JP4862294B2 - Fluorene derivatives and polymers thereof - Google Patents

Description

  The present invention relates to a fluorene derivative having an oxirane ring or an oxetane ring, a polymer obtained from the derivative, and use thereof.

  When the polymerizable compound is a liquid crystal, it is known that a polymer having optical anisotropy can be obtained by polymerizing the compound (Patent Document 1). This is because the orientation of molecules in the liquid crystal is fixed by polymerization. An example of such a compound is a liquid crystal compound having an acryloyloxy group (Patent Document 2). What is further desired is a liquid crystal compound having characteristics such as polymerization at room temperature, polymerization in air, and easy polymerization by ultraviolet irradiation.

JP 2001-55573 A JP 2001-154019 A Japanese Patent Laying-Open No. 2005-60373 (US2005 / 0031801A1)

  The object of the present invention is to polymerize at room temperature, polymerize in air, easily polymerize, wide temperature range of liquid crystal phase, chemically stable, colorless, easily soluble in solvents, other polymerizable compounds It is a liquid crystal compound that satisfies a plurality of properties in terms of properties such as good compatibility with the substrate and low adhesion tension to the support substrate. The problem is a compound with an appropriate balance for multiple properties. This subject is also a polymer obtained from this liquid crystal compound. This problem has a plurality of characteristics such as optical anisotropy, difficulty in peeling from the support substrate, sufficient hardness, colorless and transparent, high heat resistance, high weather resistance, and low photoelasticity. It is also a polymer that satisfies the above characteristics.

The present invention includes at least one compound represented by the following formula (1) or (2), a composition containing the compound, and a polymer obtained by polymerizing the composition.

In Formula (1) or (2), R ¹ is hydrogen, fluorine, chlorine, cyano, nitro, or alkyl having 1 to 20 carbons, and in this alkyl, any hydrogen may be replaced with fluorine or chlorine , And any one or two of —CH ₂ — is replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C—. Well: R ² is hydrogen or alkyl having 1 to 8 carbons, in which any hydrogen may be replaced by fluorine or chlorine; R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, Or an alkyl having 1 to 10 carbon atoms, in which any hydrogen may be replaced by fluorine or chlorine, and any one or two —CH ₂ — may be —O—, —S—, — C O—, —OCO—, —CO—, —CH═CH—, or —C≡C— may be substituted; A is 1,4-cyclohexylene, 1,4-phenylene, pyridine-2, 5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, or tetrahydronaphthalene-2,6-diyl, any hydrogen in this 1,4-phenylene May be replaced with fluorine or chlorine, and any one or two hydrogens are replaced with cyano, methyl, ethyl, methoxy, hydroxy, formyl, acetoxy, acetyl, trifluoroacetyl, difluoromethyl, or trifluoromethyl may be; single _bond, X is _{- (CH 2) 2 -,} - CH = CH -, - C≡C -, - CH 2 O -, - OCH 2 _{, -CF 2 O -, - OCF} 2 -, - COO -, - OCO -, - CONH -, - NHCO -, - (CH 2) 4 -, - (CH 2) 2 COO -, - OCO (CH 2 ₂ ), -CH = CH-COO-, or -OCO-CH = CH-; P is alkylene having 1 to 20 carbon atoms, and in this alkylene, any hydrogen may be replaced by fluorine or chlorine. Well, any —CH ₂ — may be replaced with —O—, any one or two —CH ₂ — may be replaced with —COO— or —OCO—, and any one of —CH ₂ — may be replaced by —CH═CH— or —C≡C—; and m and n are independently 0, 1 or 2, and the sum of m and n is 1, 2, 3 or 4.

  The liquid crystal compound of the present invention is polymerized at room temperature, polymerized in air, easily polymerized, wide temperature range of liquid crystal phase, chemically stable, colorless, easily soluble in solvent, other polymerizable compounds A plurality of characteristics are satisfied with respect to characteristics such as good compatibility with and low adhesion tension to the support substrate. This compound has an appropriate balance for multiple properties. The polymer of the present invention is obtained from this liquid crystal compound. This polymer has optical anisotropy, is difficult to peel off from the support substrate, has sufficient hardness, is colorless and transparent, has high heat resistance, has high weather resistance, and has low photoelasticity. 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. A polymer obtained from the composition containing the compound (1) may be referred to as a polymer (1). A polymer obtained from the composition containing the compound (2) may be referred to as a polymer (2). The weight% (wt%) of the polymerizable compound is a ratio based on the total weight of the polymerizable compound contained in the composition. The weight% of the additive is a ratio based on the total weight of the polymerizable compound.

In formulas (1) and (2), the symbol R ¹ was used. The meanings of the two symbols R ¹ may be the same or different. For example, there is a case where R ¹ in formula (1) and formula (2) is methyl. ^{R 1} is methyl of formula (1), there is a case ^{R 1} is ethyl of the formula (2). In the formula (1), symbols such as A and X are used. In-(AX) _{m- and-} (AX) _{n- in} formula (1), the meanings of the two symbols A may be the same or different. -(AX) _m -in formula (1) means -A-X-A-X- when m is 2. In this case, the meanings of the two symbols A may be the same or different.
Such a rule also applies to the meaning of the symbol X. This rule also applies to the meaning of other symbols.

  We obtain 1) a polymer having optical anisotropy by polymerizing a polymerizable liquid crystal compound, and 2) a monomer having an oxirane ring or an oxetane ring easily undergoes ring-opening polymerization. The idea was to combine these two findings. When research was conducted based on this idea, the experimental results were better than expected. Based on these results, the present invention including the following items was completed through repeated studies.

Item 1. A compound represented by formula (1) or (2).

In formula (1) or (2), R ¹ is hydrogen, fluorine, chlorine, cyano (—CN), nitro (—NO ₂ ), or alkyl having 1 to 20 carbons, and in this alkyl, any hydrogen is Any one or two —CH ₂ — may be replaced by fluorine or chlorine and —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or It may be replaced by -C≡C-.

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 groups in which any one or two —CH ₂ — in butyl (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. When any two —CH ₂ — are replaced by —O—, the oxygen and oxygen are more preferable than the adjacent CH ₃ —O—O—CH ₂ — in consideration of the stability of the compound. CH ₃ —O—CH ₂ —O— in which and are not adjacent to each other is preferred. The expression “may be replaced” has a similar meaning in other cases.

Preferred R ¹ is hydrogen, fluorine, chlorine, cyano (—CN), nitro (—NO ₂ ), trifluoromethoxy (—OCF ₃ ), difluoromethoxy (—OCF ₂ H), fluoromethoxy (—OCHF ₂ ), Tetrafluoroethyl (—CF ₂ CF ₂ H), hexafluoropropyl (—CF ₂ CHFCF ₃ ), alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkoxyalkyl having 2 to 15 carbons. . More preferable R ¹ is fluorine, chlorine, cyano, trifluoromethoxy, difluoromethoxy, fluoromethoxy, tetrafluoroethyl, hexafluoropropyl, alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or 2 carbons ~ 15 alkoxyalkyl. Particularly preferred R ¹ is alkyl having 1 to 10 carbons.

R ² is hydrogen or alkyl having 1 to 8 carbon atoms, and in this alkyl, arbitrary hydrogen may be replaced with fluorine or chlorine. Preferred R ² is hydrogen or alkyl having 1 to 5 carbons. More desirable R ² is hydrogen or alkyl having 1 to 4 carbon atoms. Particularly preferred R ² is hydrogen, methyl or ethyl.

R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 10 carbon atoms, in which any hydrogen may be replaced with fluorine or chlorine, and any one or two Two —CH ₂ — may be replaced by —O—, —S—, —COO—, —OCO—, —CO—, —CH═CH—, or —C≡C—.

Desirable R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 8 carbons. Further preferred R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 6 carbons. Particularly preferred R ³ and R ⁴ are independently hydrogen, methyl or ethyl. Preferred combinations of R ³ and R ⁴ are hydrogen and hydrogen, hydrogen and fluorine, fluorine and fluorine, hydrogen and chlorine, hydrogen and methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl. Further preferred combinations of R ³ and R ⁴ are hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl. Particularly preferred combinations of R ³ and R ⁴ are hydrogen and hydrogen, hydrogen and methyl, or methyl and methyl.

A is 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, or tetrahydro Naphthalene-2,6-diyl in which any hydrogen may be replaced by fluorine or chlorine, and any one or two hydrogens may be cyano (-CN), methyl (- CH _3), ethyl _(-CH 2 _CH 3), methoxy (-OCH _3), hydroxy (-OH), formyl (-CHO), acetoxy (-OCOCH _3), acetyl (-COCH _3), trifluoroacetyl ( -COCF _3), it may be replaced by difluoromethyl _(-CF 2 H), or trifluoromethyl (-CF _3).

  Preferred A is 1,4-cyclohexylene, 1,4-phenylene or pyridine-2,5-diyl, in which any hydrogen may be replaced by fluorine, and any 1 Two hydrogens may be replaced with methyl, ethyl, methoxy, acetoxy, or acetyl. When A is 1,4-cyclohexylene, the preferred configuration is trans rather than cis.

  More preferable A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4. -Phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, 2,3,5,6-tetrafluoro-1,4-phenylene, 2-methyl -1,4-phenylene or 2-methoxy-1,4-phenylene.

  Particularly preferred A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4- Phenylene and 2,6-difluoro-1,4-phenylene. Most preferred A is 1,4-phenylene.

X is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —COO—. , —OCO—, —CONH—, —NHCO—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CH—COO—, or —OCO -CH = CH-.

Preferred X is a single bond, — (CH ₂ ) ₂ —, —CH═CH—, —C≡C—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —COO. -, - OCO-, or - _{(CH 2) 4} - a. Further preferred X is a single bond, —C≡C—, —COO— or —OCO—. Particularly preferred X is —COO— or —OCO—.

P is alkylene having 1 to 20 carbon atoms, in which any hydrogen may be replaced with fluorine or chlorine, and any —CH ₂ — may be replaced with —O—, Or two —CH ₂ — may be replaced with —COO— or —OCO—, and any one —CH ₂ — may be replaced with —CH═CH— or —C≡C—.

Preferred P is alkylene having 1 to 12 carbons, in which any —CH ₂ — may be replaced by —O—, and any one —CH ₂ — may be —COO— or —OCO—. May be replaced. Further preferred P is —O—, — (CH ₂ ) _d —, —O— (CH ₂ ) _d —, — (CH ₂ ) _d —O—, —O— (CH ₂ ) _d —O—, or -O- _{(CH 2} CH ₂ O) a s-, d is an integer from 1 to 10, and s is an integer from 2 to 5. _-O Among them _{-, - O- (CH 2)} d -, - O- (CH 2) d -O-, and _{-O- (CH 2 CH 2 O)} s- is, - _(CH 2) _d - and - _{(CH 2)} d -O- preferred. When P is —O— (CH ₂ ) _d —, this symbol indicates that —O— is bonded to the —A— side rather than the —CH ₂ — side. This is exemplified by the compound (3a) described later. In the compound (1) having an oxirane ring, particularly preferred P is —O— (CH ₂ ) _d — and —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10. In the compound (2) having an oxetane ring, particularly preferred P is —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10.

  And m and n are independently 0, 1 or 2, and the sum of m and n is 1, 2, 3, or 4. A preferable sum of m and n is 1 or 2. A more preferable sum of m and n is 2.

Item 2. In the formula (1) or (2), R ¹ is hydrogen, fluorine, chlorine, cyano, nitro, trifluoromethoxy, difluoromethoxy, fluoromethoxy, tetrafluoroethyl, hexafluoropropyl, alkyl having 1 to 15 carbons, carbon R 1 is alkoxy or C 2-15 alkoxy; R ² is hydrogen or C 1-5 alkyl; R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, carbon An alkyl having a number of 1 to 8; A is 1,4-cyclohexylene, 1,4-phenylene, pyridine-2,5-diyl, and in this 1,4-phenylene, any hydrogen is replaced by fluorine. And any one hydrogen may be replaced by methyl, ethyl, methoxy, acetoxy, or acetyl; X is a single bond , — (CH ₂ ) ₂ —, —CH═CH—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —COO—, —OCO—, or — (CH _{2 4} ); P is alkylene having 1 to 10 carbon atoms, in which any —CH ₂ — may be replaced by —O—, and any one —CH ₂ — may be —COO; -Or -OCO- may be replaced; and m and n are independently 0, 1 or 2, and the sum of m and n is 1, 2 or 3.

Item 3. In Formula (1) or (2), P represents —O—, — (CH ₂ ) _d —, —O— (CH ₂ ) _d —, — (CH ₂ ) _d —O—, —O— (CH _{2 ) d -O -, - COO- (} CH 2) d -O -, - OCO- (CH 2) d -O-, or _-O- (CH ₂ CH ₂ O) a s-, from d 2 Item 3. The term according to Item 1 or 2, wherein s is an integer of 10, s is an integer of 2 to 5, m and n are independently 0, 1 or 2, and the sum of m and n is 1 or 2. Compound.

Item 4. Any one compound represented by following formula (3)-(8).

In the above formula, R ¹ is fluorine, chlorine, cyano, trifluoromethoxy, difluoromethoxy, fluoromethoxy, tetrafluoroethyl, hexafluoropropyl, alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or carbon number R ² is hydrogen, alkyl having 1 to 4 carbon atoms; R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 4 carbon atoms; A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, or 2,3,5,6-tetrafluoro-1, 4-phenylene; X is a single bond, —C≡C—, —COO— or —OCO—; P is —O—, —O— (CH ₂ ) _d —, —O— (CH ₂ ) _d -O- or _-O- (CH ₂ CH ₂ O) a s-, d is an integer of 1 to 15, and s is an integer from 2 to 5.

Item 5. In Formulas (3) to (8), R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 13 carbons, alkoxy having 1 to 13 carbons, or alkoxyalkyl having 2 to 13 carbons; R ² is Hydrogen, methyl, or ethyl; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and fluorine, fluorine and fluorine, hydrogen and chlorine, hydrogen and methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or Ethyl and ethyl; A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, 2,6-difluoro-1,4-phenylene; X is a single bond, —COO— or —OCO— P is —O—, —O— (CH ₂ ) _d —, —O— (CH ₂ ) _d —O—, or —O— (CH ₂ CH ₂ O) s—, and d is 1 to 10; Item 5. The compound according to Item 4, wherein s is an integer of 2 to 5.

Item 6. In formula (3), (5) or (7), R ¹ is alkyl having 1 to 10 carbons; R ² is hydrogen; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, Hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl; A is 1,4-phenylene; X is —COO— or —OCO—; P is —O—, —O—. Item 6. The compound according to Item 4 or 5, wherein the compound is (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10.

Item 7. Item 4 wherein in formula (3), (5) or (7), P is —O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is 2 to 10. 5. The compound according to 5 or 6.

Item 8. Item 8. The compound according to any one of Items 4 to 7, wherein in the formula (3), (5) or (7), the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, or methyl and methyl.

Item 9. In formula (4), (6) or (8), R ¹ is alkyl having 1 to 10 carbons; R ² is methyl or ethyl; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and Methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl; A is 1,4-phenylene; X is —COO— or —OCO—; P is —O—, — Item 6. The compound according to Item 4 or 5, wherein the compound is O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10.

Item 10. In formula (4), (6) or (8), P is —O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10 Item 10. The compound according to Item 4, 5 or 9.

Item 11. Item 11. The compound according to Item 4, 5, 9, or 10 wherein in the formula (4), (6) or (8), the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, or methyl and methyl.

Item 12. Any one compound represented by the following formulas (1A) to (1L) and formulas (2A) to (2F).

上式において、Ｒ^１はシアノ、トリフルオロメトキシ、炭素数１〜１０のアルキル、または炭素数１〜１０のアルコキシであり、ｄは２から１０の整数である。

In the above formula, R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons, and d is an integer of 2 to 10.

  Item 13. The composition containing the at least 1 compound of any one of claim | item 1 -3 as a 1st component.

  Item 14. Item 13. A composition containing at least one compound according to any one of Items 4 to 12 as a first component.

  Item 15. Item 15. The composition according to Item 14, further comprising a polymerizable compound different from the compound according to any one of Items 1 to 12 as a second component.

Item 16. The second component is at least one compound selected from the group of compounds represented by formula (M1), formula (M2), formula (M3), formula (M4), formula (M5), and formula (M6) Item 16. The composition according to Item 15.

In the formulas (M1) to (M6), Ra is hydrogen, fluorine, chlorine, cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkoxyalkyl having 2 to 20 carbons, Alkenyl having 2 to 20 carbons or alkenyloxy having 2 to 20 carbons; Rb is hydrogen or alkyl having 1 to 5 carbons; B is 1,4-cyclohexylene or 1,4-phenylene. And in this 1,4-phenylene any hydrogen may be replaced with fluorine, and any one or two hydrogens may be replaced with methyl or trifluoromethyl, and one of B is pyridine -2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene- , 7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl, or 9,9-difluorofluorene-2, 7 may be 7-diyl; Y is a single bond, —COO—, —OCO—, — (CH ₂ ) ₂ —, or —C≡C—; Q is a single bond or having 1 to 20 carbon atoms Alkylene, in which one or two —CH ₂ may be replaced by —O—; and t is 1 or 2.

Item 17. In the formulas (M1) to (M6), Ra is fluorine, cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, or alkoxy having 2 to 20 carbons; Rb is hydrogen or having 1 to 2 carbons B is 1,4-cyclohexylene or 1,4-phenylene, in which any hydrogen may be replaced by fluorine, and any one or two hydrogens May be replaced by methyl or trifluoromethyl, and one of B may be 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7-diyl; Y is a single bond , —COO—, —OCO—, or —C≡C—; Q is a single bond or alkylene having 1 to 10 carbons, and in this alkylene, one or two CH ₂ - may be replaced by -O-; and t is composition according to claim 16 which is 1 or 2.

  Item 18. The second component is selected from at least one compound selected from the group of compounds represented by formula (M1) and formula (M2), or from the group of compounds represented by formula (M3) and formula (M4) Item 18. The composition according to Item 16 or 17, which is at least one compound selected from the group of compounds represented by formula (M5) and formula (M6).

  Item 19. The second component is at least one compound represented by formula (M1) and at least one compound represented by formula (M3), or at least one compound represented by formula (M1) and formula (M4) At least one compound represented, or at least one compound represented by formula (M2) and at least one compound represented by formula (M3), or at least one compound represented by formula (M2) Item 18. The composition according to item 16 or 17, which is at least one compound represented by (M4).

  Item 20. Item 13. A polymer obtained from the compound according to any one of Items 1 to 12.

  Item 21. Item 20. A polymer obtained by polymerizing the composition according to any one of items 13 to 19.

  Item 22. Item 22 containing the polymer according to Item 20 or 21.

  Item 23. Item 22. Use of the polymer according to Item 20 or 21 as a molded article having optical anisotropy.

The compounds of the present invention have the following characteristics. This compound polymerizes at room temperature, polymerizes in air, is easy to polymerize, has a wide liquid crystal phase temperature range, is chemically stable, is colorless, is soluble in solvents, and is compatible with other polymerizable compounds. A plurality of characteristics are satisfied in characteristics such as good solubility and low adhesion tension to the support substrate. This compound has a liquid crystal phase. This liquid crystal phase has a wide temperature range. The molecular orientation in the liquid crystal phase is maintained by polymerization. That is, the molecular orientation is fixed by polymerization. Polymerization of a liquid crystal compound having an acryloyloxy group (—OCOCH═CH ₂ ) is preferably performed in an atmosphere of nitrogen, but this compound may be polymerized in air. This compound easily polymerizes even when irradiated with a small amount of accumulated ultraviolet light. Since this compound is chemically stable, it has excellent storage stability. Since this compound has good compatibility with other polymerizable compounds, compositions having various compositions can be obtained. Since this compound tends to get wet with respect to a support substrate, it is easy to obtain a uniform coating film. Of these, important are characteristics such as polymerization in the air, easy polymerization, a wide temperature range of the liquid crystal phase, and a uniform coating film being easily obtained.

  A polymer obtained from such a compound has the following characteristics. This polymer has optical anisotropy, is difficult to peel from the support substrate, has sufficient hardness, has high heat resistance, is colorless and transparent, has high weather resistance, has low photoelasticity, etc. A characteristic satisfies a plurality of characteristics. This polymer may be excellent in properties such as impact resistance, processability, electrical properties, and solvent resistance. Of these, important are characteristics such as difficulty in peeling from the support substrate, sufficient hardness, and high heat resistance.

  Compound (1) or (2) has one polymerizable group. This compound has a wider temperature range of the liquid crystal phase than the compound having two polymerizable groups (see Comparative Example 1). A compound having two polymerizable groups gives a polymer having a three-dimensional structure, whereas compound (1) or (2) gives a polymer having a two-dimensional structure. Therefore, since the polymer (1) or (2) is soft, it has a large impact resistance. Since this polymer is thermoplastic, it can be molded.

  First, the compound of the present invention will be described. Compound (1) is a liquid crystal compound having an oxirane ring. Compound (2) is a liquid crystal compound having an oxetane ring. These compounds are polymerizable and are stable under normal handling conditions. These compounds are easily polymerized at room temperature even under an air atmosphere by irradiation with ultraviolet rays or the like. This is because the compound (1) has a fast initiation reaction and the compound (2) has a high polymerization rate. Compounds (1) and (2) are easily aligned by an alignment film or the like. Therefore, the obtained polymer has no or few alignment defects.

  Compound (1) is preferable to compound (2) from the viewpoint of a high polymerization rate. The compound (1) is more preferable than the compound (2) from the viewpoint of excellent adhesiveness of the polymer (1) to be obtained. The compound (2) is more preferable than the compound (1) from the viewpoint of giving a polymer having a high degree of polymerization. The compound (2) is more preferable than the compound (1) from the viewpoint of giving a polymer having sufficient hardness.

Compounds (1) and (2) have a large dielectric anisotropy by appropriately selecting the side chains R ¹ , R ² , R ³ , R ⁴ , ring A, linking group X, and linking group P, Characteristics such as small dielectric anisotropy, large optical anisotropy, small optical anisotropy, and small viscosity can be adjusted.

When R ¹ is fluorine, chlorine, cyano, or trifluoromethoxy, the compound (1) or (2) appears to have a low melting point. When R ¹ is alkyl, the temperature range of the liquid crystal phase can be adjusted by the number of carbon atoms. When R ² is alkyl, a monomer having a small number of carbons tends to give a large heat-resistant polymer. When one or both of R ³ and R ⁴ is fluorine or chlorine, the melting point of compound (1) or (2) seems to be low. When one or both of R ³ and R ⁴ are alkyl, the temperature range of the liquid crystal phase can be adjusted by the number of carbons.

  When A is 1,4-cyclohexylene, the optical anisotropy of the compound (1) or (2) is small. When A is 1,4-phenylene, the optical anisotropy of the compound (1) or (2) is large. When at least one of X is —COO— or —OCO—, the compound (1) or (2) has better liquid crystallinity. When at least one of X is —C≡C—, the compound (1) or (2) has a large optical anisotropy. When P has oxygen (—O—), the optical anisotropy of the compound (1) or (2) is large.

Compound (1) or (2) may contain more isotope elements such as ² H (deuterium) or ¹³ C than naturally occurring. Even in such a case, there is no significant difference in the characteristics of the compound.

  The properties of compound (1) or (2) are reflected in the properties of polymer (1) or polymer (2). Among the characteristics, optical anisotropy is important for the purpose of the present invention. When the composition containing the compound (1) or the compound (2) is polymerized on the support substrate, the obtained polymer is difficult to peel from the support substrate. Since the compounds (3) to (6) have a low viscosity, they are suitable for reducing the viscosity of the composition. Since the compound (7) or (8) has a wide temperature range of the liquid crystal phase, it is suitable for expanding the temperature range of the liquid crystal phase in the composition.

Preferred compounds (1) and (2) are the compounds (3) to (8) already described. Further preferred compounds (1) and (2) are the compounds (3a) to (8b) described below. These are compounds in which P is —O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—.

In these formulas, R ¹ is hydrogen, fluorine, chlorine, cyano (—CN), nitro (—NO ₂ ), trifluoromethoxy (—OCF ₃ ), or alkyl having 1 to 20 carbon atoms. Any one or two of —CH ₂ — may be replaced by —O—. The combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, hydrogen and ethyl, or methyl and methyl. A is 1,4-cyclohexylene or 1,4-phenylene in which any hydrogen may be replaced by fluorine or chlorine and any one or two hydrogens are methyl Or it may be replaced by trifluoromethyl. X is a single bond, —C≡C—, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —CONH—, —NHCO—, — (CH ₂ ) ₂ COO—, —OCO ( _{CH 2) 2 -, - CH} = CH-COO-, or -OCO-CH = CH- is. d is an integer of 1-10.

  Next, a method for synthesizing the compounds (1) and (2) will be described. Compound (1) or (2) can be obtained from Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Syntheses (Organic Syntheses). , John Wily & Sons, Inc.), Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. Can be synthesized.

One of the starting materials in the compounds (1) and (2) is fluorenes. Commercially available products are 2-bromofluorene, 2,7-dibromofluorene, 2-bromo-7-pentylfluorene, 2-amino-7-bromofluorene, and the like. 2-Pentyl-7-hydroxyfluorene and 7-pentylfluorene-2-carboxylic acid are synthesized by methods described in the literature. The literature is Mol. Cryst. Liq. Cryst., 129 , 17 (1985). 2-Bromo-7-pentylfluorene can be synthesized by the method described in JP 2000-178211 (see Example 1, paragraph 0040). 2-acetyl-7-hydroxyfluorene is described in JP 2001-139525 A (see paragraph 0051 of Example 1).

  A fluorene derivative in which the 9-position is substituted with alkyl is synthesized by alkylating the 9-position of the fluorene ring. Fluorene substituted at the 9-position by monoalkyl is synthesized by treating fluorene with 1 equivalent of a base such as n-butyllithium and then reacting with 1 equivalent of alkyl bromide. For 9-methylfluorene derivatives, see Organic Syntheses, Collective Volume 4, page 623 or JP 2003-238491 (paragraphs 0043-0044). The 9-position dialkyl substituted fluorene derivative is synthesized by treating with 2 equivalents of a base such as n-butyllithium and then reacting with 2 equivalents of alkyl bromide. See the method described in Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 31, 2465 (1993).

  A fluorene derivative substituted at the 9-position with fluorine is synthesized by fluorination at the 9-position. The 9,9-difluorofluorene derivative is synthesized by the method described in Synlett, 191 (1991). A method for synthesizing 2,7-dihydroxy-9-methylfluorene is described in JP-A-2003-238491 (see paragraphs 0092 to 0095 of Example 4).

The oxirane ring is formed by an epoxidation reaction with an olefin peroxide. Examples of peroxides are hydrogen peroxide, peracetic acid, m-chloroperbenzoic acid and the like. For the 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 X is disclosed in JP-A-2003-277359 (paragraphs 0040 to 0053). A method for producing a linking group X connected to a fluorene ring is disclosed in JP-A-2003-238491 (paragraphs 0019 to 0038). The synthesis scheme of compound (1) or (2) is illustrated.

スキーム１．化合物（７ｂ）の合成

Scheme 1. Synthesis of compound (7b)

  Synthesis of Compound (7b) in which X is —COO— and —OCO— (oxycarbonyl) (Scheme 1): Compound by etherifying Compound [a] and a hydroxybenzoic acid ester derivative in the presence of a suitable base [B] is obtained. Examples of bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like. Compound [b] is hydrolyzed to obtain compound [c]. On the other hand, 2,7-dihydroxyfluorene [d] is reacted with an equivalent amount of acid chloride [e] to obtain monoester [f]. Diester [g] is obtained by esterification of this monoester [f] and the previously obtained compound [c]. Compound (7b) is synthesized by oxidizing this diester [g] with a peroxide. Examples of the peroxide are hydrogen peroxide solution, formic acid, peracetic acid, perbenzoic acid, m-chloroperbenzoic acid and the like.

スキーム２．化合物（８ａ）または（８ｂ）の合成

Scheme 2. Synthesis of compound (8a) or (8b)

  Synthesis of Compound (8a) or (8b) in which X is —COO— and —OCO— (oxycarbonyl) (Scheme 2): Etherification of Compound [h] and Hydroxybenzoate in the Presence of a Suitable Base To obtain compound [i]. Examples of bases are potassium hydroxide, sodium hydroxide, potassium carbonate, sodium hydride and the like. Compound [i] is hydrolyzed to obtain compound [j]. Compound (8a) or (8b) is synthesized by esterification of monoester [f] and compound [j].

スキーム３．化合物（８ａ）または（８ｂ）の合成 Synthesis of compound (8a) or (8b) in which X is —C≡C— (triple bond) is as shown in Scheme 3 below.

Scheme 3. Synthesis of compound (8a) or (8b)

スキーム４．化合物（４）および（８）の合成 The compound (4) in which X is —OCO—, the compound (8) in which X is —COO—, and the compound (8) in which X is —CH ₂ O— (methyleneoxy) are synthesized according to Scheme 4 below. Is done. Compound (5) in which X is —OCO— is synthesized according to Scheme 5.

Scheme 4. Synthesis of compounds (4) and (8)

スキーム５．化合物（５）の合成

Scheme 5. Synthesis of compound (5)

  Examples of compounds synthesized by such methods include Compound No. 1-No. 190.

  Next, the composition of the present invention will be described. This composition contains at least one of compounds (1) and (2) as a first component. This composition usually means a mixture of a plurality of compounds, but even one compound (1) or one compound (2) may be referred to as a composition. This is because a polymerization catalyst or the like may be added to one compound for polymerization, or one compound may be diluted with a solvent to form a thin film. By polymerizing the composition containing the first component, a polymer having optical anisotropy is obtained. The polymerizable compound of this composition may be only the first component. This composition may contain both the first component and a polymerizable compound (other polymerizable compound) different from the first component. This composition is classified into the following compositions A, B, C, D and the like. Composition A contains one compound selected from the group of compounds (1) and (2). Composition B contains at least two compounds selected from the group of compounds (1) and (2). Composition C contains at least one compound selected from the group of compounds (1) and (2) as the first component and at least one compound selected from the group of other polymerizable compounds as the second component. . Composition D is Composition A, B or C which further contains a non-polymerizable compound.

The “other polymerizable compound” is a polymerizable compound (monomer) different from the compounds (1) and (2). Another polymerizable compound is used as the second component of the composition C. This second component is useful for improving or modifying the properties of the resulting polymer. This second component may be optically inactive or optically active. This second component may be liquid crystalline or non-liquid crystalline. The second component may be only these same types of compounds or a combination of different types of compounds. Preferred examples of such a polymerizable compound include oxiranyl group (oxiranyl), oxetanyl group (oxetanyl), vinyloxy group (—OCH═CH ₂ ), vinyl group (—CH═CH ₂ ), acryloyloxy group (—OCOCH═ CH ₂ ), a compound having a methacryloyloxy group (—OCOC (CH ₃ ) ═CH ₂ ) and the like. Examples of these compounds are described in JP-A-8-3111. Preferred examples of the second component include a liquid crystal compound and an optically active compound. Preferred examples of the liquid crystal compound are the compounds (M1) to (M6) already described. Preferred examples of the optically active compound are compounds (OP1) to (OP14) described later.

  A preferred composition C is illustrated. The first example is composition C containing at least one of compounds (1) and (2) as the first component and at least one of compounds (M1) to (M6) as the second component. This second component compound has a polymerizable group suitable for copolymerization with compounds (1) and (2). Preferred compounds (M1) to (M6) are compounds (M1a) to (M6f).

In these formulas: R ⁵ is hydrogen, fluorine, chlorine, cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons, and R ⁶ is hydrogen or having 1 to 5 carbons. W ¹ and W ² are independently hydrogen, chlorine, fluorine, or cyano, and W ³ and W ⁴ are independently hydrogen, chlorine, fluorine, cyano, methyl, ethyl, propyl, or tri Fluoromethyl, X ⁵ and X ⁶ are independently a single bond or —O—, and o, p and r are each independently an integer of 1 to 20.

  When the first component is at least one of the compounds (3) to (8) and the second component is at least one of the compounds (M1) to (M6), examples of preferred combinations include the composition (C1 ) To (C12). Preferred compositions are summarized in Table 1. Compounds (M1) to (M6) are properties such as temperature range of liquid crystal phase, viscosity, alignment of liquid crystal phase in the composition, or properties such as film-forming property, mechanical strength, and adhesion to the support substrate in the polymer. Convenient to adjust.

  In such composition C, the ratio of the first component to the second component is as follows. A preferred ratio is in the range of 5 to 95% by weight of the first component and 5 to 95% by weight of the second component. A more desirable ratio is that the first component is in the range of 20 to 90% by weight and the second component is in the range of 20 to 80% by weight. A particularly desirable ratio is in the range of 40 to 80% by weight of the first component and in the range of 20 to 60% by weight of the second component.

Table 1. Preferred composition
Composition Compound of the first component Compound of the second component
Composition C1 (3), (5) or (7) (M2)
Composition C2 (3), (5) or (7) (M4)
Composition C3 (3), (5) or (7) (M6)
Composition C4 (3), (5) or (7) (M1) or (M2)
Composition C5 (3), (5) or (7) (M3) or (M4)
Composition C6 (3), (5) or (7) (M5) or (M6)
Composition C7 (4), (6) or (8) (M2)
Composition C8 (4), (6) or (8) (M4)
Composition C9 (4), (6) or (8) (M6)
Composition C10 (4), (6) or (8) (M1) or (M2)
Composition C11 (4), (6) or (8) (M3) or (M4)
Composition C12 (4), (6) or (8) (M5) or (M6)

  The features of the compositions (C1) to (C12) are as follows. 1) A polymer can be easily obtained by irradiating the composition with ultraviolet rays in the presence of an appropriate photocationic polymerization catalyst. 2) Polymerization proceeds not only in an atmosphere of nitrogen but also in air. 3) When it becomes a polymer (film) from a composition, it is hard to become small in size. Among compositions (C1) to (C12), particularly preferred examples are compositions (C2), (C5), (C7), and (C10). The characteristics of these compositions are as follows. 1) Polymerization is fast and a high molecular weight film can be obtained in a short time. 2) A film excellent in dimensional stability can be obtained. 3) A film excellent in heat resistance can be obtained.

  The next example is a composition C containing at least one of the compounds (1) and (2) as a first component and an optically active polymerizable compound as a second component. The second component induces a helical structure in the liquid crystal phase. The second component is preferably a compound having a large helical twist power. Preferred examples of the optically active polymerizable compound are compounds (OP1) to (OP14).

In these formulas, R ⁶ is hydrogen or alkyl having 1 to 5 carbon atoms, W ¹ and W ² are independently hydrogen, chlorine, fluorine, or cyano, and W ³ and W ⁴ are independently hydrogen. , Chlorine, fluorine, cyano, methyl, ethyl, propyl, or trifluoromethyl, X ⁶ is a single bond or —O—, o, p, and r are each independently an integer from 1 to 20, and * Is an asymmetric carbon. Compounds (OP10) to (OP13) are axially asymmetric.

  In such a composition, the ratio of the first component to the second component is as follows. A preferred ratio is in the range of 5 to 95% by weight of the first component and 5 to 95% by weight of the second component. A more desirable ratio is that the first component is in the range of 20 to 90% by weight and the second component is in the range of 20 to 80% by weight. A particularly desirable ratio is in the range of 40 to 80% by weight of the first component and in the range of 20 to 60% by weight of the second component.

  Composition A, B or C may further contain a polymerizable compound which is non-liquid crystalline and optically inactive. Examples of such compounds are ethyl vinyl ether, hydroxybutyl monovinyl ether, tert-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, di (3 -Ethyl-oxeta-3-ylmethyl), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane and the like. These compounds are suitable for adjusting the viscosity of the composition. These compounds have a great effect of making the thickness of the coating film uniform when the composition is applied.

  The composition D is a composition A, B, or C that further contains a non-polymerizable compound. Examples of such compounds are liquid crystal compounds and optically active compounds. Examples of liquid crystal compounds are described in a liquid crystal compound database (registered trademark: LiqCryst) sold by Fujitsu Kyushu Engineering. Such a compound can be expected to play a role of adjusting the viscosity of the composition and adjusting the temperature range of the liquid crystal phase. The optically active compound can be expected to play a role of adjusting the pitch of the composition.

  Compositions such as A, B, C, and D may further contain additives as necessary. Examples of additives for adjusting the properties of the polymer include surfactants, antioxidants, ultraviolet absorbers, and fine particles. Examples of the additive for polymerizing the monomer include a polymerization initiator and a brightener. Organic solvents are preferred for diluting the composition. The ratio of these additives is preferably a small amount that achieves its purpose.

  The surfactant has effects such as easy application of the composition to a support substrate and the like, and controlling the orientation of the liquid crystal phase. 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. A desirable ratio of the surfactant is in the range of 100 ppm to 5% by weight based on the total weight of the polymerizable compound, although it depends on the kind of the surfactant, the component ratio of the composition, and the like. A more desirable ratio is in the range of 0.1 to 1% by weight.

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

  Examples of ultraviolet absorbers are Tinuvin PS, Tinuvin 213, Tinuvin 109, Tinuvin 328, Tinuvin 384-2, Tinuvin 327, Tinuvin 400, Tinuvin 411L, etc. manufactured by Ciba Specialty Chemicals.

  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. 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 desirable ratio is 0.1 to 30% by weight. 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.

  A preferred polymerization initiator is an initiator for photocationic polymerization. This initiator is particularly suitable for the compositions (C1) to (C13). Examples of the initiator include diaryliodonium salts (hereinafter abbreviated as DAS), triarylsulfonium salts (hereinafter abbreviated as TAS), and the like.

  Examples of DAS are diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetra (pentafluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium Hexafluorophosphonate, 4-methoxyphenylphenyl iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis ( 4-tert-butylphenyl) iodonium di E sulfonyl iodonium trifluoromethanesulfonate and the like.

  A combination of DAS and photosensitizer is preferred. Examples of photosensitizers are thioxanthone, phenothiazine, chlorothioxanthone, xanthone, anthracene, diphenylanthracene, rubrene and the like.

  Examples of TAS are triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium tetra (pentafluorophenyl) borate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium triphenylsulfonium tetra (pentafluorophenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate 4-phenylthiophenyldi E sulfonyl sulfonium hexafluorophosphonate, and the like 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate.

  An example of a trade name of an initiator used for photocationic polymerization is DTS-102 of Midori Chemical Co., Ltd. Examples of this are U.S.C. Syracure UVI-6990, Syracure UVI-6974, Syracure UVI-6922, and the like. This example is also an Adeka optomer SP-150, SP-152, SP-170, SP-172, etc. of Asahi Denka Co., Ltd. Examples include Rhodia's PHOTOINITIATOR 2074, Ciba Specialty's Irgacure 250, GE Silicones' UV-9380C, and the like.

  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, 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.

  Next, the polymer of the present invention will be described. Compounds (1) and (2) have a polymerizable group. A polymer is obtained by polymerizing a composition containing these compounds. The obtained polymer has optical anisotropy. The types of 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 cationic polymerization. When obtaining a polymer with excellent orientation, cationic polymerization by irradiation with light is more preferred. This is because it is easy to perform polymerization under the condition that the composition has a liquid crystal phase.

Preferred types of light are 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), 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 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.

  When polymerizing composition A, a homopolymer is obtained. This homopolymer consists of one structural unit. When composition B or composition C is polymerized, a copolymer is obtained. This copolymer has at least two structural units. The arrangement of the structural units in the copolymer may be random, block, alternating, or the like. When the composition D is polymerized, a polymer containing a non-polymerizable compound inhomogeneously is obtained. The polymer has at least one structural unit.

  A thermoplastic resin can be obtained by using the compound (1) or (2) as a monomer. This resin has a linear polymer structure by using a compound having one polymerizable group as a main component. The preferred weight average molecular weight of the thermoplastic resin is 500 to 1,000,000, preferably 1,000 to 500,000, more preferably 5,000 to 100,000. When synthesizing a thermoplastic resin, the degree of polymerization is adjusted by controlling the reaction. When synthesizing the thermoplastic resin, preferred second components in the copolymerization are compounds (M1), (M3), (M5) and the like.

  A thermosetting resin can also be synthesized by using the compound (1) or (2) as a monomer. This resin can be obtained from a composition composed mainly of a compound having two polymerizable groups. Since this resin has a three-dimensional crosslinked structure, it does not dissolve in a solvent and does not melt. Therefore, the molecular weight cannot be measured. When synthesizing the thermosetting resin, preferred second components in the copolymerization are the compounds (M2), (M4), (M6) and the like.

  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 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, although the range cannot be determined strictly, the preferred thickness is in the range of 0.05 to 50 μm, and the more preferred 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. Therefore, these polymers are suitable as optically anisotropic thin films used for liquid crystal display elements.

  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, plasma treatment, UV-ozone treatment, if 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 barcode, dip coating, spray coating, meniscus coating, and cast film formation.

  Factors that determine the alignment of the liquid crystal are 1) the chemical structure of the polymerizable compound, 2) the type of the supporting substrate, and 3) the method of alignment treatment. In item 1), the orientation depends on the type of the side chain, ring, bonding group, polymerizable group and the like of the polymerizable compound. In item 2), the orientation depends on the material of the support substrate such as a polymer, glass, metal or the like. Regarding item 3), there are methods such as rubbing in one direction with a rayon cloth or the like (rubbing), oblique deposition of silicon oxide, or 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, tilt, twist, 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. 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. 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, decorations, nonlinear optical materials, information storage materials, and the like.

  Thermoplastic resins are suitable for applications such as adhesives, synthetic polymers with mechanical anisotropy, cosmetics, ornaments, nonlinear optical materials and information storage materials. The thermosetting resin is suitable for uses such as a retardation plate, a polarizing element, a liquid crystal alignment film, an antireflection film, a selective reflection film, and a viewing angle compensation film, which are constituent elements of a liquid crystal display element.

  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. 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.

  A polymer having a twist orientation is useful as a retardation plate. When the pitch of the helix 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 helix, 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.

  This polymer is also useful as a brightness enhancement film. For example, according to the method disclosed in JP-A-6-281814, a polymer in which the helical pitch continuously extends in the thickness direction can be obtained. This polymer can reflect light in a wide wavelength range corresponding to the pitch. This polymer can selectively reflect light in a region of 100 to 350 nm (or a wavelength of 350 to 750 nm).

  After describing the method of measuring the characteristics, 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 unit of the ratio in the composition is wt% (wt%).

  Phase transition temperature: A sample was placed on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope, and the temperature was increased at a rate of 1 ° C / min. The temperature at which the liquid crystal phase transitions to another liquid crystal phase was measured. C is a crystal, N is a nematic phase, 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.

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

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

  The heat resistance test was: This test was carried out at 100 ° C. for 500 hours, and the result was evaluated by the variation of retardation. A polyamic acid (PIA5310 from Chisso Corporation) was applied to the glass substrate, and then heated at 210 ° C. for 30 minutes to obtain a support 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, 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 25 ° C. After heating the polymer at 100 ° C. for 500 hours, the retardation was measured again at 25 ° C. Two values were compared to evaluate heat resistance. The retardation was measured using a Senarmont compensator according to literature methods. The wavelength used is 550 nm. Literature is written by Hiroshi Ashiya, “Introduction to Polarizing Microscopes of Polymer Materials”, p. 94, published by Agne Technology Center, 2001.

  Optical anisotropy (Δn): The value of retardation (25 ° C.) of the polymer was measured according to the method of the 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.

  Orientation: The orientation was observed with a polarizing microscope. The polymer was prepared on a support substrate. As the support substrate, a saponified TAC (triacetylcellulose) film was used. 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 18 First stage: A solution of 14 g of allyl (4-chlorobutyl) ether, 14 g of 4-hydroxybenzoic acid, and 14 g of potassium carbonate in dimethylformamide (50 ml) was stirred at 90 ° C. for 3 hours. Water was added and extracted with toluene. The toluene layer was thoroughly washed with water, and then 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. After the ethanol was distilled off, hydrochloric acid was added to the residue to make it acidic. Extraction was performed with diethyl ether, and the extract was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was recrystallized from a mixed solvent of ethanol and water to obtain 29 g of 4- (4-allyloxybutyloxy) benzoic acid. Phase transition temperature: C94N107I.

Second stage: To a solution of 10 g of 2,7-dihydroxy-9-methylfluorene and 8 g of pyridine in tetrahydrofuran (100 ml), 12.5 g of octyloxybenzoic acid chloride was added in several portions and refluxed for 5 hours. 50 ml of 5% hydrochloric acid was added to the reaction mixture, and the mixture was extracted with methylene chloride. The extract was washed with 5% hydrochloric acid until the pH became acidic, then washed with a saturated aqueous 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 (elution solvent: methylene chloride), and 10 g of 2- (4-octyloxybenzoyloxy) -7-hydroxy-9-methylfluorene (J1 ) Melting point 140-143 [deg.] C.

  Third stage: 0.84 g of 4- (4-allyloxybutyloxy) benzoic acid and 1.5 g of 2- (4-octyloxybenzoyloxy) -7-hydroxy-9-methylfluorene (J1) in methylene chloride (50 ml) ) To the solution, 0.01 g of dimethylaminopyridine and 0.8 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added while maintaining 5 ° C., and the mixture was further stirred at room temperature for 12 hours. 50 ml of water was added, and the obtained organic layer was dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, and 0.5 g of 2- [4- (4-allyloxybutyloxy) benzoyloxy] -7- (4-octyloxybenzoyloxy) -9-methylfluorene (J2) was obtained.

Fourth stage: 2- [4- (4-allyloxybutyloxy) benzoyloxy] -7- (4-octyloxybenzoyloxy) -9-methylfluorene (J2) in a solution of 0.5 g of methylene chloride (20 ml). , 1 g of m-chlorobenzoic acid was added and stirred at room temperature for 2 days. The reaction mixture was washed with a 5% aqueous sodium hydroxide solution, an aqueous sodium hydrogen sulfite solution, and an aqueous sodium hydrogen carbonate solution in that order, and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography, recrystallized from a mixed solvent of ethanol and ethyl acetate, and 0.1 g of Compound No. 18 was obtained. The phase transition temperature is as follows.

Example 2
Compound No. Synthesis of 19 First step: The following compound (J3) was synthesized in the same manner as in Example 1 and Second step. The phase transition temperature is as follows. As raw materials, p-cyanobenzoyl chloride and 2,7-dihydroxy-9-methylfluorene were used.

Second stage: The following compound (J4) was synthesized in the same manner as in Example 1 and the third stage. Compound (J3) and 4- (4-allyloxybutyloxy) benzoic acid were used as raw materials.

Third stage: In the same manner as in Example 1 and Fourth stage, the following compound No. 19 was synthesized. The phase transition temperature is as follows.

Example 3
Compound No. Synthesis of 68 First stage: Stir a solution of 500 g of 3-[(6-bromohexyloxy) methyl] -3-ethyloxetane, 297 g of 4-hydroxybenzoic acid and 490 g of potassium carbonate at 90 ° C. for 8 hours. did. 4 L of water was added to the reaction mixture, followed by extraction with 4 L of toluene. The organic layer was washed with water and the solvent was distilled off. To the obtained residue, 200 g of sodium hydroxide, 1 L of water, and 2.5 L of ethanol were added and refluxed for 4 hours. Ethanol (1 L) was distilled off at normal pressure and then acidified with hydrochloric acid to obtain a slurry. The slurry was filtered and dried to obtain 400 g of 4- [6- (3-ethyloxetane-3-ylmethoxy) hexyloxy] benzoic acid. Melting point: 58.5 ° C.

  The following compounds were synthesized by the same method. 4- [6- (3-Methyloxetane-3-ylmethoxy) hexyloxy] benzoic acid (melting point: 61 ° C.). 4- [4- (3-Ethyloxetane-3-ylmethoxy) butyloxy] benzoic acid (melting point: 75.3-77.7 ° C.). 2-Fluoro-4- [4- (3-ethyloxetane-3-ylmethoxy) butyloxy] benzoic acid (melting point: 75-80 ° C.). 4- (3-Ethyloxetane-3-ylmethoxy) benzoic acid (melting point: 127.5 ° C.).

Second stage: A solution of 0.76 g of 4- [6- (3-ethyloxetane-3-ylmethoxy) hexyloxy] benzoic acid and 0.8 g of compound (J3) in methylene chloride (50 ml) was cooled to 5 ° C. 0.05 g of dimethylaminopyridine and 0.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added and stirred at room temperature for 12 hours. 50 ml of water was added to the reaction mixture, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography, and further recrystallized from ethanol to give 3 g of Compound No. 68 was obtained. The phase transition temperature is as follows.

Example 4
In Example 3, the second step, using compound (J2), compound No. 65 was synthesized. The phase transition temperature is as follows.

Comparative Example 1
Compound No. 4 of Example 4 65 has one oxetane ring. This compound is compared with the following compound having two oxetanes. Compound No. The temperature range of the 65 nematic phase was 92 ° C. from 79 ° C. to 171 ° C. It was 71.7 ° C. from 59 ° C. to 130.7 ° C. Therefore, it is concluded that the compound of the present invention has a wider temperature range of the nematic phase.

Example 5
Compound No. Synthesis of 171 First stage: 22.4 g of 2-acetyl-7-hydroxyfluorene, 18 g of allyl (4-chlorobutyl) ether and 20 g of potassium carbonate were added to 150 ml of dimethylformamide and stirred at 90 ° C. for 8 hours. The reaction mixture was poured into 300 ml of 6N hydrochloric acid to obtain a solid. The solid was filtered off and dried, and the solid was recrystallized from ethanol to obtain 22 g of 2-acetyl-7- (4-allyloxybutyloxy) fluorene. The melting point was 77 ° C.

  Second stage: A solution of 22 g of 2-acetyl-7- (4-allyloxybutyloxy) fluorene in dioxane (380 ml) was cooled to 8 ° C. Thereto was added dropwise sodium hypobromite prepared from 209 ml of water, 42.7 g of sodium hydroxide and 15.2 ml of bromine. After dropping, the mixture was stirred at 40 ° C. for 15 minutes. After the reaction mixture was cooled to 10 ° C., a saturated aqueous sodium thiosulfate solution was added. A solid precipitated by acidifying with hydrochloric acid was filtered and dried. The solid was recrystallized from acetic acid to obtain 15 g of 2- (4-allyloxybutyloxy) fluorene-7-carboxylic acid. Phase transition temperature: C164N222I.

Third stage: A solution of 2 g of 2- (4-allyloxybutyloxy) fluorene-7-carboxylic acid and 1.17 g of 4-cyanophenol in methylene chloride (50 ml) was cooled to 5 ° C. 05 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (1.4 g) was added, and the mixture was stirred at room temperature for 12 hours. 50 ml of water was added to the reaction mixture, and the organic layer was separated and dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel chromatography and recrystallized from ethanol to obtain 2.3 g of Compound (J5).

Fourth stage: To a solution of 2.3 g of compound (J5) in methylene chloride (20 ml) was added 1.5 g of m-chlorobenzoic acid, and the mixture was stirred at room temperature for 2 days. The reaction mixture was washed with a 5% aqueous sodium hydroxide solution, an aqueous sodium hydrogen sulfite solution, and an aqueous sodium hydrogen carbonate solution in that order, and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent was purified by silica gel column chromatography and recrystallized from a mixed solvent of ethanol and ethyl acetate to obtain 1.4 g of Compound No. 171 was obtained.

Example 6
In Example 4, the third step, compound (J6) was synthesized using 3-fluoro-4-trifluoromethoxyphenol instead of 4-cyanophenol. Phase transition temperature: C110N176I. Next, the compound No. 3 was oxidized by the method of Example 3 and the fourth stage. 172 was synthesized.

Example 7
50% by weight of compound no. Composition (CL1) was prepared from 68 and 50% by weight of compound (K1). This composition had a nematic phase at room temperature. Compound No. 68 had good compatibility and never phase separated. When the composition (CL1) was applied on a rubbed TAC film, it showed homogeneous orientation.

  After saponifying the TAC film, the surface was rubbed with a rayon cloth. To this film, 1 g of composition (CL1) and 0.03 g of cyclopentanone (4 g) and toluene (4 g) solution of DTS-102 (polymerization initiator of Midori Chemical Co., Ltd.) were applied using a spin coater. . After the application, it was heated in an oven set at 60 ° C. for 5 minutes. The solvent was removed by this heat treatment to align the liquid crystal molecules. An ultra-high pressure mercury lamp (250 W / cm) was used to irradiate ultraviolet rays at 60 ° C. for 10 seconds to obtain a liquid crystal alignment film (F1). The homogeneous orientation of the composition was maintained by polymerization. In the cellophane peeling test of this film, there was no more flaking. The pencil hardness of this film was 2H.

Example 8
70% by weight of compound no. Composition (CL2) was prepared from 18 and 30% by weight of compound (K2). This composition had a nematic phase at room temperature. Compound No. 18 had good compatibility and did not phase separate. Composition (CL2) exhibited hybrid orientation when applied on a rubbed TAC film.

  After saponifying the TAC film, the surface was rubbed with a rayon cloth. A cyclopentanone (8 g) solution of 1 g of the composition (CL2) and 0.03 g of DTS-102 (Midori Chemical Co., Ltd. polymerization initiator) was applied to this film using a spin coater. After the application, it was heated in an oven set at 60 ° C. for 5 minutes. The solvent was removed by this heat treatment to align the liquid crystal molecules. An ultra-high pressure mercury lamp (250 W / cm) was used for irradiation with ultraviolet rays at 60 ° C. for 10 seconds to obtain a liquid crystal alignment film (F2). The hybrid orientation of the composition was retained by polymerization. In the cellophane peeling test of this film, there was no more flaking. The pencil hardness of this film was 2H.

The evaluation results of these films are summarized in Table 2. From these results, it was found that 1) the polymer was difficult to peel from the support substrate, and 2) the polymer was hard.

Table 2. Evaluation results
Film number Cellophane peel test Pencil hardness Orientation
F1 100/100 2H Homogeneous
F2 100/100 2H hybrid

Claims (17)

Any one compound represented by following formula (3)-(8).

In the above formula, R ¹ is fluorine, chlorine, cyano, trifluoromethoxy, difluoromethoxy, fluoromethoxy, tetrafluoroethyl, hexafluoropropyl, alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or carbon number R ² is hydrogen, alkyl having 1 to 4 carbon atoms; R ³ and R ⁴ are independently hydrogen, fluorine, chlorine, or alkyl having 1 to 4 carbon atoms; A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, or 2,3,5,6-tetrafluoro-1, 4-phenylene; X is a single bond, —C≡C—, —COO— or —OCO—; P is —O—, —O— (CH ₂ ) _d —, —O— (CH ₂ ) _d -O- or _-O- (CH ₂ CH ₂ O) a s-, d is an integer of 1 to 15, and s is an integer from 2 to 5. In Formulas (3) to (8), R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 13 carbons, alkoxy having 1 to 13 carbons, or alkoxyalkyl having 2 to 13 carbons; R ² is Hydrogen, methyl, or ethyl; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and fluorine, fluorine and fluorine, hydrogen and chlorine, hydrogen and methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or Ethyl and ethyl; A is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro- 1,4-phenylene, 2,6-difluoro-1,4-phenylene; X is a single bond, —COO— or —OCO— P is —O—, —O— (CH ₂ ) _d —, —O— (CH ₂ ) _d —O—, or —O— (CH ₂ CH ₂ O) s—, and d is 1 to 10; The compound according to claim 1 , wherein s is an integer of 2 to 5. In formula (3), (5) or (7), R ¹ is alkyl having 1 to 10 carbons; R ² is hydrogen; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, Hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl; A is 1,4-phenylene; X is —COO— or —OCO—; P is —O—, —O—. _{(CH 2) d} - or -O- _{(CH 2)} a d -O-, and a compound according to claim 1 or 2 d is an integer from 2 to 10. In formula (3), (5) or (7), P is —O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is 2 to 10. The compound according to 1 , 2 or 3 . The compound according to any one of claims 1 to 4 , wherein in the formula (3), (5) or (7), the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, or methyl and methyl. . In formula (4), (6) or (8), R ¹ is alkyl having 1 to 10 carbons; R ² is methyl or ethyl; the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and Methyl, hydrogen and ethyl, methyl and methyl, methyl and ethyl, or ethyl and ethyl; A is 1,4-phenylene; X is —COO— or —OCO—; P is —O—, — O- _{(CH 2) d} - or -O- _{(CH 2)} a d -O-, and a compound according to claim 1 or 2 d is an integer from 2 to 10. In formula (4), (6) or (8), P is —O— (CH ₂ ) _d — or —O— (CH ₂ ) _d —O—, and d is an integer of 2 to 10 The compound according to claim 1 , 2 or 6 . The compound according to claim 1 , 2 , 6 or 7 , wherein, in the formula (4), (6) or (8), the combination of R ³ and R ⁴ is hydrogen and hydrogen, hydrogen and methyl, or methyl and methyl. . Any one compound represented by the following formulas (1A) to (1L) and formulas (2A) to (2F).

In the above formula, R ¹ is cyano, trifluoromethoxy, alkyl having 1 to 10 carbons, or alkoxy having 1 to 10 carbons, and d is an integer of 2 to 10. As a first component, a liquid crystal composition containing at least one compound according to any one of claims 1-9. Wherein the second component (M1), the formula (M2), the formula (M3), the formula (M4), formula (M5), and at least one compound selected from the group of compounds represented by formula (M6) Furthermore , the liquid crystal composition of Claim 10 contained.

In the formulas (M1) to (M6), Ra is hydrogen, fluorine, chlorine, cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, alkoxyalkyl having 2 to 20 carbons, Alkenyl having 2 to 20 carbons or alkenyloxy having 2 to 20 carbons; Rb is hydrogen or alkyl having 1 to 5 carbons; B is 1,4-cyclohexylene or 1,4-phenylene. And in this 1,4-phenylene any hydrogen may be replaced with fluorine, and any one or two hydrogens may be replaced with methyl or trifluoromethyl, and one of B is pyridine -2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene- , 7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl, or 9,9-difluorofluorene-2, 7 may be 7-diyl; Y is a single bond, —COO—, —OCO—, — (CH ₂ ) ₂ —, or —C≡C—; Q is a single bond or having 1 to 20 carbon atoms Alkylene, in which one or two —CH ₂ may be replaced by —O—; and t is 1 or 2. In the formulas (M1) to (M6), Ra is fluorine, cyano, trifluoromethoxy, alkyl having 1 to 20 carbons, or alkoxy having 2 to 20 carbons; Rb is hydrogen or having 1 to 2 carbons B is 1,4-cyclohexylene or 1,4-phenylene, in which any hydrogen may be replaced by fluorine, and any one or two hydrogens May be replaced by methyl or trifluoromethyl, and one of B may be 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7-diyl; Y is a single bond , —COO—, —OCO—, or —C≡C—; Q is a single bond or alkylene having 1 to 10 carbons, and in this alkylene, one or two CH ₂ - may be replaced by -O-; and t is the liquid crystal composition according to claim 11 which is 1 or 2. The second component is selected from at least one compound selected from the group of compounds represented by formula (M1) and formula (M2), or from the group of compounds represented by formula (M3) and formula (M4) The liquid crystal composition according to claim 11 or 12 , which is at least one compound selected from the group of compounds represented by formula (M5) and formula (M6). The second component is at least one compound represented by formula (M1) and at least one compound represented by formula (M3), or at least one compound represented by formula (M1) and formula (M4) At least one compound represented, or at least one compound represented by formula (M2) and at least one compound represented by formula (M3), or at least one compound represented by formula (M2) The liquid crystal composition according to claim 11 or 12 , which is at least one compound represented by (M4). A polymer obtained from a compound according to any one of claims 1-9. A polymer obtained by polymerizing the liquid crystal composition according to any one of claims 10-14. The element containing the polymer of Claim 15 or 16 .