JP4923380B2 - Low refractive index anisotropic compounds, compositions and polymers or polymer compositions thereof - Google Patents

Description

  The present invention relates to a compound having a low refractive index anisotropy value having liquid crystallinity and a polymerizable functional group, a composition containing the compound, a polymer or a polymer composition thereof, and uses thereof.

Patent Document 1 discloses that when a polymerizable liquid crystal compound is photopolymerized in an aligned state, a uniform alignment state is fixed and a polymer having optical anisotropy is obtained. As the polymerizable liquid crystalline compound, an acrylate derivative is generally used in view of high reactivity and transparency of the obtained polymer (Patent Document 2, Patent Document 3 and the like). Examples of the liquid crystalline acrylate derivative are compounds such as the following (a) to (c).

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

  However, since known acrylate derivatives have a high liquid crystal phase development temperature, it is necessary to increase the temperature when polymerizing them in a liquid crystal state. For this reason, there are problems such as complicated polymerization operations and unintentional polymerization in the photopolymerization, partial polymerization due to heat, and disorder of orientation. Therefore, a molded article having optical anisotropy using a polymer obtained from this compound does not have sufficient characteristics in orientation, heat resistance and mechanical strength. An object of the present invention is to solve the problems of the prior art.

  As a result of research to solve the above problems, the present inventors have found that a polymerizable liquid crystal compound having an appropriate hydrocarbon chain between an acrylic group and a mesogen, or having a specific polymerizable group other than an acrylic group. The present inventors have found that the polymer has excellent properties such as an appropriate temperature range of the liquid crystal phase and suitable compatibility with other liquid crystal compounds, and has found that the polymer is excellent in heat resistance and mechanical strength. Moreover, since the compound of this application has a low refractive index anisotropy value, the freedom degree of retardation setting can be expanded by combining arbitrarily with another compound with a high refractive index anisotropy value. Furthermore, the compound of the present invention exhibits excellent polymerizability, and easily gives a polymer having a high degree of polymerization by light irradiation for a short time. Photopolymerization in a short time is advantageous for fixing the alignment of the liquid crystal. The compound of the present invention gives a polymer having a high degree of polymerization even by thermal polymerization. In addition, the polymer of the present invention is excellent in adhesion to other substrates, glass, triacetyl cellulose and the like, and is advantageous when constructing an optical compensation film for a liquid crystal display element. The present invention has the following configuration.

[1] A compound represented by the following formula (1) or formula (2).
R ^a- (A−Z) m−A−R ^b (1)
^{R c -Y- (A-Z)} m-A-R b (2)

In the formula, R ^a is a group (3-1), a group (3-2), a group (3-3), a group (3-4), a group (3-5) or a group (3-6); Here, R ^d is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms. In these alkyls, any hydrogen may be replaced by halogen, but in the group (3-6), 3 R ^d is not simultaneously hydrogen; R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —N═C═O, —N═C ═S, or alkyl having 1 to 20 carbon atoms, and in these alkyl, any —CH ₂ — is —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF-, or -C≡C-, and in these alkyls any hydrogen is It may be replaced by Gen; ^{R c} is a group (3-1), group (3-2), group (3-3), group (3-4), group (3-5), or a group (3 -6), wherein R ^d is independently hydrogen, halogen, or alkyl of 1 to 5 carbons, in which any hydrogen may be replaced by halogen; A is independently 1,4 -Cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydronaphthalene-2,6-diyl, or bicyclo [2.2.2] octane-1,4-diyl, in these rings Arbitrary —CH ₂ — may be replaced by —O—, Arbitrary —CH═ may be replaced by —N═, and in these rings, any hydrogen is halogen, alkyl having 1 to 5 carbon atoms. Or an alkyl halide having 1 to 5 carbon atoms May be replaced; Y is alkylene having 1 to 20 carbon atoms, any -CH ₂ - in these alkylene - is -O -, - S -, - COO-, or -OCO- be replaced by Well; Z is independently a single bond, — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —O (CH ₂ ) _n O—, —CH═CH— , —C≡C—, —COO—, —OCO—, — (CF ₂ ) ₂ —, —C≡C—COO—, —OCO—C≡C—, —CH═CH— (CH ₂ ) ₂ — , — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH—C≡C—, —OCF ₂ —, or —CF ₂ O— Where n is an integer from 1 to 20; m is an integer from 1 to 6. However, m is 1 or 2, ^{R c} is acryloyloxy, A in A-Z adjacent to Y is 1,4-phenylene and,, ^{R b} when Z is -OCO- are not alkyl, rather at alkoxy , M is 2, R ^c is methacryloyloxy, Y is —C ₃ H ₆ —, and in two AZs adjacent to Y, A is 1,4-cyclohexylene, Z is a single bond, and A is adjacent to R ^b When R is 1,4-phenylene, R ^b is not methyl, and m is 2, R ^c is (3-4), Y is —C ₂ H ₄ —, and A in two AZ adjacent to Y is A 1,4-cyclohexylene, Z is a single bond, ^{R b} when a adjacent ^{R b} is hydrogen ortho ^{R b} 1,4-phenylene is replaced by fluorine have name with fluorine.
that's all

[2] ^{R b} is hydrogen, _{halogen, -CF 3, -CF 2 H,} -CFH 2, -OCF 3, claim 1 is -OCF 2 H, -N = C = O or -N = C = S, Compound described in 1.

[3] R ^b is alkyl having 1 to 20 carbons, or a group in which arbitrary —CH ₂ — is replaced by —O— in these alkyls, and m is an integer of 3 to 6 Item 1. The compound according to Item 1.

[4] R ^b is alkyl having 1 to 20 carbons, or a group in which any —CH ₂ — is replaced by —O— in these alkyls, and R ^c is a group (3-1 ), A group (3-2), a group (3-3), a group (3-4), a group (3-5), or a group (3-6), wherein R ^d is independently hydrogen, halogen Or an alkyl having 1 to 5 carbon atoms in which any hydrogen may be replaced by a halogen, but in the group (3-6), three R ^{d s} are not simultaneously hydrogen, 1. The compound according to 1.

[5] R ^b is alkyl having 1 to 20 carbons, or a group in which any —CH ₂ — is replaced by —O— in these alkyls, and Y in Formula (2) A in adjacent AZ is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, or bicyclo [2.2.2] octane-1,4-diyl And in these rings any —CH ₂ — may be replaced by —O—, any —CH═ may be replaced by —N═, and in these rings any hydrogen is a halogen, Item 6. The compound according to Item 1, which may be substituted with alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms.

[6] In Formula (1) and Formula (2), R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbon atoms Or R ¹ is independently hydrogen, halogen or methyl; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane— 2,5-diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl; Y is alkylene having 1 to 20 carbon atoms, —O (CH _{2) r} , Or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond _{independently, - (CH 2) n -} , - O (CH 2) n -, - (CH _{2) n O -, - CH} = CH -, - COO -, - OCO -, - OCF 2 -, or _-CF 2 is a O-, n is an an integer from 1 to 20; m is 1 to 4 Item 2. The compound according to item 1, which is an integer.

[7] In the formulas (1) and (2), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, Or alkoxy having 1 to 5 carbon atoms; R ^d is hydrogen, fluorine or methyl; A is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 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; C 1-20 alkylene, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, r is an integer of 1 to 19; Z is independently a single bond, — (CH ₂ ) ₂ −, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ Item 6. The compound according to Item 1, wherein-, -CH = CH-, -COO-, or -OCO-; and m is an integer of 1 to 4.

[8] In Formula (1) and Formula (2), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is hydrogen, halogen, _{-CF 3, -CF 2 H, -CFH} 2, -OCF 3, -OCF 2 H, alkyl of 1 to 5 carbon atoms, or alkoxy of 1 to 5 carbon atoms; ^{R d} is independently hydrogen, halogen or Methyl is A; 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2, 5-diyl or pyrimidine-2 Be a 5-diyl; Y is C1-20 _{alkylene, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is independently A single bond, — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —CH═CH—, —C≡C—, —COO—, —OCO—, Item 2. The compound according to Item 1, which is —OCF ₂ — or —CF ₂ O—, n is an integer of 1 to 20, and m is an integer of 1 to 4.

[9] In the formulas (1) and (2), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6), wherein R ^d is independently Hydrogen, fluorine or methyl; R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or 1 to 5 carbons A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbons _{, -O (CH 2) r -} , or - (CH _{2) r} O In it, r is located at 1 to 19 integer; Z is a single bond _{independently, - (CH 2) 2 -} , - (CH 2) 4 -, - CH 2 O -, - OCH 2 -, - CH = Item 2. The compound according to Item 1, wherein the compound is CH—, —COO—, or —OCO—; and m is an integer of 1 to 4.

[10] In Formula (2), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or 1 to carbons 5 is alkoxy; R ^c is a group (3-6), wherein R ^d is independently hydrogen, fluorine or methyl; A is independently 1,4-cyclohexylene, 1,4-cyclohexeni Len, 1,3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbon atoms, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—; r is an integer from 1 to 19; Z is independently a single bond, _{(CH 2) 2 -, -} (CH 2) 4 -, - CH 2 O -, - OCH 2 -, - CH = CH -, - COO-, or a -OCO-; m is 1 to 4 integer Item 2. The compound according to Item 1, wherein

[11] The compound according to item 9 or 10 wherein m is 1 in formula (1) and formula (2).

[12] The compound according to item 9 or 10 wherein m is 2 in formula (1) and formula (2).

[13] The compound according to item 9 or 10 wherein m is 3 in formula (1) and formula (2).

[14] The compound according to item 1, wherein the compound represented by formula (1) or formula (2) is any one compound represented by the following formulas (I) to (VIII).

R ^a -AZ-A-R ^b (I)
R ^a- (A-Z) ₂ -A-R ^b (II)
R ^a- (AZ) ₃ -A-R ^b (III)
R ^a- (AZ) ₄ -A-R ^b (IV)
^{R c -Y-A-Z-} A-R b (V)
_{^{R c -Y- (A-Z)}} 2 -A-R b (VI)
_{^{R c -Y- (A-Z)}} 3 -A-R b (VII)
_{^{R c -Y- (A-Z)}} 4 -A-R b (VIII)

In the formula, R ^a and R ^c are a group (3-1), a group (3-2), a group (3-3), a group (3-4), a group (3-5) or a group (3-6). R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons ^Rd is hydrogen, halogen or methyl; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6- Diyl, pyridine-2,5-diyl, or pyrimidine-2, - be diyl; Y is alkylene having 1 to 20 carbon _{atoms, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond , — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —OCF ₂ -, or _-CF 2 is a O-, n is an integer from 1 to 20.

[15] In the formulas (I) to (VIII), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or R ¹ is hydrogen, fluorine or methyl; A is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 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; Y is carbon An alkylene having a number of 1 to 20, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, r is an integer of 1 to 19; Z is a single bond, — (CH ₂ ) ₂ — , — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH Item 15. The compound according to Item 14, wherein = CH-, -COO-, or -OCO-.

[16] In formulas (I) to (VIII), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is hydrogen, halogen,- CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; R ^d is hydrogen, halogen, or methyl A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or Pyrimidine-2,5-diyl ; Y is C1-20 _{alkylene, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond, - (CH _{2) n -, - O (} CH 2) n -, - (CH 2) n O -, - CH = CH -, - C≡C -, - COO -, - OCO -, - OCF 2 -, or - CF ₂ is O-, n is a compound according to claim 14 which is an integer from 1 to 20.

[17] In formulas (I) to (VIII), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; R ^d is hydrogen, fluorine or methyl; 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbons, —O (CH ₂ ) _r — Or — (CH ₂ ) _r O—, where r is an integer of 1 to 19 Z is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —COO—, or —OCO—. Item 15. The compound according to Item 14.

[18] In the formulas (V) to (VIII), R ^c is a group (3-6); R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; R ^d is hydrogen, fluorine or methyl; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1, 3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbon atoms, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, and r is 1 to 19 is an integer; Z is a single _{bond, - (CH 2) 2 -} , - ( _{H 2) 4 -, - CH} 2 O -, - OCH 2 -, - CH = CH -, - COO-, or a compound according to claim 14 is -OCO-.

[19] A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound described in item 1.

[20] The liquid crystal composition according to item 19, wherein at least two polymerizable compounds are the compound according to item 1.

[21] The liquid crystal composition according to item 19, wherein at least one polymerizable compound is the compound according to item 1, and the other at least one polymerizable compound is a compound different from the compound according to item 1.

[22] A liquid crystal composition comprising at least one polymerizable compound according to item 1 and at least one non-polymerizable compound having liquid crystallinity.

[23] A polymer obtained from the compound according to any one of items 1 to 18 , which has at least one of the structural units represented by formulas (6-1) to (6-6).

[24] A polymer obtained by homopolymerizing one of the compounds according to any one of items 1 to 18.

[25] A polymer obtained from the liquid crystal composition according to any one of items 19 to 21.

[26] A polymer composition obtained from the liquid crystal composition according to item 22.

[27] A film comprising the polymer according to any one of items 23 to 25 or the polymer composition according to item 26.

[28] A molded article having optical anisotropy comprising the polymer according to any one of items 23 to 25 or the polymer composition according to item 26.

[29] A liquid crystal display device comprising the polymer according to any one of items 23 to 25 or the polymer composition according to item 26.

  The compound of the present invention exhibits a low refractive index anisotropy value, an appropriate liquid crystal phase temperature range, and has excellent compatibility with other compounds. The composition containing the compound and the polymer thereof are used for a retardation plate, a polarizing element, a liquid crystal alignment film, an antireflection film, a selective reflection film, a viewing angle compensation film, and the like, which are components of a liquid crystal display element. Can do. The compound of the present invention can also be used as an adhesive, a synthetic polymer having mechanical anisotropy, a cosmetic, a decorative article, a nonlinear optical material, and an information storage material.

  In addition, the term “liquid crystallinity” in the present invention is not limited to the meaning that a compound simply exhibits a liquid crystal phase. This term is also used for compounds that do not themselves exhibit a liquid crystal phase, but can be used as components of liquid crystal compositions when mixed with other liquid crystal compounds. “(Meth) acryloyloxy” means “acryloyloxy or methacryloyloxy”. “(Meth) acrylate” means “acrylate or methacrylate”. “(Meth) acrylic acid” means “acrylic acid or methacrylic acid”.

In the claims and the detailed description of the present invention, “arbitrary” used to indicate a specific group in a chemical formula indicates that it is arbitrary not only in the position of the group but also in the number. R ^a in the formula (1) is a group (3-1), a group (3-2), a group (3-3), a group (3-4), a group (3-5) or a group (3-6). although not acryloyloxy; ^{R c} is a group of the formula (2) (3-1), group (3-2), group (3-3), group (3-4), groups (3-5 ), or a group (3-6); formula (1) or (2) a solution of ^{R b} is hydrogen, _{halogen, -CF 3, -CF 2 H,} -CFH 2, -OCF 3, -OCF 2 H , alkyl of -N = C = O, -N = C = S or C 1-20, any -CH ₂ in the alkyl - is -O -, - S -, - CO -, - COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C— may be substituted, and in these alkyls, any hydrogen may be replaced with a halogen. Preferred R ^a is vinyl ketone, vinyl ether, maleimide, epoxy, oxetane and methacryloyloxy, and particularly preferred are vinyl ketone, maleimide, epoxy and oxetane. Preferred R ^c is vinyl ketone, vinyl ether, maleimide, epoxy, oxetane, acryloyloxy, methacryloyloxy, and particularly preferred are vinyl ketone, maleimide, epoxy, oxetane, acryloyloxy. Preferred R ^b is halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl, alkoxy, and particularly preferred are —F, —Cl, —CF ₃ , — _{CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, methyl, ethyl, propyl, methoxy, ethoxy, propyloxy.

A plurality of A in the formula (1) or (2) is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydronaphthalene-2,6-diyl, or bicyclo [ 2.2.2] octane-1,4-diyl, in which any —CH ₂ — may be replaced by —O—, and any —CH═ is replaced by —N═. In these rings, any hydrogen may be replaced by halogen, alkyl having 1 to 5 carbon atoms or alkyl halide having 1 to 5 carbon atoms, and examples of halogen include fluorine and chlorine. Is preferred. As alkyl, methyl, ethyl and propyl are preferable, and as alkoxy, methoxy and ethoxypropyloxy are preferable.

Preferred A is 1,4-cyclohexylene, 2,2-difluoro-1,4-cyclohexylene, 1-fluoro-1,4-cyclohexylene, 1-trifluoromethyl-1,4-cyclohexylene, 1,4-cyclohexenylene, 2-fluoro-1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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-trifluoromethyl-1,4-phenylene, pyridine-2, 5-diyl, pyridazine-3,6-diyl, pyrimidine-2,5-diyl and the like. Particularly preferred A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 3-fluoro-1,4-phenylene, 2 , 3-difluoro-1,4-phenylene or 3,5-difluoro-1,4-phenylene.
The direction of the ring is not fixed. For example, 2,2-difluoro-1,4-cyclohexylene and 3,3-difluoro-1,4-cyclohexylene are the same ring and are not written together.

R ^a and R ^{c in} formula (1) or (2) are each independently a polymerizable group represented by formulas (3-1) to (3-6). R ^{d in} these formulas is hydrogen, halogen, or alkyl having 1 to 5 carbon atoms, and in these alkyls, arbitrary hydrogen may be replaced by halogen. Preferred R ^d is hydrogen, which is more polymerizable.

Z in the formula (1) or (2) is a linking group for bonding rings together. A plurality of Z are independently a single bond, — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —O (CH ₂ ) _n O—, —CH═ CH—, —C≡C—, —COO—, —OCO—, — (CF ₂ ) ₂ —, —C≡C—COO—, —OCO—C≡C—, —CH═CH— (CH ₂ ) ₂ —, — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH—C≡C—, —OCF ₂ —, or —CF ₂ O— and n is an integer of 1-20.
In the compound (1) or (2), Z is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, When —CH═CH— or —CF═CF—, a wide liquid crystal phase temperature range is exhibited. In particular, when it is a single bond, —COO—, —OCO—, or —CH═CH—, a wider temperature range is exhibited. When Z is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, a low birefringence is exhibited. When Z is — (CF ₂ ) ₂ —, —OCF ₂ —, or —CF ₂ O—, it exhibits a small surface energy and a relatively wide liquid crystal phase temperature range. Desired characteristics can be obtained by selecting the structure.

Y in the formula (2) is alkylene having 1 to 20 carbon atoms, and in these alkylene, any —CH ₂ — may be replaced by —O—, —S—, —COO—, or —OCO—. . Particularly preferably, Y is alkylene having 1 to 10 carbons and alkylene having 1 to 10 carbons containing 1 or 2 oxygen atoms. In alkylene, the number of carbon atoms is preferably 2 to 10, more preferably 2 to 8. If it is 11 or more, the viscosity of the compound (2) increases, which is not preferable. Further, when the chain is branched, it may have an asymmetric carbon, but it may be any optical activity. Furthermore, the conformation may be any of (R) and (S), and may be a racemate or meso form.

M in the formula (1) or (2) is an integer of 1 to 6, preferably 1 to 3. When m is 1, a wide liquid crystal phase temperature range centering on room temperature is shown. When m is 2, a wider liquid crystal phase temperature range and a high clearing point are shown. m is 3 Compound (1) or (2) is higher indicates clearing point, by mixing with a compound having a low compounds and the clearing point showing no liquid phase, preparing a composition having a suitable clearing point To help.

All of the compounds of formula (1) or (2) exhibit suitable properties, but when focusing on the following structure, preferred examples of compound (1) or (2) include the following (a-1) to ( g-12).

-(A-Z) m-A-

  In these formulas (a-1) to (g-12), X on the benzene ring in the formula represents halogen, which indicates that one or more may be substituted. In the case of a plurality, different halogens may be represented independently. Of these halogens, preferred are F and Cl.

Next, the manufacturing method of a compound (1) and a compound (2) is demonstrated.
Compound (1) or Compound (2) can be obtained from 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. it can.

The main skeleton (liquid crystal residue) of the compound (1) and the compound (2) can be synthesized by the following method or by appropriately combining them. 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 at least one ring. A plurality of MSG ¹ (or MSG ² ) used in the scheme may be the same or different. Compounds (1A) to (1L) correspond to compound (1) and compound (2).

(I) Formation of a single bond A boric acid derivative (14) and a halide (15) 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 obtained by reacting compound (16) 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 (14) can be produced by inducing the compound (16) to a Grignard reagent or a lithium reagent and acting a trialkyl borate ester.

(II) Formation of —COO— and —OCO— The compound (16) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (17). Carboxylic acid (17) and phenol or alcohol (18) synthesized by a known method are dehydrated in the presence of DCC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to give —COO— A compound (1B) having A compound having —OCO— can also be synthesized by this method.

(III) Formation of —CF ₂ O— and —OCF ₂ — Compound (1B) is treated with a sulfurizing agent such as Lawesson's reagent to obtain compound (19). Compound (19) is fluorinated with hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize compound (1C) having —CF ₂ O— (M. Kuroboshi et al., Chem. Lett., 1992 , 827). Compound (1C) can also be synthesized by fluorinating compound (19) 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 (15) is treated with n-butyllithium and then reacted with formamide such as N, N-dimethylformamide to obtain the aldehyde (20). Compound (1D) is synthesized by reacting a phosphonium salt (21) synthesized by a known method with a base such as potassium t-butoxide and reacting with aldehyde (20). 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 (22) instead of the phosphonium salt (21) 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 (16) with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper halide, the reaction was conducted under basic conditions. Deprotection gives compound (23). Compound (1G) is synthesized by reacting compound (23) with compound (15) in the presence of a catalyst of dichlorobistriphenylphosphine palladium and copper halide.

(VIII) Formation of —CF═CF— The compound (16) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (24). Compound (24) is treated with n-butyllithium and then reacted with compound (15) to synthesize compound (1H).

(IX) Formation of —CH ₂ O— or —OCH ₂ — Compound (25) is obtained by reducing compound (20) with a reducing agent such as sodium borohydride. This is halogenated with hydrobromic acid or the like to obtain compound (26). Compound (1J) is synthesized by reacting compound (26) with compound (18) in the presence of potassium carbonate or the like.

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 (27) instead of Compound (20). To do.

Formation of (XI)-(CF ₂ ) _2-
According to the method described in J. Am. Chem. Soc., 2001, 123, 5414., diketone (30) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to produce-(CF ₂ ) _2-. To obtain a compound (1L) having

The above production methods are all general methods, and the compound (1) and the compound (2) are not limited by these production methods.

The composition of the present invention is a composition containing at least one compound (1) or compound (2).

  The first of the compositions of the present invention is a composition containing one compound (1) or compound (2). In the following description, this is referred to as “Composition A”. Only one of compound (1) or compound (2) is treated as composition A.

  The second of the compositions of the present invention is a composition containing at least two compounds (1) or (2). In the following description, this is referred to as “Composition B”. The composition B may contain at least one compound (1) and at least one compound (2).

  The third of the compositions of the present invention is a composition containing at least one of compound (1) or compound (2) and at least one polymerizable compound different from compound (1) and compound (2). . In the following description, this is referred to as “Composition C”. A polymerizable compound different from the compound (1) and the compound (2) is referred to as “other polymerizable compound”. Examples of other polymerizable compounds are described in JP-A-8-3111.

  Any other polymerizable compound may be used as long as it is polymerizable. This polymerizable compound may be liquid crystalline or non-liquid crystalline as long as it does not reduce film-forming properties, mechanical strength, and the like. Examples of preferred polymerizable compounds are (meth) acrylate compounds, vinyl compounds, styrene compounds, and vinyl ether compounds.

  In addition, compound (1) and compound (2) may be optically active compounds. Since the composition to which compound (1) or compound (2), which is an optically active compound, has a helical structure, a retardation plate having a helical structure can be produced by polymerizing the composition. If the pitch of the spiral is about ½ to the same as the wavelength of light, light having that wavelength can be selectively reflected according to Bragg's law. This can be used, for example, as a circularly polarized light separating functional element. The direction of the helix depends on the configuration of the optically active compound. A desired helical direction can be induced by appropriately selecting the configuration of compound (1) or compound (2).

  Preferred non-liquid crystalline polymerizable compounds that can be used in the composition C are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, Vinyl chloride, vinyl fluoride, vinyl acetate, vinyl pivalate, vinyl 2,2-dimethylbutanoate, vinyl 2,2-dimethylpentanoate, vinyl 2-methyl-2-butanoate, vinyl propionate, vinyl stearate, 2-ethyl-2-methylbutanoic acid vinyl, N-vinylacetamide, p-t-butylvinylbenzoate, N, N-dimethylaminovinylbenzoate, vinylbenzoate, styrene, o-, m- or p-chloromethyl Styrene, α-methylstyrene, ethyl vinyl ether, hydroxybutyl Bruno vinyl ether, t-amyl vinyl ether, cyclohexanedimethanol vinyl ether, tetrafluoroethylene, and hexafluoropropene.

  In order to further increase the film-forming ability of the polymer, a polyfunctional acrylate can be used in the composition C as a non-liquid crystalline polymerizable compound. Preferred polyfunctional acrylates are 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate , Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloxyethyl phosphate, bisphenol A EO addition diacrylate, bisphenol A glycidyl di Acrylate (manufactured by Osaka Organic Chemical Co., Ltd., trade name: Biscoat 700), and polyethylene glycol diaquo Is the rate.

  A liquid crystalline polymerizable compound may be used in the composition C for the purpose of controlling the temperature range of the liquid crystal phase. A preferred polymerizable compound having liquid crystallinity is shown.

In the above formula, W is hydrogen, fluorine, chlorine, —CH ₃ , —CF ₃ , and when there are a plurality of W in the compound, they may be the same or different, and y is 1 to 20, z Is 0 or 1.

  A fourth composition of the present invention is a composition containing at least one of the compound (1) or the compound (2) and at least one non-polymerizable compound having liquid crystallinity. In the following description, this is referred to as “Composition D”. Examples of non-polymerizable compounds having liquid crystal properties are described in a liquid crystal compound database (trade name: LiqCryst) sold by Fujitsu Kyushu Engineering.

Examples of suitable optically active compounds as the polymerizable and non-polymerizable compounds having liquid crystallinity are compounds (OP-1) to (OP-21). Moreover, as a binaphthol type | system | group optically active compound, DE10221751 specification, EP0217239 specification, WO02 / 094805 specification, Mol. Cryst. Liq. Cryst. , 364 , 825 (2001) are also useful.

  The content of each component of the compositions A to D is preferably such that the composition does not impair the liquid crystallinity. Even if the atoms constituting the components of these compositions contain more isotopes than their natural abundance, it is preferable because they have similar characteristics. A solvent, an initiator, a catalyst, and the like can be added to these compositions as necessary when performing the polymerization reaction. The composition is prepared from each component by a known method. For example, the component compounds are mixed and dissolved in each other by heating as necessary.

  Examples of preferred solvents are benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, cyclopentanone, cyclohexanone and These are mixed solvents.

  Preferred initiators for radical polymerization by light are 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173; hereinafter, Darocur is a trade name), 1-hydroxycyclohexyl phenyl ketone. (Trade name: Irgacure 184; hereinafter, Irgacure indicates a trade name), 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651), Irgacure 500, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 1300, Irgacure 819, Irgacure 1700, Irgacure 1800, Irgacure 1850, Darocur 4265, Irgacure 784, p-methoxyphenyl-2,4-bis (trichloromethyl) Triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1 In a mixture of -one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, and methyl 2,4-diethylxanthone / methyl p-dimethylaminobenzoate is there.

  Preferred initiators for radical polymerization by heat are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide, t -Butyl peroxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate, azobisisobutyronitrile, azobiscyclohexanecarbonitrile and the like.

Cationic polymerization can be initiated by light irradiation and heating. A cationic polymerization initiator can be added to shorten the reaction time and increase the degree of polymerization. As the photocation, a Bronsted acid, a metal halide compound, or an onium salt can be preferably used. Specific examples can be referred to Makromolekulare Chemie, VCH Verlag, Weinheim and An Introduction to Polymer Science, VCH Verlag, Weinheim.

Anionic polymerization, preferred catalysts of coordination polymerization or living polymerization method, _{is, n-C 4 H 9 Li} , alkali metal alkyl such as _{t-C 4 H 9 Li-} R 3 Al, an aluminum compound, a transition metal compound such as It is.

Next, the polymer will be described.
Compound (1) and Compound (2) have a polymerizable site (since oxirane and oxetane do not have an unsaturated bond, they are simply referred to as sites). A polymer can be produced by polymerizing the compound (1), the compound (2) and a composition containing them. These polymers are obtained by reactions such as radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, and living polymerization. The polymer obtained from composition A consists of one constituent unit. When the composition B or the 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 composition containing a polymer is obtained. The polymer has at least one structural unit.

  Compounds (1) and (2) having group (3-1), Compounds (1) and (2) having group (3-4), Compounds (1) and (2) having group (3-5) Has high cationic polymerizability. Polymerization can also be performed in the presence of a substance that inhibits the polymerization reaction (for example, oxygen). The polymer obtained from the compound having the group (3-4) and the group (3-5) is excellent in adhesion to various substrate materials. Moreover, since the curing shrinkage rate is small, it can be suitably used for various optical functional thin films.

  The compounds (1) and (2) having the group (3-2) and the compounds (1) and (2) having the group (3-3) have high radical polymerizability. In particular, radical polymerizability by ultraviolet rays is high. Polymers obtained from these compounds have high mechanical strength, and have high surface hardness when used for surface coating.

The polymer (2) comprising the compound (2) having a group (3-6) also has high radical polymerizability by ultraviolet rays, high transparency, high heat resistance, and excellent mechanical strength and solvent resistance.

  When the composition B or the composition C is polymerized, a copolymer is obtained. By appropriately selecting the composition of the composition B or the composition C, a polymer having desired characteristics can be produced. For example, when the composition B containing the compound (2) having the group (3-3) and the compound (2) having the group (3-6) is polymerized, mechanical strength, surface hardness, heat resistance, and transparency A polymer having excellent properties can be obtained. This is because a copolymer having the characteristics of each polymer (2) obtained by homopolymerizing the compound (2) having the group (3-3) and the compound (2) having the group (3-6), respectively. It shows that it is obtained.

  A thermoplastic resin can be produced using the compounds of the present application. The preferred weight average molecular weight of the thermoplastic resin is 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 10,000. When producing a thermoplastic resin, it is necessary not to increase the degree of polymerization or to adjust the weight average molecular weight to the above-mentioned range. For this purpose, monofunctional compounds are preferred.

  Thermosetting resins can be produced using the compounds of the present application. A polymer having thermosetting property has a three-dimensional cross-linking structure, may become insoluble and infusible, and molecular weight measurement may be impossible.

  In order to produce a polymer, it is preferable to select a polymerization method according to the application. For example, in order to produce an optically anisotropic film such as a retardation film or a polarizing element, polymerization is performed while maintaining a liquid crystal state, and therefore, a method of irradiating energy such as ultraviolet rays or electron beams is preferable. When the polymer has liquid crystallinity, it can be used for similar applications even if the polymer is formed into a thin film.

  The polymer obtained by thermal polymerization or photopolymerization can be used for various protective films, liquid crystal alignment films, viewing angle compensation films, and the like. Polarized ultraviolet light polymerizes the molecular orientation of the polymerizable compound in accordance with the direction of the polarized light, so that it can be applied to an alignment film that does not require rubbing. The alignment film can be formed by using a spin coating method, a Langmuir blow jet method, a printing method, or the like. The film thickness of the obtained alignment film is preferably 1 to 100 nm from the viewpoint of liquid crystal alignment control.

  Compound (1) and Compound (2) have extremely high photopolymerizability, and a polymer can be produced by photopolymerization as it is. An initiator may be used to shorten the reaction time.

  The composition can produce a polymer by thermal polymerization. Thermal polymerization is generally carried out at a reaction temperature of 0 to 150 ° C. for 1 to 100 hours. Usually, a composition containing an initiator is used.

  A composition containing a solvent may be used for the polymerization reaction. When manufacturing alignment films, antireflection films, viewing angle compensation films, etc. by photopolymerization, a composition containing a solvent is applied onto a substrate by spin coating, and after removing the solvent, it is irradiated with light for polymerization. You may let them.

  The polymer of the present application can be dissolved in a solvent and formed into various molded articles such as films. Preferred solvents are N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylacetamide dimethyl acetal, tetrahydrofuran, chloroform, 1,4-dioxane, bis ( Methoxyethyl) ether, γ-butyrolactone, tetramethylurea, trifluoroacetic acid, ethyl trifluoroacetate, PEGMEA, cyclopentanone, cyclohexanone and hexafluoro-2-propanol. However, the solvent is not limited thereto, and may be a mixture with a general organic solvent such as acetone, benzene, toluene, heptane, methylene chloride.

  A molded article having optical anisotropy is obtained by the following method. A solution obtained by dissolving the obtained polymer in an organic solvent is applied to a transparent substrate that has been previously subjected to orientation treatment. This is heated to a temperature above the glass transition point of the polymer. Next, by cooling, a uniformly oriented polymer thin film is formed to produce a molded article having optical anisotropy. The transparent substrate is a glass plate or a polymer film. Examples of polymer films are triacetyl cellulose, “Arton” (trade name) manufactured by JSR Corporation, “ZEONEX” (trade name) and “ZEONOR” (trade name) manufactured by ZEON Corporation, Mitsui Chemicals, Inc. "Apel" (trade name) manufactured by Co., Ltd. Preferable coating methods for obtaining a uniform film thickness include a spin coating method, a micro gravure coating method, a gravure coating method, a wire barcode method, a dip coating method, a spray coating method, and a meniscus coating method.

  The thickness of the molded article having optical anisotropy varies depending on the desired retardation value. This retardation value varies depending on the birefringence of the molded article having optical anisotropy. A preferable retardation value is in the range of 0.05 to 50 μm, and a more preferable retardation value is in the range of 0.1 to 20 μm. A more preferable retardation value is in the range of 0.1 to 10 μm. The haze value of the molded article having optical anisotropy is 1.5% or less, and more preferably 1.0% or less. The transmittance correlated with the haze value is 80% or more, more preferably 85% or more. It is preferable that the transmittance satisfies these ratios in the visible light region. A haze value range of 1.5% or less is a preferable condition in order not to cause a problem in polarization performance. A transmittance range of 80% or more is a preferable condition for maintaining brightness when a molded article having this optical anisotropy is used for a liquid crystal display element.

  Since the polymer of the present application has optical anisotropy, it can be used alone for a retardation film. By combining this polymer with other retardation film, polarizing film, circular polarizing film, elliptical polarizing film, anti-reflection film, color It can be used for a compensator (color compensator), a viewing angle compensator, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these Examples. In Examples 1-2 and Examples 4-7, compound (1) or compound (2) was expressed using the compound numbers described in Example 3. The structure of the compound was confirmed by nuclear magnetic resonance spectrum, infrared absorption spectrum, mass spectrum and the like. The unit of the phase transition temperature is ° C., C represents a crystal, N represents a nematic phase, and I represents an isotropic liquid phase. Below, the measuring method of a physical-property value is shown.
<Weight average molecular weight and number average molecular weight>
Shimadzu LC-9A gel permeation chromatograph manufactured by Shimadzu Corporation and column Shodex GF-7MHQ (developing solvent: DMF) manufactured by Showa Denko were used. In the following, the liter, which is a unit of capacity, is expressed as a symbol L.

<No. Production of 2-2-2 Compound>

(First stage)
Under a nitrogen atmosphere, compound (ex1-2) (360 mmol) was added to tetrahydrofuran (THF) (1.5 L), cooled to −20 ° C., t-BuOK (360 mmol) was added, and the mixture was stirred for 30 minutes. A THF (1 L) solution of the compound (ex1-1) (300 mmol) was added dropwise at the same temperature, and the mixture was stirred for 3 hours. Water was added and extracted with toluene. The organic layer was 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 to obtain (ex1-3) (260 mmol).

(Second stage)
Compound (ex1-3) (260 mmol) and Pd / C (10 g) were added to ethanol (2 L), and the mixture was stirred at room temperature for 10 hours in a hydrogen atmosphere. Pd / C was filtered off, and the solvent was distilled off from the filtrate under reduced pressure. Purification by recrystallization gave (ex1-4) (130 mmol).

(Third stage)
Under a nitrogen atmosphere, (ex1-4) (130 mmol) and formic acid (780 mmol) were added to toluene (2 L), and the mixture was heated to reflux for 6 hours. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude (ex1-5).

(4th stage)
Under a nitrogen atmosphere, THF (1 L) of the crude compound (ex1-5) was added dropwise to a THF (300 mmol) suspension of lithium aluminum hydride (65 mmol) on an ice bath. The mixture was stirred at room temperature for 1 hour, water and dilute hydrochloric acid were added, and the mixture was extracted with toluene. The organic layer was 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 to obtain (ex1-6) (100 mmol).

(5th stage)
(Ex1-6) (100 mmol), acrylic acid (120 mmol) and 4-dimethylaminopyridine (DMAP) (30 mmol) were added to dichloromethane (1 L) and stirred under a nitrogen atmosphere. Thereto was added dropwise a solution of 1,3-dicyclohexylcarbodiimide (120 mmol) in dichloromethane (500 ml). After dropping, the mixture was stirred at room temperature for 10 hours. The deposited precipitate was separated by filtration, and the organic layer was 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 and recrystallization to obtain the title compound (62 mmol).
C 63.7 N 77.3 I

<No. 1-1-10 Production of Compound>

(First stage)
Under a nitrogen atmosphere, compound (ex2-2) (360 mmol) was added to tetrahydrofuran (THF) (1.5 L), cooled to −20 ° C., t-BuOK (360 mmol) was added, and the mixture was stirred for 30 minutes. A THF (1 L) solution of the compound (ex2-1) (300 mmol) was added dropwise at the same temperature, and the mixture was stirred for 3 hours. Water was added and extracted with toluene. The organic layer was 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. The enol ether obtained by purification and dilute hydrochloric acid were added to acetone (1.5 L), and the mixture was stirred at room temperature for 3 hours. Water was added and extracted with toluene, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was recrystallized to obtain (ex2-3) (120 mmol).

(Second stage)
Under a nitrogen atmosphere, compound (ex2-4) (140 mmol) was added to tetrahydrofuran (THF) (1 L), cooled to −20 ° C., t-BuOK (140 mmol) was added, and the mixture was stirred for 30 minutes. A solution of compound (ex2-3) (120 mmol) in THF (500 ml) was added dropwise at the same temperature and stirred for 3 hours. Water was added and extracted with toluene. The organic layer was 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 to obtain (ex2-5) (100 mmol).

(Third stage)
Under a nitrogen atmosphere, (ex2-5) (100 mmol) and m-chloroperbenzoic acid (mCPBA) (300 mmol) were added to methylene chloride (500 ml), and the mixture was stirred at room temperature for 24 hours. The extract was washed with water and an aqueous sodium thiosulfate solution and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography and recrystallization to obtain the title compound (52 mmol).

  According to the method of Examples 1-2, (2-7-14) is produced from compound (1-1-1). These compounds are summarized in the table.

15 parts by weight of the compound (2-2-2) produced in Example 1, 20 parts by weight of 4- (trans-4-propylcyclohexyl) cyanobenzene, 31 parts by weight of 4- (trans-4-pentylcyclohexyl) cyanobenzene, The clearing point of a composition comprising 21 parts by weight of 4- (trans-4-heptylcyclohexyl) cyanobenzene and 13 parts by weight of 4 ′-(trans-4-heptylcyclohexyl) -4-cyano-1,1′-biphenyl and Δn was 75 ° C. and 0.082, respectively.

80 parts by weight of the compound (2-2-2) produced in Example 1, 5 parts by weight of 4- (trans-4-propylcyclohexyl) cyanobenzene, 5 parts by weight of 4- (trans-4-pentylcyclohexyl) cyanobenzene, Photopolymerization was initiated with a composition comprising 5 parts by weight of 4- (trans-4-heptylcyclohexyl) cyanobenzene and 5 parts by weight of 4 ′-(trans-4-heptylcyclohexyl) -4-cyano-1,1′-biphenyl. 3 parts by weight of the agent Irgacure 907 (trade name: manufactured by Ciba Specialty Chemicals) is added. A polymerizable composition (103 parts by weight) containing this photopolymerization initiator was dissolved in 412 parts by weight of cyclopentanone to prepare a solution having a concentration of 20% by weight. This solution was applied to a glass substrate with a polyimide alignment film which was subjected to a rubbing alignment treatment using a bar coater capable of obtaining a wet film thickness of about 12 μm. This was placed on a hot plate heated to 70 ° C. for 120 seconds to perform solvent drying and liquid crystal alignment. Furthermore, using an ultra-high pressure mercury lamp of 250 W / cm as a radiation source at room temperature, light having an intensity of irradiance of 30 mW / cm ² (center wavelength 365 nm) was irradiated for 20 seconds to polymerize in a nitrogen atmosphere. When the optical thin film thus obtained was observed with a polarizing microscope, it was confirmed that uniform liquid crystal alignment without alignment defects was obtained. When the retardation was determined using a Berek compensator, a value of 68 nm was obtained. Further, this optical thin film was sandwiched between a crossed Nicol polarizer so that the angle formed by the rubbing direction and the absorption axis of the polarizer was 45 °, and the state of light transmission was observed on the backlight. Observation of light transmission while tilting in the rubbing direction confirmed that the change was symmetrical on the left and right with respect to the front. This suggests that the orientation vector of the liquid crystal skeleton in this optical thin film is substantially parallel to the glass substrate.

The compound (2-2-2) (10 mg) prepared in Example 1, azobiscyclohexanecarbonitrile (0.1 mg), and benzene (100 μL) were placed in a glass ampoule. This was cooled to −60 ° C., sufficiently deaerated with a vacuum pump, and sealed. The ampoule was heated at 110 ° C. for 24 hours. The obtained reaction mixture was reprecipitated three times from methanol (15 mL) to obtain a polymer (7.4 mg). The weight average molecular weight (M _w ) measured by GPC was 32,000. The polydispersity (Mw / Mn) was 2.05. The polymer (1.203 mg) was immersed in pure water (1 mL) and allowed to stand at 50 ° C. for 10 days. The polymer was taken out and dried well, and the weight was measured and found to be 1.205 mg. It turns out that the water absorption rate of this polymer is low.

  5 parts by weight of the polymer produced in Example 4 was dissolved in 100 parts by weight of NMP. This solution was applied to each of two glass substrates that had been thoroughly cleaned using a spin coater. These glass substrates were heated at 200 ° C. for 3 hours to remove the solvent, thereby forming a polymer thin film on the glass substrate. The surface of the polymer thin film formed on these glass substrates was rubbed in one direction with a roller equipped with a rubbing cloth and rubbed. The two glass substrates were bonded so that the polymer thin film faced and the rubbing directions were the same with a spacer having a thickness of 10 μm interposed therebetween to form a cell. A liquid crystal composition ZLI-1132 (trade name) manufactured by Merck was injected into this cell at room temperature. The liquid crystal composition in the liquid crystal cell showed uniform homogeneous alignment.

Preferred examples of compositions that can be prepared using the compound of formula (2) of the present invention are shown as Composition Examples 1 to 6. All are polymerized by irradiation with UV light to give a molded article having optical anisotropy. (%) In the following represents parts by weight .

Composition example 1

Composition example 2

Composition example 3

Composition Example 4

Composition example 5

Composition Example 6

Claims (29)

A compound represented by the following formula (1) or formula (2).
R ^a- (A−Z) m−A−R ^b (1)
^{R c -Y- (A-Z)} m-A-R b (2)

In the formula, R ^a is a group (3-1), a group (3-2), a group (3-3), a group (3-4), a group (3-5) or a group (3-6); Here, R ^d is independently hydrogen, halogen, or alkyl having 1 to 5 carbon atoms. In these alkyls, any hydrogen may be replaced by halogen, but in the group (3-6), 3 R ^d is not simultaneously hydrogen; R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, —N═C═O, —N═C ═S, or alkyl having 1 to 20 carbon atoms, and in these alkyl, any —CH ₂ — is —O—, —S—, —CO—, —COO—, —OCO—, —CH═CH—. , -CF = CF-, or -C≡C-, and in these alkyls any hydrogen is It may be replaced by Gen; ^{R c} is a group (3-1), group (3-2), group (3-3), group (3-4), group (3-5), or a group (3 -6), wherein R ^d is independently hydrogen, halogen, or alkyl of 1 to 5 carbons, in which any hydrogen may be replaced by halogen; A is independently 1,4 -Cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydronaphthalene-2,6-diyl, or bicyclo [2.2.2] octane-1,4-diyl, in these rings Arbitrary —CH ₂ — may be replaced by —O—, Arbitrary —CH═ may be replaced by —N═, and in these rings, any hydrogen is halogen, alkyl having 1 to 5 carbon atoms. Or an alkyl halide having 1 to 5 carbon atoms May be replaced; Y is alkylene having 1 to 20 carbon atoms, any -CH ₂ - in these alkylene - is -O -, - S -, - COO-, or -OCO- be replaced by Well; Z is independently a single bond, — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —O (CH ₂ ) _n O—, —CH═CH— , —C≡C—, —COO—, —OCO—, — (CF ₂ ) ₂ —, —C≡C—COO—, —OCO—C≡C—, —CH═CH— (CH ₂ ) ₂ — , — (CH ₂ ) ₂ —CH═CH—, —CF═CF—, —C≡C—CH═CH—, —CH═CH—C≡C—, —OCF ₂ —, or —CF ₂ O— Where n is an integer from 1 to 20; m is an integer from 1 to 6. However, m is 1 or 2, ^{R c} is acryloyloxy, A in A-Z adjacent to Y is 1,4-phenylene and,, ^{R b} when Z is -OCO- are not alkyl, rather at alkoxy , M is 2, R ^c is methacryloyloxy, Y is —C ₃ H ₆ —, and in two AZs adjacent to Y, A is 1,4-cyclohexylene, Z is a single bond, and A is adjacent to R ^b When R is 1,4-phenylene, R ^b is not methyl, and m is 2, R ^c is (3-4), Y is —C ₂ H ₄ —, and A in two AZ adjacent to Y is A 1,4-cyclohexylene, Z is a single bond, ^{R b} when a adjacent ^{R b} is hydrogen ortho ^{R b} 1,4-phenylene is replaced by fluorine have name with fluorine. R ^b is hydrogen, _{halogen, -CF 3, -CF 2 H,} -CFH 2, -OCF 3, -OCF 2 H, -N = C = O or claim 1 is -N = C = S, Compound. R ^b is alkyl having 1 to 20 carbons or a group in which any —CH ₂ — is replaced by —O— in these alkyls, and m is an integer of 3 to 6. 1. The compound according to 1. R ^b is alkyl having 1 to 20 carbon atoms, or a group in which any —CH ₂ — is replaced by —O— in these alkyls, and R ^c is a group (3-1), a group (3-2), group (3-3), group (3-4), group (3-5), or group (3-6), wherein R ^d is independently hydrogen, halogen, or carbon number. The alkyl of 1 to 5, in which any hydrogen may be replaced by halogen, but in the group (3-6), the three R ^d are not simultaneously hydrogen. The described compound. R ^b is alkyl having 1 to 20 carbons, or a group in which any —CH ₂ — is replaced by —O— in these alkyls, and A in the formula (2) is adjacent to Y A in -Z is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydronaphthalene-2,6-diyl, or bicyclo [2.2.2] octane-1,4-diyl; In these rings, any —CH ₂ — may be replaced by —O—, and any —CH═ may be replaced by —N═, and in these rings, any hydrogen is halogen, carbon number 1 The compound according to claim 1, which may be substituted by ˜5 alkyl or alkyl halide having 1 to 5 carbon atoms. In Formula (1) and Formula (2), R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or carbon R ¹ is independently hydrogen, halogen or methyl; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5 -Diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2,5-diyl; Y is alkylene having 1 to 20 carbons, —O (CH ₂ ) _r - Is - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond _{independently, - (CH 2) n -} , - O (CH 2) n -, - (CH 2 _{) n O -, - CH =} CH -, - COO -, - OCO -, - OCF 2 -, or _-CF 2 is a O-, n is an an integer from 1 to 20; m is from 1 to 4 integer The compound according to claim 1, wherein In Formula (1) and Formula (2), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or carbon number 1-5 alkoxy; R ^d is hydrogen, fluorine or methyl; A is independently 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 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; Y is 1 carbon 20 _{alkylene, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond independently, - (CH _{2) 2} - _{, - (CH 2) 4 -} , - CH 2 O -, - OCH 2 -, CH = CH -, - COO-, or a -OCO-; m is a compound of claim 1 which is an integer from 1 to 4. In formula (1) and formula (2), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; R ^d is independently hydrogen, halogen or methyl A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl Or pyrimidine-2,5- Be-yl; Y is C1-20 _{alkylene, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single independent Bond, — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —OCF ₂ -, or _-CF 2 is a O-, n is an an integer from 1 to 20; m is a compound of claim 1 which is an integer from 1 to 4. In Formula (1) and Formula (2), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6), where R ^d is independently hydrogen, fluorine Or ^Rb is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons Yes; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbons, —O (CH _{2) r} -, or - (CH _{2) r} O- der , R is located at 1 to 19 integer; Z is a single bond _{independently, - (CH 2) 2 -} , - (CH 2) 4 -, - CH 2 O -, - OCH 2 -, - CH = CH- The compound according to claim 1, —COO—, or —OCO—; m is an integer of 1 to 4. In Formula (2), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons. R ^c is a group (3-6), wherein R ^d is independently hydrogen, fluorine or methyl; A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1 , 3-Dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbons, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, and r is 1 It is an integer of ~ 19; Z is a single bond independently, - (CH _{2 ) 2 -, - (CH 2} ) 4 -, - CH 2 O -, - OCH 2 -, - CH = CH -, - COO-, or a -OCO-; m is claimed is an integer from 1 to 4 Item 1. The compound according to Item 1. The compound according to claim 9 or 10, wherein m is 1 in formula (1) and formula (2). The compound according to claim 9 or 10, wherein m is 2 in the formula (1) and the formula (2). The compound according to claim 9 or 10, wherein m is 3 in the formulas (1) and (2). The compound according to claim 1, wherein the compound represented by the formula (1) or the formula (2) is any one compound represented by the following formulas (I) to (VIII).
R ^a -AZ-A-R ^b (I)
R ^a- (A-Z) ₂ -A-R ^b (II)
R ^a- (AZ) ₃ -A-R ^b (III)
R ^a- (AZ) ₄ -A-R ^b (IV)
^{R c -Y-A-Z-} A-R b (V)
_{^{R c -Y- (A-Z)}} 2 -A-R b (VI)
_{^{R c -Y- (A-Z)}} 3 -A-R b (VII)
_{^{R c -Y- (A-Z)}} 4 -A-R b (VIII)

In the formula, R ^a and R ^c are a group (3-1), a group (3-2), a group (3-3), a group (3-4), a group (3-5) or a group (3-6). R ^b is hydrogen, halogen, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons ^Rd is hydrogen, halogen or methyl; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6- Diyl, pyridine-2,5-diyl, or pyrimidine-2, - be diyl; Y is alkylene having 1 to 20 carbon _{atoms, -O (CH 2) r -} , or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond , — (CH ₂ ) _n —, —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —OCF ₂ -, or _-CF 2 is a O-, n is an integer from 1 to 20. In the formulas (I) to (VIII), R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or carbon 1 R 3 is alkoxy, R ^d is hydrogen, fluorine or methyl; A is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, 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; 20 alkylene, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, r is an integer of 1 to 19; Z is a single bond, — (CH ₂ ) ₂ —, — ( _{CH 2) 4 -, - CH} 2 O -, - OCH 2 -, - CH = CH- The compound according to claim 14, —COO—, or —OCO—. In the formulas (I) to (VIII), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is hydrogen, halogen, —CF ₃ , _{-CF 2 H, -CFH 2, -OCF} 3, -OCF 2 H, alkyl of 1 to 5 carbon atoms, or alkoxy of 1 to 5 carbon atoms; ^{R d} is hydrogen, halogen or methyl; a is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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, tetrahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, or pyrimidine-2 , 5-diyl; Y is Alkylene prime _{1~20, -O (CH 2) r} -, or - (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond, - (CH _{2) n} - , —O (CH ₂ ) _n —, — (CH ₂ ) _n O—, —CH═CH—, —C≡C—, —COO—, —OCO—, —OCF ₂ —, or —CF ₂ O— The compound according to claim 14, wherein n is an integer of 1 to 20. In formulas (I) to (VIII), R ^a and R ^c are a group (3-4), a group (3-5) or a group (3-6); R ^b is fluorine, —CF ₃ , — CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 5 carbons, or alkoxy having 1 to 5 carbons; R ^d is hydrogen, fluorine or methyl; A is 1, 4 -Cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, 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; Y is alkylene having 1 to 20 carbons, —O (CH ₂ ) _r —, or — (CH _{2) r} is O-, r is an 1-19 integer; Z is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —COO—, or —OCO—. 14. The compound according to 14. In the formulas (V) to (VIII), R ^c is a group (3-6); R ^b is fluorine, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, C 1-5 alkyl or C 1-5 alkoxy; R ^d is hydrogen, fluorine or methyl; A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane -2,5-diyl, 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; Y is alkylene having 1 to 20 carbon atoms, —O (CH ₂ ) _r —, or — (CH ₂ ) _r O—, and r is an integer of 1 to 19 Z is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) _{4 -, - CH 2 O -} , - OCH 2 -, - CH = CH -, - COO-, or a compound according to claim 14 is -OCO-. A liquid crystal composition comprising at least two polymerizable compounds, wherein at least one polymerizable compound is the compound according to claim 1. The liquid crystal composition according to claim 19, wherein at least two polymerizable compounds are the compounds according to claim 1. The liquid crystal composition according to claim 19, wherein at least one polymerizable compound is the compound according to claim 1, and at least one other polymerizable compound is a compound different from the compound according to claim 1. A liquid crystal composition comprising at least one polymerizable compound according to claim 1 and at least one non-polymerizable compound having liquid crystallinity. The polymer obtained from the compound of any one of Claims 1-18 which has at least 1 sort (s) of the structural unit shown by Formula (6-1)-(6-6).

A polymer obtained by homopolymerizing one of the compounds according to any one of claims 1 to 18. The polymer obtained from the liquid-crystal composition of any one of Claims 19-21. A polymer composition obtained from the liquid crystal composition according to claim 22. A film comprising the polymer according to any one of claims 23 to 25 or the polymer composition according to claim 26. A molded article having optical anisotropy, comprising the polymer according to any one of claims 23 to 25 or the polymer composition according to claim 26. A liquid crystal display device comprising the polymer according to any one of claims 23 to 25 or the polymer composition according to claim 26.