KR20180089487A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element using same Download PDFInfo
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- KR20180089487A KR20180089487A KR1020187018889A KR20187018889A KR20180089487A KR 20180089487 A KR20180089487 A KR 20180089487A KR 1020187018889 A KR1020187018889 A KR 1020187018889A KR 20187018889 A KR20187018889 A KR 20187018889A KR 20180089487 A KR20180089487 A KR 20180089487A
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- KR
- South Korea
- Prior art keywords
- group
- liquid crystal
- aligning agent
- component
- carbon atoms
- Prior art date
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- JRSJRHKJPOJTMS-MDZDMXLPSA-N trimethoxy-[(e)-2-phenylethenyl]silane Chemical compound CO[Si](OC)(OC)\C=C\C1=CC=CC=C1 JRSJRHKJPOJTMS-MDZDMXLPSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
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- Liquid Crystal (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
양호한 액정 배향성, 전압 유지율, 에이징 내성 등을 갖는 액정 배향막이 얻어지는 액정 배향제를 제공한다.
하기의 성분 (A) 및 성분 (B) 를 함유하는 것을 특징으로 하는 액정 배향제.
성분 (A) : 하기 식 (1) 로 나타내는 구조 단위와 하기 식 (2) 로 나타내는 구조 단위를 갖는 공중합체.
［화학식 1］
(X1, X2 는, 독립적으로 4 가의 유기기이고, Y1, Y2 는, 독립적으로, 2 가의 유기기이며, R1 은, 탄소수 1 ∼ 5 의 알킬기이고, A1 및 A2 는, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는, 탄소수 1 ∼ 10 의 알킬기, 탄소수 2 ∼ 10 의 알케닐기 혹은 탄소수 2 ∼ 10 의 알키닐기이다.)
성분 (B) : 가교성 관능기를 2 개 이상 갖는 화합물.Provided is a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal alignability, voltage retention rate, aging resistance and the like.
A liquid crystal aligning agent characterized by containing the following components (A) and (B).
Component (A): A copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
[Chemical Formula 1]
(X 1, X 2 is a tetravalent organic group independently, Y 1, Y 2 is a, a divalent organic group independently, R 1 is an alkyl group having a carbon number of 1 ~ 5, A 1 and A 2 is , Independently of each other, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkynyl group having 2 to 10 carbon atoms, which may have a substituent)
Component (B): a compound having two or more crosslinkable functional groups.
Description
본 발명은, 폴리아믹산에스테르-폴리아믹산 공중합체를 함유하는 액정 배향제, 액정 배향막 및 그것을 사용한 액정 표시 소자에 관한 것이다.The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film containing a polyamic acid ester-polyamic acid copolymer, and a liquid crystal display device using the same.
액정 텔레비전, 액정 디스플레이 등에 사용되는 액정 표시 소자는, 통상적으로 액정의 배열 상태를 제어하기 위한 액정 배향막이 소자 내에 형성되어 있다. 액정 배향막은, 액정 표시 소자나 중합성 액정을 사용한 위상차판 등에 있어서, 액정 분자의 배향을 일정 방향으로 제어하기 위한 막이다. 예를 들어, 액정 표시 소자는, 액정층을 이루는 액정 분자가, 1 쌍의 기판의 각각의 표면에 형성된 액정 배향막 사이에 끼워진 구조를 갖는다. 그리고, 액정 표시 소자에서는, 액정 분자가, 액정 배향막에 의해서 프레틸트각을 수반하여 일정 방향으로 배향되고, 기판과 액정 배향막 사이에 형성된 전극에 대한 전압 인가에 의해서 응답을 한다. 그 결과, 액정 표시 소자는, 액정 분자의 응답에 의한 배향 변화를 이용하여 소망하는 화상의 표시를 행한다.In a liquid crystal display element used for a liquid crystal television, a liquid crystal display, or the like, a liquid crystal alignment film for controlling the alignment state of the liquid crystal is usually formed in the element. The liquid crystal alignment film is a film for controlling the alignment of liquid crystal molecules in a certain direction in a liquid crystal display element, a phase difference plate using a polymerizable liquid crystal, and the like. For example, a liquid crystal display element has a structure in which liquid crystal molecules constituting a liquid crystal layer are sandwiched between liquid crystal alignment films formed on the respective surfaces of a pair of substrates. In a liquid crystal display element, liquid crystal molecules are aligned in a certain direction with a pretilt angle by a liquid crystal alignment film, and respond by applying a voltage to electrodes formed between the substrate and the liquid crystal alignment film. As a result, the liquid crystal display element performs display of a desired image by utilizing the orientation change caused by the response of the liquid crystal molecules.
액정 배향막으로는, 지금까지, 폴리아믹산 (폴리아미드산) 등의 폴리이미드 전구체나 가용성 폴리이미드의 용액을 주성분으로 하는 액정 배향제를 유리 기판 등에 도포하고 소성한 폴리이미드계의 액정 배향막이 주로 사용되고 있다.As the liquid crystal alignment film, a polyimide-based liquid crystal alignment film obtained by applying a liquid crystal aligning agent mainly composed of a solution of a polyimide precursor such as polyamic acid (polyamic acid) or a soluble polyimide solution to a glass substrate and firing is mainly used have.
액정 표시 소자의 고기능화에 수반하여, 액정 배향막에 있어서는, 우수한 액정 배향성이나 안정적인 프레틸트각의 발현에 더하여, 높은 전압 유지율, 직류 전압을 인가했을 때의 적은 잔류 전하, 및/또는 직류 전압에 의한 축적된 잔류 전하의 빠른 완화 등의 특성이 중요하지만, 최근에는 액정 표시 소자의 전력 절약화를 목표로 높은 전압 유지율의 재료가 특히 요구되고 있다.Along with the enhancement of the liquid crystal display element, in the liquid crystal alignment film, in addition to excellent liquid crystal alignability and stable expression of the pretilt angle, a high voltage holding ratio, a small residual charge when a direct current voltage is applied and / However, in recent years, a material with a high voltage holding ratio has been particularly required in order to reduce the power consumption of liquid crystal display elements.
폴리이미드계의 액정 배향막에 있어서는, 상기와 같은 요구에 부응하기 위해서, 여러 가지 제안이 이루어져 있다. 예를 들어, 폴리아미드산이나 이미드기 함유 폴리아미드산에 더하여, 특정 구조의 3 급 아민을 함유하는 액정 배향제를 사용한 것 (특허 문헌 1 참조), 이소시아네이트 구조를 갖는 첨가제를 사용한 것 (특허 문헌 2 참조) 등이 제안되어 있다.In order to meet the above-mentioned demands, various proposals have been made for a polyimide-based liquid crystal alignment film. For example, a liquid crystal aligning agent containing a tertiary amine having a specific structure is used in addition to a polyamic acid or an imide group-containing polyamic acid (see Patent Document 1), an additive having an isocyanate structure is used 2) have been proposed.
한편, 액정 배향제를 구성하는 폴리머 성분으로서, 폴리아믹산에스테르를 사용한 액정 배향제는, 이것을 이미드화할 때의 가열 처리에 의해서, 분자량 저하를 일으키지 않기 때문에, 폴리아믹산을 사용한 액정 배향제와 비교하여, 액정의 배향 안정성·전압 유지 특성이 우수한 것이 보고되어 있다 (특허 문헌 3 참조).On the other hand, since the liquid crystal aligning agent using the polyamic acid ester as the polymer component constituting the liquid crystal aligning agent does not cause a decrease in the molecular weight by the heat treatment at the time of imidizing the liquid crystal aligning agent, , And excellent alignment stability and voltage holding property of liquid crystal (see Patent Document 3).
그러나, 폴리아미드산에 각종 가교제를 첨가한 액정 배향제를 사용하면, 전압 유지 특성이 우수한 액정 표시 소자는 얻어지기는 하지만, 액정 배향성을 저해하는 경우가 있다.However, when a liquid crystal aligning agent to which various crosslinking agents are added to a polyamic acid is used, a liquid crystal display element having excellent voltage holding characteristics can be obtained, but the liquid crystal aligning property may be deteriorated.
또, 폴리아믹산에스테르를 사용한 액정 배향제는, 상기 서술한 바와 같이, 폴리아믹산을 사용한 액정 배향제와 비교하여 전압 유지 특성이 우수한 액정 표시 소자가 얻어지기 때문에, 이것에 가교제를 첨가하면 추가적인 전압 유지 특성의 향상이 전망되었지만, 예상에 반하여 그 효과는 얻을 수 없었다.As described above, the liquid crystal aligning agent using the polyamic acid ester can provide a liquid crystal display element having excellent voltage holding characteristics as compared with the liquid crystal aligning agent using the polyamic acid. Therefore, when a cross-linking agent is added thereto, Although the improvement of the characteristics was expected, the effect could not be obtained against the expectation.
본 발명은, 양호한 액정 배향성, 전압 유지율 (Voltage Holding Ratio : 이하, VHR 라고도 한다), 및 에이징 내성을 겸비한 액정 배향막이 얻어지는 액정 배향제를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal alignability, voltage holding ratio (hereinafter also referred to as VHR), and aging resistance.
본 발명자는 예의 연구를 진행한 바, 폴리아믹산에스테르와 폴리아믹산의 공중합체 (이하, PAE-PAA 공중합체라고도 한다) 와, 특정 구조의 가교제를 병용함으로써, 상기 과제를 해결할 수 있음을 알아내고, 본 발명을 완성시켰다.The inventors of the present invention have conducted intensive studies and have found out that the above problems can be solved by using a copolymer of a polyamic acid ester and a polyamic acid (hereinafter also referred to as a PAE-PAA copolymer) and a crosslinking agent having a specific structure, Thereby completing the present invention.
즉, 본 발명은 상기한 지견에 기초하는 것으로, 하기를 요지로 하는 것이다.That is, the present invention is based on the above-described findings, and it is based on the following points.
1. 하기의 성분 (A) 및 성분 (B) 를 함유하는 것을 특징으로 하는 액정 배향제.1. A liquid crystal aligning agent comprising the following components (A) and (B).
성분 (A) : 하기 식 (1) 로 나타내는 구조 단위와 하기 식 (2) 로 나타내는 구조 단위를 갖는 공중합체.Component (A): A copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
[화학식 1] [Chemical Formula 1]
상기 식 (1), 식 (2) 중, X1 및 X2 는, 각각 독립적으로 4 가의 유기기이고, Y1 및 Y2 는, 각각 독립적으로, 2 가의 유기기이며, R1 은, 탄소수 1 ∼ 5 의 알킬기이고, A1 및 A2 는, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는, 탄소수 1 ∼ 10 의 알킬기, 탄소수 2 ∼ 10 의 알케닐기 혹은 탄소수 2 ∼ 10 의 알키닐기이다.X 1 and X 2 are each independently a tetravalent organic group; Y 1 and Y 2 are, independently of each other, a divalent organic group; and R 1 is a divalent organic group having a carbon number A 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, which may have a substituent to be.
성분 (B) : 가교성 관능기를 2 개 이상 갖는 화합물.Component (B): a compound having two or more crosslinkable functional groups.
본 발명의 액정 배향제에 따르면, 양호한 액정 배향성, 전압 유지율 및 에이징 내성 등의 특성을 겸비한 액정 배향막을 형성할 수 있다. 이것은, 본 발명의 액정 배향제로 형성되는 액정 배향막에 있어서는, 그 표면에 있어서의 미세한 요철을 저감할 수 있는 것이 요인으로 생각된다.According to the liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal alignment film having characteristics such as good liquid crystal alignability, voltage retention rate and aging resistance. This is considered to be due to the fact that, in the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention, fine irregularities on the surface thereof can be reduced.
＜성분 (A) : PAE-PAA 공중합체＞≪ Component (A): PAE-PAA copolymer >
본 발명에 사용되는 PAE-PAA 공중합체는, 폴리이미드를 얻기 위한 폴리이미드 전구체로서, 가열함으로써 하기에 나타내는 이미드화 반응이 가능한 부위를 갖는 폴리머이다.The PAE-PAA copolymer used in the present invention is a polyimide precursor for obtaining a polyimide, and is a polymer having a site capable of undergoing an imidization reaction as described below by heating.
[화학식 2] (2)
(R 은, 수소 원자 또는 탄소수 1 ∼ 5 의 알킬기이다.) (R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms)
본 발명의 액정 배향제에 함유되는 PAE-PAA 공중합체는, 하기 식 (1) 로 나타내는 구조 단위와, 하기 식 (2) 로 나타내는 구조 단위를 갖는다.The PAE-PAA copolymer contained in the liquid crystal aligning agent of the present invention has a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
[화학식 3] (3)
[화학식 4] [Chemical Formula 4]
상기 식 (1) 에 있어서, R1 은, 탄소수 1 ∼ 5 의 알킬기이고, 유리 기판에 대한 도포 용이성의 관점에서, 메틸기 또는 에틸기인 것이 바람직하다.In the above formula (1), R 1 is an alkyl group having 1 to 5 carbon atoms and is preferably a methyl group or an ethyl group in view of easy application to a glass substrate.
상기 식 (1) 및 (2) 에 있어서, A1 및 A2 는, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는, 탄소수 1 ∼ 10 의 알킬기, 탄소수 2 ∼ 10 의 알케닐기, 혹은 탄소수 2 ∼ 10 의 알키닐기이다. 상기 알킬기의 구체예로는, 메틸기, 에틸기, 프로필기, 부틸기, t-부틸기, 헥실기, 옥틸기, 데실기, 시클로펜틸기, 시클로헥실기, 비시클로헥실기 등을 들 수 있다. 알케닐기로는, 알킬기에 존재하는 1 개 이상의 CH-CH 구조를, C = C 구조로 치환한 것을 들 수 있고, 구체적으로는, 비닐기, 알릴기, 1-프로페닐기, 이소프로페닐기, 2-부테닐기, 1,3-부타디에닐기, 2-펜테닐기, 2-헥세닐기, 시클로프로페닐기, 시클로펜테닐기, 시클로헥세닐기 등을 들 수 있다. 알키닐기로는, 알킬기에 존재하는 1 개 이상의 CH2-CH2 구조를 C≡C 구조로 치환한 것을 들 수 있고, 구체적으로는, 에티닐기, 1-프로피닐기, 2-프로피닐기 등을 들 수 있다.In the formulas (1) and (2), A 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, Alkynyl group having 2 to 10 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group, a decyl group, a cyclopentyl group, a cyclohexyl group and a bicyclohexyl group. Examples of the alkenyl group include those obtained by substituting at least one CH-CH structure existing in the alkyl group with a C = C structure. Specific examples thereof include a vinyl group, an allyl group, a 1-propenyl group, A butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group, a cyclopropenyl group, a cyclopentenyl group and a cyclohexenyl group. Examples of the alkynyl group include groups in which at least one CH 2 -CH 2 structure existing in the alkyl group is substituted with a C≡C structure. Specific examples thereof include an ethynyl group, 1-propynyl group, 2-propynyl group, etc. .
상기한 알킬기, 알케닐기 및 알키닐기는 치환기를 갖고 있어도 되고, 나아가서는 치환기에 의해서 고리 구조를 형성해도 된다. 또한, 치환기에 의해서 고리 구조를 형성하는 것은, 치환기끼리 또는 치환기와 모(母) 골격의 일부가 결합하여 고리 구조가 되는 것을 의미한다.The alkyl group, alkenyl group and alkynyl group described above may have a substituent, and may form a ring structure by a substituent. The formation of a ring structure by a substituent means that a substituent group or a substituent group and a part of a parent skeleton are bonded to form a ring structure.
이 치환기의 예로는, 할로겐기, 수산기, 티올기, 니트로기, 아릴기, 오르가노옥시기, 오르가노티오기, 오르가노실릴기, 아실기, 에스테르기, 티오에스테르기, 인산에스테르기, 아미드기, 알킬기, 알케닐기, 알키닐기 등을 들 수 있다.Examples of the substituent include a halogen group, a hydroxyl group, a thiol group, a nitro group, an aryl group, an organoxy group, an organothio group, an organosilyl group, an acyl group, an ester group, a thioester group, An alkyl group, an alkenyl group, and an alkynyl group.
치환기인 할로겐기로는, 불소 원자, 염소 원자, 브롬 원자, 요오드 원자를 들 수 있다.Examples of the halogen group as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
치환기인 아릴기로는, 페닐기를 들 수 있다. 이 아릴기에는 전술한 다른 치환기가 추가로 치환되어 있어도 된다.As the aryl group as a substituent, a phenyl group can be mentioned. These aryl groups may be further substituted with other substituents described above.
치환기인 오르가노옥시기로는, O-R 로 나타내는 구조를 나타낼 수 있다. 이 R 은 동일해도 되고 상이해도 되며, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다. 오르가노옥시기의 구체예로는, 메톡시기, 에톡시기, 프로필옥시기, 부톡시기, 펜틸옥시기, 헥실옥시기, 헵틸옥시기, 옥틸옥시기 등을 들 수 있다.The organoxy group as a substituent may represent a structure represented by O-R. These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the organoxy group include a methoxy group, ethoxy group, propyloxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group and octyloxy group.
치환기인 오르가노티오기로는, -S-R 로 나타내는 구조를 나타낼 수 있다. 이 R 로는, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다. 오르가노티오기의 구체예로는, 메틸티오기, 에틸티오기, 프로필티오기, 부틸티오기, 펜틸티오기, 헥실티오기, 헵틸티오기, 옥틸티오기 등을 들 수 있다.The organotio group which is a substituent may represent a structure represented by -S-R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the organotitanium group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group and octylthio group.
치환기인 오르가노실릴기로는, -Si-(R)3 으로 나타내는 구조를 나타낼 수 있다. 이 R 은 동일해도 되고 상이해도 되며, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다. 오르가노실릴기의 구체예로는, 트리메틸실릴기, 트리에틸실릴기, 트리프로필실릴기, 트리부틸실릴기, 트리펜틸실릴기, 트리헥실실릴기, 펜틸디메틸실릴기, 헥실디메틸실릴기 등을 들 수 있다.The organosilyl group as a substituent may represent a structure represented by -Si- (R) 3 . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents. Specific examples of the organosilyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a tributylsilyl group, a tripentylsilyl group, a trihexylsilyl group, a pentyldimethylsilyl group, a hexyldimethylsilyl group, .
치환기인 아실기로는, -C(O)-R 로 나타내는 구조를 나타낼 수 있다. 이 R 로는, 전술한 알킬기, 알케닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다. 아실기의 구체예로는, 포르밀기, 아세틸기, 프로피오닐기, 부티릴기, 이소부티릴기, 발레릴기, 이소발레릴기, 벤조일기 등을 들 수 있다.The acyl group as a substituent may represent a structure represented by -C (O) -R. As R, examples of the alkyl group, alkenyl group, aryl group, and the like may be mentioned. These R may be further substituted with the aforementioned substituents. Specific examples of the acyl group include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.
치환기인 에스테르기로는, -C(O)O-R, 또는 OC(O)-R 로 나타내는 구조를 나타낼 수 있다. 이 R 로는, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다.The ester group as a substituent may represent a structure represented by -C (O) O-R or OC (O) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.
치환기인 티오에스테르기로는, -C(S)O-R, 또는 OC(S)-R 로 나타내는 구조를 나타낼 수 있다. 이 R 로는, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다.The thioester group as a substituent may represent a structure represented by -C (S) O-R or OC (S) -R. As R, examples of the alkyl group, alkenyl group, alkynyl group, aryl group and the like can be mentioned. These R may be further substituted with the aforementioned substituents.
치환기인 인산에스테르기로는, -OP(O)-(OR)2 로 나타내는 구조를 나타낼 수 있다. 이 R 은 동일해도 되고 상이해도 되며, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다.The phosphoric acid ester group which is a substituent may represent a structure represented by -OP (O) - (OR) 2 . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.
치환기인 아미드기로는, -C(O)NH2, -C(O)NHR, -NHC(O)R, -C(O)N(R)2, 또는 -NRC(O)R 로 나타내는 구조를 나타낼 수 있다. 이 R 은 동일해도 되고 상이해도 되며, 전술한 알킬기, 알케닐기, 알키닐기, 아릴기 등을 예시할 수 있다. 이들 R 에는 전술한 치환기가 추가로 치환되어 있어도 된다.The amide group which is a substituent includes a structure represented by -C (O) NH 2 , -C (O) NHR, -NHC (O) R, -C (O) N (R) 2 or -NRC . These R may be the same or different and are the above-mentioned alkyl, alkenyl, alkynyl, aryl and the like. These R may be further substituted with the aforementioned substituents.
치환기인 아릴기에는, 전술한 아릴기와 동일한 것을 들 수 있다. 이 아릴기에는 전술한 다른 치환기가 추가로 치환되어 있어도 된다.The aryl group as a substituent includes the same aryl groups as those described above. These aryl groups may be further substituted with other substituents described above.
치환기인 알킬기로는, 전술한 알킬기와 동일한 것을 들 수 있다. 이 알킬기에는 전술한 다른 치환기가 추가로 치환되어 있어도 된다.Examples of the alkyl group as the substituent include the same alkyl groups mentioned above. These alkyl groups may be further substituted with other substituents described above.
치환기인 알케닐기로는, 전술한 알케닐기와 동일한 것을 들 수 있다. 이 알케닐기에는 전술한 다른 치환기가 추가로 치환되어 있어도 된다.Examples of the alkenyl group as the substituent include the same alkenyl groups as those described above. This alkenyl group may be further substituted with another substituent as described above.
치환기인 알키닐기로는, 전술한 알키닐기와 동일한 것을 들 수 있다. 이 알키닐기에는 전술한 다른 치환기가 추가로 치환되어 있어도 된다.Examples of the alkynyl group as the substituent include the same alkynyl groups as mentioned above. These alkynyl groups may be further substituted with other substituents described above.
상기 A1 및 A2 로는, 일반적으로, 벌크한 구조를 도입하면, 아미노기의 반응성이나 액정 배향성을 저하시킬 가능성이 있기 때문에, 수소 원자, 또는 치환기를 가져도 되는 탄소수 1 ∼ 5 의 알킬기가 보다 바람직하고, 수소 원자, 메틸기 또는 에틸기가 특히 바람직하다.Generally, as the A 1 and A 2 , when introducing a bulk structure, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may have a substituent, may be more preferable because it may lower the reactivity of the amino group and the liquid crystal alignability And a hydrogen atom, a methyl group or an ethyl group is particularly preferable.
상기 식 (1) 및 식 (2) 에 있어서, X1 및 X2 는, 4 가의 유기기이면, 그 구조는 특별히 한정되는 것이 아니고, 2 종류 이상이 혼재하고 있어도 된다. X1 및 X2 의 구체예를 나타내면, 이하에 나타내는 X-1 ∼ X-47 을 들 수 있다. 그 중에서도, 모노머의 입수성 및 광조사 감도 그리고 러빙 내성 강도 등의 관점에서, X1, X2 모두, X-1, X-2, X-3, X-4, X-5, X-6, X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28, X-32 또는 X-47 이 바람직하다.In the formulas (1) and (2), when X 1 and X 2 are tetravalent organic groups, the structure thereof is not particularly limited, and two or more types may be mixed. Specific examples of X 1 and X 2 include X-1 to X-47 shown below. In view of those, to obtain a monomeric and irradiated with light sensitivity and rubbing resistance strength, X 1, X 2 both, X-1, X-2 , X-3, X-4, X-5, X-6 , X-8, X-16, X-19, X-21, X-25, X-26, X-27, X-28, X-32 or X-47.
[화학식 5] [Chemical Formula 5]
[화학식 6] [Chemical Formula 6]
[화학식 7] (7)
[화학식 8] [Chemical Formula 8]
또, 식 (1) 및 식 (2) 에 있어서, Y1 및 Y2 는, 2 가의 유기기이고, 특별히 한정되는 것은 아니다. Y1 및 Y2 는, 동일해도 되거나, 또는 상이해도 된다.In the formulas (1) and (2), Y 1 and Y 2 are divalent organic groups and are not particularly limited. Y 1 and Y 2 may be the same or different.
Y1 및 Y2 의 구체예를 나타내면, 하기의 Y-1 ∼ Y-99 를 들 수 있다. 그 중에서도, 모노머의 입수 용이성의 관점에서, Y-7, Y-8, Y-20, Y-21, Y-22, Y-28, Y-29, Y-30, Y-31, Y-41, Y-43, Y-64, Y-65, Y-66, Y-68, Y-71, Y-72, Y-98 또는 Y-99 가 바람직하고, Y-22, Y-28, Y-30, Y-31, Y-72, Y-98, Y-99, Y-100, Y-101, Y-102, Y-103 또는 Y-104 가 보다 바람직하다.Specific examples of Y 1 and Y 2 include the following Y-1 to Y-99. Y-21, Y-22, Y-28, Y-29, Y-30, Y-31 and Y-41 from the viewpoint of availability of monomers , Y-43, Y-64, Y-65, Y-66, Y-68, Y-71, Y- Y-101, Y-102, Y-103 or Y-104 are more preferable.
[화학식 9] [Chemical Formula 9]
[화학식 10] [Chemical formula 10]
[화학식 11] (11)
[화학식 12] [Chemical Formula 12]
[화학식 13] [Chemical Formula 13]
[화학식 14] [Chemical Formula 14]
[화학식 15] [Chemical Formula 15]
[화학식 16] [Chemical Formula 16]
[화학식 17] [Chemical Formula 17]
[화학식 18] [Chemical Formula 18]
[화학식 19] [Chemical Formula 19]
[화학식 20] [Chemical Formula 20]
[화학식 21] [Chemical Formula 21]
상기 PAE-PAA 공중합체에 있어서, 식 (1) 로 나타내는 구조 단위의 (함유) 비율은, 전체 구조 단위에 대해서, 50 ∼ 95 몰％ 가 바람직하고, 70 ∼ 90 몰％ 가 보다 바람직하다. 또, 상기 PAE-PAA 공중합체에 있어서, 식 (2) 로 나타내는 구조 단위의 (함유) 비율은, 전체 구조 단위에 대해서, 5 ∼ 50 몰％ 가 바람직하고, 10 ∼ 30 몰％ 가 보다 바람직하다.In the PAE-PAA copolymer, the proportion of the structural unit represented by formula (1) is preferably from 50 to 95 mol%, more preferably from 70 to 90 mol%, based on the total structural units. In the PAE-PAA copolymer, the proportion of the structural unit represented by formula (2) is preferably 5 to 50 mol%, more preferably 10 to 30 mol%, based on the total structural units .
＜PAE-PAA 공중합체의 제조 방법＞≪ Process for producing PAE-PAA copolymer >
본 발명의 PAE-PAA 공중합체는, 이하의 방법에 의해서 제조된다.The PAE-PAA copolymer of the present invention is produced by the following method.
상기 식 (1) 로 나타내는 구조 단위에 있어서 X1 을 형성하는 테트라카르복실산디에스테르와, 상기 (1) 및 식 (2) 에 있어서 Y1 및 Y2 를 형성하는 디아민을, 축합제, 염기 및 유기 용매의 존재하에서 -20 ℃ ∼ 150 ℃, 바람직하게는 0 ℃ ∼ 50 ℃ 에 있어서, 30 분 ∼ 24 시간, 바람직하게는 1 ∼ 12 시간 중축합 반응시킨 후, 염기를 중화할 목적에서 인산디페닐을 첨가하고, 상기 식 (2) 로 나타내는 구조 단위에 있어서 X2 를 형성하는 테트라카르복실산 혹은 그 2 무수물을 첨가하며, 0 ℃ ∼ 50 ℃ 의 온도하에서, 30 분 ∼ 24 시간, 바람직하게는 1 ∼ 12 시간 추가로 반응시킴으로써 제조된다.A tetracarboxylic acid diester forming X 1 in the structural unit represented by the above formula (1) and a diamine forming Y 1 and Y 2 in the above-mentioned (1) and (2) with a condensing agent, Is subjected to a polycondensation reaction in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 12 hours, Phenyl and the tetracarboxylic acid or its dianhydride which forms X 2 in the structural unit represented by the formula (2) is added and heated at a temperature of 0 ° C to 50 ° C for 30 minutes to 24 hours, Is further reacted for 1 to 12 hours.
상기한 반응에 사용하는 유기 용매는, 모노머 및 폴리머의 용해성으로부터 N,N-디메틸포름아미드, N-메틸-2-피롤리돈, 또는 γ-부티로락톤이 바람직하고, 이것들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다. 폴리머의 농도는, 폴리머의 석출이 일어나기 어려우며, 또한 고분자량체가 얻어지기 쉽다는 관점에서, 1 ∼ 30 질량％ 가 바람직하고, 5 ∼ 20 질량％ 가 보다 바람직하다.The organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of the monomer and the polymer, A mixture of two or more species may be used. The concentration of the polymer is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a high molecular weight product is easily obtained.
상기 축합제에는, 트리페닐포스파이트, 디시클로헥실카르보디이미드, 1-에틸-3-(3-디메틸아미노프로필)카르보디이미드염산염, N,N'-카르보닐디이미다졸, 디메톡시-1,3,5-트리아지닐메틸모르폴리늄, O-(벤조트리아졸-1-일)-N,N,N',N'-테트라메틸우로늄테트라플루오로보레이트, O-(벤조트리아졸-1-일)-N,N,N',N'-테트라메틸우로늄헥사플루오로포스페이트, (2,3-디하이드로-2-티옥소-3-벤조옥사졸릴)포스폰산디페닐 등을 사용할 수 있다. 축합제의 첨가량은, 테트라카르복실산디에스테르에 대해서 2 ∼ 3 배 몰인 것이 바람직하다.Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3- dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, dimethoxy- N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate and (2,3-dihydro-2-thioxo-3-benzoxazolyl) . The addition amount of the condensing agent is preferably 2 to 3 times the mole of the tetracarboxylic acid diester.
상기 염기로는, 피리딘, 트리에틸아민 등의 3 급 아민을 사용할 수 있다. 염기의 첨가량은, 제거가 용이한 양이며, 또한 고분자량체가 얻어지기 쉽다는 관점에서, 디아민 성분에 대해서 2 ∼ 4 배 몰이 바람직하다.As the base, a tertiary amine such as pyridine or triethylamine can be used. The amount of the base to be added is an amount that can be easily removed, and it is preferably 2 to 4 times the amount of the diamine component from the viewpoint of easily obtaining a high molecular weight product.
상기와 같이 하여 얻어진 PAE-PAA 공중합체는, 반응 용액을 잘 교반시키면서 빈용매에 주입함으로써, 폴리머를 석출시켜 회수할 수 있다. 또, 석출을 수 회 행하고, 빈용매로 세정 후, 상온 혹은 가열 건조시킴으로써 정제된 PAE-PAA 공중합체의 분말을 얻을 수 있다. 빈용매는, 특별히 한정되지 않지만, 물, 메탄올, 에탄올, 헥산, 부틸셀로솔브, 아세톤, 톨루엔 등을 들 수 있다.The PAE-PAA copolymer obtained as described above can be recovered by precipitating a polymer by injecting the reaction solution into a poor solvent while stirring well. It is also possible to obtain a powder of the purified PAE-PAA copolymer by precipitation several times, washing with a poor solvent, and then drying at room temperature or by heating and drying. Examples of the poor solvent include, but are not limited to, water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
PAE-PAA 공중합체의 중량 평균 분자량은, 바람직하게는 10,000 ∼ 305,000 이며, 보다 바람직하게는 10,000 ∼ 210,000 이다. 또, 수 평균 분자량은, 바람직하게는 5,000 ∼ 152,500 이며, 보다 바람직하게는 10,000 ∼ 105,000 이다.The weight average molecular weight of the PAE-PAA copolymer is preferably 10,000 to 305,000, more preferably 10,000 to 210,000. The number average molecular weight is preferably 5,000 to 152,500, and more preferably 10,000 to 105,000.
＜성분 (B) : 가교성 관능기를 2 개 이상 함유하는 화합물＞<Component (B): a compound containing two or more crosslinkable functional groups>
본 발명의 액정 배향제에 함유되는 성분 (B) 는, 가교성 관능기를 2 개 이상 함유하는 화합물이다.The component (B) contained in the liquid crystal aligning agent of the present invention is a compound containing two or more crosslinkable functional groups.
가교성 관능기로는, 하이드록실기, 하이드록시알킬아미드기, (메트)아크릴레이트기, 블록 이소시아네이트기, 옥세탄기 및 에폭시기로부터 이루어지는 군에서 선택되는 적어도 1 종을 들 수 있지만, 이에 한정되는 것은 아니다.Examples of the crosslinkable functional group include at least one member selected from the group consisting of a hydroxyl group, a hydroxyalkylamide group, a (meth) acrylate group, a block isocyanate group, an oxetane group and an epoxy group, no.
그 중에서도, 입수성 및 전압 유지율 개선 효과의 관점에서, 하이드록실기, 블록 이소시아네이트기 또는 에폭시기가 바람직하고, 하이드록실기 또는 에폭시기가 보다 바람직하다.Among them, a hydroxyl group, a block isocyanate group or an epoxy group is preferable, and a hydroxyl group or an epoxy group is more preferable from the viewpoint of availability and voltage maintaining ratio improvement effect.
또한, 성분 (B) 의 화합물은, 그 구조 중에 동일한 가교성 관능기를 2 개 이상 갖고 있어도 되고, 상이한 2 종 이상의 가교성 관능기를 2 개 이상 갖고 있어도 된다.The compound of the component (B) may have two or more of the same crosslinkable functional groups in its structure, or may have two or more different kinds of crosslinkable functional groups.
하이드록실기를 2 개 이상 함유하는 화합물로는, 예를 들어, 하기 식 (3) 으로 나타내는 화합물을 들 수 있다.Examples of the compound containing two or more hydroxyl groups include compounds represented by the following formula (3).
[화학식 22] [Chemical Formula 22]
상기 식 (3) 중, X3 은, 탄소수 1 ∼ 20 의 지방족 탄화수소기, 또는 방향족 탄화수소기를 함유하는 n 가의 유기기이다. 그 중에서도, 탄소수 1 ∼ 20, 바람직하게는 탄소수 1 ∼ 10, 보다 바람직하게는 탄소수 1 ∼ 5 의 지방족 탄화수소기가 바람직하다. R2 및 R3 은, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는 탄소수 1 ∼ 4 의 알킬기, 탄소수 2 ∼ 4 의 알케닐기, 또는 탄소수 2 ∼ 4 의 알키닐기이고, R2 및 R3 중 적어도 1 개는 하기 식 (4) 로 나타내어지는 것이지만, R2 및 R3 모두가 하기 식 (4) 로 나타내어지는 것이 바람직하다. n 은 2 ∼ 6 의 정수, 특히 2 가 바람직하다.In the formula (3), X 3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an n-valent organic group containing an aromatic hydrocarbon group. Among them, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms is preferable. R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms, which may have a substituent, and R 2 and R 3 , At least one of R < 2 > and R < 3 > is preferably represented by the following formula (4). n is an integer of 2 to 6, preferably 2.
[화학식 23] (23)
상기 식 (4) 중, R4 ∼ R7 은, 각각 독립적으로, 수소 원자, 탄화수소기 또는, 하이드록시기로 치환된 탄화수소기이고, 수소 원자가 바람직하다.In the formula (4), R 4 to R 7 are each independently a hydrogen atom, a hydrocarbon group or a hydrocarbon group substituted with a hydroxy group, and preferably a hydrogen atom.
X3 은, 지방족 탄화수소기인 것이, 상기와 마찬가지로 액정 배향성 및 용해성의 관점에서 바람직하고, 탄소수 1 ∼ 10 인 것이 보다 바람직하다. n 은 2 ∼ 6 의 정수를 나타내지만, 용해성의 관점에서 n 은 2 ∼ 4 가 바람직하다.X 3 is preferably an aliphatic hydrocarbon group from the viewpoint of liquid crystal alignability and solubility, and more preferably from 1 to 10 carbon atoms, as described above. n represents an integer of 2 to 6, but n is preferably 2 to 4 from the viewpoint of solubility.
하이드록실기를 2 개 이상 함유하는 화합물로는, 구체적으로는 이하의 화합물을 예시할 수 있다.Specific examples of the compound containing two or more hydroxyl groups include the following compounds.
[화학식 24] ≪ EMI ID =
블록 이소시아네이트기를 2 개 이상 함유하는 화합물로는, 하기 식 (5) 로 나타내는 화합물을 예시할 수 있다.As the compound containing two or more block isocyanate groups, a compound represented by the following formula (5) can be exemplified.
[화학식 25] (25)
식 (5) 중, Z 는, 각각 독립적으로, 탄소수 1 ∼ 3 의 알킬기, 수산기 또는 하기 식 (6) 으로 나타내는 유기기이고, Z 의 적어도 하나는, 하기 식 (6) 으로 나타내는 유기기이다.In the formula (5), Z is independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or an organic group represented by the following formula (6), and at least one of Z is an organic group represented by the following formula (6).
[화학식 26] (26)
블록 이소시아네이트기를 2 개 이상 함유하는 화합물로는, 구체적으로는, 이하의 화합물을 예시할 수 있다.As the compound containing two or more block isocyanate groups, specifically, the following compounds can be exemplified.
[화학식 27] (27)
상기 식 (7) 이외의 블록 이소시아네이트기를 2 개 이상 함유하는 화합물로는, 이하의 화합물을 예시할 수 있다.As the compound containing two or more block isocyanate groups other than the above-mentioned formula (7), the following compounds can be exemplified.
[화학식 28] (28)
에폭시기를 2 개 이상 함유하는 화합물로는, 구체적으로는, 이하의 화합물을 예시할 수 있다.As the compound containing two or more epoxy groups, specifically, the following compounds can be exemplified.
[화학식 29] [Chemical Formula 29]
[화학식 30] (30)
(메트)아크릴레이트기를 2 개 이상 함유하는 화합물로는, 구체적으로는, 이하의 화합물을 예시할 수 있다.Specific examples of the compound containing two or more (meth) acrylate groups include the following compounds.
[화학식 31] (31)
가교성 관능성을 2 개 이상 갖는 화합물로는, 그 밖에 이하의 화합물도 예시할 수 있다.As the compound having two or more crosslinkable functionalities, the following compounds may also be mentioned.
[화학식 32] (32)
성분 (B) 의 화합물은, 본 발명의 액정 배향제 중의 (A) 성분에 대해서 1 ∼ 30 중량％ 함유되는 것이 바람직하고, 보다 바람직하게는 3 ∼ 15 중량％ 이다.The compound of the component (B) is preferably contained in an amount of 1 to 30% by weight, more preferably 3 to 15% by weight based on the component (A) in the liquid crystal aligning agent of the present invention.
＜액정 배향제＞<Liquid Crystal Aligner>
본 발명의 액정 배향제는, 상기한 PAE-PAA 공중합체, 및 가교성 관능기를 2 개 이상 함유하는 화합물이 유기 용매 중에 용해된 용액의 형태이다. 각 성분을 유기 용매 중에서 합성한 경우에는, 얻어지는 반응 용액 그 자체여도 되고, 또, 이 반응 용액을 적절한 용매로 희석한 것이어도 된다. 또, 각 성분을 분말로서 얻은 경우에는, 이것을 유기 용매에 용해시켜 용액으로 한 것이어도 된다.The liquid crystal aligning agent of the present invention is in the form of a solution in which the above-mentioned PAE-PAA copolymer and a compound containing two or more crosslinkable functional groups are dissolved in an organic solvent. When each component is synthesized in an organic solvent, the reaction solution itself may be obtained, or the reaction solution may be diluted with an appropriate solvent. When each component is obtained as a powder, it may be dissolved in an organic solvent to form a solution.
본 발명의 액정 배향제에 있어서의, PAE-PAA 공중합체를 함유하는 폴리머 성분의 함유량 (농도) 은, 형성시키고자 하는 폴리이미드막의 두께의 설정에 따라서도 적절히 변경할 수 있는데, 균일하고 결함이 없는 도막을 형성시킨다는 점에서, 유기 용매에 대해서, 폴리머 성분의 함유량은, 0.5 질량％ 이상이 바람직하고, 용액의 보존 안정성의 점에서는 15 질량％ 이하가 바람직하며, 보다 바람직하게는 1 ∼ 10 질량％ 이다.The content (concentration) of the polymer component containing the PAE-PAA copolymer in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the setting of the thickness of the polyimide film to be formed. The content of the polymer component in the organic solvent is preferably 0.5% by mass or more, more preferably 15% by mass or less, more preferably 1 to 10% by mass or less, to be.
이 경우, 미리, 폴리머의 농후 용액을 제조하고, 이러한 농후 용액으로부터 액정 배향제로 하는 경우에 희석해도 된다. 이러한 폴리머 성분의 농후 용액의 농도는 10 ∼ 30 질량％ 가 바람직하고, 10 ∼ 15 질량％ 가 보다 바람직하다. 또, 폴리머 성분의 분말을 유기 용매에 용해시켜 용액을 제조할 때 가열해도 된다. 가열 온도는, 20 ∼ 150 ℃ 가 바람직하고, 20 ∼ 80 ℃ 가 특히 바람직하다.In this case, a polymer-rich solution may be prepared in advance and may be diluted when the liquid-crystal aligning agent is prepared from such a concentrated solution. The concentration of the concentrated solution of the polymer component is preferably 10 to 30% by mass, more preferably 10 to 15% by mass. The polymer component powder may be dissolved in an organic solvent to prepare a solution. The heating temperature is preferably 20 to 150 占 폚, particularly preferably 20 to 80 占 폚.
본 발명의 액정 배향제에 함유되는 상기 유기 용매는, 폴리머 성분이 균일하게 용해되는 것이면 특별히 한정되지 않는다. 그 구체예를 든다면, N,N-디메틸포름아미드, N,N-디에틸포름아미드, N,N-디메틸아세트아미드, N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, N-메틸카프로락탐, 2-피롤리돈, N-비닐-2-피롤리돈, 디메틸술폭시드, 디메틸술폰, γ-부티로락톤, 1,3-디메틸-이미다졸리디논, 3-메톡시-N,N-디메틸프로판아미드 등을 들 수 있다. 이것들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다. 또, 단독으로는 폴리머 성분을 균일하게 용해시킬 수 없는 용매여도, 폴리머가 석출되지 않는 범위이면, 상기한 유기 용매에 혼합해도 된다.The organic solvent contained in the liquid crystal aligning agent of the present invention is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl- Pyrrolidone, N-vinyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, gamma -butyrolactone, 1,3-dimethyl-imidazolidinone, 3- Methoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination of two or more. Insofar as the solvent alone can not dissolve the polymer component uniformly, it may be mixed with the organic solvent as long as the polymer is not precipitated.
본 발명의 액정 배향제는, 폴리머 성분을 용해시키기 위한 유기 용매 외에, 액정 배향제를 기판에 도포할 때의 도막 균일성을 향상시키기 위한 용매를 함유해도 된다. 이러한 용매는, 일반적으로 상기 유기 용매보다 낮은 표면 장력의 용매가 사용된다. 그 구체예를 들면, 에틸셀로솔브, 부틸셀로솔브, 부틸셀로솔브아세테이트, 에틸카르비톨, 부틸카르비톨, 에틸카르비톨아세테이트, 에틸렌글리콜, 1-메톡시-2-프로판올, 1-에톡시-2-프로판올, 1-부톡시-2-프로판올, 1-페녹시-2-프로판올, 프로필렌글리콜모노아세테이트, 프로필렌글리콜디아세테이트, 프로필렌글리콜-1-모노메틸에테르-2-아세테이트, 프로필렌글리콜-1-모노에틸에테르-2-아세테이트, 디프로필렌글리콜, 2-(2-에톡시프로폭시)프로판올, 락트산메틸에스테르, 락트산에틸에스테르, 락트산n-프로필에스테르, 락트산n-부틸에스테르, 락트산이소아밀에스테르 등을 들 수 있다. 이들 용매는 2 종류 이상을 병용해도 된다.The liquid crystal aligning agent of the present invention may contain, in addition to the organic solvent for dissolving the polymer component, a solvent for improving the film uniformity when the liquid crystal aligning agent is applied to the substrate. Such a solvent generally uses a solvent having a surface tension lower than that of the organic solvent. Specific examples thereof include ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Lactic acid methyl ester, lactic acid ethyl ester, lactic acid n-propyl ester, lactic acid n-butyl ester, lactic acid isoamyl ester, lactic acid ethyl ester-2-acetate, dipropylene glycol, 2- (2- ethoxypropoxy) propanol, Esters and the like. These solvents may be used in combination of two or more.
본 발명의 액정 배향제는, 상기한 것 외에, 액정 배향제를 도포했을 때의 막두께 균일성이나 표면 평활성을 향상시키는 화합물, 실란 커플링제나 가교제 등의 각종 첨가제를 함유해도 된다. The liquid crystal aligning agent of the present invention may contain various additives such as a compound which improves the film thickness uniformity and surface smoothness when the liquid crystal aligning agent is applied, a silane coupling agent and a crosslinking agent, in addition to the above.
막두께의 균일성이나 표면 평활성을 향상시키는 화합물로는, 불소계 계면 활성제, 실리콘계 계면 활성제, 논이온계 계면 활성제 등을 들 수 있다.Examples of the compound that improves film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent.
보다 구체적으로는, 예를 들어, 에프톱 (토켐 프로덕트사 상품명, EF301, EF303, EF352), 메가팩 (다이니폰 잉크사 상품명, F171, F173, R-30, 플로라이드 (스미토모 스리엠사 상품명, FC430, FC431, 아사히가드 (아사히 가라스사 상품명, AG710, 서프론 (아사히 가라스사 상품명, S-382, SC101, SC102, SC103, SC104, SC105, SC106 등을 들 수 있다.More specifically, for example, there may be mentioned, for example, a trade name of EFtop (trade name of EF301, EF303, EF352), Megapack (trade name of Dainippon Ink, F171, F173, R-30, Fluoride , FC431, Asahi Guard (trade name of Asahi Glass Co., AG710, Surflon (trade name of Asahi Glass Co., Ltd., S-382, SC101, SC102, SC103, SC104, SC105, SC106 and the like).
이들 계면 활성제의 사용 비율은, 액정 배향제에 함유되는 수지 성분의 100 질량부에 대해서, 바람직하게는 0.01 ∼ 2 질량부, 보다 바람직하게는 0.01 ∼ 1 질량부이다.The proportion of these surfactants to be used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass based on 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
실란 커플링제는, 액정 배향제가 도포되는 기판과, 그곳에 형성되는 액정 배향막의 밀착성을 향상시킬 목적에서 첨가되는 것이다. 예를 들어, 이하의 각종 실란 커플링제를 구체예로 들 수 있는데, 이것들에 한정되는 것은 아니다.The silane coupling agent is added for the purpose of improving adhesion between the substrate to which the liquid crystal aligning agent is applied and the liquid crystal alignment film formed thereon. For example, the following various silane coupling agents may be mentioned as concrete examples, but the present invention is not limited thereto.
3-아미노프로필트리에톡시실란, 3-(2-아미노에틸)아미노프로필트리메톡시실란, 3-(2-아미노에틸)아미노프로필메틸디메톡시실란, 3-아미노프로필트리메톡시실란, 3-페닐아미노프로필트리메톡시실란, 3-트리에톡시실릴-N-(1,3-디메틸부틸리덴)프로필아민, 3-아미노프로필디에톡시메틸실란 등의 아민계 ; 비닐트리메톡시실란, 비닐트리에톡시실란, 비닐트리스(2-메톡시에톡시)실란, 비닐메틸디메톡시실란, 비닐트리아세톡시실란, 비닐트리이소프로폭시실란, 알릴트리메톡시실란, p-스티릴트리메톡시실란 등의 비닐계 ; 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필트리에톡시실란, 3-글리시독시프로필메틸디에톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시시클로헥실)에틸트리메톡시실란 등의 에폭시계 ; 3-메타크릴옥시프로필메틸디메톡시실란, 3-메타크릴옥시프로필트리메톡시실란, 3-메타크릴옥시프로필메틸디에톡시실란, 3-메타크릴옥시프로필트리에톡시실란 등의 메타크릴계 ; 3-아크릴옥시프로필트리메톡시실란 등의 아크릴계 ; 3-우레이도프로필트리에톡시실란 등의 우레이드계 ; 비스(3-(트리에톡시실릴)프로필)디술파이드, 비스(3-(트리에톡시실릴)프로필)테트라술파이드 등의 술파이드계 ; 3-메르캅토프로필메틸디메톡시실란, 3-메르캅토프로필트리메톡시실란, 3-옥타노일티오-1-프로필트리에톡시실란 등의 메르캅토계 ; 3-이소시아네이트프로필트리에톡시실란, 3-이소시아네이트프로필트리메톡시실란 등의 이소시아네이트계 ; 트리에톡시실릴부틸알데히드 등의 알데히드계 ; 트리에톡시실릴프로필메틸카르바메이트, (3-트리에톡시실릴프로필)-t-부틸카르바메이트 등의 카르바메이트계.Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- Amines such as phenylaminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine and 3-aminopropyldiethoxymethylsilane; Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylmethyldimethoxysilane, vinyltriacetoxysilane, vinyltriisopropoxysilane, allyltrimethoxysilane, p Vinyl-based ones such as styryltrimethoxysilane; 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 - epoxycyclohexyl) ethyltrimethoxysilane; A methacrylic system such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; Acrylate such as 3-acryloxypropyltrimethoxysilane; 3-ureidopropyltriethoxysilane and the like; Sulfide systems such as bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide; A mercapto group such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-octanoylthio-1-propyltriethoxysilane; Isocyanate-based ones such as 3-isocyanatepropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane; Aldehyde-based compounds such as triethoxysilylbutylaldehyde; Carbamate-based compounds such as triethoxysilylpropylmethylcarbamate and (3-triethoxysilylpropyl) -t-butylcarbamate.
실란 커플링제의 첨가량은, 지나치게 많으면 미반응의 것이 액정 배향성에 악영향을 미치는 경우가 있고, 지나치게 적으면 밀착성에 대한 효과가 나타나지 않기 때문에, 폴리머의 고형분에 대해서 0.01 ∼ 5.0 중량％ 가 바람직하고, 0.1 ∼ 1.0 중량％ 가 보다 바람직하다.When the amount of the silane coupling agent is too large, the unreacted portion adversely affects the liquid crystal alignability. When the amount is too small, the silane coupling agent does not show an effect on the adhesiveness. Therefore, it is preferably 0.01 to 5.0 wt% To 1.0% by weight is more preferable.
본 발명의 액정 배향막에는, 도막을 소성할 때, PAE-PAA 공중합체 또는 폴리아믹산에스테르의 이미드화를 효율적으로 진행시키기 위해서, 이미드화 촉진제를 첨가해도 된다.In the liquid crystal alignment film of the present invention, an imidization accelerator may be added to the PAE-PAA copolymer or the polyamic acid ester in order to efficiently proceed imidization of the PAE-PAA copolymer or the polyamic acid ester when the coat film is baked.
＜액정 배향막＞≪ Liquid crystal alignment film &
본 발명의 액정 배향막은, 본 발명의 액정 배향제를 기판에 도포하고, 필요에 따라서 건조시킨 후, 소성하여 얻어지는 막이다. 본 발명의 액정 배향제를 도포하는 기판으로는 투명성이 높은 기판이면 특별히 한정되지 않고, 예를 들어, 유리 기판 외에, 아크릴 기판이나 폴리카보네이트 기판 등의 플라스틱 기판을 사용할 수 있다. 액정 표시 소자의 제조에 있어서 본 발명의 액정 배향제를 사용할 경우, 액정 구동을 위한 ITO (Indium Tin Oxide) 전극 등이 형성된 기판을 사용하여, 액정 배향막을 형성하는 것이 바람직하다. 또, 반사형의 액정 표시 소자를 제조할 경우에는, 편측의 기판에만이라면 실리콘 웨이퍼 등의 불투명한 기판에서도 사용할 수 있고, 이 경우의 전극은 알루미늄 등의 광을 반사하는 재료를 사용할 수도 있다.The liquid crystal alignment film of the present invention is a film obtained by applying the liquid crystal aligning agent of the present invention to a substrate, drying it if necessary, and then firing it. The substrate to which the liquid crystal aligning agent of the present invention is applied is not particularly limited as long as it is a substrate having high transparency. For example, in addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. When the liquid crystal aligning agent of the present invention is used in the production of a liquid crystal display element, it is preferable to form a liquid crystal alignment film by using a substrate on which an ITO (Indium Tin Oxide) electrode for liquid crystal driving is formed. When a reflection type liquid crystal display element is manufactured, it can be used for an opaque substrate such as a silicon wafer only on a substrate on one side. In this case, a material that reflects light such as aluminum can also be used.
본 발명의 액정 배향제를 기판 상에 도포하는 방법으로는, 예를 들어, 스크린 인쇄, 오프셋 인쇄, 플렉소 인쇄 또는 잉크젯법을 들 수 있다. 그 밖의 도포 방법으로는, 딥법, 롤 코터법, 슬릿 코터법, 스피너법 또는 스프레이법 등이 있고, 목적에 따라서 이것들을 사용해도 된다.As a method of applying the liquid crystal aligning agent of the present invention on a substrate, for example, screen printing, offset printing, flexographic printing or inkjet method can be mentioned. Examples of other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spraying method, and these may be used depending on the purpose.
도포막은, 통상적으로 함유되는 유기 용매를 충분히 제거하기 위해서 50 ∼ 120 ℃ 에서 1 ∼ 10 분 건조시키고, 그 후 150 ∼ 300 ℃ 에서 5 분 ∼ 120 분 소성된다. 소성 후의 도막의 두께는, 특별히 한정되지 않지만, 지나치게 얇으면 액정 표시 소자의 신뢰성이 저하되는 경우가 있기 때문에, 5 ∼ 300 ㎚, 바람직하게는 10 ∼ 200 ㎚ 이다.The coating film is dried at 50 to 120 ° C for 1 to 10 minutes and then at 150 to 300 ° C for 5 to 120 minutes in order to sufficiently remove the organic solvent ordinarily contained therein. The thickness of the coated film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may deteriorate. Therefore, it is 5 to 300 nm, preferably 10 to 200 nm.
얻어진 액정 배향막을 배향 처리하는 방법으로는, 러빙법, 광배향 처리법 등을 들 수 있다.Examples of a method for aligning the obtained liquid crystal alignment film include a rubbing method and an optical alignment treatment method.
기판 상에 형성된 도막면의 러빙 처리는, 기존의 러빙 장치를 사용할 수 있다. 이 때의 러빙 천의 재질로는, 코튼, 레이온, 나일론 등을 들 수 있다. 러빙 처리의 조건으로는, 일반적으로, 회전 속도 300 ∼ 2000 rpm, 전송 속도 5 ∼ 100 ㎜/s, 압입량 0.1 ∼ 1.0 ㎜ 라는 조건이 사용된다. 그 후, 순수나 알코올 등을 사용하여 초음파 세정으로 러빙에 의해서 발생된 잔류물이 제거된다.Conventional rubbing apparatuses can be used for rubbing the coating film surface formed on the substrate. Examples of the material of the rubbing cloth at this time include cotton, rayon, nylon and the like. Conditions for the rubbing treatment are generally a condition of a rotation speed of 300 to 2000 rpm, a transfer speed of 5 to 100 mm / s, and an indentation amount of 0.1 to 1.0 mm. Thereafter, the residue generated by rubbing is removed by ultrasonic cleaning using pure water, alcohol, or the like.
광배향 처리법으로는, 상기 도막 표면에, 일정 방향으로 편향된 방사선을 조사하고, 경우에 따라서는 추가로, 150 ∼ 250 ℃ 의 온도에서 가열 처리를 행하여, 액정 배향능을 부여하는 방법을 들 수 있다. 방사선으로는, 100 ∼ 800 ㎚ 의 파장을 갖는 자외선 및 가시 광선을 사용할 수 있다. 이 중, 100 ∼ 400 ㎚ 의 파장을 갖는 자외선이 바람직하고, 200 ∼ 400 ㎚ 의 파장을 갖는 것이 특히 바람직하다. 또, 액정 배향성을 개선하기 위해서, 도막 기판을 50 ∼ 250 ℃ 에서 가열하면서, 방사선을 조사해도 된다. 상기 방사선의 조사량은, 1 ∼ 10,000 mJ/㎠ 가 바람직하고, 100 ∼ 5,000 mJ/㎠ 가 특히 바람직하다. The photo-alignment treatment method includes a method of irradiating the surface of the above-mentioned coating film with radiation deflected in a predetermined direction, and if necessary, further heating treatment at a temperature of 150 to 250 ° C to give a liquid crystal aligning ability . As the radiation, ultraviolet rays and visible rays having a wavelength of 100 to 800 nm can be used. Of these, ultraviolet rays having a wavelength of 100 to 400 nm are preferable, and those having a wavelength of 200 to 400 nm are particularly preferable. In addition, in order to improve the liquid crystal alignment property, the coating film substrate may be irradiated with radiation while heating at 50 to 250 ° C. The irradiation dose of the radiation is preferably 1 to 10,000 mJ / cm 2, and particularly preferably 100 to 5,000 mJ / cm 2.
＜액정 표시 소자＞<Liquid crystal display element>
본 발명의 액정 표시 소자는, 상기한 수법에 의해서 본 발명의 액정 배향제로부터 액정 배향막 부착 기판을 얻은 후, 공지된 방법으로 액정셀을 제조하여, 액정 표시 소자로 한 것이다.The liquid crystal display element of the present invention is obtained by obtaining a liquid crystal alignment film-attached substrate from the liquid crystal aligning agent of the present invention by the above-mentioned technique, and then manufacturing a liquid crystal cell by a known method to obtain a liquid crystal display element.
액정 표시 소자의 제조 방법의 일례는 아래와 같다. 먼저, 액정 배향막이 형성된 1 쌍의 기판을 준비하고, 그것들을 바람직하게는 1 ∼ 30 ㎛, 보다 바람직하게는 2 ∼ 10 ㎛ 의 스페이서를 사이에 두고, 러빙 방향이 0˚∼ 270˚ 인 임의의 각도가 되도록 설치하고, 주위를 시일제로 고정시킨다. 이어서, 기판 사이에 액정을 주입하여 봉지한다. 액정 봉입의 방법에 대해서는 특별히 제한되지 않고, 제조된 액정셀 내를 감압으로 한 후에 액정을 주입하는 진공법, 액정을 적하한 후에 봉지를 행하는 적하법 등을 예시할 수 있다.An example of a method of manufacturing a liquid crystal display element is as follows. First, a pair of substrates on which a liquid crystal alignment film is formed are prepared, and they are bonded together with a spacer having a thickness of preferably 1 to 30 탆, more preferably 2 to 10 탆, Install it in an angle, and fix the surroundings with sealant. Subsequently, liquid crystal is injected between the substrates and sealed. The liquid crystal sealing method is not particularly limited, and examples thereof include a vacuum method in which liquid crystal is injected into the produced liquid crystal cell at a reduced pressure, a dropping method in which sealing is performed after liquid crystal is dropped.
[실시예] [Example]
이하에 실시예를 들어 본 발명을 구체적으로 설명하지만, 본 발명은 이것들에 한정하여 해석되는 것은 아니다. 이후에 사용하는 화합물의 약호, 및 각 특성의 측정 방법은 다음과 같다.Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not construed as being limited thereto. The abbreviations of the compounds to be used hereinafter and the measurement methods of the respective properties are as follows.
＜모노머＞<Monomer>
1,3DMCBDE-Cl : 디메틸1,3-비스(클로로카르보닐)-1,3-디메틸시클로부탄-2,4-디카르복실레이트1,3 DMCBDE-Cl: dimethyl 1,3-bis (chlorocarbonyl) -1,3-dimethylcyclobutane-2,4-dicarboxylate
1,3DMCBDA : 1,3-디메틸1,2,3,4시클로부탄테트라카르복실산 2 무수물1,3 DMCBDA: 1,3-dimethyl 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride
PMDA : 피로멜리트산 2 무수물PMDA: pyromellitic acid dianhydride
PMDE-me : 2,5-비스(메톡시카르보닐)벤젠-1,4디카르복실산PMDE-me: 2,5-bis (methoxycarbonyl) benzene-1,4-dicarboxylic acid
CBDE : 2,4-비스(메톡시카르보닐)시클로부탄1,3-디카르복실산CBDE: 2,4-bis (methoxycarbonyl) cyclobutane 1,3-dicarboxylic acid
CBDA : 1,2,3,4-시클로부탄테트라카르복실산 2 무수물CBDA: 1,2,3,4-Cyclobutane tetracarboxylic acid dianhydride
DADPA : 4,4'-디아미노디페닐아민DADPA: 4,4'-diaminodiphenylamine
p-PDA : p-페닐렌디아민p-PDA: p-phenylenediamine
DBOP : 디페닐(2,3-디하이드로-2-티옥소-3-벤조옥사졸릴)포스포네이트DBOP: diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate
[화학식 33] (33)
＜용제＞<Solvent>
NMP : N-메틸-2-피롤리돈NMP: N-methyl-2-pyrrolidone
BCS : 부틸셀로솔브BCS: butyl cellosolve
GBL : γ-부티로락톤GBL:? -Butyrolactone
＜점도＞<Viscosity>
중합체 용액의 점도는, E 형 점도계 TVE-22H (토키 산업사 제조) 를 사용하여, 샘플량 1.1 ㎖, 콘 로터 TE-1 (1˚34', R24), 온도 25 ℃ 에서 측정하였다The viscosity of the polymer solution was measured at a sample amount of 1.1 ml, a cone rotor TE-1 (1 占 34 ', R24) and a temperature of 25 占 폚 using an E-type viscometer TVE-22H
＜분자량＞<Molecular Weight>
중합체의 분자량은 GPC (상온 겔 침투 크로마토그래피) 장치에 의해서 측정하고, 폴리에틸렌글리콜, 폴리에틸렌옥사이드 환산치로 하여 수 평균 분자량 (이하, Mn 이라고도 한다.) 과 중량 평균 분자량 (이하, Mw 라고도 한다.) 을 산출하였다The molecular weight of the polymer is measured by a GPC (room temperature gel permeation chromatography) apparatus, and the number average molecular weight (hereinafter also referred to as Mn) and the weight average molecular weight (hereinafter also referred to as Mw) are determined as polyethylene glycol and polyethylene oxide equivalent Respectively.
GPC 장치 : Shodex 사 제조 (GPC-101) GPC apparatus: manufactured by Shodex Corp. (GPC-101)
칼럼 : Shodex 사 제조 (KD803, KD805 의 직렬) Column: manufactured by Shodex Co., Ltd. (serial of KD803, KD805)
칼럼 온도 : 50 ℃ Column temperature: 50 ° C
용리액 : N,N-디메틸포름아미드 (첨가제로서 브롬화 리튬-수화물 (LiBr·H2O) 을 30 m㏖/ℓ, 인산·무수 결정 (o-인산) 을 30 m㏖/ℓ, 테트라하이드로푸란 (THF) 을 10 ㎖ /ℓ 함유한다) Eluent: N, N- dimethylformamide (lithium bromide as an additive-hydrate (LiBr · H 2 O) for 30 m㏖ / ℓ, phosphoric acid, anhydrous crystals (o- phosphoric acid) 30 m㏖ / ℓ, tetrahydrofuran ( THF) at 10 ml / l)
유속 : 1.0 ㎖ /분Flow rate: 1.0 ml / min
검량선 작성용 표준 샘플 : 토소사 제조 TSK 표준 폴리에틸렌옥사이드 (중량 평균 분자량 (Mw) 약 900,000, 150,000, 100,000, 30,000), 및, 폴리머 레버러토리사 제조 폴리에틸렌글리콜 (피크 탑 분자량 (Mp) 약 12,000, 4,000, 1,000). 측정은, 피크가 중첩되는 것을 피하기 위해서, 900,000, 100,000, 12,000, 1,000 의 4 종류를 혼합한 샘플, 및 150,000, 30,000, 4,000 의 3 종류를 혼합한 샘플의 2 샘플을 따로 따로 측정하였다Standard sample for preparing calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol (polymer peak molecular weight (Mp) 4,000, 1,000). In order to avoid overlapping of the peaks, two samples of samples mixed with four types of 900,000, 100,000, 12,000 and 1,000 and three samples of 150,000, 30,000 and 4,000 were separately measured
(합성예 1) (Synthesis Example 1)
교반 장치 및 질소 도입관 부착 2 ℓ 의 4 구 플라스크에, p-PDA 를 1.30 g (12.02 m㏖) 및 DA-A 를 1.76 g (7.21 m㏖), DA-B 를 1.64 g (4.81 m㏖) 취하고, NMP 를 46.10 g 과 GBL 을 106.9 g 및 피리딘 3.58 g (0.44 ㏖) 을 첨가하여, 용해시켰다. 다음으로, 이 용액을 교반하면서 1,3DMCBDA 를 1.07 g (4.81 m㏖) 을 첨가하고, 수랭하에서 5 시간 반응시켰다. 이로써 얻어진 용액에 대해서, 1,3DMCBDE-Cl 을 6.02 g (18.5 m㏖) 을 첨가하고, 수랭하에서 추가로 14 시간 반응시켰다.1.31 g (12.02 mmol) of p-PDA and 1.76 g (7.21 mmol) of DA-A and 1.64 g (4.81 mmol) of DA-B were placed in a 2 L four- necked flask equipped with a stirrer and a nitrogen- 46.10 g of NMP, 106.9 g of GBL and 3.58 g (0.44 mol) of pyridine were added to dissolve. Next, while stirring this solution, 1.07 g (4.81 mmol) of 1,3 DMCBDA was added and reacted under water cooling for 5 hours. To the thus obtained solution, 6.02 g (18.5 mmol) of 1,3-DMCBDE-Cl was added, and the mixture was further reacted under water cooling for 14 hours.
얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 용액에 아크릴로일클로라이드를 2.39 g (2.64 m㏖) 첨가하고, 추가로, 4 시간 반응시킨 후, 이 용액을 1061 ㎖ 의 이소프로판올에 교반하면서 투입하고, 석출된 백색 침전을 여과 채취하였다 계속해서, 2655 ㎖ 의 이소프로판올을 5 회로 나누어 사용하여 세정하고, 건조시킴으로써, 백색의 폴리아미드산에스테르-폴리아미드산 코폴리머 수지 분말 (PWD-1) 을 얻었다. 이 폴리아미드산에스테르-폴리아미드산 코폴리머의 분자량은 Mn = 13,493 이고, Mw = 27,207 이었다.2.39 g (2.64 mmol) of acryloyl chloride was added to the obtained polyamide acid ester-polyamic acid copolymer solution, and the mixture was further reacted for 4 hours. Then, this solution was added to 1061 ml of isopropanol with stirring, The precipitated white precipitate was collected by filtration. Thereafter, 2655 ml of isopropanol was divided into five portions, washed, and dried to obtain white polyamide acid ester-polyamide acid copolymer resin powder (PWD-1). The molecular weight of the polyamide acid ester-polyamic acid copolymer was Mn = 13,493 and Mw = 27,207.
상기에서 얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 수지 분말 (PWD-1) 을 GBL 에 용해시켜, 고형분 농도 12 질량％ 의 폴리아미드산에스테르-폴리아미드산 코폴리머 용액 (Copolymer-1) 을 얻었다.The polyamide acid ester-polyamic acid copolymer resin powder (PWD-1) obtained above was dissolved in GBL to obtain a polyamic acid ester-polyamic acid copolymer solution (Copolymer-1) having a solid concentration of 12 mass% .
(합성예 2) (Synthesis Example 2)
교반 장치 및 질소 도입관 부착 200 ㎖ 의 4 구 플라스크에, CBDE 를 8.40 g (3.23 m㏖) 및 DA-A 를 5.57 g (2.28 m㏖), DADPA 를 3.03 g (1.52 m㏖) 취하고, NMP 를 106.57 g 및 트리에틸아민 6.92 g (6.84 m㏖) 을 첨가하여, 용해시켰다. 다음으로, 이 용액을 교반하면서 DBOP 를 24.77 g (6.46 m㏖) 첨가하고, 수랭하에서 5 시간 반응시켰다. 이 후, 추가로 용액을 교반하면서, 인산디페닐을 1.90 g (0.76 m㏖), PMDA 를 1.08 g (0.49 m㏖), NMP 를 22.84 g 추가하고, 수랭하에서 다시, 5 시간 반응시켰다.8.40 g (3.23 mmol) of CBDE and 5.57 g (2.28 mmol) of DA-A and 3.03 g (1.52 mmol) of DADPA were placed in a 200 ml four-necked flask equipped with a stirrer and a nitrogen- 106.57 g and 6.92 g (6.84 mmol) of triethylamine were added to dissolve. Next, while stirring this solution, 24.77 g (6.46 mmol) of DBOP was added and reacted under water cooling for 5 hours. Thereafter, while stirring the solution, 1.90 g (0.76 mmol) of diphenyl phosphate, 1.08 g (0.49 mmol) of PMDA and 22.84 g of NMP were added and reacted again for 5 hours under cooling.
얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 용액을 2000 ㎖ 의 이소프로판올에 교반하면서 투입하고, 석출된 백색 침전을 여과 채취하고, 계속해서, 407.83 ㎖ 의 메탄올을 4 회로 나누어 사용하여 세정하고, 건조시킴으로써, 백색의 폴리아미드산에스테르-폴리아미드산 코폴리머 수지 분말 (PWD-2) 을 얻었다.The obtained polyamide acid ester-polyamic acid copolymer solution was added to 2000 ml of isopropanol with stirring, and the precipitated white precipitate was collected by filtration. Subsequently, 407.83 ml of methanol was divided into four portions, followed by washing and drying , White polyamide acid ester-polyamide acid copolymer resin powder (PWD-2) was obtained.
상기에서 얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 수지 분말 (PWD-2) 을 NMP 에 용해시켜, 고형분 농도 12 질량％ 의 폴리아미드산에스테르-폴리아미드산 코폴리머 용액 (Copolymer-2) 을 얻었다.The polyamide acid ester-polyamic acid copolymer resin powder (PWD-2) obtained above was dissolved in NMP to obtain a polyamic acid ester-polyamic acid copolymer solution (Copolymer-2) having a solid content concentration of 12 mass% .
(비교 합성예 1) (Comparative Synthesis Example 1)
교반 장치 및 질소 도입관 부착 2 ℓ 의 4 구 플라스크에, p-PDA 를 10.00 g (92.4 m㏖) 및 DA-A 를 13.60 g (55.5 m㏖), DA-B 를 12.60 g (37.0 m㏖) 취하고, NMP 를 379.00 g 과 GBL 을 1023.00 g 및 피리딘 34.60 g (0.43 ㏖) 을 첨가하여, 용해시켰다. 다음으로, 이 용액을 교반하면서 1,3DMCBDE-Cl 을 58.30 g (179.4 m㏖) 을 첨가하고, 수랭하에서 14 시간 반응시켰다.10.00 g (92.4 mmol) of p-PDA and 13.60 g (55.5 mmol) of DA-A and 12.60 g (37.0 mmol) of DA-B were placed in a 2 L four- necked flask equipped with a stirrer and a nitrogen- 379.00 g of NMP, 1023.00 g of GBL and 34.60 g (0.43 mol) of pyridine were added to dissolve. Next, while stirring this solution, 58.30 g (179.4 mmol) of 1,3-DMCBDE-Cl was added and reacted under water cooling for 14 hours.
얻어진 폴리아미드산 용액에 아크릴로일클로라이드를 2.41 g (26.6 m㏖) 첨가하고, 추가로, 4 시간 반응시킨 후, 이 용액을 8653 ㎖ 의 이소프로판올에 교반하면서 투입하여, 석출된 백색 침전을 여과 채취하였다 계속해서, 21635 ㎖ 의 이소프로판올을 5 회로 나누어 사용하여 세정하고, 건조시킴으로써, 백색의 폴리아미드산에스테르 수지 분말 (PWD-3) 을 얻었다. 이 폴리아미드산에스테르의 분자량은 Mn = 24,366 이고, Mw = 54,808 이었다.2.41 g (26.6 mmol) of acryloyl chloride was added to the resulting polyamic acid solution, and the solution was further reacted for 4 hours. Then, this solution was added to 8653 ml of isopropanol while stirring, and the precipitated white precipitate was collected by filtration Subsequently, 21635 ml of isopropanol was divided into five portions, followed by washing and drying, thereby obtaining white polyamide acid ester resin powder (PWD-3). The molecular weight of this polyamic acid ester was Mn = 24,366 and Mw = 54,808.
상기에서 얻어진 폴리아미드산에스테르 수지 분말 (PWD-3) 을 GBL 에 용해시켜, 고형분 농도 12 질량％ 의 폴리아미드산에스테르 용액 (PAE-1) 을 얻었다.The polyamide acid ester resin powder (PWD-3) obtained above was dissolved in GBL to obtain a polyamide acid ester solution (PAE-1) having a solid content concentration of 12 mass%.
(비교 합성예 2) (Comparative Synthesis Example 2)
교반 장치 및 질소 도입관 부착 15 ℓ 의 4 구 플라스크에, p-PDA 를 761.05 g (1.75 ㏖) 및 DA-A 를 256.50 g (1.05 ㏖), DA-B 를 258.56 g (0.7 ㏖) 취하고, NMP 를 9671.41 g 첨가하여, 용해시켰다. 다음으로, 이 용액을 교반하면서 1,3DMCBDA 를 761.05 g (3.39 ㏖) 을 첨가하고, 용액의 고형분 농도가 12％ 가 되도록 NMP 로 희석하였다 이 용액을 수랭하에서 14 시간 반응시켜, 폴리아미드산 용액 (PAA-1) 을 얻었다. 이 폴리아미드산의 분자량은 Mn = 14,366 이고, Mw = 28,508 이었다.761.05 g (1.75 mol) of p-PDA and 256.50 g (1.05 mol) of DA-A and 258.56 g (0.7 mol) of DA-B were taken in a 15-liter four-necked flask equipped with a stirrer and a nitrogen- Were added to dissolve. Next, 761.05 g (3.39 mol) of 1,3 DMCBDA was added while stirring the solution, and the solution was diluted with NMP so that the solid concentration of the solution became 12%. The solution was reacted under water cooling for 14 hours to obtain a polyamic acid solution PAA-1). The molecular weight of this polyamic acid was Mn = 14,366 and Mw = 28,508.
(실시예 1) (Example 1)
교반자를 넣은 20 ㎖ 샘플관에, 합성예 1 에서 얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 용액 (Copolymer-1) 을 5.50 g 취하고, AD-A 의 NMP (10 질량％ 희석) 용액을 0.28 g, 추가로 NMP 로 1.0 질량％ 로 희석한 3-글리시독시프로필메틸디에톡시실란 용액을 0.55 g, NMP 를 1.70 g 첨가하였다 그 후, BCS 를 2.00 g 첨가하고, 마그네틱 스터러로 30 분간 교반하여, 액정 배향제 (A-1) 를 얻었다. (A-1) 의 점도는 35 mPa·S 였다. 액정 배향제 (A-1) 을 -20 ℃ 에서 1 주일 보관해도 고형물의 석출이 확인되지 않아, 균일한 용액이었다.5.50 g of the polyamic acid ester-polyamic acid copolymer solution (Copolymer-1) obtained in Synthetic Example 1 and 20 ml of a NMP (10 mass% diluted) solution of AD-A were added to a 20 ml sample tube containing the stirrer, , 0.55 g of a 3-glycidoxypropylmethyldiethoxysilane solution diluted to 1.0% by mass with NMP and 1.70 g of NMP were added. Then, 2.00 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes To obtain liquid crystal aligning agent (A-1). (A-1) had a viscosity of 35 mPa · S. Even if the liquid crystal aligning agent (A-1) was stored at -20 占 폚 for one week, precipitation of solid matter could not be confirmed, and it was a uniform solution.
(실시예 2) (Example 2)
교반자를 넣은 20 ㎖ 샘플관에, 합성예 2 에서 얻어진 폴리아미드산에스테르-폴리아미드산 코폴리머 용액 (Copolymer-2) 을 7.50 g 취하고, AD-A 의 NMP (10 질량％ 희석) 용액을 0.45 g, 추가로 NMP 로 1.0 질량％ 로 희석한 3-글리시독시프로필메틸디에톡시실란 용액을 0.9 g, NMP 를 3.12 g 첨가하였다 그 후, BCS 를 3.00 g 첨가하고, 마그네틱 스터러로 30 분간 교반하여, 액정 배향제 (A-2) 를 얻었다. (A-2) 의 점도는 37 mPa·S 였다. 액정 배향제 (A-2) 를 -20 ℃ 에서 1 주일 보관한 결과, 고형물의 석출이 확인되지 않아, 균일한 용액이었다.7.50 g of the polyamic acid ester-polyamic acid copolymer solution (Copolymer-2) obtained in Synthetic Example 2 was taken in a 20 ml sample tube equipped with a stirrer, and 0.45 g of a NMP (10% by mass dilution) solution of AD-A , 0.9 g of a 3-glycidoxypropylmethyldiethoxysilane solution diluted to 1.0% by mass with NMP and 3.12 g of NMP were added. Then, 3.00 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes To obtain liquid crystal aligning agent (A-2). (A-2) had a viscosity of 37 mPa · S. When the liquid crystal aligning agent (A-2) was stored at -20 占 폚 for one week, precipitation of solids was not observed and the solution was uniform.
(비교예 1) (Comparative Example 1)
교반자를 넣은 20 ㎖ 샘플관에, 비교 합성예 1 에서 얻어진 폴리아미드산에스테르 용액 (PAE-1) 을 7.50 g 취하고, AD-A 의 NMP (10 질량％ 희석) 용액을 0.45 g, 추가로 NMP 로 1.0 질량％ 로 희석한 3-글리시독시프로필메틸디에톡시실란 용액을 0.90 g, NMP 를 2.48 g 첨가하였다 그 후, BCS 를 3.00 g 첨가하고, 마그네틱 스터러로 30 분간 교반하여, 액정 배향제 (B-1) 를 얻었다. (B-1) 의 점도는 32 mPa·S 였다. 액정 배향제 (B-1) 을 -20 ℃ 에서 1 주일 보관한 결과, 고형물의 석출이 확인되지 않아, 균일한 용액이었다.7.50 g of the polyamide acid ester solution (PAE-1) obtained in Comparative Synthesis Example 1 was placed in a 20 ml sample tube equipped with a stirrer and 0.45 g of AD-A NMP (10 mass% diluted) solution was further added thereto with NMP 0.90 g of a 3-glycidoxypropylmethyldiethoxysilane solution diluted to 1.0% by mass and 2.48 g of NMP were added. Then, 3.00 g of BCS was added, and the mixture was stirred for 30 minutes using a magnetic stirrer to obtain a liquid crystal aligning agent B-1). (B-1) had a viscosity of 32 mPa · S. When the liquid crystal aligning agent (B-1) was stored at -20 占 폚 for one week, precipitation of solids was not observed and the solution was uniform.
(비교예 2) (Comparative Example 2)
교반자를 넣은 20 ㎖ 샘플관에, 비교 합성예 2 에서 얻어진 폴리아미드산 용액 (PAA-1) 을 8.21 g 취하고, AD-A 의 NMP (10 질량％ 희석) 용액을 0.45 g, 추가로 NMP 로 1.0 질량％ 로 희석한 3-글리시독시프로필메틸디에톡시실란 용액을 0.90 g, NMP 를 3.12 g 첨가하였다 그 후, BCS 를 3.00 g 첨가하고, 마그네틱 스터러로 30 분간 교반하여, 액정 배향제 (B-2) 를 얻었다. (B-2) 의 점도는 35 mPa·S 였다. 액정 배향제 (B-2) 를 -20 ℃ 에서 1 주일 보관한 결과, 고형물의 석출이 확인되지 않아, 균일한 용액이었다.8.21 g of the polyamic acid solution (PAA-1) obtained in Comparative Synthesis Example 2 was placed in a 20 ml sample tube equipped with a stirrer, 0.45 g of AD-A NMP (10 mass% diluted) solution and further 1.0 , 0.90 g of a 3-glycidoxypropylmethyldiethoxysilane solution diluted in terms of mass%, and 3.12 g of NMP were added. Then, 3.00 g of BCS was added, and the mixture was stirred with a magnetic stirrer for 30 minutes to obtain a liquid crystal aligning agent (B -2). (B-2) had a viscosity of 35 mPa · S. When the liquid crystal aligning agent (B-2) was stored at -20 占 폚 for one week, precipitation of solids was not observed and the solution was uniform.
(실시예 3) (Example 3)
실시예 1 에서 얻어진 액정 배향제 (A-1) 을 1.0 ㎛ 의 필터로 여과한 후, 투명 전극 부착 유리 기판 상에 스핀 코트하여, 온도 80 ℃ 의 핫 플레이트 상에서 5 분간 건조시켰다. 그 후, 온도 230 ℃ 의 열풍 순환식 오븐에서 10 분간의 소성을 거쳐, 막두께 100 ㎚ 의 이미드화된 막을 얻었다. 소성막에 대해서, 편광판을 통한 254 ㎚ 의 자외선을 250 mJ/㎠ 조사하였다 이로써, 액정 배향막 부착 기판을 얻었다.The liquid crystal aligning agent (A-1) obtained in Example 1 was filtered with a filter of 1.0 탆, spin-coated on a glass substrate with a transparent electrode, and dried on a hot plate at 80 캜 for 5 minutes. Thereafter, the film was fired in a hot-air circulating oven at 230 캜 for 10 minutes to obtain an imidized film having a film thickness of 100 nm. The fired film was irradiated with ultraviolet light of 254 nm through the polarizing plate at 250 mJ / cm 2, whereby a substrate with a liquid crystal alignment film was obtained.
액정셀의 전기 특성을 평가하기 위해서, 상기 액정 배향막 부착 기판을 2 장 준비하고, 그 1 장의 액정 배향막 상에 6 ㎛ 의 스페이서를 산포하였다 그 위로부터 시일제를 인쇄하고, 다른 1 장의 기판을 액정 배향막면이 마주 보고 광배향 방향이 직교하도록 하여 붙인 후, 시일제를 경화시켜 공셀을 만들었다 이 공셀에 감압 주입법에 의해서, 액정 ML-7026-100 (메르크·쟈판 제조) 을 주입하고, 주입구를 봉지하여, IPS 액정셀을 얻었다. 이 액정셀을 120 ℃ 30 분 열처리하고, 그 후 실온까지 제랭 (除冷) 하여 셀의 관찰을 행한 결과, 배향성은 양호하였다In order to evaluate the electric characteristics of the liquid crystal cell, two liquid crystal alignment film-attached substrates were prepared, spacers of 6 mu m were dispersed on the liquid crystal alignment film, and a sealant was printed thereon, The sealing agent was cured to form a vacant cell. The liquid crystal ML-7026-100 (manufactured by Merck Japan) was injected into the vacant cell by a vacuum injection method, and an inlet And sealed to obtain an IPS liquid crystal cell. The liquid crystal cell was subjected to heat treatment at 120 DEG C for 30 minutes and then cooled to room temperature to observe the cell. As a result, the alignment property was good
＜전압 유지율의 측정＞≪ Measurement of voltage holding ratio &
상기 액정셀에 60 ℃ 의 온도하에서 1 V 의 전압을 60 ㎲ 동안 인가하고, 500 ㎳ 후의 전압을 측정하여, 전압을 어느 정도 유지할 수 있는지를 전압 유지율로서 계산하였다A voltage of 1 V was applied to the liquid crystal cell at a temperature of 60 占 폚 for 60 占 퐏 and a voltage after 500 ms was measured to determine the degree of voltage retention as a voltage retention rate
이 결과, 배향제 (A-1) 로 이루어지는 배향막 1 의 60 ℃ 에 있어서의 전압 유지율은 85.4 ％ 였다.As a result, the voltage holding ratio of the alignment layer 1 made of the alignment agent (A-1) at 60 캜 was 85.4%.
(실시예 4) (Example 4)
합성예 2 에서 얻어진 본 발명의 액정 배향제를 사용하여, 실시예 3 과 동일한 평가를 행하였다 단, 배향 처리 레이온 천에 의한 러빙 처리 (롤 직경 120 ㎜, 회전수 1000 rpm, 이동 속도 20 ㎜/sec, 압입 길이 0.3 ㎜) 로 행하였다. 이 결과는 후술하는 표 1 에 기재한다.Using the liquid crystal aligning agent of the present invention obtained in Synthesis Example 2, the same evaluation as in Example 3 was carried out. The rubbing treatment with an orientation treatment rayon cloth (roll diameter 120 mm, rotation number 1000 rpm, moving speed 20 mm / sec, and press-in length 0.3 mm). The results are shown in Table 1 to be described later.
(비교예 3) (Comparative Example 3)
비교예 1 에서 얻어진 본 발명의 액정 배향제를 사용하여, 실시예 3 과 동일한 평가를 행하였다 이 결과는 후술하는 표 1 에 기재한다.Using the liquid crystal aligning agent of the present invention obtained in Comparative Example 1, the same evaluation as in Example 3 was carried out. The results are shown in Table 1 to be described later.
(비교예 4) (Comparative Example 4)
비교예 1 에서 얻어진 본 발명의 액정 배향제를 사용하여, 실시예 3 과 동일한 평가를 행하였다 단, 광조사는 편광판을 통하여, 254 ㎚ 의 자외선을 500 mJ/㎠ 조사하여 행하였다.Using the liquid crystal aligning agent of the present invention obtained in Comparative Example 1, the same evaluations as in Example 3 were carried out. The light irradiation was conducted by irradiating ultraviolet rays of 254 nm through the polarizing plate at 500 mJ / cm 2.
상기 실시예 3, 4 및 비교예 3, 4 의 결과는 후술하는 표 1 에 기재한다.The results of Examples 3 and 4 and Comparative Examples 3 and 4 are shown in Table 1 to be described later.
산업상 이용가능성Industrial availability
본 발명의 액정 배향제를 사용하여 형성되는 액정 배향막은, 액정 배향성이 향상될 뿐만 아니라, 전압 유지율, 직류 전압의 잔류 등의 전기적 특성도 개선된다. 그 결과, TN 소자, STN 소자, TFT 액정 소자, 나아가서는, 수직 배향형의 액정 표시 소자 등에 널리 유용하다.The liquid crystal alignment film formed using the liquid crystal aligning agent of the present invention not only improves the liquid crystal alignability but also improves the electrical characteristics such as the voltage retention rate and the residual DC voltage. As a result, it is widely useful for TN devices, STN devices, TFT liquid crystal devices, and vertically aligned liquid crystal display devices.
또한, 2015년 12월 3일에 출원된 일본 특허출원 2015-236340호의 명세서, 특허청구범위, 도면 및 요약서의 내용 전체를 여기에 인용하고, 본 발명의 명세서의 개시로서 받아들이는 것이다.Further, the contents of the specification, claims, drawings and summary of Japanese Patent Application No. 2015-236340 filed on December 3, 2015 are incorporated herein by reference and the disclosure of the specification of the present invention.
Claims (12)
성분 (A) : 하기 식 (1) 로 나타내는 구조 단위와 하기 식 (2) 로 나타내는 구조 단위를 갖는 공중합체.
[화학식 1]
(X1 및 X2 는, 각각 독립적으로 4 가의 유기기이다. Y1 및 Y2 는, 각각 독립적으로, 2 가의 유기기이다. R1 은, 탄소수 1 ∼ 5 의 알킬기이다. A1 및 A2 는, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는, 탄소수 1 ∼ 10 의 알킬기, 탄소수 2 ∼ 10 의 알케닐기 혹은 탄소수 2 ∼ 10 의 알키닐기이다.)
성분 (B) : 가교성 관능기를 2 개 이상 갖는 화합물.A liquid crystal aligning agent characterized by containing the following components (A) and (B).
Component (A): A copolymer having a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
[Chemical Formula 1]
(X 1 and X 2 are, each is independently a tetravalent organic group. Y 1 and Y 2 are, each independently, a divalent organic group. R 1 is an alkyl group having a carbon number of 1 ~ 5. A 1 and A 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms, which may have a substituent.
Component (B): a compound having two or more crosslinkable functional groups.
상기 성분 (B) 가, 하이드록실기, 하이드록시알킬아미드기, (메트)아크릴레이트기, 블록 이소시아네이트기, 옥세탄기 및 에폭시기에서 선택되는 적어도 1 종의 관능기를 2 개 이상 함유하는 화합물인, 액정 배향제.The method according to claim 1,
Wherein the component (B) is a compound containing at least two functional groups selected from a hydroxyl group, a hydroxyalkylamide group, a (meth) acrylate group, a block isocyanate group, an oxetane group and an epoxy group, Liquid crystal aligning agent.
상기 성분 (B) 가, 하기 식 (3) 으로 나타내는 화합물인, 액정 배향제.
[화학식 2]
(X3 은, 탄소수 1 ∼ 20 의 지방족 탄화수소기, 또는 방향족 탄화수소기를 함유하는 n 가의 유기기이다. R2 및 R3 은, 각각 독립적으로, 수소 원자, 또는 치환기를 가져도 되는, 탄소수 1 ∼ 4 의 알킬기, 탄소수 2 ∼ 4 의 알케닐기 혹은 탄소수 2 ∼ 4 의 알키닐기이고, R2 및 R3 중 적어도 1 개는 하기 식 (4) 로 나타낸다. n 은 2 ∼ 6 의 정수이다.)
[화학식 3]
(R4 ∼ R7 은, 각각 독립적으로, 수소 원자, 탄화수소기, 또는 하이드록시기로 치환된 탄화수소기이다.)The method according to claim 1,
Wherein the component (B) is a compound represented by the following formula (3).
(2)
(Wherein X 3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group, R 2 and R 3 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, An alkenyl group having 2 to 4 carbon atoms or an alkynyl group having 2 to 4 carbon atoms, and at least one of R 2 and R 3 is represented by the following formula (4): wherein n is an integer of 2 to 6.
(3)
(R 4 to R 7 are each independently a hydrogen atom, a hydrocarbon group, or a hydrocarbon group substituted with a hydroxy group)
상기 성분 (A) 의 공중합체가, 그것의 갖는 전체 구조 단위에 대해서, 식 (1) 로 나타내는 구조 단위를 50 ∼ 95 몰％ 가지며, 또한 식 (2) 로 나타내는 구조 단위를 5 ∼ 50 몰％ 갖는, 액정 배향제.4. The method according to any one of claims 1 to 3,
Wherein the copolymer of the component (A) has 50 to 95 mol% of the structural unit represented by the formula (1) and 5 to 50 mol% of the structural unit represented by the formula (2) ≪ / RTI >
상기 성분 (B) 의 함유량이, 성분 (A) 에 대해서 1 ∼ 30 중량％ 인, 액정 배향제.5. The method according to any one of claims 1 to 4,
Wherein the content of the component (B) is 1 to 30% by weight based on the component (A).
추가로, 유기 용매를 함유하고, 상기 성분 (A) 및 상기 성분 (B) 의 합계 함유량이, 그 유기 용매에 대해서 0.5 ∼ 15 질량％ 인, 액정 배향제.6. The method according to any one of claims 1 to 5,
The liquid crystal aligning agent further contains an organic solvent and the total content of the component (A) and the component (B) is 0.5 to 15% by mass with respect to the organic solvent.
상기 식 (1) 및 식 (2) 에 있어서의, X1 및 X2 가, 각각 독립적으로, 하기 식으로 나타내는 구조로 이루어지는 군에서 선택되는 적어도 1 종인, 액정 배향제.
[화학식 4]
Wherein X 1 and X 2 in the formulas (1) and (2) are each independently at least one selected from the group consisting of structures represented by the following formulas.
[Chemical Formula 4]
상기 식 (1) 및 식 (2) 에 있어서의, Y1 및 Y2 가, 각각 독립적으로, 하기 식으로 나타내는 구조로 이루어지는 군에서 선택되는 적어도 1 종인, 액정 배향제.
[화학식 5]
Wherein Y 1 and Y 2 in the formulas (1) and (2) are each independently at least one selected from the group consisting of structures represented by the following formulas.
[Chemical Formula 5]
상기 블록 이소시아네이트기가, 하기의 식 (6) 으로 나타내는 유기기인, 액정 배향제.
[화학식 6]
Wherein the block isocyanate group is an organic group represented by the following formula (6).
[Chemical Formula 6]
상기 식 (3) 으로 나타내는 화합물이, 하기의 화합물인, 액정 배향제.
[화학식 7]
The liquid crystal aligning agent wherein the compound represented by the formula (3) is the following compound.
(7)
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