KR20010011184A - Polyamic acid random copolymer and Polyimide random copolymer - Google Patents
Polyamic acid random copolymer and Polyimide random copolymer Download PDFInfo
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- KR20010011184A KR20010011184A KR1019990030428A KR19990030428A KR20010011184A KR 20010011184 A KR20010011184 A KR 20010011184A KR 1019990030428 A KR1019990030428 A KR 1019990030428A KR 19990030428 A KR19990030428 A KR 19990030428A KR 20010011184 A KR20010011184 A KR 20010011184A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
- B23Q1/00—Members which are comprised in the general build-up of a form of machine, particularly relatively large fixed members
- B23Q1/25—Movable or adjustable work or tool supports
- B23Q1/26—Movable or adjustable work or tool supports characterised by constructional features relating to the co-operation of relatively movable members; Means for preventing relative movement of such members
- B23Q1/262—Movable or adjustable work or tool supports characterised by constructional features relating to the co-operation of relatively movable members; Means for preventing relative movement of such members with means to adjust the distance between the relatively slidable members
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23Q—DETAILS, COMPONENTS, OR ACCESSORIES FOR MACHINE TOOLS, e.g. ARRANGEMENTS FOR COPYING OR CONTROLLING; MACHINE TOOLS IN GENERAL CHARACTERISED BY THE CONSTRUCTION OF PARTICULAR DETAILS OR COMPONENTS; COMBINATIONS OR ASSOCIATIONS OF METAL-WORKING MACHINES, NOT DIRECTED TO A PARTICULAR RESULT
- B23Q5/00—Driving or feeding mechanisms; Control arrangements therefor
- B23Q5/02—Driving main working members
- B23Q5/04—Driving main working members rotary shafts, e.g. working-spindles
- B23Q5/043—Accessories for spindle drives
Abstract
Description
본 발명은 신규 폴리아믹산 및 폴리이미드 랜덤 공중합체에 관한 것으로서, 더욱 상세하게는 지방족 테트라카르복실산이무수물과 지방족 측쇄를 갖는 방향족 디아민을 합성하여 제조한 폴리아믹산 랜덤 공중합체 및 이를 경화하여 제조한 폴리이미드 랜덤 공중합체에 관한 것이다. 본 발명에 의한 폴리아믹산은 인쇄성, 투명성, 용해성이 우수하고 본 발명에 의한 폴리이미드 수지는 내열성, 투명성이 우수하고 프리틸트 각(pretilt angle)을 2∼10。를 유지할 수 있으므로, 특히 액정표시장치의 액정배향막으로서 적합하다.The present invention relates to a novel polyamic acid and a polyimide random copolymer, and more particularly, to a polyamic acid random copolymer prepared by synthesizing an aromatic diamine having an aliphatic tetracarboxylic dianhydride and an aliphatic side chain and a polyimide prepared by curing the same. It relates to a mid random copolymer. The polyamic acid according to the present invention is excellent in printability, transparency and solubility, and the polyimide resin according to the present invention is excellent in heat resistance and transparency, and can maintain a pretilt angle of 2 to 10 °. It is suitable as a liquid crystal aligning film of a device.
일반적으로 폴리이미드 수지라 함은 방향족 테트라카르복실산 또는 그 유도체와 방향족 디아민 또는 방향족 디이소시아네이트를 축중합 후 이미드화하여 제조되는 고내열 수지를 말한다. 이러한 폴리이미드 수지는 사용되는 단량체의 종류에 따라 여러 가지의 분자구조 및 물성을 가질 수 있다. 일반적으로 방향족 테트라카르복실산 성분으로서는 피로멜리트산이무수물(pyromellitic dianhydride, PMDA), 바이프탈산이무수물(biphthalic dianhydride, BPDA), 벤조페논테트라카르복실산이무수물(benzophenone tetracarboxylic dianhydride, BTDA) 등을 사용하고 있고, 방향족 디아민 성분으로는 옥시디아닐린(oxydianiline, ODA), 파라페닐렌디아민(p-phenylene diamine, p-PDA)을 사용하여 축합중합시켜 제조하고 있다. 일반적으로 하기의 반응식 1과 같이 카르복실산이무수물과 방향족 디아민을 축합중합시키면 1단계로 폴리아믹산이 제조되고 이어서 이를 고온에서 탈수반응시키면 폴리이미드가 제조된다. 가장 대표적인 폴리이미드 수지의 합성방법은 다음과 같다.In general, the polyimide resin refers to a high heat-resistant resin prepared by condensation polymerization of aromatic tetracarboxylic acid or a derivative thereof and aromatic diamine or aromatic diisocyanate followed by imidization. Such polyimide resin may have various molecular structures and physical properties depending on the type of monomer used. Generally, as aromatic tetracarboxylic acid component, pyromellitic dianhydride (PMDA), biphthalic dianhydride (BPDA), benzophenone tetracarboxylic dianhydride (BTDA) and the like are used. The aromatic diamine component is prepared by condensation polymerization using oxydianiline (ODA) and paraphenylenediamine (p-phenylene diamine, p-PDA). In general, when the carboxylic acid dianhydride and the aromatic diamine are condensation-polymerized as in Scheme 1 below, a polyamic acid is prepared in one step, followed by dehydration at a high temperature to produce a polyimide. Synthesis method of the most representative polyimide resin is as follows.
―→― →
―→― →
상기와 같은 폴리이미드 수지는 불융, 불용의 초고내열성 수지로서, ⑴뛰어난 내열산화성을 보유하고 ⑵장기 사용온도는 약 260℃, 단기 사용온도는 480℃ 정도로 사용가능 온도가 매우 높은 내열특성을 보유할 뿐만 아니라 ⑶뛰어난 전기화학적, 기계적 특성 ⑷우수한 내방사선성 및 저온특성 ⑸고유 난연성 및 ⑹우수한 내약품성을 갖는다. 이러한 장점 때문에 자동차 재료, 항공소재, 우주선 소재 그리고 전자재료 등 광범위한 분야에 사용되고, 최근에는 광섬유나 액정배향막 같은 표시재료 등에도 이용되고 있다.The above polyimide resin is an insoluble, insoluble ultra high heat resistant resin, and has excellent heat oxidation resistance, and a long-term use temperature of about 260 ° C and a short-term use temperature of about 480 ° C. In addition, it has excellent electrochemical and mechanical properties. Excellent radiation resistance and low temperature properties. It has inherent flame retardancy and excellent chemical resistance. Because of these advantages, it is used in a wide range of fields such as automotive materials, aviation materials, spacecraft materials and electronic materials, and recently, it is also used in display materials such as optical fibers and liquid crystal alignment films.
그러나 상기와 같은 방향족 폴리이미드 수지는 보통 진한 황변색을 띠는 단점이 있다. 이러한 단점은 광투과율을 낮게 하여 표시재료 분야에 응용하기에 많은 제약을 받게 되므로 이를 개선하기 위한 다양한 방법이 시험되었다.However, such aromatic polyimide resins usually have a disadvantage of dark yellow discoloration. These drawbacks are lowered in light transmittance, which makes them difficult to apply to the display material field.
그 예로써 단량체를 고순도로 정제하여 중합을 하는 방법이 시도되었으나 투과율의 개선이 다소 미흡하였고, 방향족 테트라카르복실산 대신 지방족 고리계 테트라카르복실산 성분을 사용하는 방법(미국 특허 제 5,053,480호)은 이전 방법에 비해 개선되긴 하였으나, 그 액정배향제로서 사용할 때 충분히 만족스러운 폴리이미드 수지를 수득하기는 어려웠다.As an example, a method of polymerization by purifying monomers with high purity was attempted, but the improvement of transmittance was somewhat insufficient, and a method of using an aliphatic cyclic tetracarboxylic acid component instead of aromatic tetracarboxylic acid (US Pat. No. 5,053,480) Although improved over the previous method, it was difficult to obtain a sufficiently satisfactory polyimide resin when used as the liquid crystal aligning agent.
또한, 액정배향막 등의 용도로서 폴리이미드를 직접 사용할 경우에는 그 폴리이미드가 가용성이라고 하더라도 프리틸트 각의 조절이 어렵고 그 안정성이 떨어지며, 인쇄성과 기판에 대한 접착력도 약하기 때문에, 폴리이미드 수지를 직접 적용하기 보다는 폴리아믹산 용액을 적용하고 이후 경화시켜 사용하는 방법이 바람직한데, 이를 위해 용해성이 우수한 폴리아믹산이 요구되고 있었다.In addition, when the polyimide is directly used as a liquid crystal alignment film or the like, even if the polyimide is soluble, it is difficult to control the pretilt angle, the stability thereof is poor, and the printability and adhesion to the substrate are weak. Therefore, the polyimide resin is directly applied. Rather than applying a polyamic acid solution, and then hardened by using a method that is preferred, for this purpose a polyamic acid excellent in solubility was required.
본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 인쇄성, 투명성 및 용해성이 우수한 새로운 폴리아믹산을 제공하고, 이를 경화시켜 제조하는, 내열성, 투명성이 우수하고 높은 프리틸트 각을 보유하여 액정배향막으로서 적합한 새로운 폴리이미드 수지를 제공하는데 본 발명의 목적이 있다.The present invention is to solve the above problems, to provide a new polyamic acid excellent in printability, transparency and solubility, and to produce by curing it, having a high heat resistance, transparency and high pretilt angle as a liquid crystal alignment film It is an object of the present invention to provide suitable new polyimide resins.
이러한 본 발명의 목적은 지방족 고리계 카르복실산이무수물 중에서 선택된 카르복실산이무수물과 지방족 측쇄가 달린 방향족 디아민을 축합중합하여 제조한 폴리아믹산 랜덤 공중합체 및 이를 경화시켜 제조한 폴리이미드 랜덤 공중합체를 제공함에 의해 달성될 수 있다.An object of the present invention is to provide a polyamic acid random copolymer prepared by condensation polymerization of a carboxylic dianhydride selected from an aliphatic cyclic carboxylic dianhydride and an aromatic diamine having an aliphatic side chain, and a polyimide random copolymer prepared by curing the same. Can be achieved by
즉, 본 발명은 지방족 고리계 카르복실산이무수물의 혼합물과 지방족 측쇄를 갖는 방향족 디아민을 중축합반응시켜 제조되는, 불규칙하게 배열된 반복단위로서 화학식 1로 표시되는 구조식을 포함하는 폴리아믹산 랜덤(random) 공중합체 및 이러한 폴리아믹산을 경화시켜 제조되는, 불규칙하게 배열된 반복단위로서 화학식 2로 표시되는 구조식을 포함하는 폴리이미드 랜덤 공중합체 에 관한 것이다.That is, the present invention is a polyamic acid random comprising a structural formula represented by the formula (1) as an irregularly arranged repeating unit prepared by polycondensation of a mixture of aliphatic cyclic carboxylic dianhydride and an aromatic diamine having an aliphatic side chain. ) And a polyimide random copolymer comprising a structural formula represented by Formula 2 as an irregularly arranged repeating unit prepared by curing such a polyamic acid.
단, 상기의 화학식 1 및 2에서 Q는 지방족 고리계 탄화수소이고,Provided that in Formulas 1 and 2, Q is an aliphatic cyclic hydrocarbon,
R은이다(단, m 또는 n은 2∼18의 정수이다).R is (M or n is an integer of 2 to 18).
이하 본 발명에 대하여 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명에서 사용되는 디아민은 하기 화학식 3의 디아민(이하, "DA-L-m,nDAM"이라 한다)을 사용한다. DA-L-m,nDAM은 본 발명의 하나의 특징을 이루는 변성 디아민으로서 본 발명의 폴리이미드 수지가 높은 프리틸트 각을 가질 수 있도록 하며, m,n의 값을 조절함으로써 프리틸트 각을 조절할 수 있도록 한다. 본 발명의 수지가 이러한 효과를 나타내기 위해서는 상기 DA-L-m,nDAM을 총 디아민성분 중 5몰% 이상 사용하여 반응시키는 것이 바람직하다.The diamine used in the present invention uses a diamine of the formula (hereinafter referred to as "DA-L-m, nDAM"). DA-Lm, nDAM is a modified diamine which is one of the characteristics of the present invention so that the polyimide resin of the present invention can have a high pretilt angle, and the pretilt angle can be adjusted by adjusting the values of m and n. . In order for the resin of this invention to show such an effect, it is preferable to make it react using 5 mol% or more of said DA-L-m, nDAM in a total diamine component.
단, m 또는 n은 2∼18의 정수이다.However, m or n is an integer of 2-18.
본 발명의 디아민으로서는 상기의 DA-L-m,nDAM 외에 하기의 화학식 4에 개시된 파라페닐렌디아민(p-PDA), 메타페닐렌디아민(m-PDA), 옥시디아닐린, 메틸렌디아닐린, 메타비스아미노페녹시디페닐설폰, 파라비스아미노페녹시디페닐설폰 등에서 1종 이상을 선택하여 혼합한 디아민 혼합물을 사용할 수도 있으며, 이러한 방향족 디아민 혼합물은 생성되는 폴리아믹산 및 폴리이미드 수지의 내열성을 높여주는 역할을 한다.Examples of the diamine of the present invention include paraphenylenediamine (p-PDA), metaphenylenediamine (m-PDA), oxydianiline, methylenedianiline, and metabisamino, in addition to DA-Lm and nDAM. A diamine mixture in which at least one selected from phenoxydiphenylsulfone and parabisaminophenoxydiphenylsulfone is selected and mixed may be used, and such an aromatic diamine mixture serves to enhance the heat resistance of the resulting polyamic acid and polyimide resin.
본 발명에서 테트라카르복실산이무수물로는 지방족 고리계 카르복실산이무수물을 혼합하여 사용하는데, 특히 화학식 5로 표시되는 디옥시테트라히드로퓨란-3-메틸시클로헥산-1,2-디카르복실산이무수물(DOCDA)이나 화학식 6으로 표시되는 비사이클로[2,2,2]옥트-7-덴-2,3,5,6-테트라카르복실산이무수물(BODA) 등이 바람직하다. DOCDA와 BODA는 지방족 고리계 카르복실산이무수물의 일종으로서 폴리아믹산 및 폴리이미드 수지의 내열성을 유지하면서도 인쇄성, 투명성을 개선시킬 수 있다. DOCDA와 BODA를 본 발명의 카르복실산이무수물로서 혼합하여 사용할 경우 100 : 0 ∼ 5 : 95의 몰비로 혼합하는 것이 바람직하며, DOCDA의 함량이 높아질수록 제조되는 폴리아믹산 및 폴리이미드 수지의 분자량이 높아지게 된다.In the present invention, as the tetracarboxylic dianhydride, an aliphatic cyclic carboxylic dianhydride is mixed and used, in particular, dioxytetrahydrofuran-3-methylcyclohexane-1,2-dicarboxylic dianhydride represented by the formula (5). Preferable examples thereof include (DOCDA) and bicyclo [2,2,2] oct-7-den-2,3,5,6-tetracarboxylic dianhydride (BODA) represented by the general formula (6). DOCDA and BODA are a kind of aliphatic carboxylic dianhydride and can improve printability and transparency while maintaining the heat resistance of polyamic acid and polyimide resin. When DOCDA and BODA are mixed and used as the carboxylic anhydride of the present invention, it is preferable to mix them in a molar ratio of 100: 0 to 5: 95.The higher the DOCDA content, the higher the molecular weight of the polyamic acid and polyimide resin produced. do.
본 발명에서 폴리아믹산 중합시 사용되는 유기용제는 N-메틸-2-피롤리디논(N-methyl-2-pyrrolidinone, NMP), 디메틸아세트아마이드 (Dimethyl acetamide, DMAc), 디메틸포름아마이드(Dimethyl formamide, DMF) 등을 예로 들 수 있는데, 이 3가지 용매는 폴리아믹산의 중합시 중합반응의 촉매작용을 하고 이후의 이미드화 과정에서 이미드화를 촉진하는 역할을 하므로 바람직하다. 이 외에도 테트라하이드로퓨란, 클로로포름 등을 용매로 사용할 수 있다.The organic solvent used in the polymerization of the polyamic acid in the present invention is N-methyl-2-pyrrolidinone (N-methyl-2-pyrrolidinone, NMP), dimethyl acetamide (dimethyl acetamide, DMAc), dimethyl formamide (dimethyl formamide, DMF), etc. These three solvents are preferable because they catalyze the polymerization reaction during the polymerization of the polyamic acid and promote imidization in the subsequent imidization process. In addition, tetrahydrofuran, chloroform, etc. may be used as a solvent.
본 발명에서 폴리아믹산 중합시에 반응하게 되는 이무수물과 디아민의 반응비는 1 : 1이므로 두 단량체를 같은 몰비로 반응시키게 되며, 전체 반응용액에 있어 이무수물과 디아민 단량체를 합하여 2∼30중량%를 반응시키며, 결과적으로 얻어지는 폴리아믹산 용액에는 폴리아믹산 고형분이 2∼30중량%가 녹아있게 된다. 폴리아믹산의 농도가 2중량% 미만이면 본 발명의 효과를 달성하기 위한 폴리이미드 수지를 수득하기가 어려워지고, 30중량%를 초과하면 용액의 점도가 높아져 핸들링하기가 어려워지게 된다.In the present invention, since the reaction ratio of dianhydride and diamine to be reacted at the time of polyamic acid polymerization is 1: 1, the two monomers are reacted in the same molar ratio, and the total amount of the dianhydride and diamine monomer is 2 to 30% by weight. 2-30% by weight of the polyamic acid solid content is dissolved in the resulting polyamic acid solution. When the concentration of the polyamic acid is less than 2% by weight, it is difficult to obtain a polyimide resin for achieving the effect of the present invention, and when the concentration of the polyamic acid is more than 30% by weight, the viscosity of the solution becomes high and the handling becomes difficult.
본 발명에서 폴리아믹산의 합성은 반응온도 0∼100℃에서 1∼48시간 동안 반응시킴으로써 이루어진다. 생성되는 폴리아믹산은 고형분 함량이 15중량%일 때 25℃에서 1,000∼20,000cps의 점도를 나타내고, 0.5g/dL로 희석한 후 30℃에서 점도를 측정할 경우, 0.32∼1.50dL/g의 분자량을 갖는 중합체가 얻어짐을 알 수 있다..In the present invention, the synthesis of the polyamic acid is carried out by reacting at a reaction temperature of 0 to 100 ° C. for 1 to 48 hours. The resulting polyamic acid showed a viscosity of 1,000 to 20,000 cps at 25 ° C. when the solid content was 15% by weight, and a molecular weight of 0.32 to 1.50 dL / g when the viscosity was measured at 30 ° C. after dilution to 0.5 g / dL. It can be seen that a polymer having
또한, 본 발명의 폴리아믹산은 DMAc, DMF, NMP, 디메틸술폭사이드(DMSO), m-크레졸, 아세톤 또는 디에틸아세테이트와 같은 유기용매에 대해 상온에서 쉽게 용해되는 우수한 용해성을 보이고, 테트라하이드로퓨란(THF), 클로로포름과 같은 저비점 용액 또는 γ-부티로락톤과 같은 저흡수성 용매에 대해서도 상온에서 5중량% 이상의 높은 용해도를 나타낸다.In addition, the polyamic acid of the present invention shows excellent solubility easily dissolved at room temperature in organic solvents such as DMAc, DMF, NMP, dimethyl sulfoxide (DMSO), m-cresol, acetone or diethyl acetate, and tetrahydrofuran ( THF), low boiling point solutions such as chloroform, or low absorbing solvents such as γ-butyrolactone also exhibit high solubility of 5% by weight or more at room temperature.
본 발명의 폴리이미드 수지는 상기의 방법에 의해 수득된 폴리아믹산을 열경화시켜 제조된다. 경화조건은 가열판이나 오븐을 사용하여 100∼120℃에서 건조시키고, 질소분위기하의 오븐에서 서서히 승온하여 250∼400℃의 온도범위에서 30분∼2시간 정도 가열하는 것이 바람직하다. 경화후 수득된 본 발명의 폴리이미드 수지는 250∼400℃의 유리전이 온도를 가지며 350℃ 이상의 내열성을 보유한다.The polyimide resin of the present invention is produced by thermosetting the polyamic acid obtained by the above method. It is preferable to dry hardening conditions at 100-120 degreeC using a heating plate or an oven, and to heat up in an oven under nitrogen atmosphere gradually, and to heat for 30 minutes-2 hours in the temperature range of 250-400 degreeC. The polyimide resin of the present invention obtained after curing has a glass transition temperature of 250-400 ° C. and heat resistance of 350 ° C. or higher.
본 발명에 의해 제조된 폴리이미드 수지는 높은 프리틸트 각을 갖는다. 프리틸트 각이란 액정에 전압을 가하여 액정을 일정방향으로 배열시킬 때, 전압에 대한 응답속도를 빠르게 해주기 위하여 미리 약간 액정을 세워두는 각을 말하는 것으로, 본 발명의 폴리이미드 수지는 2∼10°의 프리틸트 각을 갖는 특징이 있다.The polyimide resin produced by the present invention has a high pretilt angle. The pretilt angle refers to an angle in which the liquid crystal is set up in advance in order to increase the response speed to the voltage when the liquid crystals are arranged in a predetermined direction by applying a voltage to the liquid crystal. It is characterized by having a pretilt angle.
따라서 본 발명의 폴리아믹산 및 폴리이미드 수지를 이용하여 표시 성능이 개선된 액정표시소자를 제조할 수 있다. 본 발명의 액정표시소자는 포토레지스트 (Photoresist)를 현상, 박리하여 패턴화된 ITO유리상에 롤러 코팅(roller coating) 등의 방법으로 본 발명의 폴리아믹산을 도포하고 상기에 기재한 조건으로 경화시켜 폴리이미드 막을 형성한 후, 러빙 천(rubbing cloth)러 문질러 원하는 방향으로 배향시킨 폴리이미드 배향막을 제조하고, 이 후 실 프린트(seal print), 스페이서 스캐터링(spacer scarttering), 조립, 실링(sealing), 액정주입, 편광판 부착 등의 공정을 행하여 액정표시소자를 제작한다.Accordingly, the liquid crystal display device having improved display performance may be manufactured using the polyamic acid and the polyimide resin of the present invention. In the liquid crystal display device of the present invention, a polyamic acid of the present invention is coated on a patterned ITO glass by developing and peeling a photoresist, and then cured under the conditions described above. After the mid film was formed, a polyimide alignment film was prepared by rubbing with a rubbing cloth and oriented in the desired direction, followed by seal print, spacer scarttering, assembly, sealing, The liquid crystal display element is manufactured by performing processes, such as a liquid crystal injection and a polarizing plate attachment.
이하 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명의 특허청구범위가 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the scope of the claims of the present invention.
실시예 1Example 1
교반기, 온도조절장치, 질소주입장치, 적하깔대기 및 냉각기를 부착한 50㎖의 반응기에 질소가스를 서서히 통과시키면서 p-PDA 9.72g(0.09mole)과 변성 디아민 DA-L-4,4DAM 2.21g(0.01mole)을 반응용매 NMP에 용해시킨 후 질소가스를 통과시키면서 고체상의 DOCDA 23.76g(0.09mole)와 BODA 2.48g(0.01mole)을 서서히 첨가하였다. 이 때 고형분 농도는 10중량%로 고정하였으며, 반응온도 10℃에서 48시간 반응시켰다. 반응이 종료된 후, γ-부티로락톤으로 희석하여 5중량%의 폴리아믹산 용액을 얻었다. 반응 혼합물을 NMP용매로 하여 0.5g/dL의 농도로 30℃에서 고유점도를 측정하였고 그 결과를 표 1에 나타내었다.9.72 g (0.09 mole) of p-PDA and 2.21 g of modified diamine DA-L-4,4DAM while slowly passing nitrogen gas through a 50 ml reactor equipped with a stirrer, temperature controller, nitrogen injector, dropping funnel and cooler. 0.01 mole) was dissolved in the reaction solvent NMP and slowly added 23.76 g (0.09 mole) of DOCDA and 2.48 g (0.01 mole) of BODA while passing through nitrogen gas. At this time, the solid content concentration was fixed at 10% by weight and reacted for 48 hours at a reaction temperature of 10 ℃. After the reaction was completed, the mixture was diluted with γ-butyrolactone to obtain a 5% by weight polyamic acid solution. Intrinsic viscosity was measured at 30 ° C. at a concentration of 0.5 g / dL using the reaction mixture as NMP solvent. The results are shown in Table 1.
수득된 폴리아믹산을 스핀코터(spincoater)로서 700rpm/5sec ∼ 1700rpm/30sec 박막코팅하고 가열판(Hot Plate) 상에서 프리베이크(prebake)한 후 코팅막의 상태를 관찰하여 막 균일도 및 핀홀(pinhole)의 발생 갯수를 파악함으로써 수지막의 인쇄성을 조사하였다. 또한 코팅막을 250℃에서 30분간 경화하여 폴리이미드 수지를 얻었고, 이를 러빙(rubbing)한 후 액정셀을 제작하여 그 특성을 표 1에 나타내었다. 액정의 배향성은 편광현미경을 사용하여 관찰하였고, 결정 회전법(crystal rotation method)를 이용하여 각 액정셀의 프리틸트 각을 측정하였다.The obtained polyamic acid was coated with a thin film of 700 rpm / 5 sec to 1700 rpm / 30 sec as a spin coater, prebaked on a hot plate, and then the state of the coating film was observed to observe the uniformity of the film and the number of pinholes. The printability of the resin film was examined by grasping the. In addition, the coating film was cured at 250 ° C. for 30 minutes to obtain a polyimide resin. After rubbing it, a liquid crystal cell was manufactured, and the characteristics thereof are shown in Table 1 below. The orientation of the liquid crystal was observed using a polarizing microscope, and the pretilt angle of each liquid crystal cell was measured using a crystal rotation method.
또한 제조된 폴리이미드 필름의 인장강도를 측정하여 필름 특성을 파악하였고, 시차주사 열량계(Differential Scanning Calorimeter, DSC)를 이용하여 유리전이온도를 측정하여 그 결과를 표 1에 나타내었다.In addition, the film properties were determined by measuring the tensile strength of the prepared polyimide film, and the glass transition temperature was measured by using a differential scanning calorimeter (DSC).
실시예 2Example 2
DOCDA 13.20g(0.05mole), BODA 12.40g(0.05mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.Except for adding DOCDA 13.20g (0.05mole), BODA 12.40g (0.05mole) was the same experiment as Example 1 and the results are shown in Table 1.
실시예 3Example 3
DOCDA 2.64g(0.01mole), BODA 22.32g(0.09mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.Except that 2.64 g (0.01 mole) of DOCDA and 22.32 g (0.09 mole) of BODA were added, the same results were obtained as in Example 1, and the results are shown in Table 1.
실시예 4Example 4
변성 디아민으로서 DA-L-18,18DAM 4.03g(0.01mole)을 사용하고, DOCDA 2.64g(0.01mole), BODA 22.32g(0.09mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.Experiment was carried out in the same manner as in Example 1 except that DA-L-18,18DAM 4.03 g (0.01 mole) was used as a modified diamine, and DOCDA 2.64 g (0.01 mole) and 22.32 g (0.09 mole) of BODA were added. The results are shown in Table 1.
실시예 5Example 5
변성 디아민으로서 DA-L-6,6DAM 2.35g(0.01mole)을 사용하고, DOCDA 13.20g(0.05mole), BODA 12.40g(0.05mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.DA-L-6,6DAM 2.35g (0.01mole) was used as the modified diamine, except that DOCDA 13.20g (0.05mole) and BODA 12.40g (0.05mole) were added in the same manner as in Example 1 The results are shown in Table 1.
실시예 6Example 6
디아민 혼합물로서 m-PDA 9.72g(0.09mole)과 DA-L-4,4DAM 2.21g(0.01mole)을 사용하고, DOCDA 13.20g(0.05mole), BODA 12.40g(0.05mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.9.72 g (0.09 mole) of m-PDA and 2.21 g (0.01 mole) of DA-L-4,4DAM were used as the diamine mixture, except that 13.20 g (0.05 mole) of DOCDA and 12.40 g (0.05 mole) of BODA were added. And the experiment in the same manner as in Example 1 and the results are shown in Table 1.
비교예 1Comparative Example 1
디아민으로서 p-PDA 1.08g(0.01mole)을 사용하고, 카르복실산이무수물로서 DOCDA 2.64g(0.01mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.Except that 1.08 g (0.01 mole) of p-PDA was used as the diamine and 2.64 g (0.01 mole) of DOCDA was added as the carboxylic acid dianhydride, and the results were shown in Table 1, and the results are shown in Table 1. .
비교예 2Comparative Example 2
디아민으로서 p-PDA 1.08g(0.01mole)을 사용하고, 카르복실산이무수물로서 BODA 2.48g(0.01mole)을 첨가한 것을 제외하고는 실시예 1과 동일하게 실험하여 그 결과를 표 1에 나타내었다.Except that 1.08 g (0.01 mole) of p-PDA was used as the diamine, and 2.48 g (0.01 mole) of BODA was added as the carboxylic dianhydride. .
본 발명의 폴리아믹산 및 폴리이미드는 모두 무정형의 투명한 수지로서 그 필름의 물성이 양호하고, 이로부터 제조한 액정배향막은 매우 우수한 인쇄성, 액정배향성을 나타내며, 프리틸트 각이 2∼10。로서 특히 TFT-LCD용 액정배향막으로서의 사용에 적합한 특성을 갖는다. 이외에도 본 발명의 폴리이미드는 내열성이 우수하여 각종 첨단 내열구조 재료로서 유용하다.Both the polyamic acid and the polyimide of the present invention are amorphous transparent resins, and the physical properties of the film are good, and the liquid crystal alignment film prepared therefrom exhibits very good printability and liquid crystal alignment, and has a pretilt angle of 2 to 10 °. It has the characteristic suitable for use as a liquid crystal aligning film for TFT-LCD. In addition, the polyimide of the present invention is excellent in heat resistance and is useful as various advanced heat-resistant structural materials.
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| KR100383869B1 (en) * | 2000-12-28 | 2003-05-14 | 제일모직주식회사 | Polyimide resin |
| KR100414206B1 (en) * | 2000-12-28 | 2004-01-07 | 제일모직주식회사 | Polyimide resin |
| KR100561565B1 (en) * | 1999-12-20 | 2006-03-17 | 제일모직주식회사 | Polyimide resin and preparation method thereof |
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| CN107338058A (en) * | 2016-04-28 | 2017-11-10 | Jsr株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and its manufacture method, liquid crystal cell, polymer and compound |
| WO2019164067A1 (en) * | 2018-02-26 | 2019-08-29 | 에스케이씨코오롱피아이 주식회사 | Polyimide film for graphite sheet having improved thermal conductivity, method for manufacturing same, and graphite sheet manufactured using same |
| WO2019164068A1 (en) * | 2018-02-26 | 2019-08-29 | 에스케이씨코오롱피아이 주식회사 | Graphite sheet polyimide film comprising spherical pi-based filler, manufacturing method therefor, and graphite sheet manufactured using same |
| WO2019168245A1 (en) * | 2018-02-28 | 2019-09-06 | 에스케이씨코오롱피아이 주식회사 | Graphite sheet polyimide film comprising graphene-containing spherical pi-based filler, manufacturing method therefor, and graphite sheet manufactured using same |
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| KR100383869B1 (en) * | 2000-12-28 | 2003-05-14 | 제일모직주식회사 | Polyimide resin |
| KR100414206B1 (en) * | 2000-12-28 | 2004-01-07 | 제일모직주식회사 | Polyimide resin |
| KR100952588B1 (en) * | 2001-11-02 | 2010-04-15 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Transparent electrically-conductive film and its use |
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| WO2019164067A1 (en) * | 2018-02-26 | 2019-08-29 | 에스케이씨코오롱피아이 주식회사 | Polyimide film for graphite sheet having improved thermal conductivity, method for manufacturing same, and graphite sheet manufactured using same |
| WO2019164068A1 (en) * | 2018-02-26 | 2019-08-29 | 에스케이씨코오롱피아이 주식회사 | Graphite sheet polyimide film comprising spherical pi-based filler, manufacturing method therefor, and graphite sheet manufactured using same |
| CN111819225A (en) * | 2018-02-26 | 2020-10-23 | Pi尖端素材株式会社 | Polyimide film for graphite sheet having improved thermal conductivity, method for manufacturing same, and graphite sheet manufactured using same |
| JP2021515075A (en) * | 2018-02-26 | 2021-06-17 | ピーアイ アドヴァンスド マテリアルズ カンパニー リミテッドＰＩ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ ＣＯ．， Ｌｔｄ． | A polyimide film for a graphite sheet containing a spherical PI-based filler, a manufacturing method thereof, and a graphite sheet manufactured using the same. |
| CN111819225B (en) * | 2018-02-26 | 2023-02-28 | Pi尖端素材株式会社 | Polyimide film for graphite sheet having improved thermal conductivity, method for manufacturing same, and graphite sheet manufactured using same |
| US11731908B2 (en) | 2018-02-26 | 2023-08-22 | Pi Advanced Materials Co., Ltd. | Graphite sheet polyimide film comprising spherical PI-based filler, manufacturing method therefor, and graphite sheet manufactured using same |
| WO2019168245A1 (en) * | 2018-02-28 | 2019-09-06 | 에스케이씨코오롱피아이 주식회사 | Graphite sheet polyimide film comprising graphene-containing spherical pi-based filler, manufacturing method therefor, and graphite sheet manufactured using same |
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