KR101988377B1 - Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film - Google Patents

Polymer, composition containing said polymer, and single-layer-coated horizontally oriented film Download PDF

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KR101988377B1
KR101988377B1 KR1020147021693A KR20147021693A KR101988377B1 KR 101988377 B1 KR101988377 B1 KR 101988377B1 KR 1020147021693 A KR1020147021693 A KR 1020147021693A KR 20147021693 A KR20147021693 A KR 20147021693A KR 101988377 B1 KR101988377 B1 KR 101988377B1
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다니엘 안토니오 사하데
쇼지로 유카와
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닛산 가가쿠 가부시키가이샤
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Abstract

하기 식 [1a], [1b] 및 [1c]로 표시되는 반복 단위를 함유하는 것을 특징으로 하는 중합체. 상기 중합체에 의해, 간단한 프로세스에 의한 단층 도포형 수평 배향 필름 제작이 가능하게 된다.

Figure 112014073140464-pct00044

[식 중, X 및 Y는 각각 독립적으로 하기 식 [2] 또는 [3]으로 표시되는 기이고,
Figure 112014073140464-pct00045

M1 및 M2는 각각 하기 식 [4] 및 [5]로 표시되는 기이고,
Figure 112014073140464-pct00046

A는 탄소수 2∼15의 직쇄상 또는 분지상의 알킬기이고, m, n 및 p는 각각 0<m<1, 0<n<1, 0≤p≤0.5 또한 m+n+p≤1을 충족시키는 수이며, q 및 r은 각각 독립적으로 2∼9의 정수이다.]A polymer comprising repeating units represented by the following formulas [1a], [1b] and [1c]. With the above polymer, it becomes possible to manufacture a single layer-coated horizontally oriented film by a simple process.
Figure 112014073140464-pct00044

[Wherein X and Y are each independently a group represented by the following formula [2] or [3]
Figure 112014073140464-pct00045

M 1 and M 2 are groups represented by the following formulas [4] and [5], respectively,
Figure 112014073140464-pct00046

A is a linear or branched alkyl group having 2 to 15 carbon atoms, and m, n and p satisfy 0 <m <1, 0 <n <1, 0 p <0.5 and m + n + And q and r each independently represent an integer of 2 to 9.]

Description

중합체, 이 중합체를 포함하는 조성물 및 단층 도포형 수평 배향 필름{POLYMER, COMPOSITION CONTAINING SAID POLYMER, AND SINGLE-LAYER-COATED HORIZONTALLY ORIENTED FILM}POLYMER, COMPOSITION CONTAINING THE POLYMER, AND COMPOSITION CONTAINING SAID POLYMER, AND SINGLE-LAYER-COATED HORIZONTALLY ORIENTED FILM,

본 발명은 중합체, 이 중합체를 포함하는 조성물 및 단층 도포형 수평 배향 필름에 관한 것이다. 상세하게는, 표시 장치나 기록 재료 등의 용도에 적합한 광학 특성을 갖는 재료, 특히, 액정 디스플레이용의 편광판 및 위상차판 등의 광학 보상 필름에 적합하게 이용할 수 있는 액정성 중합체, 이 중합체를 포함하는 조성물 및 이 조성물로부터 얻어지는 단층 도포형 수평 배향 필름에 관한 것이다. The present invention relates to a polymer, a composition comprising the polymer, and a single layer-applied horizontally oriented film. More specifically, the present invention relates to a liquid crystalline polymer suitable for use as a material having optical properties suitable for applications such as display devices and recording materials, particularly, optical compensation films such as polarizing plates and retarders for liquid crystal displays, And a single-layer coating type horizontally oriented film obtained from the composition.

액정 표시 장치의 표시 품위의 향상이나 경량화 등의 요구로부터, 편광판이나 위상차판 등의 광학 보상 필름으로서 내부의 분자 배향 구조가 제어된 고분자 필름의 요구가 높아지고 있다. 이 요구에 부응하기 위해, 중합성 액정 화합물이 갖는 광학 이방성을 이용한 필름의 개발이 이루어졌다. There has been an increasing demand for a polymer film whose inner molecular alignment structure is controlled as an optical compensation film such as a polarizing plate or a retardation plate due to demands for improvement in display quality and light weight of a liquid crystal display device. In order to meet this demand, development of a film using optical anisotropy of a polymerizable liquid crystal compound has been made.

여기에서 사용되는 중합성 액정 화합물은, 일반적으로, 중합성 기와 액정 구조 부위(스페이서부와 메소젠부를 갖는 구조 부위)를 갖는 액정 화합물이며, 이 중합성 기로서 아크릴기가 널리 사용되고 있다. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structural portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group.

이러한 중합성 액정 화합물은, 일반적으로, 자외선 등의 방사선을 조사하여 중합하는 방법으로 중합체(필름)로 된다. Such a polymerizable liquid crystal compound generally becomes a polymer (film) by a method of polymerizing by irradiation with radiation such as ultraviolet rays.

예를 들면, 아크릴기를 갖는 특정 중합성 액정 화합물을 지지체 사이에 담지하고, 이 화합물을 액정 상태로 유지하면서 방사선을 조사하여 중합체를 얻는 방법(특허문헌 1)이나, 아크릴기를 갖는 2종류의 중합성 액정 화합물의 혼합물 또는 이 혼합물에 카이럴 액정을 혼합한 조성물에 광중합개시제를 첨가하고, 자외선을 조사하여 중합체를 얻는 방법(특허문헌 2)이 알려져 있다. For example, there is a method (Patent Document 1) in which a specific polymerizable liquid crystal compound having an acrylic group is supported between supports and irradiated with radiation while keeping the compound in a liquid crystal state (Patent Document 1) A method of adding a photopolymerization initiator to a composition obtained by mixing a liquid crystal compound or a mixture thereof with a chiral liquid crystal and irradiating ultraviolet rays to obtain a polymer (Patent Document 2) is known.

또한 액정 배향막을 필요로 하지 않는 중합성 액정 화합물이나 중합체를 사용한 배향 필름(특허문헌 3, 4) 또는 광가교 부위를 함유한 중합체를 사용한 배향 필름(특허문헌 5, 6) 등, 여러 단층 도포형 배향 필름이 보고되어 왔다. 그러나, 상기 필름 제작 프로세스는, 중합체의 용해성이 낮고, 사용되는 중합체의 용매로서 NMP, 클로로폼, 클로로벤젠 등의 용해력이 우수한 용매를 사용할 필요가 있는 등의 문제가 있어, 이러한 문제를 해결하는 재료는 지금까지 찾아내지 못했다. (Patent Documents 3 and 4) using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film, or an orientation film (Patent Documents 5 and 6) using a polymer containing a photo-crosslinking site Oriented films have been reported. However, the above-mentioned film producing process has a problem that the solubility of the polymer is low and a solvent having excellent solubility such as NMP, chloroform, and chlorobenzene is required to be used as a solvent of the polymer to be used. Have not been found until now.

일본 특개 소62-70407호 공보Japanese Patent Laid-Open No. 62-70407 일본 특개 평9-208957호 공보Japanese Patent Application Laid-Open No. 9-208957 유럽특허출원 공개 제1090325호 명세서European Patent Application Publication No. 1090325 국제공개 제2008/031243호International Publication No. 2008/031243 일본 특개 2008-164925호 공보Japanese Patent Application Laid-Open No. 2008-164925 일본 특개 평11-189665호 공보Japanese Patent Application Laid-Open No. 11-189665

본 발명은 상기 문제를 감안하여 이루어진 것으로, 보다 간단한 프로세스에 의한 단층 도포형 수평 배향 필름 제작을 가능하게 하는 신규 중합체, 이 중합체를 함유하는 조성물 및 이 조성물로부터 얻어지는 단층 도포형 수평 배향 필름을 제공하는 것을 목적으로 한다. The present invention has been made in view of the above problems and provides a novel polymer capable of producing a single layer coated horizontally oriented film by a simpler process, a composition containing the polymer, and a single layer coated horizontally oriented film obtained from the composition .

본 발명자들은 상기 과제를 해결하기 위해 예의 검토를 거듭한 결과, γ-뷰티로락톤 골격을 주쇄에 함유함과 아울러, 락톤환의 γ위치로부터 연장되는 측쇄 상에 신남산 에스터 구조를 갖는 중합체를 사용함으로써 편광 자외선 노광 후에 안정한 네트워크 구조가 형성되기 때문에, 액정 배향막을 사용하지 않고, 높은 굴절률 이방성(Δn)을 갖는 수평 배향 필름이 얻어지는 것, 또한 당해 중합체에 알킬쇄를 도입함으로써 유기 용매에 대한 용해성이 향상되어, 보다 높은 Δn을 갖는 수평 배향 필름을 저온 조건하에서 제작 가능하게 되는 것을 발견하고, 본 발명을 완성하였다. As a result of intensive investigations to solve the above problems, the present inventors have found that by using a polymer having a? -Butyrolactone skeleton in its main chain and a polymer having a cinnamate ester structure on a side chain extending from the? -Position of a lactone ring It is possible to obtain a horizontally oriented film having a high refractive index anisotropy (DELTA n) without using a liquid crystal alignment film because the stable network structure is formed after the polarized ultraviolet ray exposure and the solubility in an organic solvent is improved by introducing an alkyl chain into the polymer Thus, a horizontally oriented film having a higher? N can be produced under a low temperature condition, and the present invention has been completed.

즉, 본 발명은,That is,

1. 하기 식 [1a], [1b] 및 [1c]로 표시되는 반복 단위를 함유하는 것을 특징으로 하는 중합체,1. A polymer characterized by containing a repeating unit represented by the following formula [1a], [1b] and [1c]

Figure 112014073140464-pct00001
Figure 112014073140464-pct00001

[식 중, X 및 Y는 각각 독립적으로 하기 식 [2] 또는 [3]으로 표시되는 기이고,[Wherein X and Y are each independently a group represented by the following formula [2] or [3]

Figure 112014073140464-pct00002
Figure 112014073140464-pct00002

(식 [3] 중, R1은 수소 원자 또는 메틸기이다. 파선은 결합손이다.)(In the formula [3], R 1 is a hydrogen atom or a methyl group.

M1은 하기 식 [4]로 표시되는 기이고, M2는 하기 식 [5]로 표시되는 기이고,M 1 is a group represented by the following formula [4], M 2 is a group represented by the following formula [5]

Figure 112014073140464-pct00003
Figure 112014073140464-pct00003

(식 [4] 및 [5] 중, s1, s2, s3 및 s4는 각각 독립적으로 1 또는 2이고, G1 및 G2는 각각 독립적으로 단결합, -COO- 또는 -OCO-이며, R2 및 R3은 각각 독립적으로 수소 원자, 할로젠 원자, 사이아노기, 탄소수 1∼10의 알킬기 또는 탄소수 1∼10의 알콕시기이다. 파선은 결합손이다.)(Formula [4] and [5] and of the, s1, s2, s3 and s4 are each independently 1 or 2, G 1 and G 2 represents a single bond, -COO- or -OCO-, each independently, R 2 And R 3 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

A는 탄소수 2∼15의 직쇄상 또는 분지상의 알킬기이고,A is a straight or branched alkyl group having 2 to 15 carbon atoms,

m, n 및 p는 각각 0<m<1, 0<n<1, 0≤p≤0.5 또한 m+n+p≤1을 충족시키는 수이며,m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0? p? 0.5 and m + n + p?

q 및 r은 각각 독립적으로 2∼9의 정수이다.]q and r each independently represent an integer of 2 to 9.]

2. 상기 X 및 Y가 상기 식 [3]으로 표시되는 기인 1의 중합체,2. The polymer of 1 wherein X and Y are the groups represented by the above formula [3]

3. 상기 m, n 및 p가 각각 0.2≤m≤0.9, 0.1≤n≤0.8, 0≤p≤0.4를 충족시키는 수인 1 또는 2의 중합체,3. The polymer of 1 or 2, wherein m, n and p are numbers satisfying 0.2? M? 0.9, 0.1? N? 0.8, 0? P? 0.4,

4. 상기 m, n 및 p가 각각 0.2≤m≤0.8, 0.1≤n≤0.5, 0.1≤p≤0.3을 충족시키는 수인 3의 중합체,4. The polymer of claim 3, wherein m, n and p are numbers satisfying 0.2? M? 0.8, 0.1? N? 0.5 and 0.1? P?

5. 1∼4 중 어느 하나의 중합체와 유기 용매를 함유하는 조성물,5. A composition containing any one of polymers 1 to 4 and an organic solvent,

6. 5의 조성물을 기판에 도포하고, 이어서 편광을 조사하고, 경화시킴으로써 얻어지는 단층 도포형 수평 배향 필름,A single-layer coating type horizontally oriented film obtained by applying a composition of 6. 5 to a substrate, and then irradiating and curing the polarized light,

7. 상기 편광이 직선 편광 자외선인 6의 단층 도포형 수평 배향 필름,7. The single-layer application type horizontally oriented film of 6 wherein the polarized light is linearly polarized ultraviolet ray,

8. 6 또는 7의 단층 도포형 수평 배향 필름을 구비하는 광학 부재,8. An optical member having a single layer coating type horizontally oriented film of 6 or 7,

9. 하기 식 [7]로 표시되는 것을 특징으로 하는 중합성 화합물9. A polymerizable compound represented by the following formula [7]

Figure 112014073140464-pct00004
Figure 112014073140464-pct00004

(식 [7] 중, r은 2∼9의 정수이며, s3 및 s4는 각각 독립적으로 1 또는 2이고, G2는 단결합, -COO- 또는 -OCO-이며, R3은 수소 원자, 할로젠 원자, 사이아노기, 탄소수 1∼10의 알킬기 또는 탄소수 1∼10의 알콕시기이다.)(Wherein r is an integer of 2 to 9, s 3 and s 4 are each independently 1 or 2, G 2 is a single bond, -COO- or -OCO-, R 3 is a hydrogen atom, A cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

를 제공한다. Lt; / RTI &gt;

본 발명의 중합체는 γ-뷰티로락톤 골격을 주쇄에 함유한다. 그 때문에 이 중합체를 함유하는 조성물을 도포하고, 실온에서 직선 편광을 조사하고, 포스트 베이크를 행하는 프로세스에 의해, 높은 Δn을 나타내는 단층 도포형 수평 배향 필름을 제작하는 것이 가능하다. 또한 알킬기 측쇄를 갖는 단위를 더 포함하는 중합체로 함으로써, 용매에 대한 용해성의 향상이 얻어진다. The polymer of the present invention contains a? -Butyrolactone skeleton in the main chain. Therefore, it is possible to produce a single-layer coating type horizontally oriented film exhibiting a high Δn by applying a composition containing this polymer, irradiating linearly polarized light at room temperature, and performing post-baking. Further, by making the polymer further comprising a unit having an alkyl group side chain, the solubility in a solvent can be improved.

도 1은 실시예 11∼16에서 얻어진 각 필름의 파장 550nm에서의 리타데이션값 각도 의존성을 나타내는 도면이다.
도 2는 비교예 3, 4에서 얻어진 각 필름의 파장 550nm에서의 리타데이션값 각도 의존성을 나타내는 도면이다. Fig. 1 is a diagram showing the retardation value angle dependency of each film obtained in Examples 11 to 16 at a wavelength of 550 nm. Fig.
Fig. 2 is a diagram showing the dependence of retardation angle on each film obtained in Comparative Examples 3 and 4 at a wavelength of 550 nm. Fig.

이하, 본 발명에 대해 더욱 자세하게 설명한다. Hereinafter, the present invention will be described in more detail.

[중합체][polymer]

본 발명의 중합체는 하기 식 [1a] 및 [1b]로 표시되는 반복 단위를 함유하고, 필요에 따라, 하기 식 [1c]로 표시되는 반복 단위를 더 함유하는 것이다. The polymer of the present invention contains the repeating units represented by the following formulas [1a] and [1b] and, if necessary, further contains the repeating unit represented by the following formula [1c].

Figure 112014073140464-pct00005
Figure 112014073140464-pct00005

식 [1a] 및 [1c] 중, X 및 Y는 각각 독립적으로 하기 식 [2] 또는 [3]으로 표시되는 기이다. Among the formulas [1a] and [1c], X and Y are each independently a group represented by the following formula [2] or [3].

Figure 112014073140464-pct00006
Figure 112014073140464-pct00006

(식 [3] 중, R1은 수소 원자 또는 메틸기이다. 파선은 결합손이다(이하 동일).)(In the formula [3], R 1 is a hydrogen atom or a methyl group.

이들 중, X, Y 모두 식 [3]으로 표시되는 기가 바람직하다. Of these, all of X and Y are preferably groups represented by the formula [3].

식 [1a] 중, M1은 하기 식 [4]로 표시되는 기이며, 식 [1b] 중, M2는 하기 식 [5]로 표시되는 기이다. In the formula [1a], M 1 is a group represented by the following formula [4], and M 2 in the formula [1b] is a group represented by the following formula [5].

Figure 112014073140464-pct00007
Figure 112014073140464-pct00007

(식 [4] 및 [5] 중, s1, s2, s3 및 s4는 각각 독립적으로 1 또는 2이고, G1 및 G2는 각각 독립적으로 단결합, -COO- 또는 -OCO-이며, R2 및 R3은 각각 독립적으로 수소 원자, 할로젠 원자, 사이아노기, 탄소수 1∼10의 알킬기 또는 탄소수 1∼10의 알콕시기이다.)(Formula [4] and [5] and of the, s1, s2, s3 and s4 are each independently 1 or 2, G 1 and G 2 represents a single bond, -COO- or -OCO-, each independently, R 2 And R 3 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

여기에서, 상기 할로젠 원자로서는 불소, 염소, 브롬, 아이오딘 원자를 들 수 있지만, 본 발명에서는 불소 원자가 바람직하다. Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms, but fluorine atoms are preferred in the present invention.

상기 알킬기로서는 직쇄, 분지, 환상 중 어떤 것이어도 되고, 또한 그 탄소수도 특별히 한정되는 것은 아니지만, 본 발명에서는 직쇄의 탄소수 1∼10의 알킬기가 바람직하다. 상기 알킬기의 구체예로서는 메틸기, 에틸기, n-프로필기, 아이소프로필기, 사이클로프로필기, n-뷰틸기, 아이소뷰틸기, s-뷰틸기, t-뷰틸기, 사이클로뷰틸기, n-펜틸기, 사이클로펜틸기, n-헥실기, 사이클로헥실기, n-헵틸기, n-옥틸기, n-노닐기, n-데실기 등을 들 수 있다. 이들 중, 탄소수 1∼3의 알킬기가 더욱 바람직하고, 특히 메틸기, 에틸기 등이 바람직하다. The alkyl group may be any of linear, branched, and cyclic, and the carbon number thereof is not particularly limited. In the present invention, a straight-chain alkyl group having 1 to 10 carbon atoms is preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a n-butyl group, an isobutyl group, a sec- N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group and n-decyl group. Among them, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are particularly preferable.

상기 알콕시기로서는 직쇄, 분지, 환상의 어떤 것이어도 되고, 또한 그 탄소수도 특별히 한정되는 것은 아니지만, 본 발명에서는 직쇄의 탄소수 1∼10의 알콕시기가 바람직하다. 상기 알콕시기의 구체예로서는 메톡시기, 에톡시기, n-프로폭시기, 아이소프로폭시기, n-뷰톡시기, 아이소뷰톡시기, s-뷰톡시기, t-뷰톡시기, n-펜톡시기, n-헥실옥시기, n-헵틸옥시기, n-옥틸옥시기, n-노닐옥시기, n-데실옥시기 등을 들 수 있다. 이들 중, 탄소수 1∼3의 알콕시기가 더욱 바람직하고, 특히 메톡시기, 에톡시기 등이 바람직하다. The alkoxy group may be any of linear, branched and cyclic, and the carbon number thereof is not particularly limited. In the present invention, an alkoxy group having 1 to 10 carbon atoms in the straight chain is preferable. Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, A siloxane group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, and a n-decyloxy group. Among them, an alkoxy group having 1 to 3 carbon atoms is more preferable, and a methoxy group and an ethoxy group are particularly preferable.

또한, 상기 알킬기, 알콕시기에서, 그 수소 원자의 일부 또는 전부가 불소 원자 등의 할로젠 원자로 치환되어 있어도 된다. In the alkyl group and the alkoxy group, a part or all of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

상기 R2 또는 R3으로서 보다 바람직하게는 수소 원자, 불소 원자, 사이아노기, 메틸기, 메톡시기이다. More preferably, R 2 or R 3 is a hydrogen atom, a fluorine atom, a cyano group, a methyl group or a methoxy group.

상기 G1로서는 -COO- 또는 -OCO-가 바람직하고, G2로서는 단결합이 바람직하다.G 1 is preferably -COO- or -OCO-, and G 2 is preferably a single bond.

식 [1c] 중, A는 직쇄상 또는 분지상의 탄소수 2∼15의 알킬기이다. 상기 알킬기로서 구체적으로는 에틸기, n-프로필기, i-프로필기, n-뷰틸기, i-뷰틸기, s-뷰틸기, t-뷰틸기, n-펜틸기, 1-메틸-n-뷰틸기, 2-메틸-n-뷰틸기, 3-메틸-n-뷰틸기, 1,1-다이메틸-n-프로필기, 1,2-다이메틸-n-프로필기, 2,2-다이메틸-n-프로필기, 1-에틸-n-프로필기, n-헥실기, 1-메틸-n-펜틸기, 2-메틸-n-펜틸기, 3-메틸-n-펜틸기, 4-메틸-n-펜틸기, 1,1-다이메틸-n-뷰틸기, 1,2-다이메틸-n-뷰틸기, 1,3-다이메틸-n-뷰틸기, 2,2-다이메틸-n-뷰틸기, 2,3-다이메틸-n-뷰틸기, 3,3-다이메틸-n-뷰틸기, 1-에틸-n-뷰틸기, 2-에틸-n-뷰틸기, 1,1,2-트라이메틸-n-프로필기, 1,2,2-트라이메틸-n-프로필기, 1-에틸-1-메틸-n-프로필기, 1-에틸-2-메틸-n-프로필기, n-헵틸기, 1-메틸-n-헥실기, 2-메틸-n-헥실기, 3-메틸-n-헥실기, 1,1-다이메틸-n-펜틸기, 1,2-다이메틸-n-펜틸기, 1,3-다이메틸-n-펜틸기, 2,2-다이메틸-n-펜틸기, 2,3-다이메틸-n-펜틸기, 3,3-다이메틸-n-펜틸기, 1-에틸-n-펜틸기, 2-에틸-n-펜틸기, 3-에틸-n-펜틸기, 1-메틸-1-에틸-n-뷰틸기, 1-메틸-2-에틸-n-뷰틸기, 1-에틸-2-메틸-n-뷰틸기, 2-메틸-2-에틸-n-뷰틸기, 2-에틸-3-메틸-n-뷰틸기, n-옥틸기, 1-메틸-n-헵틸기, 2-메틸-n-헵틸기, 3-메틸-n-헵틸기, 1,1-다이메틸-n-헥실기, 1,2-다이메틸-n-헥실기, 1,3-다이메틸-n-헥실기, 2,2-다이메틸-n-헥실기, 2,3-다이메틸-n-헥실기, 3,3-다이메틸-n-헥실기, 1-에틸-n-헥실기, 2-에틸-n-헥실기, 3-에틸-n-헥실기, 1-메틸-1-에틸-n-펜틸기, 1-메틸-2-에틸-n-펜틸기, 1-메틸-3-에틸-n-펜틸기, 2-메틸-2-에틸-n-펜틸기, 2-메틸-3-에틸-n-펜틸기, 3-메틸-3-에틸-n-펜틸기, n-노닐기, n-데실기, n-운데실기, n-도데실기, n-트라이데실기, n-테트라데실기, n-펜타데실기 등을 들 수 있다. In the formula [1c], A represents a linear or branched alkyl group having 2 to 15 carbon atoms. Specific examples of the alkyl group include an alkyl group such as an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, Methyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, dimethyl-n-butyl group, 1, 3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, Ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1-diethyl-n-butyl group, Methyl-n-propyl group, a 1-ethyl-2-methyl-n-propyl group, n-hexyl group, 1-methyl-n-hexyl group, 1-methyl-n-pentyl group, n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl- N-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, Methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, methyl-n-heptyl group, a 3-methyl-n-heptyl group, a 2-methyl-n-pentyl group, Dimethyl-n-hexyl group, 2, 2-dimethyl-n-hexyl group, 2, N-hexyl group, 3-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, Methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group, Methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n- A decyl group, an n-tetradecyl group, and an n-pentadecyl group.

이들 중, 얻어지는 중합체의 유기 용매에 대한 용해성 등을 고려하면, 탄소수 4∼15, 특히 4∼12의 알킬기가 바람직하고, n-뷰틸기, 2-에틸-n-헥실기, n-도데실기 등이 보다 바람직하다. Among them, an alkyl group having 4 to 15 carbon atoms, particularly 4 to 12 carbon atoms is preferable in view of the solubility of the obtained polymer in an organic solvent and the like, and an n-butyl group, a 2-ethyl-n-hexyl group, Is more preferable.

식 [1a]∼[1c] 중, m, n 및 p는 각각 0<m<1, 0<n<1, 0≤p≤0.5, 또한 m+n+p≤1을 충족시키는 수이다. Δn의 향상이나 중합체의 용해성의 향상 등의 점으로부터, m, n 및 p는 각각 0.2≤m≤0.9, 0.1≤n≤0.8, 0≤p≤0.4를 충족시키는 수인 것이 바람직하고, 0.2≤m≤0.8, 0.1≤n≤0.5, 0.1≤p≤0.3을 충족시키는 수인 것이 더욱 바람직하다. In the formula [1a] to [1c], m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0 p? 0.5 and m + n + p? M, n and p are preferably numbers satisfying 0.2? M? 0.9, 0.1? N? 0.8 and 0? P? 0.4, respectively, from the viewpoints of improvement of? N and improvement of solubility of the polymer, 0.8, 0.1? N? 0.5, and 0.1? P? 0.3.

또한 식 [1a] 및 [1b] 중, q 및 r은 각각 독립적으로 2∼9의 정수이지만, 3∼6이 바람직하고, 특히 q로서는 5 또는 6이 보다 바람직하다. Among the formulas [1a] and [1b], q and r each independently represent an integer of 2 to 9, preferably 3 to 6, more preferably 5 or 6 as q.

[중합성 화합물][Polymerizable compound]

본 발명의 중합체의 원료가 되는 중합성 화합물은 하기 식 [6], [7] 또는 [8]로 표시된다. The polymerizable compound to be a raw material of the polymer of the present invention is represented by the following formula [6], [7] or [8].

Figure 112014073140464-pct00008
Figure 112014073140464-pct00008

Figure 112014073140464-pct00009
Figure 112014073140464-pct00009

Figure 112014073140464-pct00010
Figure 112014073140464-pct00010

[식 중, R2, R3, G1, G2, A, q, r 및 s1∼s4는 상기와 같다. R 2 , R 3 , G 1 , G 2 , A, q, r and s 1 to s 4 are as defined above.

X' 및 Y'은 각각 독립적으로 하기 식 [9] 또는 [10]으로 표시되는 중합성 기이다. X 'and Y' are each independently a polymerizable group represented by the following formula [9] or [10].

Figure 112014073140464-pct00011
Figure 112014073140464-pct00011

(식 중, R1은 상기와 같다.)](Wherein R &lt; 1 &gt; is as defined above)]

[중합성 화합물의 합성][Synthesis of polymerizable compound]

상기 식 [6]으로 표시되는 중합성 화합물은, 예를 들면, 이하와 같이 하여 제조된다. The polymerizable compound represented by the above formula [6] is produced, for example, as follows.

G1이 -COO-인 경우, 하기 반응식으로 표시되는 바와 같이, 식 [12]로 표시되는 벤조산 유도체와 페놀 유도체를, 용매 중, 축합제의 존재하에서 축합시킴으로써 제조된다. When G 1 is -COO-, as shown in the following reaction formula, the benzoic acid derivative represented by the formula [12] and the phenol derivative are condensed in a solvent in the presence of a condensing agent.

Figure 112014073140464-pct00012
Figure 112014073140464-pct00012

(식 중, R2, X', q, s1 및 s2는 상기와 같다. DCC는 N,N'-다이사이클로헥실카보다이이미드, DMAp는 4-다이메틸아미노피리딘을 나타낸다.)(Wherein R 2 , X ', q, s 1 and s 2 are as defined above, DCC represents N, N'-dicyclohexylcarbodiimide and DMAp represents 4-dimethylaminopyridine.

G1이 -OCO-인 경우, 하기 반응식으로 표시되는 바와 같이, 식 [13]으로 표시되는 페놀 유도체와 벤조산 유도체를, 용매 중, 축합제의 존재하에서 축합시킴으로써 제조된다. When G 1 is -OCO-, the phenol derivative represented by the formula [13] and the benzoic acid derivative are condensed in a solvent in the presence of a condensing agent as shown in the following reaction formula.

Figure 112014073140464-pct00013
Figure 112014073140464-pct00013

(식 중, R2, X',q, s1 및 s2는 상기와 같다.)(Wherein R 2 , X ', q, s 1 and s 2 are as defined above)

상기 식 [12] 및 [13]으로 표시되는 화합물은, X'이 식 [9]로 표시되는 기의 경우에는, SYNTHON Chemicals사 또는 미도리카가쿠 가부시키가이샤로부터 시판품으로서 입수 가능하다. The compounds represented by the above formulas [12] and [13] are commercially available from SYNTHON Chemicals or Midorikagaku Co., Ltd. in the case where X 'is a group represented by the formula [9].

또한 상기 식 [12] 및 [13]으로 표시되는 화합물은 X'이 식 [10]으로 표시되는 기인 경우에는, 예를 들면, Talaga 등(P. Talaga, M. Schaeffer, C. Benezra and J. L. Stampf, Synthesis, 530(1990))이 제안하는 수법을 사용하여 합성할 수 있다. 이 수법은, 하기 합성 반응식(A1)으로 나타내는 바와 같이, SnCl2를 사용하여 2-(브로모메틸)아크릴산(2-(bromomethyl)propenoic acid)과, 알데하이드 또는 케톤을 반응시키는 방법이다. 또한, 2-(브로모메틸)아크릴산은 Ramarajan 등이 제안하는 방법으로 얻을 수 있다(K. Ramarajan, K. Kamalingam, D. J. O'Donnell and K. D. Berlin, Organic Synthesis, vol. 61, pp.56-59(1983)).Compounds represented by the above formulas [12] and [13] can be prepared by the method described in Talaga et al. (P. Talaga, M. Schaeffer, C. Benezra and JL Stampf , Synthesis, 530 (1990)). This method is a method of reacting 2- (bromomethyl) propenoic acid with an aldehyde or ketone using SnCl 2 as shown in the following synthesis reaction formula (A1). In addition, 2- (bromomethyl) acrylic acid can be obtained by a method proposed by Ramarajan et al. (K. Ramarajan, K. Kamalingam, DJ O'Donnell and KD Berlin, Organic Synthesis, vol. 61, pp. (1983)).

Figure 112014073140464-pct00014
Figure 112014073140464-pct00014

(식 중, R'은 1가의 유기기를 나타내고, Amberlyst(등록상표) 15는 롬 앤드 하스사제 이온교환 수지이다. THF는 테트라하이드로퓨란을 나타낸다. Et는 에틸기를 나타낸다.)(Wherein R 'represents a monovalent organic group, and Amberlyst (registered trademark) 15 is an ion exchange resin manufactured by Rohm and Haas), THF represents tetrahydrofuran, Et represents ethyl group.

또한 SnCl2를 사용한 2-(브로모메틸)아크릴산의 반응에서는, 알데하이드 또는 케톤 대신에 대응하는 아세탈 또는 케탈과의 반응에 의해, α-메틸렌-γ-뷰티로락톤 구조를 얻을 수도 있다. Further, in the reaction of 2- (bromomethyl) acrylic acid using SnCl 2 , an α-methylene-γ-butyrolactone structure can be obtained by reaction with a corresponding acetal or ketal instead of aldehyde or ketone.

아세탈 또는 케탈로서는 다이메틸아세탈기, 다이에틸아세탈기, 1,3-다이옥세인기, 1,3-다이옥솔레인기 등을 갖는 화합물을 들 수 있다. 하기 합성 반응식 (A2)에, 아세탈 또는 케탈을 사용한 경우의 합성법 및 보호기를 나타낸다. Examples of the acetal or ketal include compounds having a dimethyl acetal group, diethylacetal group, 1,3-dioxolane group, 1,3-dioxolane group, and the like. The synthesis method and the protecting group in the case of using acetal or ketal in the following synthesis reaction formula (A2).

Figure 112014073140464-pct00015
Figure 112014073140464-pct00015

(식 중, R'은 상기와 같다.)(Wherein R 'is as defined above).

상기 합성 반응식 (A1) 또는 (A2)의 수법을 응용한 하기 합성 반응식 (B) 또는 (C)의 수법에 의해, 식 [12] 또는 [13]으로 표시되는 화합물을 합성할 수 있다. The compound represented by the formula [12] or [13] can be synthesized by the following synthesis reaction scheme (B) or (C) employing the synthesis reaction scheme (A1) or (A2).

Figure 112014073140464-pct00016
Figure 112014073140464-pct00016

(식 중, q 및 s1은 상기와 같다. Me는 메틸기를 나타낸다. PCC는 피리디늄클로로크로메이트를 나타낸다.)(Wherein, q and s1 are as defined above, Me represents a methyl group, and PCC represents pyridinium chlorochromate).

Figure 112014073140464-pct00017
Figure 112014073140464-pct00017

(식 중, q 및 s1은 상기와 같다.)(Wherein q and s1 are as defined above.)

식 [7]로 표시되는 화합물은, 예를 들면, 하기 반응식으로 나타내는 바와 같이, 식 [14]로 표시되는 화합물과 신남산 화합물을, 용매 중, 축합제의 존재하에서 축합시킴으로써 제조된다. The compound represented by the formula [7] is prepared, for example, by condensing a compound represented by the formula [14] and a cinnamic acid compound in a solvent in the presence of a condensing agent as shown by the following reaction formula.

Figure 112014073140464-pct00018
Figure 112014073140464-pct00018

(식 중, R3, G2, r, s3 및 s4는 상기와 같다.)(Wherein R 3 , G 2 , r, s 3 and s 4 are as defined above)

식 [14]로 표시되는 화합물은, 예를 들면, 하기 합성 반응식 (D)에 표시되는 방법에 의해 얻어진다. The compound represented by the formula [14] is obtained, for example, by the method shown in the following synthesis reaction formula (D).

Figure 112014073140464-pct00019
Figure 112014073140464-pct00019

(식 중, G2, r, s3 및 s4는 상기와 같다.)(Wherein G 2 , r, s 3 and s 4 are as defined above).

식 [8]로 표시되는 화합물은, Y'이 식 [9]로 표시되는 기인 경우에는, 시판품으로서 입수 가능하다. The compound represented by the formula [8] is available as a commercial product when Y 'is a group represented by the formula [9].

또한 식 [8]로 표시되는 화합물은 Y'이 식 [10]으로 표시되는 기인 경우에는, 하기 합성 반응식 (E)에 표시하는 방법에 의해 합성할 수도 있다. When the compound represented by the formula [8] is a group represented by the formula [10], the compound represented by the formula [8] can also be synthesized by the method shown in the following synthesis reaction formula (E).

Figure 112014073140464-pct00020
Figure 112014073140464-pct00020

(식 중, A는 상기와 같다.)(Wherein A is as defined above).

[중합체의 합성][Synthesis of Polymer]

본 발명의 중합체를 합성하는 방법으로서는 특별히 한정되지 않고, 래디컬 중합, 음이온 중합, 양이온 중합 등을 채용할 수 있다. 이들 중, 특히 래디컬 중합이 바람직하고, 구체적으로는, 용매 중, 상기 중합성 화합물을 중합개시제의 존재하에서 가열하여, 중합시키면 된다. The method for synthesizing the polymer of the present invention is not particularly limited, and radical polymerization, anionic polymerization, cationic polymerization, and the like can be employed. Of these, radical polymerization is particularly preferable. Specifically, polymerization may be carried out by heating the above-mentioned polymerizable compound in a solvent in the presence of a polymerization initiator.

상기 중합개시제로서는 종래 공지의 것으로부터 적당하게 선택하여 사용할 수 있다. 예를 들면, 과산화 벤조일, 쿠멘하이드로퍼옥사이드, t-뷰틸하이드로퍼옥사이드 등의 과산화물; 과황산 나트륨, 과황산 칼륨, 과황산 암모늄 등의 과황산염; 아조비스아이소뷰티로나이트릴(AIBN), 아조비스메틸뷰티로나이트릴, 아조비스아이소발레로나이트릴 등의 아조계 화합물 등을 들 수 있다. 이것들은 1종 단독으로 또는 2종 이상 조합하여 사용할 수 있다. As the polymerization initiator, conventionally known ones can be appropriately selected and used. Peroxides such as benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide and the like; Persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate; Azo compounds such as azobisisobutyronitrile (AIBN), azobismethylbutyronitrile and azobisisovaleronitrile, and the like can be given. These may be used singly or in combination of two or more.

상기 중합개시제의 사용량은, 중합성 화합물 1mol에 대하여, 0.01∼0.05mol 정도가 바람직하다. The amount of the polymerization initiator to be used is preferably about 0.01 to 0.05 mol based on 1 mol of the polymerizable compound.

반응온도는 0℃부터 사용하는 용매의 비점까지 적당히 설정하면 되는데, 20∼100℃ 정도가 바람직하다. 반응시간은 0.1∼30시간 정도가 바람직하다. The reaction temperature may be appropriately set from 0 ° C to the boiling point of the solvent to be used, and is preferably about 20 to 100 ° C. The reaction time is preferably about 0.1 to 30 hours.

중합 반응에 사용되는 용매로서는 특별히 한정되는 것은 아니고, 상기 중합 반응에서 일반적으로 사용되고 있는 각종 용매로부터 적당히 선택하여 사용하면 된다. 구체적으로는 물; 메탄올, 에탄올, 1-프로판올, 2-프로판올, 1-뷰탄올, 2-뷰탄올, i-뷰탄올, t-뷰탄올, 1-펜탄올, 2-펜탄올, 3-펜탄올, i-펜탄올, t-펜탄올, 1-헥산올, 1-헵탄올, 2-헵탄올, 3-헵탄올, 2-옥탄올, 2-에틸-1-헥산올, 벤질알코올, 사이클로헥산올 등의 알코올류; 다이에틸에터, 다이아이소프로필에터, 다이뷰틸에터, 사이클로펜틸메틸에터, 테트라하이드로퓨란, 1,4-다이옥세인 등의 에터류; 클로로폼, 다이클로로메테인, 다이클로로에테인, 사염화탄소 등의 할로젠화 탄화수소류; 메틸셀로솔브, 에틸셀로솔브, 아이소프로필셀로솔브, 뷰틸셀로솔브, 다이에틸렌글라이콜 모노뷰틸에터 등의 에터 알코올류;아세톤, 메틸에틸케톤, 메틸아이소뷰틸케톤, 사이클로헥산온 등의 케톤류; 아세트산 에틸, 아세트산 뷰틸, 프로피온산 에틸, 셀로솔브 아세테이트 등의 에스터류; n-펜테인, n-헥세인, n-헵테인, n-옥테인, n-노네인, n-데케인, 사이클로펜테인, 메틸사이클로펜테인, 사이클로헥세인, 메틸사이클로헥세인, 벤젠, 톨루엔, 자일렌, 에틸벤젠, 아니솔 등의 지방족 또는 방향족 탄화수소류; 메틸알, 다이에틸아세탈 등의 아세탈류; 폼산, 아세트산, 프로피온산 등의 지방산류; 나이트로프로페인, 나이트로벤젠, 다이메틸아민, 모노에탄올아민, 파이리딘, N-메틸-2-파이롤리돈(NMP), N,N-다이메틸폼아마이드, 다이메틸설폭사이드, 아세토나이트릴 등을 들 수 있다. 이것들은 1종 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. The solvent used in the polymerization reaction is not particularly limited, and it may be suitably selected from various solvents generally used in the polymerization reaction. Specifically, water; But are not limited to, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, There may be mentioned alcohols such as t-butanol, t-pentanol, 1-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl-1-hexanol, benzyl alcohol and cyclohexanol Ryu; Ethers such as diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran and 1,4-dioxane; Halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane and carbon tetrachloride; Ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve and diethylene glycol monobutyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones; Esters such as ethyl acetate, butyl acetate, ethyl propionate and cellosolve acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonene, n-decane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, Aliphatic or aromatic hydrocarbons such as toluene, xylene, ethylbenzene and anisole; Acetals such as methylal, diethyl acetal and the like; Fatty acids such as formic acid, acetic acid and propionic acid; (NMP), N, N-dimethylformamide, dimethylsulfoxide, acetonitrile, N, N-dimethylformamide, N-methylpyrrolidone And the like. These may be used alone or in combination of two or more.

본 발명의 중합체는 중량평균 분자량이 3,000∼200,000인 것이 바람직하고, 4,000∼150,000인 것이 보다 바람직하고, 5,000∼100,000인 것이 더욱 바람직하다. 중량평균 분자량이 200,000을 초과하면, 용제에 대한 용해성이 저하하여 핸들링성이 저하하는 경우가 있고, 중량평균 분자량이 3,000 미만이면, 열경화시에 경화 부족으로 되어 용제 내성 및 내열성이 저하되는 경우가 있다. The polymer of the present invention preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. When the weight average molecular weight is more than 200,000, the solubility in a solvent is lowered and handling properties are lowered in some cases. When the weight average molecular weight is less than 3,000, hardening becomes insufficient at the time of thermosetting and the solvent resistance and heat resistance are lowered have.

또한, 중량평균 분자량은 겔 퍼미에이션 크로마토그래피(GPC)에 의한 폴리스타이렌 환산 측정값이다. The weight average molecular weight is a polystyrene reduced value measured by gel permeation chromatography (GPC).

또한 본 발명의 중합체는, 본 발명의 효과를 손상시키지 않는 한, 상기 식 [1a]∼[1c] 이외의 다른 반복 단위를 포함해도 된다. 상기 다른 반복 단위를 제공하는 중합성 화합물로서는 아크릴산 에스터 화합물, 메타크릴산 에스터 화합물, 말레이미드 화합물, 아크릴아마이드 화합물, 아크릴로나이트릴, 말레산 무수물, 스타이렌 화합물 등을 들 수 있다. The polymer of the present invention may contain a repeating unit other than the above-mentioned formulas [1a] to [1c], so long as the effect of the present invention is not impaired. Examples of the polymerizable compound providing the above other repeating unit include an acrylate ester compound, a methacrylate ester compound, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, and a styrene compound.

상기 다른 반복 단위의 함유율은 전체 반복 단위 100몰% 중, 0∼10몰%가 바람직하다. 상기 다른 반복 단위의 함유율이 지나치게 크면, 본 발명의 중합체의 특성, 예를 들면, 액정성 등의 특성이 저하되는 경우가 있다. The content of the other repeating units is preferably 0 to 10 mol% in 100 mol% of all repeating units. If the content of the other repeating units is excessively large, the properties of the polymer of the present invention, such as the liquid crystallinity, may be deteriorated.

본 발명의 중합체가 상기 다른 반복 단위를 포함하는 경우, 그 합성 방법으로서는, 상기 중합 시에, 상기 다른 반복 단위를 제공하는 중합성 화합물을 공존시켜 중합하면 된다. When the polymer of the present invention contains the above other repeating units, the polymerization method may be a polymerization method in which the above-mentioned other repeating unit-providing polymerizable compound coexists at the time of polymerization.

또한, 본 발명의 중합체는 랜덤 공중합체, 교호 공중합체, 블록 공중합체의 어떤 것이어도 된다. Further, the polymer of the present invention may be any of a random copolymer, an alternating copolymer and a block copolymer.

[조성물][Composition]

본 발명의 조성물은 상기 중합체의 적어도 1종과 유기 용매를 혼합함으로써 얻어진다. The composition of the present invention is obtained by mixing at least one kind of the polymer with an organic solvent.

상기 유기 용매로서는, 예를 들면, 테트라하이드로퓨란, 다이옥세인 등의 에터류; 벤젠, 톨루엔, 자일렌 등의 방향족 탄화수소류; N,N-다이메틸폼아마이드, N-메틸-2-파이롤리돈 등의 극성 용매; 아세트산 에틸, 아세트산 뷰틸, 락트산 에틸 등의 에스터류; 3-메톡시프로피온산 메틸, 2-메톡시프로피온산 메틸, 3-메톡시프로피온산 에틸, 2-메톡시프로피온산 에틸, 3-에톡시프로피온산 에틸, 2-에톡시프로피온산 에틸 등의 알콕시 에스터류; 에틸렌글라이콜 다이메틸에터, 프로필렌글라이콜 다이메틸에터 등의 글라이콜 다이알킬에터류; 다이에틸렌글라이콜 다이메틸에터, 다이에틸렌글라이콜 다이에틸에터, 다이에틸렌글라이콜 메틸에틸에터, 다이프로필렌글라이콜 다이메틸에터 등의 다이글라이콜 다이알킬에터류; 에틸렌글라이콜 모노메틸에터, 에틸렌글라이콜 모노에틸에터, 프로필렌글라이콜 모노메틸에터, 프로필렌글라이콜 모노에틸에터 등의 글라이콜 모노알킬에터류; 다이에틸렌글라이콜 모노메틸에터, 다이에틸렌글라이콜 모노에틸에터, 다이프로필렌글라이콜 모노메틸에터, 다이프로필렌글라이콜 모노에틸에터 등의 다이글라이콜 모노알킬에터류; 프로필렌글라이콜 모노메틸에터아세테이트, 카비톨 아세테이트, 에틸셀로솔브 아세테이트 등의 글라이콜 모노알킬에터에스터류; 사이클로헥산온, 메틸에틸케톤, 메틸아이소뷰틸케톤, 2-헵탄온 등의 케톤류를 들 수 있다. 이들 유기 용매는 단독이어도 2종류 이상을 조합하여 사용할 수도 있다. Examples of the organic solvent include ethers such as tetrahydrofuran and dioxane; Aromatic hydrocarbons such as benzene, toluene and xylene; Polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone; Esters such as ethyl acetate, butyl acetate, and ethyl lactate; Alkoxy esters such as methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate; Glycol dialkyl ethers such as ethylene glycol dimethyl ether and propylene glycol dimethyl ether; Dialkyl dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, and dipropylene glycol dimethyl ether; Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Diglycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, and dipropylene glycol monoethyl ether; Glycol monoalkyl ether esters such as propylene glycol monomethyl ether acetate, carbitol acetate and ethyl cellosolve acetate; Ketones such as cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. These organic solvents may be used alone or in combination of two or more.

이들 중에서도, 프로필렌글라이콜 모노메틸에터, 프로필렌글라이콜 모노메틸에터아세테이트, 락트산 에틸, 사이클로헥산온 등이 바람직하다. Among these, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, cyclohexanone and the like are preferable.

유기 용매의 사용량은 조성물 중 60∼95질량% 정도로 하는 것이 적합하다. The amount of the organic solvent used is preferably about 60 to 95% by mass in the composition.

또한 본 발명의 조성물에는 기판과의 친화성을 향상시킬 목적으로 계면활성제를 첨가해도 된다. 계면활성제로서는 특별히 한정되는 것은 아니고, 불소계 계면활성제, 실리콘계 계면활성제, 비이온계 계면활성제 등을 들 수 있지만, 기판과의 친화성 개선 효과가 높은 불소계 계면활성제가 바람직하다. A surfactant may be added to the composition of the present invention for the purpose of improving the affinity with the substrate. The surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a silicon-based surfactant, and a nonionic surface-active agent, but a fluorine-based surfactant having a high affinity for improving affinity with a substrate is preferable.

불소계 계면활성제의 구체예로서는(이하, 상품명), 에프톱 EF301, EF303, EF352((주)토켐프로덕츠제), 메가팍 F171, F173, R-30(DIC(주)제), 플로라도FC430, FC431(스미토모쓰리엠(주)제), 아사히가드 AG710, 서플론 S-382, SC101, SC102, SC103, SC104, SC105, SC106(아사히가라스(주)제) 등을 들 수 있는데, 이것들에 한정되는 것은 아니다. 또한, 계면활성제는 단독으로도 복수종을 조합하여 사용할 수도 있고, 그 첨가량은 중합체 100질량부에 대하여 5질량부 이하가 바람직하다. Specific examples of the fluorochemical surfactant include Fafto EF301, EF303 and EF352 (manufactured by Tohchem Products Corporation), Megafac F171, F173 and R-30 (manufactured by DIC Corporation), Florado FC430 and FC431 (Manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105 and SC106 (manufactured by Asahi Garas Co., Ltd.) no. The surfactant may be used singly or in combination of plural species, and the addition amount thereof is preferably 5 parts by mass or less based on 100 parts by mass of the polymer.

또한 본 발명의 조성물에는, 기판과의 밀착성을 향상시킬 목적으로, 밀착 촉진제를 첨가해도 된다. In addition, an adhesion promoter may be added to the composition of the present invention for the purpose of improving adhesion with a substrate.

밀착 촉진제로서는 트라이메틸클로로실레인, 다이메틸바이닐클로로실레인, 메틸다이페닐클로로실레인, 클로로메틸다이메틸클로로실레인 등의 클로로실레인류; 트라이메틸메톡시실레인, 다이메틸다이에톡시실레인, 메틸다이메톡시실레인, 다이메틸바이닐에톡시실레인, 다이페닐다이메톡시실레인, 페닐트라이에톡시실레인 등의 알콕시실레인류; 헥사메틸다이실라잔, N,N'-비스(트라이메틸실릴)유레아, 다이메틸트라이메틸실릴아민, 트라이메틸실릴이미다졸 등의 실라잔류; 바이닐트라이클로로실레인, γ-클로로프로필트라이메톡시실레인, γ-아미노프로필트라이에톡시실레인, γ-메타크릴록시프로필트라이메톡시실레인, γ-글라이시독시프로필트라이메톡시실레인, γ-(N-피페리딘일)프로필트라이메톡시실레인 등의 실레인류; 벤조트라이아졸, 벤즈이미다졸, 인다졸, 이미다졸, 2-머캡토벤즈이미다졸, 2-머캡토벤조싸이아졸, 2-머캡토벤조옥사졸, 유라졸, 유라실, 머캡토 이미다졸, 머캡토 피리미딘 등의 복소 환상 화합물; 1,1-다이메틸유레아, 1,3-다이메틸 유레아 등의 유레아 화합물; 싸이오유레아 화합물 등을 들 수 있다. Examples of the adhesion promoter include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane; Alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane and the like; Silane residues such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilylimidazole and the like; Vinyl trichlorosilane,? -Chloropropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Methacryloxypropyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane, silanes such as? - (N-piperidinyl) propyltrimethoxysilane; Benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, uracil, mercaptothiazole, Heterocyclic compounds such as cappyrimidine; Urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea; Thiourea compounds, and the like.

밀착 촉진제는 단독으로도 복수종을 조합하여 사용할 수도 있고, 그 첨가량은 중합체 100질량부에 대하여 1질량부 이하가 바람직하다. The adhesion promoter may be used singly or in combination of plural species, and the amount thereof is preferably 1 part by mass or less based on 100 parts by mass of the polymer.

[단층 도포형 수평 배향 필름][Horizontal Orientation Film of Single Layer Coating Type]

이상에서 설명한 본 발명의 조성물을 기판(예를 들면, 실리콘/이산화실리콘 피복 기판, 실리콘 나이트라이드 기판, 금속, 예를 들면, 알루미늄, 몰리브덴, 크롬 등이 피복된 기판, 유리 기판, 석영 기판, ITO 기판 등)이나 필름(예를 들면, 트라이아세틸셀룰로스(TAC) 필름, 사이클로올레핀 폴리머 필름, 폴리에틸렌테레프탈레이트 필름, 아크릴 필름 등의 수지 필름) 등 위에, 바 코팅, 스핀 코팅, 플로우 코팅, 롤 코팅, 슬릿 코팅, 슬릿 코팅에 이은 스핀 코팅, 잉크젯법, 인쇄법 등의 방법에 의해 도포하여 도포막을 형성하고, 그 후 핫플레이트 또는 오븐 등에서 가열 건조함으로써 막을 형성할 수 있다. The composition of the present invention may be applied to a substrate (e.g., a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum or chromium, a glass substrate, Spin coating, flow coating, roll coating, or the like) on a substrate (e.g., a substrate), a film (e.g., a triacetylcellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, A slit coating, a slit coating, a spin coating, an inkjet method, a printing method or the like to form a coating film, and then the film can be formed by heating and drying in a hot plate or an oven.

가열 건조의 조건으로서는, 예를 들면, 온도 50∼100℃, 시간 0.1∼60분간의 범위 속에서 적당하게 선택된 가열온도 및 가열시간이 채용된다. 상기 가열온도 및 가열시간은 바람직하게는 50∼80℃, 0.1∼2분간이다. As the heating and drying conditions, for example, heating temperature and heating time suitably selected in the temperature range of 50 to 100 占 폚 for 0.1 to 60 minutes are employed. The heating temperature and the heating time are preferably 50 to 80 DEG C for 0.1 to 2 minutes.

이렇게 하여 형성된 막은 직선 편광 조사를 행하고, 포스트 베이크를 행함으로써, 단층 도포형 수평 배향 필름이 얻어진다. The thus formed film is irradiated with linearly polarized light and subjected to post-baking to obtain a single layer coated horizontally oriented film.

직선 편광의 조사 방법으로서는 통상 150∼450nm 파장의 자외선∼가시광선이 사용되고, 실온 또는 가열한 상태에서, 직선 편광을 조사함으로써 행해진다. As a method of irradiating linearly polarized light, ultraviolet rays to visible rays having a wavelength of 150 to 450 nm are usually used and irradiated with linearly polarized light at room temperature or in a heated state.

또한 포스트 베이크는 핫플레이트 또는 오븐 등으로 가열하면 되고, 그 온도 및 시간은 바람직하게는 90∼150℃, 2∼20분간이며, 보다 바람직하게는 95∼120℃, 5∼20분간이다. The post bake may be heated by a hot plate or an oven, and the temperature and time are preferably 90 to 150 DEG C for 2 to 20 minutes, more preferably 95 to 120 DEG C for 5 to 20 minutes.

본 발명의 단층 도포형 수평 배향 필름의 막 두께는 사용하는 기판의 단차나 광학적, 전기적 성질을 고려하여 적당하게 선택할 수 있고, 예를 들면, 0.1∼3㎛가 적합하다. The film thickness of the single-layer coating type horizontally oriented film of the present invention can be suitably selected in consideration of the step difference of the substrate to be used and the optical and electrical properties. For example, 0.1 to 3 m is suitable.

이렇게 하여 얻어진 본 발명의 단층 도포형 수평 배향 필름은 표시 장치나 기록 재료 등의 용도에 적합한 광학 특성을 갖는 재료이며, 특히, 액정 디스플레이용의 편광판 및 위상차판 등의 광학 보상 필름으로서 적합하다. The thus obtained single-layer coating type horizontally oriented film of the present invention is a material having optical properties suitable for applications such as display devices and recording materials, and is particularly suitable as an optical compensation film such as a polarizing plate and a retarder for a liquid crystal display.

(실시예)(Example)

이하, 합성예, 실시예 및 비교예를 들어 본 발명을 보다 구체적으로 설명하지만, 본 발명은 하기의 실시예에 한정되는 것은 아니다. 또한, 실시예에서의 각 물성의 측정 방법 및 측정 조건은 이하와 같다. Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The measuring method and the measuring condition of each physical property in the examples are as follows.

[1] NMR[1] NMR

화합물을 중수소화 클로로폼(CDCl3)에 용해하고, 핵자기 공명 장치(300MHz, 디올사제)를 사용하여 1H-NMR을 측정했다. The compound was dissolved in deuterated chloroform (CDCl 3 ), and 1 H-NMR was measured using a nuclear magnetic resonance apparatus (300 MHz, manufactured by Dior).

[2] 평균 분자량 측정[2] Average molecular weight measurement

쇼와덴코(주)제 Shodex GPC-101(용매: 테트라하이드로퓨란, 검량선: 표준 폴리스타이렌)을 사용하여, 수평균 분자량(Mn), 중량평균 분자량(Mw)을 측정했다. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko K.K.

[3] 헤이즈값[3] Haze value

(유)도쿄덴쇼쿠제 Spectral Haze Meter(TC-1800H)를 사용하여 필름의 헤이즈값을 측정했다. The haze value of the film was measured using Spectral Haze Meter (TC-1800H) manufactured by Tokyo Denshoku Co., Ltd.

[4] 필름의 리타데이션값[4] Retardation value of the film

리타데이션 측정 장치(RETS-100, 오츠카덴시(주)제)를 사용하여 파장 550nm의 리타데이션값을 측정했다. The retardation value at a wavelength of 550 nm was measured using a retardation measurement apparatus (RETS-100, manufactured by Otsuka Denshi Co., Ltd.).

[5] 편광 현미경 관찰[5] polarizing microscope observation

(주)니콘제의 편광 현미경 E600-Pol을 사용하여 관찰을 행했다. Observation was carried out using a polarizing microscope E600-Pol manufactured by Nikon Corporation.

[합성예 1] 중합성 화합물 (M1)의 합성[Synthesis Example 1] Synthesis of polymerizable compound (M1)

Figure 112014073140464-pct00021
Figure 112014073140464-pct00021

4-(6-아크릴로일옥시-1-헥실옥시)벤조산(SYNTHON Chemicals사제) 29.2g(100mmol), 4-하이드록시바이페닐 17.0g(100mmol), DMAP 0.6g 및 소량의 다이뷰틸하이드록시톨루엔(BHT)을 실온에서 교반하에, 염화 메틸렌 200mL에 현탁시키고, 거기에 염화 메틸렌 100mL에 DCC 24.0g(116mmol)을 용해시킨 용액을 가하고 밤새 교반했다. 석출한 DCC 유레아를 여과하여 분리하고, 그 여과액을 0.5mol/L 염산 150mL, 포화 탄산수소나트륨 수용액 150mL, 포화 식염수 150mL로 차례로 2회씩 세정하고, 황산 마그네슘으로 건조 후, 용매를 증류 제거하고, 에탄올에 의한 재결정으로 정제하여, 목적의 중합성 화합물 (M1) 39.6g을 얻었다(수율 89%). NMR의 측정 결과를 이하에 나타낸다. (100 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (SYNTHON Chemicals), 17.0 g (100 mmol) of 4-hydroxybiphenyl, 0.6 g of DMAP and a small amount of dibutylhydroxy Toluene (BHT) was suspended in 200 mL of methylene chloride with stirring at room temperature, and a solution of 24.0 g (116 mmol) of DCC dissolved in 100 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 150 ml of 0.5 mol / L hydrochloric acid, 150 mL of saturated aqueous sodium hydrogencarbonate solution and 150 mL of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, The resultant product was purified by recrystallization with ethanol to obtain 39.6 g of a desired polymerizable compound (M1) (yield: 89%). The measurement results of NMR are shown below.

1H-NMR(CDCl3)δ: 1.57(m, 4H), 1.70(m, 2H), 1.86(m, 2H), 4.00(m, 2H), 4.19(m, 2H), 5.82(m, 1H), 6.12(m, 1H), 6.39(m, 1H), 6.97(d, 2H), 7.29(m, 2H), 7.36(m, 1H), 7.47(m, 2H), 7.62(m, 4H), 8.18(m, 2H) 1 H-NMR (CDCl 3) δ: 1.57 (m, 4H), 1.70 (m, 2H), 1.86 (m, 2H), 4.00 (m, 2H), 4.19 (m, 2H), 5.82 (m, 1H 2H), 7.36 (m, 2H), 7.62 (m, 4H), 6.97 (m, , &Lt; / RTI &gt; 8.18 (m, 2H)

[실시예 1] 중합성 화합물 (M2)의 합성[Example 1] Synthesis of polymerizable compound (M2)

(1) 중간체 화합물 (P2)의 합성(1) Synthesis of intermediate compound (P2)

Figure 112014073140464-pct00022
Figure 112014073140464-pct00022

냉각관이 부착된 500mL 가지 플라스크에 바이페놀 18.6g(100mmol), 2-(4-브로모-1-뷰틸)-1,3-다이옥솔레인 10.0g(48mmol), 탄산 칼륨 13.8g(100mmol) 및 아세톤 200mL를 가하여 혼합물로 하고, 온도 64℃에서 24시간 교반하면서 반응시켰다. 반응 종료 후, 반응액을 순수 500mL에 붓고, 백색의 고체를 얻었다. 이 고체를 메탄올과 혼합하고, 여과를 행하고, 용매를 증류 제거한 바, 백색의 고체를 얻었다. 다음에 이 고체를 클로로폼과 혼합하고, 여과를 행하고, 용매를 증류 제거하여, 백색의 고체 7.2g을 얻었다. 이 고체를 NMR로 측정한 결과를 이하에 나타낸다. 이 결과로부터, 이 백색 고체가 중간체 화합물 (P2)인 것이 확인되었다(수율 48%). (100 mmol) of biphenol, 10.0 g (48 mmol) of 2- (4-bromo-1-butyl) -1,3-dioxolane and 13.8 g (100 mmol) of potassium carbonate were placed in a 500- And acetone (200 mL) were added to the mixture, and the mixture was reacted at 64 ° C for 24 hours with stirring. After completion of the reaction, the reaction solution was poured into 500 mL of pure water to obtain a white solid. This solid was mixed with methanol, filtered, and the solvent was distilled off to obtain a white solid. Then, this solid was mixed with chloroform, filtered, and the solvent was distilled off to obtain 7.2 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (P2) (yield: 48%).

1H-NMR(CDCl3)δ: 1.62(m, 2H), 1.76(m, 2H), 1.87(m, 2H), 3.85(m, 2H), 4.00(m, 4H), 4.90(m, 1H), 6.87(m, 4H), 7.42(m, 4H) 1 H-NMR (CDCl 3) δ: 1.62 (m, 2H), 1.76 (m, 2H), 1.87 (m, 2H), 3.85 (m, 2H), 4.00 (m, 4H), 4.90 (m, 1H ), 6.87 (m, 4H), 7.42 (m, 4H)

(2) 중간체 화합물 (Z2)의 합성(2) Synthesis of intermediate compound (Z2)

Figure 112014073140464-pct00023
Figure 112014073140464-pct00023

다음에 냉각관이 부착된 300mL 가지 플라스크에 상기에서 얻어진 중간체 화합물 (P2) 7.2g(23mmol), 2-(브로모메틸)아크릴산 4.1g(25mmol), THF 60mL, 염화 주석 (II) 4.7g(25mmol) 및 10질량% HCl 수용액 19mL를 가하여 혼합물로 하고, 온도 70℃에서 5시간 교반하여 반응시켰다. 반응 종료 후, 반응액을 순수 200mL에 붓고, 백색 고체 6.1g을 얻었다. 이 고체를 NMR로 측정한 결과를 이하에 나타낸다. 이 결과로부터, 이 백색 고체가 중간체 화합물 (Z2)인 것이 확인되었다(수율 78%). Next, 7.2 g (23 mmol) of the intermediate compound (P2) obtained above, 4.1 g (25 mmol) of 2- (bromomethyl) acrylic acid, 60 ml of THF and 4.7 g And 19 mL of a 10% by mass aqueous solution of HCl were added to the mixture, and the mixture was stirred at a temperature of 70 ° C for 5 hours. After completion of the reaction, the reaction solution was poured into 200 mL of pure water to obtain 6.1 g of a white solid. The result of measurement of this solid by NMR is shown below. From this result, it was confirmed that the white solid was the intermediate compound (Z2) (yield: 78%).

1H-NMR(CDCl3)δ: 1.60-1.95(m, 6H), 2.64(m, 1H), 3.11(s, 1H), 4.02(t, 2H), 4.60(m, 1H), 4.82(s, 1H), 5.64(s, 1H), 6.24(s, 1H), 6.88(d, 2H), 6.94(d, 2H), 7.44(m, 4H) 1 H-NMR (CDCl 3) δ: 1.60-1.95 (m, 6H), 2.64 (m, 1H), 3.11 (s, 1H), 4.02 (t, 2H), 4.60 (m, 1H), 4.82 (s 2H), 7.44 (m, 4H), 6.94 (d, IH)

(3) 중합성 화합물 (M2)의 합성(3) Synthesis of polymerizable compound (M2)

Figure 112014073140464-pct00024
Figure 112014073140464-pct00024

화합물 (Z2) 3.4g(10mmol), 4-메톡시신남산 1.8g(10mmol), DMAP 0.08g 및 소량의 BHT를 실온에서 교반하에, 염화 메틸렌 30mL에 현탁시키고, 거기에 염화 메틸렌 15mL에 DCC 2.6g(13mmol)을 용해시킨 용액을 가하고 밤새 교반했다. 석출한 DCC 유레아를 여과하여 분리하고, 그 여과액을 0.5mol/L 염산 50mL, 포화 탄산수소나트륨 수용액 50mL, 포화 식염수 50mL로 차례로 2회씩 세정하고, 황산 마그네슘으로 건조 후, 용매를 증류 제거하고, 에탄올에 의한 재결정으로 정제하여, 목적의 중합성 화합물 (M2) 4.3g을 얻었다(수율 86%). NMR의 측정 결과를 이하에 나타낸다. 3.4 g (10 mmol) of the compound (Z2), 1.8 g (10 mmol) of 4-methoxycinnamic acid, 0.08 g of DMAP and a small amount of BHT were suspended in 30 ml of methylene chloride while stirring at room temperature. To this, (13 mmol) was added thereto, and the mixture was stirred overnight. The precipitated DCC urea was separated by filtration. The filtrate was washed twice with 50 ml of 0.5 mol / L hydrochloric acid, 50 mL of a saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, and dried with magnesium sulfate. The solvent was distilled off, The residue was purified by recrystallization with ethanol to obtain 4.3 g of the target polymerizable compound (M2) (yield: 86%). The measurement results of NMR are shown below.

1H-NMR(CDCl3)δ: 1.60-1.90(m, 6H), 2.63(m, 1H), 3.09(m, 1H), 3.87(s, 3H), 4.03(m, 2H), 4.57(m, 1H), 5.64(m, 1H), 6.24(d, 1H), 6.54(d, 1H), 6.95(m, 4H), 7.26(m, 2H), 7.44(m, 2H), 7.57(m, 4H), 7.86(d, 1H) 1 H-NMR (CDCl 3) δ: 1.60-1.90 (m, 6H), 2.63 (m, 1H), 3.09 (m, 1H), 3.87 (s, 3H), 4.03 (m, 2H), 4.57 (m 2H), 7.44 (m, 2H), 7.57 (m, 2H), 5.64 (m, 4H), 7.86 (d, 1 H)

[합성예 2] 중합성 화합물 (M3)의 합성[Synthesis Example 2] Synthesis of polymerizable compound (M3)

Figure 112014073140464-pct00025
Figure 112014073140464-pct00025

화합물 (Z3)(미도리카가쿠(주)제) 3.1g(10.0mmol), 4-메톡시신남산 1.8g(10.0mmol), DMAP 0.08g 및 소량의 BHT를 실온에서 교반하에, 염화 메틸렌 30mL에 현탁시키고, 거기에 염화 메틸렌 15mL에 DCC 2.6g(12.5mmol)을 용해시킨 용액을 가하고 밤새 교반했다. 석출한 DCC 유레아를 여과하여 분리하고, 그 여과액을 0.5mol/L 염산 50mL, 포화 탄산수소나트륨 수용액 50mL, 포화 식염수 50mL로 차례로 2회씩 세정하고, 황산 마그네슘으로 건조 후, 용매를 증류 제거하고, 에탄올에 의한 재결정으로 정제하여, 목적의 중합성 화합물 (M3) 3.4g을 얻었다(수율 72%). NMR의 측정 결과를 이하에 나타낸다. (10.0 mmol) of 4-methoxycinnamic acid, 0.08 g of DMAP and a small amount of BHT were suspended in 30 mL of methylene chloride with stirring at room temperature, And a solution prepared by dissolving 2.6 g (12.5 mmol) of DCC in 15 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration. The filtrate was washed twice with 50 ml of 0.5 mol / L hydrochloric acid, 50 mL of a saturated aqueous sodium hydrogen carbonate solution and 50 mL of saturated brine successively, and dried with magnesium sulfate. The solvent was distilled off, And purified by recrystallization with ethanol to obtain 3.4 g of a target polymerizable compound (M3) (yield: 72%). The measurement results of NMR are shown below.

1H-NMR(CDCl3)δ: 1.93(m, 4H), 3.87(s, 3H), 4.03(m, 2H), 4.26(m, 2H), 5.85(m, 1H), 6.14(m, 1H), 6.17(d, 1H), 6.44(d, 1H), 6.95(m, 4H), 7.19(m, 2H), 7.55(m, 6H), 7.82(d, 1H) 1 H-NMR (CDCl 3) δ: 1.93 (m, 4H), 3.87 (s, 3H), 4.03 (m, 2H), 4.26 (m, 2H), 5.85 (m, 1H), 6.14 (m, 1H ), 6.17 (d, 1 H), 6.44 (d, 1 H), 6.95 (m, 4H)

[합성예 3] 중합성 화합물 (M4)의 합성[Synthesis Example 3] Synthesis of polymerizable compound (M4)

Figure 112014073140464-pct00026
Figure 112014073140464-pct00026

4-(6-아크릴로일옥시-1-헥실옥시)벤조산(SYNTHON Chemicals사제) 29.2g(100mmol), 4-메톡시페놀 12.4g(100mmol), DMAP 0.8g 및 소량의 BHT를 실온에서 교반하에, 염화 메틸렌 200mL에 현탁시키고, 거기에 염화 메틸렌 100mL에 DCC 24.0g(116mmol)을 용해시킨 용액을 가하고 밤새 교반했다. 석출한 DCC유레아를 여과하여 분리하고, 그 여과액을 0.5mol/L 염산 150mL, 포화 탄산수소나트륨 수용액 150mL, 포화 식염수 150mL로 차례로 2회씩 세정하고, 황산 마그네슘으로 건조 후, 용매를 증류 제거하고, 에탄올에 의한 재결정으로 정제하고, 목적의 중합성 화합물 (M4) 21.5g을 얻었다(수율 54%). NMR의 측정 결과를 이하에 나타낸다. (100 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (SYNTHON Chemicals), 12.4 g (100 mmol) of 4-methoxyphenol, 0.8 g of DMAP and a small amount of BHT were stirred , And a solution prepared by dissolving 24.0 g (116 mmol) of DCC in 100 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration, and the filtrate was washed twice with 150 ml of 0.5 mol / L hydrochloric acid, 150 mL of saturated aqueous sodium hydrogencarbonate solution and 150 mL of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, The residue was purified by recrystallization with ethanol to obtain 21.5 g of a desired polymerizable compound (M4) (yield: 54%). The measurement results of NMR are shown below.

1H-NMR(CDCl3)δ: 1.57(m, 4H), 1.70(m, 2H), 1.86(m, 2H), 3.82(s, 3H), 4.00(m, 2H), 4.19(m, 2H), 5.84(m, 1H), 6.13(m, 1H), 6.39(m, 1H), 6.97(m, 4H), 7.10(m, 2H), 8.11(m, 2H) 1 H-NMR (CDCl 3) δ: 1.57 (m, 4H), 1.70 (m, 2H), 1.86 (m, 2H), 3.82 (s, 3H), 4.00 (m, 2H), 4.19 (m, 2H 2H), 8.11 (m, 2H), 5.84 (m, IH)

[합성예 4] 중합성 화합물 (M5)의 합성[Synthesis Example 4] Synthesis of polymerizable compound (M5)

Figure 112014073140464-pct00027
Figure 112014073140464-pct00027

4-(6-아크릴로일옥시-1-헥실옥시)벤조산(SYNTHON Chemicals사제) 14.6g(50mmol), 4-사이아노페놀 5.9g(50mmol), DMAP 0.4g 및 소량의 BHT를 실온에서 교반하에, 염화 메틸렌 100mL에 현탁시키고, 거기에 염화 메틸렌 50mL에 DCC 12.0g(58mmol)을 용해시킨 용액을 가하고 밤새 교반했다. 석출한 DCC 유레아를 여과하여 분리하고, 그 여과액을 0.5mol/L 염산 100mL, 포화 탄산수소나트륨 수용액 100mL, 포화 식염수 100mL로 차례로 2회씩 세정하고, 황산 마그네슘으로 건조 후, 용매를 증류 제거하고, 에탄올에 의한 재결정으로 정제하여, 목적의 중합성 화합물 (M5) 14.5g을 얻었다(수율 74%). NMR의 측정 결과를 이하에 나타낸다. (50 mmol) of 4- (6-acryloyloxy-1-hexyloxy) benzoic acid (SYNTHON Chemicals), 5.9 g (50 mmol) of 4-cyanophenol, 0.4 g of DMAP and a small amount of BHT were stirred , And a solution prepared by dissolving 12.0 g (58 mmol) of DCC in 50 mL of methylene chloride was added thereto, followed by stirring overnight. The precipitated DCC urea was separated by filtration. The filtrate was washed twice with 100 ml of 0.5 mol / L hydrochloric acid, 100 mL of saturated aqueous sodium hydrogencarbonate solution and 100 mL of saturated brine, and dried with magnesium sulfate. The solvent was distilled off, The resultant product was purified by recrystallization with ethanol to obtain 14.5 g of a desired polymerizable compound (M5) (yield: 74%). The measurement results of NMR are shown below.

1H-NMR(CDCl3)δ: 1.57(m, 4H), 1.71(m, 2H), 1.86(m, 2H), 4.00(m, 2H), 4.19(m, 2H), 5.84(m, 1H), 6.13(m, 1H), 6.39(m, 1H), 6.99(m, 2H), 7.36(m, 2H), 7.72(m, 2H), 8.11(m, 2H) 1 H-NMR (CDCl 3) δ: 1.57 (m, 4H), 1.71 (m, 2H), 1.86 (m, 2H), 4.00 (m, 2H), 4.19 (m, 2H), 5.84 (m, 1H ), 6.13 (m, IH), 6.39 (m, IH), 6.99 (m, 2H), 7.36

[실시예 2] 중합체 (1)의 합성[Example 2] Synthesis of polymer (1)

Figure 112014073140464-pct00028
Figure 112014073140464-pct00028

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.62g(1.4mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), NMP 8.3g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (1)을 0.65g 얻었다(수율 71%). 0.62 g (1.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 8.3 g of NMP and 17 mg of AIBN were placed in a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. This white powder was filtered and vacuum-dried at room temperature to obtain 0.65 g of polymer (1) (yield: 71%).

얻어진 중합체 (1)의 Mn은 10,975, Mw는 19,206이었다(Mw/Mn=1.75). The obtained polymer (1) had Mn of 10,975 and Mw of 19,206 (Mw / Mn = 1.75).

[비교예 1] 중합체 (2)의 합성[Comparative Example 1] Synthesis of Polymer (2)

Figure 112014073140464-pct00029
Figure 112014073140464-pct00029

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.62g(1.4mmol), 합성예 2에서 얻어진 중합성 화합물 (M3) 0.28g(0.6mmol), NMP 9.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (2)를 0.67g 얻었다(수율 74%). 0.42 g (1.4 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.28 g (0.6 mmol) of the polymerizable compound (M3) obtained in Synthesis Example 2, 9.0 g of NMP and 17 mg of AIBN were placed in a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.67 g (yield: 74%) of polymer (2).

얻어진 중합체 (2)의 Mn은 7,068, Mw는 9,542이었다(Mw/Mn=1.35). The obtained polymer (2) had Mn of 7,068 and Mw of 9,542 (Mw / Mn = 1.35).

[실시예 3] 중합체 (3)의 합성[Example 3] Synthesis of Polymer (3)

Figure 112014073140464-pct00030
Figure 112014073140464-pct00030

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.44g(1.0mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), n-뷰틸메타크릴레이트 0.06g(0.4mmol), NMP 7.2g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (3)을 0.71g 얻었다(수율 89%). 0.44 g (1.0 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.06 g g (0.4 mmol) of NMP, 7.2 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.71 g (yield: 89%) of polymer (3).

얻어진 중합체의 Mn은 12,664, Mw는 39,258이었다(Mw/Mn=3.10). The Mn of the obtained polymer was 12,664 and the Mw was 39,258 (Mw / Mn = 3.10).

[실시예 4] 중합체 (4)의 합성[Example 4] Synthesis of Polymer (4)

Figure 112014073140464-pct00031
Figure 112014073140464-pct00031

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.44g(1.0mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), 2-에틸헥실아크릴레이트 0.07g(0.4mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (4)을 0.54g 얻었다(수율 67%). 0.44 g (1.0 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.07 g g (0.4 mmol) of NMP, 8.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.54 g (yield 67%) of polymer (4).

얻어진 중합체의 Mn은 10,357, Mw는 23,925이었다(Mw/Mn=2.31). The obtained polymer had Mn of 10,357 and Mw of 23,925 (Mw / Mn = 2.31).

[실시예 5] 중합체 (5)의 합성[Example 5] Synthesis of polymer (5)

Figure 112014073140464-pct00032
Figure 112014073140464-pct00032

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.36g(0.8mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), 2-에틸헥실아크릴레이트 0.11g(0.6mmol), NMP 7.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (5)를 0.45g 얻었다(수율 58%). 0.36g (0.8mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30g (0.6mmol) of the polymerizable compound (M2) obtained in Example 1, 0.10g of 2-ethylhexyl acrylate g (0.6 mmol) of NMP, 7.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.45 g of polymer (5) (yield: 58%).

얻어진 중합체의 Mn은 11,065, Mw는 28,769이었다(Mw/Mn=2.6). The Mn of the obtained polymer was 11,065 and the Mw was 28,769 (Mw / Mn = 2.6).

[실시예 6] 중합체 (6)의 합성[Example 6] Synthesis of polymer (6)

Figure 112014073140464-pct00033
Figure 112014073140464-pct00033

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.44g(1.0mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), n-도데실아크릴레이트 0.10g(0.4mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (6)을 0.60g 얻었다(수율 71%). 0.44 g (1.0 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.10 g of n-dodecyl acrylate g (0.4 mmol) of NMP, 8.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.60 g of polymer (6) (yield: 71%).

얻어진 중합체의 Mn은 10,828, Mw는 23,822이었다(Mw/Mn=2.2).The obtained polymer had Mn of 10,828 and Mw of 23,822 (Mw / Mn = 2.2).

[실시예 7] 중합체 (7)의 합성[Example 7] Synthesis of polymer (7)

Figure 112014073140464-pct00034
Figure 112014073140464-pct00034

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.36g(0.8mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), n-도데실아크릴레이트 0.14g(0.6mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (7)을 0.50g 얻었다(수율 63%). 0.36 g (0.8 mmol) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.14 g (0.6 mmol) of NMP, 8.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.50 g of polymer (7) (yield: 63%).

얻어진 중합체의 Mn은 12,455, Mw는 22,544이었다(Mw/Mn=1.81).The Mn of the obtained polymer was 12,455 and the Mw was 22,544 (Mw / Mn = 1.81).

[비교예 2] 중합체 (8)의 합성[Comparative Example 2] Synthesis of Polymer (8)

Figure 112014073140464-pct00035
Figure 112014073140464-pct00035

냉각관을 구비한 플라스크에 합성예 1에서 얻어진 중합성 화합물 (M1) 0.44g(1.0mmol), 합성예 2에서 얻어진 중합성 화합물 (M3) 0.28g(0.6mmol), n-도데실아크릴레이트 0.10g(0.4mmol), NMP 8.2g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (8)을 0.58g 얻었다(수율 71%). 0.44 g (1.0 mmole) of the polymerizable compound (M1) obtained in Synthesis Example 1, 0.28 g (0.6 mmole) of the polymerizable compound (M3) obtained in Synthesis Example 2, 0.10 g of n-dodecyl acrylate g (0.4 mmol), NMP (8.2 g) and AIBN (17 mg) were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.58 g of polymer (8) (yield: 71%).

얻어진 중합체의 Mn은 8,025, Mw는 11,556이었다(Mw/Mn=1.44). The obtained polymer had Mn of 8,025 and Mw of 11,556 (Mw / Mn = 1.44).

[실시예 8] 중합체 (9)의 합성[Example 8] Synthesis of polymer (9)

Figure 112014073140464-pct00036
Figure 112014073140464-pct00036

냉각관을 구비한 플라스크에 합성예 4에서 얻어진 중합성 화합물 (M5) 0.55g(1.4mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (9)를 0.60g 얻었다(수율 71%). 0.55 g (1.4 mmol) of the polymerizable compound (M5) obtained in Synthesis Example 4, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 8.0 g of NMP and 17 mg of AIBN were added to a flask equipped with a cooling tube The inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.60 g (yield: 71%) of polymer (9).

얻어진 중합체 (9)의 Mn은 15,269, Mw는 24,430이었다(Mw/Mn=1.60). The obtained polymer (9) had Mn of 15,269 and Mw of 24,430 (Mw / Mn = 1.60).

[실시예 9] 중합체 (10)의 합성[Example 9] Synthesis of polymer (10)

Figure 112014073140464-pct00037
Figure 112014073140464-pct00037

냉각관을 구비한 플라스크에 합성예 4에서 얻어진 중합성 화합물 (M5) 0.39g(1.0mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), n-도데실아크릴레이트 0.10g(0.4mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (10)을 0.55g 얻었다(수율 69%). 0.39 g (1.0 mmol) of the polymerizable compound (M5) obtained in Synthesis Example 4, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.10 g of n-dodecyl acrylate g (0.4 mmol) of NMP, 8.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.55 g of polymer (10) (yield: 69%).

얻어진 중합체의 Mn은 15,040, Mw는 35,795이었다(Mw/Mn=2.38). The obtained polymer had Mn of 15,040 and Mw of 35,795 (Mw / Mn = 2.38).

[실시예 10] 중합체 (11)의 합성[Example 10] Synthesis of polymer (11)

Figure 112014073140464-pct00038
Figure 112014073140464-pct00038

냉각관을 구비한 플라스크에 합성예 3에서 얻어진 중합성 화합물 (M4) 0.40g(1.0mmol), 실시예 1에서 얻어진 중합성 화합물 (M2) 0.30g(0.6mmol), n-도데실아크릴레이트 0.10g(0.4mmol), NMP 8.0g 및 AIBN 17mg을 장입하고, 플라스크 내를 질소 치환한 후, 온도 60℃에서 20시간 교반하여 반응시켰다. 얻어진 반응 용액을 200mL의 메탄올에 투입하여, 백색 분말을 침전시켰다. 이 백색 분말을 여과한 후, 실온에서 진공 건조를 행하여, 중합체 (11)을 0.55g 얻었다(수율 69%). 0.40 g (1.0 mmol) of the polymerizable compound (M4) obtained in Synthesis Example 3, 0.30 g (0.6 mmol) of the polymerizable compound (M2) obtained in Example 1, 0.10 g of n-dodecyl acrylate g (0.4 mmol) of NMP, 8.0 g of NMP and 17 mg of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 DEG C for 20 hours with stirring. The obtained reaction solution was poured into 200 mL of methanol to precipitate a white powder. The white powder was filtered and vacuum-dried at room temperature to obtain 0.55 g of polymer (11) (yield: 69%).

얻어진 중합체의 Mn은 11,873, Mw는 26,358이었다(Mw/Mn=2.22). The Mn of the obtained polymer was 11,873 and the Mw was 26,358 (Mw / Mn = 2.22).

[조성물의 조제 및 필름 제작·평가][Preparation of composition and film production and evaluation]

상기 실시예, 비교예에서 얻어진 중합체를 사용하여 조성물을 조제하고, 하기 조건에 따라 필름을 제작하고, 그 특성을 검토했다. A composition was prepared using the polymers obtained in the above-mentioned Examples and Comparative Examples, and films were prepared according to the following conditions, and their properties were examined.

필름 제작 조건:Film production conditions:

스핀코트: 300rpm/5초, 800-2,000rpm/20초Spin coat: 300 rpm / 5 seconds, 800-2,000 rpm / 20 seconds

프리 베이크: 50℃/20초(핫플레이트)Pre-baking: 50 ℃ / 20 seconds (hot plate)

노광: 직선 편광 자외선, 파장 313nm, 수직 조사, 조사선량 500mJ/cm2 Exposure: linearly polarized ultraviolet ray, wavelength 313 nm, vertical irradiation, irradiation dose 500 mJ / cm 2

포스트 베이크: 100℃/10분(핫플레이트)Post bake: 100 占 폚 / 10 minutes (hot plate)

[실시예 11][Example 11]

중합체 (1) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (1)의 용액을 얻었다. 150 mg of the polymer (1) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (1).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상이 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the film on which the substrate image was obtained was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.8㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 리타데이션값(Δnd)은 62.3nm이며, 헤이즈값은 2.1%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.8 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The retardation value? Nd was 62.3 nm, and the haze value was 2.1%.

[비교예 3][Comparative Example 3]

중합체 (2) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (2)의 용액을 얻었다. 150 mg of the polymer (2) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (2).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.7㎛이며, 편광 현미경으로 그것을 관찰한 바, 수평 배향 필름이 얻어지지 않고, 그 Δnd는 7.6nm이며, 헤이즈값은 10.5%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.7 탆, which was observed by a polarizing microscope. As a result, a horizontally oriented film could not be obtained. The nd was 7.6 nm and the haze value was 10.5%.

[실시예 12][Example 12]

중합체 (3) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (3)의 용액을 얻었다. 150 mg of the polymer (3) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (3).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.8㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 96.7nm이며, 헤이즈값은 1.3%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.8 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 96.7 nm, and the haze value was 1.3%.

[실시예 13][Example 13]

중합체 (4) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (4)의 용액을 얻었다. 150 mg of the polymer (4) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (4).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.9㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 118.8nm이며, 헤이즈값은 0.9%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.9 mu m and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 118.8 nm, and the haze value was 0.9%.

[실시예 14][Example 14]

중합체 (5) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (5)의 용액을 얻었다. 150 mg of the polymer (5) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (5).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. 다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.9㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 99.1nm이며, 헤이즈값은 0.4%이었다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.9 mu m and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 99.1 nm, and the haze value was 0.4%.

[실시예 15][Example 15]

중합체 (6) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (6)의 용액을 얻었다. 150 mg of the polymer (6) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (6).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. 다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.8㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 113.3nm이며 헤이즈값은 0.9%이었다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.8 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The Δnd was 113.3 nm and the haze value was 0.9%.

[실시예 16][Example 16]

중합체 (7) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (7)의 용액을 얻었다. 150 mg of the polymer (7) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (7).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은, 막 두께가 0.9㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 118.3nm이며, 헤이즈값은 1.8%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.9 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 118.3 nm and the haze value was 1.8%.

[비교예 4][Comparative Example 4]

중합체 (8) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (8)의 용액을 얻었다. 150 mg of the polymer (8) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (8).

이 용액을, 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.8㎛이며, 편광 현미경으로 그것을 관찰한 바, 수평 배향 필름이 얻어지지 않고, 그 Δnd는 8.4nm이며, 헤이즈값은 4.7%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.8 占 퐉 and it was observed with a polarizing microscope. As a result, a horizontally oriented film was not obtained, and its Δnd was 8.4 nm and the haze value was 4.7%.

[실시예 17][Example 17]

중합체 (9) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온 850mg에 용해하여, 중합체 (9)의 용액을 얻었다. 150 mg of the polymer (9) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone to obtain a solution of the polymer (9).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.8㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 86.0nm이며, 헤이즈값은 2.2%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.8 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 86.0 nm, and the haze value was 2.2%.

[실시예 18][Example 18]

중합체 (10) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온/톨루엔(25/75, 질량비) 850mg에 용해하여, 중합체 (10)의 용액을 얻었다. 150 mg of the polymer (10) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone / toluene (25/75, mass ratio) to obtain a solution of the polymer (10).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후, 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후 포스트 베이크했다. 얻어진 필름은 막 두께가 1.0㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 77.3nm이며, 헤이즈값은 0.5%이었다. Then, a coating film formed on the glass substrate was exposed and post-baked. The obtained film had a film thickness of 1.0 占 퐉 and was observed with a polarizing microscope. It was confirmed that the film was horizontally aligned with respect to the substrate surface. The? Nd was 77.3 nm, and the haze value was 0.5%.

[실시예 19][Example 19]

중합체 (11) 150mg 및 계면활성제인 R-30(DIC(주)제) 0.3mg을 사이클로헥산온/톨루엔(25/75, 질량비) 850mg에 용해하여, 중합체 (11)의 용액을 얻었다. 150 mg of the polymer (11) and 0.3 mg of the surfactant R-30 (manufactured by DIC) were dissolved in 850 mg of cyclohexanone / toluene (25/75, mass ratio) to obtain a solution of the polymer (11).

이 용액을 유리 기판에 스핀 코팅에 의해 도포하고, 프리 베이크한 후 실온까지 방냉했다. 이 때, 기판 상의 얻어진 막은 투명했다. This solution was applied to a glass substrate by spin coating, pre-baked, and then allowed to cool to room temperature. At this time, the obtained film on the substrate was transparent.

다음에 유리 기판에 형성된 도포막을 노광한 후, 포스트 베이크했다. 얻어진 필름은 막 두께가 0.9㎛이며, 편광 현미경으로 그것을 관찰한 바, 필름이 기판면에 대하여 수평 배향되어 있는 것을 확인했다. 그리고, 그 Δnd는 76.2nm이며, 헤이즈값은 0.5%이었다. Then, a coating film formed on the glass substrate was exposed, and post-baked. The obtained film had a film thickness of 0.9 mu m and was observed with a polarizing microscope. It was confirmed that the film was oriented horizontally with respect to the substrate surface. The? Nd was 76.2 nm, and the haze value was 0.5%.

이상의 결과를 정리하여, 하기 표 1에 나타낸다. The above results are summarized in Table 1 below.

Figure 112014073140464-pct00039
Figure 112014073140464-pct00039

도 1 및 도 2에 실시예 11∼16 및 비교예 3 및 4에서 제작한 필름의 리타데이션값(Δnd)의 각도 의존성을 나타낸다. 실시예 11∼16(도 1)과 비교예 3 및 4(도 2)를 비교하면, 실시예 11∼16에서는, 수평 배향을 나타내는 것에 반해, 비교예 3 및 4에서는 완전한 수평 배향을 나타내지 않고, Δnd도 낮은 것을 알 수 있었다.Figs. 1 and 2 show the angle dependency of the retardation value (? Nd) of the films produced in Examples 11 to 16 and Comparative Examples 3 and 4. In comparison between Examples 11 to 16 (FIG. 1) and Comparative Examples 3 and 4 (FIG. 2), Horizontal alignment was shown in Examples 11 to 16, Comparative Examples 3 and 4 did not show complete horizontal alignment, It was found that Δnd was also low.

Claims (9)

하기 식 [1a], [1b] 및 [1c]로 표시되는 반복 단위를 함유하는 것을 특징으로 하는 중합체.
Figure 112014073140464-pct00040

[식 중, X 및 Y는 각각 독립적으로 하기 식 [2] 또는 [3]으로 표시되는 기이고,
Figure 112014073140464-pct00041

(식 [3] 중, R1은 수소 원자 또는 메틸기이다. 파선은 결합손이다.)
M1은 하기 식 [4]로 표시되는 기이며, M2는 하기 식 [5]로 표시되는 기이고,
Figure 112014073140464-pct00042

(식 [4] 및 [5] 중, s1, s2, s3 및 s4는 각각 독립적으로 1 또는 2이고, G1 및 G2는 각각 독립적으로 단결합, -COO- 또는 -OCO- 이고, R2 및 R3은 각각 독립적으로 수소 원자, 할로젠 원자, 사이아노기, 탄소수 1∼10의 알킬기 또는 탄소수 1∼10의 알콕시기이다. 파선은 결합손이다.)
A는 탄소수 2∼15의 직쇄상 또는 분지상의 알킬기이고,
m, n 및 p는 각각 0<m<1, 0<n<1, 0≤p≤0.5 또한 m+n+p≤1을 충족시키는 수이며, q 및 r은 각각 독립적으로 2∼9의 정수이다.]A polymer comprising repeating units represented by the following formulas [1a], [1b] and [1c].
Figure 112014073140464-pct00040

[Wherein X and Y are each independently a group represented by the following formula [2] or [3]
Figure 112014073140464-pct00041

(In the formula [3], R 1 is a hydrogen atom or a methyl group.
M 1 is a group represented by the following formula [4], M 2 is a group represented by the following formula [5]
Figure 112014073140464-pct00042

And (equation [4] and [5] of, s1, s2, s3 and s4 are each independently 1 or 2, G 1 and G 2 represents a single bond, -COO- or -OCO-, each independently, R 2 And R 3 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.
A is a straight or branched alkyl group having 2 to 15 carbon atoms,
m, n and p are numbers satisfying 0 <m <1, 0 <n <1, 0? p? 0.5 and m + n + p? 1, q and r are each independently an integer of 2 to 9 to be.] 제 1 항에 있어서, 상기 X 및 Y가 상기 식 [3]으로 표시되는 기인 것을 특징으로 하는 중합체.The polymer according to claim 1, wherein X and Y are groups represented by the above formula [3]. 제 1 항에 있어서, 상기 m, n 및 p가 각각 0.2≤m≤0.9, 0.1≤n≤0.8, 0≤p≤0.4를 충족시키는 수인 것을 특징으로 하는 중합체.2. The polymer according to claim 1, wherein m, n and p satisfy the following inequality: 0.2? M? 0.9, 0.1? N? 0.8, 0? 제 3 항에 있어서, 상기 m, n 및 p가 각각 0.2≤m≤0.8, 0.1≤n≤0.5, 0.1≤p≤0.3을 충족시키는 수인 것을 특징으로 하는 중합체.4. The polymer according to claim 3, wherein m, n and p satisfy the following inequality: 0.2? M? 0.8, 0.1? N? 0.5, 0.1? 제 1 항 내지 제 4 항 중 어느 한 항에 기재된 중합체와 유기 용매를 함유하는 조성물.A composition containing the polymer according to any one of claims 1 to 4 and an organic solvent. 제 5 항에 기재된 조성물을 기판에 도포하고, 이어서 편광을 조사하고, 경화시킴으로써 얻어지는 단층 도포형 수평 배향 필름.A single-layer coating type horizontally oriented film obtained by applying the composition according to claim 5 to a substrate, and then irradiating and curing the polarized light. 제 6 항에 있어서, 상기 편광이 직선 편광 자외선인 것을 특징으로 하는 단층 도포형 수평 배향 필름.The single-layer coating type horizontally oriented film according to claim 6, wherein the polarized light is a linearly polarized ultraviolet ray. 제 6 항에 기재된 단층 도포형 수평 배향 필름을 구비하는 광학 부재.An optical member comprising the single-layer coating type horizontally oriented film according to claim 6. 하기 식 [7]로 표시되는 것을 특징으로 하는 중합성 화합물.
Figure 112019006035211-pct00043

(식 [7] 중, r은 2∼9의 정수이며, s3 및 s4는 각각 독립적으로 1 또는 2이고, G2는 단결합, -COO- 또는 -OCO-이며, R3은 수소 원자, 할로젠 원자, 사이아노기, 탄소수 1∼10의 알킬기 또는 탄소수 1∼10의 알콕시기이다.)A polymerizable compound represented by the following formula [7].
Figure 112019006035211-pct00043

(Wherein r is an integer of 2 to 9, s 3 and s 4 are each independently 1 or 2, G 2 is a single bond, -COO- or -OCO-, R 3 is a hydrogen atom, A cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
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