, high voltage retention and low pretilt angle by thinning the prepared polyamic acid resin and irradiating polarized ultraviolet rays. It was.

따라서, 본 발명은 낮은 광량의 편광자외선을 조사하여 우수한 광배향성 및 전기광학적 성질을 갖는 신규한 방향족 고리 측쇄기를 함유하는 방향족 디아민 화합물을 단량체로 함유하는 폴리아믹산, 상기 폴리아믹산으로부터 제조된 광배향막 및 상기 광배향막을 포함하는 액정 셀을 제공하는데 그 목적이 있다. Accordingly, the present invention provides a polyamic acid containing, as a monomer, an aromatic diamine compound containing a novel aromatic ring side chain group having excellent photo-alignment and electro-optical properties by irradiating low-light polarized ultraviolet rays, an optical alignment film prepared from the polyamic acid, and It is an object of the present invention to provide a liquid crystal cell including the optical alignment layer.

본 발명은 기존의 방향족 측쇄기를 함유하지 않는 광배향막으로부터 제작된 액정 셀과 비교하여 300 nm이상의 장파장 배향성, 200 mJ/cm2이하의 낮은 광량, 4H 이상의 뛰어난 표면경도, 우수한 전압보유율, 및 낮은 선경사각을 갖는 액정 셀을 제공하는데 그 목적이 있다.Compared to the liquid crystal cell fabricated from the optical alignment film containing no aromatic side chain, the present invention has a long wavelength orientation of 300 nm or more, low light quantity of 200 mJ / cm 2 or less, excellent surface hardness of 4H or more, excellent voltage retention, and low wire diameter. The object is to provide a liquid crystal cell having a blind spot.

본 발명은 하기 화학식 1로 표시되는 방향족 측쇄기를 함유하는 신규한 방향족 디아민 화합물을 단량체로 함유하는 하기 화학식 2로 표시되는 폴리아믹산 및 이로부터 제조되는 광배향막에 관한 것이다. 또한, 본 발명은 하기 화학식 1의 신규한 방향족 디아민 화합물에 관한 것이다.The present invention relates to a polyamic acid represented by the following formula (2) containing a novel aromatic diamine compound containing an aromatic side chain group represented by the following formula (1) as a monomer and a photoalignment film prepared therefrom. The present invention also relates to novel aromatic diamine compounds of the general formula (1).

[화학식 1][Formula 1]

Figure 112007042667994-pat00001
Figure 112007042667994-pat00001

[상기 화학식 1에서 [In Formula 1

a는 1 내지 10의 정수이며;a is an integer from 1 to 10;

b는 0 내지 10의 정수이며;b is an integer from 0 to 10;

b가 1 내지 10의 정수인 경우 A는

Figure 112007042667994-pat00002
이며;when b is an integer from 1 to 10, then A is
Figure 112007042667994-pat00002
Is;

R1, R2, R3, R4 및 R5는 서로 독립적으로 할로겐이 치환되거나 치환되지 않은 (C1-C10)알킬, 시아노, 니트로, 카복실산 또는 아미노카보닐이고;R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other a substituted or unsubstituted (C1-C10) alkyl, cyano, nitro, carboxylic acid or aminocarbonyl;

b가 0인 경우 A는

Figure 112007042667994-pat00003
이다.]If b is 0 then A is
Figure 112007042667994-pat00003
to be.]

[화학식 2][Formula 2]

Figure 112007042667994-pat00004
Figure 112007042667994-pat00004

[상기 화학식 2에서 [In Formula 2]

m은 1 내지 500의 정수이고;m is an integer from 1 to 500;

Figure 112007042667994-pat00005
는
Figure 112007042667994-pat00006
,
Figure 112007042667994-pat00007
,
Figure 112007042667994-pat00008
,
Figure 112007042667994-pat00009
,
Figure 112007042667994-pat00010
중에서 선택된 1종 또는 2종 이상의 4가기이며;
Figure 112007042667994-pat00005
Is
Figure 112007042667994-pat00006
,
Figure 112007042667994-pat00007
,
Figure 112007042667994-pat00008
,
Figure 112007042667994-pat00009
,
Figure 112007042667994-pat00010
1 type, or 2 or more types of tetravalent groups chosen from;

B는 화학결합이거나 (C1-C2)알킬렌,

Figure 112007042667994-pat00011
,
Figure 112007042667994-pat00012
,
Figure 112007042667994-pat00013
,
Figure 112007042667994-pat00014
,
Figure 112007042667994-pat00015
,
Figure 112007042667994-pat00016
또는
Figure 112007042667994-pat00017
이고, 상기 알킬렌은 플루오르가 치환되거나 치환되지 않은 (C1-C5)알킬이 더 치환될 수 있으며;B is a chemical bond or (C1-C2) alkylene,
Figure 112007042667994-pat00011
,
Figure 112007042667994-pat00012
,
Figure 112007042667994-pat00013
,
Figure 112007042667994-pat00014
,
Figure 112007042667994-pat00015
,
Figure 112007042667994-pat00016
or
Figure 112007042667994-pat00017
Wherein the alkylene may be further substituted with (C1-C5) alkyl which is substituted or unsubstituted fluorine;

R11, R12, R13 및 R14는 서로 독립적으로 수소, (C1-C10)알킬 또는 페닐이며;R 11 , R 12 , R 13 and R 14 are independently of each other hydrogen, (C1-C10) alkyl or phenyl;

Figure 112007042667994-pat00018
는
Figure 112007042667994-pat00019
,
Figure 112007042667994-pat00020
,
Figure 112007042667994-pat00021
,
Figure 112007042667994-pat00022
,
Figure 112007042667994-pat00023
,
Figure 112007042667994-pat00024
,
Figure 112007042667994-pat00025
,
Figure 112007042667994-pat00026
,
Figure 112007042667994-pat00027
,
Figure 112007042667994-pat00028
,
Figure 112007042667994-pat00029
,
Figure 112007042667994-pat00030
중에서 선택된 1종 또는 2종 이상의 2가기로서, 상기 구조식 (g)의 방향족 고리 측쇄를 가지는 방향족 2가기를 반드시 포함한다.]
Figure 112007042667994-pat00018
Is
Figure 112007042667994-pat00019
,
Figure 112007042667994-pat00020
,
Figure 112007042667994-pat00021
,
Figure 112007042667994-pat00022
,
Figure 112007042667994-pat00023
,
Figure 112007042667994-pat00024
,
Figure 112007042667994-pat00025
,
Figure 112007042667994-pat00026
,
Figure 112007042667994-pat00027
,
Figure 112007042667994-pat00028
,
Figure 112007042667994-pat00029
,
Figure 112007042667994-pat00030
And one or two or more divalent groups selected from the foregoing, and must include an aromatic divalent group having an aromatic ring side chain of the formula (g).]

본 발명에 따른 상기 화학식 2로 표시되는 폴리아믹산은 광배향막용으로, 테트라카르복실산이무수물 단량체와 디아민 단량체를 용액중합시켜 제조한다. 즉, 테 트라카르복실산이무수물 단량체로서는 트리카르복시시클로펜틸아세트산 무수물(TCA-AH), 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA), 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물(DOTDA), 1,2,3,4-시클로부탄 테트라카르복실산이무수물(CBDA), 1,3-디메틸-1,2,3,4-시클로부탄 테트라카르복실산이무수물(DM-CBDA), 1,2,3,4-시클로펜탄 테트라카르복실산이무수물(CPDA), 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물(BODA)과 피로멜리트산이무수물(PMDA), 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물(BPDA) 및 헥사플루오로이소프로필리덴디프탈산이무수물 등 중에서 선택 사용하고 있으며, 이에 한정되는 것은 아니다. The polyamic acid represented by Chemical Formula 2 according to the present invention is prepared by solution polymerization of a tetracarboxylic dianhydride monomer and a diamine monomer for an optical alignment film. That is, as the tetracarboxylic dianhydride monomer, tricarboxycyclopentylacetic anhydride (TCA-AH) and 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic acid are Anhydride (DOCDA), 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride (DOTDA), 1,2,3,4-cyclobutane Tetracarboxylic dianhydride (CBDA), 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride (DM-CBDA), 1,2,3,4-cyclopentane tetracarboxylic acid Anhydride (CPDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA) and pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, non It is selected from phthalic dianhydride (BPDA) and hexafluoroisopropylidene diphthalic dianhydride and the like, but is not limited thereto.

또한, 방향족 디아민 단량체로서는 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 있으며, 이에 한정되는 것은 아니나, 반드시 화학식 1의 방향족 고리 측쇄기를 함유하는 방향족 디아민 화합물을 단량체로 함유한다. In addition, examples of the aromatic diamine monomers 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), 2,2-bisaminophenoxyphenylhexapulopropane (HFBAPP) or the like, and is not limited thereto, but an aromatic diamine compound containing an aromatic ring side chain group of the general formula (1) as a monomer.

즉, 본 발명은 상기 화학식 2로 표시되는 폴리아믹산을 제조함에 있어, 테트라카르복실산이무수물 단량체를 적절한 비율로 혼합 사용하여 기계적 특성과 내열 성의 저하를 최소로 하면서도 인쇄성이 개선된 폴리아믹산 유도체를 제조할 수가 있다.That is, the present invention is to prepare a polyamic acid represented by the formula (2), by using a mixture of tetracarboxylic dianhydride monomer in an appropriate ratio to minimize the decrease in mechanical properties and heat resistance, while improving the printability polyamic acid derivative It can manufacture.

즉, 본 발명에서는 테트라카르복실산이무수물을 전체 산이무수물 사용량에 대하여 1 내지 100 몰% 범위로 사용한다. 즉, 테트라카르복실산이무수물 단량체로서는 트리카르복시시클로펜틸아세트산 무수물(TCA-AH), 5-(2,5-디옥소테트라히드로퓨릴)-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA), 4-(2,5-디옥소테트라히드로퓨릴-3-일)-테트랄린-1,2-디카르복실산이무수물(DOTDA), 1,2,3,4-시클로부탄 테트라카르복실산이무수물(CBDA), 1,3-디메틸-1,2,3,4-시클로부탄 테트라카르복실산이무수물(DM-CBDA), 1,2,3,4-시클로펜탄 테트라카르복실산이무수물(CPDA), 바이시클로옥텐-2,3,5,6-테트라카르복실산이무수물(BODA)과 피로멜리트산이무수물(PMDA), 벤조페논테트라카르복실산이무수물, 옥시디프탈산이무수물, 비프탈산이무수물(BPDA) 및 헥사플루오로이소프로필리덴디프탈산이무수물 등 중에서 선택 사용하고 있으며, 이에 한정되는 것은 아니다. 상기 화학식 1로 표시되는 방향족 디아민 화합물(g)을 전체 디아민 사용량에 대하여 1 내지 100 몰% 범위로 사용하는 경우에 본 발명이 목적으로 하는 물성을 충분히 발현하는 물질을 제조할 수 있는 것을 특징으로 한다.That is, in the present invention, tetracarboxylic dianhydride is used in the range of 1 to 100 mol% based on the total amount of acid dianhydride used. That is, as the tetracarboxylic dianhydride monomer, tricarboxycyclopentyl acetic anhydride (TCA-AH), 5- (2,5-dioxotetrahydrofuryl) -3-methylcyclohexane-1,2-dicarboxylic dianhydride (DOCDA), 4- (2,5-dioxotetrahydrofuryl-3-yl) -tetraline-1,2-dicarboxylic dianhydride (DOTDA), 1,2,3,4-cyclobutane tetra Carboxylic dianhydride (CBDA), 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride (DM-CBDA), 1,2,3,4-cyclopentane tetracarboxylic dianhydride (CPDA), bicyclooctene-2,3,5,6-tetracarboxylic dianhydride (BODA) and pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic dianhydride, oxydiphthalic dianhydride, nonphthalic acid It is selected from dianhydride (BPDA) and hexafluoroisopropylidenediphthalic dianhydride and the like, but is not limited thereto. When using the aromatic diamine compound (g) represented by the formula (1) in the range of 1 to 100 mol% based on the total amount of diamine used, it is possible to produce a substance sufficiently expressing the physical properties of the present invention. .

본 발명에 따른 상기 화학식 1로 표시되는 방향족 디아민 화합물(g)을 필수 단량체로 사용하여 제조된 본 발명에 따른 폴리아믹산 유도체는 기존에 제조된 바 없는 신규한 물질로서, 광반응형 방향족 고리 측쇄가 도입됨에 의하여 장파장 및 낮은 광량에서 높은 광배향성을 가지며, 투명성, 인쇄성, 기계적 특성이 개선되었고, 상기 물질의 적용에 의하여 제조된 액정 셀의 선경사각 및 전기광학적 특성이 특히 개선된 신규한 고분자 조성물이다.Polyamic acid derivatives according to the present invention prepared by using the aromatic diamine compound (g) represented by the formula (1) according to the present invention as an essential monomer is a novel material that has not been prepared before, a photoreactive aromatic ring side chain The new polymer composition has high optical orientation at long wavelength and low light amount, improves transparency, printability, mechanical properties, and especially improves the pretilt angle and electro-optical properties of the liquid crystal cell prepared by the application of the material. to be.

본 발명에 따른 폴리아믹산 유도체는 중량평균 분자량(Mw) 10,000 내지 500,000 g/mol, 고유점도 범위 0.3 ~ 2.0 dL/g, 유리전이온도 범위 200 ~ 400 ℃, 이미드화 온도범위 200 ~ 350 ℃ 범위의 특성을 가진다. 또한, 본 발명에 따른 폴리아믹산 유도체는 디메틸아세트아미드(DMAc), 디메틸포름아미드(DMF), N-메틸-2-피롤리돈(NMP), 아세톤, 및 에틸아세테이트(EA)와 같은 비양성자성 극성용매를 비롯하여 메타-크레졸(m-cresol)과 같은 유기용매에 대해 상온에서 쉽게 용해되는 특성을 가진다. 특히, 테트라히드로퓨란(THF) 및 감마-부티로락톤(GBL)과 같은 저흡수성 용매에 대해서도 상온에서 10 중량% 이상의 높은 용해도를 나타낸다. 또한, 상기 용매들의 혼합용매에 대해서도 높은 용해도를 나타낸다.The polyamic acid derivative according to the present invention has a weight average molecular weight (Mw) of 10,000 to 500,000 g / mol, an intrinsic viscosity range of 0.3 to 2.0 dL / g, a glass transition temperature range of 200 to 400 ° C., an imidization temperature range of 200 to 350 ° C. Has characteristics. In addition, the polyamic acid derivatives according to the present invention are aprotic such as dimethylacetamide (DMAc), dimethylformamide (DMF), N -methyl-2-pyrrolidone (NMP), acetone, and ethyl acetate (EA). In addition to polar solvents, organic solvents such as meta-cresol (m-cresol) are easily dissolved at room temperature. In particular, low solubility solvents such as tetrahydrofuran (THF) and gamma-butyrolactone (GBL) also exhibit high solubility of at least 10% by weight at room temperature. In addition, it exhibits high solubility in mixed solvents of the above solvents.

본 발명은 상기의 물성을 가지는 폴리아믹산들을 혼합한 혼합물의 경우에도 본 발명의 목적하는 물성을 얻을 수 있다. The present invention can obtain the desired physical properties of the present invention even in the case of a mixture of the polyamic acid having the above properties.

또한, 본 발명의 상기 폴리아믹산으로부터 300~460 nm 파장에서 100~1000 mJ/cm2 세기의 편광자외선을 조사하여 제조된 광배향막을 포함하는 액정 셀의 전기 광학적 특성을 평가한 결과 선경사각(pretilt angle)은 0.01~2.0°의 범위에 있으 며, 25 ℃, 3V 전압하에서의 전압보유율은 99.0~99.5%의 범위에 있었다.In addition, as a result of evaluating the electro-optical characteristics of the liquid crystal cell including a photoalignment film prepared by irradiating polarized ultraviolet rays of 100 to 1000 mJ / cm 2 intensity at 300 ~ 460 nm wavelength from the polyamic acid of the present invention pretilt angle) was in the range of 0.01 ~ 2.0 °, and the voltage retention at 25 ℃ and 3V voltage was in the range of 99.0 ~ 99.5%.

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

이하, 본 발명을 하기의 제조예 및 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명의 사상이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following Preparation Examples and Examples, but the inventive concept is not limited thereto.

[[ 제조예Production Example 1-4]  1-4] 광반응형Photoresponse 방향족 고리  Aromatic ring 측쇄기를Side chain 함유한 방향족  Aromatic 디아민의Diamine 제조 Produce

[[ 제조예Production Example 1] 3-비페닐-4-일- 1] 3-biphenyl-4-yl- 아크릴릭Acrylic 산 3,5- Acid 3,5- 디아미노Diamino -벤질 에스터(3-Benzyl ester (3- BiphenylBiphenyl -4--4- ylyl -- acrylicacrylic acidacid 3,5-diamino-benzyl  3,5-diamino-benzyl esterester ) () ( DADA -1)의 제조-1) Preparation

(1) 가열 환류장치가 장착된 250ml의 둥근바닥 플라스크에 비페닐-4-카르발데히드(biphenyl-4-carbaldehyde) 2g을 넣고 100ml 벤젠에 용해시킨 후, (카르베톡시메틸렌)-트리페닐포스포란((carbethoxymethylene)-triphenylphosphorane) 4.2g을 첨가하여 80℃에서 8시간동안 환류 교반하였다. 반응혼합물을 상온까지 식힌 후 포화소금물 과량을 사용하여 벤젠내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(1) 2 g of biphenyl-4-carbaldehyde was added to a 250 ml round bottom flask equipped with a heating reflux apparatus, dissolved in 100 ml benzene, and then (carbetoxymethylene) -triphenylforce. 4.2 g of porane ((carbethoxymethylene) -triphenylphosphorane) was added thereto, and the mixture was stirred under reflux at 80 ° C. for 8 hours. After cooling the reaction mixture to room temperature, excess saturated salt The polar solvent in the benzene was removed, and the reaction product was finally concentrated under reduced pressure with anhydrous magnesium sulfate to prepare a reaction product containing trace impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 1: 4) afforded a white solid.

(2) 250ml의 둥근바닥 플라스크에 3-비스페닐-4-일-아크릴릭 산 에틸 에스터(3-biphenyl-4-yl-acrylic acid ethyl ester) 4.55g을 넣고 100ml의 THF/ EtOH/ H2O (부피비 1/1/1) 혼합용매를 첨가하여 용해시킨 후 리튬 하이드록사이드(lithium hydroxide) 5g 을 넣고 2시간동안 교반하였다. 반응혼합물을 염산으로 적정하여 중화시킨 후 침전물을 여과, 건조하여 백색의 3-비페닐-4-일-아크릴릭 산을 수득하였다.(2) In a 250 ml round bottom flask, 4.55 g of 3-biphenyl-4-yl-acrylic acid ethyl ester was added and 100 ml of THF / EtOH / H 2 O ( Volume ratio 1/1/1) After mixing and dissolving a mixed solvent, 5g of lithium hydroxide was added and stirred for 2 hours. The reaction mixture was neutralized with hydrochloric acid, and then the precipitate was filtered and dried to yield a white 3-biphenyl-4-yl-acrylic acid.

(3) 500ml의 둥근바닥 플라스크에 3-비페닐-4-일-아크릴릭산(3-biphenyl-4-yl-acrylic acid) 2g을 넣고 200ml 메타크레졸에 용해시킨 후 옥살릴 클로라이드 2ml를 첨가하여 교반하였다. 이어 디메틸포름아미드 2-3방울을 넣고 상온에서 2시간 교반하였다. 반응혼합물을 감압농축 하여 휘발성 물질 제거하고 노란색의 3-비페닐-4-일-아크릴로일 클로라이드(3-biphenyl-4-yl-acryloyl chloride)를 얻었다.(3) 2 g of 3-biphenyl-4-yl-acrylic acid was added to a 500 ml round bottom flask, dissolved in 200 ml of methacresol, and stirred with 2 ml of oxalyl chloride. It was. Then, 2-3 drops of dimethylformamide were added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles, and yellow 3-biphenyl-4-yl-acryloyl chloride was obtained.

(4) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 디-터트-부틸 5-(하이드록시 메틸)-1,3-페닐렌디카바메이트(di-tert-butyl 5-(hydroxy methyl)-1,3-phenylenedicarbamate) 3.02g을 넣고 250ml 메타크레졸에 용해시킨 후, 3-비페닐-4-일-아크릴로일 클로라이드(3-Biphenyl-4-yl-acryloyl chloride) 2.0g을 첨가하여 교반하였다. 0℃에서 트리에틸아민 1.1g을 천천히 주입한 후 온도를 상온까지 승온시킨 후 12시간동안 교반을 계속하였다. 반응혼합물을 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(4) 500 ml round-bottomed flasks equipped with an ice bath were used for di-tert-butyl 5- (hydroxy methyl) -1,3-phenylenedicarbamate (di-tert-butyl 5- (hydroxy methyl) -1, 3.02 g of 3-phenylenedicarbamate) was added thereto, dissolved in 250 ml of metacresol, and 2.0 g of 3-biphenyl-4-yl-acryloyl chloride was added thereto and stirred. 1.1 g of triethylamine was slowly injected at 0 ° C., the temperature was raised to room temperature, and stirring was continued for 12 hours. The reaction mixture is saturated with saturated salt The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 1: 4) afforded a white solid.

(5) 500ml의 둥근바닥 플라스크에 3-비페닐-4-일-아크릴릭 산 3,5-비스-터트-부톡시카르보닐아미노-벤질 에스터(3-biphenyl-4-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino- benzyl ester) 4.5g 을 넣고 200ml 메타크레졸에 용해시킨 후 트리플루오로아세틱 산 100ml를 첨가하여 상온에서 4시간 교반 하였다. 반응혼합물을 감압농축 하여 휘발성 물질을 제거하고 250ml 메타크레졸로 희석하였다. 희석된 반응혼합물을 탄산수소나트륨으로 중화 시킨 뒤 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=3:2)로 정제하여 노란색의 3-비페닐-4-일-아크릴릭 산 3,5-디아미노-벤질 에스터( DA -1)를 수득하였으며 이의 NMR 데이터를 도 1에 나타내었다.(5) 3-biphenyl-4-yl-acrylic acid 3,5-bis-tert-butoxycarbonylamino-benzyl ester (3-biphenyl-4-yl-acrylic acid 3,5 in a 500 ml round bottom flask 4.5 g of -bis-tert-butoxycarbonylamino-benzyl ester) was added thereto, dissolved in 200 ml of metacresol, and 100 ml of trifluoroacetic acid was added thereto, followed by stirring at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and diluted with 250 ml methacresol. The diluted reaction mixture was neutralized with sodium hydrogen carbonate and saturated salts were excess. The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Then purified by silica gel column chromatography (EA: Hx = 3: 2) to give yellow 3-biphenyl-4-yl-acrylic acid 3,5-diamino-benzyl ester ( DA- 1) and its NMR data Is shown in FIG.

[[ 제조예Production Example 2] 3-나프탈렌-1-일- 2] 3-naphthalen-1-yl- 아크릴릭Acrylic 산 3,5- Acid 3,5- 디아미노Diamino -벤질 에스터(3-Benzyl ester (3- NaphthalenNaphthalen -1--One- ylyl -- acrylicacrylic acid 3,5- acid 3,5- diaminodiamino -- benzylbenzyl esterester ) () ( DADA -2)의 제조-2) Preparation

(1) 500ml의 둥근바닥 플라스크에 3-나프탈렌-1-일 아크릴릭 산(3- Naphthalene-1-yl acrylic acid) 2g을 넣고 200ml 메타크레졸에 용해시킨 후 옥살릴 클로라이드(oxalyl chloride) 2ml를 첨가하여 교반하였다. 이어 N,N-디메틸포름아미드(N,N-dimethylformamide; DMF) 2-3방울을 넣고 상온에서 2시간 교반하였다. 반응혼합물을 감압농축 하여 휘발성 물질 제거하고 노란색의 3-나프탈렌-1-일-아크릴로일 클로라이드(3-Naphthalen-1-yl-acryloyl chloride)를 얻었다. (1) 2 g of 3-naphthalene-1-yl acrylic acid was added to a 500 ml round bottom flask, dissolved in 200 ml metacresol, and then 2 ml of oxalyl chloride was added. Stirred. Then, 2-3 drops of N, N-dimethylformamide (N, N-dimethylformamide; DMF) were added thereto, followed by stirring at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles, thereby obtaining yellow 3-naphthalen-1-yl-acryloyl chloride (3-Naphthalen-1-yl-acryloyl chloride).

(2) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 디-터트-부틸 5-(하드록시 메틸)-1,3-페닐렌 디카바메이트(di-tert-butyl 5-(hydroxy methyl)-1,3-phenylene dicarbamate) 6g을 넣고 250ml 메타크레졸에 용해시킨 후, 3-나프탈렌-1-일-아크릴로일 클로라이드(3-Naphthalen-1-yl-acryloyl chloride) 2.01g을 첨가하여 교반하였다. 0℃에서 트리에틸아민 1.51g을 천천히 주입 한 후 온도를 상온까지 승온시키고 12시간동안 교반을 계속하였다. 반응혼합물을 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(2) 500 ml round-bottomed flasks equipped with ice baths were used for di-tert-butyl 5- (hydroxy methyl) -1,3-phenylene dicarbamate (di-tert-butyl 5- (hydroxy methyl) -1, 6 g of 3-phenylene dicarbamate) was added thereto, dissolved in 250 ml of metacresol, and then 2.01 g of 3-naphthalen-1-yl-acryloyl chloride was added thereto and stirred. After slowly injecting 1.51 g of triethylamine at 0 ° C., the temperature was raised to room temperature and stirring was continued for 12 hours. The reaction mixture is saturated with saturated salt The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 1: 4) afforded a white solid.

(3) 500ml의 둥근바닥 플라스크에 3-나프탈렌-1-일-아크릴릭 산 3,5-비스-터트-부톡시카르보닐 아미노 에스터(3-naphthalen-1-yl-acrylic acid 3,5-bis-tert-butoxycarbonyl amino benzyl ester) 6g 을 넣고 200ml 메타크레졸에 용해시킨 후 트리플루오로아세틱 산 100ml를 첨가하여 상온에서 4시간 교반 하였다. 반응혼합물을 감압농축 하여 휘발성 물질을 제거하고 250ml 메타크레졸로 희석하였다. 희석된 반응혼합물을 탄산수소나트륨으로 중화 시킨 뒤 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=3:2)로 정제하여 노란색의 3-나프탈렌-2-일-아크릴릭 산 3,5-디아미노-벤질 에스터( DA -2)를 수득하여 그 NMR 데이터를 도 2에 나타내었다.(3) 3-naphthalen-1-yl-acrylic acid 3,5-bis-tert-butoxycarbonyl amino ester (3-naphthalen-1-yl-acrylic acid 3,5-bis-) in a 500 ml round bottom flask 6 g of tert-butoxycarbonyl amino benzyl ester) was dissolved in 200 ml of methacresol, and 100 ml of trifluoroacetic acid was added thereto, followed by stirring at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and diluted with 250 ml methacresol. The diluted reaction mixture was neutralized with sodium hydrogen carbonate and saturated salts were excess. The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 3: 2) afforded yellow 3-naphthalen-2-yl-acrylic acid 3,5-diamino-benzyl ester ( DA- 2) to give its NMR data. 2 is shown.

[제조예 3] 3-나프탈렌-1-일-아크릴릭 산 3-(3,5-디아미노-페닐)-프로필 에스터(3-Naphthalen-1-yl-acrylic acid 3-(3,5-diamino-phenyl)-propyl ester) (DA-3)의 제조Preparation Example 3 3-naphthalen-1-yl-acrylic acid 3- (3,5-diamino-phenyl) -propyl ester (3-Naphthalen-1-yl-acrylic acid 3- (3,5-diamino- Preparation of phenyl) -propyl ester) (DA-3)

(1) 가열 환류장치가 장착된 100ml의 둥근바닥 플라스크에 디-터트-부틸 5-(하이드록시메틸)-1,3-페닐렌디카바메이트(di-tert-butyl 5-(hydroxymethyl)-1,3-phenylenedicarbamate) 2g을 넣고 20ml 벤젠에 용해시킨 후, 촉매로 MnO2 1.23g을 넣어 80℃에서 6시간동안 가열 환류 교반 하였다. 반응혼합물을 상온까지 식힌 후 셀라이트 필터(celite filter)를 통해 여과 후 농축하였다. 이어 에테르로 고체화 하여 백색 고체를 얻었다.(1) Di-tert-butyl 5- (hydroxymethyl) -1,3-phenylenedicarbamate (di-tert-butyl 5- (hydroxymethyl) -1) in a 100 ml round bottom flask equipped with a heating reflux apparatus. , 3-phenylenedicarbamate) was added thereto, dissolved in 20 ml of benzene, 1.23 g of MnO 2 was added as a catalyst, and the mixture was stirred under heating at 80 ° C. for 6 hours. The reaction mixture was cooled to room temperature, filtered through a celite filter, and concentrated. It was then solidified with ether to give a white solid.

(2) 가열 환류장치가 장착된 100ml의 둥근바닥 플라스크에 (3-터트-부톡시 카르보닐아미노-5-포밀-페닐)-카바믹 산 부틸 에스터((3-tert-Butoxy carbonylamino-5-formyl-phenyl) -carbamic acid tert butyl ester) 1.8g을 넣고 30ml 벤젠에 용해시킨 후, (카르베톡시메틸렌)-트리페닐포스포란((carbethoxymethylene)-triphenylphosphorane) 2.16g을 첨가하여 90℃에서 24시간동안 환류 교반 하였다. 반응혼합물을 상온까지 식힌 후 감압농축하여 휘발성 물질을 제거하였다. 이어 실리카겔 컬럼 크로마토그래피(EA:Hx=1:2)로 정제하여 백색의 고체 화합물를 수득하였다.(2) In a 100 ml round bottom flask equipped with a heating reflux apparatus, (3-tert-butoxy carbonylamino-5-formyl-phenyl) -carbamic acid butyl ester ((3-tert-Butoxy carbonylamino-5-formyl) 1.8 g of -phenyl) -carbamic acid tert butyl ester) was dissolved in 30 ml benzene, and then 2.16 g of (carbethoxymethylene) -triphenylphosphorane was added for 24 hours at 90 ° C. It was stirred at reflux. The reaction mixture was cooled to room temperature and concentrated under reduced pressure to remove volatiles. Then purified by silica gel column chromatography (EA: Hx = 1: 2) to give a white solid compound.

(3) 수소 반응기에 40ml의 에탄올을 넣고 3-(3,5-비스-터트-부톡시카르보닐아미노-페닐)-아크릴릭 산 에틸 에스터(3-(3,5-bis-tert-butoxycarbonyl amino-phenyl)-acrylic acid ethyl ester) 2.12g을 용해시키고, 촉매로서 팔라듐/탄소(Pd/C)(10%) 0.5g을 첨가한 후, 3.5 atm의 압력 하에서 5-6시간 환원반응을 수행하였다. 멤브레인 필터를 사용하여 팔라듐/탄소(Pd/C)를 제거한 후 반응 혼합물을 감압농축하여 백색 고체를 얻었다.(3) 40 ml of ethanol was added to a hydrogen reactor and 3- (3,5-bis-tert-butoxycarbonylamino-phenyl) -acrylic acid ethyl ester (3- (3,5-bis-tert-butoxycarbonyl amino- 2.12 g of phenyl) -acrylic acid ethyl ester) were dissolved, and 0.5 g of palladium / carbon (Pd / C) (10%) was added as a catalyst, and then a reduction reaction was performed at a pressure of 3.5 atm for 5-6 hours. After removing palladium / carbon (Pd / C) using a membrane filter, the reaction mixture was concentrated under reduced pressure to give a white solid.

(4) 얼음조가 장착된 100ml의 둥근바닥 플라스크에 3-(3,5-비스-터트-부톡시 카르보닐아미노-페닐) 1-아크릴릭 산 에틸 에스터(3-(3,5-bis-tert-butoxy carbonylamino-pheny) l-acrylic acid ethyl ester) 2g을 넣고 30ml THF에 용해시킨 후, 0℃에서 리튬 알루미늄 하이드라이드(lithium aluminum hydride) 0.39g을 천천히 넣어 5시간동안 교반하였다. 반응 혼합물에 메탄올을 천천히 가해 기체 발생이 멈출 때까지 식힌 후 에틸 에테르(ethyl ether) 30ml에 넣고 소금물을 소량 (1ml)첨가하여 1시간동안 교반하였다. 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축한 후 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(4) 100 (3,5-bis-tert-butoxy carbonylamino-phenyl) 1-acrylic acid ethyl ester (3- (3,5-bis-tert-) in a 100 ml round bottom flask equipped with an ice bath 2 g of butoxy carbonylamino-pheny) l-acrylic acid ethyl ester) was dissolved in 30 ml THF, and 0.39 g of lithium aluminum hydride was slowly added at 0 ° C. and stirred for 5 hours. Methanol was slowly added to the reaction mixture, which was cooled until gas evolution stopped. Then, 30 ml of ethyl ether was added, and a small amount of brine (1 ml) was added thereto, followed by stirring for 1 hour. The solution from which moisture was removed with anhydrous magnesium sulfate was concentrated under reduced pressure and purified by silica gel column chromatography (EA: Hx = 1: 4) to obtain a white solid.

(5) 얼음조가 장착된 100ml의 둥근바닥 플라스크에 [3-터트-부톡시카르보닐 아미노-5-(3-하이드록시-프로필)-페닐]-카바믹 산 터트-부틸 에스터([3-tert -butoxycarboyl amino-5-(3-hydroxy-propyl)-phenyl]-carbamic acid tert-butyl ester) 0.51g을 넣고 30ml 메타크레졸에 용해시킨 후, 3-나프탈렌-1-일-아크릴로일 클로라이드(3-naphthalen-1-yl -acryloyl chloride) 0.78g을 첨가하여 교반하였다. 0℃에서 트리에틸아민 0.477g을 천천히 주입 한 후 온도를 상온까지 승온시킨 후 12시간동안 교반을 계속하였다. 반응혼합물을 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(5) In a 100 ml round bottom flask equipped with an ice bath, [3-tert-butoxycarbonyl amino-5- (3-hydroxy-propyl) -phenyl] -carbamic acid tert-butyl ester ([3-tert 0.51 g of -butoxycarboyl amino-5- (3-hydroxy-propyl) -phenyl] -carbamic acid tert-butyl ester) was dissolved in 30 ml methacresol, followed by 3-naphthalen-1-yl-acryloyl chloride (3 0.78 g of -naphthalen-1-yl -acryloyl chloride) was added thereto and stirred. 0.477 g of triethylamine was slowly injected at 0 ° C, the temperature was raised to room temperature, and stirring was continued for 12 hours. The reaction mixture was removed with a saturated salt of excess salt to remove the polar solvent in the metacresol, and finally, a solution obtained by removing the moisture with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing a trace amount of impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 1: 4) afforded a white solid.

(6) 100ml의 둥근바닥 플라스크에 3-나프탈렌-1-일-아크릴릭 산 3-(3,5-비스-터트-부톡시카르보닐아미노-페닐)-프로필 에스터(3-naphthalen-1-yl-acrylic acid 3-(3,5- bis-tert-butoxycarbonyl amino-pheyl)-propyl ester) 0.65g 을 넣고 50ml 메타크레졸에 용해시킨 후 트리플루오로아세틱 산 20ml를 첨가하여 상온에서 4시간 교반하였다. 반응혼합물을 감압농축 하여 휘발성 물질을 제거하고 50ml 메타크레졸로 희석하였다. 희석된 반응혼합물을 탄산수소나트륨으로 중화 시킨 뒤 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=3:2)로 정제하여 노란색 액상의 3-나프탈렌-1-일-아크릴릭 산 3-(3,5-디아미노-페닐)-프로필 에스터(DA-3)를 수득하여 그 NMR 데이터를 도 3에 나타내었다.(6) 3-naphthalen-1-yl-acrylic acid 3- (3,5-bis-tert-butoxycarbonylamino-phenyl) -propyl ester (3-naphthalen-1-yl- in a 100 ml round bottom flask 0.65 g of acrylic acid 3- (3,5-bis-tert-butoxycarbonyl amino-pheyl) -propyl ester) was added, dissolved in 50 ml of metacresol, and 20 ml of trifluoroacetic acid was added thereto, followed by stirring at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and diluted with 50 ml methacresol. The diluted reaction mixture was neutralized with sodium hydrogen carbonate, and then the excess salt solution was used to remove the polar solvent in the metacresol. Prepared. Then purified by silica gel column chromatography (EA: Hx = 3: 2) to give 3-naphthalen-1-yl-acrylic acid 3- (3,5-diamino-phenyl) -propyl ester as a yellow liquid (DA-3). Was obtained and the NMR data are shown in FIG.

[[ 제조예Production Example 4] 3-나프탈렌-1-일- 4] 3-naphthalen-1-yl- 아크릴릭Acrylic 산 5-(3,5- Acid 5- (3,5- 디아미노Diamino -- 페닐Phenyl )-)- 펜틸Pentyl 에스터(3- Ester (3- NaphthanlenNaphthanlen -1--One- ylyl -acrylic -acrylic acidacid 5-(3,5- 5- (3,5- diaminodiamino -- phenylphenyl )-)- pentlypently esterester ) () ( DADA -4)의 제조-4) Preparation

(1) 가열 환류장치가 장착된 250ml의 둥근바닥 플라스크에 (3-터트-부톡시 카르보닐아미노-5-포밀-페닐)-카바믹 산 터트 부틸 에스터((3-tert-Butoxy carbonylamino-5-formyl- phenyl)-carbamic acid tert butyl ester) 11.63g을 넣고 100ml 건조된 THF에 용해시킨 후, 트리에틸 4-포스포노크로토네이트(triethyl 4-phosphonocrotonate) 9.4ml와 리튬 하이드록사이드(lithium hydroxide) 1.6g을 첨가하여 70℃에서 9시간동안 환류 교반하였다. 반응 혼합물을 상온으로 식히고 셀라이트로 여과한 후 여액을 감압농축 하고, 감압농축한 혼합물을 실리카겔 컬럼 크로 마토그래피(EA:Hx=1:4)로 정제하여 노란색의 고체 화합물를 수득하였다.(1) In a 250 ml round bottom flask equipped with a heating reflux apparatus, (3-tert-butoxy carbonylamino-5-formyl-phenyl) -carbamic acid tert butyl ester ((3-tert-Butoxy carbonylamino-5- 11.63 g of formyl-phenyl) -carbamic acid tert butyl ester) was dissolved in 100 ml of dried THF, followed by 9.4 ml of triethyl 4-phosphonocrotonate and lithium hydroxide. 1.6 g was added and stirred under reflux at 70 ° C. for 9 hours. The reaction mixture was cooled to room temperature, filtered through celite, and the filtrate was concentrated under reduced pressure, and the concentrated mixture under reduced pressure was purified by silica gel column chromatography (EA: Hx = 1: 4) to obtain a yellow solid compound.

(2) 수소 반응기에 100ml의 에탄올을 넣고 5-(3,5-비스-터트-부톡시카르보닐아미노-페닐) -펜타-2,4-디에노익 산 에틸 에스터(5-(3,5-bis-tert-butoxycarbonyl amino-phenyl)-penta-2,4-dienoic acid ethyl ester) 14.6g을 용해시켰다. 촉매로서 팔라듐/탄소(Pd/C)(10%) 1g을 첨가한 후, 3.5 atm의 압력 하에서 5-6시간 환원반응을 수행하였다. 멤브레인 필터를 사용하여 팔라듐/탄소(Pd/C)를 제거하고, 여과한 반응 혼합물을 감압농축하여 백색 고체를 얻었다.(2) 100 ml of ethanol was added to a hydrogen reactor and 5- (3,5-bis-tert-butoxycarbonylamino-phenyl) -penta-2,4-dienoic acid ethyl ester (5- (3,5- 14.6 g of bis-tert-butoxycarbonyl amino-phenyl) -penta-2,4-dienoic acid ethyl ester) was dissolved. After adding 1 g of palladium / carbon (Pd / C) (10%) as a catalyst, a reduction reaction was performed for 5-6 hours under a pressure of 3.5 atm. Palladium / carbon (Pd / C) was removed using a membrane filter and the filtered reaction mixture was concentrated under reduced pressure to give a white solid.

(3) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 5-(3,5-비스-터트-부톡시카르보닐아미노-페닐) 1-아크릴릭 산 에틸 에스터(5-(3,5-bis-tert-butoxy carbonylamino-pheny)l-acrylic acid ethyl ester) 14.9g을 넣고 200ml THF에 용해시킨 후, 0℃에서 리튬 알루미늄 하이드라이드(lithium aluminum hydride) 3.4g을 천천히 넣어 5시간동안 교반하였다. 반응 혼합물에 메탄올을 천천히 가해 기체 발생이 멈출 때까지 식힌 후 ethyl ether 150ml에 넣고 소금물을 소량 (2ml)첨가하여 1시간동안 교반하였다. 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축한 후 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(3) 500 ml round bottom flask equipped with ice bath, 5- (3,5-bis-tert-butoxycarbonylamino-phenyl) 1-acrylic acid ethyl ester (5- (3,5-bis-tert- Butoxy carbonylamino-pheny) l-acrylic acid ethyl ester) was added 14.9 g, dissolved in 200 ml THF, and slowly added 3.4 g of lithium aluminum hydride at 0 ° C. and stirred for 5 hours. Methanol was slowly added to the reaction mixture, and the mixture was cooled until gas evolution stopped. The mixture was added to 150 ml of ethyl ether, and a small amount of brine (2 ml) was added thereto, followed by stirring for 1 hour. The solution from which moisture was removed with anhydrous magnesium sulfate was concentrated under reduced pressure and purified by silica gel column chromatography (EA: Hx = 1: 4) to obtain a white solid.

(4) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 [3-터트-부톡시카르보닐 아미노-5-(5-하이드록시-프로필)-페닐]-카바믹 산 터트-부틸 에스터([3-tert-Butoxycarboylamino-5-(5-hydroxy-propyl)-phenyl]-carbamic acid tert-butyl ester) 11.58g을 넣고 250ml 메카크레졸에 용해시킨 후, 3-나프탈렌-1-일-아크릴로일 클로라이드(3-naphthalen-1-yl-acryloyl chloride) 10.81g을 첨가하여 교반하였다. 0℃에서 트리에틸아민 8.2ml 을 천천히 주입 한 후 온도를 상온까지 승온시키고, 12시간동안 교반을 계속하였다. 상기 반응혼합물을 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=1:4)로 정제하여 백색의 고체를 수득하였다.(4) In a 500 ml round bottom flask equipped with an ice bath, [3-tert-butoxycarbonyl amino-5- (5-hydroxy-propyl) -phenyl] -carbamic acid tert-butyl ester ([3-tert 11.58 g of -Butoxycarboylamino-5- (5-hydroxy-propyl) -phenyl] -carbamic acid tert-butyl ester) was dissolved in 250 ml mecacresol and 3-naphthalen-1-yl-acryloyl chloride (3- 10.81 g of naphthalen-1-yl-acryloyl chloride) was added and stirred. After slowly injecting 8.2 ml of triethylamine at 0 ° C., the temperature was raised to room temperature, and stirring was continued for 12 hours. The reaction mixture is saturated with excess salt The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Subsequent purification by silica gel column chromatography (EA: Hx = 1: 4) afforded a white solid.

(5) 500ml의 둥근바닥 플라스크에 3-나프탈렌-1-일-아크릴릭 산 5-(3,5-비스-터트-부톡시카르보닐아미노-페닐)-프로필 에스터(3-naphthalen-1-yl-acrylic acid 5-(3,5-bis-tert-butoxycarbonyl amino-pheyl)-propyl ester) 14.6g 을 넣고 200ml 메타크레졸에 용해시킨 후 트리플루오로아세틱 산 100ml를 첨가하여 상온에서 4시간 교반 하였다. 반응혼합물을 감압농축 하여 휘발성 물질을 제거하고 200ml 메타크레졸로 희석하였다. 희석된 반응혼합물을 탄산수소나트륨으로 중화 시킨 뒤 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어서 실리카겔 컬럼 크로마토그래피(EA:Hx=3:2)로 정제하여 노란색 액상의 3-나프탈렌-1-일-아크릴릭 산 5-(3,5-디아미노-페닐)-펜틸 에스터( DA -4)를 수득하여 그 NMR 데이터를 도 4에 나타내었다. (5) 3-naphthalen-1-yl-acrylic acid 5- (3,5-bis-tert-butoxycarbonylamino-phenyl) -propyl ester (3-naphthalen-1-yl- in 500 ml round bottom flask 14.6 g of acrylic acid 5- (3,5-bis-tert-butoxycarbonyl amino-pheyl) -propyl ester) was added, dissolved in 200 ml of metacresol, and 100 ml of trifluoroacetic acid was added thereto, followed by stirring at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and diluted with 200 ml methacresol. The diluted reaction mixture was neutralized with sodium hydrogen carbonate and saturated salts were excess. The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Then purified by silica gel column chromatography (EA: Hx = 3: 2) to give 3-naphthalen-1-yl-acrylic acid 5- (3,5-diamino-phenyl) -pentyl ester as a yellow liquid ( DA- 4). Was obtained and the NMR data are shown in FIG.

[[ 비교제조예Comparative Production Example 1] 3,5- 1] 3,5- 디아미노Diamino 벤질  benzyl 신나메이트Cinnamate (3,5-(3,5- DiaminoDiamino benzylbenzyl cinnamatecinnamate ) () ( DADA -5)의 제조-5) Preparation

(1) 수소 반응기에 100ml의 에탄올(ethanol)을 넣고 3,5-디니트로 벤질 알코올(3,5-dinitro benzyl alcohol) 10g을 용해하였다. 촉매로서 팔라듐/탄소(Pd/C)(5%) 1g을 첨가한 후, 3.5 atm의 압력 하에서 6시간 환원반응을 수행하였다. 멤브레인 필터(Membrane filter)를 사용하여 팔라듐/탄소(Pd/C)가 제거된 반응 혼합물을 감압 농축하여 얻어진 고체를 에탄올로 재결정하여 수득물을 얻었다.(1) 100 ml of ethanol was added to a hydrogen reactor, and 10 g of 3,5-dinitro benzyl alcohol was dissolved. After adding 1 g of palladium / carbon (Pd / C) (5%) as a catalyst, a reduction reaction was performed for 6 hours under a pressure of 3.5 atm. A solid obtained by concentrating the reaction mixture from which palladium / carbon (Pd / C) was removed using a membrane filter under reduced pressure was recrystallized with ethanol to obtain a product.

(2) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 6g의 3,5-디아미노 벤질 알코올을 넣고 240ml의 1,4-다이옥산(1,4-dioxane)/물(H2O) (부피비 4/1) 혼합용매를 첨가하여 용해시킨 후, 촉매로서 탄산나트륨(Na2CO3) 13.8g과 디-터트-부틸 디카보네이트(di-tert-butyl dicarbonate; t-BOC) 23.22g을 넣고 0℃에서 5분 동안 교반하였다. 이어 온도를 상온까지 승온시킨 후 7시간동안 교반을 계속 진행하였다. 반응혼합물을 여과하여 탄산나트륨을 제거하였으며, 감암농축된 반응물에 200ml의 에틸아세테이트(ethyl acetate)를 가하여 희석하였다. 포화소금물 과량을 사용하 여 에틸아세테이트내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트(anhydrous MgSO4)로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이후 에틸아세테이트로 재결정하여 백색의 고체를 수득하였다.(2) In a 500 ml round bottom flask equipped with an ice bath, 6 g of 3,5-diamino benzyl alcohol was added and 240 ml of 1,4-dioxane / water (H 2 O) (volume ratio 4 / 1) After mixing and dissolving the mixture, 13.8 g of sodium carbonate (Na 2 CO 3 ) and 23.22 g of di-tert-butyl dicarbonate (t-BOC) were added as catalysts. Stir for minutes. Then, after the temperature was raised to room temperature, stirring was continued for 7 hours. The reaction mixture was filtered to remove sodium carbonate, and 200 ml of ethyl acetate was added to the reaction mixture. Saturated salt excess The polar solvent in ethyl acetate was removed, and the reaction product was finally concentrated under reduced pressure with anhydrous magnesium sulfate (anhydrous MgSO 4 ) to prepare a reaction product containing trace impurities. After recrystallization with ethyl acetate to give a white solid.

(3) 얼음조가 장착된 500ml의 둥근바닥 플라스크에 디-터트-부틸 5-(하이드록시 메틸)-1,3-페닐렌 디카바메이트(di-tert-butyl 5-(hydroxymethyl)-1,3-phenylene dicarbamate) 6g을 넣고 250ml 메타크레졸에 용해시킨 후, 신나모일 클로라이드(cinnamoyl chloride) 3.5g을 첨가하여 교반하였다. 0℃에서 트리에틸아민(triethylamine; TEA) 4g을 천천히 주입 한 후 온도를 상온까지 승온시키고 12시간동안 교반을 계속하였다. 반응혼합물을 포화소금물 과량을 사용하여 메타크레졸 내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어 실리카겔 컬럼 크로마토그래피(에틸아세테이트(EA):헥산(Hx)=1:4)로 정제하여 백색의 고체를 수득하였다.(3) 500 ml round bottom flask equipped with ice bath di-tert-butyl 5- (hydroxy methyl) -1,3-phenylene dicarbamate (di-tert-butyl 5- (hydroxymethyl) -1,3 6 g of -phenylene dicarbamate) was added thereto, dissolved in 250 ml metacresol, and 3.5 g of cinnamoyl chloride was added thereto and stirred. After slowly injecting 4 g of triethylamine (TEA) at 0 ° C., the temperature was raised to room temperature and stirring was continued for 12 hours. The reaction mixture is saturated with saturated salt The polar solvent in the metacresol was removed, and the reaction product was finally concentrated under reduced pressure with anhydrous magnesium sulfate to prepare a reaction product containing trace impurities. Then purified by silica gel column chromatography (ethyl acetate (EA): hexane (Hx) = 1: 4) to give a white solid.

(4) 500ml의 둥근바닥 플라스크에 3,5-비스(터트-부톡시카르보닐아미노)벤질 신나메이트(3,5-bis(tert-butoxycarbonylamino)benzyl cinnamate) 6g을 넣고 200ml 메타크레졸에 용해시킨 후 트리플로오로아세틱산(triflouroacetic acid; CF3COOH) 100ml를 첨가하여 상온에서 4시간 교반하였다. 반응혼합물을 감압농축 하여 휘발성 물질을 제거하고 250ml 메타크레졸로 희석하였다. 희석된 반응혼합물을 탄산수소나트륨으로 중화 시킨 뒤 포화소금물 과량을 사용하여 메타크레졸내의 극성용제를 제거하였으며, 최종적으로 무수 마그네슘설페이트로 수분을 제거한 용액을 감압 농축하여 미량의 불순물이 함유된 반응생성물을 제조하였다. 이어 실리카겔 컬럼 크로마토그래피(EA:Hx=3:2)로 정제하여 노란색의 액상 화합물를 수득하였다.(4) 6 g of 3,5-bis (tert-butoxycarbonylamino) benzyl cinnamate was added to a 500 ml round bottom flask and dissolved in 200 ml methacresol. 100 ml of triflouroacetic acid (CF 3 COOH) was added and stirred at room temperature for 4 hours. The reaction mixture was concentrated under reduced pressure to remove volatiles and diluted with 250 ml methacresol. The diluted reaction mixture was neutralized with sodium hydrogen carbonate and saturated salts were excess. The polar solvent in the metacresol was removed, and finally, a solution obtained by removing water with anhydrous magnesium sulfate was concentrated under reduced pressure to prepare a reaction product containing trace impurities. Then purified by silica gel column chromatography (EA: Hx = 3: 2) to give a yellow liquid compound.

[제조예 5-] 알킬기를 갖는 지방족 산이무수물(화학식 3)의 제조Preparation Example 5- Preparation of Aliphatic Acid Anhydride Having the Alkyl Group (Formula 3)

[화학식 3][Formula 3]

Figure 112007042667994-pat00031
Figure 112007042667994-pat00031

[[ 제조예Production Example 5] 1,2,3,4-시클로부탄테트라카르복실산이무수물( 5] 1,2,3,4-cyclobutanetetracarboxylic dianhydride ( CBDACBDA )의 제조Manufacturing

16개의 300nm 자외선 램프가 부착된 2L의 석영유리 광반응기에 교반기와 냉각기를 설치하고, 석영유리 반응기에 아세트산에틸 250ml와 무수말레익산(maleic anhydride) 100g을 넣고 완전히 혼합되도록 교반하였다. 자외선 램프로 인하여 온도가 너무 높게 올라가는 것을 방지하기 위해 공랭식 냉각기를 먼저 가동시킨 후 자외선 램프를 켜서 240시간 동안 반응기 벽에 반응물이 달라붙지 않도록 교반시켜 주면서 광반응 하여 71g의 흰색 고체를 얻었다. 얻어진 흰색의 고체를 걸러낸 다음 60 ℃의 감압건조기에서 24시간동안 건조하였다. 건조된 고체를 아세트산무수물에 넣고 녹이면서 150℃까지 천천히 가열한 후 24시간동안 반응하였다. 반응용액을 뜨거운 상태에서 거름종이로 불순물을 걸러낸 후 0 ℃ 이하의 냉장고에 넣어 냉각시킨 상태로 24시간동안 재결정해서 노란색의 고체를 얻었다. 얻어진 고체를 거른 후 1,4-디옥신으로 3회 세척하여 아세트산무수물을 제거한 다음 60 ℃의 감압오븐에서 48시간동안 건조시켜서 1,2,3,4-시클로부탄테트라카르복실산이무수물(CBDA) 64g을 수득하여 그 NMR 데이터를 도 5에 나타내었다. A stirrer and a cooler were installed in a 2L quartz glass photoreactor equipped with 16 300 nm UV lamps, and 250 ml of ethyl acetate and 100 g of maleic anhydride were added to the quartz glass reactor, and the mixture was stirred. In order to prevent the temperature from rising too high due to the ultraviolet lamp, the air-cooled cooler was first started, and the ultraviolet lamp was turned on to react with the reactant to prevent the reactant from sticking to the reactor wall for 240 hours, thereby obtaining 71 g of a white solid. The white solid obtained was filtered and dried in a vacuum dryer at 60 ° C. for 24 hours. The dried solid was slowly added to anhydrous acetic anhydride, heated slowly to 150 ° C., and reacted for 24 hours. The reaction solution was filtered through a filter paper in a hot state and then recrystallized in a refrigerator at 0 ° C. or lower for 24 hours to obtain a yellow solid. The obtained solid was filtered and washed three times with 1,4-dioxin to remove acetic anhydride, and then dried in a vacuum oven at 60 ° C. for 48 hours to produce 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA). 64 g were obtained and the NMR data thereof are shown in FIG. 5.

[[ 제조예Production Example 6] 1,3-디메틸-1,2,3,4-시클로부탄테트라카르복실산이무수물( 6] 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride ( DMDM -- CBDACBDA )의 제조Manufacturing

16개의 300nm 자외선 램프가 부착된 2L의 석영유리 광반응기에 교반기와 냉각기를 설치하고, 석영유리 반응기에 아세트산에틸 250ml와 무수시트라콘산(citraconic anhydride) 100g 을 넣고 완전히 혼합되도록 교반하였다. 자외선 램프로 인하여 온도가 너무 높게 올라가는 것을 방지하기 위해 공랭식 냉각기를 먼저 가동시킨 후 자외선 램프를 켜서 150시간 동안 반응기 벽에 반응물이 달라붙지 않도록 교반시켜 주면서 광반응 하여 40g의 흰색 고체를 얻었다. 얻어진 흰색의 고체를 걸러낸 다음 60 ℃의 감압건조기에서 24시간동안 건조하였다. 건조된 고체를 아세트산무수물에 넣고 녹이면서 150 ℃까지 천천히 가열한 후 24시간동안 반응하였다. 반응용액을 뜨거운 상태에서 거름종이로 불순물을 걸러낸 후 0 ℃ 이하의 냉장고에 넣어 냉각시킨 상태로 24시간동안 재결정해서 노란색의 고체를 얻었다. 얻어 진 고체를 거른 후 1,4-디옥신으로 3회 세척하여 아세트산무수물을 제거한 다음 60 ℃ 의 감압오븐에서 48시간동안 건조시켜서 연노란색의 1,3-디메틸-1,2,3,4-시클로부탄테트라카르복실산이무수물(DM-CBDA) 35g을 수득하여 그 NMR 데이터를 도 6에 나타내었다.A stirrer and a cooler were installed in a 2L quartz glass photoreactor equipped with 16 300 nm UV lamps, and 250 ml of ethyl acetate and 100 g of citraconic anhydride were added to the quartz glass reactor, and the mixture was thoroughly mixed. In order to prevent the temperature from rising too high due to the ultraviolet lamp, the air-cooled cooler was started first, and then the ultraviolet lamp was turned on and photoreacted while stirring to prevent the reactants from sticking to the reactor wall for 150 hours, thereby obtaining 40 g of a white solid. The white solid obtained was filtered and dried in a vacuum dryer at 60 ° C. for 24 hours. The dried solid was added to anhydrous acetic anhydride and slowly heated to 150 ° C. while melting to react for 24 hours. The reaction solution was filtered through a filter paper in a hot state and then recrystallized in a refrigerator at 0 ° C. or lower for 24 hours to obtain a yellow solid. The obtained solid was filtered, washed three times with 1,4-dioxin to remove acetic anhydride, and then dried in a vacuum oven at 60 ° C. for 48 hours to give a pale yellow 1,3-dimethyl-1,2,3,4- 35 g of cyclobutanetetracarboxylic dianhydride (DM-CBDA) was obtained and its NMR data is shown in FIG. 6.

[[ 실시예Example 1-16 및  1-16 and 비교예Comparative example 1-6]  1-6] 폴리아믹산Polyamic acid 광배향막의Photo-alignment film 제조 Produce

하기 표 1에 기재된 구성성분 및 몰%로 실시예 1-16 및 비교예 1-6의 폴리아믹산 광배향막을 제조하였으며, 상세한 제조방법은 하기와 같다.The polyamic acid photoalignment films of Examples 1-16 and Comparative Examples 1-6 were prepared using the constituents and mole% shown in Table 1 below, and the detailed preparation method is as follows.

[표 1] 폴리아믹산의 단량체 조성TABLE 1 Monomer Composition of Polyamic Acid

Figure 112007042667994-pat00032
Figure 112007042667994-pat00032

Figure 112007042667994-pat00033
Figure 112007042667994-pat00033

[[ 실시예Example 1]  One] 폴리아믹산Polyamic acid 광배향막(PAA-1)의Of photo-alignment layer (PAA-1) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1에 의해 만들어진 DA-1 3.44 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-1)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며 그 NMR 데이터를 도 7에 나타내었다. 3.44 g (0.01 mole) of DA-1 produced in Preparation Example 1 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injection device, followed by nitrogen. 1.96 g (0.01 mole) of CBDA in solid form prepared in Preparation Example 5 was slowly added while passing the gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After the polarized ultraviolet light of 200 mJ / cm 2 intensity at 300 ~ 400 nm wavelength to obtain a photo-oriented polyamic acid thin film ( PAA-1 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2, and the NMR data thereof are shown in FIG.

나타내었으며, 상기 수득된 폴리아믹산 용액의 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, 0.14 ㎛의 두께로 스핀 코팅한 후, 230 ℃의 온도에서 30 분동 안 열경화하여 얻은 박막에 편광자외선을 조사하여 제작한 액정 셀의 선경사각 및 전압보유율 측정 결과를 하기 표 3에 나타내었다. 노광시 자외선의 파장은 300~460nm 범위로 조절하였으며, 200~1,000 mJ/cm2의 조사광량에 의해 액정의 균일한 배향이 관찰되었다. 이때 사용한 액정은 Merck사의 E-7을 사용하였으며, 편광자외선은 상기 박막과 자외선램프사이에 편광판을 개입시켜 편광자외선을 발생시켰으며, 이때 사용한 편광판은 편광도 99% 이상, 광량 투과율 30± 2% 이었다. 액정의 배향상태는 편광현미경을 사용하여 육안으로 관찰하였으며, 결정회전법(crystal rotation method)을 이용하여 각 액정셀의 선경사각(pretilt angles)을 측정하였고, 25℃, 3V 하에서 전압보유율을 측정하였다.After maintaining the solution viscosity at room temperature of the obtained polyamic acid solution at 30 cp, spin-coated to a thickness of 0.14 μm, polarized ultraviolet ray was applied to the thin film obtained by thermosetting at a temperature of 230 ° C. for 30 minutes. Table 3 shows the measurement results of the pretilt angle and voltage retention of the prepared liquid crystal cell. The wavelength of the ultraviolet ray during exposure was adjusted in the range of 300 to 460 nm, and uniform alignment of the liquid crystal was observed by the irradiation amount of 200 to 1,000 mJ / cm 2 . In this case, the liquid crystal used was Merck E-7, and the polarized ultraviolet rays generated polarized ultraviolet rays through the polarizing plate between the thin film and the ultraviolet lamp, and the polarizing plates used were more than 99% polarization degree and 30 ± 2% light transmittance. It was. The alignment state of the liquid crystal was visually observed using a polarizing microscope, the pretilt angles of each liquid crystal cell were measured using a crystal rotation method, and the voltage retention was measured at 25 ° C. and 3V. .

[[ 실시예Example 2]  2] 폴리아믹산Polyamic acid 광배향막(PAA-2)의Of photo-alignment layer (PAA-2) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 2에 의해 만들어진 DA -2 3.18 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -2)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.18 g (0.01 mole) of DA- 2 produced in Preparation Example 2 were dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. 1.96 g (0.01 mole) of CBDA in solid form prepared in Preparation Example 5 was slowly added while passing the gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiation of polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 2 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 3]  3] 폴리아믹산Polyamic acid 광배향막Photo-alignment layer (( PAAPAA -3) 의 제조-3) manufacturing

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 3에 의해 만들어진 DA -3 3.48 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -3)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.48 g (0.01 mole) of DA - 3 produced in Preparation Example 3 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. 1.96 g (0.01 mole) of CBDA in solid form prepared in Preparation Example 5 was slowly added while passing the gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiation of polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 3 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 4] 폴리아믹산 광배향막(PAA-4)의 제조Example 4 Preparation of Polyamic Acid Photoalignment Film (PAA-4)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 4에 의해 만들어진 DA-4 3.76 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -4)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.76 g (0.01 mole) of DA-4 produced in Preparation Example 4 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. 1.96 g (0.01 mole) of CBDA in solid form prepared in Preparation Example 5 was slowly added while passing the gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiation of polarized ultraviolet light of the intensity to obtain a photo-aligned polyamic acid thin film ( PAA- 4 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 5]  5] 폴리아믹산Polyamic acid 광배향막(PAA-5)의Of photo-alignment layer (PAA-5) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1에 의해 만들어진 DA -1 3.44 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-5)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.44 g (0.01 mole) of DA- 1 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 1 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then solid CBDA prepared in Preparation Example 5 while passing through nitrogen gas. 3.92 g (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After irradiation with polarized ultraviolet rays of 200 mJ / cm 2 intensity at a wavelength of 300 ~ 400 nm to obtain a photo-oriented polyamic acid thin film ( PAA-5 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 6] 폴리아믹산 광배향막(PAA-6)의 제조Example 6 Preparation of Polyamic Acid Photoalignment Film (PAA-6)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 2에 의해 만들어진 DA-2 3.18 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -6)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.18 g (0.01 mole) of DA-2 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 2 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. After dissolving 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) in N-methyl-2-pyrrolidone, 3.92 g (0.02 mole) of solid CBDA prepared in Preparation Example 5 was slowly added while passing through nitrogen gas. . At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiating polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 6 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 7]  7] 폴리아믹산Polyamic acid 광배향막(PAA-7)의Of photo-alignment layer (PAA-7) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 3에 의해 만들어진 DA -3 3.48 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-7)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과 를 하기 표 3에 각각 나타내었다.3.48 g (0.01 mole) of DA- 3 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 3 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then solid CBDA prepared in Preparation Example 5 while passing through nitrogen gas. 3.92 g (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After the polarized ultraviolet ray of 200 mJ / cm 2 intensity at 300 ~ 400 nm wavelength to obtain a photo-oriented polyamic acid thin film ( PAA-7 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the results of the pretilt angle and the voltage retention measured under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 8] 폴리아믹산 광배향막(PAA-8)의 제조Example 8 Preparation of Polyamic Acid Photoalignment Film (PAA-8)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 4에 의해 만들어진 DA-4 3.76 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -8)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.76 g (0.01 mole) of DA-4 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 4 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then solid CBDA prepared in Preparation Example 5 while passing through nitrogen gas. 3.92 g (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiating polarized ultraviolet light of the intensity to obtain a photo-aligned polyamic acid thin film ( PAA- 8 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 9]  9] 폴리아믹산Polyamic acid 광배향막(PAA-9)의Of photo-alignment layer (PAA-9) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과 시키면서 제조예 1에 의해 만들어진 DA -1 3.44 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM - CBDA 2.24 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-9)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.44 g (0.01 mole) of DA- 1 produced in Preparation Example 1 were dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. While passing the gas, 2.24 g (0.01 mole) of DM - CBDA in the solid phase prepared in Preparation Example 6 were slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After the polarized ultraviolet ray of 200 mJ / cm 2 intensity at 300 ~ 400 nm wavelength to obtain a photo-oriented polyamic acid thin film ( PAA-9 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 10] 폴리아믹산 광배향막(PAA-10)의 제조Example 10 Preparation of Polyamic Acid Photoalignment Film (PAA-10)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 2에 의해 만들어진 DA-2 3.18 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM-CBDA 2.24 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -10)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.18 g (0.01 mole) of DA-2 produced in Preparation Example 2 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. While passing the gas, 2.24 g (0.01 mole) of DM-CBDA in the solid phase prepared in Preparation Example 6 was slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiating polarized ultraviolet light of the intensity to obtain a photo-aligned polyamic acid thin film ( PAA- 10 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 11]  11] 폴리아믹산Polyamic acid 광배향막(PAA-11)의Of photo-alignment layer (PAA-11) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 1에 의해 만들어진 DA -1 3.44 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM - CBDA 4.48 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-11)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으 며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.44 g (0.01 mole) of DA- 1 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 1 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then slowly added 4.48 g (0.02 mole) of DM - CBDA prepared in Preparation Example 6 while passing through nitrogen gas. Added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After the polarized ultraviolet light of 200 mJ / cm 2 intensity at 300 ~ 400 nm wavelength to obtain a photo-oriented polyamic acid thin film ( PAA-11 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the results of the measurement of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 12] 폴리아믹산 광배향막(PAA-12)의 제조Example 12 Preparation of Polyamic Acid Photoalignment Film (PAA-12)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 2에 의해 만들어진 DA-2 3.18 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM-CBDA 4.48 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -12)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.18 g (0.01 mole) of DA-2 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 2 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then slowly added 4.48 g (0.02 mole) of DM-CBDA prepared in Preparation Example 6 while passing through nitrogen gas. Added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiation of polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 12 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 13]  13] 폴리아믹산Polyamic acid 광배향막(PAA-13)의Of photo-alignment layer (PAA-13) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 3에 의해 만들어진 DA -3 3.48 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM - CBDA 2.24 g (0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-13)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.48 g (0.01 mole) of DA - 3 produced in Preparation Example 3 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. While passing the gas, 2.24 g (0.01 mole) of DM - CBDA in solid phase prepared in Preparation Example 6 were slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After irradiating polarized ultraviolet rays of 200 mJ / cm 2 intensity at a wavelength of 300 ~ 400 nm to obtain a photo-oriented polyamic acid thin film ( PAA-13 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 14]  14] 폴리아믹산Polyamic acid 광배향막(PAA-14)의Of photo-alignment layer (PAA-14) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 4에 의해 만들어진 DA-4 3.76 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM-CBDA 2.24 g (0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -14)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.76 g (0.01 mole) of DA-4 produced in Preparation Example 4 was dissolved in N-methyl-2-pyrrolidone while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector, followed by nitrogen. While passing the gas, 2.24 g (0.01 mole) of DM-CBDA in solid phase prepared in Preparation Example 6 was slowly added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiating polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 14 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 실시예Example 15]  15] 폴리아믹산Polyamic acid 광배향막(PAA-15)의Of photo-alignment layer (PAA-15) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 3에 의해 만들어진 DA -3 3.48 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g (0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM - CBDA 4.48 g (0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹 산 박막(PAA-15)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.48 g (0.01 mole) of DA- 3 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 3 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, followed by nitrogen gas, followed by solid DM - CBDA prepared in Preparation Example 6. 4.48 g (0.02 mole) was added slowly. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After irradiation with polarized ultraviolet rays of 200 mJ / cm 2 intensity at a wavelength of 300 ~ 400 nm to obtain a photo-oriented polyamic acid thin film ( PAA-15 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[실시예 16] 폴리아믹산 광배향막(PAA-16)의 제조Example 16 Preparation of Polyamic Acid Photoalignment Film (PAA-16)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 제조예 4에 의해 만들어진 DA-4 3.76 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 6에 의해 만들어진 고체상의 DM-CBDA 4.48 g (0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 200 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -16)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.3.76 g (0.01 mole) of DA-4 and 4- (4-aminobenzyl) benzeneamine (4- (4) produced by Preparation Example 4 while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. 1.98 g (0.01 mole) of -aminobenzyl) benzenamine) was dissolved in N-methyl-2-pyrrolidone, and then slowly added 4.48 g (0.02 mole) of DM-CBDA prepared in Preparation Example 6 while passing through nitrogen gas. Added. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. 200 mJ / cm 2 at a wavelength of 300 to 400 nm Irradiating polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 16 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 비교예Comparative example 1]  One] 폴리아믹산Polyamic acid 광배향막(PAA-17)의Of photo-alignment layer (PAA-17) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 비교제조예 1에 의해 만들어진 DA -5 2.68 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 600mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-17)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.After slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injection device, 2.68 g (0.01 mole) of DA- 5 produced by Comparative Production Example 1 was dissolved in N-methyl-2-pyrrolidone, CBDA of solid phase made by Preparation Example 5 while passing nitrogen gas 1.96 g (0.01 mole) was added slowly. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After the polarized ultraviolet rays of 600mJ / cm 2 intensity at 300 ~ 400 nm wavelength to obtain a photo-oriented polyamic acid thin film ( PAA-17 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[비교예 2] 폴리아믹산 광배향막(PAA-18)의 제조Comparative Example 2 Preparation of Polyamic Acid Photoalignment Film (PAA-18)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 비교제조예 1에 의해 만들어진 DA -5 2.68 g(0.01 mole) 및 4-(4-아미노벤질)벤젠아민(4-(4-aminobenzyl)benzenamine) 1.98 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 3.92 g(0.02 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 600 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -18)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.2.68 g (0.01 mole) of DA- 5 and 4- (4-aminobenzyl) benzeneamine (4- (made by Comparative Preparation Example 1) while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. Dissolve 1.98 g (0.01 mole) of 4-aminobenzyl) benzenamine) in N-methyl-2-pyrrolidone, and then slowly add 3.92 g (0.02 mole) of solid CBDA prepared in Preparation Example 5 while passing through nitrogen gas. It was. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After 600 mJ / cm 2 at 300-400 nm wavelength Irradiating polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 18 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 비교예Comparative example 3]  3] 폴리아믹산Polyamic acid 광배향막(PAA-19)의Of photo-alignment layer (PAA-19) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 벤젠-1,4-디아민(benzene-1,4-diamine) 1.08 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 CBDA 1.96 g (0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파 장에서 1500 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -19)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.1.08 g (0.01 mole) of benzene-1,4-diamine was added to N-methyl-2-pyrroli while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. After dissolving in pigs, 1.96 g (0.01 mole) of CBDA produced in Preparation Example 5 was slowly added while passing through nitrogen gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After 1500 mJ / cm 2 at 300 ~ 400 nm wavelength Irradiation of polarized ultraviolet light of the intensity to obtain a photo-aligned polyamic acid thin film ( PAA- 19 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[비교예 4] 폴리아믹산 광배향막(PAA-20)의 제조Comparative Example 4 Preparation of Polyamic Acid Photoalignment Film (PAA-20)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 벤젠-1,3-디아민(benzene-1,3-diamine) 1.08 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 1,500 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -20)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.1.08 g (0.01 mole) of benzene-1,3-diamine was added to N-methyl-2-pyrroli while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. After dissolving in pigs, 1.96 g (0.01 mole) of solid CBDA produced in Preparation Example 5 was slowly added while passing through nitrogen gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After 1500 mJ / cm 2 at 300-400 nm wavelength Irradiation of polarized ultraviolet light of the intensity to obtain a photo-oriented polyamic acid thin film ( PAA- 20 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[[ 비교예Comparative example 5]  5] 폴리아믹산Polyamic acid 광배향막(PAA-21)의Of photo-alignment layer (PAA-21) 제조 Produce

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 4-(4-아미노페녹시)벤젠아민(4-(4-aminophenoxy)benzenamine) 2.00 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 1,500 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA-21)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.2.00 g (0.01 mole) of N-methyl (4- (4-aminophenoxy) benzenamine) was added slowly while passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. After dissolving in 2-pyrrolidone, 1.96 g (0.01 mole) of CBDA of solid phase prepared in Preparation Example 5 was slowly added while passing through nitrogen gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After irradiating polarized ultraviolet rays of 1,500 mJ / cm 2 intensity at a wavelength of 300 ~ 400 nm to obtain a photo-oriented polyamic acid thin film ( PAA-21 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[비교예 6] 폴리아믹산 광배향막(PAA-22)의 제조Comparative Example 6 Preparation of Polyamic Acid Photoalignment Film (PAA-22)

교반기, 질소주입장치가 부착된 500 ml의 반응기에 질소가스를 서서히 통과시키면서 4-(2-(4-아미노페닐)-1,1,1,3,3,3-헥사플루오로프로판-2-일)벤젠아민(4-(2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl)benzenamine) 3.34 g(0.01 mole)을 N-메틸-2-피롤리돈에 용해시킨 후, 질소가스를 통과시키면서 제조예 5에 의해 만들어진 고체상의 CBDA 1.96 g(0.01 mole)을 서서히 첨가하였다. 이때 고형분 농도(solid content)는 15 중량%로 고정하였으며, 반응온도를 0 ℃ 이하로 유지시키면서 36시간 동안 교반하여 폴리아믹산 용액을 수득하였다. 상기 수득된 폴리아믹산 용액을 상온에서의 용액 점도를 30 cp로 유지시킨 뒤, ITO 유리판 위에 0.11 ㎛의 두께로 스핀 코팅하여 90 ℃의 온도에서 2 분, 230 ℃의 온도에서 30 분동안 열경화한 후 300~400 nm 파장에서 1,500 mJ/cm2 세기의 편광자외선을 조사하여 광배향된 폴리아믹산 박막(PAA -22)을 수득하였다. 또한 제조한 폴리아믹산 박막의 물성을 하기 표 2에 나타내었으며, 또한 실시예 1과 동일한 조건에서 선경사각 및 전압보유율 측정결과를 하기 표 3에 각각 나타내었다.4- (2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane-2- while slowly passing nitrogen gas through a 500 ml reactor equipped with a stirrer and a nitrogen injector. I) benzeneamine (4- (2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropan-2-yl) benzenamine) 3.34 g (0.01 mole) N-methyl-2-pi After dissolving in rolidone, 1.96 g (0.01 mole) of CBDA of solid phase prepared in Preparation Example 5 was slowly added while passing through nitrogen gas. At this time, the solid content (solid content) was fixed to 15% by weight, and stirred for 36 hours while maintaining the reaction temperature below 0 ℃ to obtain a polyamic acid solution. The obtained polyamic acid solution was maintained at a solution viscosity of 30 cp at room temperature, spin-coated to a thickness of 0.11 μm on an ITO glass plate, and thermally cured at 90 ° C. for 2 minutes and at 230 ° C. for 30 minutes. After irradiating polarized ultraviolet light of 1,500 mJ / cm 2 intensity at a wavelength of 300 ~ 400 nm to obtain a photo-oriented polyamic acid thin film ( PAA- 22 ). In addition, the physical properties of the prepared polyamic acid thin film are shown in Table 2 below, and the measurement results of the pretilt angle and the voltage retention under the same conditions as in Example 1 are shown in Table 3, respectively.

[표 2] 폴리아믹산 수지를 이용한 광배향막의 특성[Table 2] Characteristics of optical alignment layer using polyamic acid resin

Figure 112007042667994-pat00034
Figure 112007042667994-pat00034

상기 표 2에서 나타난 바와 같이, 본 발명에 따른 폴리아믹산 수지는 0.3 dL/g 이상의 고유점도를 가지는 것으로 확인되었다. 또한 상기 수지들은 용매주형에 의한 필름성형성 및 기계적 특성이 매우 우수한 것으로 나타났다. As shown in Table 2, the polyamic acid resin according to the present invention was confirmed to have an intrinsic viscosity of 0.3 dL / g or more. In addition, the resins were found to have excellent film forming and mechanical properties by solvent casting.

상기 표 2에서 나타난 바와 같이, 광반응형 방향족 고리 측쇄기가 도입된 실시예 1 내지 16의 폴리아믹산으로부터 제조된 본 발명에 따른 폴리아믹산 박막의 연필경도는 4H 이상으로, 이들이 도입되지 않은 비교예 1 내지 6의 폴리아믹산으로부터 제조된 박막의 연필경도와 비교하여 크게 개선되었다.As shown in Table 2, the pencil hardness of the polyamic acid thin film according to the present invention prepared from the polyamic acid of Examples 1 to 16 with the photoreactive aromatic ring side chain group introduced is not less than 4H, Comparative Example 1 Compared with the pencil hardness of the thin film prepared from the polyamic acid of 6 to 6 was greatly improved.

[표 3] 폴리아믹산 수지를 이용한 액정 셀의 특성[Table 3] Characteristics of liquid crystal cell using polyamic acid resin

Figure 112007042667994-pat00035
Figure 112007042667994-pat00035

상기 표 3에 나타난 바와 같이, 실시예 1~16으로부터 제조된 본 발명에 따른 폴리아믹산을 이용하여 제조된 액정 셀은 모든 경우에 있어서 200 mJ/cm2의 낮은 광량에서 우수한 배향성을 보였으며, 본 발명에서 제조된 신규한 방향족 고리 측쇄기를 함유하는 방향족 디아민이 도입되지 않은 비교예 3~6에 비해 낮은 광량에서 우 수한 배향성이 나타남을 알 수 있었다. 따라서 상대적으로 낮은 선경사각 및 우수한 전압보유율을 나타내었다. 실시예 1~16의 경우 선경사각은 0.05~0.25° 정도로서 비교예 1~6의 경우보다 감소하였으며, 상온에서의 전압보유율은 약 99% 이상인 결과를 나타내었다.As shown in Table 3, the liquid crystal cell prepared using the polyamic acid according to the present invention prepared from Examples 1 to 16 showed excellent orientation at low light amount of 200 mJ / cm 2 in all cases. Compared with Comparative Examples 3 to 6, in which the aromatic diamine containing the novel aromatic ring side chain group prepared in the present invention was not introduced, it was found that excellent orientation was obtained at a low light amount. Therefore, it showed relatively low pretilt angle and excellent voltage retention. In the case of Examples 1 to 16, the pretilt angle was about 0.05 to 0.25 °, which was lower than that of Comparative Examples 1 to 6, and the voltage retention at room temperature was about 99% or more.

즉, 본 발명에서 제조된 실시예 1~16의 폴리아믹산으로부터 제작된 액정셀은 낮은 선경사각 및 높은 전압보유율이 요구되는 평면구동형(in plane switching, IPS) TFT-TN 및 STN LCD용 액정배향막으로의 사용에 적합한 특성을 나타냄을 확인하였다.That is, the liquid crystal cell manufactured from the polyamic acid of Examples 1 to 16 manufactured in the present invention is a liquid crystal alignment film for in-plane switching (IPS) TFT-TN and STN LCD requiring low pretilt angle and high voltage retention. It was confirmed that the properties suitable for use as.

상기한 바와 같이, 본 발명에 의해 광투과성, 내열성, 기계적 특성이 매우 우수할 뿐만 아니라 우수한 광배향 특성, 낮은 선경사각 및 우수한 전압보유율을 갖는 새로운 구조의 액정배향막이 제조되었으며, 이들은 까다로운 전기광학적 특성이 요구되는 TFT-TN 및 STN LCD용 액정배향막 및 각종 첨단 내열구조 재료로 유용함이 확인되었다.As described above, according to the present invention, a liquid crystal aligning film having a new structure having not only excellent light transmittance, heat resistance, and mechanical properties but also excellent light alignment property, low pretilt angle and excellent voltage retention is produced, and these are demanding electro-optical properties. It has been found to be useful as the liquid crystal alignment film for TFT-TN and STN LCDs required and various advanced heat-resistant structural materials.

본 발명에서는 기재된 실시예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical spirit of the present invention, and such modifications and modifications belong to the appended claims.

Claims (13)

하기 화학식 1로 표시되는 신규한 방향족 디아민 화합물.The novel aromatic diamine compound represented by following formula (1). [화학식 1][Formula 1]
Figure 112007042667994-pat00036
Figure 112007042667994-pat00036
 [상기 화학식 1에서 [In Formula 1 a는 1 내지 10의 정수이며;a is an integer from 1 to 10; b는 0 내지 10의 정수이며;b is an integer from 0 to 10; b가 1 내지 10의 정수인 경우 A는
Figure 112007042667994-pat00037
이며;when b is an integer from 1 to 10, then A is
Figure 112007042667994-pat00037
Is; R1, R2, R3, R4 및 R5는 서로 독립적으로 할로겐이 치환되거나 치환되지 않은 (C1-C10)알킬, 시아노, 니트로, 카복실산 또는 아미노카보닐이고;R 1 , R 2 , R 3 , R 4 and R 5 are independently of each other a substituted or unsubstituted (C1-C10) alkyl, cyano, nitro, carboxylic acid or aminocarbonyl; b가 0인 경우 A는
Figure 112007042667994-pat00038
이다.]If b is 0 then A is
Figure 112007042667994-pat00038
to be.] 하기 화학식 1의 방향족 고리 측쇄기를 함유하는 방향족 디아민 화합물을 단량체로 함유하는 하기 화학식 2로 표시되는 폴리아믹산.The polyamic acid represented by following formula (2) containing the aromatic diamine compound containing the aromatic ring side chain group of following formula (1) as a monomer. [화학식 1][Formula 1]
Figure 112007042667994-pat00039
Figure 112007042667994-pat00039
 [화학식 2][Formula 2]
Figure 112007042667994-pat00040
Figure 112007042667994-pat00040
 [[상기 화학식 1 및 화학식 2에서 [[In Formula 1 and Formula 2 a, b, A, R1, R2, R3, R4 및 R5는 청구항 제1항의 정의와 동일하며;a, b, A, R 1 , R 2 , R 3 , R 4 and R 5 are as defined in claim 1; m은 1 내지 500의 정수이고;m is an integer from 1 to 500;
Figure 112007042667994-pat00041
는
Figure 112007042667994-pat00042
,
Figure 112007042667994-pat00043
,
Figure 112007042667994-pat00044
,
Figure 112007042667994-pat00045
,
Figure 112007042667994-pat00046
중에서 선택된 1종 또는 2종 이상의 4가기이며;
Figure 112007042667994-pat00041
Is
Figure 112007042667994-pat00042
,
Figure 112007042667994-pat00043
,
Figure 112007042667994-pat00044
,
Figure 112007042667994-pat00045
,
Figure 112007042667994-pat00046
1 type, or 2 or more types of tetravalent groups chosen from; B는 화학결합이거나 (C1-C2)알킬렌,
Figure 112007042667994-pat00047
,
Figure 112007042667994-pat00048
,
Figure 112007042667994-pat00049
,
Figure 112007042667994-pat00050
,
Figure 112007042667994-pat00051
,
Figure 112007042667994-pat00052
또는
Figure 112007042667994-pat00053
이고, 상기 알킬렌은 플루오르가 치환되거나 치환되지 않은 (C1-C5)알킬이 더 치환될 수 있으며;B is a chemical bond or (C1-C2) alkylene,
Figure 112007042667994-pat00047
,
Figure 112007042667994-pat00048
,
Figure 112007042667994-pat00049
,
Figure 112007042667994-pat00050
,
Figure 112007042667994-pat00051
,
Figure 112007042667994-pat00052
or
Figure 112007042667994-pat00053
Wherein the alkylene may be further substituted with (C1-C5) alkyl which is substituted or unsubstituted fluorine; R11, R12, R13 및 R14는 서로 독립적으로 수소, (C1-C10)알킬 또는 페닐이며;R 11 , R 12 , R 13 and R 14 are independently of each other hydrogen, (C1-C10) alkyl or phenyl;
Figure 112007042667994-pat00054
는
Figure 112007042667994-pat00055
,
Figure 112007042667994-pat00056
,
Figure 112007042667994-pat00057
,
Figure 112007042667994-pat00058
,
Figure 112007042667994-pat00059
,
Figure 112007042667994-pat00060
,
Figure 112007042667994-pat00061
,
Figure 112007042667994-pat00062
,
Figure 112007042667994-pat00063
,
Figure 112007042667994-pat00064
,
Figure 112007042667994-pat00065
,
Figure 112007042667994-pat00066
중에서 선택된 1종 또는 2종 이상의 2가기로서, 상기 구조식 (g)의 방향족 고리 측쇄를 가지는 방향족 2가기를 반드시 포함한다.]
Figure 112007042667994-pat00054
Is
Figure 112007042667994-pat00055
,
Figure 112007042667994-pat00056
,
Figure 112007042667994-pat00057
,
Figure 112007042667994-pat00058
,
Figure 112007042667994-pat00059
,
Figure 112007042667994-pat00060
,
Figure 112007042667994-pat00061
,
Figure 112007042667994-pat00062
,
Figure 112007042667994-pat00063
,
Figure 112007042667994-pat00064
,
Figure 112007042667994-pat00065
,
Figure 112007042667994-pat00066
And one or two or more divalent groups selected from the foregoing, and must include an aromatic divalent group having an aromatic ring side chain of the formula (g).] 제 2 항에 있어서,The method of claim 2, 상기 폴리아믹산은 광배향막용인 것을 특징으로 하는 폴리아믹산.The polyamic acid is a polyamic acid, characterized in that for the optical alignment film. 제 2 항에 있어서, The method of claim 2, 상기 폴리아믹산은 고유점도가 0.3 내지 2.0 dL/g의 범위이며, 중량평균분자량이 10,000 내지 500,000 g/mol의 범위인 것을 특징으로 하는 폴리아믹산.The polyamic acid is intrinsic viscosity is in the range of 0.3 to 2.0 dL / g, polyamic acid, characterized in that the weight average molecular weight is in the range of 10,000 to 500,000 g / mol. 제 2 항에 있어서, The method of claim 2, 상기 폴리아믹산의 이미드화 온도범위가 200 내지 350℃인 것을 특징으로 하는 폴리아믹산.Polyamic acid, characterized in that the imidation temperature range of the polyamic acid is 200 to 350 ℃. 제 2 항에 있어서, The method of claim 2, 상기 폴리아믹산은 디메틸아세트아미드, 디메틸포름아미드, N-메틸-2-피롤리돈, 아세톤, 에틸아세테이트, 메타-크레졸, 테트라히드로퓨란 및 감마-부티로락톤 중에서 선택된 용매에 대해 상온에서 용해되는 것을 특징으로 하는 폴리아믹산.The polyamic acid is dissolved at room temperature for a solvent selected from dimethylacetamide, dimethylformamide, N -methyl-2-pyrrolidone, acetone, ethyl acetate, meta-cresol, tetrahydrofuran and gamma-butyrolactone. Polyamic acid characterized by the above. 제 2 항 내지 제 6 항에서 선택되는 어느 한 항의 폴리아믹산의 용액을 코팅하고 열경화시킨 다음, 편광자외선을 조사시켜 제조되는 것을 특징으로 하는 광배향막.A photoalignment film, which is prepared by coating a solution of the polyamic acid of any one of claims 2 to 6, thermosetting, and irradiating polarized ultraviolet rays. 제 7 항에 있어서, The method of claim 7, wherein 상기 편광자외선의 조사파장은 300 내지 460nm 인 것을 특징으로 하는 광배향막.The radiation wavelength of the polarized ultraviolet ray is an optical alignment film, characterized in that 300 to 460nm. 제 8 항에 있어서,The method of claim 8, 상기 편광자외선의 조사량은 100 내지 1000 mJ/cm2 인 것을 특징으로 하는 광배향막.The irradiation amount of the polarizing ultraviolet ray is an optical alignment film, characterized in that 100 to 1000 mJ / cm 2 . 제 9 항에 있어서,The method of claim 9, 상기 편광자외선의 조사량은 200 mJ/cm2 인 것을 특징으로 하는 광배향막.The radiation amount of the polarizing ultraviolet ray is an optical alignment film, characterized in that 200 mJ / cm 2 . 제 7 항에 따른 광배향막을 포함하는 것을 특징으로 하는 액정 셀.A liquid crystal cell comprising the optical alignment film according to claim 7. 제 11 항에 있어서,The method of claim 11, 상기 액정셀의 선경사각(pretilt angle)이 0.01 내지 1.0° 범위 인 것을 특징으로 하는 액정 셀.A pretilt angle of the liquid crystal cell is in a range of 0.01 to 1.0 °. 제 11 항에 있어서, The method of claim 11, 상기 액정 셀은 25℃, 3C 전압 하에서 99.0 내지 99.5%의 전압보유율을 가지는 것을 특징으로 하는 액정 셀.Wherein the liquid crystal cell has a voltage retention of 99.0 to 99.5% at 25 ° C. and 3C voltage.
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