JP5125076B2 - Polymerizable compound and polymer thereof - Google Patents

Description

  The present invention relates to a compound having a bisphenol skeleton, a composition containing the compound, a polymer obtained from the composition, its use, and the like.

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 alignment of liquid crystal molecules is fixed by polymerization. An example of such a compound is a liquid crystal compound having —O—CO—CH═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 can be copolymerized with a polymerizable compound having no liquid crystallinity. At this time, the non-liquid crystal compound has a role of controlling characteristics of the obtained copolymer. Therefore, development of a polymerizable non-liquid crystal compound is important for obtaining a polymer having appropriate optical anisotropy. Up to now, as a liquid crystal composition of PDLC (Polymer Dispersed Liquid Crystal), a polymerizable compound having a non-linear structure having a divalent ether group having a divalent central group angle of less than 180 degrees as a central skeleton is used. Although the composition containing it is introduced, there is no invention of the film which has the optical anisotropy using this (patent document 4).

JP 2001-055573 A JP 2001-154019 A JP-A-2005-060373 JP-A-8-209129

  The present invention relates to a polymerizable compound that does not exhibit a liquid crystal phase and is easily polymerized at room temperature, easily photopolymerized, easily dissolved in a solvent, colorless, chemically stable, and a polymerizable liquid crystal compound. An object of the present invention is to provide a compound that satisfies a plurality of characteristics in properties such as good compatibility and good wettability with respect to a supporting substrate, and has an appropriate balance with respect to the plurality of characteristics. Another object of the present invention is to provide a composition containing such a polymerizable compound and a polymer obtained from the composition.

  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. The present inventors have studied a method for controlling the alignment of liquid crystal molecules by copolymerizing a polymerizable compound that does not exhibit a liquid crystal phase with a polymerizable liquid crystal compound, and have found a compound (1). That is, the problem of the present invention is solved by the compound represented by the following item [1].

ここに、Ｚ^１は−ＣＨ_２−、−ＣＯ−、−（ＣＨ_２）_２−ＣＯ−または−ＣＨ＝ＣＨ−ＣＯ−であり、そしてＺ^２は−ＣＨ_２−、−ＣＯ−、−ＣＯ−（ＣＨ_２）_２−または−ＣＯ−ＣＨ＝ＣＨ−であり；Ａは独立して１，４−シクロへキシレン、１，４−フェニレン、ピリジン−２，５−ジイル、ナフタレン−２，６−ジイルまたはテトラヒドロナフタレン−２，６−ジイルであり、そしてこの１，４−フェニレンにおいて、任意の水素は塩素またはフッ素で置き換えられてもよく、任意の１つまたは２つの水素はシアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、またはトリフルオロメチルで置き換えられてもよく；Ｘ^１は−Ｏ−、−Ｏ−（ＣＨ_２）_ｒ−、−Ｏ−（ＣＨ_２）_ｒ−Ｏ−または−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｓ−であり、Ｘ^２は−Ｏ−、−（ＣＨ_２）_ｒ−Ｏ−、−Ｏ−（ＣＨ_２）_ｒ−Ｏ−または−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｓ−であり、ｒは１〜２０の整数であり、そしてｓは２〜５の整数であり；Ｐ^１は独立して式（Ｐ１）〜式（Ｐ８）のいずれか１つで表される重合性の基であり；そして、Ｑは式（Ｑ１）〜式（Ｑ１７）のいずれか１つで表される基である：

（ここに、ｎは０〜１５の整数である。）

[1] Compound represented by formula (1):

Here, Z ¹ is —CH ₂ —, —CO—, — (CH ₂ ) ₂ —CO— or —CH═CH—CO—, and Z ² is —CH ₂ —, —CO—, —CO - _{(CH 2) 2} - or -CO-CH = CH- and is; a is xylene independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, naphthalene-2,6 -Diyl or tetrahydronaphthalene-2,6-diyl and in this 1,4-phenylene any hydrogen may be replaced by chlorine or fluorine, and any one or two hydrogens are cyano, methyl, May be replaced by ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl; X ¹ is —O—, —O— (CH _{2 ) R -, - O- (CH} 2) r -O- or _{-O- (CH 2 CH 2 O)} s - a and, ^{X 2} is _{-O -, - (CH 2)} r -O -, - O - _{(CH 2)} r -O- or _{-O- (CH 2 CH 2 O)} s - a and, r is an integer from 1 to 20, and s is 2-5 integer; ^{P 1} is independently A polymerizable group represented by any one of formulas (P1) to (P8); and Q is a group represented by any one of formulas (Q1) to (Q17) Is:

(Here, n is an integer from 0 to 15.)

  The compound of the present invention is easily polymerized at room temperature, easily photopolymerized, easily dissolved in a solvent, colorless, chemically stable, and has good compatibility with a polymerizable liquid crystal compound, and wettability to a supporting substrate. In the characteristics such as “good”, a plurality of characteristics are satisfied, and an appropriate balance is provided regarding these characteristics. . This compound can be used to control the alignment of liquid crystal molecules. Since this compound can use a commercially available compound, it can manufacture easily and can also manufacture in low cost. The polymer of the present invention has homogeneous, homeotropic, hybrid, etc. orientation and few orientation defects. This polymer film has optical anisotropy, 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 multiple characteristics.

  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 formula (1), formula (M1), or the like may be represented as compound (1), compound (M1), or the like. Acrylate and methacrylate may be collectively referred to as (meth) acrylate.

  The term “arbitrary” means “can be freely selected not only in position but also in number”. For example, the expression “any A may be replaced with B, C, D, or E” means that one A may be replaced with B, C, D, or E, and In addition to the meaning that any may be replaced by any one of B, C, D and E, A replaced by B, A replaced by C, A replaced by D, and E replaced It also means that at least two of A may be mixed.

The present invention comprises the above-mentioned item [1] and the following items [2] to [21].
[2] Q is a group represented by any one of formula (Q1), formula (Q6) to formula (Q9), formula (Q14), formula (Q16), and formula (Q17); 1,4-cyclohexylene or 1,4-phenylene, and any hydrogen in 1,4-phenylene may be replaced by chlorine or fluorine; X ¹ is —O—, —O— ( CH ₂ ) _r — or —O— (CH ₂ ) _r —O—, and X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—. And the compound according to item [1], wherein r is an integer of 1 to 15.

[3] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14), and formula (Q16); A is independently 1,4 -Cyclohexylene or 1,4-phenylene, and any hydrogen in the 1,4-phenylene may be replaced by chlorine or fluorine; X ¹ is -O-, -O- (CH ₂ ) _r — Or —O— (CH ₂ ) _r —O—, X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is The compound according to item [1], which is an integer of 1 to 15.

[4] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14), and formula (Q16); A is independently 1,4 - cyclohexylene, it is 1,4-phenylene or 2-fluoro-1,4-phenylene; ^{X 1} is _{-O -, - O- (CH 2} ) r - or -O- _{(CH 2)} r -O The item [1], wherein X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 15. Compound described in 1.

[5] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14), and formula (Q16); A is independently 1,4 -Cyclohexylene, 1,4-phenylene or 2-fluoro-1,4-phenylene; a polymerizable compound wherein P ¹ is independently represented by any one of formulas (P3) to (P6) A group; X ¹ is —O—, —O— (CH ₂ ) _r — or —O— (CH ₂ ) _r —O—, X ² is —O—, — (CH ₂ ) _r —O; The compound according to item [1], which is — or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 15.

[6] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Yes; both Z ¹ and Z ² are —CO—; P ¹ is a polymerizable group independently represented by any one of formulas (P1) to (P4); and X ¹ And X ² is independently —O— or —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 10,

[7] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Yes; Z ¹ and Z ² are both —CO—; P ¹ is a polymerizable group represented by any ^one of formulas (P1) to (P4); and X ¹ and X ² there a both -O- or _{-O- (CH 2) r -O-,} r is an integer from 1 to 6, [1] a compound according to claim.

[8] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Yes; Z ¹ and Z ² are both —CO—; P ¹ is a polymerizable group independently represented by any one of formulas (P5) to (P7); and X ¹ And X ² is independently —O— or —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 10,

[9] Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Yes; Z ¹ and Z ² are both —CO—; P ¹ is a polymerizable group represented by any ^one of formulas (P5) to (P7); and X ¹ and X ² there a both -O- or _{-O- (CH 2) r -O-,} r is an integer from 1 to 6, [1] a compound according to claim.

[10] A composition comprising at least one compound according to any one of [1] to [9].

ここに、Ｚ^１は−ＣＨ_２−、−ＣＯ−、−（ＣＨ_２）_２−ＣＯ−または−ＣＨ＝ＣＨ−ＣＯ−であり、そしてＺ^２は−ＣＨ_２−、−ＣＯ−、−ＣＯ−（ＣＨ_２）_２−または−ＣＯ−ＣＨ＝ＣＨ−であり；Ａは独立して１，４−シクロへキシレン、１，４−フェニレン、ピリジン−２，５−ジイル、ナフタレン−２，６−ジイルまたはテトラヒドロナフタレン−２，６−ジイルであり、そしてこの１，４−フェニレンにおいて、任意の水素は塩素またはフッ素で置き換えられてもよく、任意の１つまたは２つの水素はシアノ、メチル、エチル、メトキシ、ヒドロキシ、ホルミル、アセトキシ、アセチル、トリフルオロアセチル、ジフルオロメチル、またはトリフルオロメチルで置き換えられてもよく；Ｘ^１は−Ｏ−、−Ｏ−（ＣＨ_２）_ｒ−、−Ｏ−（ＣＨ_２）_ｒ−Ｏ−または−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｓ−であり、Ｘ^２は−Ｏ−、−（ＣＨ_２）_ｒ−Ｏ−、−Ｏ−（ＣＨ_２）_ｒ−Ｏ−または−Ｏ−（ＣＨ_２ＣＨ_２Ｏ）_ｓ−であり、ｒは１〜２０の整数であり、そしてｓは２〜５の整数であり；Ｐ^１は独立して式（Ｐ１）〜式（Ｐ８）のいずれか１つで表される重合性の基であり；そして、Ｑは式（Ｑ１）〜式（Ｑ１７）のいずれか１つで表される基である：

（ここに、ｎは０〜１５の整数である。）

式（Ｍ１）〜式（Ｍ４）において、Ｒ^１はフッ素、塩素、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^１は独立して水素、フッ素、塩素、メチル、エチル、シアノまたはトリフルオロメチルであり；Ｚ^３は単結合、−ＣＯ−Ｏ−または−Ｏ−ＣＯ−であり、Ｚ^４は独立して−Ｏ−または−Ｏ−ＣＯ−Ｏ−であり、そしてＺ^５は独立して単結合または−Ｏ−であり；Ｐ^２は独立して前記の式（Ｐ１）〜式（Ｐ８）のいずれか１つで表される重合性の基であり；そして、ｊおよびｋは独立して２〜１５の整数である。 [11] At least one of the compounds represented by formula (1) and at least selected from the group of compounds represented by each of formula (M1), formula (M2), formula (M3) and formula (M4) A composition containing one compound:

Here, Z ¹ is —CH ₂ —, —CO—, — (CH ₂ ) ₂ —CO— or —CH═CH—CO—, and Z ² is —CH ₂ —, —CO—, —CO - _{(CH 2) 2} - or -CO-CH = CH- and is; a is xylene independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, naphthalene-2,6 -Diyl or tetrahydronaphthalene-2,6-diyl and in this 1,4-phenylene any hydrogen may be replaced by chlorine or fluorine, and any one or two hydrogens are cyano, methyl, May be replaced by ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl; X ¹ is —O—, —O— (CH _{2 ) R -, - O- (CH} 2) r -O- or _{-O- (CH 2 CH 2 O)} s - a and, ^{X 2} is _{-O -, - (CH 2)} r -O -, - O - _{(CH 2)} r -O- or _{-O- (CH 2 CH 2 O)} s - a and, r is an integer from 1 to 20, and s is 2-5 integer; ^{P 1} is independently A polymerizable group represented by any one of formulas (P1) to (P8); and Q is a group represented by any one of formulas (Q1) to (Q17) Is:

(Here, n is an integer from 0 to 15.)

In Formula (M1) to Formula (M4), R ¹ is fluorine, chlorine, cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; W ¹ is independently hydrogen , Fluorine, chlorine, methyl, ethyl, cyano or trifluoromethyl; Z ³ is a single bond, —CO—O— or —O—CO—, and Z ⁴ is independently —O— or —O—. CO—O— and Z ⁵ is independently a single bond or —O—; P ² is a polymerization independently represented by any one of the above formulas (P1) to (P8) And j and k are each independently an integer of 2-15.

[12] In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); 1, 4-phenylene; both Z ¹ and Z ² are —CO—; and P ¹ is a polymerizable group independently represented by any one of formulas (P1) to (P4). And X ¹ and X ² are independently —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 10:
And in formulas (M1) to (M4), R ¹ is cyano or trifluoromethoxy; W ¹ is independently hydrogen, fluorine or methyl; Z ⁴ and Z ⁵ are both —O—; The composition according to item [11], wherein P ² is a polymerizable group independently represented by any one of formulas (P1) to (P4).

[13] In the formula (1), Q is a group represented by any one of the formula (Q6), the formula (Q8), the formula (Q9), the formula (Q14), and the formula (Q16); 1,4-phenylene; Z ¹ and Z ² are both —CO—; P ¹ is a polymerizable group represented by any ^one of formulas (P1) to (P4); and , X ¹ and X ² are both —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 6:
In Formulas (M1) to (M4), R ¹ is cyano; W ¹ is independently hydrogen or methyl; Z ³ is a single bond, and Z ⁴ and Z ⁵ are both —O—. Yes; and the composition according to item [11], wherein P ² is a polymerizable group represented by any one of formulas (P1) to (P4).

[14] In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); 1, 4-phenylene; both Z ¹ and Z ² are —CO—; and P ¹ is a polymerizable group independently represented by any one of formulas (P5) to (P7). And X ¹ and X ² are independently —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 10:
And in Formula (M1) to Formula (M4), R ¹ is cyano or trifluoromethoxy; W ¹ is independently hydrogen, fluorine or methyl; Z ⁴ is —O—; P ² is independently The composition according to item [11], which is a polymerizable group represented by any one of formulas (P5) to (P7).

[15] In the formula (1), Q is a group represented by any one of the formula (Q6), the formula (Q8), the formula (Q9), the formula (Q14), and the formula (Q16); 1,4-phenylene; Z ¹ and Z ² are both —CO—; P ¹ is a polymerizable group represented by any ^one of formulas (P5) to (P7); and , X ¹ and X ² are both —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 6:
In Formulas (M1) to (M4), R ¹ is cyano; W ¹ is independently hydrogen or methyl; Z ³ is a single bond; P ² is Formula (P5) to Formula (P7) The composition according to item [11], which is a polymerizable group represented by any one of

[16] In the formula (1), Q is a group represented by any one of the formula (Q6), the formula (Q8), the formula (Q9), the formula (Q14), and the formula (Q16); Independently 1,4-cyclohexylene, 1,4-phenylene or 2-fluoro-1,4-phenylene; X ¹ is —O—, —O— (CH ₂ ) _r — or —O— ( CH ₂ ) _r —O—, X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is an integer from 1 to 10 Yes:
And the ratio of the compound represented by Formula (1) is 5-30 on the basis of the total amount of the compound represented by each of the compound represented by Formula (1), and Formula (M1)-Formula (M4). The composition according to item [11], wherein the proportion of the compound selected from the group of compounds represented by each of the formulas (M1) to (M4) is 70 to 95% by weight.

ここに、Ｒ^２はメチルまたはエチルであり、そしてｍは１〜５の整数である。 [17] The composition according to item [16], further comprising a silane coupling agent represented by formula (2), wherein the weight ratio of the silane coupling agent to the total amount of the polymerizable compound is 0.01. A composition that is -0.1:

Here, R ² is methyl or ethyl, and m is an integer of 1-5.

[18] A polymer obtained by polymerizing the composition according to any one of [10] to [17].

[19] A polymer film having optical anisotropy obtained by polymerizing the composition according to any one of [10] to [17].

[20] Use of the polymer film having optical anisotropy according to the item [19] as a retardation plate.
[21] A liquid crystal display device comprising the polymer film having optical anisotropy according to the item [20].

式（１）における２つのＰ^１は、同一の基であってもよいし、または異なってもよい。Ａについても同様である。左右対称である化合物は、左右非対称である化合物に比べて安価であり、そして合成が容易である点で好ましい。非対称である化合物は、対称である化合物に比べて液晶分子の配向を広い範囲で制御しうる点で好ましい。 First, the characteristics of the compound (1) of the present invention will be described.

Two P ¹ in the formula (1) may be the same group or different. The same applies to A. A compound that is bilaterally symmetric is preferable in that it is less expensive and easier to synthesize than a compound that is bilaterally asymmetric. An asymmetric compound is preferable in that the alignment of liquid crystal molecules can be controlled over a wide range compared to a symmetric compound.

  Compound (1) has two polymerizable groups. This compound gives a hard polymer compared to a compound having one polymerizable group. 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, 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 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.

Next, the meaning range indicated by the symbols in the formula (1) will be described. Q is a divalent group of the bisphenol skeleton shown below.

  The compound (1) can be easily manufactured and can be manufactured at low cost because the raw material H-Q-H (that is, a compound having two phenol groups) can be obtained as a commercially available reagent.

  Preferred Q is a group represented by any of formula (Q1), formula (Q6) to formula (Q9), formula (Q14), formula (Q16) and formula (Q17). More preferable Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16). These are halogen-substituted or dimethyl-substituted compounds. The compound (1) containing this skeleton tends to have a lower melting point than an unsubstituted compound.

Z ¹ is —CH ₂ —, —CO—, — (CH ₂ ) ₂ —CO— or —CH═CH—CO—, and Z ² is —CH ₂ —, —CO—, —CO— (CH ₂ ) _2- or -CO-CH = CH-. A preferred example of Z ¹ is —CO—. A preferred example of Z ² is also —CO—.

  Two A's are each independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, naphthalene-2,6-diyl or tetrahydronaphthalene-2,6-diyl. In this 1,4-phenylene, any hydrogen may be replaced by chlorine or fluorine, and any one or two hydrogens may be cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl. , Difluoromethyl or trifluoromethyl.

  Preferred A is 1,4-cyclohexylene or 1,4-phenylene, and in this 1,4-phenylene, any hydrogen may be replaced with chlorine or fluorine. More preferable A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2-chloro-1,4-phenylene, 2- Methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or 2,6-difluoro- 1,4-phenylene.

  Particularly preferred A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene. Most preferred A is 1,4-phenylene.

X ¹ is —O—, —O— (CH ₂ ) _r —, —O— (CH ₂ ) _r —O— or —O— (CH ₂ CH ₂ O) _s —, and X ² is —O—. _{, - (CH 2) r -O} -, - O- (CH 2) r -O- or _{-O- (CH 2 CH 2 O)} s - a and, r is an integer from 1 to 20, and s Is an integer of 2-5.

Preferred X ¹ is —O—, —O— (CH ₂ ) _r — or —O— (CH ₂ ) _r —O—, and preferred X ² is —O—, — (CH ₂ ) _r —O— or -O- _{(CH 2)} a r -O-, and r is an integer from 1 to 15. More preferred examples of X ¹ and X ² are —O— and —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 10. At this time, the more preferable range of r is 1-6.

P ¹ is a polymerizable group represented by any ^one of formulas (P1) to (P8). N in the formula (P7) is an integer of 0 to 15. The names of these groups are acryloyl, methacryloyl, α-trifluoromethacryloyl, α-fluoroacryloyl, 3-ethyl-3-oxetanylmethyl, 3-methyl-3-oxetanylmethyl, 2-oxiranylalkyl, respectively. And vinyl. Preferred P ¹ is a group represented by any one of formula (P1), formula (P5), formula (P6) and formula (P7). In addition, the preferable range of n in Formula (P7) is 0-10, and a more preferable range is 0-6. In the compound (1), when left and right P ¹ are the same group, this compound is more preferable in that synthesis is easy.

  Next, the composition of the present invention will be described. The composition of the present invention is a composition containing at least one compound (1). A preferred composition of the present invention is a composition comprising at least one compound (1) and at least one polymerizable compound selected from the group consisting of compounds (M1) to (M4). The compounds (M1) to (M4) are polymerizable liquid crystal compounds. That is, the composition of the present invention is a polymerizable composition containing a liquid crystal compound.

In Formula (M1) to Formula (M4), R ¹ is chlorine, fluorine, cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons. Preferred examples of R ¹ are cyano and trifluoromethoxy, and a more preferred example is cyano.

W ¹ is independently hydrogen, fluorine, chlorine, methyl, ethyl, cyano or trifluoromethyl. Preferred examples of W ¹ are hydrogen, fluorine and methyl, and more preferred examples are hydrogen and methyl.

Z ³ is a single bond, —CO—O— or —O—CO—. Preferred Z ³ is a single bond. Z ⁴ is independently —O— or —O—CO—O—. Preferred Z ⁴ is —O—.
Z ⁵ is a single bond or —O—, and preferred Z ⁵ is —O—.

P ² is independently a group represented by any one of the above formulas (P1) to (P8). That is, P ² has the same meaning as P ¹ in formula (1), and preferred examples are also the same as P ¹ .

  j and k are independently integers of 2 to 15. A preferred range for j or k is 2-8. More preferably, j and k are the same.

Preferred examples of the compounds represented by formula (M1) to formula (M4) are shown below.

Preferred examples of the composition of the present invention are shown below. The weight% shown here is a ratio based on the total amount of polymerizable compounds.
<Composition Example 1>
First component: at least one of compounds (1) in which P ¹ is ^one of (P1) to (P4)
: 5 to 30% by weight
Second component: ^{P 2} is (P1) ~ at least one selected from the group which is one compound of (P4) (M1) ~ compound (M4): 70 to 95 wt%
<Composition Example 2>
First component: at least one of compounds (1) in which P ¹ is ^one of (P5) to (P7)
: 5 to 30% by weight
Second component: ^{P 2} is (P5) ~ 1 On One compound of (P7) (M1) at least one selected from the group of - compound (M4): 70 to 95 wt%

The more preferable example of the composition of this invention is shown next.
<Composition Example 3>
First component: at least one of compounds (1) in which P ¹ is ^one of (P1) to (P4)
: 5 to 30% by weight
Second component: ^{P 2} is (P1) ~ one in which the compound of (P4) (M1), at least one selected from the group of compounds (M2) and the compound (M4): 70 to 95 wt%
<Composition Example 4>
First component: at least one of compounds (1) in which P ¹ is ^one of (P5) to (P7)
: 5 to 30% by weight
Second component: ^{P 2} is (P5) ~ one in which the compound of (P7) (M1), at least one selected from the group of compounds (M3) and the compound (M4): 70 to 95 wt%

  A silane coupling agent may be added to Composition Example 1 and Composition Example 3. A preferable addition ratio of the silane coupling agent is 0.01 to 0.1 by weight ratio with respect to the total amount of the polymerizable compound.

式（２）において、Ｒ^２はメチルまたはエチルであり、ｍ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 (2) is preferable.

In the formula (2), R ² is methyl or ethyl, and m is an integer of 1 to 5.

  The polymerizable liquid crystal composition of the present invention may further contain other polymerizable compounds and additives as necessary. Other polymerizable compounds are used to further adjust 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, and a non-liquid crystalline polyfunctional monomer. 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 these compounds where one of the alkoxy groups (three) is replaced by methyl. 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 the range of 100 ppm to 5% by weight based on the total amount 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. Preferable commercial products are Irganox 245, Irganox 1035, etc. manufactured by Ciba Specialties.

  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 0.001 to 0.1 μm. A more preferable particle size is 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 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 a radical photopolymerization initiator is suitable for the composition (MIX1) or (MIX3).

  Examples of the cationic photopolymerization initiator include diaryliodonium salts and triarylsulfonium salts.

  An example of a trade name of the photocationic polymerization initiator is DTS-102 from Midori Chemical Co., Ltd. Examples of this are U.S.C. 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 are Rhodia's PHOTOINITIATOR 2074, Ciba Specialty's IRGACURE250, GE Silicones' UV-9380C, and the like. Such an initiator is suitable for the composition (MIX2) or (MIX4).

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, 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, four Carbon chloride, dichloroethane, tetrachloroethylene, trichlorethylene Tetrachlorethylene, 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. These solvents may be used when the polymerizable liquid crystal composition of the present invention is applied 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 (Osaka Organic Chemical Co., Ltd., trade name: Biscoat 7 0), and polyethylene glycol diacrylate. These compounds are sometimes added to the compositions (MIX1) and (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. When a polymer having an excellent orientation is obtained, 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.

Preferred types of light used for photopolymerization include ultraviolet light, visible light, infrared light, and the like. Electromagnetic waves such as electron beams and X-rays may be used. Usually, ultraviolet rays or visible rays are preferable. 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 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 . A preferable illuminance is 0.1 to 5000 mW / cm ² . Further preferable illuminance is 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, factors that determine the alignment of liquid crystal molecules are 1) the type of compound contained in the composition, 2) the type of support substrate, and 3) the method of alignment treatment. 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.

  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.

  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) .

Compound (1) of the present invention is synthesized as follows. For the synthesis of a compound 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). A method for producing the linking group Z is disclosed in JP-A-2003-277359 (paragraphs 0040 to 0053). The synthesis scheme of compound (1) will be exemplified and described.

In formula (1), compound (1-A) in which Z ¹ and Z ² are both —CO— is synthesized according to scheme 1. That is, the compound (1-A) is synthesized by esterification of HQH [a] and 2 equivalents of [b].

<Scheme 1>
Synthesis of compound (1-A)

The compound (1-B) in which Z ¹ and Z ² are both —CH ₂ — is synthesized according to Scheme 2. That is, the compound (1-B) is synthesized by an etherification reaction between HQH [a] and 2 equivalents of bromide [c]. Bases used for the etherification reaction include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like.

<Scheme 2>
Synthesis of compound (1-B)

（ｎは１から１５の整数である）

(N is an integer from 1 to 15)

  Examples of compounds that can be synthesized by such a method are compounds (1-1-1) to (1-17-4).

A method for synthesizing the compounds (M1) to (M4) used as components of the composition of the present invention will be described. First, compounds having —O—CO—CH═CH ₂ are exemplified. A compound (M1) in which P ² is the formula (P1), W ¹ is hydrogen or methyl, Z ⁵ is —O—, and j and k are 4 or 6 is disclosed in JP-A-2003-238491. It is synthesized by the method described in 1. Compound (M2) wherein P ¹ is the formula (P1), W ¹ is hydrogen or methyl, Z ⁴ is —O—, Z ⁵ is —O—, and j and k are 4 or 6. Is synthesized according to the method described in Makromol. Chem., 190, 3201-3215 (1998). The compound (M3) in which P ² is the formula (P1), Z ⁵ is —O—, and j and k are 4 or 6 is synthesized according to the method described in JP-A No. 5-178794. A compound in which P ² is the formula (P1), W ¹ is hydrogen, R ¹ is cyano, Z ³ is —CO—O—, X ³ is —O—, and j is 6. (M4) is synthesized according to the method described in DE 19504224. A compound (M4) in which W ¹ is hydrogen, R ³ is cyano, Z ³ is a single bond, Z ⁵ is —O—, and j is 6 is Macromolecules, 26, 6132-6134 ( 1993).

Next, a method for synthesizing a compound having an oxetane ring is illustrated. A compound (M1) in which P ² is the formula (P5) or (P6), W ¹ is hydrogen or methyl, Z ⁵ is —O—, and j and k are 4 or 6 The compound is synthesized according to the method described in JP 2005-60373 A. A compound in which P ² is the formula (P5) or (P6), W ¹ is hydrogen or methyl, Z ⁴ is —O—, Z ⁵ is —O—, and j and k are 6 (M2) is synthesized according to the method described in WO02 / 28985 pamphlet. A compound (M4) in which R ¹ is cyano or fluorine, W ¹ is hydrogen, Z ³ is a single bond, Z ⁵ is —O—, and j is 3, 4 or 5, 24, 4531-4537 (1991).

Finally, the synthesis of a compound having an oxirane ring is illustrated. A compound (M1) in which P ² is the formula (P7), W ¹ is hydrogen or methyl, Z ⁵ is —O—, and j and k are 4 is described in JP-A-2005-60373. Synthesize according to the method. The compound (M2) in which P ² is the formula (P7), W ¹ is hydrogen or methyl, Z ⁴ is —O—, Z ⁵ is a single bond, and j is 0 is described in German Patent DE 19504224. Synthesize according to the method described in the specification. The compound (M3) in which P ² is the formula (P7), Z ⁵ is a single bond, and j and k are 1 is synthesized according to the method described in Macromolecules, 26, 1244-1247 (1993). A compound in which P ² is the formula (P7), R ¹ is cyano, W ¹ is hydrogen, Z ³ is a single bond, Z ⁵ is —O—, and j is 6 or 11. M4) is synthesized according to the method described in Macromol Chem. Phys, 196, 2941-2954 (1995).

  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. In the following examples, the unit liter of capacity is indicated by L. Display milliliters in mL.

<Confirmation of compound structure>
The structure of the synthesized compound was confirmed by measurement of proton NMR (Bruker: DRX-500) at 500 MHz. 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 measuring apparatus equipped with a polarizing microscope, and the temperature was raised 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, SA is a smectic A 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.

<Optical anisotropy (Δn)>
The retardation value (25 ° C.) of the polymer film was measured according to the above heat resistance test method. The thickness (d) of the polymer film was also measured. Since 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 visually by the following method based on the angle dependence of the transmitted light intensity.
(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.

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 of Compound (1-5-1)>

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

(First stage)
Under a nitrogen atmosphere, AK1 (28.6 g), 4,4′-ethylidenebisphenol (10.0 g) and 4-dimethylaminopyridine (0.55 g) were added to dichloromethane (200 mL). A solution of N′-dicyclohexylcarbodiimide (20.2 g) in dichloromethane (30 mL) was added dropwise, and the mixture was stirred at room temperature for 16 hours. The precipitated insoluble material was filtered, water was added to the filtrate, and the mixture was washed successively 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 (1-5-1) (20.0 g).
Melting point: 79-83 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.13 (d, 4H), 7.27 (d, 4H), 7.13 (d, 4H), 6.96 (d, 4H), 6. 41 (dd, 2H), 6.13 (dd, 2H), 5.82 (dd, 2H), 4.21 (s, 1H), 4.18 (t, 4H), 4.05 (t, 4H) ), 1.87-1.81 (m, 4H), 1.76-1.70 (m, 4H), 1.66 (d, 3H), 1.57-1.44 (m, 8H).

（第１段階）
窒素雰囲気下、ジクロロメタン（３０ｍＬ）にＡＫ１（１．４９ｇ）、２，２−ビス−（２，６−ジフルオロ−４−ヒドロキシフェニル）ヘキサフルオロプロパン（１．０ｇ）、４−ジメチルアミノピリジン（１．５ｍｇ）を加え、氷冷下でＮ，Ｎ’−ジシクロヘキシルカルボジイミド（１．０６ｇ）のジクロロメタン（５ｍＬ）溶液を滴下し室温で１６時間撹拌した。析出した不溶物をろ過し、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した後、減圧下で溶剤を留去した。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＝１９／１）で分取後、トルエンとエタノールの混合溶剤から再結晶し、化合物（１−９−３）（０．７０ｇ）を得た。
融点：６９−７９℃．
^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１６（ｄ，４Ｈ），７．１２（ｄ，４Ｈ），６．９９（ｄ，４Ｈ），６．４１（ｄｄ，２Ｈ），６．１３（ｄｄ，２Ｈ），５．８３（ｄｄ，２Ｈ），４．１９（ｔ，４Ｈ），４．０７（ｔ，４Ｈ），１．８８−１．８２（ｍ，４Ｈ），１．７６−１．７０（ｍ，４Ｈ），１．５７−１．４４（ｍ，８Ｈ）．
^１９Ｆ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：−６４．３（ｓ，６Ｆ），−１２３．１（ｄ，４Ｆ）． [Example 2]
<Synthesis of Compound (1-9-3)>

(First stage)
Under a nitrogen atmosphere, AK1 (1.49 g), 2,2-bis- (2,6-difluoro-4-hydroxyphenyl) hexafluoropropane (1.0 g), 4-dimethylaminopyridine (1) were added to dichloromethane (30 mL). 0.5 mg) was added, and a solution of N, N′-dicyclohexylcarbodiimide (1.06 g) in dichloromethane (5 mL) was added dropwise under ice cooling, followed by stirring at room temperature for 16 hours. The precipitated insoluble matter was filtered, water was added to the filtrate, and the mixture was washed with hydrochloric acid, a sodium hydroxide aqueous 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 (1-9-3) (0.70 g).
Melting point: 69-79 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.16 (d, 4H), 7.12 (d, 4H), 6.99 (d, 4H), 6.41 (dd, 2H), 6. 13 (dd, 2H), 5.83 (dd, 2H), 4.19 (t, 4H), 4.07 (t, 4H), 1.88-1.82 (m, 4H), 1.76 -1.70 (m, 4H), 1.57-1.44 (m, 8H).
¹⁹ F-NMR (CDCl ₃ ; δ ppm): -64.3 (s, 6F), -123.1 (d, 4F).

（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、撹拌しながら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時間撹拌した後、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。溶剤を留去して３−（（トシルオキシ）メチル）−３−エチルオキセタン（２４３ｇ）を得た。 [Example 3]
<Synthesis of Compound (1-6-2)>

(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 (OX1; 60 g).
Melting point: 128 ° C.

(3rd stage)
Under a nitrogen atmosphere, OX1 (4.8 g), 2,2-bis (4-hydroxy-3-methylphenyl) propane (2.5 g), 4-dimethylamino obtained in the second step was added to dichloromethane (50 mL). Pyridine (0.25 g) was added, and a solution of N, N′-dicyclohexylcarbodiimide (4.5 g) in dichloromethane (5 mL) was added dropwise under ice cooling, followed by stirring at room temperature for 12 hours. The precipitated insoluble matter was filtered, water was added to the filtrate, and the mixture was washed successively 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 compound (1-6-2) (5.5 g).
Melting point: 118 ° C.
¹ H-NMR (CDCl ₃ ; δ ppm): 8.18 (d, 4H), 7.11-7.14 (m, 4H), 7.02-7.05 (m, 4H), 4.59 (D, 4H), 4.52 (d, 4H), 4.18 (s, 4H), 2.19 (s, 6H), 1.91 (q, 4H), 1.69 (s, 6H) , 0.96 (t, 6H).

[Example 4]
<Preparation of composition (PLC-1)>
A composition (MIX1) of 10% by weight of compound (1-6-1), 70% by weight of compound (K1), and 20% by weight of compound (K2) was prepared. Compound (K1) was synthesized by the method described in JP-A No. 2003-238491. Compound (K2) was synthesized by the method described in Macromolecules, 3938-3943, (23), 1990.

  Next, a polymerization initiator (trade name: IRGACURE 907 manufactured by Ciba Specialty Chemicals) having a weight ratio of 0.03 was added to the composition (MIX1), and then toluene was added to form a solution having a polymerizable compound concentration of 25% by weight. Prepared. This is designated as composition (PLC-1). Compound (1-6-1) showed good compatibility without phase separation. Further, the composition (PLC-1) was not immediately crystallized even at room temperature.

[Example 5]
<Preparation of composition (PLC-2)>
A composition (MIX2) containing 10% by weight of the compound (1-9-3), 70% by weight of the compound (K1), and 20% by weight of the compound (K2) was prepared.

  Next, a polymerization initiator (IRGACURE 907) with a weight ratio of 0.03 was added to the composition (MIX2), and then toluene was added to prepare a solution having a polymerizable compound concentration of 15% by weight. This is designated as a composition (PLC-2). The compound (1-9-3) showed good compatibility without phase separation. Further, the composition (PLC-2) was not immediately crystallized even at room temperature.

[Example 6]
<Preparation of composition (PLC-3)>
A composition (MIX3) containing 10% by weight of the compound (1-6-2), 70% by weight of the compound (K3), and 20% by weight of the compound (K4) was prepared. Compound (K3) was synthesized by the method described in JP-A-2005-60373. Compound (K4) was synthesized by performing an etherification reaction of 4′-hydroxy-cyanobiphenyl and 6-bromohexene and then oxidizing with m-chloroperbenzoic acid.

  Next, a polymerization initiator having a weight ratio of 0.03 (manufactured by Sun Apro; trade name CPI-100) was added to the composition (MIX3), and then cyclopentanone was added to obtain a solution having a polymerizable compound concentration of 20 wt% Was prepared. This is designated as a composition (PLC-3). Compound (1-6-2) showed good compatibility without phase separation. Further, the composition (PLC-3) was not immediately crystallized even at room temperature.

[Example 7]
<Preparation of composition (PLC-4)>
To the composition (PLC-1) described in Example 4, 10% by weight of the compound (5) based on the composition (MIX1) was added. Compound (5) is trade name Sila Ace S-330 manufactured by Chisso Corporation. This is designated as a composition (PLC-4).

[Example 8]
<Preparation of composition (PLC-5)>
To the composition (PLC-2) described in Example 5, 10% by weight of compound (5) based on composition (MIX2) was added. This is designated as a composition (PLC-5).

[Example 9]
<Preparation of composition (PLC-6)>
A composition (MIX4) containing 10% by weight of the compound (1-6-1), 60% by weight of the compound (K5), and 30% by weight of the compound (K2) was prepared. Compound (K5) can be synthesized by the method described in WO97 / 00600 pamphlet.

  Next, a polymerization initiator (IRGACURE 907) having a weight ratio of 0.03 was added to the composition (MIX4), and then cyclopentanone was added to prepare a solution having a polymerizable compound concentration of 20% by weight. This is designated as a composition (PLC-6). Compound (1-6-1) showed good compatibility without phase separation. Further, the composition (PLC-6) was not immediately crystallized even at room temperature.

[Example 10]
<Evaluation of polymer film (F1)>
A polyamic acid (Rixon aligner: PIA-5310 manufactured by Chisso Corporation) was applied onto a glass substrate (Matsunami slide glass: S-1112), dried at 80 ° C. for 3 minutes, and then baked at 210 ° C. for 30 minutes. The surface of the substrate was rubbed with a rayon cloth. The composition (PLC-1) described in Example 4 was applied onto the glass substrate using a bar coater. After application, the liquid crystal layer was aligned by removing the solvent by heat treatment in an oven set at 70 ° C. for 5 minutes. 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. Polymerization produced a polymer film (F1). In visual observation, the orientation of the film (F1) was hybrid.

[Example 11]
<Evaluation of polymer film (F2)>
The polymer film (F2) was treated in the same manner as in Example 10 except that the composition (PLC-2) described in Example 5 was used and a glass substrate (Matsunami slide glass: S-1112) was used as the support substrate. Got. In visual observation, the orientation of the film (F2) was homeotropic.

[Example 12]
<Evaluation of polymer film (F3)>
The polymer film (F3) was treated in the same manner as in Example 10 except that the composition (PLC-3) described in Example 6 was used and a glass substrate (Matsunami slide glass: S-1112) was used as the support substrate. Got. By visual observation, the orientation of the film (F3) was homeotropic.

[Example 13]
<Evaluation of polymer film (F4)>
The polymer film (F4) was treated in the same manner as in Example 10 except that the composition (PLC-4) described in Example 7 was used and a glass substrate (Matsunami slide glass: S-1112) was used as the support substrate. Got. In visual observation, the orientation of the film (F4) was homeotropic.

[Example 14]
<Evaluation of polymer film (F5)>
A polymer film was processed in the same manner as in Example 10 except that the composition (PLC-5) described in Example 8 was used, and a saponified TAC film (the film was not rubbed) was used as a support substrate. (F5) was obtained. By visual observation, the orientation of the film (F5) was homeotropic.

[Example 15]
<Evaluation of polymer film (F6)>
The polymer film (F6) was treated in the same manner as in Example 10 except that the composition (PLC-6) described in Example 9 was used and a glass substrate (Matsunami slide glass: S-1112) was used as the support substrate. Got. In visual observation, the orientation of the film (F6) was homeotropic.

Claims (21)

Compound represented by formula (1):

Here, Z ¹ is —CH ₂ —, —CO—, — (CH ₂ ) ₂ —CO— or —CH═CH—CO—, and Z ² is —CH ₂ —, —CO—, —CO - _{(CH 2) 2} - or -CO-CH = CH- and is; a is, xylene, 1,4-phenylene 1,4-cyclohexylene independently, and in this 1,4-phenylene, optionally the hydrogen may be replaced by chlorine or fluorine, any one or two hydrogen methylmercury, main butoxy, may be replaced by di-fluoromethyl or trifluoromethyl,; X ¹ is -O-, _{-O- (CH 2) r -,} - O- (CH 2) r -O- or _{-O- (CH 2 CH 2 O)} s - a and, ^{X 2} is _{-O -, - (CH 2)} r _{-O -, - O- (CH 2} ) r -O- or -O- _{(CH 2 CH} 2 ) _S - a and, r is an integer of 1-10, and s is integer of 2 or 3; ^{P 1} is represented by any one of independent equations (P1) ~ formula (P8) Q is a group represented by any one of formula (Q1) to formula (Q17):

(Here, n is an integer from 0 to 15.)

Q is a group represented by any one of formula (Q1), formula (Q6) to formula (Q9), formula (Q14), formula (Q16), and formula (Q17); A is independently 1 , 4-cyclohexylene or 1,4-phenylene, any hydrogen in the 1,4-phenylene may be replaced by chlorine or fluorine; X ¹ is —O—, —O— (CH ₂ ) _r − or —O— (CH ₂ ) _r —O—, X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r The compound of Claim 1 whose is an integer of 1-15. Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is independently 1,4-cyclo Xylene or 1,4-phenylene, and any hydrogen in the 1,4-phenylene may be replaced by chlorine or fluorine; X ¹ is —O—, —O— (CH ₂ ) _r — or — O— (CH ₂ ) _r —O—, X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is 1 to 15 The compound of claim 1, which is an integer of Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is independently 1,4-cyclo Xylene, 1,4-phenylene or 2-fluoro-1,4-phenylene; X ¹ is —O—, —O— (CH ₂ ) _r — or —O— (CH ₂ ) _r —O—. ^2. The compound according to claim 1, wherein X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1-15. . Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is independently 1,4-cyclo Xylene, 1,4-phenylene or 2-fluoro-1,4-phenylene; P ¹ is a polymerizable group independently represented by any one of formulas (P3) to (P6) X ¹ is —O—, —O— (CH ₂ ) _r — or —O— (CH ₂ ) _r —O—, and X ² is —O—, — (CH ₂ ) _r —O— or —; The compound of claim 1, which is O— (CH ₂ ) _r —O— and r is an integer from 1 to 15. Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Z ¹ and Z ² are both —CO—; P ¹ is independently a polymerizable group represented by any one of formulas (P1) to (P4); and X ¹ and X ² The compound according to claim 1, wherein is independently —O— or —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 10. Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group represented by any ^one of formulas (P1) to (P4); and X ¹ and X ² are both- O- or -O- _{(CH 2)} a r -O-, r is an integer from 1 to 6 a compound according to claim 1. Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Z ¹ and Z ² are both —CO—; P ¹ is independently a polymerizable group represented by any one of formulas (P5) to (P7); and X ¹ and X ² The compound according to claim 1, wherein is independently —O— or —O— (CH ₂ ) _r —O—, wherein r is an integer of 1 to 10. Q is a group represented by any one of formula (Q6), formula (Q8), formula (Q9), formula (Q14) and formula (Q16); A is 1,4-phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group represented by any ^one of formulas (P5) to (P7); and X ¹ and X ² are both- O- or -O- _{(CH 2)} a r -O-, r is an integer from 1 to 6 a compound according to claim 1.   A composition comprising at least one compound according to any one of claims 1 to 9. At least one compound represented by formula (1) and at least one compound selected from the group of compounds represented by formula (M1), formula (M2), formula (M3) and formula (M4), respectively A composition containing:

Here, Z ¹ is —CH ₂ —, —CO—, — (CH ₂ ) ₂ —CO— or —CH═CH—CO—, and Z ² is —CH ₂ —, —CO—, —CO - _{(CH 2) 2} - or -CO-CH = CH- and is; a is, xylene, 1,4-phenylene 1,4-cyclohexylene independently, and in this 1,4-phenylene, optionally the hydrogen may be replaced by chlorine or fluorine, any one or two hydrogen methylmercury, main butoxy, may be replaced by di-fluoromethyl or trifluoromethyl,; X ¹ is -O-, _{-O- (CH 2) r -,} - O- (CH 2) r -O- or _{-O- (CH 2 CH 2 O)} s - a and, ^{X 2} is _{-O -, - (CH 2)} r _{-O -, - O- (CH 2} ) r -O- or -O- _{(CH 2 CH} 2 ) _S - a and, r is an integer of 1-10, and s is integer of 2 or 3; ^{P 1} is represented by any one of independent equations (P1) ~ formula (P8) Q is a group represented by any one of formula (Q1) to formula (Q17):

(Here, n is an integer from 0 to 15.)

In Formula (M1) to Formula (M4), R ¹ is fluorine, chlorine, cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; W ¹ is independently hydrogen , Fluorine, chlorine, methyl, ethyl, cyano or trifluoromethyl; Z ³ is a single bond, —CO—O— or —O—CO—, and Z ⁴ is independently —O— or —O—. CO—O— and Z ⁵ is independently a single bond or —O—; P ² is a polymerization independently represented by any one of the above formulas (P1) to (P8) And j and k are each independently an integer of 2-15. In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); A is 1,4 -Phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group independently represented by any one of formulas (P1) to (P4); and , X ¹ and X ² are independently —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 10:
And in formulas (M1) to (M4), R ¹ is cyano or trifluoromethoxy; W ¹ is independently hydrogen, fluorine or methyl; Z ⁴ and Z ⁵ are both —O—; The composition according to claim 11, wherein P ² is a polymerizable group independently represented by any one of formulas (P1) to (P4). In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); A is 1,4 -Phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group represented by any ^one of formulas (P1) to (P4); and X ¹ And X ² are both —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 6:
In Formulas (M1) to (M4), R ¹ is cyano; W ¹ is independently hydrogen or methyl; Z ³ is a single bond, and Z ⁴ and Z ⁵ are both —O—. Yes; and the composition according to claim 11, wherein P ² is a polymerizable group represented by any one of formulas (P1) to (P4). In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); A is 1,4 -Phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group independently represented by any one of formulas (P5) to (P7); and , X ¹ and X ² are independently —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 10:
And in Formula (M1) to Formula (M4), R ¹ is cyano or trifluoromethoxy; W ¹ is independently hydrogen, fluorine or methyl; Z ⁴ is —O—; P ² is independently The composition according to claim 11, which is a polymerizable group represented by any one of formulas (P5) to (P7). In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); A is 1,4 -Phenylene; Z ¹ and Z ² are both -CO-; P ¹ is a polymerizable group represented by any ^one of formulas (P5) to (P7); and X ¹ And X ² are both —O— or —O— (CH ₂ ) _r —O—, and r is an integer of 1 to 6:
In Formulas (M1) to (M4), R ¹ is cyano; W ¹ is independently hydrogen or methyl; Z ³ is a single bond; P ² is Formula (P5) to Formula (P7) The composition of Claim 11 which is a polymeric group represented by any one of these. In Formula (1), Q is a group represented by any one of Formula (Q6), Formula (Q8), Formula (Q9), Formula (Q14), and Formula (Q16); A is independently 1,4-cyclohexylene, 1,4-phenylene or 2-fluoro-1,4-phenylene; X ¹ is —O—, —O— (CH ₂ ) _r — or —O— (CH ₂ ) _r ² —O—, X ² is —O—, — (CH ₂ ) _r —O— or —O— (CH ₂ ) _r —O—, and r is an integer from 1 to 10:
And the ratio of the compound represented by Formula (1) is 5-30 on the basis of the total amount of the compound represented by each of the compound represented by Formula (1), and Formula (M1)-Formula (M4). The composition according to claim 11, wherein the proportion of the compound selected from the group of compounds represented by each of the formulas (M1) to (M4) is 70 to 95% by weight. It is a composition of Claim 16 which further contains the silane coupling agent represented by Formula (2), Comprising: The weight ratio of the silane coupling agent with respect to the total amount of a polymeric compound is 0.01-0.1. The composition is:

Here, R ² is methyl or ethyl, and m is an integer of 1-5.   The polymer obtained by polymerizing the composition of any one of Claims 10-17.   The polymer film which has an optical anisotropy obtained by polymerizing the composition of any one of Claims 10-17.   Use of the polymer film having optical anisotropy according to claim 19 as a retardation plate.   The liquid crystal display element containing the polymer film which has the optical anisotropy of Claim 20.