JP4934971B2 - Polymerizable liquid crystal compound having cyclic sulfide and polymer thereof - Google Patents

Description

  The present invention relates to a polymerizable liquid crystal compound having a cyclic sulfide, a polymer obtained from the compound, 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 acrylic group (Patent Document 2). What is further desired is a liquid crystal compound having physical properties such as polymerization at room temperature, polymerization in the air, and easy polymerization by ultraviolet irradiation.

JP 2001-55573 A JP 2001-154019 A

  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, and other polymerizable compounds It is a liquid crystal compound that satisfies a plurality of characteristics in terms of characteristics such as good compatibility 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. The problems are physical properties 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 having

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

Wherein R ^a is a polymerizable group represented by the group (3); R ^b is hydrogen, halogen, —CN, —NO ₂ , —N═C═O, —N═C═S, or carbon. In the alkyl, any one or two of —CH ₂ — is —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—, Or -C≡C-, where any hydrogen in the alkyl may be replaced by a halogen; R ^c is hydrogen, halogen, or alkyl of 1 to 5 carbons, Hydrogen may be replaced by halogen; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6 -Diyl, fluorene- A 7-diyl or bicyclo [2.2.2] octane-1,4-diyl, any -CH ₂ - in the ring - may be replaced by -O-, arbitrary -CH = may may be replaced by -N =, arbitrary hydrogen in the rings may be replaced by halogen, and any one or two hydrogen _{-CN, -OH, -CHO, -OCOCH 3} , -COCH ₃ , —COCF ₃ , —CF ₂ H, —CF ₃ , alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; Z is independently a single bond or 1 to 20 alkylene, in which any —CH ₂ — may be replaced by —O— or —S—, and any one or two —CH ₂ — may be —COO—, —OCO—, -CONH-, Ma Or any one —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen may be replaced with a halogen. Well; m is an integer of 1 to 4; q is 0 or 1, and a plurality of R ^a , A and Z may be the same group or different groups.

  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 physical properties 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. .

  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 a composition containing the compound (1) or the like may be referred to as a polymer (1). A polymer obtained from a composition containing the compound (2) or the like may be referred to as a polymer (2).

  The present inventor has obtained 1) a polymer having optical anisotropy by polymerizing a polymerizable liquid crystal compound, and 2) a monomer having a cyclic sulfide is a monomer having a cyclic ether; In comparison with this, it was conceived to combine the two findings that the polymerization temperature decreases and the polymerization rate increases because ring-opening polymerization is easier. 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 (1) or formula (2).

In the formula (1), it was used A, Z, symbols such as ^{R a.} The meanings of the two symbols A may be the same or different. This rule also applies the symbols Z and R ^a. This rule also applies to other expressions.

In Formula (1) or Formula (2), R ^a is a polymerizable group represented by Group (3), and R ^b is hydrogen, halogen, —CN, —NO ₂ , —N═C═O, — N = C = S, or alkyl having 1 to 20 carbon atoms, and in this alkyl, any one or two of —CH ₂ — represents —O—, —S—, —CO—, —COO—, —OCO. -, -CH = CH-, or -C≡C- may be substituted, and in this alkyl, any hydrogen may be replaced by a halogen.

In this alkyl, —CH ₂ — may be replaced with —O— or the like, and hydrogen may be replaced with fluorine or the like at the same time. That is, R ^b contains alkyl in which —CH ₂ — is replaced by —O— or the like, and hydrogen is replaced by fluorine or the like. The meaning of the phrase “any —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 —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- Etc. 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 more preferable than CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent. The expression “may be replaced” has a similar meaning elsewhere.

Preferred R ^b is hydrogen, fluorine, chlorine, —CN, —NO ₂ , —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCFH ₂ , alkyl having 1 to 15 carbon atoms. , Alkoxy having 1 to 15 carbons, or alkoxyalkyl having 2 to 15 carbons. More preferable R ^b is hydrogen, fluorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCFH ₂ , alkyl having 1 to 15 carbons, or 1 to carbon atoms. 15 alkoxy, or alkoxyalkyl having 2 to 15 carbon atoms. Further preferred R ^b is hydrogen, fluorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCFH ₂ , alkyl having 1 to 13 carbons, or 1 to carbons 13 alkoxy or C2-C13 alkoxyalkyl. Particularly preferred R ^b is alkyl having 1 to 10 carbons.

R ^c is hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in this alkyl, arbitrary hydrogen may be replaced by halogen. Preferred R ^c is hydrogen, fluorine, chlorine, or alkyl having 1 to 5 carbon atoms, and in this alkyl, arbitrary hydrogen may be replaced with fluorine or chlorine. More preferable R ^c is hydrogen or alkyl having 1 to 5 carbons. More preferred R ^c is hydrogen.

A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl. Or bicyclo [2.2.2] octane-1,4-diyl, in which the optional —CH ₂ — may be replaced by —O—, where optional —CH═ is —N═. Any hydrogen in the ring may be replaced with a halogen, and any one or two hydrogens may be —CN, —OH, —CHO, —OCOCH ₃ , —COCH ₃ , —COCF _{3, -CF 2 H, -CF 3} , alkyl of 1 to 5 carbon atoms, or may be replaced by alkoxy having 1 to 5 carbon atoms.

Preferred A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7. -Diyl, pyridine-2,5-diyl, pyridazine-3,6-diyl, or pyrimidine-2,5-diyl, in which any hydrogen may be replaced by fluorine or chlorine, One of hydrogen -CN, methyl, ethyl, propyl, methoxy, ethoxy, acetoxy, acetyl, may be replaced by -CF ₃ or -OCF _3,.

More preferred A is independently 1,4-cyclohexylene, 1,4-phenylene, fluorene-2,7-diyl, or pyridine-2,5-diyl, in which any hydrogen is replaced by fluorine. Any one hydrogen may be replaced with methyl, ethyl, propyl, methoxy, ethoxy, acetoxy, acetyl, —CF ₃ , or —OCF ₃ . Further preferred A is independently 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 is there. Particularly preferred A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1 , 4-phenylene, or 2,6-difluoro-1,4-phenylene. Most preferred A is independently 1,4-phenylene.

Z is independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any —CH ₂ — may be replaced by —O— or —S—, and any one or two — CH ₂ — may be replaced with —COO—, —OCO—, —CONH—, or —NHCO—, and any one —CH ₂ — may be replaced with —CH═CH— or —C≡C—. And any hydrogen may be replaced with a halogen.

Preferred Z is independently a single bond or alkylene having 1 to 15 carbon atoms, and in this alkylene, any —CH ₂ — may be replaced by —O— or —S—, and any one or two of —CH ₂ — may be replaced with —COO— or —OCO—, any one —CH ₂ — may be replaced with —CH═CH— or —C≡C—, and any hydrogen May be replaced by fluorine or chlorine.

More preferable Z is independently a single bond, —O—, — (CH ₂ ) _r —, —O (CH ₂ ) _r —, — (CH ₂ ) _r O—, —O— (CH ₂ ) _r —O. -, - CH = CH-OCO -, - COO-CH = CH -, - OCO- (CH 2) 2 -, - (CH 2) 2 -COO -, - COO- (CH 2) r -O-, _{-OCO- (CH 2) r -O -} , - O- (CH 2 CH 2 O) s -, - CH = CH -, - C≡C -, - COO -, - OCO -, - OCF 2 -, or _-CF 2 is a O-, r is an integer from 1 to 10, s is an integer of 1 to 5. Further preferred Z is independently a single bond, —O—, — (CH ₂ ) _r —, —O (CH ₂ ) _r —, — (CH ₂ ) _r O—, —O— (CH ₂ ) _r —O. _{-, - O- (CH 2 CH} 2 O) s -, - COO-, or a -OCO-, r is an integer from 1 to 10, s is an integer of 1 to 5. Particularly preferred Z is independently a single bond, —O—, — (CH ₂ ) _r —, —O (CH ₂ ) _r —, — (CH ₂ ) _r O—, —O— (CH ₂ ) _r —O. -, -COO-, or -OCO-, and r is an integer of 2 to 10. Most preferred Z is independently —O (CH ₂ ) _r —, —O— (CH ₂ ) _r —O—, —COO—, or —OCO—, and r is an integer of 2 to 10.

R ^a is a polymerizable group represented by the group (3), and q is 0 or 1. Preferred q is 0.

  And m is an integer of 1-4. Preferred m is an integer of 1 to 3. More preferable m is an integer of 1 to 2.

[2] The compound according to item 1, wherein q is 0 in the group (3).

[3] In Formula (1) or Formula (2), R ^a is a polymerizable group represented by Group (3); R ^b is hydrogen, fluorine, chlorine, —CN, —NO ₂ , —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCHF ₂ , alkyl having 1 to 15 carbons, alkoxy having 1 to 15 carbons, or alkoxyalkyl having 2 to 15 carbons ^Rc is hydrogen, fluorine, chlorine, or alkyl having 1 to 5 carbons, and in this alkyl, any hydrogen may be replaced by fluorine or chlorine; A is independently 1,4-cyclohexylene; 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, pyridazine- , 6-diyl, or pyrimidine-2,5-diyl, in which any hydrogen may be replaced by fluorine or chlorine, and any one hydrogen is -CN, methyl, ethyl, propyl, methoxy, May be replaced by ethoxy, acetoxy, acetyl, —CF ₃ , or —OCF ₃ ; Z is independently a single bond or alkylene having 1 to 15 carbons, in which any —CH ₂ — is — O— or —S— may be replaced, any one 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— and any hydrogen may be replaced by fluorine or chlorine; m is an integer from 1 to 3; q is 0 or 1 There, the compound according to claim 1.

[4] In Formula (1) or Formula (2), R ^a is a polymerizable group represented by the group (3); R ^b is hydrogen, fluorine, —CN, —CF ₃ , —CF ₂ H, _{-CFH 2, -OCF 3, -OCF 2} H, -OCFH 2, alkyl of 1 to 15 carbon atoms, alkoxyalkyl of alkoxy having 1 to 15 carbon atoms, or 2 to 15 carbon atoms,,; ^{R c} is hydrogen Or an alkyl having 1 to 5 carbons; A is independently 1,4-cyclohexylene, 1,4-phenylene, fluorene-2,7-diyl, or pyridine-2,5-diyl, arbitrary hydrogen ring may be replaced by fluorine, any one hydrogen methyl, ethyl, propyl, methoxy, ethoxy, acetoxy, acetyl, may be replaced by -CF 3 or -OCF _3,; Z Germany Standing single _{bond, -O -, - (CH 2} ) r -, - O (CH 2) r -, - (CH 2) r O -, - O- (CH 2) r -O -, - CH _{= CH-OCO -, - COO} -CH = CH -, - OCO- (CH 2) 2 -, - (CH 2) 2 -COO -, - COO- (CH 2) r -O -, - OCO- ( _{CH 2) r -O -, -} O- (CH 2 CH 2 O) s -, - CH = CH -, - C≡C -, - COO -, - OCO -, - OCF 2 -, or -CF ₂ Item 2. The compound according to Item 1, wherein r is an integer of 1 to 10, s is an integer of 1 to 5, m is an integer of 1 to 2, and q is 0.

[5] A compound represented by any one of the following formulas (1a) to (1d) or (2a) to (2d).

In the formula, R ^a is a polymerizable group represented by the group (3); R ^b is hydrogen, fluorine, chlorine, —CN, —NO ₂ , —CF ₃ , —CF ₂ H, —CFH ₂ , — OCF ₃ , —OCF ₂ H, —OCHF ₂ , alkyl having 1 to 15 carbon atoms, alkoxy having 1 to 15 carbon atoms, or alkoxyalkyl having 2 to 15 carbon atoms; R ^c is hydrogen or 1 to 1 carbon atoms 5 is alkyl; A is independently 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; Z is independently single _{, -O -, - (CH 2} ) r -, - O (CH 2) r -, - (CH 2) r O -, - O- (CH 2) r -O -, - CH = CH-OCO- _{, -COO-CH = CH -,} - OCO- (CH 2) 2 -, - (CH 2) 2 -COO -, - COO- (CH 2) r -O -, - OCO- (CH 2) r - O—, —O— (CH ₂ CH ₂ O) _s —, —CH═CH—, —C≡C—, —COO—, —OCO—, —OCF ₂ —, or —CF ₂ O—, r is an integer of 1 to 10, s is an integer of 1 to 5; q is 0 or 1, and a plurality of R ^a , A and Z may be the same group or different groups. There may be.

[6] In the formulas (1a) to (1d) and (2a) to (2d), R ^a is a polymerizable group represented by the group (3); R ^b is hydrogen, fluorine, —CN , —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCHFH ₂ , alkyl having 1 to 13 carbons, alkoxy having 1 to 13 carbons, or 2 to 13 carbons alkoxyalkyl; ^{R c} is hydrogen; A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4 - phenylene, 2,5-difluoro-1,4-phenylene or be 2,6-difluoro-1,4-phenylene,; Z is independently a single _{bond, -O -, - (CH 2} ) r -, _{-O (CH 2) r -,} - (CH 2) r O -, - O- ( CH ₂ ) _r —O—, —O— (CH ₂ CH ₂ O) _s —, —COO—, or —OCO—, r is an integer of 1 to 10, and s is an integer of 1 to 5. Item 6. The compound according to Item 5, wherein q is 0.

[7] In formula (1a) to formula (1d) and formula (2a) to formula (2d), R ^a is a polymerizable group represented by group (3); R ^b has 1 to 10 carbon atoms ^Rc is hydrogen; A is independently 1,4-phenylene; Z is independently a single bond, —O—, — (CH ₂ ) _r —, —O (CH _{2 ) r -, - (CH 2} ) r O -, - O- (CH 2) r -O -, - COO-, or a -OCO-, r is an integer from 2 to 10; in q is 0 Item 6. The compound according to Item 5.

[8] In Formula (1a) to Formula (1d) and Formula (2a) to Formula (2d), R ^a is a polymerizable group represented by the group (3); R ^b has 1 to 10 carbon atoms ^Rc is hydrogen; A is independently 1,4-phenylene; Z is independently —O (CH ₂ ) _r —, —O— (CH ₂ ) _r —O—. Item 6. The compound according to Item 5, which is -COO- or -OCO-, r is an integer of 2 to 10, and q is 0.

[9] A composition containing at least one compound according to any one of items 1 to 4 as a first component.

[10] A composition containing at least one compound according to any one of items 5 to 8 as a first component.

[11] The composition according to item 10, further comprising a polymerizable compound different from the compound according to any one of items 1 to 8, as the second component.

[12] The second component is at least one selected from the group of compounds represented by formula (M1), formula (M2), formula (M3), formula (M4), formula (M5), and formula (M6). Item 12. The composition according to Item 11, which is one compound.

In Formulas (M1) to (M6), R ^d is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or carbon 2 ˜20 alkoxyalkyl, C2-20 alkenyl, or C2-20 alkenyloxy; R ^e is hydrogen or C1-5 alkyl; B is independently 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 is pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methyl Luolene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl, or 9,9-difluorofluorene May be -2,7-diyl; Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any one or two -CH ₂ is replaced by -O-. Any one —CH ₂ may be replaced by —COO—, —OCO—, —C═C—, or —C≡C—; and t is 1 or 2, B and Y may be the same group or different groups.

[13] In the formulas (M1) to (M6), R ^d is fluorine, —CN, —CF ₃ , —OCF ₃ , alkyl having 1 to 20 carbons, or alkoxy having 2 to 20 carbons; R ^e is hydrogen or alkyl having 1 to 2 carbon atoms; B is independently 1,4-cyclohexylene or 1,4-phenylene, in which any hydrogen is replaced by fluorine. And any one or two hydrogens may be replaced with methyl or trifluoromethyl, and one of B is 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7 Y may independently be a single bond, —COO—, —OCO—, —C≡C—, or alkylene having 1 to 10 carbons, and any one of these alkylenes Or the two —CH ₂ — may be replaced by —O—; and the composition according to Item 12, wherein t is 1 or 2.

[14] The second component is at least one compound selected from the group of compounds represented by formula (M1) and formula (M2), or a group of compounds represented by formula (M3) and formula (M4) Item 14. The composition according to Item 12 or Item 13, wherein the composition is at least one compound selected from: or at least one compound selected from the group of compounds represented by Formula (M5) and Formula (M6).

[15] The composition according to item 12 or 13, wherein the second component is at least one compound selected from the group of compounds represented by formula (M3) and formula (M4).

[16] A polymer obtained by polymerizing the compound according to any one of items 1 to 8.

[17] A polymer obtained by polymerizing the composition according to any one of items 9 to 15.

[18] A device comprising the polymer according to item 16 or item 17.

[19] Use of the polymer according to item 16 or item 17 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 easily polymerized, has a wide liquid crystal phase temperature range, is chemically stable, is colorless, is easily soluble in solvents, and other polymerizable liquid crystal compounds. It has characteristics such as good compatibility 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. The polymerization of the liquid crystal compound having an acrylic group 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 easily wets the support substrate, it is easy to obtain a uniform paint film. Among these, important are the 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 physical properties such as optical anisotropy, difficulty in peeling from the support substrate, sufficient hardness, high heat resistance, colorless and transparent, high weather resistance, and low photoelasticity. . This polymer is also excellent in properties such as impact resistance, processability, electrical properties, and solvent resistance. Of these, important characteristics are characteristics such as difficulty in peeling from the support substrate, sufficient hardness, and high heat resistance.

  Compound (1) is a liquid crystal compound having a monofunctional cyclic sulfide group. Compound (2) is a liquid crystal compound having a bifunctional cyclic sulfide group. These compounds are polymerizable and are stable under normal handling conditions. These compounds have a higher polymerization rate than a compound having a cyclic ether group which is an analog, and polymerization starts at a lower temperature. The compound (1) and the compound (2) are easily oriented by the orientation-treated substrate. Thus, the resulting polymer has no or few alignment defects.

Compound (1) and Compound (2) have a large dielectric anisotropy, a small dielectric anisotropy and a large optical difference by appropriately selecting the side chains R ^b , R ^c , ring A, and linking group Z. Physical properties such as isotropic, small optical anisotropy, and small viscosity can be adjusted.

When R ^b is fluorine, chlorine, —CN, or —OCF ₃ , it seems that the melting points of compound (1) and compound (2) are low. When ^Rb is alkyl, the temperature range of the liquid crystal phase can be adjusted by the number of carbon atoms. When R ^c is alkyl, monomers having a small number of carbons tend to give large heat-resistant polymers.

  Compound (1) and compound (2) having at least two cyclohexane rings have a high clearing point, a small optical anisotropy, and a small viscosity. The compound (1) and the compound (2) having at least one benzene ring have a relatively large optical anisotropy and a large liquid crystal alignment order. Compound (1) and compound (2) having at least two benzene rings have particularly high optical anisotropy, a wide temperature range of the liquid crystal phase and high chemical stability under normal handling conditions.

Compound (1) and compound (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 great difference in the physical properties of the compound.

  The physical properties of the compound (1) and the compound (2) are reflected in the physical properties of the polymer (1) and the polymer (2). Among the physical properties, 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.

  In order to set the temperature range of the liquid crystal phase to the low temperature side, the compound (1a) or the compound (2a) having two ring structures may be selected. When it is desired to set the temperature range of the liquid crystal phase to a relatively high temperature side, the compound (1b) or compound (2b) having three ring structures, or the compound (1c) or compound (2c) having four ring structures is selected. That's fine. In order to set the temperature range of the liquid crystal phase to a higher temperature side, the compound (1d) or the compound (2d) having five ring structures may be selected.

  Compound (1) is a monofunctional compound having a polymerizable group at one end of the molecule. Compound (2) is a bifunctional compound having a polymerizable group at both ends of the molecule. The bifunctional compound exhibits higher polymerizability than the monofunctional compound. That is, the bifunctional compound has a higher polymerization rate, completes the polymerization in a shorter time, and a polymer having a higher degree of polymerization can be obtained. The resulting polymer has higher heat resistance, lower water absorption, water permeability and gas permeability, and higher mechanical strength (particularly hardness).

In the formula (1) and the formula (2), the partial structure excluding the groups R ^a and R ^b at both molecular ends, that is, the partial structure shown below is the temperature of the liquid crystal phase in the compound (1) and the compound (2). It greatly contributes to the physical properties of the liquid crystal such as range, dielectric anisotropy, optical anisotropy and viscosity.

  This partial structure can be embodied in preferred formulas represented by formula (1-1) to formula (1-73). In Formula (1-1) to Formula (1-73), the ring is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, Tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, etc., each represented by the following formula in which any hydrogen is replaced: It may be a group.

  Of the formula (1-1) to the formula (1-73), as the partial structure that greatly contributes to the physical property value as the liquid crystal, the formula (1-1) to the formula (1-70) are more preferable. 1-1) to formula (1-33) are more preferable.

  Next, the manufacturing method of a compound (1) and a compound (2) is demonstrated. Compound (1) and Compound (2) are produced by Houben Wyle (Methoden der Organischen Chemie, Georg Thieme Verlag, Stuttgart), Organic Reactions (Organic Reactions, John Wily & Sons Inc.), Organic Synthetics (Organic). Synthes, John Wily & Sons, Inc.), Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. Can be manufactured.

The thiirane compound can be produced by replacing the oxygen atom of the oxirane ring in the oxirane compound with a sulfur atom using the corresponding oxirane compound or a ring-opening derivative thereof and potassium thiocyanate or thiourea. As a method for synthesizing a thiirane compound, for example, a method shown in J. Polym. Sci. Polym. Phys., 17 , 329 (1979) in which an oxirane compound and a thiocyanate are reacted is used. And the method shown in J. Org. Chem., 27 , 2832 (1962) from cyclic carbonate, such as the method shown in J. Org. Chem., 26 , 3467 (1961). is not.

  A thiirane compound can be constructed, for example, by the following method. It can be produced by reacting the corresponding oxirane compound with thiourea.

The main skeleton (liquid crystal residue) of compound (1) and compound (2) can be constructed by appropriately combining the following methods. That is, with respect to an example of a method for generating the bonding group Z, a scheme is first shown, and then a method for producing the scheme is described. In this scheme, MSG ¹ or MSG ² is a monovalent organic group having an arbitrary ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. From compound (1A) to compound (1L) corresponds to compound (1).

(I) Formation of a single bond A boric acid derivative (11) and a halide (12) synthesized by a known method are reacted in the presence of a catalyst such as an aqueous carbonate solution and tetrakis (triphenylphosphine) palladium. Compound (1A) is synthesized. This compound (1A) is prepared by reacting compound (13) synthesized by a known method with n-butyllithium and then with zinc chloride, and in the presence of a catalyst such as dichlorobis (triphenylphosphine) palladium. ) Is also reacted. The boric acid derivative (11) can be produced by inducing the compound (13) to a Grignard reagent or a lithium reagent and acting a trialkyl borate ester.

(II) Formation of —COO— and —OCO— The compound (13) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (14). Compound having —COO— by dehydrating compound (14) and phenol (15) synthesized by a known method in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) Synthesize (1B). A compound having —OCO— can also be synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (16) is obtained by treating compound (1B) with a sulfurizing agent such as Lawson's reagent. The compound (16) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1C) having —CF ₂ O—. See M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) can also be synthesized by fluorinating compound (16) with (diethylamino) sulfur trifluoride. See William H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having —OCF ₂ — can also be synthesized by this method.

(IV) Formation of —CH═CH— The compound (6) is treated with n-butyllithium and then reacted with formamide such as DMF (N, N-dimethylformamide) to obtain the aldehyde (17). A phosphonium salt (18) synthesized by a known method is treated with a base such as potassium t-butoxide, and a phosphorus ylide is reacted with an aldehyde (17) to synthesize a compound (1D). Since a cis isomer is generated depending on the reaction conditions, the cis isomer is isomerized to a trans isomer by a known method as necessary.

(V) Formation of — (CH ₂ ) ₂ — Compound (1E) is synthesized by hydrogenating compound (1D) in the presence of a catalyst such as palladium carbon.

(VI) Formation of — (CH ₂ ) ₄ — A compound having — (CH ₂ ) ₂ —CH═CH— is prepared by using the phosphonium salt (19) instead of the phosphonium salt (18) and according to the method of the item (IV). obtain. This is catalytically hydrogenated to synthesize compound (1F).

(VII) Formation of —C≡C— After reacting compound (13) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, under basic conditions Deprotection gives compound (20). Compound (1G) is synthesized by reacting compound (20) with compound (14) in the presence of a catalyst of dichloropalladium and copper halide.

(VIII) Formation of —CF═CF— The compound (13) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (21). Compound (21) is treated with n-butyllithium and then reacted with compound (14) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (22) is obtained by reducing compound (17) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (23). Compound (1J) is synthesized by reacting compound (23) with compound (24) in the presence of a base such as potassium carbonate.

Formation of (X)-(CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — Compound (1K) was synthesized according to the method of Item (IX) using Compound (25) instead of Compound (17). To do.

Formation of (XI)-(CF ₂ ) _2-
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., diketone (28) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to give-(CF ₂ ) _2-. To obtain a compound (1L) having

  Next, the liquid crystal composition of the present invention will be described. This composition contains at least one of compound (1) or compound (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. By polymerizing the composition containing the first component, a polymer having optical anisotropy is obtained. The polymerizable compound may be only the first component. This composition is classified into the following compositions A, B, C and the like. Composition A contains one compound selected from the group consisting of compound (1) and compound (2). Composition B 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. To do. The composition C is the composition A or B further containing a non-polymerizable compound.

  The “other polymerizable compound” is a polymerizable compound (monomer) different from the compound (1) and the compound (2). Other polymerizable compounds are useful for improving or modifying the properties of the resulting polymer. Other polymerizable compounds may or may not be optically active. Preferred examples of other polymerizable compounds that are not optically active include compounds having a thiranyl group, compounds having an oxiranyl group, compounds having an oxetanyl group, compounds having a vinyloxy group, compounds having a vinyl group, compounds having an acryloyloxy group, And compounds having a methacryloyloxy group. Examples of these compounds are described in JP-A-8-3111.

  Preferred second components in the composition B are the compounds (M1) to (M6) already described. Composition B comprises ethyl vinyl ether, hydroxybutyl monovinyl ether, t-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-hydroxymethyl oxetane, di (3-ethyl- A compound such as oxetane-3-ylmethyl) and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane may further be contained. 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 may contain an optically active compound or a dichroic dye. Since the composition containing an optically active compound exhibits a helical structure, a retardation plate having a helical structure can be produced by polymerizing the composition. The optically active compound to be added may be any optically active compound as long as it induces a helical structure and can be appropriately mixed with other compositions, and may be polymerizable or non-polymerizable. Then, it may be an optically active compound (1) or compound (2), or an optically active compound different from the compound (1) or compound (2). Of the optically active compounds different from the compound (1) or the compound (2), (Op-1) to (Op-12) shown below as non-polymerizable compounds and (Op-21) as polymerizable compounds -(Op-34) is preferable. In view of heat resistance and solvent resistance, a polymerizable compound is more preferable. Further, an optically active compound to be added is preferably a compound having a large helical twist power in order to shorten the helical pitch. In the formula, * represents an asymmetric carbon. 1,4-cyclohexylene marked with a-represents a trans-type cyclohexane ring.

In these formulas (Op-21) to (Op-34): R ⁶ is methyl or ethyl, W ¹ and W ² are each independently hydrogen, chlorine, fluorine, or cyano; ³ and W ⁴ are each independently hydrogen, chlorine, fluorine, cyano, methyl or trifluoromethyl, X ⁶ is independently a single bond or —O—, and o, p and r are each independently And it is an integer of 0-20. Compounds (Op-30) to (Op-34) are axially asymmetric.

  The composition C contains a non-polymerizable liquid crystal compound or an optically active compound. 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. In the case of an optically active compound, the role of adjusting the pitch of the composition can be expected.

  A preferred composition contains at least one of compound (1) or (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 compound (1) or (2). Preferred compounds (M1) to (M6) are more preferred, and (M1a) to (M6f) are more preferred compounds.

In this formula: R ⁵ is hydrogen, fluorine, chlorine, —CN, —OCF ₃ , alkyl having 1 to 20 carbons, or alkoxy having 1 to 20 carbons, and R ⁶ is hydrogen or having 1 to 5 carbons. Alkyl, W ¹ and W ² are independently hydrogen, chlorine, fluorine, or cyano, W ³ and W ⁴ are independently hydrogen, chlorine, fluorine, methyl, or ethyl, X ⁵ and X ⁶ is 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 (1a) to (2d) and the second component is at least one of the compounds (M1) to (M6), examples of preferred combinations include compositions (C1 ) To (C8). Preferred compositions are summarized in Table 1. The compounds (M1) to (M6) are used to adjust the temperature range of the liquid crystal phase, the viscosity, the orientation of the liquid crystal phase, the film-forming property in the polymer, the mechanical strength, the adhesion to the support substrate, and the like. convenient. The content of each component of these compositions is as follows based on the total weight of the composition. The content of the first component is 1 to 99% by weight, more preferably 5 to 95% by weight. The content of the second component is 1 to 99% by weight, more preferably 10 to 95% by weight.

Table 1. Preferred composition
Composition Compound of the first component Compound of the second component
Composition C1 (1a), (1b), (1c) or (1d) (M1) or (M2)
Composition C2 (1a), (1b), (1c) or (1d) (M3) or (M4)
Composition C3 (1a), (1b), (1c) or (1d) (M5) or (M6)
Composition C4 (2a), (2b), (2c) or (2d) (M1) or (M2)
Composition C5 (2a), (2b), (2c) or (2d) (M3) or (M4)
Composition C6 (2a), (2b), (2c) or (2d) (M5) or (M6)
Composition C7 (1a) or (1b) (M4)
Composition C8 (2a) or (2b) (M3)

  The features of the compositions (C1) to (C8) 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. 1) 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 (C8), particularly preferred examples are compositions (C7) and (C8). The characteristics of these compositions are as follows. 1) A high molecular weight film can be obtained in a short time with a fast polymerization reaction. 2) A film excellent in dimensional stability can be obtained. 3) A film excellent in heat resistance can be obtained.

  Compositions such as Compositions A, B, and C may further contain additives as necessary. Additives for adjusting the physical properties of the polymer include surfactants, antioxidants, ultraviolet absorbers, and fine particles. Additives for polymerizing the monomer include a polymerization initiator and a photosensitizer. Organic solvents are preferred for diluting the composition. The amount of these additives is preferably small enough to achieve the 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. 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. Preferable commercially available 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. Fine particles may be added to adjust the optical anisotropy or increase the strength of the polymer. Preferred fine particle materials are inorganic materials, organic materials, metals, 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) ₂ , 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.

  A preferred polymerization initiator is an initiator for photocationic polymerization. This initiator is particularly suitable for the compositions (C1) to (C16). Preferred initiators 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-methoxyphenyliodonium tetrafluoroborate, 4-methoxyphenyliodonium hexafluoro Phosphonate, 4-methoxyphenyliodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium diphenyliodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium diphenyliodonium hexafluoroarsenate, bis (4-t -Butylphenyl) iodonium diphenyliodonium trifluoromethanesulfur Sulfonate, 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-phenylthiophenyl Sulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate and the like.

  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 UCC's Silacure UVI-6990, UVI-6974, UVI-6922, and the like. Examples thereof include Adeka optomer SP-150, SP-152, SP-170, SP-172, etc. from Asahi Denka Kogyo Co., Ltd. Examples include Rhodia's PHOTOINITIATOR 2074, Ciba Specialty Chemicals 'Irgacure 250, GE Silicones' UV-9380C, and the like.

  Examples of solvents (solvents) are benzene, toluene, xylene, methylene, n-butylbenzene, diethylbenzene, tetralin, methoxybenzene, 1,2-dimethoxybenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone. , Methyl isobutyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, γ-butyllactone, 2-pyrrolidone, N-methyl-2 -Pyrrolidone, dimethylformamide, chloroform, dichloromethane, carbon tetrachloride, dichloro Tan, trichlorethylene, tetrachlorethylene, chlorobenzene, t- butyl alcohol, diacetone alcohol, glycerin, monoacetin, ethylene glycol, triethyl glycol, hexylene glycol, ethyl cellosolve, and the like butyl cellosolve. The solvent may be a single compound or a mixture.

  Next, the polymer 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 is liquid crystal.

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 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 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 the composition B 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 C is polymerized, a polymer composition containing the polymer (1) or (2) and a non-polymerizable compound is obtained. This polymer (1) or (2) has at least one structural unit.

  A thermoplastic resin can be obtained by using the compound (1) or (2) as a monomer. This resin is obtained by polymerizing a composition mainly composed of a compound having one polymerizable group, and has a linear polymer structure. 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, a preferred second component in the copolymerization is the compound (M1), (M3) or (M5).

  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, a preferred second component in the copolymerization is the compound (M2), (M4) or (M6).

  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 a composition on a supporting substrate and polymerizing a paint film (paint film) having a liquid crystal phase such as nematic alignment formed in the liquid crystal state. 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. 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 are triacetyl cellulose, 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 (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 cast film formation.

  Factors that determine the orientation of the composition are 1) the chemical structure of the polymerizable compound, 2) the type of the supporting substrate, 3) the method of the orientation 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. Regarding item 2), it depends on the material of the support substrate such as polymer, glass, metal and 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, 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, 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 having a helical pitch extending continuously 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 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%). In the following, the liter, which is a unit of capacity, is denoted by the symbol L. The composition ratio of the elution solvent for chromatography indicates the volume ratio.

The phase transition temperature was raised at a rate of 1 ° C./min by placing a sample on a hot plate of a melting point measurement apparatus equipped with a polarizing microscope. The temperature at which the liquid crystal phase transitions was measured. C is a crystal, N is a nematic phase, Ch is a cholesteric 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. The chemical structure of the synthesized compound was confirmed by ¹ H-NMR.

  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 performed at 100 ° C. for 500 hours, and the result was evaluated by the variation of retardation. After applying polyamic acid (PIA5310 manufactured by Chisso Corporation) to a glass substrate, the substrate was 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. 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 (support substrate). 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.

下記の経路により化合物（１−１−４−４）を製造した。

Example 1
Production of Compound (1-1-4-4)

Compound (1-1-4-4) was produced by the following route.

三口フラスコに温度計、撹拌機および滴下漏斗を取り付け、窒素雰囲気下、アリルアルコール（500 g, 3.84 mol）とテトラヒドロフラン（300 mL, 3.69 mol）を加え、−６０℃で１時間撹拌した。ここに塩化チオニル（500 g, 4.20 mol）を滴下し、さらに−６０℃で１時間撹拌後、２時間加熱還流した。減圧下で溶媒を留去し、残渣を減圧蒸留（5 mmHg, 110-110 ℃）により精製し、無色油状化合物（a）（471 g, 87％）を得た。 Production of compound (a)

A three-necked flask was equipped with a thermometer, stirrer and dropping funnel, allyl alcohol (500 g, 3.84 mol) and tetrahydrofuran (300 mL, 3.69 mol) were added under a nitrogen atmosphere, and the mixture was stirred at −60 ° C. for 1 hour. Thionyl chloride (500 g, 4.20 mol) was added dropwise thereto, and the mixture was further stirred at −60 ° C. for 1 hour and then heated to reflux for 2 hours. The solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure (5 mmHg, 110-110 ° C.) to obtain a colorless oily compound (a) (471 g, 87%).

三口フラスコ、滴下漏斗、還流冷却器、撹拌子および温度計を組み立てた装置に、５５％水素化ナトリウム（7.5 g, 0.17 mol）とＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）（100 mL）を加え、ここに、窒素雰囲気下、室温で（b）（30.5 g, 0.16 mol）をＤＭＦ（400 mL）に溶解した溶液を滴下し、３０分間撹拌した。次に、（a）（19.3 g, 0.13 mol）を加え、６０℃で２日間撹拌した。反応混合物に水を加え、トルエンで抽出し、水洗後、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣をカラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）により精製し無色油状物質化合物（c）（33.15 g, 98%）を得た。 Production of compound (c)

55% sodium hydride (7.5 g, 0.17 mol) and N, N-dimethylformamide (DMF) (100 mL) were added to an apparatus in which a three-necked flask, a dropping funnel, a reflux condenser, a stirring bar and a thermometer were assembled. A solution prepared by dissolving (b) (30.5 g, 0.16 mol) in DMF (400 mL) was added dropwise at room temperature under a nitrogen atmosphere, and the mixture was stirred for 30 minutes. Next, (a) (19.3 g, 0.13 mol) was added, and the mixture was stirred at 60 ° C. for 2 days. Water was added to the reaction mixture, extracted with toluene, washed with water, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent toluene / ethyl acetate: 8/2) to obtain a colorless oily compound (c) (33.15 g, 98%).

三口フラスコ、滴下漏斗、撹拌子および温度計を組み立てた装置に、純度７７％のｍ−クロロ過安息香酸（26.58 g, 0.12 mol）とジクロロメタン（300 mL）を加え、窒素雰囲気下、０℃に冷却した。ここに（c）（33.15 g. 0.11 mol）のジクロロメタン溶液（100 mL）を滴下し、終夜撹拌した。白色析出物をろ別し、炭酸水素ナトリウム水溶液および硫酸水素ナトリウム水溶液で洗浄し、残留過酸化物を処理した。無水硫酸マグネシウムで乾燥し、減圧下で溶媒を留去した。カラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）で分取し、エタノールにより再結晶を行い、白色結晶化合物（d）（18.14 g, 51%）を得た。 Production of compound (d)

77% pure m-chloroperbenzoic acid (26.58 g, 0.12 mol) and dichloromethane (300 mL) were added to a device assembled with a three-necked flask, a dropping funnel, a stirring bar and a thermometer. Cooled down. A dichloromethane solution (100 mL) of (c) (33.15 g. 0.11 mol) was added dropwise thereto and stirred overnight. The white precipitate was filtered off and washed with an aqueous sodium hydrogen carbonate solution and an aqueous sodium hydrogen sulfate solution to treat the residual peroxide. The extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The fraction was separated by column chromatography (developing solvent: toluene / ethyl acetate: 8/2) and recrystallized from ethanol to obtain white crystalline compound (d) (18.14 g, 51%).

撹拌子を入れた三口フラスコに、窒素雰囲気下（d）（1.00 g, 3.10 mol）、ジクロロメタン（3 mL）およびメタノール（3 mL）を入れ撹拌した。ここにチオ尿素（0.35 g, 4.65 mmol）を添加し、終夜撹拌した。反応混合物を水洗し、硫酸マグネシウムで乾燥した後、減圧下で溶媒を留去した。残渣をカラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）により分取を行い、エタノールより再結晶し、無色結晶化合物（１−１−４−４）（0.81 g, 77%）を得た。相転移温度：Ｃ（Ｎ３５）６３Ｉ（℃）。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：７．６３−７．７０（ｍ， ４Ｈ）， ７．５３（ｄ， ２Ｈ），６．９９（ｄ， ２Ｈ），４．０５（ｔ， ２Ｈ）， ３．６１−３．６４（ｍ， １Ｈ），３．５９（ｔ， ２Ｈ）， ３．４８−３．５２（ｍ， １Ｈ），３．０６−３．１１（ｍ， １Ｈ）， ２．５３（ｄ， １Ｈ），２．２２（ｄ， １Ｈ），１．８９−１．９４（ｍ， ２Ｈ），１．７８−１．８３（ｍ，２Ｈ）。
Production of Compound (1-1-4-4)

A three-necked flask containing a stirrer was stirred under nitrogen atmosphere (d) (1.00 g, 3.10 mol), dichloromethane (3 mL) and methanol (3 mL). To this was added thiourea (0.35 g, 4.65 mmol), and the mixture was stirred overnight. The reaction mixture was washed with water and dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was fractionated by column chromatography (developing solvent toluene / ethyl acetate: 8/2) and recrystallized from ethanol to obtain colorless crystalline compound (1-1-4-4) (0.81 g, 77%). It was. Phase transition temperature: C (N35) 63I (° C.). ¹ H-NMR (CDCl ₃ ; δ ppm): 7.63-7.70 (m, 4H), 7.53 (d, 2H), 6.99 (d, 2H), 4.05 (t, 2H) ), 3.61-3.64 (m, 1H), 3.59 (t, 2H), 3.48-3.52 (m, 1H), 3.06-3.11 (m, 1H), 2.53 (d, 1H), 2.22 (d, 1H), 1.89-1.94 (m, 2H), 1.78-1.83 (m, 2H).

下記の経路により化合物（１−２−４−１）を製造した。

Example 2
Production of compound (1-2-4-1)

Compound (1-2-4-1) was produced by the following route.

三口フラスコ、撹拌機および温度計を取り付けた装置に、窒素雰囲気下、ＤＭＦ（3 L）、（e）（637 g, 3.83 mol）、４−ブロモブテン（575 g, 4.26 mol）および炭酸カリウム（636 g, 4.60 mol）を加え、１００℃で３時間撹拌した。放冷後、析出した不溶物をろ別し、ろ液に水を加え、トルエンで抽出した。０．５Ｍ水酸化ナトリウム水溶液と水で洗浄後、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣を減圧蒸留（4 mmHg, 143-145 ℃）で精製し、無色油状化合物（f）（264 g, 28%）を得た。 Production of compound (f)

An apparatus equipped with a three-necked flask, a stirrer, and a thermometer was charged with DMF (3 L), (e) (637 g, 3.83 mol), 4-bromobutene (575 g, 4.26 mol) and potassium carbonate (636 under a nitrogen atmosphere. g, 4.60 mol) was added, and the mixture was stirred at 100 ° C. for 3 hours. After standing to cool, the precipitated insoluble matter was filtered off, water was added to the filtrate, and the mixture was extracted with toluene. After washing with 0.5M aqueous sodium hydroxide solution and water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by distillation under reduced pressure (4 mmHg, 143-145 ° C.) to obtain a colorless oily compound (f) (264 g, 28%).

三口フラスコ、撹拌機、還流冷却器、および温度計を取り付けた装置に、窒素雰囲気下、メチルエチルケトン（ＭＥＫ）（600 mL）、炭酸カリウム（108 g, 0.78 mol）および（g）（108 g, 0.65 mol）を加え撹拌した。ここに４−ブロモブテン（97 g, 0.72 mol）を加え１５時間加熱還流した。反応溶液に水を加え、トルエンで抽出し。有機層を０．５Ｍ水酸化ナトリウム水溶液、飽和食塩水で順次洗浄し、無水硫酸マグネシウムで乾燥した後、減圧下で溶媒を留去した。残渣をカラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）により精製し、無色結晶化合物（h）（100.74 g, 70%）を得た。 Production of compound (h)

To a device equipped with a three-necked flask, stirrer, reflux condenser, and thermometer, in a nitrogen atmosphere, methyl ethyl ketone (MEK) (600 mL), potassium carbonate (108 g, 0.78 mol) and (g) (108 g, 0.65 mol) was added and stirred. 4-Bromobutene (97 g, 0.72 mol) was added thereto, and the mixture was heated to reflux for 15 hours. Water was added to the reaction solution and extracted with toluene. The organic layer was washed successively with 0.5M aqueous sodium hydroxide solution and saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by column chromatography (developing solvent toluene / ethyl acetate: 8/2) to obtain a colorless crystalline compound (h) (100.74 g, 70%).

三口フラスコ、撹拌機、還流冷却器、および温度計を取り付けた装置に、（h）（100.74 g, 0.46 mol）、エタノール（200 mL）に水酸化ナトリウム（27.44 g, 0.69mol）水溶液（200 mL）を加え、５時間加熱還流した。室温まで放冷後、反応混合物中のエタノールを減圧下で留去した。これに水（200 mL）を加えた後、６Ｍ塩酸により反応混合物を酸性にしたところ、無色結晶が析出した。析出物をろ別し、水でよく洗浄した後、残渣をトルエンにより共沸脱水を行い、真空ポンプで乾燥し、無色結晶化合物（i）（63.12 g, 72%）を得た。 Production of compound (i)

A device equipped with a three-necked flask, stirrer, reflux condenser, and thermometer was combined with (h) (100.74 g, 0.46 mol), ethanol (200 mL) in aqueous sodium hydroxide (27.44 g, 0.69 mol) (200 mL). ) And heated to reflux for 5 hours. After allowing to cool to room temperature, ethanol in the reaction mixture was distilled off under reduced pressure. Water (200 mL) was added thereto, and the reaction mixture was acidified with 6M hydrochloric acid to deposit colorless crystals. The precipitate was filtered off and washed well with water. The residue was azeotropically dehydrated with toluene and dried with a vacuum pump to obtain colorless crystalline compound (i) (63.12 g, 72%).

三口フラスコ、撹拌機、滴下漏斗、および温度計を取り付けた装置に、窒素雰囲気下、ジクロロメタン（1000 mL）、（f）（51.73 g, 0.32 mol）、（i）（60.00 g, 0.31 mol）、および４−ジメチルアミノピリジン（ＤＭＡＰ）（11.11 g, 0.09 mol）を加え０℃に冷却した。ここに、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）（70.13 g, 0.34 mol ）をジクロロメタン（100 mL）に溶解した溶液を滴下し、終夜撹拌した。析出物をろ別し、ろ液を１Ｍ塩酸、炭酸水素ナトリウム水溶液で順次洗浄し、無水硫酸マグネシウムで乾燥後、減圧下で溶媒を留去した。残渣をカラムクロマトグラフィー（展開溶媒 ヘプタン／酢酸エチル：７／３）で分取した後、ヘプタンより再結晶し無色結晶化合物（j）（87.45 g, 83%）を得た。 Production of compound (j)

To a device equipped with a three-neck flask, stirrer, dropping funnel, and thermometer, under a nitrogen atmosphere, dichloromethane (1000 mL), (f) (51.73 g, 0.32 mol), (i) (60.00 g, 0.31 mol), And 4-dimethylaminopyridine (DMAP) (11.11 g, 0.09 mol) was added and cooled to 0 ° C. A solution prepared by dissolving N, N′-dicyclohexylcarbodiimide (DCC) (70.13 g, 0.34 mol) in dichloromethane (100 mL) was added dropwise thereto and stirred overnight. The precipitate was filtered off, and the filtrate was washed successively with 1M hydrochloric acid and aqueous sodium hydrogen carbonate solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by column chromatography (developing solvent: heptane / ethyl acetate: 7/3) and recrystallized from heptane to obtain colorless crystalline compound (j) (87.45 g, 83%).

三口フラスコに撹拌機、滴下漏斗および温度計を取り付けた装置に、窒素雰囲気下、ジクロロメタン（1300 mL）、メタクロロ過安息香酸（純度６５％）（87.06 g）を加え０℃に冷却した。ここに（j）（52.22 g, 0.15 mol）をジクロロメタン（200 mL）に溶解した溶液を滴下し、室温で終夜撹拌した。析出物をろ過し、ろ液を硫酸水素ナトリウム水溶液と５％水酸化ナトリウム水溶液で洗浄し、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣をカラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）で分取した。粗結晶をトルエン、エタノール混合溶媒により再結晶を行い、無色結晶化合物（k）（36.12 g, 65%）を得た。相転移温度：Ｃ４８Ｎ６３Ｉ（℃）。 Production of compound (k)

To a device equipped with a stirrer, a dropping funnel and a thermometer in a three-necked flask, dichloromethane (1300 mL) and metachloroperbenzoic acid (purity 65%) (87.06 g) were added and cooled to 0 ° C. under a nitrogen atmosphere. A solution prepared by dissolving (j) (52.22 g, 0.15 mol) in dichloromethane (200 mL) was added dropwise thereto and stirred at room temperature overnight. The precipitate was filtered, and the filtrate was washed with a sodium hydrogen sulfate aqueous solution and a 5% sodium hydroxide aqueous solution, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was fractionated by column chromatography (developing solvent: toluene / ethyl acetate: 8/2). The crude crystals were recrystallized from a mixed solvent of toluene and ethanol to obtain colorless crystalline compound (k) (36.12 g, 65%). Phase transition temperature: C48N63I (° C.).

フラスコに撹拌子を入れ、ジクロロメタン（5 mL）、メタノール（10 mL）、（k）（2.00 g, 5.40 mmol）、およびチオ尿素（1.23 g, 16.2 mmol）を加え、室温で２日間撹拌した。反応混合物に水を加え、メタノールを留去した後、ジクロロメタンで抽出し、無水硫酸マグネシウムで乾燥した。減圧下で溶媒を留去し、残渣をカラムクロマトグラフィー（展開溶媒 トルエン／酢酸エチル：８／２）で分取した。粗結晶をジクロロメタンとエタノールの混合溶媒により再結晶し、無色結晶化合物（１−２−４−１）（1.13 g, 52%）を得た。相転移温度：Ｃ５６Ｎ ６3Ｉ（℃）。^１Ｈ−ＮＭＲ（ＣＤＣｌ_３；δ ｐｐｍ）：８．１５（ｄ， ２Ｈ）， ７．１２（ｄ， ２Ｈ），６．９９（ｄ， ２Ｈ）， ６．９４（ｄ， ２Ｈ），４．１０−４．２５（ｍ， ４Ｈ）， ３．１０−３．１５（ｍ， ２Ｈ），２．６１（ｔ， ２Ｈ）， ２．３９−２．５２（ｍ， ２Ｈ），２．２９（ｔ， ２Ｈ），１．７９−１．８６（ｍ， ２Ｈ）。
Production of compound (1-2-4-1)

A stirring bar was placed in the flask, dichloromethane (5 mL), methanol (10 mL), (k) (2.00 g, 5.40 mmol), and thiourea (1.23 g, 16.2 mmol) were added, and the mixture was stirred at room temperature for 2 days. Water was added to the reaction mixture, methanol was distilled off, extracted with dichloromethane, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was fractionated by column chromatography (developing solvent: toluene / ethyl acetate: 8/2). The crude crystals were recrystallized with a mixed solvent of dichloromethane and ethanol to obtain colorless crystalline compound (1-2-4-1) (1.13 g, 52%). Phase transition temperature: C56N 63 I (° C). ¹ H-NMR (CDCl ₃ ; δ ppm): 8.15 (d, 2H), 7.12 (d, 2H), 6.99 (d, 2H), 6.94 (d, 2H), 4. 10-4.25 (m, 4H), 3.10-3.15 (m, 2H), 2.61 (t, 2H), 2.39-2.52 (m, 2H), 2.29 ( t, 2H), 1.79-1.86 (m, 2H).

  Examples of compounds produced according to the methods of Examples 1 and 2 are (1-1-1-1) to (1-2-70-4) and (1-1-Op-1) to (1 -2-Op-2).

Example 3
A composition (CL1) was prepared from 50 wt% of the compound (1-1-4-4) and 50 wt% of the compound (K1). Compound (K1) was synthesized by the method described in Japanese Patent Application No. 2004-201562. This composition had a nematic phase at room temperature. The compound (1-1-4-4) had good compatibility and was not 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. A solution obtained by dissolving 1 g of the composition (CL1) and 0.03 g of DTS-102 (polymerization initiator of Midori Chemical Co., Ltd.) in cyclopentanone (8 g) 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 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 4
A composition (CL2) was prepared from 60 wt% of the compound (1-2-4-1) and 40 wt% of the compound (K2). Compound (K2) was synthesized by the method described in Japanese Patent Application No. 2004-112720. This composition had a nematic phase at room temperature. The compound (1-2-4-1) had good compatibility and was not phase separated. 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 solution obtained by dissolving 1 g of the composition (CL2) and 0.03 g of DTS-102 (polymerization initiator of Midori Chemical Co., Ltd.) in cyclopentanone (8 g) 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 (15)

The compound represented by Formula (1) or Formula (2).

In the formula, R ^a is a polymerizable group represented by the group (3); R ^b is fluorine, chlorine, —CN or alkyl having 1 to 10 carbons, and in this alkyl, any one or two of them —CH ₂ — may be replaced by —O— or —CH═CH—, in which any hydrogen may be replaced by fluorine; R ^c is hydrogen, halogen, or alkyl having 1 to 5 carbons. Any hydrogen in this alkyl may be replaced by halogen; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6- Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, or bicyclo [2.2.2] octane-1,4-diyl, in which any —CH _2- can be replaced with -O-, any -CH = can be replaced with -N =, any hydrogen in the ring can be replaced with fluorine, and any one or two hydrogen -CF _3, alkyl having 1 to 5 carbon atoms, or may be replaced by alkoxy having 1 to 5 carbon atoms; Z is independently a single bond or alkylene having 1 to 10 carbon atoms, the may be replaced by -O-, arbitrary one or two -CH ₂ - - any -CH ₂ - in the alkylene may be replaced by -COO- or -OCO-, its to any Hydrogen may be replaced by fluorine; m is an integer of 1 to 4; q is 0; and a plurality of R ^a , A and Z may be the same group or different groups. Also good. However, the following compounds are excluded .
Bi scan [4- (2,3-epithiopropyl) phenyl] methane, 4,4'-bis (2,3-epithiopropyl oxy) -3,3 ', 5,5'-tetramethyl biphenyl In Formula (1) or Formula (2), R ^a is a polymerizable group represented by the group (3); R ^b is fluorine, chlorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —OCHF ₂ , alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 2 to 9 carbons; R ^c is hydrogen, fluorine, chlorine Or an alkyl having 1 to 5 carbon atoms in which any hydrogen may be replaced by fluorine or chlorine; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, pyridine-2,5-diyl, pyridazine-3,6-diyl, or pyrimi A down-2,5-diyl, arbitrary hydrogen in the rings may be replaced by fluorine and arbitrary one hydrogen methyl, ethyl, propyl, methoxy, ethoxy, or be replaced by -CF ₃ Well; Z is independently a single bond or alkylene having 1 to 10 carbons, in which any —CH ₂ — may be replaced by —O—, and any one or two —CH ₂ - may be replaced by -COO- or -OCO-, any hydrogen its may be replaced by fluorine; m is there an integer from 1 to 3; q is 0, claim 1 Compound described in 1. In Formula (1) or Formula (2), R ^a is a polymerizable group represented by the group (3); R ^b is fluorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , — OCF ₃ , —OCF ₂ H, —OCHF ₂ , alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 2 to 9 carbons; R ^c is hydrogen or 1 to 5 carbons A is independently 1,4-cyclohexylene, 1,4-phenylene, fluorene-2,7-diyl, or pyridine-2,5-diyl, in which any hydrogen is Fluorine may be replaced and any one hydrogen may be replaced with methyl, ethyl, propyl, methoxy, ethoxy, or —CF ₃ ; Z is independently a single bond, —O—, — (CH _{2) r -, - O (} CH _{) R-1 -, - (} CH 2) r-1 O -, - -O- O- (CH 2) r-2, - OCO- (CH 2) 2 -, - (CH 2) 2 -COO- _{, -COO- (CH 2) r-} 2 -O -, - OCO- (CH 2) r-2 -O -, - O- (CH 2 CH 2 O) s -, - COO -, - OCO-, -OCF ₂ -, or _-CF 2 O-a and; r is located at integer from 1 to 10; s is located an integer from 1 to 3; m is located at 1-2 integer; q is 0, The compound of claim 1. A compound represented by any one of formula (1a) to formula (1d) or formula (2a) to formula (2d).

In the formula, R ^a is a polymerizable group represented by the group (3); R ^b is fluorine, chlorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF _2. H, —OCHF ₂ , alkyl having 1 to 10 carbons, alkoxy having 1 to 9 carbons, or alkoxyalkyl having 2 to 9 carbons; R ^c is hydrogen or alkyl having 1 to 5 carbons; A is independently 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; Z is independently a single bond, —O—, — (CH _{2 ) R -, - O (CH} 2) r-1 -, - (CH 2) r-1 O -, - -O- O- (CH 2) r-2, - OCO- (CH 2) 2 -, _{- (CH 2) 2 -COO -} , - COO- (CH 2) r-2 -O -, - OCO- (CH 2) r-2 -O -, - O- (CH 2 CH 2 O) s - , —COO—, —OCO—, —OCF ₂ —, or —CF ₂ O—, r is an integer of 1 to 10, s is an integer of 1 to 3; R ^a , A and Z may be the same group or different groups. However, the following compounds are excluded.
Bis [4- (2,3-epithiopropyloxy) phenyl] methane In formula (1a) to formula (1d) and formula (2a) to formula (2d), R ^a is a polymerizable group represented by group (3); R ^b is fluorine, —CN, —CF ₃ , _{-CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, -OCFH 2, alkyl having 1 to 10 carbon atoms, alkoxy having 1 to 9 carbon atoms, or alkoxyalkyl having 2 to 9 carbons; R ^c is hydrogen; A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2, 5-difluoro-1,4-phenylene or 2,6-difluoro-1,4-phenylene; Z is independently a single bond, —O—, — (CH ₂ ) _r —, —O (CH _{2 ) r-1 -, - (} CH 2) r-1 O -, - O- (CH 2 _{r-2 -O -, - O-} (CH 2 CH 2 O) s -, - COO-, or a -OCO-, r is an integer from 1 to 10, s is there an integer from 1 to 3 A compound according to claim 4 wherein q is 0. In formula (1a) to formula (1d) and formula (2a) to formula (2d), R ^a is a polymerizable group represented by group (3); R ^b is alkyl having 1 to 10 carbons ; ^{R c} is hydrogen; A is independently a 1,4-phenylene; Z is independently a single _{bond, -O -, - (CH 2} ) r -, - O (CH 2) r- _{1 -, - (CH 2)} r-1 O -, - O- (CH 2) r-2 -O -, - COO-, or a -OCO-, r is an integer from 2 to 10; q 5. The compound of claim 4, wherein is 0. In formula (1a) to formula (1d) and formula (2a) to formula (2d), R ^a is a polymerizable group represented by group (3); R ^b is alkyl having 1 to 10 carbons ; ^{R c} is hydrogen; A is independently a 1,4-phenylene; Z is independently _{-O (CH 2) r-1} -, - O- (CH 2) r-2 -O 5. A compound according to claim 4 which is-, -COO-, or -OCO-, r is an integer from 2 to 10 and q is 0. As a first component, at least one compound according to any one of claims 1 to 7 and as a second component, a formula (M1), a formula (M2), a formula (M3), a formula (M4) ), A liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (M5) and formula (M6).

In Formulas (M1) to (M6), R ^d is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, or carbon 2 ˜20 alkoxyalkyl, C2-20 alkenyl, or C2-20 alkenyloxy; R ^e is hydrogen or C1-5 alkyl; B is independently 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 is pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methyl Luolene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-chlorofluorene-2,7-diyl, or 9,9-difluorofluorene May be -2,7-diyl; Y is independently a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, any one or two -CH ₂ is replaced by -O-. Any one —CH ₂ may be replaced by —COO—, —OCO—, —C═C—, or —C≡C—; and t is 1 or 2, B and Y may be the same group or different groups. In the formula (M1) ~ formula (M6), ^{R d} is fluorine, _-CN, -CF 3, -OCF _3, alkyl having 1 to 20 carbon atoms, or alkoxy having 2 to 20 carbon atoms; ^{R e} is hydrogen Or alkyl having 1 to 2 carbon atoms; B is independently 1,4-cyclohexylene or 1,4-phenylene, and in this 1,4-phenylene, any hydrogen may be replaced by fluorine And any one or two hydrogens may be replaced with methyl or trifluoromethyl, and one of B is 9-methylfluorene-2,7-diyl or 9-ethylfluorene-2,7-diyl Y is independently a single bond, —COO—, —OCO—, —C≡C—, or alkylene having 1 to 10 carbons, and in the alkylene, any one or two -CH ₂ - may be replaced by -O-; and t is 1 or 2, the liquid crystal composition according to claim 8.   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) 10. The liquid crystal composition according to claim 8, wherein the liquid crystal composition is at least one compound selected from the group of compounds represented by formula (M5) and formula (M6).   10. The liquid crystal composition according to claim 8, wherein the second component is at least one compound selected from the group of compounds represented by formula (M3) and formula (M4).   The polymer obtained by polymerizing the compound of any one of Claims 1-7.   The polymer obtained by superposing | polymerizing the liquid-crystal composition of any one of Claims 8-11.   A liquid crystal display device containing the polymer according to claim 12.   Use of the polymer according to claim 12 or 13 as a molded article having optical anisotropy.