JP4599948B2 - α-Fluoroacrylate compound, composition and polymer thereof - Google Patents

Description

  The present invention relates to a compound having a polymerizable group α-fluoroacryloyloxy, a composition containing the compound, a polymer of the compound, and uses thereof.

  By aligning molecules of a polymerizable compound having liquid crystallinity in a certain direction and performing photopolymerization, a polymer having a fixed molecular arrangement can be obtained. This polymer has optical anisotropy (see Patent Document 1). Examples of the polymerizable compound having liquid crystallinity are the following acrylates (see Patent Documents 2 and 3). These acrylates have high reactivity, and the resulting polymer has high transparency, but further improvements in properties such as heat resistance and mechanical strength are required.

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

  The first object of the present invention is a compound having a polymerizable group and having properties such as high polymerization reactivity, a wide temperature range of the liquid crystal phase, and good miscibility. The second problem is a composition containing this compound and having good coatability and the like. The third challenge is obtained by polymerization of this composition and has good optical anisotropy, high transparency, good chemical stability, good heat resistance, low water permeability, low water absorption, low gas permeability. It is a polymer having properties such as degree, good hardness, and good mechanical strength. Mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like. The fourth problem is the search for applications using the characteristics of the polymer.

  The aspect of the present invention for solving the problem is as described in the following section. Preferred examples of the terminal group, ring and bonding group in the compounds (1) and (2) are also described.

式（１）、（２）において、ＰはＣＨ_２＝ＣＦＣＯＯ−であり、Ｒ^ａは水素、ハロゲン、−ＣＦ_３、−ＣＦ_２Ｈ、−ＣＦＨ_２、−ＯＣＦ_３、−ＯＣＦ_２Ｈ、−Ｎ＝Ｃ＝Ｏ、−Ｎ＝Ｃ＝Ｓ、または炭素数１〜２０のアルキルであり、これらのアルキルにおいて任意の−ＣＨ₂−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、または−Ｃ≡Ｃ−で置き換えられてもよく、これらのアルキルにおいて任意の水素はハロゲンで置き換えられてもよい。 1. A compound represented by the following formula (1) or (2).
PY- (AZ) _m -R ^a (1)
P-Y- (AZ) _m -Y-P (2)

In the formulas (1) and (2), P is CH ₂ ═CFCOO—, and ^Ra 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 may be replaced with a halogen.

The meaning of the phrase “any —CH ₂ — in alkyl may be replaced by —O—, —CH═CH—, etc.” is shown by way of example. The group in which any —CH ₂ — in C ₄ H ₉ — is replaced by —O— or —CH═CH— is C ₃ H ₇ O—, CH ₃ —O— (CH ₂ ) ₂ —, CH _3. —O—CH ₂ —O—, H ₂ C═CH— (CH ₂ ) ₃ —, CH ₃ —CH═CH— (CH ₂ ) ₂ —, CH ₃ —CH═CH—CH ₂ —O— and the like. is there. Thus, the term “arbitrary” means “at least one selected without distinction”. Considering the stability of the compound, CH ₃ —O—CH ₂ —O— in which oxygen and oxygen are not adjacent to each other is preferable to CH ₃ —O—O—CH ₂ — in which oxygen and oxygen are adjacent to each other. .

Preferred R ^a is hydrogen, chlorine, fluorine, —CN, —N═C═O, —N═C═S, alkyl, alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylthio, alkylthioalkoxy, alkenyl, alkenyloxy, alkenyloxy. Alkyl, alkoxyalkenyl, alkynyl, alkynyloxy and the like. Also preferred are those groups in which at least one hydrogen has been replaced by a halogen. Preferred halogens are fluorine and chlorine. A more preferred halogen is fluorine. Specific examples are monofluoroalkyl, polyfluoroalkyl, perfluoroalkyl, monofluoroalkoxy, polyfluoroalkoxy, perfluoroalkoxy and the like. These groups are preferably linear rather than branched. In order to obtain the optically active compound (1) or (2), branched R ^a is preferred.

More preferable R ^a is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, alkyl having 1 to 10 carbons, Alkoxy having 10 or alkoxyalkyl having 2 to 10 carbon atoms. Examples of alkyl, alkoxy and alkoxyalkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, octyloxy , Nonyloxy, decyloxy, methoxymethyl, methoxyethyl. Particularly preferred R ^a is alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons.

A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo [ 2.2.2] octane-1,4-diyl or a divalent group represented by formulas (3-1) to (3-10), and in these rings, any —CH ₂ — is — O— may be substituted and any —CH═ may be substituted with —N═, and in these rings, any hydrogen is halogen, alkyl having 1 to 5 carbons or halogen having 1 to 5 carbons. May be replaced by alkyl halide.

  Preferred A is 1,4-cyclohexylene, 1,4-cyclohexenylene, 2,2-difluoro-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, 2,6-difluoro-1,4-phenylene, 2,3 , 5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3-fluoropyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene-2 , 6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methyl-fluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9- Fluorofluorene-2,7-diyl, 9,9-difluorofluorene-2,7-diyl or the formula (3-1), (3-2), (3-6), (3-8) or (3 -10).

  Trans is preferable to cis in the configuration of 1,4-cyclohexylene and 1,3-dioxane-2,5-diyl. Since 2-fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are structurally identical, the latter was not exemplified. This rule also applies to the relationship with 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene. When m is an integer of 2 to 10, two arbitrarily selected A may be the same or different from each other.

  More preferable 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, and 2,6-difluoro-1,4-phenylene.

Z is a single bond or alkylene having 1 to 20 carbon atoms, and in this alkylene, arbitrary —CH ₂ — is —O—, —CO—, —COO—, —OCO—, —CH═CH—, —CF═CF—, or —C≡C— may be replaced, and any hydrogen may be replaced with a halogen.

Preferred Z is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF. ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —. More preferable Z is a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH. -, -C≡C-. Particularly preferred Z is a single bond, — (CH ₂ ) ₂ —, —COO— or —OCO—. When m is an integer of 2 to 10, two arbitrarily selected Zs may be the same or different from each other.

Y is a single bond, alkylene having 1 to 20 carbon atoms, and in these alkylene, arbitrary —CH ₂ — is replaced by —O—, —S—, —COO—, —CH═CH— or —OCO—. May be.

Preferred Y is alkylene having 1 to 10 carbons, and in these alkylenes, any —CH ₂ — may be replaced by —O— except that —O— is adjacent. Particularly preferred Y is alkylene having 1 to 10 carbon atoms, or alkylene in which —CH ₂ — adjacent to — (AZ) — is replaced by —O—.

m is independently an integer of 1 to 10, but when m is 2, 2 A is 1,4-phenylene, 2 Z is a single bond and Y is — (CH ₂ ) ₆ O—, R ^a -OCH _3, not one of the _-OC 8 _{H 17} and -CN is.

Preferred m is an integer of 2 to 7. Further preferred m is an integer of 2-4.
2. Item 8. The compound according to item 1, wherein m is an integer of 1 to 7 in formula (1) or (2).

3. Item 3. The compound according to item 1 or 2 represented by formula (1).

4). Item 4. The compound according to item 3, wherein the compound represented by the formula (1) is any one of compounds represented by the following formulas (I) to (IV).
PY-A-R ^a (I)
P-Y-A-Z-R ^a (II)
P-Y-A-Z- A-Z-A-R a (III)
P-Y-A-Z- A-Z-A-Z-A-R a (IV)
Here, P, Y, A, Z, and Ra are as described above.

5). In the formula (1) or formulas (I) to (IV), R ^a is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —CF ₂ H, —CFH ₂ , —OCF ₃ , —OCF ₂ H, carbon Item 5. The compound according to Item 3 or 4, which is alkyl having 1 to 10, alkoxy having 1 to 10 carbons, or alkoxyalkyl having 2 to 10 carbons.

6). In the formula (1), m is 2, two Zs are single bonds, and at least one of A is 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, and any- CH ₂ — may be replaced by —O—, and arbitrary —CH═ may be replaced by —N═, and in these rings, any hydrogen is halogen, alkyl having 1 to 5 carbon atoms or carbon atoms. Item 6. The compound according to item 1, which may be substituted with 1 to 5 alkyl halides or is a divalent group represented by formulas (3-1) to (3-10).

7). Item 3. The compound according to item 1 or 2 represented by formula (2).

8). Item 4. The compound according to item 3, wherein the compound represented by the formula (2) is any one of compounds represented by the following formulas (V) to (IX).
PYAYYP (V)
P-Y-A-Z-A-Y-P (VI)
P-Y-A-Z-A-Z-A-Y-P (VII)
P-Y-A-Z-A-Z-A-Z-A-Y-P (VIII)
P-Y-A-Z-A-Z-A-Z-A-Z-A-Y-P (IX)
Here, P, Y, A and Z are as described above.

9. In formula (1), (2) or formula (I)-(IX), A is independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl. 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl or fluorene-2,7-diyl, in which any hydrogen is F , An alkyl having 1 or 2 carbon atoms or a fluoroalkyl having 1 or 2 carbon atoms, or a divalent group represented by formulas (3-1) to (3-10) 9. The compound according to any one of 5, 7, and 8.

10. In formula (1), (2) or formula (I)-(IX), 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, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4- Phenylene, 2-trifluoromethyl-1,4-phenylene, 2-difluoromethyl-1,4-phenylene, 2,3-bistrifluoromethyl-1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2 , 5-diyl, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9-fluorofluorene 2,7-diyl, 9,9-difluoro-2,7-diyl or formula (3-1) to the compound according to claim 9, which is a divalent group represented by (3-10).

11. In formula (1), (2) or formula (I)-(IX), Z is independently a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO. —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₂ COO— , —OCO (CH ₂ ) ₂ —, —CH═CHCOO—, —OCOCH═CH—, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O— or —O (CH ₂ ) ₃ — 9. The compound according to 9 or 10.

12 In formula (1) or formulas (I) to (IV), 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, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2- Trifluoromethyl-1,4-phenylene, 2-difluoromethyl-1,4-phenylene, 2,3-bistrifluoromethyl-1,4-phenylene, pyridine-2,5-diyl or pyrimidine-2,5 diyl or Item 12. The compound according to item 11, which is a divalent group represented by formula (3-1), (3-2), (3-6), (3-8) or (3-10).

13. In the formula (1) or formulas (I) to (IV), Z is independently a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, —COO—, —OCO—, —CH. ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH—, —CF═CF—, —C≡C—, — (CH ₂ ) ₄ —, — (CH ₂ The compound according to Item 11 or 12, wherein the compound is ₃ O— or —O (CH ₂ ) ₃ —.

14 In formula (2) or formula (V) to (IX), A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4-phenylene, 2-difluoromethyl-1,4-phenylene, 2,3-bistrifluoromethyl-1,4 -Phenylene, naphthalene-2,6-diyl, fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7- Item 11 which is diyl, 9,9-difluorofluorene-2,7-diyl or a divalent group represented by formulas (3-1) to (3-5), (3-7) or (3-9) Compound described in 1.

15. In formula (2) or formulas (V) to (IX), Z is independently a single bond, — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH _2. -, - CH = CH -, - C≡C -, - (CH 2) 2 COO -, - OCO (CH 2) 2 -, - CH = CHCOO- or claim 11 or 14 is -OCOCH = CH- The described compound.

16. In Formula (1), R ^a is —Cl, —Br, —I, —COOH, —COCl, —COBr, —CHO, —OH, —OSO ₂ CH ₃ or —OSO ₂ C ₆ H ₄ CH ₃ . Item 1. The compound according to Item 1.

17. Item 18. The compound according to Item 16, wherein m is 1 or 2 in the formula (1).

18. In the formula (1), A is independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or naphthalene-2,6- Item 18. The compound according to Item 16 or 17 which is diyl.

19. Item 19. The compound according to any one of Items 16 to 18, wherein in the formula (1), Z is independently a single bond, alkyl having 1 to 4 carbon atoms, —CH═CH— or —C≡C—.

20. In Formula (1), (2) or Formula (I) to (IX), Y is independently alkylene having 1 to 10 carbons, or methylene adjacent to-(AZ)- Item 16. The compound according to any one of Items 1 to 15, which is a group substituted with O-.

21. In Formula (1) or (2), R ^a is alkyl having 1 to 10 carbons or alkoxy having 1 to 10 carbons, and A is independently 1,4-cyclohexylene, 1,4-cyclohexyl. Senylene, 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, Z is independently a single bond, — (CH ₂ ) ₂ —, —COO— or —OCO—, and Y is independently Item 2. The alkylene according to Item 1, wherein the alkylene has 1 to 10 carbon atoms, or alkylene in which —CH ₂ — adjacent to — (AZ) — is replaced by —O—, and m is an integer of 2 to 4. Compound.

22. Item 21. The optically active compound according to any one of Items 1 to 21.

23. Item 23. A composition comprising any one of the compounds according to any one of Items 1 to 22 or the compound represented by the formula (II +).
_{CH 2 = CFCOO- (CH 2)} 6 O-A-A-R a + (II +)
In the formula (II +), A is 1,4-phenylene, R ^{a +} is —OCH ₃ , —OC ₈ H ₁₇ or —CN.

24. Item 23. A composition comprising the compound according to any one of Items 1 to 22 and two compounds selected from the compounds represented by Formula (II +):
_{CH 2 = CFCOO- (CH 2)} 6 O-A-A-R a + (II +)
In the formula (II +), A is 1,4-phenylene, R ^{a +} is —OCH ₃ , —OC ₈ H ₁₇ or —CN.

25. Item 23. A composition comprising at least one compound described in any one of Items 1 to 22 and a polymerizable compound different from the compound described in Item 1.

26. Item 26. The composition according to any one of Items 23 to 25, comprising at least one non-polymerizable liquid crystal compound.

27. Item 26. The composition according to any one of Items 23 to 25, which contains a polymerizable optically active compound different from at least one compound described in Item 1.

28. Item 26. The composition according to any one of Items 23 to 25, which comprises a non-polymerizable optically active compound different from at least one compound described in Item 1.

29. Item 28. A polymer obtained by polymerizing the composition according to item 23, 24, 25 or 27.

30. Item 29. A polymer composition obtained by polymerizing the composition according to item 26 or 28.

31. Item 30. The polymer according to Item 29, having a weight average molecular weight of 500 to 1,000,000.

32. Item 30. The polymer according to Item 29, wherein the weight average molecular weight is 1,000 to 500,000.

33. Item 33. The polymer according to item 29, 31 or 32, wherein the polymer is an optically active compound.

34. Item 31. The polymer composition according to item 30, wherein the polymer is an optically active compound.

35. Item 36. A film obtained from the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

36. Item 34. A molded article having optical anisotropy, comprising the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

37. Item 34. A retardation film comprising the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

38. Item 35. A liquid crystal alignment film comprising the polymer according to item 29, 31, 32, or 33, or the polymer composition according to item 30 or 34.

39. Item 35. The antireflection film containing the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

40. Item 36. A viewing angle compensation film comprising the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

41. Item 35. A polarizing element comprising the polymer according to Item 29, 31, 32, or 33, or the polymer composition according to Item 30 or 34.

42. Item 42. The film according to any one of Items 35 to 41, containing at least one of a film having optical anisotropy, a retardation film, a liquid crystal alignment film, an antireflection film, a viewing angle compensation film, and a polarizing element. Liquid crystal display element.

43. Item 29. A liquid crystal display device comprising the composition according to any one of items 23 to 28.

  The compounds (1) and (2) have properties such as high polymerization reactivity, a wide temperature range of the liquid crystal phase, and good miscibility. A composition containing this compound has good coatability and the like. The polymer obtained by polymerization of this composition has good optical anisotropy, high transparency, good chemical stability, good heat resistance, low water permeability, low water absorption, low gas permeability, good It has properties such as hardness and good mechanical strength. This polymer is suitable for retardation films, polarizing elements, circularly polarizing elements, elliptically polarizing elements, antireflection films, selective reflection films, color compensation films, viewing angle compensation films, liquid crystal alignment films, and the like.

  Terms used in this specification are as follows. “Liquid crystal compound” is a general term for compounds having a liquid crystal phase such as a nematic phase and a smectic phase, and compounds having no liquid crystal phase but useful as components of a liquid crystal composition. “Compound (1)” and “Compound (2)” mean compounds represented by Formula (1) and Formula (2), respectively. It may mean at least one of the compounds represented by formula (1). “Composition (1)” means a composition containing at least one compound selected from compound (1), compound (2) and compound (II +). “Polymer (1)” means a polymer obtained by polymerizing the composition (1). When one compound has a plurality of A, any two A may be the same or different. When two or more compounds have A, any two A may be the same or different. This rule also applies to symbols such as Y and Z, terms of polymerizable groups, and notation of the group (3) and the like. “(Meth) acryloyloxy” means acryloyloxy or methacryloyloxy. “(Meth) acrylate” means acrylate or methacrylate. “(Meth) acrylic acid” means acrylic acid or methacrylic acid.

  Compounds (1), (2) and (II +) have a polymerizable group α-fluoroacryloyloxy and have high polymerization reactivity, wide temperature range of liquid crystal phase, appropriate optical anisotropy, good miscibility It has sex etc. When this compound is mixed with a liquid crystal compound, other polymerizable compound, etc., it tends to become uniform easily. Part of the compounds (1), (2) and (II +) has a characteristic of having liquid crystallinity. Part of the compounds (1), (2) and (II +) is characterized by having optical anisotropy. A part of the compounds (1), (2) and (II +) is characterized by having both liquid crystallinity and optical anisotropy.

  Compounds (1) and (II +) are compounds having α-fluoroacryloyloxy only at one terminal group. Compound (2) is a compound having α-fluoroacryloyloxy at both terminal groups. Compound (1) tends to have a wider range of liquid crystal phase than (2). Compound (2) has a higher polymerization reactivity than (1) and (II +), tends to give a polymer having a higher polymerization rate, a shorter polymerization time, and a higher degree of polymerization. is there. The resulting polymer has higher heat resistance, lower water permeability, lower water absorption, lower gas permeability, higher hardness, higher mechanical strength, and the like.

The physical properties such as optical anisotropy can be arbitrarily adjusted by appropriately selecting the terminal groups, rings and bonding groups of the compounds (1), (2) and (II +). The effects of the types of the terminal group R ^a , the ring A, and the bonding group Z on the physical properties of the compounds (1), (2), and (II +) will be described below. When R ^a of the compound (1) is ^a linear alkyl, the temperature range of the liquid crystal phase is wide and the viscosity is small. When R ^a is a branched alkyl, compatibility with other liquid crystal compounds is good. Even when R ^a is —CN, halogen, —CF ₃ , or —OCF ₃ , it exhibits a good liquid crystal phase temperature range and has an appropriate compatibility. It has a sexual value, -F, if the -CF ₃ or -OCF _3, has a small optical anisotropy value.

  In the compounds (1), (2) and (II +), ring A is 1,4-phenylene, and arbitrary hydrogen is replaced by fluorine, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2 , 5-diyl or pyridazine-3,6-diyl has a large optical anisotropy. When this ring is 1,4-cyclohexylene, 1,4-cyclohexenylene or 1,3-dioxane-2,5-diyl, the optical anisotropy is small. When at least two rings are 1,4-cyclohexylene, the clearing point is high, the optical anisotropy is small, and the viscosity is small. When at least one ring is 1,4-phenylene, the optical anisotropy is relatively large and the orientational order parameter is large. When at least two rings are 1,4-phenylene, the optical anisotropy is large, the temperature range of the liquid crystal phase is wide, and the clearing point is high. When it has group (3-1)-(3-10), a twist induction force is large.

The bonding group Z of the compounds (1) and (2) is a single bond, — (CH ₂ ) ₂ —, —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —OCF ₂ —, —CH═CH -, - CF = CF- or - (CH _{2) 4} - has a small viscosity when. When this bonding group is a single bond, — (CH ₂ ) ₂ —, —OCF ₂ —, —CF ₂ O—, —CH═CH— or — (CH ₂ ) ₄ —, the viscosity is smaller. When the bonding group is —CH═CH— or —CF═CF—, the temperature range of the liquid crystal phase is wide and the elastic constant ratio is large. When the bonding group is —C≡C—, the optical anisotropy is large.

When the compounds (1), (2) and (II +) have 3 or less rings, the viscosity is low, and when they have 3 or more rings, the clearing point is high. Here, a six-membered ring is regarded as a ring, and a three-membered ring is not regarded as a ring. Compounds (1), (2) and (II +) may be optically active or optically inactive. When optically active, compounds (1), (2) and (II +) have an asymmetric carbon. The configuration of the asymmetric carbon may be R or S. The asymmetric carbon may be located at R ^a or A. When it has axial asymmetry, the twist-inducing force is large and preferable. When it has asymmetric carbon, it has good compatibility. As described above, a compound having desired physical properties can be obtained by appropriately selecting the types of terminal groups, rings and bonding groups, and the number of rings.

In addition, the compound (1) has two or less rings, and R ^a is —Cl, —Br, —I, —COOH, —COCl, —COBr, —CHO, —OH, —OSO ₂ CH ₃ or — If it is _{OSO 2 C 6 H 4 CH 3} -p, it is particularly useful as a synthetic intermediate. For example, when R ^a is —COOH, —COCl, or —COBr, it can be derived into an ester compound using a corresponding alcohol or phenol derivative. Similarly can be derived -Cl, -Br, -I, -OH, the ether compound if -OSO ₂ CH ₃ or _{-OSO 2 C 6 H 4 CH 3} -p. When ^Ra is -CHO, it can be induced to -CH = CH- by a Wittig reagent or the like. It is possible to derive these compounds to further synthetic intermediates by combining organic synthetic chemistry methods within the range in which the CH ₂ ═CFCOO— group is stably present.

  Preferred compounds (1) and (2) are the following compounds (a-1) to (g-21).

In these formulas, the meanings of R ^a and Y are the same as those in formulas (1) and (2) described in the section of the embodiment of the present invention. Z ¹ is a single bond, — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═ CHCOO—, —OCOCH═CH—, —C≡C—, —C≡C—COO—, —OCO—C≡C—, —C≡C—CH═CH—, —CH═CH—C≡C— , —OCF ₂ —, or —CF ₂ O—, and Z ² represents — (CH ₂ ) ₂ —, — (CF ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH. ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₂ COO—, _{-OCO (CH 2) 2 -,} - CH = HCOO—, —OCOCH═CH—, —C≡C—, —C≡C—COO—, —OCO—C≡C—, —C≡C—CH═CH—, —CH═CH—C≡C— , —OCF ₂ —, or —CF ₂ O—, and Z ³ is a single bond, — (CH ₂ ) ₂ —, — (CH ₂ ) ₄ —, —CH ₂ O—, —OCH ₂ —, — (CH ₂ ) ₃ O—, —O (CH ₂ ) ₃ —, —COO—, —OCO—, —CH═CH—, —CF═CF—, — (CH ₂ ) ₂ COO—, —OCO (CH ₂ ) ₂ —, —CH═CHCOO—, —OCOCH═CH—, —C≡C—, —OCF ₂ — or —CF ₂ O—, and a plurality of Z ¹ and Z ³ may or may not be the same May be. In 1,4-phenylene and fluorene-2,7-diyl having (X) in the compound, X represents halogen, alkyl or fluorinated alkyl, where X is any hydrogen, halogen, alkyl or fluorinated alkyl. It corresponds to the substituents of 1,4-phenylene and fluorene-2,7-diyl which may be replaced.

  Compounds (1) and (2) can be synthesized by combining techniques of organic synthetic chemistry. Methods for introducing the desired end groups, rings and linking groups into the starting materials are described in Houben-Wyle, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Organic Syntheses, John Wily & Sons. , Inc.), Organic Reactions (John Wily & Sons Inc.), Comprehensive Organic Synthesis, Pergamon Press, New Experimental Chemistry Course (Maruzen), etc. ing.

Although α-fluoroacrylic acid and α-fluoroacrylic acid chloride can be used for introducing α-fluoroacryloyloxy, a method of allowing α-fluoroacrylic acid fluoride (CH ₂ ═CFCOOF) to act is useful. . J. Org. Chem., 1989, 54, 5640, JP-A-60-158137, JP-A-61-85345, etc. describe synthesis methods of α-fluoroacrylic acid fluoride, and those methods Can be synthesized according to the above. It has been reported. Compounds (1) and (2) are synthesized by using these compounds as starting materials.

The synthesis of the linking group Z is described in Schemes 1-12. 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 (1M) correspond to compound (1) or (2). These methods can be applied to the optically active compounds (1) and (2) and the optically inactive compounds (1) and (2).
Scheme 1: Compound in which Z is a single bond

  Compound (1A) is synthesized by reacting arylboric acid (S1) with compound (S2) synthesized by a known method in the presence of a carbonate aqueous solution and a catalyst such as tetrakis (triphenylphosphine) palladium. This compound (1A) is prepared by reacting compound (S3) 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.

Scheme 2: Compound in which Z is —CH═CH—

  Compound (1B) is synthesized by reacting a phosphonium salt (S5) synthesized by a known method with a base such as potassium t-butoxide and a phosphorus ylide generated with aldehyde (S4). Since a cis isomer is generated depending on the reaction conditions and the substrate, the cis isomer is isomerized to a trans isomer by a known method as necessary.

化合物（１Ｂ）をパラジウム炭素のような触媒の存在下で水素化することにより、化合物（１Ｃ）を合成する。 Scheme 3: Compound in which Z is — (CH ₂ ) ₂ —

Compound (1C) is synthesized by hydrogenating compound (1B) in the presence of a catalyst such as palladium on carbon.

J. Am. Chem. Soc., 2001, 123, 5414 に記載された方法に従い、ジケトン（Ｓ６）をフッ化水素触媒の存在下、四フッ化硫黄でフッ素化して−（ＣＦ₂）₂−を有する化合物（１Ｄ）を得る。 Scheme 4: Compound in which Z is — (CF ₂ ) ₂ —

According to the method described in J. Am. Chem. Soc., 2001, 123, 5414, diketone (S6) is fluorinated with sulfur tetrafluoride in the presence of a hydrogen fluoride catalyst to give-(CF ₂ ) _2- . The compound (1D) having is obtained.

ホスホニウム塩（Ｓ５）の代わりにホスホニウム塩（Ｓ７）を用い、スキーム２の方法に従って−（ＣＨ₂）₂−ＣＨ＝ＣＨ−を有する化合物を得る。これを接触水素化して化合物（１Ｅ）を合成する。 Scheme 5: Compound in which Z is — (CH ₂ ) ₄ —

Using phosphonium salt (S7) instead of phosphonium salt (S5), a compound having — (CH ₂ ) ₂ —CH═CH— is obtained according to the method of Scheme 2. This is catalytically hydrogenated to synthesize compound (1E).

Scheme 6: Compound in which Z is —CH ₂ O— or —OCH ₂ —

Compound (S4) is reduced with a reducing agent such as sodium borohydride to obtain compound (S8). This is halogenated with hydrobromic acid or the like to obtain compound (S9). Compound (1F) is synthesized by reacting compound (S9) with compound (S10) in the presence of potassium carbonate or the like. A compound having —CH ₂ O— can also be synthesized by this method.

Scheme 7: Compound in which Z is —COO— and —OCO—

  The compound (S3) is reacted with n-butyllithium and subsequently with carbon dioxide to obtain a carboxylic acid (S11). Compound (S11) and phenol (S10) are dehydrated in the presence of DDC (1,3-dicyclohexylcarbodiimide) and DMAP (4-dimethylaminopyridine) to synthesize compound (1G) having —COO—. A compound having —OCO— can also be synthesized by this method.

化合物（Ｓ３）をｎ−ブチルリチウムで処理したあと、テトラフルオロエチレンを反応させて化合物（Ｓ１２）を得る。化合物（Ｓ２）をｎ−ブチルリチウムで処理したあと化合物（Ｓ１２）と反応させて化合物（１Ｈ）を合成する。合成条件を選択する事で、シス体の化合物（１Ｈ）を製造する事も可能である。 Scheme 8: Compound in which Z is —CF═CF—

The compound (S3) is treated with n-butyllithium and then reacted with tetrafluoroethylene to obtain the compound (S12). Compound (S2) is treated with n-butyllithium and then reacted with compound (S12) to synthesize compound (1H). By selecting the synthesis conditions, it is also possible to produce a cis-form compound (1H).

ジクロロパラジウムとハロゲン化銅との触媒存在下、化合物（Ｓ１３）を化合物（Ｓ２）と反応させて、化合物（１Ｊ）を合成する。 Scheme 9: Compound in which Z is —C≡C—

Compound (1J) is synthesized by reacting compound (S13) with compound (S2) in the presence of a catalyst of dichloropalladium and copper halide.

化合物（Ｓ１３）をｎ−ブチルリチウムでリチオ化した後、二酸化炭素を作用しカルボン酸（Ｓ１４）を得る。カルボン酸（Ｓ１４）とフェノール（Ｓ１０）とをＤＤＣとＤＭＡＰの存在下で脱水させて−Ｃ≡Ｃ−ＣＯＯ−を有する化合物（１Ｋ）を合成する。この方法によって−ＯＣＯ−Ｃ≡Ｃ−を有する化合物も合成できる。 Scheme 10: Compound in which Z is —C≡C—COO—

The compound (S13) is lithiated with n-butyllithium and then reacted with carbon dioxide to obtain a carboxylic acid (S14). Carboxylic acid (S14) and phenol (S10) are dehydrated in the presence of DDC and DMAP to synthesize compound (1K) having -C≡C-COO-. A compound having —OCO—C≡C— can also be synthesized by this method.

化合物（Ｓ１３）とビニルブロミド（Ｓ１５）とのクロスカップリング反応により、−Ｃ≡Ｃ−ＣＨ＝ＣＨ−を有する化合物（１Ｌ）を合成できる。シス体の化合物（Ｓ１５）を使用すれば、シス体の（１Ｌ）を製造できる。 Scheme 11: Compound in which Z is —C≡C—CH═CH— and —CH═CH—C≡C—

A compound (1L) having —C≡C—CH═CH— can be synthesized by a cross-coupling reaction between the compound (S13) and vinyl bromide (S15). When the cis-isomer compound (S15) is used, a cis-isomer (1L) can be produced.

Scheme 12: Compound in which Z is —CF ₂ O— and —OCF ₂ —

Compound (1G) is treated with a sulfurizing agent such as Lawson's reagent to obtain compound (S16). The compound (S16) is fluorinated with a hydrogen fluoride pyridine complex and NBS (N-bromosuccinimide) to synthesize a compound (1M) having —CF ₂ O—. Compound (1M) can also be synthesized by fluorinating compound (S16) with (diethylamino) sulfur trifluoride (DAST). A compound having —OCF ₂ — can also be synthesized by this method. These linking groups can also be generated by the method described in P. Kirsch et al., Angew. Chem. Int. Ed. 2001, 40, 1480.

  The composition of the present invention is expressed as the composition (1) as described above, but has good coating properties and the like. The first of this composition contains one compound (1), (2) or (II +). A homopolymer is obtained by polymerization of this composition. The second of composition (1) contains at least two compounds selected from compounds (1), (2) and (II +). A copolymer is obtained by polymerization of this composition. These compositions may further contain additives. The third of the composition (1) contains at least one compound (1), (2) or (II +) and other polymerizable compounds. Other polymerizable compounds are compounds having a polymerizable group, but are different from the compounds (1), (2) and (II +). A copolymer is also obtained by polymerization of this composition. The composition (1) may further contain additives such as a liquid crystalline compound, an optically active compound, a polymerization initiator, and a solvent. These additives will be described in the following order. 1) Other polymerizable compounds, 2) liquid crystalline compounds, 3) optically active compounds, 4) polymerization initiators, and 5) solvents.

1) Other polymerizable compounds The composition (1) may contain other polymerizable compounds. A compound that does not lower the film-forming property and mechanical strength is preferred. This compound is classified into a compound having no liquid crystallinity and a compound having liquid crystallinity. Polymerizable compounds having no liquid crystallinity include vinyl derivatives, styrene derivatives, (meth) acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, and the like. Preferred derivatives thereof are as follows.

  Preferred vinyl derivatives are 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, vinyl 2-ethyl-2-methylbutanoate, N-vinylacetamide, vinyl tert-butylbenzoate, vinyl N, N-dimethylaminobenzoate, vinyl benzoate, ethyl vinyl ether, hydroxybutyl monovinyl ether T-amyl vinyl ether, cyclohexanedimethanol methyl vinyl ether, α, β-vinyl naphthalene, methyl vinyl ketone, isobutyl vinyl ketone and the like. Preferred styrene derivatives are styrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-chloromethylstyrene, m-chloromethylstyrene, p-chloromethylstyrene, α-methylstyrene and the like.

  Preferred (meth) acrylic acid derivatives are methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, 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, trimethylol Propane triacrylate, trimethylol EO addition triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, bis Phenol A EO addition diacrylate, bisphenol A glycidyl Jijiru diacrylate (trade name: Osaka Organic Chemical Industry Co., Viscoat 700), polyethylene glycol diacrylate dimethyl itaconate.

  Preferred sorbic acid derivatives are sodium sorbate, potassium sorbate, lithium sorbate, 1-naphthylmethylammonium sorbate, benzylammonium sorbate, dodecylammonium sorbate, octadecylammonium sorbate, methyl sorbate, methyl sorbate, sorbine In propyl acid, isopropyl sorbate, butyl sorbate, t-butyl sorbate, hexyl sorbate, octyl sorbate, octadecyl sorbate, cyclopentyl sorbate, cyclohexyl sorbate, vinyl sorbate, allyl sorbate, propargyl sorbate, etc. is there.

  Preferred fumaric acid derivatives are dimethyl fumarate, diethyl fumarate, diisopropyl fumarate, dibutyl fumarate, dicyclopentyl fumarate, dicyclohexyl fumarate and the like. Preferred itaconic acid derivatives are diethyl itaconate, dibutyl itaconate, diisopropyl itaconate and the like. In addition, many polymerizable compounds such as butadiene, isoprene, and maleimide can be used.

  Other polymerizable compounds having liquid crystallinity are unsaturated carboxylic acids having a liquid crystalline group, derivatives thereof, and the like. A liquid crystal group is a monovalent group formed by removing hydrogen from a liquid crystal compound. Specific examples are acrylic acid, fumaric acid, itaconic acid, sorbic acid and their esters. Other examples are maleimide and the like. Among these, acrylic acid esters are preferable because they contribute to the production of a polymer having high transparency and high mechanical strength. This compound is also preferable for adjusting the temperature range of the liquid crystal phase in the composition (1). Acrylic esters have high reactivity. On the other hand, other compounds may have a lower reactivity than acrylic esters. Low reactivity is preferable because it suppresses the formation of by-products and improves the mechanical strength and thermal stability of the polymer.

  The other polymerizable compound having liquid crystallinity is a liquid crystal compound having an acryloyloxy group, a methacryloyloxy group, a fumaroyloxy group, a maleimidyl group, an oxirane ring, an oxetane ring or the like as a functional group, and the compound (1), ( Examples that are not 2) can be mentioned. Of these, liquid crystalline acrylic acid derivatives are preferred because they give a transparent polymer with high mechanical strength. This compound can also be used to adjust the liquid crystal phase temperature range of the polymerizable composition.

Of the other polymerizable compounds having liquid crystal properties described above, the compounds other than the liquid crystalline acrylic acid derivative may require a longer time for polymerization than the acrylic acid derivative. However, these polymerizable compounds are useful because they suppress the formation of by-products and improve the mechanical strength and thermal stability of the polymer. In order to maintain the characteristics of the polymer of the present invention and to remarkably express the characteristics of such a copolymer, the structural unit derived from a compound other than the compound of the present invention is preferably 5-95 mol%, More preferably, it is necessary to contain 60 to 95 mol%. Each of the structural unit having liquid crystallinity and the structural unit having no liquid crystallinity can be freely changed within this range, and the total amount thereof may be within the above-described range. Also, either one may be used.
Examples of polymerizable compounds other than the compounds represented by formulas (1) and (2) having liquid crystallinity include formulas (BRM-1) to (BRM-16).

In the formulas (BRM-1) to (BRM-16), P ⁰ is a polymerizable group containing an acryloyloxy group, a methacryloyloxy group, a fumaroyloxy group, a maleimidyl group, an oxirane ring or an oxetane ring, and γ is a carbon number. 2 to 15 alkylene, δ represents 0 or 1, and X ⁰ represents alkyl or alkoxy having 1 to 15 carbon atoms, halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms, -CN or -O ( CH ₂ ) _γ P ⁰ and L ¹ , L ² , L ³ and L ⁴ independently represent hydrogen, halogen, alkyl or alkoxy having 1 to 15 carbon atoms, or halogenated alkyl or alkoxy having 1 to 3 carbon atoms. Show.

  Among these, polymerizable compounds other than the compounds represented by formulas (1) and (2) having particularly preferred liquid crystallinity are represented by the following formulas (BRM-a-1) to (BRM-a-11) and formulas (BRM-). As exemplified in b-1) to (BRM-b-13), any liquid crystalline compound having the same physical properties can be suitably used, and thus this illustration restricts the composition of the composition of the present invention. It is not a thing.

2) Liquid crystalline compound The composition (1) may contain a liquid crystalline compound having no polymerizable group. Examples of this compound are described in Licris (LiqCryst, LCI Publisher GmbH, Hamburg, Germany) which is a database of liquid crystal compounds. Compounds (1) and (2) have a wide temperature range of the liquid crystal phase and good compatibility with other liquid crystal compounds. Therefore, the composition (1) containing a liquid crystal compound can be used as a liquid crystal composition sealed in a liquid crystal display element. The composition may further contain an additive such as a dichroic dye. Since compounds (1) and (2) which are optically active have a high twist-inducing force, they are useful for adjusting the helical pitch of the liquid crystal composition. By polymerizing the composition (1) containing a liquid crystal compound, a composite material of the polymer of the compound (1) or (2) and the liquid crystal compound can be obtained.

3) an optically active compound,
The composition (1) may contain an optically active compound. A composition containing an appropriate amount of an optically active compound (1) or (2), or a composition obtained by adding an appropriate amount of an optically active compound to a non-optically active compound (1) or (2) A retardation film exhibiting a helical structure (twisted structure) is obtained by coating on a treated substrate and polymerizing. This helical structure is fixed by polymerization of the compound (1) or (2). The properties of the obtained optical anisotropy depend on the helical pitch of the obtained helical structure. The helical pitch length can be adjusted by the type and amount of the optically active compound. One optically active compound may be added, but a plurality of optically active compounds may be used for the purpose of offsetting the temperature dependence of the helical pitch. In addition to the compound (1) or (2) and the optically active compound, polymerizable compounds other than the compounds (1) and (2) may be included.

  In the selective reflection of visible light, which is a characteristic of this optically anisotropic material, the helical structure acts on incident light and reflects circularly polarized light and elliptically polarized light. Since the selective reflection characteristic is expressed by λ = n · Pitch (λ is the selective reflection center wavelength, n is the average refractive index, and Pitch is the helical pitch), λ and its band (Δλ) are appropriately adjusted by n or Pitch. be able to. In order to improve color purity, Δλ should be reduced, and Δλ should be increased when broadband reflection is desired. Further, this selective reflection is greatly affected by the cell thickness. In order to maintain color purity, the cell thickness must be kept from becoming too small. In order to maintain the uniformity of orientation, the cell thickness must not be too large. Accordingly, it is necessary to adjust the cell thickness appropriately, and 0.5 to 25 μm is preferable, and 0.5 to 5 μm is more preferable.

By making the helical pitch shorter than visible light, a negative c-plate described in WH de Jeu, Physical Properties of Liquid Crystalline Materials, Gordon and Breach, New York (1980) can be prepared. In order to shorten the helical pitch, it can be achieved by using an optically active compound having a large twisting force (HTP: helical twisting power) and further increasing the amount of addition.
Specifically, a negative c plate can be prepared by setting λ to 350 nm or less, preferably 200 nm or less. This negative c plate is an optical compensation film suitable for VAN type, VAC type, OCB type and the like among liquid crystal display elements.

As the optically active compound to be added, any optically active compound may be used as long as it induces a helical structure and can be appropriately mixed with the polymerizable liquid crystal composition as a base. For example, the following optically active compounds (Op-1) to (Op-19) are suitable. In the formula, R ^b represents alkyl or alkoxy having 1 to 10 carbon atoms, and the CH ₃ group at the chain end may be substituted with —OCOCH═CH ₂ . R ^b may or may not be the same. Carbon with * is an asymmetric carbon. The optically active compound to be added may be either a polymerizable compound or a non-polymerizable compound. An optimum compound can be added according to the purpose. In view of heat resistance and solvent resistance, a polymerizable compound is more preferable. Further, the optically active compound to be added has a larger twisting force (HTP: helical twisting power), which is preferable for shortening the helical pitch. Representative examples of compounds having a large twisting force are disclosed in GB2298202 specification and DE10221751 specification. Particularly preferred compounds are the following (Op-14) to (Op-19).

式中、Ｒ^bは炭素数１〜１０のアルキルを示し、＊が付与された炭素は不斉炭素である。

In the formula, R ^b represents alkyl having 1 to 10 carbon atoms, and the carbon to which * is attached is an asymmetric carbon.

4) Polymerization initiator The composition (1) may contain a polymerization initiator. Preferred initiators for photo radical polymerization are 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184), 2 , 2-Dimethoxy-1,2-diphenylethane-1-one (product name: Irgacure 651), Irgacure 500 (product name), Irgacure 2959 (product name), Irgacure 907 (product name), Irgacure 369 (product name), Irgacure 1300 (product name), Irgacure 819 (product name), Irgacure 1700 (product name), Irgacure 1800 (product name), Irgacure 1850 (product name), Darocur 4265 (product) Name), Irgacure 784 (trade name), p-methoxy Enyl-2,4-bis (trichloromethyl) triazine, 2- (p-butoxystyryl) -5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, benzyldimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1,2,4-diethylxanthone / p-dimethyl A methyl aminobenzoate mixture and the like.

  Preferred initiators for thermal radical polymerization are benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, di-t-butyl peroxide (DTBPO ), T-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2′-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN) and the like.

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

5) Solvent The composition (1) may contain a solvent. The polymerization may be performed in a solvent or without a solvent. The composition (1) containing a solvent may be applied on a substrate, and then the solvent may be removed, followed by photopolymerization. Preferred solvents are benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethyl sulfoxide, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, PGMEA etc. At least two solvents may be mixed. When manufacturing an alignment film, antireflection film, viewing angle compensation film, etc. by photopolymerization, the solution of the composition is applied onto the substrate by spin coating, and after removing the solvent, it is irradiated with light and polymerized. May be. For coating the composition on the substrate, a known coater (doctor blade, coating apparatus, etc.) may be used. It is not meaningful to limit the ratio of the solvent used during the polymerization. In consideration of polymerization efficiency, solvent cost, energy cost, etc., it may be determined for each case.

  The polymer of the present invention can be obtained by polymerizing the composition (1) containing at least one compound selected from the formulas (1), (2) and (II +). This polymer is denoted as polymer (1). This polymer has properties such as good optical anisotropy, high transparency, good chemical stability, good heat resistance, low water absorption, low gas permeability, good hardness, good mechanical strength, etc. Have. Mechanical strength includes Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength, and the like. This polymer has a structural unit derived from the polymerizable group of the compound (1), (2) or (II +).

  The kind of polymerization is radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization and the like. The preferred reaction temperature is in the range of 0-150 ° C. The preferred reaction time is 1 to 100 hours. The kind of polymer obtained is a homopolymer, a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, or the like. It is preferred to select a polymerization method and polymer suitable for the application. The polymer (1) is a thermoplastic resin or a thermosetting resin. The preferred weight average molecular weight of the thermoplastic resin is in the range of 500 to 1,000,000. A more preferred range of weight average molecular weight is 1,000 to 500,000. A particularly preferred range of weight average molecular weight is 5,000 to 100,000. Since such a polymer (1) is soluble in a solvent, it can be easily formed into a shape suitable for the application. In order to obtain a thermoplastic resin, it is preferable to use the compound (1) having a polymerizable group at one end. On the other hand, when the compound (2) having both polymerizable groups is used, a thermosetting resin is easily obtained. The thermosetting resin has a three-dimensional crosslinked structure. Since such a polymer (1) is insoluble in a solvent, the molecular weight cannot be measured. When the composition of the present invention is applied and polymerized on a substrate to fix the molecular orientation and obtain optical anisotropy, no further processing is performed, so the size of the molecular weight is not a problem. What is necessary is just to satisfy conditions in a use environment. In order to further increase the molecular weight, it is possible to add a crosslinking agent. The molecular weight becomes infinite, and it is possible to obtain a polymer having extremely excellent chemical resistance and heat resistance. Any crosslinking agent known to those skilled in the art can be used, and examples thereof include tris (3-mercaptopropionate).

  The compounds and compositions of the present invention have high polymerizability. Stabilizers can be added to facilitate handling. Any stabilizer can be used as long as it is known to those skilled in the art, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-tert-butyl-4-hydroxytoluene (BHT). .

  The obtained polymer (1) is used in the form of a film, fiber, molded article or the like. A preferred shape is a film. A film is obtained by applying a polymerizable composition to a substrate and polymerizing it. A film can also be obtained by applying a polymer solution to an oriented substrate and removing the solvent. A film can also be obtained by press molding a polymer.

  When the optically anisotropic thin film is formed on the substrate, any substrate can be suitably used as long as it is known to those skilled in the art. For example, glass, polyester such as polyethylene terephthalate (PET), polyvinyl alcohol (PVA), polycarbonate (PC), triacetyl cellulose (TAC), and ZEONOR (registered trademark: manufactured by ZEON) and ZEONEX (registered trademark: ZEON) And norbornene-based polymers such as Arton (registered trademark: manufactured by JSR). The polymer of the present invention is excellent in adhesion to these substrates and is suitable.

  The alignment of the composition of the present invention on the substrate can be obtained by rubbing the alignment film applied on the substrate and coating the composition of the present invention on the alignment film. As long as the orientation can be controlled, the purpose can be achieved by using any of orientation films known to those skilled in the art, but polyimide, polyamide and polyvinyl alcohol-based orientation films are preferred. Alternatively, the orientation can also be obtained by rubbing the substrate itself with a rubbing cloth or the like and directly applying the composition of the present invention. The oriented composition is an industrially advantageous method because it is polymerized by light irradiation or the like to give an optically anisotropic material.

  The polymer (1) has a feature of fixing the molecular arrangement. Due to the immobilized molecular arrangement, this polymer has optical anisotropy. Therefore, this polymer is also called an optical anisotropic body. Another feature is the immobilization of the helical structure. When the compound (1), (2) or (II +) is optically active, the polymer (1) has an immobilized helical structure. When the compound (1), (2) or (II +) is optically inactive, the polymer (1) having an immobilized helical structure is obtained by adding the optically active compound to the composition. Obtainable

  The polymer (1) in which both the molecular arrangement and the helical structure are fixed includes a retardation film, a polarizing element, a circular polarizing element, an elliptical polarizing element, an antireflection film, a selective reflection film, a color compensation film, and a viewing angle compensation film. Suitable for applications such as liquid crystal alignment films. The polymer (1) in which the molecular arrangement is fixed is suitable for uses such as a retardation film, a circularly polarizing element, an elliptically polarizing element, a selective reflection film, a color compensation film, and a viewing angle compensation film. The polymer (1) in which the helical structure is fixed is suitable for an antireflection film, a color compensation film and the like. The polymer (1) in which both the molecular arrangement and the helical structure are not fixed is suitable for an antireflection film, a liquid crystal alignment film and the like. In any case, it can be used as an adhesive, a synthetic polymer having mechanical anisotropy, a cosmetic, a decorative article, a nonlinear optical material, an information storage material, and the like.

  Thermal polymerization or photopolymerization is suitable for fixing the molecular arrangement and fixing the helical structure. The thermal polymerization is preferably performed in the presence of a radical polymerization initiator. Photopolymerization is preferably carried out in the presence of a radical photopolymerization initiator. For example, a polymer in which molecules are arranged in the direction of polarization can be obtained by a polymerization method in which ultraviolet rays or electron beams are irradiated in the presence of a radical photopolymerization initiator. Such a polymer can be used for a liquid crystal alignment film or the like without being rubbed.

  The retardation film is obtained by polymerizing a composition containing the optically active compound (1), (2) or (II +). The retardation film can also be obtained by polymerizing a composition containing optically inactive compounds (1) and (2) and an appropriate amount of an optically active compound. Since these compositions are optically active, they have a helical structure. When these compositions are polymerized on an alignment-treated substrate, a polymer having a fixed helical structure and molecular arrangement is obtained. The characteristics of the retardation film depend on the pitch in the helical structure. This helical pitch can be adjusted by the type and amount of the optically active compound. This addition amount is usually 0.01 to 50% by weight, preferably 1 to 30% by weight. One optically active compound may be used, but a plurality of optically active compounds may be added for the purpose of offsetting the temperature dependence of the helical pitch.

  The isolated polymer can be dissolved in a solvent and processed into a film or the like. Two polymers may be mixed and processed. A polymer may be laminated. 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, hexafluoro-2-propanol, 2-methoxyethyl acetate, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like. These solvents may be mixed with common organic solvents such as acetone, benzene, toluene, heptane, methylene chloride.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these Examples. In Examples 1 and 2 and Examples 4 to 7, compounds (1) and (2) were represented 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, and I represents an isotropic liquid phase. Below, the measuring method of a physical-property value is shown.

1) Helical pitch: A composition in which 1% by weight of a sample compound is dissolved in 99% by weight of the following composition (M-1), and the Cano wedge method (Applied Physics, 1974, 43, 125) and measured at 25 ° C.

2) Weight average molecular weight and number average molecular weight: Shimadzu LC-9A type gel permeation chromatograph manufactured by Shimadzu Corporation and column Shodex GF-7M HQ manufactured by Showa Denko were used. The developing solvent is DMF.

3) Pencil hardness: Measured according to the method of JIS standard “JIS-K-5400 8.4 Pencil Scratch Test”.

4) Properties such as mechanical strength were measured based on methods such as JIS standards.

Synthesis of the following compound (b-2-2)

(First stage)
Under a nitrogen atmosphere, the compound (ex 1-2) (36 mmol) was added to tetrahydrofuran (THF) (150 ml), cooled to −20 ° C., t-BuOK (36 mmol) was added, and the mixture was stirred for 30 minutes. A solution of compound (ex 1-1) (30 mmol) in THF (100 ml) 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) (28 mmol).

(Second stage)
The compound (ex 1-3) (28 mmol) and dilute hydrochloric acid were added to acetone (100 ml), and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere. Water was added and extracted with toluene. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude (ex1-4) (25 mmol).

(Third stage)
Under a nitrogen atmosphere, a solution of the crude compound (ex 1-4) (25 mmol) in THF (100 ml) was added dropwise to a suspension of lithium aluminum hydride (LAH) (19 mmol) in THF (100 ml) 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 purification by recrystallization gave (ex1-5) (10 mmol).

(4th stage)
Under a nitrogen atmosphere, a solution of (ex 1-5) (10 mmol) in N, N-dimethylformamide (30 ml) was cooled to −20 ° C. Thereto was added dropwise a toluene (20 ml) solution of α-fluoroacrylic acid fluoride (30 mmol). The mixture was stirred at room temperature for 3 hours, added with water, 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 and recrystallization to obtain the title compound (5 mmol).
C 63.5 I

Synthesis of the following compound (f-2-2)

(First stage)
(Ex 2-1) (25 mmol), 2-methyl-hydroquinone (10 mmol) and 4-dimethylaminopyridine (DMAP) (6 mmol) were added to dichloromethane (75 ml) and stirred under a nitrogen atmosphere. Thereto was added dropwise a solution of 1,3-dicyclohexylcarbodiimide (DCC) (25 mmol) in dichloromethane (25 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 to obtain crude (ex 2-2) (6 mmol).

(Second stage)
Compound (ex 2-2) (6 mmol) and dilute hydrochloric acid were added to acetone (50 ml), and the mixture was stirred at room temperature for 5 hours in a nitrogen atmosphere. Water was added and extracted with ethyl acetate. After washing with water, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain crude (ex 2-3) (6 mmol).

(Third stage)
Under a nitrogen atmosphere, a solution of (ex 2-3) (6 mmol) in N, N-dimethylformamide (60 ml) was cooled to -20 ° C. Thereto was added dropwise a solution of α-fluoroacrylic acid fluoride (36 mmol) in N, N-dimethylformamide (30 ml). The mixture was stirred at room temperature for 3 hours, water was 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 and recrystallization to obtain the title compound (5 mmol).
C 58.9 N 108.5 I

Synthesis of the following compound (f-2-4)

(First stage)
Under a nitrogen atmosphere, a solution of (ex 3-1) (30 mmol) in N, N-dimethylformamide (100 ml) was cooled to -20 ° C. Thereto was added dropwise a toluene (30 ml) solution of α-fluoroacrylic acid fluoride (36 mmol). The mixture was stirred at room temperature for 3 hours, water was 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 to obtain crude (ex3-2) (18 mmol).

(Second stage)
(Ex3-2) (18 mmol), 2-methyl-hydroquinone (7 mmol) and 4-dimethylaminopyridine (DMAP) (4 mmol) were added to dichloromethane (50 ml) and stirred under a nitrogen atmosphere. Thereto was added dropwise a solution of 1,3-dicyclohexylcarbodiimide (DCC) (18 mmol) in dichloromethane (20 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 (3 mmol).
C 82.0 N 85.6 I

(H-2-5) is synthesized from compound (a-1-1) according to the methods of Examples 1 to 3. These compounds are summarized in the table.
In the table, (a-1-1) to (e-12-1), (g-1-1) to (g-9-1) and (h-1-1) to (h-2-5) Is the structure of the general formula (1). (F-1-1) to (f-14-2) and (g-10-1) to (g-21-1) represent the structure of the general formula (2), and two Y's are the same. Indicates the group.

10 parts by weight of the compound (b-2-2) produced in Example 1, 25 parts by weight of the compound (OP-15), 35 parts by weight of 1,4-bis (4- (6-acryloyloxyhexyloxy) benzoyloxy) benzene 3 parts by weight of a photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) is added to a composition comprising 27 parts by weight of 4- (trans-4-propylcyclohexyl) cyanobenzene. 100 parts by weight of the polymerizable composition containing the photopolymerization initiator was dissolved in 200 parts by weight of cyclopentanone to prepare a solution having a concentration of about 33% by weight. This solution was applied to a glass substrate having a rubbed polyimide alignment film. The thickness of the solution was adjusted to about 12 μm with a bar coater. The glass substrate was placed on a hot plate heated to 70 ° C. for 120 seconds to evaporate the solvent. This operation seems to fix the molecular orientation. Next, while heating at 70 ° C. with a hot plate in a nitrogen atmosphere, polymerization was performed by irradiating light with an intensity of 30 mW / cm ² (center wavelength 365 nm) for 20 seconds using a 250 W ultrahigh pressure mercury lamp. The obtained film exhibited red selective reflection.

The compound (b-2-2) (10 mg) produced in Example 1, the polymerization initiator azobiscyclohexanecarbonitrile (0.1 mg), and benzene (100 μl) were placed in a glass ampule. 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 from methanol (15 ml) three times to obtain a polymer (6.8 mg). The weight average molecular weight (M _w ) measured by GPC was 31,000. The polydispersity (Mw / Mn) was 2.03. The polymer (1.378 mg) was immersed in pure water (1 ml) and allowed to stand at 50 ° C. for 10 days. The polymer was taken out, thoroughly dried and measured for weight, which was 1.381 mg. It was found that the water absorption rate of this polymer was low.

  5 parts by weight of the polymer produced in Example 6 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 the composition that can be prepared using the compounds of the present invention formulas (1) and (2) are shown as Composition Examples 1 to 6. All are polymerized by irradiation with UV light to give a polymer having optical anisotropy. (%) In the following represents% by weight.
Composition example 1

Composition example 2

Composition example 3

Composition Example 4

Composition example 5

Composition Example 6

The use of the composition of the present invention is a liquid crystal composition for a liquid crystal display element. Polymers are used for retardation films, polarizing elements, circularly polarized light elements, elliptically polarized light elements, anti-reflection films A selective reflection film, a color compensator, a viewing angle compensator, a liquid crystal alignment film, and the like.

Claims (35)

A compound represented by the following formula (1) or (2).
PY- (AZ) m-R ^a (1)
PY- (AZ) mYYP (2)
In the formulas (1) and (2), P is CH ₂ ═CFCOO—; ^Ra is hydrogen, halogen, —CN, —CF ₃ , —OCF ₃ , or alkyl having 1 to 10 carbons, and Any —CH ₂ — in the alkyl of may be replaced by —O— , —COO—, —OCO—, —CH═CH— ; A is independently 1,4-cyclohexylene , 1,4 - phenylene or 2,7-diyl, arbitrary hydrogen in these rings are halogen, may be replaced by an alkyl or halogenated alkyl of 1 to 5 carbon atoms of 1 to 5 carbon atoms; Z is Independently, a single bond , — (CH ₂ ) ₂ —, —COO—, —OCO—, —CH ₂ O—, —OCH ₂ —, —CH═CH—, —C≡C—, — (CH _{2) ) 2 COO -, - OCO (} CH 2) 2 -, - C = CHCOO- or -OCOCH = CH- and is; Y is independently a single bond or alkylene having 1 to 20 carbon atoms, any -CH ₂ - in these alkylene - it can be replaced by -O- Well; m is an integer from 2 to 4 , but when m is 2, 2 A is 1,4-phenylene, 2 Z is a single bond and Y is — (CH ₂ ) ₆ O—, R ^a -OCH _3, not one of the _-OC 8 _{H 17} and -CN is. A compound according to claim 1 of the formula (1). The compound according to claim 2 , wherein the compound represented by the formula (1) is any one of the compounds represented by the following formulas (II) to (IV) .
P-Y-A-Z-R ^a (II)
P-Y-A-Z- A-Z-A-R a (III)
P-Y-A-Z- A-Z-A-Z-A-R a (IV)
Here, P, Y, A, Z, and Ra are as described above. In formula (1) or formulas (II) to (IV), R ^a is hydrogen, fluorine, chlorine, —CN, —CF ₃ , —OCF ₃ , alkyl having 1 to 10 carbons, or 1 to 9 carbons. The compound according to claim 2 or 3 , which is alkoxy having 1 to 9 carbon atoms or alkoxyalkyl having 2 to 9 carbon atoms. In the formula (1), m is 2, two Zs are single bonds, and at least one of A is 1,4-cyclohexylene , 1,4-phenylene or fluorene-2,7-diyl. There, any hydrogen in these rings halogen, but it may also be replaced by an alkyl halide of 1 to 5 alkyl carbon atoms or 1 to 5 carbon atoms, a compound according to claim 1. A compound according to claim 1 represented by the formula (2). The compound according to claim 6 , wherein the compound represented by the formula (2) is any one of the compounds represented by the following formulas (VI) to (VIII) .
P-Y-A-Z-A-Y-P (VI)
P-Y-A-Z-A-Z-A-Y-P (VII)
P-Y-A-Z-A-Z-A-Z-A-Y-P (VIII)
In here, P, Y, A and Z are as defined above. Equation (1), (2) or in formula (II) ~ (IV) and (VI) ~ (VIII), A is independently 1,4-cyclohexylene, 1,4-phenylene young properly fluorene -2 a 7-diyl, arbitrary hydrogen in these rings are F, but it may also be replaced by alkyl or C 1 or 2 fluoroalkyl carbon of 1 or 2 carbon atoms, claim 2, 3, 4, 6 Or the compound according to any one of 7 ; In formulas (1), (2) or formulas (II)-(IV) and (VI)-(VIII) , A is independently 1,4-cyclohexylene , 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-trifluoromethyl-1,4- Phenylene, 2-difluoromethyl-1,4-phenylene, 2,3-bistrifluoromethyl-1,4-phenylene , fluorene-2,7-diyl, 9-methylfluorene-2,7-diyl, 9-ethylfluorene 9. The compound according to claim 8 , which is -2,7-diyl, 9-fluorofluorene-2,7-diyl or 9,9-difluorofluorene-2,7-diyl. In the formula (1), ^{R a} is -Cl, -Br, -I, -COOH, compound of Claim 1 which is -CHO or -OH. The compound according to claim 10 , wherein m is 2 in the formula (1). In the formula (1), A is independently 1,4-cyclohexylene, 1,4-phenylene, claim 10 or 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene 11 Compound described in 1. The compound according to any one of claims 10 to 12 , wherein in formula (1), Z is independently a single bond, alkyl having 1 to 4 carbon atoms, -CH = CH- or -C≡C-. In the formulas (1), (2) or formulas (II) to (IV) and (VI) to (VIII) , Y is independently alkylene having 1 to 10 carbons, or alkylene thereof is — (AZ) ) - a compound according to any one of claim 1 to 9, which is a substituted group with methylene adjacent is -O- on. Compounds or compositions containing any one of the compounds of the compounds shown in the formula (II +) according to any one of claims 1-14.
_{CH 2 = CFCOO- (CH 2)} 6 O-A-A-R a + (II +)
In the formula (II +), A is 1,4-phenylene, R ^{a +} is —OCH ₃ , —OC ₈ H ₁₇ or —CN. A composition comprising two compounds selected from the compound according to any one of claims 1 to 14 and the compound represented by formula (II +).
_{CH 2 = CFCOO- (CH 2)} 6 O-A-A-R a + (II +)
In the formula (II +), A is 1,4-phenylene, R ^{a +} is —OCH ₃ , —OC ₈ H ₁₇ or —CN. A composition comprising at least one compound described in any one of claims 1 to 14 and a polymerizable compound different from the compound described in claim 1. The composition according to any one of claims 15 to 17, containing at least one non-polymerizable liquid crystal compound. A composition according to any one of claims 15-17 containing different polymerizable optically active compound from the compound described in at least one of claims 1. At least one composition according to any one of claims 1 to 15-17 which contain different non-polymerizable optically active compound from the compounds described in. A polymer obtained by polymerizing the composition according to claim 15, 16, 17 or 19 . A polymer composition obtained by polymerizing the composition according to claim 18 or 20 . The polymer according to claim 21 , which has a weight average molecular weight of 500 to 1,000,000. The polymer according to claim 21 , which has a weight average molecular weight of 1,000 to 500,000. The polymer according to claim 21, 23 or 24 , wherein the polymer is an optically active compound. The polymer composition according to claim 22 , wherein the polymer is an optically active compound. A film obtained from the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . A molded article having optical anisotropy, comprising the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . A retardation film comprising the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . A liquid crystal alignment film containing the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . An antireflection film containing the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . A viewing angle compensation film comprising the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . A polarizing element containing the polymer according to claim 21, 23, 24 or 25 , or the polymer composition according to claim 22 or 26 . 34. The film according to any one of claims 27 to 33, the molded article having optical anisotropy, a retardation film, a liquid crystal alignment film, an antireflection film, a viewing angle compensation film, and a polarizing element. Liquid crystal display element. A liquid crystal display device containing the composition according to any one of claims 15-20.