JP5098223B2 - Polymerizable liquid crystal composition and polymer thereof - Google Patents

Description

The present invention relates to a compound having —C (CF ₃ ) _2- (hexafluoroisopropylidene) or —SO ₂ — (sulfonyl), a polymerizable liquid crystal composition containing the compound, and a polymer obtained from the composition , And its uses.

When the polymerizable compound has liquid crystallinity, it is known that a polymer having optical anisotropy can be obtained by polymerizing the compound (Patent Document 1). This is because the orientation of liquid crystal molecules is fixed by polymerization. An example of such a compound is a liquid crystal compound having —OCOCH═CH ₂ (Patent Document 2). A liquid crystal compound that polymerizes at room temperature by irradiation with ultraviolet rays is also known (Patent Document 3). Such a polymerizable liquid crystal compound is copolymerized with a polymerizable compound having no liquid crystallinity. This non-liquid crystal compound has a role of controlling the properties of the obtained copolymer. Therefore, development of a polymerizable non-liquid crystal compound is important for obtaining a polymer having appropriate optical anisotropy.

JP 2001-55573 A JP 2001-154019 A JP 2005-60373 A

  An object of the present invention is a polymerizable liquid crystal composition that can be applied to a transparent plastic film such as a triacetyl cellulose film or a cycloolefin polymer film, or a supporting substrate such as glass, and the orientation thereof is homogeneous and homeotropic. , Having a hybrid orientation. The subject is a film in which the polymerizable liquid crystal composition is oriented on a substrate and polymerized while maintaining the orientation. This problem has a plurality of characteristics such as optical anisotropy, colorless and transparent, low photoelasticity, difficult to peel off from the support substrate, sufficient hardness, high heat resistance, and high light resistance. It is also a polymer film that satisfies the above characteristics. Moreover, the subject of this invention is the polymeric compound which can stabilize the orientation and can obtain a coating film with few orientation defects by adding to a polymeric liquid crystal composition.

式（１−１）および式（１−２）において；Ｙ^１およびＹ^２は独立して単結合、−（ＣＨ_２）_２−または−ＣＨ＝ＣＨ−であり；Ｗ^１およびＷ^２は独立して水素またはフッ素であり；ｍ^１、ｍ^２、ｎ^１およびｎ^２は独立して２から１５の整数であり、
式（２−１）および式（２−２）において；Ｗ^３は水素またはフッ素であり；Ｗ^４およびＷ^５は独立して水素またはメチルであり；Ｗ^６は水素またはメチルであり；Ｘ^１は−Ｏ−または式（Ｘ^１−２）で表される基であり；ｍ^３、ｍ^４、ｎ^３およびｎ^４は独立して２から１５の整数であり、

式（３−１）において；Ｒ^１はシアノ、トリフルオロメトキシ、炭素数１〜１０のアルキル、または炭素数１〜１０のアルコキシであり；Ｗ^７は水素またはフッ素であり；Ｘ^２は単結合、−ＣＯＯ−、または−ＯＣＯ−であり；ｍ^５は２から１５の整数である。 The present invention provides at least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula as the second component. Containing at least one compound selected from the group of compounds represented by (2-2) and at least one compound selected from the group of compounds represented by formula (3-1) as a third component Polymerizable liquid crystal composition, polymer obtained by polymerizing the composition, use of the polymer, and formulas (7), (8), (9), (10), and (11) Containing polymerizable compounds.

In Formula (1-1) and Formula (1-2); Y ¹ and Y ² are each independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ¹ and W ² are independently Hydrogen or fluorine; m ¹ , m ² , n ¹ and n ² are each independently an integer from 2 to 15;
In formula (2-1) and formula (2-2); W ³ is hydrogen or fluorine; W ⁴ and W ⁵ are independently hydrogen or methyl; W ⁶ is hydrogen or methyl; X ¹ Is a group represented by —O— or formula (X ¹ -2); m ³ , m ⁴ , n ³ and n ⁴ are each independently an integer of 2 to 15;

In Formula (3-1), R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; W ⁷ is hydrogen or fluorine; X ² is a single bond , —COO—, or —OCO—; m ⁵ is an integer from 2 to 15.

  The present invention is a polymerizable liquid crystal composition containing a non-liquid crystalline polymerizable compound. When this composition is applied to a substrate, it exhibits orientation such as homeotropic, homogeneous, and hybrid. The polymer obtained from such a composition has optical anisotropy, is colorless and transparent, has low photoelasticity, is difficult to peel from the support substrate, has sufficient hardness, has high heat resistance, and has light resistance. A plurality of characteristics are satisfied in characteristics such as large. The present invention is a compound that has polymerizability and does not have liquid crystallinity. This compound is easily polymerized at room temperature, easily photopolymerized, easily dissolved in a solvent, colorless, chemically stable, has good compatibility with polymerizable liquid crystal compounds, and has good wettability to a support substrate. A plurality of characteristics are satisfied among the characteristics such as. This compound stabilizes the polymerizable liquid crystal composition to which it is added over a long period of time and further controls the alignment of liquid crystal molecules. This compound has an appropriate balance for multiple properties.

  Terms used in this specification are as follows. A liquid crystal compound is a generic term for a compound having a liquid crystal phase and a compound having no liquid crystal phase but useful as a component of a liquid crystal composition. The liquid crystal phase is a nematic phase, a smectic phase, a cholesteric phase or the like, and often means a nematic phase. Polymerizability means the ability of a monomer to polymerize and give a polymer by means such as light, heat, or catalyst. A compound represented by the formula (1-1) or the like may be represented as a compound (1-1) or the like. The weight% of the polymerizable compound is a ratio based on the total weight of the polymerizable compound contained in the composition. The weight% of the additive is a ratio based on the total weight of the polymerizable compound.

  A polymer obtained from a polymerizable liquid crystal compound has optical anisotropy. This is because the orientation of the liquid crystal molecules is fixed by polymerization. By adding the compound (1-1), the compound (1-2), the compound (5-1) or the compound (5-2) which is a non-liquid crystalline polymerizable compound, to the polymerizable liquid crystal composition, The alignment of the polymerizable liquid crystal composition is stabilized, and there is no alignment defect, a polymerizable liquid crystal coating film is obtained, and when the coating film is polymerized, the polymerization proceeds while the alignment of the liquid crystal molecules is fixed, It has been found that an optically anisotropic film free of alignment defects can be obtained. In addition, the molecular structure of non-liquid crystalline polymerizable compounds has been reviewed, a compound having excellent compatibility with the polymerizable liquid crystal composition and further stabilizing the polymerizable liquid crystal composition to which it is added for a long period of time has been found. The present invention including the terms has been completed.

式（１−１）および式（１−２）において；Ｙ^１およびＹ^２は独立して単結合、−（ＣＨ_２）_２−または−ＣＨ＝ＣＨ−であり；Ｗ^１およびＷ^２は独立して水素またはフッ素であり；ｍ^１、ｍ^２、ｎ^１およびｎ^２は独立して２から１５の整数であり、式（２−１）および式（２−２）において；Ｗ^３は水素またはフッ素であり；Ｗ^４およびＷ^５は独立して水素またはメチルであり；Ｗ^６は水素またはメチルであり；Ｘ^１は−Ｏ−または式（Ｘ^１−２）で表される基であり；ｍ^３、ｍ^４、ｎ^３およびｎ^４は独立して２から１５の整数であり、

式（３−１）において；Ｒ^１はシアノ、トリフルオロメトキシ、炭素数１〜１０のアルキル、または炭素数１〜１０のアルコキシであり；Ｗ^７は水素またはフッ素であり；Ｘ^２は単結合、−ＣＯＯ−、または−ＯＣＯ−であり；ｍ^５は２から１５の整数である。 (1) At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2) as the second component -2) Polymerization containing at least one compound selected from the group of compounds represented by formula (2) and at least one compound selected from the group of compounds represented by formula (3-1) as the third component Liquid crystal composition.

In Formula (1-1) and Formula (1-2); Y ¹ and Y ² are each independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ¹ and W ² are independently And m ¹ , m ² , n ¹ and n ² are each independently an integer of 2 to 15, and in formula (2-1) and formula (2-2); W ³ is hydrogen Or W ⁴ and W ⁵ are independently hydrogen or methyl; W ⁶ is hydrogen or methyl; X ¹ is —O— or a group represented by the formula (X ¹ -2) M ³ , m ⁴ , n ³ and n ⁴ are each independently an integer from 2 to 15;

In Formula (3-1), R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; W ⁷ is hydrogen or fluorine; X ² is a single bond , —COO—, or —OCO—; m ⁵ is an integer from 2 to 15.

(2) The second component is at least one compound selected from the group of compounds represented by formula (2-1), and the content ratio of the first component to the polymerizable liquid crystal composition is 1 to 25% by weight. The content ratio of the second component is in the range of 50 to 98% by weight, the content ratio of the third component is in the range of 1 to 25% by weight, and the formula (1-1) and the formula (1- 2); Y ¹ and Y ² are independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² are independently hydrogen or fluorine; m ¹ , m ² , n ¹ , And n ² is independently an integer from 2 to 10, in formula (2-1); W ³ is hydrogen; W ⁴ is hydrogen; W ⁵ is methyl; and m ³ and n ³ are independently is an integer from 2 to 10, in the formula (3-1); ^{X 2} is a single bond, -COO-, also A -OCO-; ^{W 7} is hydrogen; ^{m 5} is an integer from 2 to 10; ^{R 1} is cyano, alkyl of 2-8 carbon atoms, or alkoxy of 2-8 carbon atoms, said first 2. The polymerizable liquid crystal composition according to item 1.

(3) The content ratio of the first component with respect to the polymerizable liquid crystal composition is in the range of 7 to 22% by weight, the content ratio of the second component is in the range of 56 to 86% by weight, and the content ratio of the third component. Is in the range of 7 to 22% by weight, and in Formula (1-1) and Formula (1-2); Y ¹ and Y ² are each independently a single bond or — (CH ₂ ) ₂ —; W ¹ And W ² is hydrogen; m ¹ , m ² , n ¹ , and n ² are each independently an integer of 4 to 6, and in formula (2-1); W ³ is hydrogen; W ⁴ is W ⁵ is methyl; m ³ and n ³ are independently an integer of 4 to 6, and in formula (3-1); X ² is a single bond; W ⁷ is hydrogen The polymerizable liquid crystal composition according to item 2, wherein m ⁵ is an integer of 4 to 6; and R ¹ is cyano.

式（３−１）において；Ｘ^２は単結合、−ＣＯＯ−、または−ＯＣＯ−であり；Ｗ^７は水素であり；ｍ^５は２から１０の整数であり、Ｒ^１はシアノ、炭素数２〜８のアルキル、または炭素数２〜８のアルコキシである、前記第１項に記載の重合性液晶組成物。 (4) The second component is at least one compound selected from the group of compounds represented by formula (2-2), and the content ratio of the first component to the polymerizable liquid crystal composition is 1 to 25% by weight. The content ratio of the second component is in the range of 50 to 98% by weight, the content ratio of the third component is in the range of 1 to 25% by weight, and the formula (1-1) and the formula (1- 2); Y ¹ and Y ² are independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² are independently hydrogen or fluorine; m ¹ , m ² , n ¹ , And n ² is independently an integer of 2 to 10, in formula (2-2); X ¹ is a group represented by —O— or (X ¹ -2); W ⁶ is hydrogen or methyl M ⁴ and n ⁴ are each independently an integer from 2 to 10;

In Formula (3-1), X ² is a single bond, —COO—, or —OCO—; W ⁷ is hydrogen; m ⁵ is an integer of 2 to 10, R ¹ is cyano, and the number of carbon atoms 2. The polymerizable liquid crystal composition according to item 1, which is alkyl having 2 to 8 or alkoxy having 2 to 8 carbon atoms.

(5) The content ratio of the first component with respect to the polymerizable liquid crystal composition is in the range of 7 to 22% by weight, the content ratio of the second component is in the range of 56 to 86% by weight, and the content ratio of the third component. In the formula (1-1) and formula (1-2); Y ¹ and Y ² are each independently a single bond or — (CH ₂ ) ₂ —; W ¹ And W ² is hydrogen; m ¹ , m ² , n ¹ , and n ² are each independently an integer of 4 to 6, and in formula (2-2); W ⁶ is methyl; X ¹ is —O—; m ⁴ and n ⁴ are each independently an integer of 4 to 6, and in formula (3-1); X ² is a single bond; W ⁷ is hydrogen; m ⁵ is 4 The polymerizable liquid crystal composition according to item 4, wherein R ¹ is cyano.

式（４）中、Ｒ^４はメチルまたはエチルであり、ｎ^８は１〜５の整数である。 (6) A polymerizable liquid crystal composition comprising the polymerizable liquid crystal composition according to any one of items 1 to 5 and a silane coupling agent represented by formula (4), A polymerizable liquid crystal composition, wherein the ratio between the polymerizable liquid crystal composition and the silane coupling agent is in the range of 100: 1 to 100: 10 by weight.

In formula (4), R ⁴ is methyl or ethyl, and n ⁸ is an integer of 1 to 5.

式（５−１）および式（５−２）において；Ｒ^２およびＲ^３は独立してメチルまたはエチルであり；Ｙ^３およびＹ^４は独立して単結合、−（ＣＨ_２）_２−または−ＣＨ＝ＣＨ−であり；Ｗ^８およびＷ^９は独立して水素またはフッ素であり；Ｑ^１およびＱ^２は独立して単結合、−Ｏ−（ＣＨ_２）ｒ^１−または−（ＣＨ_２）ｒ^１−Ｏ−であり、ｒ^１は１から１５の整数であり、式（６−１）および式（６−２）において；Ｗ^１０およびＷ^１１は独立して水素またはメチルであり；ｍ^６、ｍ^７、ｎ^６およびｎ^７は独立して２から１５の整数であり、式（７−１）において；Ｘ^３は単結合、−ＣＯＯ−、または−ＯＣＯ−であり；Ｒ^５はシアノ、炭素数２〜８のアルキルまたは炭素数２〜８のアルコキシであり；ｍ^８は２〜１５の整数である。 (7) At least one compound selected from the group of compounds represented by formula (5-1) and formula (5-2) as the first component, and formula (6-1) and formula (6) as the second component -2) Polymerization containing at least one compound selected from the group of compounds represented by formula (2) and at least one compound selected from the group of compounds represented by formula (7-1) as the third component Liquid crystal composition.

In formula (5-1) and formula (5-2); R ² and R ³ are independently methyl or ethyl; Y ³ and Y ⁴ are independently a single bond, — (CH ₂ ) ₂ — or a -CH = CH-; ^{W 8} and ^{W 9} is hydrogen or fluorine independently; ^{Q 1} and ^{Q 2} are independently a single ^{_{bond, -O- (CH 2) r 1}} - or - (CH ₂ ) R ¹ —O—, wherein r ¹ is an integer from 1 to 15, in formulas (6-1) and (6-2); W ¹⁰ and W ¹¹ are independently hydrogen or methyl; m ⁶ , m ⁷ , n ⁶ and n ⁷ are each independently an integer of 2 to 15, and in formula (7-1); X ³ is a single bond, —COO— or —OCO—; R ⁵ is cyano, alkoxy alkyl or 2 to 8 carbon atoms having 2 to 8 carbon atoms; ^{m 8} is 2 to 1 Of an integer.

(8) The first component is at least one compound selected from the group of compounds represented by formula (5-1), and the second component is selected from the group of compounds represented by formula (6-1) The content ratio of the first component to the polymerizable liquid crystal composition is in the range of 1 to 20% by weight, and the content ratio of the second component is in the range of 60 to 98% by weight. The content ratio of the third component is in the range of 1 to 20% by weight, and in Formula (5-1); R ² is methyl or ethyl; Y ³ is a single bond or — (CH ₂ ) ₂ —; W ⁸ is hydrogen or fluorine; Q ¹ is a single bond, —O— (CH ₂ ) r ¹ — or — (CH ₂ ) r ¹ —O—, and r ¹ is an integer of 1 to 10, In formula (6-1); W ¹⁰ and W ¹¹ are independently hydrogen or methyl; m ⁶ and n ⁶ are independently an integer of 2 to 10, and in formula (7-1); X ³ is a single bond; R ⁵ is cyano; m ⁸ is an integer of 2 to 10; 8. The polymerizable liquid crystal composition according to item 7.

(9) The content ratio of the first component with respect to the polymerizable liquid crystal composition is in the range of 7 to 20% by weight, the content ratio of the second component is in the range of 60 to 86% by weight, and the content ratio of the third component. In the formula (5-1); R ² is ethyl; Y ³ is a single bond; W ⁸ is hydrogen; Q ¹ is a single bond; In (6-1); W ¹⁰ and W ¹¹ are independently hydrogen or methyl; m ⁶ and n ⁶ are independently an integer from 4 to 6, and in formula (7-1); X ³ is The polymerizable liquid crystal composition according to the above item 8, wherein the polymerizable liquid crystal composition is a single bond; R ⁵ is cyano; m ⁸ is an integer of 2 to 4.

(10) A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of items 1 to 9.

(11) A polymer film having optical anisotropy obtained by polymerizing the composition according to any one of items 1 to 9.

(12) Use of the polymer film having optical anisotropy described in item 11 as a retardation plate.

(13) A liquid crystal display device using the polymer film having optical anisotropy according to item 12.

式（１−１）において；Ｙ ^１ は独立して単結合、−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−であり；Ｗ ^１ は独立して水素またはフッ素であり；ｍ ^１ およびｎ ^１ は独立して２から１５の整数である。
（１５）式（７）で表される化合物。

式（７）において；Ｙ^５は−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−であり；ｍ^８、ｎ^８は独立して２から１５の整数である。 (14) A compound represented by formula (1-1).

In formula (1-1); Y ¹ is independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ¹ is independently hydrogen or fluorine; m ¹ and n ¹ Are independently an integer from 2 to 15.
(15) A compound represented by formula (7).

In Formula (7); Y ⁵ is — (CH ₂ ) ₂ — or —CH═CH—; m ⁸ and n ⁸ are each independently an integer of 2 to 15.

式（８）において；Ｗ ^１ は独立して水素またはフッ素であり；ｍ^９、ｎ^９は独立して２から１５の整数である。 (16) A compound represented by formula (8).

In Formula (8); W ¹ is independently hydrogen or fluorine ; m ⁹ and n ⁹ are each independently an integer of 2 to 15.

式（９）において；Ｙ^６は単結合、−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−であり；Ｗ ^２ は独立して水素またはフッ素であり；ｍ^１０、ｎ^１０は独立して２から１５の整数であり；Ｗ ^２ が水素のときＹ ^６ は独立して−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−である。 (17) A compound represented by formula (9).

In formula (9); Y ⁶ is a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ² is independently hydrogen or fluorine ; m ¹⁰ and n ¹⁰ are independently 2 from Ri integer der of 15; when ^{W 2} is hydrogen ^{Y 6} are independently - _{(CH 2) 2} - or -CH = CH-.

式（１０）において；Ｒ^７は水素、メチルまたはエチルであり；Ａ^４は１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、ナフタレン−２，６−ジイルまたはピリジン−２，５−ジイルであり；Ｙ^７は単結合、−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−であり；Ｑ^３は単結合、−Ｏ−（ＣＨ_２）ｒ^２−または−（ＣＨ_２）ｒ^２−Ｏ−であり、ｒ^２は１から１５の整数である。 (18) A compound represented by formula (10).

In formula (10); R ⁷ is hydrogen, methyl or ethyl; A ⁴ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, naphthalene-2, It is 6-diyl or pyridine-2,5-diyl; ^{Y 7} is a single bond, - _{(CH 2) 2} - or -CH = CH- and is; ^{Q 3} is a single bond, -O- _(CH 2) r ² - or _- (CH ²⁾ r 2 -O-, ^{r 2} is an integer from 1 to 15.

(19) In (10); ^{R 7} is methyl or ethyl; ^{A 4} is located at the 1,4-phenylene; ^{Y 7} represents a single bond; ^{Q 3} is a single bond, to the paragraph 18 The described compound.

式（１１）において；Ｒ^８は水素、メチルまたはエチルであり；Ａ^５は１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、ナフタレン−２，６−ジイルまたはピリジン−２，５−ジイルであり；Ｙ^８は単結合、−（ＣＨ _２ ） _２ −または−ＣＨ＝ＣＨ−であり；Ｑ^４は単結合、−Ｏ−（ＣＨ_２）ｒ^３−または−（ＣＨ_２）ｒ^３−Ｏ−であり；ｒ^３は１から１５の整数である。 (20) A compound represented by formula (11).

In formula (11); R ⁸ is hydrogen, methyl or ethyl; A ⁵ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, naphthalene-2, 6-diyl or pyridine-2,5-diyl; Y ⁸ is a single bond, — (CH ₂ ) ₂ — or —CH═CH—; Q ⁴ is a single bond, —O— (CH ₂ ) r ³ - or _- (CH ²⁾ r 3 -O- and is; ^{r 3} is an integer from 1 to 15.

(21) In the formula (11); ^{R 8} is ethyl; ^{A 5} is located at the 1,4-phenylene; ^{Y 8} represents a single bond; ^{Q 4} is a single bond, according to the paragraph 20 Compound.

(22) In the formula (11); R ⁸ is methyl or ethyl; A ⁵ is 1,4-phenylene; Y ⁸ is a single bond; and Q ⁴ is —O— (CH ₂ ) r ³ —. or _- (CH ²⁾ r 3 -O- and is; ^{r 3} is an integer from 1 to 10, compounds described in the paragraph 20.

The polymerizable composition of the present invention can be classified into five composition groups according to the kind of the group of compounds constituting the polymerizable composition.
The first composition group (hereinafter sometimes referred to as “MIX1”) is at least one selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component. One compound, at least one compound selected from the group of compounds represented by formula (2-1) and formula (2-2) as the second component, and represented by formula (3-1) as the third component A polymerizable liquid crystal composition containing at least one compound selected from the group of compounds.

<MIX1>

  The second composition group (hereinafter sometimes referred to as “MIX2”) is at least one selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component. At least one compound selected from the group of compounds represented by formula (2-1) as the second component, and from the group of compounds represented by formula (3-1) as the third component A polymerizable liquid crystal composition containing at least one compound.

<MIX2>

  The third composition group (hereinafter sometimes referred to as “MIX3”) is at least one selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component. At least one compound selected from the group of compounds represented by formula (2-2) as the second component, and from the group of compounds represented by formula (3-1) as the third component A polymerizable liquid crystal composition containing at least one compound.

<MIX3>

  The fourth composition group (hereinafter sometimes referred to as “MIX4”) is at least one selected from the group of compounds represented by formula (5-1) and formula (5-2) as the first component. One compound, at least one compound selected from the group of compounds represented by formula (6-1) and formula (6-2) as the second component, and represented by formula (7-1) as the third component A polymerizable liquid crystal composition containing at least one compound selected from the group of compounds.

<MIX4>

  The fifth composition group (hereinafter sometimes referred to as “MIX5”) includes, as the first component, at least one compound selected from the group of compounds represented by formula (5-1), and the second component Containing at least one compound selected from the group of compounds represented by formula (6-1) and at least one compound selected from the group of compounds represented by formula (7-1) as the third component It is a polymerizable liquid crystal composition.

<MIX5>

First, a polymerizable liquid crystal composition composed of a compound having an acryloyloxy group will be described. MIX1, MIX2, and MIX3 exhibit liquid crystallinity and are polymerizable. These polymerizable liquid crystal compositions include polymerization catalysts, sensitizers, fine particles, solvents, polymerization inhibitors, ultraviolet absorbers, antioxidants, surfactants, silane coupling agents, non-liquid crystalline polyfunctional monomers, etc. An additive may be further contained.

The first component used in MIX1, MIX2, and MIX3 is a non-liquid crystalline polymerizable compound. The first component is a compound represented by formula (1-1) or formula (1-2). This compound has _{-Ph-C (CF 3) 2} -Ph- or _-Ph-SO 2 -Ph- skeleton. Ph is 1,4-phenylene. Both skeletons have strong electron withdrawing groups. Therefore, since it has a large dipole moment, it was predicted that the alignment of liquid crystal molecules could be controlled. Moreover, since these compounds have a bent molecular structure, it was estimated that the ability to control the orientation was increased. _{-Ph-C (CF} 3) compounds having 2 -Ph- is as good compatibility with other polymerizable compounds in comparison with the compound having _-Ph-SO 2 -Ph-. Compound having _-Ph-SO 2 -Ph- is inexpensive to synthesize compared to _{-Ph-C (CF} 3) compounds having 2 -Ph-. As a compound having a bent structure, compounds having no polymerizable group are disclosed in Molecules 2000, 5, p383 and Chem. Mater. 2003, 15, P3443. A compound having a polymerizable group is also disclosed in EP703287. However, it is not a compound synthesized for the purpose of controlling the orientation by adding to the polymerizable liquid crystal composition.

In the compound (1-1) and compound (1-2) having an acryloyloxy group at both ends, Y ¹ and Y ² are independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—. , W ¹ and W ² are independently hydrogen or fluorine, and m ¹ , m ² , n ¹ and n ² are independently integers from 2 to 15. Of these, preferred compounds are illustrated.

Next, a method for synthesizing the compound will be described. Compounds used in the present invention include Houben Wyle, Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart, Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Syntheses, John Can be synthesized by appropriately combining synthesis methods in organic chemistry such as those described in Wily & Sons, Inc., Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen) .

The compound (1-1) or compound (1-2) of the present invention is synthesized as follows. The carboxylic acid derivative [b-1] having —OCOCH═CH ₂ is synthesized according to the method described in Polymer Journal, Vol. 35, No. 2, pp 160-166 (2003). A method for producing a diester is disclosed in Japanese Unexamined Patent Publication No. 2003-277359 (paragraphs 0040 to 0053). An example of a compound synthesis scheme will be described.

スキーム１．化合物（１−１）の合成

Scheme 1. Synthesis of compound (1-1)

  The synthesis of compound (1-1) is shown in Scheme 1. Compound (1-1) is synthesized by esterification of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane [a] and 2 equivalents of acid derivative [b-1]. To synthesize the compound (1-2), the following 2,2-bis (4-hydroxyphenyl) sulfone [S] was used instead of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane [a]. The same esterification reaction is carried out.

The second component is a compound having two acryloyloxy groups and showing a liquid crystal phase. The second component is formula (2-1) or formula (2-2). This compound exhibits a liquid crystal phase over a wide temperature range. By adjusting the amount of this compound, the temperature of the NI point (nematic phase-isotropic phase transition point) of the polymerizable liquid crystal composition of the present invention is adjusted.

In the compound (2-1) and the compound (2-2) having an acryloyloxy group at both ends, W ³ is hydrogen or fluorine, W ⁴ and W ⁵ are independently hydrogen or methyl, and W ⁶ is Hydrogen or methyl, X ¹ is —O— or a group represented by the formula (X ¹ -2), and m ³ , m ⁴ , n ³ and n ⁴ are each independently an integer of 2 to 15 .

First, preferred compounds (2-1-1) to (2-1-8) among the compounds (2-1) are illustrated.

These compounds are synthesized by the method described in JP-A-2003-238491.

Of the compounds (2-2), preferred compounds (2-2-1) to (2-2-10) are illustrated.

Compound (2-2-1) and compound (2-2-7) are synthesized according to the method described in Makromol. Chem., 190, 3201-3215 (1998). Compound (2-2-9) and compound (2-2-10) are synthesized by the method described in WO97 / 00600.

The third component is a compound having one acryloyloxy group. This group of compounds may or may not show a liquid crystal phase. This third component is represented by formula (3-1). The melting point of this compound is 100 ° C. or lower. This compound is used for the purpose of adjusting the melting point of the polymerizable liquid crystal composition of the present invention.

In the compound (3-1) having one acryloyloxy group, R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons, and W ⁷ is hydrogen or fluorine. X ² is a single bond, —COO—, or —OCO—, and m ⁵ is an integer of 2 to 15. Of these, preferred compounds (3-1-1) to (3-1-7) are illustrated.

Compound (3-1-1) to Compound (3-1-3) are synthesized according to the method described in Macromolecules, 26, 6132-6134 (1993). Compound (3-1-4) to Compound (3-1-7) are synthesized by the method described in Makromol. Chem. 183, 2311-2321 (1982).

  In MIX1, MIX2, and MIX3, the content ratios of the first component, the second component, and the third component are not particularly limited, but in the present invention, the content ratio of the first component is 1 to 25 weights. %, The content ratio of the second component is preferably in the range of 50 to 98% by weight, and the content ratio of the third component is preferably in the range of 1 to 25% by weight. Particularly preferably, the content of the first component is in the range of 7 to 22% by weight, the content of the second component is in the range of 56 to 86% by weight, and the content of the third component is in the range of 7 to 22% by weight. .

Of MIX1, MIX2, and MIX3 introduced above, MIX2 and MIX3 tend to exhibit homogeneous orientation. Furthermore, when a silane coupling agent is added to MIX2 or MIX3, each orientation can be changed to a homeotropic orientation.

The addition ratio of the silane coupling agent is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition. That is, the range of polymerizable liquid crystal compound: silane coupling agent = 100: 1 to 100: 10 (weight ratio) is preferable.

式（４）中、Ｒ^４はメチルまたはエチルであり、ｎ^８は１〜５の整数である。 Although the silane coupling agent used for this invention is not specifically limited, The silane coupling agent represented by following formula (4) is preferable.

In formula (4), R ⁴ is methyl or ethyl, and n ⁸ is an integer of 1 to 5.

Table 1 shows preferred compositions for the polymerizable liquid crystal composition of the present invention.
Table 1
Composition First component ratio Second component ratio Third component ratio
MIX2 (1-1) or (1-2) 1-25wt% (2-1) 50-98wt% (3-1) 1-25wt%
MIX3 (1-2) or (1-2) 1-25wt% (2-2) 50-98wt% (3-1) 1-25wt%
Note) MIX2 and MIX3 were polymerized at room temperature by irradiating ultraviolet rays or the like in a nitrogen atmosphere in the presence of a photoradical polymerization catalyst.

1) MIX2 or MIX3 with homogeneous orientation
MIX2 or MIX3 was applied to a transparent support substrate that was rubbed. The support substrate is a saponified triacetyl cellulose film or a hydrophilized norbornene resin film. Hydrophilization was performed by corona treatment or plasma treatment. The orientation of the liquid crystal molecules in this composition was homogeneous. A polymer was easily obtained by adding 1 to 15% by weight of a photo-radical polymerization catalyst to the composition based on the total weight of the polymerizable compound and then irradiating it with ultraviolet rays in a nitrogen atmosphere. This polymer maintained the orientation in the composition.

2) Homeotropically aligned polymerizable liquid crystal composition A mixture of aminopropyltriethoxysilane was added to MIX2 or MIX3 so as to have a ratio of 1 to 10 parts by weight of aminopropyltriethoxysilane to 100 parts by weight of the polymerizable compound. The obtained composition was applied to the above support substrate that was not rubbed. The orientation in this composition was homeotropic. This orientation was maintained after polymerization as in section 1). The orientation was also homeotropic when applied to a glass substrate that had not been oriented.

  Next, MIX4 and MIX5 will be described. MIX4 is composed of a compound having an oxetanyl group or an oxiranyl group as a polymerizable functional group. This composition exhibits liquid crystallinity and has polymerizability. This polymerizable liquid crystal composition further contains additives such as a polymerization catalyst, a sensitizer, fine particles, a solvent, a polymerization inhibitor, an ultraviolet absorber, a surfactant, a silane coupling agent, and a non-liquid crystalline polyfunctional monomer. May be.

The first component used in MIX4 and MIX5 is a non-liquid crystalline polymerizable compound. The first component is a compound represented by formula (5-1) or formula (5-2). This compound has _{-Ph-C (CF 3) 2} -Ph- or _-Ph-SO 2 -Ph- skeleton. Ph is 1,4-phenylene. These compounds have the ability to control and stabilize the orientation.

In the compounds (5-1) and (5-2), R ² and R ³ are independently methyl or ethyl, Y ³ and Y ⁴ are independently a single bond, — (CH ₂ ) ₂ — or — CH═CH—, W ⁸ and W ⁹ are independently hydrogen or fluorine, Q ¹ and Q ² are independently a single bond, —O— (CH ₂ ) r ¹ — or — (CH ₂ ). r ¹ —O—, and r ¹ is an integer of 1 to 15. Of these, preferred compounds are illustrated.

Compound (5-1) and compound (5-2) are synthesized as follows. For the synthesis of the carboxylic acid derivative [b-2] having an oxetane ring, 3-alkyl-3-oxetanemethanol can be used as a starting material. 3-ethyl-3-oxetanemethanol and 3-methyl-3-oxetanemethanol are commercially available. By reacting these compounds with α, ω-dibromomethylene such as 1,2-dibromoethane, 1,4-dibromobutane, 1,6-dibromohexane, 1,8-dibromooctane according to literature methods. , Can extend the carbon chain length. The literature is Macromolecules, 24 , 4531-4537 (1991).

  Compound (5-1) can be synthesized by esterification of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane [a] with 2 equivalents of benzoic acid derivative [b-2]. -1) is synthesized. To synthesize the compound (5-2), the following 2,2-bis (4-hydroxyphenyl) sulfone [S] was used instead of 2,2-bis (4-hydroxyphenyl) -hexafluoropropane [a]. The reaction is carried out in the same manner.

The second component is a polymerizable compound group having two oxiranyl groups and having a liquid crystal phase, and is represented by Formula (6-1) or Formula (6-2). This compound exhibits a liquid crystal phase over a wide temperature range. By adjusting the amount of this compound, the temperature of the NI point (nematic phase-isotropic phase transition point) of the polymerizable liquid crystal composition of the present invention is adjusted.

In the compounds (6-1) and (6-2), W ¹⁰ and W ¹¹ are independently hydrogen or methyl, and m ⁶ , m ⁷ , n ⁶ and n ⁷ are independently an integer of 2 to 15 is there. Of these, preferred compounds (6-1-1) to (6-2-4) are illustrated.

Compound (6-1-1) to Compound (6-1-6) are synthesized according to the method described in JP-A-2005-60373. Compound (6-2-1) to Compound (6-2-4) are synthesized according to the method described in Macromolecules, 26, 1244-1247 (1993).

The third component is a polymerizable compound having an oxiranyl group. This group of compounds may or may not show a liquid crystal phase. This third component is represented by formula (7-1). This compound has a low melting point of 100 ° C. or lower. This compound is used for the purpose of adjusting the melting point of the polymerizable liquid crystal composition of the present invention.

In the compound (7-1), X ³ is a single bond, —COO—, or —OCO—, R ⁵ is cyano, C 2-8 alkyl or alkoxy, and m ⁸ is an integer of 2-15. It is. Of these, preferred compounds (7-1-1) to (7-1-4) are illustrated.

  Compound (7-1-1) to Compound (7-1-4) are synthesized according to the method described in Macromol Chem. Phys, 196, 2941-2954 (1995).

  In MIX4 and MIX5, the content ratios of the first component, the second component, and the third component are not particularly limited, but in the present invention, the content ratio of the first component is in the range of 1 to 20% by weight. The content ratio of the second component is preferably in the range of 60 to 98% by weight, and the content ratio of the third component is preferably in the range of 1 to 20% by weight. Particularly preferably, the content of the first component is in the range of 7 to 20% by weight, the content of the second component is in the range of 60 to 86% by weight, and the content of the third component is in the range of 7 to 20% by weight. .

Of the MIX4 and MIX5 introduced above, the preferred composition is MIX5. A particularly preferred composition of MIX5 is that the proportion of the first component is in the range of 1 to 20 wt%, the proportion of the second component is in the range of 60 to 98 wt%, and the proportion of the third component is 1 to The composition is in the range of 20% by weight.

1) MIX5 with homogeneous orientation
MIX5 was applied to the above-mentioned rubbing-treated support substrate. The orientation in this composition was homogeneous. A polymer was easily obtained by adding 1-15% by weight of a cationic photopolymerization catalyst based on the total weight of the polymerizable compound to the composition and then irradiating it with ultraviolet light. Polymerization proceeded in air. This polymer maintained the orientation in the composition.

The polymerizable liquid crystal composition of the present invention may further contain additives as necessary. Other polymerizable compounds are suitable for further adjusting the properties of the composition or polymer. Examples of the additive include a silane coupling agent, a surfactant, an antioxidant, an ultraviolet absorber, fine particles, a solvent, a non-liquid crystalline polyfunctional monomer, and the like. These additives are used to adjust the properties of the composition or polymer. Examples of additives necessary for the polymerization include a polymerization initiator and a sensitizer. Organic solvents are preferred for diluting the composition. Examples of other polymerizable compounds and additives are shown below.

  Examples of the silane coupling agent include vinyl trialkoxysilane, 3-aminopropyltrialkoxysilane, N- (2-aminoethyl) 3-aminopropyltrialkoxysilane, 3-glycidoxypropyltrialkoxysilane, 3- Chlorotrialkoxysilane, 3-methacryloxypropyltrialkoxysilane and the like. Another example is dialkoxymethylsilane in which one of the alkoxy groups (three) is replaced by methyl in these compounds. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

  Examples of surfactants include quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, lauryl sulfate amines, alkyl-substituted fragrances. Group sulfonates, alkyl phosphates, perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl trimethyl ammonium salts, and the like. The surfactant has effects such as facilitating application of the composition to a support substrate or the like. A desirable ratio of the surfactant varies depending on the kind of the surfactant, the composition ratio of the composition, and the like, but is in a range of 100 ppm to 5 wt% based on the total weight of the polymerizable compound. A more desirable ratio is in the range of 0.1 to 1% by weight.

  Examples of antioxidants are hydroquinone, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butylphenol, triphenyl phosphite, trialkyl phosphite and the like. Preferred commercial products are Irganox 245 and Irganox 1035 manufactured by Ciba Specialty Chemicals.

  Examples of the ultraviolet absorber include TINUVIN PS, TINUVIN 292, TINUVIN 109, TINUVIN 328, TINUVIN 384-2, TINUVIN 123, TINUVIN 400, and TINUVIN 400L manufactured by Ciba Specialty Chemicals.

  Examples of the material of the fine particles are inorganic materials, organic materials, metals, and the like. The preferred particle size of the fine particles is in the range of 0.001 to 0.1 μm. A more preferable particle size is in the range of 0.001 to 0.05 μm. Depending on the material, a small particle size is preferred to prevent agglomeration. Sharper particle size distribution is preferred. Such fine particles are useful for adjusting the optical anisotropy and increasing the strength of the polymer. A desirable ratio is in the range of 0.1 to 30% by weight based on the total weight of the polymerizable compound. A small proportion is preferable as long as the purpose of addition is achieved.

Examples of inorganic materials are ceramics, fluorine phlogopite, tetrasilica mica, teniolite, fluorine vermiculite, fluorine hectorite, hectorite, saponite, stevensite, montmorillonite, beidellite, kaolinite, frypontite, ZnO, TiO ₂ , CeO _2. , Al ₂ O ₃ , Fe ₂ O ₃ , ZrO ₂ , MgF ₂ , SiO ₂ , SrCO ₃ , Ba (OH) ₂ , Ca (OH) ₂ , Ga (OH) ₃ , Al (OH) ₃ , Mg (OH ) ₂ , Zr (OH) ₄ and the like. Fine particles such as calcium carbonate needle crystals have optical anisotropy. Such fine particles can adjust the optical anisotropy of the polymer. Examples of the organic substance are carbon nanotube, fullerene, dendrimer, polyvinyl alcohol, polymethacrylate, polyimide and the like.

  The radical photopolymerization initiator may be a general-purpose product. Examples of the initiator include DAROCUR 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and IRGACURE 184 (1-hydroxycyclohexyl phenyl ketone) from products of Ciba Specialty Chemicals Co., Ltd. ), IRGACURE651 (2,2-dimethoxy-1,2-diphenylethane-1-one), IRGACURE500, IRGACURE2959, IRGACURE907, IRGACURE369, IRGACURE1300, IRGACURE819, IRGACURE1700, IRGACURE1850, IRGACURE1850, IRGACURE1850, IRGACURE1850,

Other examples of photo radical polymerization initiators include p-methoxyphenyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole 9-phenylacridine, 9,10-benzphenazine, benzophenone / Michler's ketone mixture, hexaarylbiimidazole / mercaptobenzimidazole mixture, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate, benzophenone / methyltriethanolamine Such as a mixture. Such photoradical polymerization initiators are suitable for MIX1, MIX2 and MIX3. This is because the main component of this composition is a compound having —OCOCH═CH ₂ .

  Examples of the cationic photopolymerization initiator include diaryliodonium salts and triarylsulfonium salts. Such initiators are suitable for MIX4 or MIX5. This is because the main component of this composition is a compound having an oxetane ring or an oxirane ring.

  An example of a trade name of the photocationic polymerization initiator is DTS-102 from Midori Chemical Co., Ltd. Examples of this include Dow Chemical's Syracure UVI-6990, Syracure UVI-6974, Syracure UVI-6922, and the like. Examples of this include Adeka optomer SP-150, SP-152, SP-170, SP-172, etc. of Asahi Denka Co., Ltd. Examples include Rhodia's PHOTOINITIATOR 2074, Ciba Specialty Chemicals 'IRGACURE 250, GE Silicones' UV-9380C, and the like. Such a cationic photopolymerization initiator is suitable for MIX4 and MIX5. This is because the main component of this composition is a compound having oxetanyl or oxiranyl.

Examples of the sensitizer include thioxanthone or Kawasaki Kasei Corporation's Anthracure UVS-1331.

  Examples of solvents are benzene, toluene, xylene, mesitylene, butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone. , Ethyl acetate, ethyl lactate, methyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyrolactone, 2-pyrrolidone, N-methyl-2-pyrrolidone, dimethylformamide, chloroform, Dichloromethane, carbon tetrachloride, dichloroethane, tetrachlorethylene, Roechiren, chlorobenzene, t- butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethyl cellosolve, and the like butyl cellosolve. The solvent may be a single compound or a mixture. A solvent is used when apply | coating the polymeric liquid crystal composition of this invention to a support substrate.

Examples of non-liquid crystalline polyfunctional monomers are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, Dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, Bisphenol A EO addition diacrylate, bisphenol A glycidyl diacrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: Biscote 70) ), And polyethylene glycol diacrylate. These compounds can be added to MIX1, MIX2, or MIX3 to adjust the viscosity or to increase the hardness of the polymer.

  Next, the polymerization conditions of the composition of the present invention will be described. A polymer is obtained by polymerizing the polymerizable liquid crystal composition of the present invention. In order to obtain a polymer having an excellent orientation, polymerization using a photopolymerization catalyst is preferable to thermal polymerization. This is because it is easy to perform polymerization under the condition that the composition is liquid crystal.

The preferred type of light used for photopolymerization depends on the absorption wavelength of the photopolymerization initiator used. Usually, ultraviolet rays, visible rays, infrared rays and the like are used. Electromagnetic waves such as electron beams and X-rays may be used. A preferable wavelength range is 150 to 500 nm. A more preferable range is 250 to 450 nm, and a most preferable range is 300 to 400 nm. The light source is a low-pressure mercury lamp (sterilization lamp, fluorescent chemical lamp, black light), high-pressure discharge lamp (high-pressure mercury lamp, metal halide lamp), short arc discharge lamp (ultra-high pressure mercury lamp, xenon lamp, mercury xenon lamp), etc. . A preferred light source is an ultra high pressure mercury lamp. You may irradiate the composition with the light from a light source as it is. The composition may be irradiated with a specific wavelength (or a specific wavelength region) selected by a filter. A preferable irradiation energy density is in the range of ^{2 to} 5000 mJ / cm ² . A more preferable range is 10 to 3000 mJ / cm ² . A particularly preferable range is 100 to 2000 mJ / cm ² . The preferred illuminance is in the range of 0.1 to 5000 mW / cm ² . Further preferable illuminance is in the range of 1 to 2000 mW / cm ² . The temperature at which light is irradiated is set so that the composition has a liquid crystal phase. A preferable irradiation temperature is 100 ° C. or less. Since polymerization by heat can occur at a temperature of 100 ° C. or higher, there are cases where good orientation cannot be obtained.

  The shape of the polymer is a film, plate, grain, powder or the like. The polymer may be molded. To obtain a film polymer, a support substrate is generally used. A film is obtained by applying the composition on a support substrate and polymerizing a paint film having a liquid crystal phase. The preferred polymer thickness depends on the value of the optical anisotropy of the polymer and the application. Therefore, the range cannot be determined strictly, but the preferred thickness is in the range of 0.05 to 50 μm. A more preferable thickness is in the range of 0.1 to 20 μm. A particularly preferred thickness is in the range of 0.5 to 10 μm. The haze value (haze value) of these polymers is generally 1.5% or less. The transmittance of these polymers is generally 80% or more in the visible light region. Such a polymer is suitable as an optically anisotropic thin film used for a liquid crystal display element.

  Examples of the support substrate include triacetyl cellulose (sometimes referred to as TAC), polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, and the like. Examples of product names include “Arton” from JSR Corporation, “Zeonex” and “Zeonoa” from Nippon Zeon Corporation, “Apel” from Mitsui Chemicals, Inc., and the like. The support substrate is a uniaxially stretched film, a biaxially stretched film, or the like. A preferred support substrate is a triacetyl cellulose film. You may use this film as it is, without pre-processing. This film may be subjected to surface treatment such as saponification treatment, corona discharge treatment, or UV-ozone treatment as necessary. Other examples include a support substrate made of metal such as aluminum, iron and copper, and a support substrate made of glass such as alkali glass, borosilicate glass and flint glass.

  The coating film on the support substrate is prepared by applying the composition as it is. The coating film can also be prepared by dissolving the composition in a suitable solvent and applying it, and then removing the solvent. Examples of the coating method include spin coating, roll coating, curtain coating, flow coating, printing, micro gravure coating, gravure coating, wire barcode, dip coating, spray coating, meniscus coating, and cast film formation.

  In the polymerizable liquid crystal composition of the present invention, the factors that determine the alignment of the liquid crystal molecules are 1) the type and compounding ratio of the compound contained in the composition, 2) the type of the supporting substrate, 3) the method of alignment treatment, etc. However, the substrate alignment method is particularly important. A preferred orientation treatment method is a method such as oblique vapor deposition of silicon oxide or etching into a slit shape. A particularly preferred orientation treatment method is rubbing in one direction with a rayon cloth or the like. In the rubbing process, the support substrate may be directly rubbed. The support substrate may be coated with a thin film such as polyimide or polyvinyl alcohol, and the thin film may be rubbed. Special thin films that give good orientation without rubbing are also known. Alternatively, the support substrate may be coated with a side chain type liquid crystal polymer.

  The alignment of the liquid crystal molecules includes homogenous (parallel), homeotropic (vertical), and hybrid. Homogeneous means a state in which the orientation vector is parallel to the substrate and in one direction. Homeotropic means a state in which the orientation vector is perpendicular to the substrate. Hybrid refers to a state in which the orientation vector rises from parallel to vertical as the distance from the substrate increases. These orientations are observed in a composition having a nematic phase or the like.

  Next, the polymer of the present invention will be described. This polymer is obtained by polymerizing the polymerizable liquid crystal composition of the present invention. This polymer is colorless and transparent, has low photoelasticity, is difficult to peel off from the support substrate, has sufficient hardness, has high heat resistance, and has high weather resistance. Satisfy. This polymer is also excellent in properties such as impact resistance, processability, electrical properties, and solvent resistance. Important characteristics for preparing the polymer film are characteristics such as difficulty in peeling from the support substrate, sufficient hardness, and high heat resistance.

  The uses of the polymer are as follows. This polymer can be used as a molded product having optical anisotropy. Examples of the use of this polymer are optical films such as retardation plates (1/2 wavelength plates, 1/4 wavelength plates, etc.), antireflection films, selective reflection films, and viewing angle compensation films. Polymers having orientation such as homogeneous, hybrid, and homeotropic can be used for retardation plates, polarizing elements, liquid crystal alignment films, antireflection films, selective reflection films, viewing angle compensation films, and the like. Such a polymer is used for the purpose of optical compensation in a phase difference plate of a liquid crystal display element, a viewing angle compensation film, and the like. An example of an important industrial application is viewing angle compensation in liquid crystal display elements such as VA mode, IPS mode, TN mode, and MVA mode. This polymer can also be used for highly heat-conductive epoxy resins, adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorations, non-linear optical materials, information storage materials, and the like.

  A phase difference plate, which is an example of a use of a polymer, has a function of converting a polarization state. The half-wave function plate has a function of rotating the vibration direction of linearly polarized light by 90 degrees. The composition is applied onto the support substrate so as to satisfy the formula d = λ / 2 × Δn. Here, d is the thickness of the composition, λ is the wavelength, and Δn is the optical anisotropy. After the composition is oriented, it is photopolymerized to obtain a half-wavelength functional plate. On the other hand, the 1/4 wavelength functional plate has a function of converting linearly polarized light into circularly polarized light or converting circularly polarized light into linearly polarized light. In this case, a coating film of the composition may be prepared so as to satisfy the condition of d = λ / 4 × Δn. The thickness (d) of the polymer is adjusted as follows. In the method of applying the composition on a support substrate after diluting the composition with a solvent, a coating film having a desired thickness can be obtained by appropriately selecting the concentration of the composition, the application method, the application conditions, and the like. Can do. A method using a liquid crystal cell is also preferable. The liquid crystal cell is convenient because it has an alignment film such as polyimide. When injecting the composition into the liquid crystal cell, the thickness of the coating film can be adjusted by the interval of the liquid crystal cell.

  This compound is polymerized at room temperature, photopolymerized in the presence of a suitable initiator, chemically stable, colorless, easily soluble in solvents, compatible with other polymerizable compounds, support It has characteristics such as low adhesion tension to the substrate. Since this compound tends to get wet with respect to a support substrate, it is easy to obtain a uniform coating film. This compound is easily polymerized with a small amount of accumulated ultraviolet light in the presence of a photopolymerization initiator. Since this compound is chemically stable, it has excellent storage stability in a cool and dark place.

  Since the compound (1-1), the compound (1-2), the compound (5-1), and the compound (5-2) have good compatibility with other compounds, it is easy to prepare a composition. The properties of this compound are reflected in the properties of the composition containing this compound. The properties of this composition are reflected in the properties of the resulting polymer. Compound (1-1), compound (1-2), compound (5-1) and compound (5-2) are mixed with various polymerizable liquid crystal compounds to give a uniform composition. At this time, this compound can stabilize the alignment of the liquid crystal molecules. Therefore, a uniform coating film having no alignment defect can be obtained. This orientation is maintained by polymerization. Therefore, it is possible to obtain a polymer film in which the alignment of liquid crystal molecules is controlled and there is no alignment defect. When the composition is a thin film, a polymer film having optical anisotropy can be obtained. A polymer film having an orientation such as homogeneous, homeotropic, or hybrid can be used as an optical compensation film.

The compound (7), compound (8), compound (9), compound (10), and compound (11) of the present invention will be described. These compounds have a _{-Ph-C (CF 3) 2} -Ph- or _-Ph-SO 2 -Ph- skeleton. Ph is 1,4-phenylene. Both skeletons are bent and not straight. This feature is greatly different from polymerizable liquid crystal compounds generally having a linear molecular structure. In addition, since the compound (7), the compound (8), and the compound (9) have a melting point lower than that of the compound (1-1-3) or the compound (1-2-3), they are difficult to recrystallize, and further, polymerization Excellent compatibility with luminescent liquid crystal composition.

  A compound having a symmetric structure is preferable in that it is cheaper and easier to synthesize than a compound having an asymmetric structure.

  The compound of the present invention has two polymerizable groups. This compound gives a hard polymer. This is because this compound gives a three-dimensional structure by polymerization. This compound is preferable in terms of imparting high hardness to the polymer.

  This compound is polymerized at room temperature, photopolymerized in the presence of a suitable initiator, chemically stable, colorless, easily soluble in solvents, and compatible with other polymerizable compounds. Since the compound is chemically stable, it has excellent storage stability in a cool and dark place.

  Since this compound has good compatibility with other compounds, it is easy to prepare a composition. The properties of this compound are reflected in the properties of the composition containing this compound. The properties of this composition are reflected in the properties of the resulting polymer. This compound is mixed with various polymerizable liquid crystal compounds to give a uniform composition. At this time, this compound can control the alignment of the liquid crystal molecules. This compound is useful as an alignment control agent. This orientation is maintained by polymerization. Therefore, by copolymerizing this compound with a polymerizable liquid crystal compound, it is possible to obtain a polymer in which the alignment of liquid crystal molecules is controlled. When the composition is a thin film, a polymer film having optical anisotropy can be obtained. This compound is particularly useful in that it has an effect of controlling the alignment of liquid crystal molecules. A polymer film having an orientation such as homogeneous, hybrid, or homeotropic has an action such as optical compensation.

  After describing the measurement methods of physical properties, the present invention will be described in detail by examples. The example is an example of the present invention. The present invention is not limited by the following examples. The proportion of the compound in the composition is wt% (wt%).

The structure of the synthesized compound was confirmed by measurement of 500 MHz proton NMR (Bruker: DRX-500). The described numerical value represents ppm, s represents a singlet, d represents a doublet, t represents a triplet, and m represents a multiplet.

  Phase transition temperature: A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope, and the temperature was increased at a rate of 1 ° C / min. The temperature at which the liquid crystal phase transitions to another liquid crystal phase was measured. C is a crystal, N is a nematic phase, and I is an isotropic liquid. The NI point is the upper limit temperature of the nematic phase or the transition temperature from the nematic phase to the isotropic liquid. “C50N63I” indicates that the crystal transitioned to the nematic phase at 50 ° C., and the transition from the nematic phase to the isotropic liquid at 63 ° C.

  Sellotape (registered trademark) peel test: The measurement was performed according to the test method of JIS standard “JIS-K-5400, 8.5, Adhesion (8.5.2, Cross-cut tape method)”. That is, the result was evaluated by the number of squares that did not peel out of 100 squares.

  Pencil hardness: The measurement was performed according to the method of JIS standard “JIS-K-5400, 8.4, pencil scratch test”. The result was expressed by the hardness of the pencil lead.

  Heat resistance test: This test was carried out at 100 ° C. for 500 hours, and the result was evaluated by the variation of retardation. After applying polyamic acid (PIA5310 from Chisso Corp.) to a glass substrate, it was heated at 210 ° C. for 30 minutes to prepare a support substrate. The surface of the produced polyimide was rubbed with a rayon cloth. The composition of the sample was diluted with a mixed solvent of toluene and cyclopentanone (2: 1 by weight) to prepare a 30% by weight solution. The solution was applied to a support substrate with a spin coater, heated at 70 ° C. for 3 minutes, and then the produced coating film was irradiated with ultraviolet rays at 60 ° C. for 10 seconds using an ultrahigh pressure mercury lamp (250 W / cm). The retardation of the obtained polymer film was measured at 25 ° C. After heating the polymer at 100 ° C. for 500 hours, the retardation was measured again at 25 ° C. Two values were compared to evaluate heat resistance. The retardation was measured using a Senarmont compensator according to literature methods. The wavelength used is 550 nm. Literature is written by Hiroshi Ashiya, “Introduction to Polarizing Microscopes of Polymer Materials”, p. 94, published by Agne Technology Center, 2001.

  Optical anisotropy (Δn): The value of retardation (25 ° C.) of the polymer film was measured according to the method of heat resistance test described above. The thickness (d) of the polymer film was also measured. Since the retardation is Δn × d, the value of optical anisotropy was calculated from this relationship.

Alignment of liquid crystal molecules: A polymer film (liquid crystal alignment film) was prepared on a saponified TAC (triacetylcellulose) film. The orientation of the polymer was determined by two methods of visual observation and analysis by a measuring device based on the angle dependency of the transmitted light intensity.
1) Visual observation-A polymer film was sandwiched between two polarizing plates arranged in crossed Nicols, and light was irradiated from the direction perpendicular to the film surface (the tilt angle was 0 degree). The change in transmitted light was observed while increasing the tilt angle of irradiation from 0 degrees to, for example, 50 degrees. The direction of tilting the irradiation was matched with the rubbing direction (long axis direction of liquid crystal molecules). The orientation was judged to be homogeneous when the transmitted light from the vertical direction was maximal. This is because in homogeneous alignment, the alignment vector of liquid crystal molecules is parallel to the TAC film. On the other hand, when the transmitted light from the vertical direction is the smallest and the transmitted light increases as the tilt angle increases, the orientation is judged to be homeotropic. This is because in homeotropic alignment, the alignment vector of liquid crystal molecules is perpendicular to the TAC film.
2) Measurement by ellipsometer-An OPTIPRO ellipsometer manufactured by Shintech Co., Ltd. was used. The polymer film was irradiated with light having a wavelength of 550 nm. The retardation (Δn × d) was measured while decreasing the incident angle of this light from 90 degrees with respect to the film surface.

原料である４−［６−（アクリロイルオキシ）ヘキシルオキシ］安息香酸（ＡＫ１）は、Makromol. Chem., 190, ２２５５〜２２６８ページ、１９８９年に記載された方法で合成した。

Example 1 (Synthesis example of compound represented by formula (1-1))
Compound (1-1-3)

The raw material 4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK1) was synthesized by the method described in Makromol. Chem., 190, 2255-2268, 1989.

(First stage)
Under nitrogen atmosphere, dichloromethane (100 mL) was charged with 4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK1; 6.0 g), 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (3.2 g). ), 4-dimethylaminopyridine (0.06 g) was added, and a solution of N, N′-dicyclohexylcarbodiimide (4.1 g) in dichloromethane (50 mL) was added dropwise under ice cooling, followed by stirring at room temperature for 12 hours. Insoluble matter was removed by filtration, water was added to the filtrate, and the mixture was washed with hydrochloric acid, aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 19/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compounds (1-1-3) and (4.3 g). Melting point: 93-95 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.14 (d, 4H), 7.48 (d, 4H), 7.25 (d, 4H), 6.98 (d, 4H), 6. 41 (dd, 2H), 6.13 (dd, 2H), 5.83 (dd, 2H), 4.19 (t, 4H), 4.06 (t, 4H), 1.82-1.88 (M, 4H), 1.70-1.76 (m, 4H), 1.44-1.57 (m, 8H).

（第１段階）
３−（４−ヒドロキシフェニル）プロピオン酸（１１５０ｇ）のエタノール（１，５００ｍＬ）溶液に硫酸（２３０ｇ）をかくはんしながら１０分で滴下し、続いて５時間還流させた。反応混合物を濃縮し、得られた濃縮液を水（１，０００ｍＬ）に注ぎ入れ、酢酸エチルを加えてかくはんした。分液した後、酢酸エチル層を飽和炭酸ナトリウム水溶液で中和し、少量の水で水洗した後、無水硫酸マグネシウムで乾燥した。この酢酸エチル層から酢酸エチルおよび未反応成分を留去して、濃縮物（１４００ｇ）を得た。濃縮物を減圧蒸留により精製して３−（４−ヒドロキシフェニル）プロピオン酸エチル（１，１４４ｇ）を得た。沸点は１６０℃／４．０ｈＰａであった。 Example 2 (Synthesis example of the compound of the present invention represented by the formula (7))
Synthesis of compound (1-1-8)

(First stage)
To a solution of 3- (4-hydroxyphenyl) propionic acid (1150 g) in ethanol (1,500 mL), sulfuric acid (230 g) was added dropwise over 10 minutes with stirring, and then refluxed for 5 hours. The reaction mixture was concentrated, and the resulting concentrate was poured into water (1,000 mL), and stirred with ethyl acetate. After liquid separation, the ethyl acetate layer was neutralized with a saturated aqueous sodium carbonate solution, washed with a small amount of water, and dried over anhydrous magnesium sulfate. Ethyl acetate and unreacted components were distilled off from this ethyl acetate layer to obtain a concentrate (1400 g). The concentrate was purified by distillation under reduced pressure to give ethyl 3- (4-hydroxyphenyl) propionate (1,144 g). The boiling point was 160 ° C./4.0 hPa.

(Second stage)
6-Chlorohexanol (800 g) was added to acetic anhydride (1,200 mL) cooled to 10 ° C. in an ice bath, and then pyridine (934 g) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was refluxed for 2 hours. The reaction mixture was poured into water, and further toluene was added and stirred. The toluene layer was neutralized with a saturated aqueous sodium carbonate solution, washed with a small amount of water, and dried over anhydrous magnesium sulfate. Toluene and unreacted components were distilled off from this toluene layer to obtain a concentrate. The concentrate was purified by distillation under reduced pressure to obtain 6-acetoxychlorohexane (983 g). The boiling point was 82 ° C./5.3 hPa.

(3rd stage)
Sodium hydroxide (98 g) was added to a solution of ethyl 3- (4-hydroxyphenyl) propionate (400 g) in dimethylformamide (2,800 mL), and the mixture was stirred at 40 ° C. for 30 minutes. The formation of salt could be observed visually. 6-Acetoxychlorohexane (515 g) was added and the mixture was stirred at 80 ° C. for 7 hours. The reaction mixture was poured into water (2,000 mL), and further toluene was added and stirred. After separation, the toluene layer was washed with 6N hydrochloric acid, saturated aqueous sodium carbonate solution and water in this order, and dried over anhydrous magnesium sulfate. The solvent was distilled off from this toluene layer to obtain 709 g of a concentrate. Sodium hydroxide (185 g) was dissolved in water (400 mL), ethanol (600 mL) and concentrate 709 g were added thereto, heated and refluxed for 2 hours. The reaction mixture was concentrated under reduced pressure using an evaporator, and the resulting concentrate was poured into 6N hydrochloric acid. The resulting slurry was filtered to obtain a solid. Recrystallization from ethanol gave (4- (6-hydroxyhexyloxy) phenyl) propionic acid (281 g). Melting point: 109-112 ° C.

(Fourth stage)
A mixture of (4- (6-hydroxyhexyloxy) phenyl) propionic acid (200 g), N, N-dimethylaniline (100 g), BHT (0.3 g), and dioxane (1,000 ml) was mixed with acrylic acid chloride (74 .3 g) was added dropwise in 10 minutes. After stirring at 60 ° C. for 5 hours, the reaction mixture was poured into water and stirred with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off from the ethyl acetate layer to obtain a solid. This solid was dissolved in toluene, poured into a large amount of heptane and reprecipitated to obtain (4- (6-acryloyloxyhexyloxy) phenyl) propionic acid (AK2; 213 g). Melting point: 64-68 ° C.

(5th stage)
Under a nitrogen atmosphere, (4- (6-acryloyloxyhexyloxy) phenyl) propionic acid (AK2; 3.0 g), 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (1.5 g), 4- To a mixture of dimethylaminopyridine (0.03 g) and dichloromethane (50 mL), a solution of N, N′-dicyclohexylcarbodiimide (1.9 g) in dichloromethane (20 mL) was added dropwise under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 19/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compound (1-1-8) and (2.1 g). Melting point: 57-58 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 7.38 (d, 4H), 7.17 (d, 4H), 7.04 (d, 4H), 6.85 (d, 4H), 6. 40 (dd, 2H), 6.12 (dd, 2H), 5.82 (dd, 2H), 4.19 (t, 4H), 3.94 (t, 4H), 3.01 (t, 4H) ), 2.86 (t, 4H), 1.76-1.82 (m, 4H), 1.68-1.74 (m, 4H), 1.42-1.53 (m, 8H).

（第１段階）
２−フルオロ−４−［６−（アクリロイルオキシ）ヘキシルオキシ］安息香酸（ＡＫ３）は２−フルオロ−４−ヒドロキシ安息香酸エチルを原料としてMakromol. Chem., 190, ２２５５〜２２６８ページ、１９８９年に記載された方法を用いて合成した。化合物（ＡＫ３）の融点は９８〜９９℃。

Example 3 (Synthesis example of compound represented by formula (8))
Synthesis of compound (1-1-12)

(First stage)
2-Fluoro-4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK3) was prepared from ethyl 2-fluoro-4-hydroxybenzoate as a raw material in Makromol. Chem., 190, 2255-2268, 1989. Synthesized using the method described. The melting point of compound (AK3) is 98-99 ° C.

(Second stage)
2-Fluoro-4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK3; 3.0 g), 2,2-bis (4-hydroxyphenyl) -hexafluoropropane in dichloromethane (50 mL) under nitrogen atmosphere (1.6 g) and 4-dimethylaminopyridine (0.03 g) were added, and a solution of N, N′-dicyclohexylcarbodiimide (2.0 g) in dichloromethane (20 mL) was added dropwise under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 19/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compounds (1-1-12) and (2.6 g). Melting point: 75-77 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.04 (t, 2H), 7.48 (d, 4H), 7.26 (d, 4H), 6.78 (dd, 2H), 6. 69 (dd, 2H), 6.41 (dd, 2H), 6.13 (dd, 2H), 5.83 (dd, 2H), 4.18 (t, 4H), 4.04 (t, 4H) ), 1.82-1.87 (m, 4H), 1.70-1.76 (m, 4H), 1.44-1.55 (m, 8H).

The melting points of the compound (1-1-3), the compound (1-1-8) and the compound (1-1-12) of the present invention were compared.

Compound (1-1-3) Melting point 93-95 ° C
Compound (1-1-8) Melting point: 57-58 ° C
Compound (1-1-12) Melting point: 75-77 ° C

Differences in melting point due to differences in molecular structure were observed. Compound (1-1-8) in which the linking group is an ethane bond has a melting point lower than that of Compound (1-1-3), and Compound (1-1-12) in which the liquid crystal skeleton is substituted with fluorine is Compound (1-12). It can be seen that the melting point is lower than that of 1-3. That is, when a composition is prepared by adding the compound of the present invention to a polymerizable liquid crystal composition, it is considered that recrystallization hardly occurs.

（第１段階）
窒素雰囲気下、４−［６−（アクリロイルオキシ）ヘキシルオキシ］安息香酸（ＡＫ１；２．０ｇ）、ビス（４−ヒドロキシフェニル）スルホン（０．８ｇ）、４−ジメチルアミノピリジン（０．０２ｇ）、およびジクロロメタン（５０ｍＬ）の混合物に、氷冷下でＮ，Ｎ’−ジシクロヘキシルカルボジイミド（１．４ｇ）のジクロロメタン（２０ｍＬ）溶液を滴下した。室温で１２時間撹拌したあと、不溶物をろ過し取り除いた。ろ液に水を加え、塩酸、水酸化ナトリウム水溶液、水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣をシリカゲルクロマトグラフィー（トルエン／酢酸エチル＝９／１）で分取後、トルエンとエタノールの混合溶媒から再結晶し、化合物（１−２−３）、（１．７６ｇ）を得た。融点：８８−９０℃。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１２（ｄ，４Ｈ），８．０２（ｄ，４Ｈ），７．３８（ｄ，４Ｈ），６．９７（ｄ，４Ｈ），６．４１（ｄｄ，２Ｈ），６．１３（ｄｄ，２Ｈ），５．８３（ｄｄ，２Ｈ），４．１８（ｔ，４Ｈ），４．０５（ｔ，４Ｈ），１．８２−１．８７（ｍ，４Ｈ），１．７０−１．７６（ｍ，４Ｈ），１．４４−１．５７（ｍ，８Ｈ）。 Example 4 (Synthesis Example of Compound Represented by Formula (1-2))
Synthesis of compound (1-2-3)

(First stage)
Under nitrogen atmosphere, 4- [6- (acryloyloxy) hexyloxy] benzoic acid (AK1; 2.0 g), bis (4-hydroxyphenyl) sulfone (0.8 g), 4-dimethylaminopyridine (0.02 g) , And a mixture of dichloromethane (50 mL) was added dropwise a solution of N, N′-dicyclohexylcarbodiimide (1.4 g) in dichloromethane (20 mL) under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 9/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compounds (1-2-3) and (1.76 g). Melting point: 88-90 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.12 (d, 4H), 8.02 (d, 4H), 7.38 (d, 4H), 6.97 (d, 4H), 6. 41 (dd, 2H), 6.13 (dd, 2H), 5.83 (dd, 2H), 4.18 (t, 4H), 4.05 (t, 4H), 1.82-1.87 (M, 4H), 1.70-1.76 (m, 4H), 1.44-1.57 (m, 8H).

（第１段階）
窒素雰囲気下、（４−（６−アクリロイルオキシヘキシルオキシ）フェニル）プロピオン酸（ＡＫ２；５．１ｇ）、ビス（４−ヒドロキシフェニル）スルホン（２ｇ）、４−ジメチルアミノピリジン（０．１ｇ）、およびジクロロメタン（８０ｍＬ）の混合物に、氷冷下でＮ，Ｎ’−ジシクロヘキシルカルボジイミド（３．５ｇ）のジクロロメタン（１０ｍＬ）溶液を滴下した。室温で１２時間撹拌したあと、不溶物をろ過し取り除いた。ろ液に水を加え、塩酸、水酸化ナトリウム水溶液、水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣をシリカゲルクロマトグラフィー（トルエン／酢酸エチル＝９／１）で分取後、トルエンとエタノールの混合溶媒から再結晶し、化合物（１−２−８）、（１．７６ｇ）を得た。融点：６７−６８℃。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：７．９２（ｄ，４Ｈ），７．１５（ｄ，４Ｈ），７．１５（ｄ，４Ｈ），６．８３（ｄ，４Ｈ），６．３９（ｄｄ，２Ｈ），６．１２（ｄｄ，２Ｈ），５．８１（ｄｄ，２Ｈ），４．１７（ｔ，４Ｈ），３．９３（ｔ，４Ｈ），２．９９（ｔ，４Ｈ），２．８５（ｔ，４Ｈ），１．８０−１．７７（ｍ，４Ｈ），１．７２−１．６９（ｍ，４Ｈ），１．５１−１．４５（ｍ，８Ｈ）。 Example 5 (Synthesis example of the compound of the present invention represented by the formula (9))
Synthesis of compound (1-2-8)

(First stage)
Under a nitrogen atmosphere, (4- (6-acryloyloxyhexyloxy) phenyl) propionic acid (AK2; 5.1 g), bis (4-hydroxyphenyl) sulfone (2 g), 4-dimethylaminopyridine (0.1 g), And a solution of N, N′-dicyclohexylcarbodiimide (3.5 g) in dichloromethane (10 mL) was added dropwise to a mixture of dichloromethane and 80 mL. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 9/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compounds (1-2-8) and (1.76 g). Melting point: 67-68 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 7.92 (d, 4H), 7.15 (d, 4H), 7.15 (d, 4H), 6.83 (d, 4H), 6. 39 (dd, 2H), 6.12 (dd, 2H), 5.81 (dd, 2H), 4.17 (t, 4H), 3.93 (t, 4H), 2.99 (t, 4H) ), 2.85 (t, 4H), 1.80-1.77 (m, 4H), 1.72-1.69 (m, 4H), 1.51-1.45 (m, 8H).

The melting points of the compound (1-2-3) and the compound (1-2-8) of the present invention were compared.

Compound (1-2-3) Melting point 88-90 ° C
Compound (1-2-8) Melting point 67-68 ° C

Differences in melting point due to differences in molecular structure were observed. It can be seen that the compound (1-2-8) in which the linking group is an ethane bond has a lower melting point than the compound (1-2-3). That is, when a composition is prepared by adding the compound of the present invention to a polymerizable liquid crystal composition, it is considered that recrystallization hardly occurs.

（第１段階）
３−［（６−ブロモヘキシルオキシ）メチル］−３−メチルオキセタン（８４ｇ）、４−ヒドロキシ安息香酸エチル（５０ｇ）、炭酸カリウム（５０ｇ）、およびジメチルホルムアミド（６００ｍＬ）の混合物を９０℃で４時間かくはんした。反応混合物に水を加え反応を終了させ、酢酸エチルで抽出したあと、抽出液を２Ｎ−水酸化ナトリウム水溶液、水の順に洗浄、有機層を無水硫酸マグネシウムで乾燥した。溶媒を留去して得られた残渣をシリカゲルクロマトグラフィー（トルエン/酢酸エチル＝８/２）で精製して４−［６−（３−メチルオキセタン−３−イルメトキシ）ヘキシルオキシ］安息香酸エチル（８５ｇ）を得た。
Example 6 (Synthesis Example of Compound Represented by Formula (10))
Synthesis of compound (5-1-5)

(First stage)
A mixture of 3-[(6-bromohexyloxy) methyl] -3-methyloxetane (84 g), ethyl 4-hydroxybenzoate (50 g), potassium carbonate (50 g), and dimethylformamide (600 mL) at 90 ° C. Stirred in time. Water was added to the reaction mixture to terminate the reaction, and the mixture was extracted with ethyl acetate. The extract was washed with a 2N aqueous sodium hydroxide solution and water in this order, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography (toluene / ethyl acetate = 8/2) to give ethyl 4- [6- (3-methyloxetan-3-ylmethoxy) hexyloxy] benzoate ( 85 g) was obtained.

Second Stage of 4- [6- (3-Methyloxetane-3-ylmethoxy) hexyloxy] benzoate (83 g), sodium hydroxide (12 g), water (50 mL), and Solmix® (200 mL) The mixture was refluxed for 2 hours. The reaction mixture was acidified with hydrochloric acid, extracted with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 4- [6- (3-methyloxetane-3-ylmethoxy) hexyloxy] benzoic acid (OX1; 63 g). Melting point: 58.5 ° C.

The following compounds were produced by the same production method.

(3rd stage)
2-fluoro-4- [4- (3-ethyloxetane-3-ylmethoxy) butyloxy] benzoic acid (OX4; 3.1 g), 2,2-bis (4-hydroxyphenyl) -hexafluoropropane under nitrogen atmosphere (1.5 g), 4-dimethylaminopyridine (0.02 g), and dichloromethane (80 mL) were added dropwise with a solution of N, N′-dicyclohexylcarbodiimide (1.9 g) in dichloromethane (20 mL) under ice-cooling. did. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 9/1) to obtain an oily compound (5-1-5) at room temperature. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.04 (t, 2H), 7.48 (d, 4H), 7.28 (d, 4H), 6.78 (dd, 2H), 6. 69 (dd, 2H), 4.46 (d, 4H), 4.38 (d, 4H), 4.07 (t, 4H), 3.55 (s, 8H), 1.89-1.94. (M, 4H), 1.72-1.81 (m, 8H), 0.89 (t, 6H).

（第１段階）
３−エチル３−ヒドロキシメチル−オキセタン（東亜合成（株）製：商品名ＯＸＴ−１０１；１１６ｇ）をピリジン（５００ｍＬ）に加え、かくはんしながら０℃に冷却した。この溶液にｐ−トルエンスルホニルクロリド（１９０ｇ）を数回に分けて加えた。０℃を保ちながら５時間かくはんした後、氷水（１Ｌ）に反応混合物を注いだ。ジエチルエーテル（５００ｍＬ）で抽出し、３％の塩酸でｐＨが酸性になるまで、抽出液を水で洗浄した。次に、抽出液を飽和炭酸ナトリウム溶液、水で順次洗浄し、無水硫酸マグネシウムで乾燥した。溶媒を留去して３−［（トシルオキシ）メチル］−３−エチルオキセタン（２４３ｇ）を得た。 Example 7
Synthesis of Compound (5-1-1) (Synthesis Example of Compound Represented by Formula (10))

(First stage)
3-ethyl 3-hydroxymethyl-oxetane (manufactured by Toagosei Co., Ltd .: trade name OXT-101; 116 g) was added to pyridine (500 mL), and the mixture was cooled to 0 ° C. with stirring. To this solution, p-toluenesulfonyl chloride (190 g) was added in several portions. After stirring for 5 hours while maintaining 0 ° C., the reaction mixture was poured into ice water (1 L). Extracted with diethyl ether (500 mL), and the extract was washed with water until the pH was acidic with 3% hydrochloric acid. Next, the extract was washed successively with a saturated sodium carbonate solution and water, and dried over anhydrous magnesium sulfate. The solvent was distilled off to give 3-[(tosyloxy) methyl] -3-ethyloxetane (243 g).

(Second stage)
A mixture of ethyl hydroxybenzoate (50 g), potassium hydroxide (21 g) and dimethylformamide (400 mL) was stirred at 70 ° C. for 1 hour. After the temperature was lowered to 45 ° C., 3-[(tosyloxy) methyl] -3-ethyloxetane (100 g) was added dropwise to the reaction mixture. The mixture was stirred for 3 hours while maintaining at 45 ° C. Water and toluene were added for liquid separation, and the toluene layer was washed with 3% hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution, and water. To the residue obtained by distilling off toluene, sodium hydroxide (50 g), ethanol (500 mL) and water (200 mL) were added and refluxed for 2 hours. The residue obtained by distilling off ethanol was poured into 5% hydrochloric acid (500 mL) to obtain crystals. Crystals obtained by filtration were recrystallized from a mixed solvent of ethanol and water to obtain 4- (3-ethyloxetane-3-ylmethoxy) benzoic acid (OX5; 60 g). Melting point: 127.5 ° C.

(3rd stage)
Under a nitrogen atmosphere, 4- (3-ethyloxetane-3-ylmethoxy) benzoic acid (OX5; 15 g), 2,2-bis (4-hydroxyphenyl) -hexafluoropropane (10 g), 4-dimethylaminopyridine (0 0.2 g) and a mixture of dichloromethane (300 mL) were added dropwise a solution of N, N′-dicyclohexylcarbodiimide (12 g) in dichloromethane (100 mL) under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was separated by silica gel chromatography (toluene / ethyl acetate = 9/1) and recrystallized from a mixed solvent of toluene and ethanol to obtain compounds (5-1-1) and (16 g). Melting point: 182 ° C (decomposition). ¹ H-NMR (CDCl ₃ ; δ ppm): 8.17 (d, 4H), 7.49 (d, 4H), 7.26 (d, 4H), 7.04 (d, 4H), 4. 59 (d, 4H), 4.52 (d, 4H), 4.19 (s, 4H), 1.89-1.94 (m, 4H), 0.96 (t, 6H).

（第１段階）
窒素雰囲気下、４−（３−エチルオキセタン−３−イルメトキシ）安息香酸（ＯＸ５；５．０ｇ）、ビス（４−ヒドロキシフェニル）スルホン（２．５ｇ）、４−ジメチルアミノピリジン（０．０６ｇ）、およびジクロロメタン（１００ｍＬ）の混合物に、氷冷下でＮ，Ｎ’−ジシクロヘキシルカルボジイミド（４．４ｇ）のジクロロメタン（４０ｍＬ）溶液を滴下した。室温で１２時間撹拌したあと、不溶物をろ過し取り除いた。ろ液に水を加え、塩酸、水酸化ナトリウム水溶液、水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣を塩化メチレンとエタノールの混合溶媒から再結晶して、化合物（５−２−１）、（５．３ｇ）を得た。融点：２０７−２０８℃。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１５（ｄ，４Ｈ），８．０３（ｄ，４Ｈ），７．３９（ｄ，４Ｈ），７．０４（ｄ，４Ｈ），４．５９（ｄ，４Ｈ），４．５２（ｄ，４Ｈ），４．１９（ｓ，４Ｈ），１．８９−１．９３（ｍ，４Ｈ），０．９６（ｔ，６Ｈ）。 Example 8 (Synthesis example of compound represented by formula (11))
Synthesis of compound (5-2-1)

(First stage)
Under nitrogen atmosphere, 4- (3-ethyloxetane-3-ylmethoxy) benzoic acid (OX5; 5.0 g), bis (4-hydroxyphenyl) sulfone (2.5 g), 4-dimethylaminopyridine (0.06 g) A solution of N, N′-dicyclohexylcarbodiimide (4.4 g) in dichloromethane (40 mL) was added dropwise to a mixture of and dichloromethane (100 mL) under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of methylene chloride and ethanol to obtain compounds (5-2-1) and (5.3 g). Melting point: 207-208 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.15 (d, 4H), 8.03 (d, 4H), 7.39 (d, 4H), 7.04 (d, 4H), 4. 59 (d, 4H), 4.52 (d, 4H), 4.19 (s, 4H), 1.89-1.93 (m, 4H), 0.96 (t, 6H).

化合物（５−２−１１）の合成

（第１段階）
窒素雰囲気下、４−［６−（３−メチルオキセタン−３−イルメトキシ）ヘキシルオキシ］安息香酸（ＯＸ１；４ｇ）、ビス（４−ヒドロキシフェニル）スルホン（１．５ｇ）、４−ジメチルアミノピリジン（０．１ｇ）、およびジクロロメタン（８０ｍＬ）の混合物に、氷冷下でＮ，Ｎ’−ジシクロヘキシルカルボジイミド（２．７ｇ）のジクロロメタン（１０ｍＬ）溶液を滴下した。室温で１２時間撹拌したあと、不溶物をろ過し取り除いた。ろ液に水を加え、塩酸、水酸化ナトリウム水溶液、水で洗浄した。有機層を無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣を塩化メチレンとエタノールの混合溶媒から再結晶して、化合物（５−２−１１）、（２．３ｇ）を得た。融点：６６−６８℃。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１９（ｄ，４Ｈ），８．０２（ｄ，４Ｈ），７．３８（ｄ，４Ｈ），６．９７（ｄ，４Ｈ），４．５１（ｄ，４Ｈ），４．３５（ｄ，４Ｈ），４．０５（ｔ、４Ｈ）、３．４８（ｔ，８Ｈ），１．８５−１．８２（ｍ，４Ｈ），１．６５−１．６０（ｍ，４Ｈ），１．５１−１．４５（ｍ，８Ｈ）、１．３１（ｓ，６Ｈ）。 Example 9 (Synthesis example of compound represented by formula (11))

Synthesis of compound (5-2-11)

(First stage)
Under a nitrogen atmosphere, 4- [6- (3-methyloxetan-3-ylmethoxy) hexyloxy] benzoic acid (OX1; 4 g), bis (4-hydroxyphenyl) sulfone (1.5 g), 4-dimethylaminopyridine ( To a mixture of 0.1 g) and dichloromethane (80 mL), a solution of N, N′-dicyclohexylcarbodiimide (2.7 g) in dichloromethane (10 mL) was added dropwise under ice cooling. After stirring at room temperature for 12 hours, insoluble matters were removed by filtration. Water was added to the filtrate, and the mixture was washed with hydrochloric acid, an aqueous sodium hydroxide solution, and water. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was recrystallized from a mixed solvent of methylene chloride and ethanol to obtain compounds (5-2-11) and (2.3 g). Melting point: 66-68 ° C. ¹ H-NMR (CDCl ₃ ; δ ppm): 8.19 (d, 4H), 8.02 (d, 4H), 7.38 (d, 4H), 6.97 (d, 4H), 4. 51 (d, 4H), 4.35 (d, 4H), 4.05 (t, 4H), 3.48 (t, 8H), 1.85 to 1.82 (m, 4H), 1.65 -1.60 (m, 4H), 1.51-1.45 (m, 8H), 1.31 (s, 6H).

Example 10
<Preparation of composition (P-1)>
A polymerizable liquid crystal composition (M-1) comprising 20% by weight of the compound (1-1-3), 60% by weight of the compound (2-1-3), and 20% by weight of the compound (3-1-3) was prepared. . Compound (2-1-3) was synthesized by the method described in JP-A No. 2003-238491. Compound (3-1-3) was synthesized by the method described in Macromolecules, 3938-3943, (23), 1990.

  Next, 3% by weight of a polymerization initiator (trade name IRGACURE 907 manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition (M-1), and then toluene was added to prepare a 25% by weight solution. . This is the composition (P-1).

Example 11
<Preparation of composition (P-2)>
A polymerizable liquid crystal composition (M-2) comprising 10% by weight of the compound (1-2-3), 70% by weight of the compound (2-1-3), and 20% by weight of the compound (3-1-3) was prepared. .

  Next, 3 wt% of a polymerization initiator (trade name IRGACURE 907 manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition (M-2), and then toluene was added to prepare a 25 wt% solution. . This is the composition (P-2).

Example 12
<Preparation of composition (P-3)>
A polymerizable liquid crystal composition (M-3) comprising 20% by weight of the compound (1-2-3), 60% by weight of the compound (2-2-7) and 20% by weight of the compound (3-1-3) was prepared. .

  Next, 3 wt% of a polymerization initiator (trade name IRGACURE 907 manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition (M-3), and then toluene was added to prepare a 25 wt% solution. . This is the composition (P-3).

Example 13
<Preparation of composition (P-4)>
A polymerizable liquid crystal composition (M-4) comprising 20% by weight of the compound (1-1-8), 60% by weight of the compound (2-1-3), and 20% by weight of the compound (3-1-3) was prepared. .

  Next, 3% by weight of a polymerization initiator (trade name IRGACURE 907 manufactured by Ciba Specialty Chemicals) was added to the polymerizable liquid crystal composition (M-4), and then toluene was added to prepare a 25% by weight solution. . This is the composition (P-4).

Example 14
<Preparation of composition (P-5)>
A polymerizable liquid crystal composition (M-5) comprising 20% by weight of the compound (5-1-1), 60% by weight of the compound (6-1-1), and 20% by weight of the compound (7-1-4) was prepared. . Compound (6-1-1) was synthesized by the method described in JP-A-2005-60373. Compound (7-1-4) was synthesized by performing an etherification reaction of 4′-hydroxy-cyanobiphenyl and 6-bromohexene and then oxidizing with m-chloroperbenzoic acid. The phase transition temperature was C68N701.

  Next, 3% by weight of a polymerization initiator (DTS-102 manufactured by Midori Kagaku) was added to the polymerizable liquid crystal composition (M-5), and then a mixed solvent (toluene / cyclopentanone was mixed at a weight ratio of 2). / 1) was added to prepare a 20 wt% solution. This is the composition (P-5).

Example 15
<Preparation of composition (P-6)>
In the composition (P-1) described in Example 10, the compound (4-1) was mixed at a ratio of 10 parts by weight with respect to 100 parts by weight of the polymerizable liquid crystal composition (M-1). 4-1) was added. Compound (5) is trade name Sila Ace S-330 manufactured by Chisso Corporation. This is the composition (P-6).

Example 16
<Preparation of composition (P-7)>
Based on the polymerizable liquid crystal composition (M-3), 10% by weight of the compound (4-1) was added to the composition (P-3) described in Example 12. This is the composition (P-7).

Example 17
<Evaluation of polymer film (F1)>
A TAC saponified TAC film was used as the support substrate. The surface of the film was rubbed with a rayon cloth. The composition (P-1) described in Example 10 was applied to a TAC film using a bar coater. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. The produced coating film was irradiated with ultraviolet rays (30 mW / cm ² ; 365 nm) using an ultrahigh pressure mercury lamp (250 W) at 25 ° C. for 30 seconds in a nitrogen atmosphere. A polymer film (F-1) was produced by polymerization. In visual observation, the orientation of the film (F-1) was homogeneous. The orientation was homogeneous according to the measurement result (shown in FIG. 1) by the apparatus. The surface hardness of the film (F-1) was HB of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-1) was difficult to peel from the support substrate, and had optical anisotropy and sufficient hardness.

Example 18
<Evaluation of polymer film (F2)>
A TAC saponified TAC film was used as the support substrate. The surface of the film was rubbed with a rayon cloth. The composition (P-2) described in Example 11 was applied to a TAC film using a bar coater. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. The produced coating film was irradiated with ultraviolet rays (30 mW / cm ² ; 365 nm) using an ultrahigh pressure mercury lamp (250 W) at 25 ° C. for 30 seconds in a nitrogen atmosphere. A polymer film (F-2) was produced by polymerization. In visual observation, the orientation of the film (F-2) was homogeneous. The orientation was homogeneous according to the measurement results obtained by the apparatus. The surface hardness of the film (F-2) was HB of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-2) was difficult to peel from the support substrate, and had optical anisotropy and sufficient hardness.

Example 19
<Evaluation of polymer film (F3)>
A TAC saponified TAC film was used as the support substrate. The surface of the film was rubbed with a rayon cloth. The composition (P-3) described in Example 12 was applied to a TAC film using a bar coater. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. The produced coating film was irradiated with ultraviolet rays (30 mW / cm ² ; 365 nm) using an ultrahigh pressure mercury lamp (250 W) at 25 ° C. for 30 seconds in a nitrogen atmosphere. A polymer film (F-3) was produced by polymerization. In visual observation, the orientation of the film (F-3) was homogeneous. The orientation was homogeneous according to the measurement result (shown in FIG. 1) by the apparatus. The surface hardness of the film (F-3) was HB of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-3) was difficult to peel from the support substrate, and had optical anisotropy and sufficient hardness.

Example 20
<Evaluation of polymer film (F4)>
The composition (P-4) described in Example 13 was treated in the same manner as in Example 19 to obtain a polymer film (F-4). In visual observation, the orientation of the film (F-4) was homogeneous. This was consistent with the measurement results from the instrument. The surface hardness of the film (F-4) was HB of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-4) was hardly peeled off from the support substrate, and had optical anisotropy and sufficient hardness.

Example 21
<Evaluation of polymer film (F5)>
The composition (P-5) described in Example 14 was treated in the same manner as in Example 19 to obtain a polymer film (F-5). In visual observation, the orientation of the film (F-5) was homogeneous. This was consistent with the measurement results from the instrument. The surface hardness of the film (F-5) was pencil hardness HB. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-5) was hardly peeled off from the support substrate, and had optical anisotropy and sufficient hardness.

Example 22
<Evaluation of polymer film (F-6)>
A TAC saponified TAC film was used as the support substrate. The film was not rubbed. The composition (P-6) described in Example 11 was applied to a TAC film using a bar coater. After the application, the solution was heat-treated in an oven set at 70 ° C. for 5 minutes to remove the solvent and align the liquid crystal layer. The produced coating film was irradiated with ultraviolet rays (30 mW / cm ² ; 365 nm) using an ultrahigh pressure mercury lamp (250 W) at 25 ° C. for 30 seconds under a nitrogen atmosphere. A polymer film (F-6) was produced by polymerization. In visual observation, the orientation of the film (F-6) was homeotropic (vertical orientation). This coincided with the measurement result by the apparatus (shown in FIG. 2). The surface hardness of the film (F-6) was H of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-6) was difficult to peel from the support substrate, and had optical anisotropy and sufficient hardness.

Example 23
<Evaluation of polymer film (F-7)>
The composition (P-7) described in Example 16 was treated in the same manner as in Example 22 to obtain a polymer film (F-7). In visual observation, the orientation of the film (F-7) was homeotropic (vertical orientation). This was consistent with the measurement results from the instrument. The surface hardness of the film (F-7) was H of pencil hardness. In the cellophane peeling test, no peeling occurred, and all the mushroom remained. There was no change in the retardation after the heat resistance test at 100 ° C. for 500 hours. Thus, the liquid crystal alignment film (F-7) was hardly peeled from the support substrate, and had optical anisotropy and sufficient hardness.

Homogenous orientation: the result of measuring the retardation of the polymer film (F-1) obtained in Example 17. Homeotropic orientation: the result of measuring the retardation of the polymer film (F-6) obtained in Example 22.

Claims (14)

At least one compound selected from the group of compounds represented by formula (1-1) and formula (1-2) as the first component, and formula (2-1) and formula (2-2) as the second component A polymerizable liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (II) and at least one compound selected from the group of compounds represented by formula (3-1) as the third component: .

In Formula (1-1) and Formula (1-2); Y ¹ and Y ² are each independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ¹ and W ² are independently And m ¹ , m ² , n ¹ and n ² are each independently an integer of 2 to 15, and in formula (2-1) and formula (2-2); W ³ is hydrogen Or W ⁴ and W ⁵ are independently hydrogen or methyl; W ⁶ is hydrogen or methyl; X ¹ is —O— or a group represented by the formula (X ¹ -2) M ³ , m ⁴ , n ³ and n ⁴ are each independently an integer from 2 to 15;

In Formula (3-1), R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; W ⁷ is hydrogen or fluorine; X ² is a single bond , —COO—, or —OCO—; m ⁵ is an integer from 2 to 15. The second component is at least one compound selected from the group of compounds represented by formula (2-1), and the content ratio of the first component to the polymerizable liquid crystal composition is in the range of 1 to 25% by weight. Yes, the content ratio of the second component is in the range of 50 to 98% by weight, the content ratio of the third component is in the range of 1 to 25% by weight, and in the formulas (1-1) and (1-2) Y ¹ and Y ² are independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² are independently hydrogen or fluorine; m ¹ , m ² , n ¹ , and n ^2; Are independently an integer from 2 to 10; in Formula (2-1); W ³ is hydrogen; W ⁴ is hydrogen; W ⁵ is methyl; m ³ and n ³ are independently is an integer from 2 to 10, in the formula (3-1); ^{X 2} is a single bond, -COO-, or -O An O-; ^{W 7} is hydrogen; ^{m 5} is an integer from 2 to 10; ^{R 1} is cyano, alkyl of 2-8 carbon atoms, or alkoxy of 2-8 carbon atoms, according to claim 1, The polymerizable liquid crystal composition described in 1. The content ratio of the first component relative to the polymerizable liquid crystal composition is in the range of 7 to 22% by weight, the content ratio of the second component is in the range of 56 to 86% by weight, and the content ratio of the third component is 7 to 7%. In the formula (1-1) and formula (1-2); Y ¹ and Y ² are each independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² Is hydrogen; m ¹ , m ² , n ¹ , and n ² are each independently an integer of 4 to 6, and in formula (2-1); W ³ is hydrogen; W ⁴ is hydrogen ; ^{W 5} is methyl; is an integer of ^{m 3} and ^{n 3} from 4 independently is 6, in the formula (3-1); ^{X 2} represents a single bond; ^{W 7} is hydrogen; ^{m 5} The polymerizable liquid crystal composition according to claim 2, wherein R is an integer of 4 to 6; and R ¹ is cyano. The second component is at least one compound selected from the group of compounds represented by formula (2-2), and the content ratio of the first component to the polymerizable liquid crystal composition is in the range of 1 to 25% by weight. Yes, the content ratio of the second component is in the range of 50 to 98% by weight, the content ratio of the third component is in the range of 1 to 25% by weight, and in the formulas (1-1) and (1-2) Y ¹ and Y ² are independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² are independently hydrogen or fluorine; m ¹ , m ² , n ¹ , and n ^2; Are independently an integer of 2 to 10, in formula (2-2); X ¹ is a group represented by —O— or (X ¹ -2); W ⁶ is hydrogen or methyl; m ⁴ and n ⁴ are independently an integer from 2 to 10,

In Formula (3-1), X ² is a single bond, —COO—, or —OCO—; W ⁷ is hydrogen; m ⁵ is an integer of 2 to 10, R ¹ is cyano, and the number of carbon atoms The polymerizable liquid crystal composition according to claim 1, which is alkyl having 2 to 8 or alkoxy having 2 to 8 carbon atoms. The content ratio of the first component relative to the polymerizable liquid crystal composition is in the range of 7 to 22% by weight, the content ratio of the second component is in the range of 56 to 86% by weight, and the content ratio of the third component is 7 to 7%. In the formula (1-1) and formula (1-2); Y ¹ and Y ² are each independently a single bond or — (CH ₂ ) ₂ —; W ¹ and W ² Is hydrogen; m ¹ , m ² , n ¹ , and n ² are each independently an integer of 4 to 6, and in formula (2-2); W ⁶ is methyl; X ¹ is —O— M ⁴ and n ⁴ are each independently an integer of 4 to 6, and in formula (3-1); X ² is a single bond; W ⁷ is hydrogen; m ⁵ is 4 to 6 The polymerizable liquid crystal composition according to claim 4, which is an integer; and R ¹ is cyano. A polymerizable liquid crystal composition comprising the polymerizable liquid crystal composition according to any one of claims 1 to 5 and a silane coupling agent represented by the formula (4), wherein the polymerizable liquid crystal composition: A polymerizable liquid crystal composition having a ratio of 100: 1 to 100: 10 by weight with respect to the silane coupling agent.

In formula (4), R ⁴ is methyl or ethyl, and n ⁸ is an integer of 1 to 5. A polymer obtained by polymerizing the polymerizable liquid crystal composition according to any one of claims 1 to 6 . The polymer film which has optical anisotropy obtained by polymerizing the composition of any one of Claim 1 to 6 . Use of the polymer film having optical anisotropy according to claim 8 as a retardation plate. A liquid crystal display device using the polymer film having optical anisotropy according to claim 9 . Compound represented by formula (1-1).

In formula (1-1); Y ¹ is independently a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ¹ is independently hydrogen or fluorine; m ¹ and n ¹ Are independently an integer from 2 to 15. The compound represented by Formula (7).

In Formula (7); Y ⁵ is — (CH ₂ ) ₂ — or —CH═CH—; m ⁸ and n ⁸ are each independently an integer of 2 to 15. The compound represented by Formula (8).

In Formula (8); W ¹ is independently hydrogen or fluorine; m ⁹ and n ⁹ are each independently an integer of 2 to 15. The compound represented by Formula (9).

In Formula (9); Y ⁶ is a single bond, — (CH ₂ ) ₂ — or —CH═CH—; W ² is independently hydrogen or fluorine; m ¹⁰ and n ¹⁰ are independently 2 And when W ² is hydrogen, Y ⁶ is independently — (CH ₂ ) ₂ — or —CH═CH—.

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