JP5055757B2 - Liquid crystalline polyfunctional acrylate derivative and polymer thereof - Google Patents

Description

  The present invention relates to a liquid crystal compound having at least two acryloyloxy groups in the side chain, a composition containing this compound, a polymer obtained from this compound, and this use.

  In recent years, polymerizable liquid crystal compounds have been used for polymers having optical anisotropy such as polarizing plates and retardation plates. This is because this compound has optical anisotropy in the liquid crystal state, and the orientation of molecules in the liquid crystal is fixed by polymerization. Since the optical characteristics required for the polymer having optical anisotropy vary depending on the problem, a compound having the characteristics suitable for the problem is required. This compound is generally used after being formed into a polymer. In addition to the optical anisotropy, the compound used for such a problem has important characteristics regarding the polymer. These properties include polymerization rate, polymer transparency, mechanical strength, applicability, solubility, crystallinity, shrinkage, water permeability, water absorption, melting point, glass transition point, clearing point, chemical resistance, etc. .

  So far, liquid crystal compounds having various polymerization properties are known (for example, see Patent Documents 1 to 3). However, these compounds have room for improvement in properties such as liquid crystallinity, compatibility with other compounds, and optical anisotropy. Further, the polymer does not necessarily have suitable heat resistance, mechanical strength, chemical resistance, and the like. Therefore, a high upper limit temperature of the liquid crystal phase, a lower lower limit temperature of the liquid crystal phase, a wide temperature range of the liquid crystal phase, a compound having excellent compatibility, and a plurality of heat resistance, mechanical strength, chemical resistance, etc. using this compound. Development of a polymer that is excellent in the properties is a problem.

JP-A-7-17910 JP-A-8-3111 JP-A-9-316032

  The first object of the present invention is to provide a polymerizable liquid crystal compound having necessary characteristics such as optical anisotropy and a polymerizable liquid crystal composition containing the compound. The second problem is to provide a polymer excellent in a plurality of characteristics such as heat resistance, mechanical strength and chemical resistance, and a molded article having optical anisotropy obtained by using this polymer. . The third problem is an application utilizing the characteristics of the polymer. A fourth problem is to provide a liquid crystal display element containing this polymer.

  The present invention includes at least one compound represented by the following formula (1a) or (1b), a liquid crystal composition containing the compound, and a polymer obtained by polymerizing the compound or composition.

In Formula (1a) and Formula (1b), R ¹ is hydrogen, fluorine, chlorine, —CN, —NO ₂ , or alkyl having 1 to 20 carbons, and in this alkyl, any hydrogen is fluorine or chlorine. Any one or two of —CH ₂ — may be replaced with —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C. -In which case R ¹ may be an optically active group; Y ¹ and Y ² are independently alkylene having 1 to 20 carbons, in which any hydrogen is fluorine or May be replaced with chlorine, any —CH ₂ — may be replaced with —O—, and any one or two —CH ₂ — may be replaced with —COO— or —OCO—; And any one -CH ₂ - may be replaced by -CH = CH- or -C≡C-, in this case, ^{Y 1} or ^{Y 2} may be optically active ^{group; A 1, A 2, B} 1, and B ² is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6- Diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene- 2,7-diyl, 9,9-difluorofluorene-2,7-diyl, or a group selected from (K1), (K2) and (K3), and in this 1,4-phenylene, any hydrogen is F Any one or two hydrogens may be replaced by cyano, methyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl. X ¹ and X ² are each independently a single bond, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CONH—, —NHCO—, —CH═CH—COO—, _{-OOC-HC = CH -, -} (CH 2) 2 -COO -, - OOC- (CH 2) 2 -, - (CH 2) 2 -, or a -C≡C-; m is 0, 1 or 2, may be two of a ¹ and X ¹ are the same in each group when m is 2, may be a different group; G is hydrogen, fluorine, methyl, cyano or triflate, A Romechiru, the plurality of G may be the same group or may be different groups.

  The compound of the present invention is characterized by having two or four acryloyloxy groups in a liquid crystal molecule. Further, it has excellent compatibility with other polymerizable liquid crystal compounds, and further has necessary characteristics such as optical anisotropy. The polymer of the present invention is obtained by polymerizing this compound. Since this polymer has a high-density crosslinked structure, it has a large surface hardness and excellent heat resistance. A molded product obtained from this polymer has optical anisotropy and can be suitably used for a liquid crystal display element such as a retardation film.

  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 liquid crystal compound, a liquid crystal composition, and a liquid crystal display element may be referred to as a compound, a composition, and an element, respectively. Expressions (1a) and (1b) may be collectively referred to as Expression (1). The compounds represented by formula (1), formula (M1), formula (M2), and formula (M3) are referred to as compound (1), compound (M1), compound (M2), and compound (M3), respectively. There is. A polymer obtained from a composition containing the compound (1) or the like may be referred to as a polymer (1). “(Meth) acryloyloxy” means “acryloyloxy or methacryloyloxy”. “(Meth) acrylate” means “acrylate or methacrylate”. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”.

When the present invention attaches two or four polymerizable acryloyloxy groups to the side chain of a liquid crystal molecule, the compound polymerizes the compound, thereby polymerizing the compound having an optical anisotropy crosslinked at high density. The idea was that coalescence could be obtained. When research was conducted based on this idea, the experimental results were better than expected. Based on these results, studies were repeated and the present invention including the following items was completed.

[1] A compound represented by formula (1a) or formula (1b).

In formula (1a) and formula (1b), symbols such as A ¹ , B ¹ and Y ¹ were used. It means two symbols A ¹ may be the same or different. This rule also applies the symbols X ¹ and G. This rule also applies to other expressions.

In Formula (1a) and Formula (1b), R ¹ is hydrogen, fluorine, chlorine, —CN, —NO ₂ , or alkyl having 1 to 20 carbons, and in this alkyl, any hydrogen is fluorine or chlorine. Any one or two of —CH ₂ — may be replaced with —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C. -In which case R ¹ may be an optically active group,

In this alkyl, hydrogen may be replaced with fluorine or the like, and —CH ₂ — may be replaced with —O— or the like at the same time. That is, R ¹ contains alkyl in which hydrogen is replaced with fluorine or the like, and —CH ₂ — is replaced with —O—. The meaning of the phrase “any one or two of —CH ₂ — in alkyl may be replaced by —O—, —CH═CH—, etc.” is shown by way of example. Examples of the group in which any one or two of —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— are C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) ₂₋ , CH ₃ —O—CH ₂ —O—, H ₂ C═CH— (CH ₂ ) ₃ —, CH ₃ —CH═CH— (CH ₂ ) ₂ —, CH ₃ —CH═CH—CH _2- O- and the like. Thus, “arbitrary” means being randomly selected. That is, the term “arbitrary” means “not only a position but also a number can be freely selected”. 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. Considering the stability of the compound, CH ₃ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other is preferable to CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. . The expression “may be replaced” has a similar meaning elsewhere.

Preferred R ¹ is fluorine, chlorine, —CN, —NO ₂ , —OCF ₃ , alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons, and more preferred R ¹ is fluorine, chlorine, —CN , —OCF ₃ , alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons, in which case R ¹ may be an optically active group. More desirable R ¹ is fluorine, —CN, —OCF ₃ , alkyl having 1 to 13 carbons, or alkoxy having 1 to 13 carbons. In this case, R ¹ may be an optically active group. Particularly preferred R ¹ is —CN, —OCF ₃ , alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons. Specific examples of alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons are as follows: Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy or decyloxy.

Y ¹ and Y ² are independently alkylene having 1 to 20 carbon atoms, in which arbitrary hydrogen may be replaced by fluorine or chlorine, and arbitrary —CH ₂ — is replaced by —O—. Any one or two —CH ₂ — may be replaced by —COO— or —OCO—, and any one —CH ₂ — may be —CH═CH— or —C≡C; -In which case Y ¹ or Y ² may be an optically active group,

Preferred Y ¹ and Y ² are independently —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —, — (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 10, s is an integer of 1 to 5. More preferable Y ¹ and Y ² are —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, —O— (CH ₂ ) _r —. O—, or —O— (CH ₂ CH ₂ O) _s —, r is an integer of 2 to 10, and s is an integer of 1 to 5, in which Y ¹ or Y ² is optically active. It may be a basic group. Further preferred Y ¹ or Y ² is represented by the formula (Y3), wherein X ³ is a single bond or —O—, and q is an integer of 0 to 10.

Specific examples of preferred Y ¹ and Y ² are —O—, —CH ₂ —O—, —CH ₂ CH ₂ —O—, —CH ₂ CH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ CH ₂ O. _{-, - CH 2 CH 2 CH} 2 CH 2 CH 2 O -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -O -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -O _{-, - CH 2 CH 2 CH} 2 CH 2 CH 2 CH 2 CH 2 CH 2 -O -, - CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -O -, - CH 2 CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —O—, —O—CH ₂ —O—, —O—CH ₂ CH ₂ —O—, —O—CH ₂ CH ₂ CH _{2 -O -, - O-CH 2} CH 2 CH 2 CH 2 -O- _{-O-CH 2 CH 2 CH 2} CH 2 CH 2 -O -, - O-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -O -, - O-CH 2 CH 2 CH 2 CH 2 CH 2 CH ₂ CH ₂ —O—, —O—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —O—, —O—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -O-, or _{-O-CH 2 CH 2 CH 2} CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 is -O-.

A ¹ , A ² , B ¹ and B ² are each independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2, 6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene- 2,7-diyl, 9-chlorofluorene-2,7-diyl, 9,9-difluorofluorene-2,7-diyl, or a group selected from (K1), (K2) and (K3); In this 1,4-phenylene, any hydrogen may be replaced by fluorine or chlorine, and any one or two hydrogens may be cyano, methyl, methoxy, hydroxy, formyl , Acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl.

Preferred A ¹ , A ² , B ¹ and B ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methyl. Fluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl or a group selected from (K1), (K2) and (K3) In this 1,4-phenylene, any hydrogen may be replaced with fluorine, any one hydrogen may be replaced with methyl, trifluoromethyl, methoxy, acetoxy, or acetyl, and any two Hydrogen may be replaced with trifluoromethyl,

More preferred A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6 -Difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, or 2-trifluoromethyl-1,4-phenylene, more preferred A ¹ and A ² are independently 1,4-cyclo Hexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2-methyl-1,4-phenylene.

More preferable B ¹ and B ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-. Diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2, 3,5,6-tetrafluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2-methoxy-1,4-phenylene, 2-acetyl -1,4-phenylene, or 2,3-ditrifluoromethyl-1,4-phenylene, and more preferable B ¹ and B ² are independently 1,4-cyclohexylene, 1,4-fluoro Enylene, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoro Methyl-1,4-phenylene or 2,3-ditrifluoromethyl-1,4-phenylene.

These ring structures may be bonded in the opposite directions in Formula (1). When compound (1) has 1,4-cyclohexylene, its steric configuration is preferably trans rather than cis. Compound (1) may contain an isotope element such as ² H (deuterium) or ¹³ C in an amount higher than the naturally existing ratio, and even in this case, there is no significant difference in the physical properties of the compound.

X ¹ and X ² are each independently a single bond, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CONH—, —NHCO—, —CH═CH—COO—, —OOC— HC═CH—, — (CH ₂ ) ₂ —COO—, —OOC— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —, or —C≡C—.

Preferred X ¹ or X ² is independently a single bond, —COO—, —OCO—, —CH═CH—COO—, —OOC—HC═CH—, — (CH ₂ ) ₂ —COO—, —OOC—. (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —, or —C≡C—, and more preferable X ¹ and X ² are independently a single bond, —COO— or —OCO—.

m is 0, 1 or 2, and when m is 2, the two A ¹ and X ¹ may be the same group or different groups. Preferred m is 0 or 1.

  G is hydrogen, fluorine, methyl, cyano, or trifluoromethyl, and a plurality of G may be the same group or different groups. Preferred G is methyl, fluorine or hydrogen, and more preferred G is hydrogen.

[2] In Formula (1a) and Formula (1b), R ¹ is fluorine, chlorine, —CN, —NO ₂ , —OCF ₃ , alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons. Y ¹ and Y ² are each independently —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, —O— (CH ₂ ) _r; —O— or —O— (CH ₂ CH ₂ O) _s —, r is an integer from 1 to 10, and s is an integer from 1 to 5; A ¹ , A ² , B ¹ , and B ² is independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene. -2,7-diyl, 9,9-dimethylfluorene-2,7-diyl or (K1), A group selected from (K2) and (K3), and in this 1,4-phenylene, any hydrogen may be replaced by fluorine, and any one hydrogen may be methyl, trifluoromethyl, methoxy, acetoxy, Or acetyl, and any two hydrogens may be replaced with trifluoromethyl; X ¹ or X ² are independently a single bond, —COO—, —OCO—, —CH═CH _{-COO -, - OOC-HC =} CH -, - (CH 2) 2 -COO -, - OOC- (CH 2) 2 -, - (CH 2) 2 -, or a -C≡C-, m The compound according to [1], wherein is 0 or 1; G is methyl, fluorine or hydrogen.

[3] A compound represented by any one of formulas (3) to (6).

In Formulas (3) to (6), R ¹ is —CN, —OCF ₃ , alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; A ¹ and A ² are independently 1, 4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl- 1,4-phenylene or 2-trifluoromethyl-1,4-phenylene; B ¹ and B ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6- Diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1 , 4-Fe Nylene, 2,3-difluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4 -Phenylene, 2-methoxy-1,4-phenylene, 2-acetyl-1,4-phenylene, or 2,3-ditrifluoromethyl-1,4-phenylene; X ¹ and X ² are each independently a single bond, -COO -, - OCO -, - CH = CH-COO -, - OOC-HC = CH -, - (CH 2) 2 -COO -, - OOC- (CH 2) 2 -, - (CH 2) 2 —, Or —C≡C—; X ³ is a single bond or —O—; q is an integer of 0 to 10, and a plurality of X ³ and q may be the same or different. May be.

[4] In the formulas (3) to (6), R ¹ is —CN, —OCF ₃ , alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; A ¹ and A ² are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2-methyl-1,4-phenylene; B ¹ and B ² are independently 1,4 -Cyclohexylene, 1,4-phenylene, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1,4-phenylene, 2-methyl-1 , 4-phenylene, 2-trifluoromethyl-1,4-phenylene, or 2,3-ditrifluoromethyl-1,4-phenylene; X ¹ and X ² are independently a single bond, —COO— or -OCO- The compound according to [3], wherein X ³ is a single bond or —O—; and q is an integer of 0 to 10.

[5] A compound represented by formula (3), wherein in formula (3), R ¹ is —CN; A ² is 1,4-phenylene; B ¹ is 1,4-phenylene. The compound according to [3], wherein X ² is a single bond; X ³ is a single bond or —O—; and q is an integer of 0 to 10.

[6] A compound represented by formula (5), wherein in formula (5), A ² is 1,4-phenylene; B ² is 1,4-phenylene; X ² is —COO—. Yes; The compound according to [3], wherein X ³ is a single bond or —O—; and q is an integer of 0 to 10.

[7] A compound represented by formula (6), wherein in formula (6), A ¹ and A ² are 1,4-phenylene; B ² is 1,4-phenylene, 9-methylfluorene-2 , 7-diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is a single bond or —O—; q is The compound according to [3], which is an integer of 0 to 10.

[8] A composition containing at least one compound according to any one of [1] to [2] as a first component.

[9] A composition containing at least one compound according to any one of [3] to [7] as a first component.

[10] The composition according to [9], further containing a polymerizable compound different from the compound according to any one of [1] to [7] as a second component.

[11] The composition according to [10], wherein the second component is at least one compound selected from the group of compounds represented by formula (M1), formula (M2) and formula (M3).

In the formulas (M1), (M2) and (M3), B ³ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1 , 4-phenylene, 2,3-ditrifluoromethyl-1,4-phenylene, naphthalene-2,6-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, or 9,9-dimethylfluorene-2,7-diyl; R ² is fluorine, —OCF ₃ , —CN, alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons; X ⁵ is independently A single bond, — (CH ₂ ) ₂ — or —C═C—; X ⁶ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —OOC—HC═CH— Or -C≡C- P and t are each independently an integer from 1 to 20; G ² is hydrogen, fluorine, methyl or trifluoromethyl; W ¹ , W ² , W ³ , W ⁴ and W ⁵ are independently hydrogen Or fluorine; W ⁶ and W ⁷ are independently hydrogen or methyl, the carbon to which * is attached is an asymmetric carbon, and a plurality of X ⁵ , t, and G ² may be the same , May be different.

[12] The first component is a compound represented by the formula (6) described in [3], wherein in the formula (6), A ¹ and A ² are 1,4-phenylene; B ² is 1 , 4-phenylene, 9-methylfluorene-2,7-diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is A single bond or -O-; comprising at least one compound selected from the group consisting of compounds wherein q is an integer of 0 to 10;
The second component is a compound represented by the formula (M1), and in the formula (M1), B ³ is 1,4-phenylene, 2-methyl-1,4-phenylene, 2,3-ditrifluoromethyl- 1,4-phenylene, it is a 9-methyl-2,7-diyl or 9,9-dimethyl-2,7-diyl,; ^{X 5} is a single bond or - _{(CH 2) 2} - a is; p And t is an integer of 1 to 20; G ² is hydrogen; and W ¹ , W ² , W ³ and W ⁴ are at least one compound selected from the group consisting of hydrogen or fluorine,
[11] The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to the total amount of the first component and the second component of 100% by weight. The composition as described.

[13] The first component is a compound represented by the formula (6) described in [3], wherein in the formula (6), A ¹ and A ² are 1,4-phenylene; B ² is 1 , 4-phenylene, 9-methylfluorene-2,7-diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is A single bond or -O-; comprising at least one compound selected from the group consisting of compounds wherein q is an integer of 0 to 10;
A compound represented by formula (M3) as a second component, wherein in formula (M3), G ² is hydrogen; at least one selected from the group consisting of compounds wherein W ⁶ and W ⁷ are hydrogen or methyl Containing a compound,
[11] The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to the total amount of the first component and the second component of 100% by weight. The composition as described.

[14] A polymer obtained by polymerizing the compound according to any one of [1] to [7].

[15] A polymer obtained by polymerizing the composition according to any one of [8] to [13].

[16] A molded article having optical anisotropy comprising the polymer according to [14] or [15].

[17] A liquid crystal display device containing the molded article having optical anisotropy according to [16].

[18] Use of the polymer according to [14] or [15] as a molded article having optical anisotropy.

First, the compound of the present invention will be described. Compound (1a) or (1b) has the following characteristics.
a) The compound (1a) is a polymerizable liquid crystal compound having two acryloyloxy groups or α-substituted acryloyloxy groups in the side chain of the liquid crystal skeleton.
b) Compound (1b) is a polymerizable liquid crystal compound having four acryloyloxy groups or α-substituted acryloyloxy groups in the side chain of the liquid crystal skeleton.
c) Compounds (1a) and (1b) are extremely physically and chemically stable under the conditions usually used, and have good compatibility with other compounds.
d) By appropriately selecting the ring, bonding group or side chain constituting the compounds (1a) and (1b), a large dielectric anisotropy, a small dielectric anisotropy, a large optical anisotropy, a small optical anisotropy are obtained. It is possible to adjust physical property values such as isotropic and small viscosity.
e) Since the compound (1a) or (1b) has two or four acryloyloxy groups or α-substituted acryloyloxy groups with respect to the liquid crystal molecular skeleton, it gives a high-density crosslinked structure by polymerization. .

When R ¹ is alkyl or alkoxy, the temperature range of the liquid crystal phase can be adjusted by the difference in alkyl length. When R ¹ is fluorine or chlorine, an effect of lowering the melting point of the compound (1) can be expected. When R ¹ is an optically active group, a helical induction force can be imparted to the composition.

When at least one of X ¹ and X ² is —COO—, —OCO—, —CH═CH—COO—, or —OOC—CH═CH—, the liquid crystallinity of the compound tends to be improved, and —C≡ When C-, a compound having a large optical anisotropy value tends to be obtained.

  When G is methyl, fluorine or hydrogen, the compound is easily polymerized.

  By appropriately selecting a ring, a side chain, a linking group and a polymerizable group, the compound (1) having the desired physical properties can be obtained.

Next, a method for synthesizing the compounds (1a) and (1b) will be described. In order to synthesize the compound (1a), a monofunctional liquid crystalline epoxy compound (EP1) is used as a raw material. In order to synthesize the compound (1b), a bifunctional liquid crystalline epoxy compound (EP2) is used as a raw material. (EP1) and (EP2) can be easily synthesized by methods such as Documents 1-9.
Reference 1: Macromol. Chem. Phys, 1995, 196, 3415 page 2: JP 7-258638 A document 3: WO 95/7308 pamphlet document 4: WO 97/34862 pamphlet document 5: West German patent 19406619 Document 6: British Patent No. 2338240 Specification Document 7: Macromolecules, 1993, 26, page 1244 Document 8: POLYMER, 1994, Vol35, Number 3, page 622 Document 9: JP 2005-60373 A

  Next, the monofunctional epoxy compound (EP1) or the bifunctional epoxy compound (EP2) is reacted with an acrylic acid derivative (Ac1) such as acrylic acid, methacrylic acid, trifluoromethacrylic acid or α-fluoroacrylic acid, and the corresponding acrylic. An adduct (epoxy acrylate) is obtained. This reaction is carried out at a temperature in the range of 50 to 150 ° C. for about 1 to 8 hours. In the reaction, it is preferable to use a catalyst. Examples of the catalyst include amines such as triethylamine, dimethylbutylamine and tri-n-butylamine, quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrabutylammonium salt and benzyltriethylammonium salt, quaternary phosphonium salt, Phosphins such as phenylphosphine or imidazoles such as 2-methylimidazole and 2-methyl-4-methylimidazole, magnesium hydroxide, magnesium acetate, magnesium (meth) acrylate, magnesium chloride, zinc hydroxide, zinc acetate And alkaline earth metal salts such as zinc (meth) acrylate and zinc chloride, and oxides of alkaline earth metals such as magnesium oxide and zinc oxide. These may be used alone or in combination. The reaction may use no solvent or a solvent. Examples of the solvent include benzene, toluene, xylene, hexane, heptane, octane, cyclohexane, acetone, 2-butanone, methyl isobutyl ketone, dipropyl ether, dipropylene glycol diethyl ether, ethyl acetate, butyl acetate and the like. In order to prevent polymerization of the produced epoxy acrylate, the reaction is preferably performed in the presence of a polymerization inhibitor. In order to further enhance the polymerization preventing effect, it is preferable to introduce air or a mixed gas of oxygen and argon into the reaction mixture. Polymerization inhibitors include hydroquinone, P-methoxyphenol, 2,4-dimethyl-t-butylphenol, 3-hydroxythiophenol, p-benzoquinone, 2,5-dihydroxy-p-benzoquinone, t-butylcatechol, diphenylenediamine , Phenyl-α-naphthylamine, diethanolamine, triethanolamine, phenothiazine, copper powder, copper dithiocarbamate, copper oxide, cuprous chloride, copper sulfate, sulfur, ferric chloride and the like. These compounds can be used alone or in combination of two or more.

  Epoxy acrylate is not purified, but once isolated, and then in the presence of a base, an acrylic acid chloride derivative such as an acrylic acid chloride, methacrylic acid chloride, trifluoromethacrylic acid chloride, or α-fluoroacrylic acid chloride (1a) or (1b) can be synthesized by reacting (Ac2). As the base, triethylamine, tributylamine, pyridine, dimethylaminopyridine, dimethylaniline and the like can be used.

  Examples of compounds synthesized by such a method are compounds No. 1 to No. 65.

  Next, the composition of the present invention will be described. This composition contains at least one of compound (1a) or (1b) as the first component. This composition is classified into the following compositions A, B and the like. The composition A contains two or more kinds of compounds selected from the group of the compound (1a) or (1b). Composition B contains at least one compound selected from the group of compounds (1a) or (1b) as the first component and at least one compound selected from the group of other polymerizable liquid crystal compounds as the second component. To do.

  Preferred composition B contains at least one of compound (1a) or (1b) as the first component and at least one of compound (M1), (M2) or (M3) as the second component. This second component compound is suitable for copolymerization with compound (1a) or (1b). The compound (M1) is a bifunctional liquid crystal acrylate compound. The compound (M2) is a monofunctional liquid crystal acrylate compound. The compound (M3) is a bifunctional optically active liquid crystalline acrylate compound.

In the formulas (M1), (M2) and (M3), B ³ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1 , 4-phenylene, 2,3-ditrifluoromethyl-1,4-phenylene, naphthalene-2,6-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, or 9,9-dimethylfluorene-2,7-diyl; R ² is fluorine, —OCF ₃ , —CN, alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons; X ⁵ is independently A single bond, — (CH ₂ ) ₂ — or —C═C—; X ⁶ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —OOC—HC═CH— Or -C≡C- P and t are each independently an integer from 1 to 20; G ² is hydrogen, fluorine, methyl or trifluoromethyl; W ¹ , W ² , W ³ , W ⁴ and W ⁵ are independently hydrogen Or fluorine; W ⁶ and W ⁷ are independently hydrogen or methyl, the carbon to which * is attached is an asymmetric carbon, and a plurality of X ⁵ , t, and G ² may be the same , May be different.

Preferred compounds (M1) that can be used in the composition are compounds (M1-1) to (M1-9).

Compounds (M1-1) to (M1-3) can be synthesized by the method described in JP-A-2003-238491. Compounds (M1-5) to (M1-7) can be synthesized by the method described in Makromol. Chem., 190, 2255-2268 (1989). Compound (M1-8) can be synthesized by the method described in JP-A No. 2004-231638.

Preferred compounds (M2) that can be used in the composition are compounds (M2-1) to (M2-6).

  A synthesis method of the compounds (M2-1) and (M2-2) is described in Macromolecules, 26, 6132-6134 (1993).

Preferred compounds (M3) that can be used in the composition are the compounds (M3-1) and (M3-2).

A method for synthesizing the compounds (M3-1) and (M3-2) is described in JP-A-2005-97281.

  Examples of preferred combinations when the first component is at least one of the compounds (3) to (6) and the second component is at least one of the compounds (M1), (M2) or (M3) Are the compositions (C1), (C2) and (C3). Compound Formulas (3) to (6) mean compounds represented by Formula (3) to Formula (6), respectively. Preferred compositions are summarized in Table 1. Compound (M1), (M2) or (M3) adjusts the temperature range of liquid crystal phase, viscosity, orientation of liquid crystal phase, film-forming property in polymer, mechanical strength, heat resistance, solvent resistance, etc. Convenient to do. The composition ratio of the first component and the second component is preferably such that the content of the first component is 20 to 80% by weight with respect to the total amount of 100% by weight of the first component and the second component, and the content of the second component An amount of 20-80% by weight is preferred.

Table 1. Preferred composition
Composition First component Second component
Composition C1: Compound Formula (6) Compound (M1)
Composition C2: Compound Formula (6) Compound (M2)
Composition C3: Compound Formula (6) Compound (M3)

  The features of the compositions (C1), (C2) and (C3) are as follows. 1) By adding a polymerization initiator, rapid polymerization can be performed by irradiating an electron beam such as ultraviolet rays. 2) Excellent orientation. 3) Excellent compatibility with other polymerizable liquid crystal compounds.

  Compositions such as compositions A and B may further contain additives as necessary. Additives for adjusting the physical properties of the polymer are non-liquid crystalline polymerizable compounds, surfactants, antioxidants, ultraviolet absorbers, fine particles, and the like. Additives for polymerizing the monomer include a polymerization initiator, a brightening agent, a chain transfer agent and the like. Organic solvents are preferred for diluting the composition. The amount of these additives is preferably small enough to achieve the purpose. Even if the atoms constituting the components of the composition contain more isotopes than their natural abundance, it is preferable because they have similar characteristics.

  A non-liquid crystalline polymerizable compound can also be added to the composition for the purpose of adjusting film-forming properties, mechanical strength, and the like. Examples of preferred non-liquid crystalline polymerizable compounds are (meth) acrylate compounds, vinyl compounds, styrene compounds, vinyl ether compounds, and polyfunctional acrylates.

  Preferred examples of the non-liquid crystalline polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, vinyl chloride, and vinyl fluoride. , Vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2- Vinyl methylbutanoate, N-vinylacetamide, vinyl pt-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, styrene, o-, m- or p-chloromethylstyrene, α-methylstyrene , Tetrafluoroethylene, and hexafluoropropene. These non-liquid crystalline polymerizable compounds have a low molecular weight and are suitable for adjusting the viscosity of the composition.

  Preferred examples of the polyfunctional acrylate include 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, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A Glycidyl diacrylate (trade name: Biscoat 700, manufactured by Osaka Organic Chemical Co., Ltd.), polyethylene glycol diacryl It is over bets, and ethylene oxide-modified trimethylolpropane acrylate. These polyfunctional acrylates can be used to further increase the film-forming ability of the polymer

  The surfactant has effects such as facilitating application of the composition to a support substrate and the like, and controlling the orientation of the liquid crystal phase. Examples of surfactants include imidazoline, quaternary ammonium salts, alkylamine oxides, polyamine derivatives, polyoxyethylene-polyoxypropylene condensates, polyethylene glycol and esters thereof, sodium lauryl sulfate, ammonium lauryl sulfate, amines of lauryl sulfate, alkyl Substituted aromatic sulfonates, alkyl phosphates, aliphatic or aromatic sulfonic acid formalin condensates, laurylamidopropylbetaine, laurylaminoacetic acid betaine, polyethylene glycol fatty acid esters, polyoxyethylene alkylamine, perfluoroalkylsulfonic acid Salt, perfluoroalkyl carboxylate, perfluoroalkylethylene oxide adduct, perfluoroalkyltrimethylammonium salt, perfluoroalkyl And a hydrophilic group-containing oligomer, perfluoroalkyl group and lipophilic group-containing oligomer, a perfluoroalkyl group-containing urethanes. The preferred amount of the surfactant varies depending on the kind of the surfactant, the composition ratio of the composition, etc., but is in the range of 100 ppm to 5% by weight based on the total weight of the composition. A more preferred amount is in the range of 0.1 to 1% by weight.

  Preferred 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.

Preferred UV absorbers are Tinuvin PS, Tinuvin 213, Tinuvin 109, Tinuvin 328, Tinuvin 384-2, Tinuvin 327, etc. manufactured by Ciba Specialty Chemicals Co., Ltd. Fine particles may be added to adjust the optical anisotropy or increase the strength of the polymer. Preferred fine particle materials are inorganic, organic, metal, and the like. Preferred 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.

  Preferred organic materials are carbon nanotubes, fullerenes, dendrimers, polyvinyl alcohol, polymethacrylates, polyimides 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. A preferred addition amount is 0.1 to 30% by weight based on the total weight of the composition. A small proportion is preferable as long as the purpose of addition is achieved.

  The composition is used for the polymerization reaction with the addition of a normal photoradical polymerization initiator. Examples of the radical photopolymerization initiator include Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one) and Irgacure 184 (1) from the products of Ciba Specialty Chemicals Co., Ltd. -Hydroxycyclohexyl phenyl ketone), Irgacure 651 (2,2-dimethoxy-1,2-diphenylethane-1-one), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure Cure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, Irgacure 784, and the like.

  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.

  Examples of solvents are benzene, toluene, xylene, mesitylene, n-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, methyl lactate, 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, carbon tetrachloride, dichloroethane, tetrachloroethylene, Chloroethylene, chlorobenzene, t- butyl alcohol, diacetone alcohol, glycerin, 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.

  Next, the polymer will be described. Compounds (1a) and (1b) have a polymerizable group. A polymer is obtained by polymerizing a composition containing these compounds. The obtained polymer has optical anisotropy. The polymer has a large surface hardness and excellent heat resistance. Types of the polymerization reaction include radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, living polymerization and the like. Considering the nature of the polymerizable group, the preferred reaction is radical polymerization. When obtaining a polymer with excellent orientation, radical polymerization by light irradiation is more preferred. This is because it is easy to perform polymerization under the condition that the composition is liquid crystal.

Preferred types of light are ultraviolet light, visible light, infrared light, and the like. The wavelength of light is selected according to the absorption wavelength of the radical photopolymerization initiator used. A preferable light 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), or short arc discharge lamp (super high pressure mercury lamp, xenon lamp, mercury xenon lamp). is there. 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 range of 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 due to heat hardly occurs at a temperature of 100 ° C. or less, good orientation is easily obtained.

  The shape of the polymer is a film, a plate or the like. The polymer may be molded. In order to obtain a film polymer, a support substrate is generally used. A film in which molecular orientation is fixed by applying a composition on a support substrate and polymerizing a paint film having a liquid crystal phase such as nematic orientation formed in the liquid crystal state of the composition. Is obtained. The preferred polymer thickness depends on the value of the optical anisotropy of the polymer and the application. Therefore, although the range cannot be determined strictly, the preferable thickness is in the range of 0.05 to 50 μm, and the 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, preferably 1.0% or less. The transmittance of these polymers is generally 80% or more, preferably 85% or more in the visible light region. A haze value range of 1.5% or less is a preferable condition in order not to cause a problem in polarization performance. A transmittance range of 80% or more is a preferable condition for maintaining brightness when this optically anisotropic thin film is used in a liquid crystal display element. Therefore, these polymers are suitable as optically anisotropic thin films used for liquid crystal display elements.

  Examples of the support substrate are triacetyl cellulose, polyvinyl alcohol, polyimide, polyester, polyarylate, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, and the like. Examples of product names are “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 (TAC) film. You may use this film as it is, without pre-processing. This film may be subjected to a surface treatment such as a saponification treatment, a corona discharge treatment, or a 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, caten coating, flow coating, printing, micro gravure coating, gravure coating, wire bar coating, dip coating, spray coating, meniscus coating, and the like.

  Factors that determine the alignment of the liquid crystal composition are 1) the chemical structure of the polymerizable compound, 2) the type of the supporting substrate, 3) the method of alignment treatment, and the like. The item 1) depends on the type of the side chain, ring, bonding group, polymerizable group and the like of the polymerizable compound. Item 2) depends on the material of the support substrate such as polymer, glass (alkali glass, borosilicate glass, flint glass, etc.), metal (aluminum, iron, copper, etc.). Regarding item 3), rubbing in one direction with a rayon cloth (rubbing), oblique deposition of silicon oxide, stretching, polarized UV alignment, rubbing-free alignment using ion beam, etc., slit-like grooves on the surface There are methods such as attaching and etching into a slit shape. 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.

  The alignment of the liquid crystal compound includes homogenous (parallel), homeotropic (vertical), hybrid, tilted, twisted, and the like. 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. Tilt refers to a state in which the orientation vector is rising with a constant tilt angle with respect to the substrate. These orientations are observed in a composition having a nematic phase or the like. On the other hand, twist orientation is observed in a composition having a chiral nematic phase, a cholesteric phase, or the like. The twist refers to a state in which the orientation vector is parallel to the substrate but gradually twists as the distance from the substrate increases. This twist is caused by the action of an optically active group.

  The use of the polymer will be described. This polymer can be used as a molded product having optical anisotropy. The element containing this polymer is an optical film such as a retardation plate (a half-wave plate, a quarter-wave plate, etc.), an antireflection film, a selective reflection film, and a viewing angle compensation film. 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. Polymers having an orientation such as twist can be used for retardation plates, polarizing elements, selective reflection films, viewing angle compensation films, and the like. Such a polymer is used for the purpose of optical compensation in a retardation plate of a liquid crystal display, a viewing angle compensation film, and the like. Such a polymer can also be used for highly heat-conductive epoxy resins, adhesives, synthetic polymers having mechanical anisotropy, cosmetics, decorative articles, nonlinear optical materials, information storage materials, and the like.

  The retardation plate has a function of converting the 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. A half-wave functional plate can be obtained by aligning this composition wave and polymerizable liquid crystal compound and then photopolymerizing it. 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.

  A polymer having a twist orientation is useful as a retardation plate. When the helical pitch is 1 / n of the wavelength (n is the average refractive index of the polymer), light of this wavelength is reflected according to Bragg's law and converted to circularly polarized light. The direction of circularly polarized light depends on the direction of the spiral, that is, the configuration of the optically active compound. The direction of circularly polarized light can be determined by appropriately selecting the configuration of the optical compound. This polymer is useful as a circularly polarized light separating functional element.

  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 composition is% by weight (wt%).

  The phase transition temperature was measured by placing a sample on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope and raising the temperature at a rate of 1 ° C./min to measure the temperature at which the liquid crystal phase transitions. C represents a crystal, N represents a nematic phase, Ch represents a cholesteric phase, I represents an isotropic liquid, and the parenthesis represents a monotropic liquid crystal phase. 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.

  The cellotape (registered trademark) peel test was in accordance with 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 followed the method of JIS standard "JIS-K-5400, 8.4, pencil scratch test". The result was expressed by the hardness of the pencil lead.

  The heat resistance test was conducted at 150 ° 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 obtain a supporting substrate. The surface of the polyimide produced by heating 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 and 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 was measured at 20 ° C. After heating the polymer at 150 ° C. for 500 hours, the retardation was measured again at 20 ° C. Two values were compared to evaluate heat resistance. 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.

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

  The orientation was observed with a polarizing microscope. The polymer was prepared on a saponified TAC film (supporting substrate) having a degree of acetylation of 2.9. This sample was sandwiched between two polarizing plates arranged in crossed Nicols. The type of orientation was judged from the angle dependency of transmitted light intensity.

Example 1
Compound No. Synthesis of 1 (first stage)
A reaction mixture in which 20 g of 4-cyano-4′-hydroxybiphenyl, 20 g of allyl bromide and 25 g of potassium carbonate were added to 250 ml of 2-butanone was refluxed for 7 hours. Water was added to the reaction mixture for liquid separation, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography using toluene as an elution solvent, and further recrystallized from ethanol to obtain 22 g of 4-allyloxy-4′-cyanobiphenyl.

  4- (4-Allyloxybutyloxy) -4'-cyanobiphenyl was synthesized in the same manner as in Example 1, Step 1. The phase transition temperatures of the two synthesized compounds are shown.

（第２段階）
４−アリルオキシ−４’−シアノビフェニル１９ｇを塩化メチレン１５０ｍｌに溶解した反応混合物に、ｍ−クロロ過安息香酸２０ｇを数回に分けて加え、室温で２４時間かくはんした。析出した不溶物をろ過して取り除き、水を加え分液を行い、有機層をハイドロサルファイトナトリウム飽和水溶液で洗浄した後、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カラムクロマトグラフィーで精製し、さらにエタノールで再結晶することで１３ｇの４−シアノ−４’−グリシジルビフェニルを得た。

(Second stage)
To a reaction mixture in which 19 g of 4-allyloxy-4′-cyanobiphenyl was dissolved in 150 ml of methylene chloride, 20 g of m-chloroperbenzoic acid was added in several portions and stirred at room temperature for 24 hours. The precipitated insoluble matter was removed by filtration, and water was added for liquid separation, and the organic layer was washed with a saturated aqueous solution of sodium hydrosulfite and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography, and further recrystallized from ethanol to obtain 13 g of 4-cyano-4′-glycidylbiphenyl.

  The phase transition temperature of the compound synthesize | combined by the method similar to the 4-cyano-4'-glycidyl biphenyl and Example 1, the 2nd step is shown.

（第３段階）
４−シアノ−４’−グリシジルビフェニル１ｇ、アクリル酸０．５ｇ、テトラブチルアンモニウムブロマイド０．０７ｇ、および２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．０２ｇをトルエン５０ｍｌに加えた反応混合物に空気をバブリングしながら５時間還流した。１００ｍｌのクロロホルムと水を加え分液を行い、有機層を無水硫酸マグネシウムで乾燥した。溶媒を留去して油状物の残渣を得た。この油状物にジオキサン２０ｍｌおよびジメチルアニリン１．２ｇを加え５０℃に加熱し、そこへアクリロイルクロライド０．８ｇを滴下し、同温度を保ちながら２時間かくはんした。トルエンと水を加え分液を行い、トルエン層を炭酸ナトリウム水溶液で洗浄した後、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カラムクロマトグラフィー、再結晶により精製して化合物Ｎｏ．１を得た。

(3rd stage)
A reaction mixture in which 1 g of 4-cyano-4′-glycidylbiphenyl, 0.5 g of acrylic acid, 0.07 g of tetrabutylammonium bromide, and 0.02 g of 2,6-di-t-butyl-p-cresol were added to 50 ml of toluene. The mixture was refluxed for 5 hours while bubbling air. 100 ml of chloroform and water were added for liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain an oily residue. To this oily substance, 20 ml of dioxane and 1.2 g of dimethylaniline were added and heated to 50 ° C., and 0.8 g of acryloyl chloride was added dropwise thereto and stirred for 2 hours while maintaining the same temperature. Toluene and water were added for liquid separation, and the toluene layer was washed with an aqueous sodium carbonate solution and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography and recrystallization to give Compound No. 1 was obtained.

According to the method of Example 1 and the third step, Compound No. 5 was synthesized. Compound No. 1 and no. 5 shows the phase transition temperature and properties.

Example 2
(First stage)
A reaction mixture consisting of 14 g of allyl (4-chlorobutyl) ether, 14 g of 4-hydroxybenzoic acid, 14 g of potassium carbonate, and 50 ml of dimethylformamide was stirred at 90 ° C. for 3 hours. Water was added and the mixture was extracted with toluene. The toluene layer was washed thoroughly with water, and toluene was distilled off. To the obtained residue, 20 g of sodium hydroxide, 50 ml of water and 200 ml of ethanol were added and refluxed for 2 hours. Ethanol was distilled off and hydrochloric acid was added to make it acidic, followed by extraction with diethyl ether and drying over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized with a mixed solvent of ethanol and water to obtain 29 g of 4- (4-allyloxybutyloxy) benzoic acid.
Phase transition temperature: C94N107I.

The following benzoic acid derivatives were synthesized by the method of Example 2 and the first step.
4-allyloxybenzoic acid (melting point: 164-165 ° C.)
4- (3-Butenyloxy) benzoic acid (phase transition temperature: C 121 N 141.5 I)

(Second stage)
1.34 g of 4- (4-allyloxybutyloxy) benzoic acid and 0.46 g of 2,7-dihydroxy-9-methylfluorene are dissolved in 30 ml of methylene chloride and cooled to 5 ° C., and 0.01 g and 1 of dimethylaminopyridine are added thereto. 1.15 g of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred at room temperature for 12 hours. 50 ml of water was added for liquid separation, and the organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, recrystallized from a mixed solvent of ethanol and ethyl acetate, and 0.6 g of 2,7-di [4- (4-allyloxybutyloxy). ) Benzoyloxy) 9-methylfluorene was obtained.

  The following compounds were synthesized by the method of Example 2 and the second step. The phase transition temperature of 2,7-di [4- (4-allyloxybutyloxy) benzoyloxy] 9-methylfluorene and the synthesized compound is shown.

(3rd stage)
To a reaction mixture of 2,7-di [4- (4-allyloxybutyloxy) benzoyloxy] 9-methylfluorene (0.64 g) and methylene chloride (10 ml) was added 0.5 g of m-chlorobenzoic acid, and the mixture was stirred at room temperature for 2 days. did. The reaction mixture was washed with 5% sodium hydroxide solution, washed successively with sodium hydrogen sulfite solution and sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography and recrystallized with a mixed solvent of ethanol and ethyl acetate to give 0.56 g of 2,7-di [4- (4-glycidyloxybutyl). Oxy) benzoyloxy] 9-methylfluorene was obtained.

  The following compounds were synthesized by the method of Example 2 and the third step. The phase transition temperature of 2,7-di [4- (4-glycidyloxybutyloxy) benzoyloxy] 9-methylfluorene and the synthesized compound is shown.

(Fourth stage)
2,7-di [4- (4-glycidyloxybutyloxy) benzoyloxy] 9-methylfluorene 5 g, acrylic acid 5 g, tetrabutylammonium bromide 0.1 g, magnesium hydroxide 0.2 g, and 2,6-di The reaction mixture obtained by adding 0.04 g of t-butyl-p-cresol to 100 ml of toluene was refluxed for 5 hours while bubbling air. 100 ml of chloroform and water were added for liquid separation, followed by drying over anhydrous magnesium sulfate. When the solvent was distilled off, an oily residue was obtained. To this oily substance, 20 ml of dioxane and 2.4 g of dimethylaniline were added and heated to 50 ° C., and 1.8 g of acryloyl chloride was added dropwise thereto and stirred for 2 hours while maintaining the same temperature. Toluene and water were added to the reaction mixture for liquid separation, and the toluene layer was washed with an aqueous sodium carbonate solution and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography and recrystallization to give Compound No. 71 was obtained.

  According to the method of Example 2, the fourth step, the following compound No. 42 was synthesized. Compound No. 42 and compound no. A phase transition temperature of 56 is shown.

Example 3
Example of composition having homogeneous orientation A composition (CL1) was prepared from 50% by weight of the compound (No. 56) and 50% by weight of the compound (M1-2). The compound (M1-2) was synthesized by the method described in JP2003-238491A. This composition had a nematic liquid crystal phase at room temperature and had an NI point of 155 ° C. The compound (No. 56) had good compatibility and was not phase separated. The composition (CL1) did not crystallize immediately even at room temperature but maintained the liquid crystal state. When the composition (CL1) was applied on a rubbed TAC film, it showed homogeneous orientation.

Example 4
Example of composition showing selective reflection in part of visible light region (wavelength 350 to 750 nm) A composition (CL2) was prepared from 70% by weight of compound (No. 56) and 30% by weight of compound (M3-1). . Compound (M3-1) was synthesized by the method described in JP-A-2005-97281. This composition had a cholesteric liquid crystal phase at room temperature and had a Ch-I transition point of 77 ° C. The compound (No. 56) had good compatibility and was not phase separated. The composition (CL2) did not crystallize immediately even at room temperature, but maintained the liquid crystal state. When the composition (CL2) was applied on a rubbed TAC film, it showed red selective reflection visually.

Example 5 (Production of oriented film by ultraviolet irradiation)
A TAC saponification-treated TAC film having a degree of acetylation of 2.9 having a surface rubbed with rayon cloth, a solution of 10 g of composition (CL1) and 0.3 g of Irgacure 907 (trade name) in 80 g of cyclopentanone The substrate was coated using a micro gravure coater. After coating, the mixture was allowed to stand at room temperature for 5 minutes, and the solvent was removed to align the liquid crystal phase. While maintaining the room temperature, ultraviolet rays were irradiated for 10 seconds using a high-pressure mercury lamp (120 W / cm) under a nitrogen atmosphere to obtain a liquid crystal alignment film (F1). The homogeneous orientation of the composition was retained by polymerization. The pencil hardness of this film was 3H. The change in retardation due to temperature change (20 to 150 ° C.) of this film was within 3%, and it was a film having high heat resistance.

  A TAC saponification-treated TAC film having a degree of acetylation of 2.9 (supported) obtained by rubbing the surface of a solution of 10 g of composition (CL2) and 0.3 g of Irgacure 907 (trade name) in 80 g of cyclopentanone with a rayon cloth The substrate was coated using a micro gravure coater. After coating, the mixture was allowed to stand at room temperature for 5 minutes, and the solvent was removed to align the liquid crystal phase. While maintaining the room temperature, ultraviolet rays were irradiated for 10 seconds using a high-pressure mercury lamp (120 W / cm) under a nitrogen atmosphere to obtain a liquid crystal alignment film (F2). The Grandjean orientation of the composition was retained by polymerization. This composition had good orientation and polymerizability by ultraviolet rays. The pencil hardness of this film was 3H. The change in retardation due to temperature change (20 to 150 ° C.) of this film was within 3%, and it was a film having high heat resistance.

The evaluation results of these films are summarized in Table 2. From these results, it was found that 1) the polymer has high hardness, and 2) the polymer has high heat resistance.
Table 2. Evaluation results
Film number Orientation state Pencil hardness Heat resistance
F1 homogeneous orientation 3H within 3%
F2 twist orientation (red selective reflection) 3H within 3%

Claims (18)

A compound represented by formula (1a) or formula (1b).

In Formula (1a) and Formula (1b), R ¹ is hydrogen, fluorine, chlorine, —CN, —NO ₂ , or alkyl having 1 to 20 carbons, and in this alkyl, any hydrogen is fluorine or chlorine. Any one or two of —CH ₂ — may be replaced with —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C. -In which case R ¹ may be an optically active group; Y ¹ and Y ² are independently alkylene having 1 to 20 carbons, in which any hydrogen is fluorine or May be replaced with chlorine, any —CH ₂ — may be replaced with —O—, and any one or two —CH ₂ — may be replaced with —COO— or —OCO—; And any one -CH ₂ - may be replaced by -CH = CH- or -C≡C-, in this case, ^{Y 1} or ^{Y 2} may be optically active ^{group; A 1, A 2, B} 1, and B ² is independently 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6- Diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene- 2,7-diyl, 9,9-difluorofluorene-2,7-diyl, or a group selected from (K1), (K2) and (K3), and in this 1,4-phenylene, any hydrogen is F Any one or two hydrogens may be replaced by cyano, methyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl. X ¹ and X ² are each independently a single bond, —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CONH—, —NHCO—, —CH═CH—COO—, _{-OOC-HC = CH -, -} (CH 2) 2 -COO -, - OOC- (CH 2) 2 -, - (CH 2) 2 -, or a -C≡C-; m is 0, 1 or 2, may be two of a ¹ and X ¹ are the same in each group when m is 2, may be a different group; G is hydrogen, fluorine, methyl, cyano or triflate, A Romechiru, the plurality of G may be the same group or may be different groups. However, in the formula (1a), A ² is not 2,3-difluoro-1,4-phenylene.

In Formula (1a) and Formula (1b), R ¹ is fluorine, chlorine, —CN, —NO ₂ , —OCF ₃ , alkyl having 1 to 15 carbons, or alkoxy having 1 to 15 carbons; Y ¹ And Y ² are independently —O—, — (CH ₂ ) _r —, —O— (CH ₂ ) _r —, — (CH ₂ ) _r —O—, —O— (CH ₂ ) _r —O—. Or —O— (CH ₂ CH ₂ O) _s —, r is an integer of 1 to 10, s is an integer of 1 to 5; A ¹ , A ² , B ¹ , and B ² are independent. 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2, 7-diyl, 9,9-dimethylfluorene-2,7-diyl or (K1), (K2 And in this 1,4-phenylene, any hydrogen may be replaced by fluorine, and any one hydrogen may be methyl, trifluoromethyl, methoxy, acetoxy, or acetyl. And any two hydrogens may be replaced with trifluoromethyl; X ¹ and X ² are independently a single bond, —COO—, —OCO—, —CH═CH—COO—. , —OOC—HC═CH—, — (CH ₂ ) ₂ —COO—, —OOC— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —, or —C≡C—, and m is 0 or 2. A compound according to claim 1 wherein G is methyl, fluorine or hydrogen. A compound represented by any one of formulas (3) to (6).

In Formulas (3) to (6), R ¹ is —CN, —OCF ₃ , alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; A ¹ and A ² are independently 1, 4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2-methyl- 1,4-phenylene or 2-trifluoromethyl-1,4-phenylene; B ¹ and B ² are independently 1,4-cyclohexylene, 1,4-phenylene, naphthalene-2,6- Diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1 , 4-Fe Nylene, 2,3-difluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4 -Phenylene, 2-methoxy-1,4-phenylene, 2-acetyl-1,4-phenylene, or 2,3-ditrifluoromethyl-1,4-phenylene; X ¹ and X ² are each independently a single bond, -COO -, - OCO -, - CH = CH-COO -, - OOC-HC = CH -, - (CH 2) 2 -COO -, - OOC- (CH 2) 2 -, - (CH 2) 2 —, Or —C≡C—; X ³ is a single bond or —O—; q is an integer of 0 to 10, and a plurality of X ³ and q may be the same or different. May be. In formulas (3) to (6), R ¹ is —CN, —OCF ₃ , alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons; A ¹ and A ² are independently 1, 4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2-methyl-1,4-phenylene; B ¹ and B ² are independently 1,4-cyclo Xylene, 1,4-phenylene, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 2-fluoro-1,4-phenylene, 2-methyl-1,4- Phenylene, 2-trifluoromethyl-1,4-phenylene, or 2,3-ditrifluoromethyl-1,4-phenylene; X ¹ and X ² are each independently a single bond, —COO— or —OCO—; in it; ^{X 3} The compound according to claim 3, wherein is a single bond or —O—; q is an integer of 0 to 10. A compound represented by formula (3), wherein in formula (3), R ¹ is —CN; A ² is 1,4-phenylene; B ¹ is 1,4-phenylene; X ² The compound according to claim ³ , wherein X is a single bond; X ³ is a single bond or —O—; and q is an integer of 0 to 10. A compound represented by formula (5), wherein A ² is 1,4-phenylene; B ² is 1,4-phenylene; X ² is —COO—; X The compound according to claim 3, wherein ³ is a single bond or -O-; and q is an integer of 0 to 10. A compound represented by formula (6), wherein in formula (6), A ¹ and A ² are 1,4-phenylene; B ² is 1,4-phenylene, 9-methylfluorene-2,7- Diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is a single bond or —O—; q is 0-10 The compound according to claim 3, which is an integer of The composition containing the at least 1 compound of any one of Claims 1-2 as a 1st component. The composition containing the at least 1 compound of any one of Claims 3-7 as a 1st component. The composition according to claim 9, further comprising a polymerizable compound different from the compound according to any one of claims 1 to 7 as a second component. The composition according to claim 10, wherein the second component is at least one compound selected from the group of compounds represented by formula (M1), formula (M2) and formula (M3).

In the formulas (M1), (M2) and (M3), B ³ is 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1 , 4-phenylene, 2,3-ditrifluoromethyl-1,4-phenylene, naphthalene-2,6-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, or 9,9-dimethylfluorene-2,7-diyl; R ² is fluorine, —OCF ₃ , —CN, alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons; X ⁵ is independently A single bond, — (CH ₂ ) ₂ — or —C═C—; X ⁶ is a single bond, —COO—, —OCO—, —CH═CH—COO—, —OOC—HC═CH— Or -C≡C- P and t are each independently an integer from 1 to 20; G ² is hydrogen, fluorine, methyl or trifluoromethyl; W ¹ , W ² , W ³ , W ⁴ and W ⁵ are independently hydrogen Or fluorine; W ⁶ and W ⁷ are independently hydrogen or methyl, the carbon to which * is attached is an asymmetric carbon, and a plurality of X ⁵ , t, and G ² may be the same , May be different. As a first component, a compound represented by the formula (6) according to claim 3, in the formula (6), ^{A 1} and ^{A 2} be a 1,4-phenylene; ^{B 2} 1,4 Phenylene, 9-methylfluorene-2,7-diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is a single bond or -O-; comprising at least one compound selected from the group consisting of compounds wherein q is an integer from 0 to 10,
The second component is a compound represented by the formula (M1), and in the formula (M1), B ³ is 1,4-phenylene, 2-methyl-1,4-phenylene, 2,3-ditrifluoromethyl- 1,4-phenylene, it is a 9-methyl-2,7-diyl or 9,9-dimethyl-2,7-diyl,; ^{X 5} is a single bond or - _{(CH 2) 2} - a is; p And t is an integer of 1 to 20; G ² is hydrogen; and W ¹ , W ² , W ³ and W ⁴ are at least one compound selected from the group consisting of hydrogen or fluorine,
The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. The composition as described. As a first component, a compound represented by the formula (6) according to claim 3, in the formula (6), ^{A 1} and ^{A 2} be a 1,4-phenylene; ^{B 2} 1,4 Phenylene, 9-methylfluorene-2,7-diyl or 2-methyl-1,4-phenylene; X ¹ and X ² are independently —COO— or —OCO—; X ³ is a single bond or -O-; comprising at least one compound selected from the group consisting of compounds wherein q is an integer from 0 to 10,
A compound represented by formula (M3) as a second component, wherein in formula (M3), G ² is hydrogen; at least one selected from the group consisting of compounds wherein W ⁶ and W ⁷ are hydrogen or methyl Containing a compound,
The content of the first component is 20 to 80% by weight and the content of the second component is 20 to 80% by weight with respect to 100% by weight of the total amount of the first component and the second component. The composition as described. The polymer obtained by polymerizing the compound of any one of Claims 1-7. The polymer obtained by polymerizing the composition of any one of Claims 8-13. The molded object which has the optical anisotropy which consists of a polymer of Claim 14 or 15. The liquid crystal display element containing the molded object which has the optical anisotropy of Claim 16. Use of the polymer according to claim 14 or 15 as a molded product having optical anisotropy.