POLYMERIZABLE POLAR COMPOUND, LIQUID CRYSTAL COMPOSITION AND LIQUID CRYSTAL DISPLAY DEVICE

Abstract

Provide is a polar compound having high chemical stability, high capability of aligning liquid crystal molecules, high solubility in a liquid crystal composition, and a large voltage holding ratio when the compound is used in a liquid crystal display device. The problem is solved by a compound represented by formula (1).

##STR00001##

For example, R.sup.1 is alkyl having 1 to 15 carbons; rings A.sup.1 to A.sup.5 are cyclohexylene or phenylene; Z.sup.1, Z.sup.4 and Z.sup.5 are a single bond or alkylene having 1 to 10 carbons; a, b and c are 0 to 4; d and e are 1 to 4; P.sup.2 and P.sup.3 are a polymerizable group; and Sp.sup.2 and Sp.sup.3 are a single bond or alkylene having 1 to 10 carbons.

Claims

1. A compound, represented by formula (1): ##STR00127## wherein, in formula (1), R.sup.1 is hydrogen, -Sp.sup.2-P.sup.2, -Sp.sup.3-P.sup.3 or alkyl having 1 to 15 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, S or NH, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; ring A.sup.1, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene, phenylene, naphthylene, decahydronaphthylene, tetrahydronaphthylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl or pyridinediyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; ring A.sup.2 and ring A.sup.3 are independently cyclohexylene or phenylene, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; Z.sup.1, Z.sup.4 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; and P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1); ##STR00128## wherein, in formula (P-1), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; and R.sup.4 is a group selected from groups represented by any one of formulas (1a), (1b) and (1c); ##STR00129## wherein, in formulas (1a), (1b) and (1c), Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; S.sup.1 is >CH or >N; S.sup.2 is >C< or >Si<; X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen; a, b and c are independently 0, 1, 2, 3 or 4; d and e are independently 0, 1, 2, 3 or 4; and a sum of d and e is 2, 3 or 4.

2. The compound according to claim 1, wherein in formula (P-1), R.sup.4 is a group represented by formula (1a) or (1b).

3. The compound according to claim 1, wherein in formula (P-1), R.sup.4 is represented by formula (1a), and in formula (1), b and c are 0, and a sum of d and e is 2, 3 or 4,

4. The compound according to claim 1, represented by formula (1-1): ##STR00130## wherein, in formula (1-1), P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1-1); ##STR00131## wherein, in formula (P-1-1), M.sup.1 and M.sup.2 are independently hydrogen, fluorine or methyl; Sp.sup.5 is independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen; Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O; and R.sup.1, ring A.sup.1, ring A.sup.2, ring A.sup.3, Z.sup.1 and a are defined in a manner identical with the definitions in claim 1.

5. A liquid crystal composition, containing at least one compound according to claim 1.

6. The liquid crystal composition according to claim 5, further containing at least one compound selected from the group of compounds represented by any one of formulas (2) to (4): ##STR00132## wherein, in formulas (2) to (4), R.sup.11 and R.sup.12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; ring B.sup.1, ring B.sup.2, ring B.sup.3 and ring B.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; and Z.sup.11, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC or COO.

7. The liquid crystal composition according to claim 5, further containing at least one compound selected from the group of compounds represented by any one of formulas (5) to (7): ##STR00133## wherein, in formulas (5) to (7), R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3; ring C.sup.1, ring C.sup.2 and ring C.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.14, Z.sup.15 and Z.sup.16 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC, COO, CF.sub.2O, OCF.sub.2, CH.sub.2O or (CH.sub.2).sub.4; and L.sup.11 and L.sup.12 are independently hydrogen or fluorine.

8. The liquid crystal composition according to claim 5, further containing a compound represented by formula (8): ##STR00134## wherein, in formula (8), R.sup.14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; X.sup.12 is CN or CCCN; ring D.sup.1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl; Z.sup.17 is a single bond, CH.sub.2CH.sub.2, CC, COO, CF.sub.2O, OCF.sub.2 or CH.sub.2O; L.sup.13 and L.sup.14 are independently hydrogen or fluorine; and i is 1, 2, 3 or 4.

9. The liquid crystal composition according to claim 5, further containing at least one compound selected from the group of compounds represented by any one of formulas (9) to (15): ##STR00135## wherein, in formulas (9) to (15), R.sup.15 and R.sup.16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; R.sup.17 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; ring E.sup.1, ring E.sup.2, ring E.sup.3 and ring E.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; ring E.sup.5 and ring E.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl; Z.sup.18, Z.sup.19, Z.sup.20 and Z.sup.21 are independently a single bond, CH.sub.2CH.sub.2, COO, CH.sub.2O, OCF.sub.2 or OCF.sub.2CH.sub.2CH.sub.2; L.sup.15 and L.sup.16 are independently fluorine or chlorine; S.sup.11 is hydrogen or methyl; X is CHF or CF.sub.2; and j, k, m, n, p, q, r and s are independently 0 or 1, a sum of k, m, n and p is 1 or 2, a sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

10. The liquid crystal composition according to claim 5, containing a polymerizable compound represented by formula (16): ##STR00136## wherein, in formula (16), ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl 1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen; Z.sup.22 and Z.sup.23 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO or OCO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, C(CH.sub.3)CH, CHC(CH.sub.3) or C(CH.sub.3)C(CH.sub.3), and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group; Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine; d is 0, 1 or 2; and e, f and g are independently 0, 1, 2, 3 or 4, and a sum of e, f and g is 1 or more.

11. The liquid crystal composition according to claim 10, wherein, in formula (16), P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group selected from the group of groups represented by any one of formulas (P-1) to (P-5): ##STR00137## wherein, in formulas (P-1) to (P-5), M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.

12. The liquid crystal composition according to claim 5, containing at least one polymerizable compound selected from the group of polymerizable compounds represented by any one of formulas (16-1) to (16-7): ##STR00138## wherein, in formulas (16-1) to (16-7), P.sup.4, P.sup.5 and P.sup.6 are independently a polymerizable group selected from the group of groups represented by any one of formulas (P-1) to (P-3), in which M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; ##STR00139## wherein, L.sup.21, L.sup.22, L.sup.23, L.sup.24, L.sup.25, L.sup.26, L.sup.27 and L.sup.28 are independently hydrogen, fluorine or methyl; and Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

13. The liquid crystal composition according to claim 5, further containing at least one of any other polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer and an antifoaming agent.

14. A liquid crystal display device, including at least one of the liquid crystal compositions according to claim 5.

Description

DESCRIPTION OF EMBODIMENTS

[0032] Usage of terms herein is as described below. Terms liquid crystal composition and liquid crystal display device may be occasionally abbreviated as composition and device, respectively. Liquid crystal display device is a generic term for a liquid crystal display panel and a liquid crystal display module. Liquid crystal compound is a generic term for a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound having no liquid crystal phase but to be mixed with the composition for the purpose of adjusting characteristics such as a temperature range of a nematic phase, viscosity and dielectric anisotropy. The compound has a six-membered ring such as 1,4-cyclohexylene and 1,4-phenylene, and rod like molecular structure. Polymerizable compound is a compound to be added for the purpose of forming a polymer in the composition. Polar compound assists alignment of liquid crystal molecules by interaction of a polar group with substrate surface.

[0033] The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. A proportion (content) of the liquid crystal compounds is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition. An additive such as an optically active compound, an antioxidant, an ultraviolet light absorber, a dye, an antifoaming agent, the polymerizable compound, a polymerization initiator, a polymerization inhibitor and a polar compound is added to the liquid crystal composition when necessary. A proportion (amount of addition) of the additive is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition in a manner similar to the proportion of the liquid crystal compound. Weight parts per million (ppm) may be occasionally used. A proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

[0034] A compound represented by formula (1) may be occasionally abbreviated as compound (1). Compound (1) means one compound, a mixture of two compounds or a mixture of three or more compounds represented by formula (1). A same rule applies also to at least one compound selected from the group of compounds represented by formula (2), or the like. Symbol B.sup.1, C.sup.1, F or the like surrounded by a hexagonal shape corresponds to ring B.sup.1, ring C.sup.1 and ring F, respectively. The hexagonal shape represents a six-membered ring such as a cyclohexane ring and a benzene ring, or a condensed ring such as a naphthalene ring. An oblique line crossing the hexagonal shape represents that arbitrary hydrogen on the ring may be replaced by a group such as -Sp.sup.1-P.sup.1. A subscript such as e represents the number of groups subjected to replacement. When the subscript is 0, no such replacement exists.

[0035] An expression at least one piece of A means that the number of A is arbitrary. An expression at least one piece of A may be replaced by B means that, when the number of A is 1, a position of A is arbitrary, and also when the number of A is 2 or more, positions thereof can be selected without restriction. A same rule applies also to an expression at least one piece of A is replaced by B. An expression at least one piece of A may be replaced by B, C or D includes a case where at least one piece of A is replaced by B, a case where at least one piece of A is replaced by C, and a case where at least one piece of A is replaced by D, and also a case where a plurality of pieces of A are replaced by at least two pieces of B, C and D. For example, alkyl in which at least one piece of CH.sub.2 (or CH.sub.2CH.sub.2) may be replaced by O (or CHCH) includes alkyl, alkenyl, alkoxy, alkoxyalkyl, alkoxyalkenyl and alkenyloxyalkyl. In addition, a case where two pieces of consecutive CH.sub.2 are replaced by O to form OO is not preferred. In alkyl or the like, a case where CH.sub.2 of a methyl part (CH.sub.2H) is replaced by O to form OH is not preferred, either.

[0036] Halogen means fluorine, chlorine, bromine or iodine. Preferred halogen is fluorine or chlorine. Further preferred halogen is fluorine. Alkyl is straight-chain alkyl or branched-chain alkyl, but includes no cyclic alkyl. In general, straight-chain alkyl is preferred to branched-chain alkyl. A same rule applies also to a terminal group such as alkoxy and alkenyl. With regard to a configuration of 1,4-cyclohexylene, trans is preferred to cis for increasing the maximum temperature of the nematic phase. Then, 2-fluoro-1,4-phenylene means two divalent groups described below. In a chemical formula, fluorine may be leftward (L) or rightward (R). A same rule applies also to an asymmetrical divalent group formed by eliminating two hydrogens from a ring, such as tetrahydropyran-2,5-diyl.

##STR00006##

[0037] The invention includes items described below.

[0038] Item 1. A compound, represented by formula (1):

##STR00007##

wherein, in formula (1),

[0039] R.sup.1 is hydrogen, -Sp.sup.2-P.sup.2, -Sp.sup.3-P.sup.3 or alkyl having 1 to 15 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, S or NH, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0040] ring A.sup.1, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene, phenylene, naphthylene, decahydronaphthylene, tetrahydronaphthylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl or pyridinediyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0041] ring A.sup.2 and ring A.sup.3 are independently cyclohexylene or phenylene, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, or alkenyloxy having 2 to 11 carbons, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0042] Z.sup.1, Z.sup.4 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0043] Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0044] P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1);

##STR00008##

wherein, in formula (P-1),

[0045] M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen; R.sup.4 is a group selected from groups represented by any one of formulas (1a), (1b) and (1c);

##STR00009##

wherein, in formulas (1a), (1b) and (1c),

[0046] Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0047] S.sup.1 is >CH or >N;

[0048] S.sup.2 is >C< or >Si<;

[0049] X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen;

[0050] a, b and c are independently 0, 1, 2, 3 or 4;

[0051] d and e are independently 0, 1, 2, 3 or 4; and

[0052] a sum of d and e is 2, 3 or 4.

[0053] Item 2. The compound according to item 1, wherein in formula (P-1), R.sup.4 is a group represented by formula (1a) or formula (1b).

[0054] Item 3. The compound according to item 1 or 2, wherein in formula (P-1), R.sup.4 is represented by formula (1a), and in formula (1), b and c are 0, and a sum of d and e is 2, 3 or 4.

[0055] Item 4. The compound according to any one of items 1 to 3, represented by formula (1-1):

##STR00010##

wherein, in formula (1-1),

[0056] P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1-1);

##STR00011##

wherein, in formula (P-1-1),

[0057] M.sup.1 and M.sup.2 are independently hydrogen, fluorine or methyl;

[0058] Sp.sup.5 is independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0059] Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O; and

[0060] R.sup.1, ring A.sup.1, ring A.sup.2, ring A.sup.3, Z.sup.1 and a are defined in a manner identical with the definitions in claim 1.

[0061] Item 5. A liquid crystal composition, containing at least one compound according to any one of items 1 to 4.

[0062] Item 6. The liquid crystal composition according to item 5, further containing at least one compound selected from the group of compounds represented by any one of formulas (2) to formula (4):

##STR00012##

wherein, in formulas (2) to (4),

[0063] R.sup.11 and R.sup.12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine;

[0064] ring B.sup.1, ring B.sup.2, ring B.sup.3 and ring B.sup.4 are independently 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene or pyrimidine-2,5-diyl; and

[0065] Z.sup.11, Z.sup.12 and Z.sup.13 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC or COO.

[0066] Item 7. The liquid crystal composition according to item 5 or 6, further containing at least one compound selected from the group of compounds represented by any one of formulas (5) to formula (7):

##STR00013##

wherein, in formulas (5) to (7),

[0067] R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine;

[0068] X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3;

[0069] ring C.sup.1, ring C.sup.2 and ring C.sup.3 are independently 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;

[0070] Z.sup.14, Z.sup.15 and Z.sup.16 are independently a single bond, CH.sub.2CH.sub.2, CHCH, CC, COO, CF.sub.2O, OCF.sub.2, CH.sub.2O or (CH.sub.2).sub.4; and

[0071] L.sup.11 and L.sup.12 are independently hydrogen or fluorine.

[0072] Item 8. The liquid crystal composition according to any one of items 5 to 7, further containing a compound represented by formula (8):

##STR00014##

wherein, in formula (8),

[0073] R.sup.14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; X.sup.12 is CN or CCCN;

[0074] ring D.sup.1 is 1,4-cyclohexylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl or pyrimidine-2,5-diyl;

[0075] Z.sup.17 is a single bond, CH.sub.2CH.sub.2, CC, COO, CF.sub.2O, OCF.sub.2 or CH.sub.2O;

[0076] L.sup.13 and L.sup.14 are independently hydrogen or fluorine; and

[0077] i is 1, 2, 3 or 4.

[0078] Item 9. The liquid crystal composition according to any one of items 5 to 8, further containing at least one compound selected from the group of compounds represented by any one of formulas (9) to formula (15):

##STR00015##

wherein, in formulas (9) to (15),

[0079] R.sup.15 and R.sup.16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine;

[0080] R.sup.17 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine;

[0081] ring E.sup.1, ring E.sup.2, ring E.sup.3 and ring E.sup.4 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene in which at least one hydrogen may be replaced by fluorine, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;

[0082] ring E.sup.5 and ring E.sup.6 are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, tetrahydropyran-2,5-diyl or decahydronaphthalene-2,6-diyl;

[0083] Z.sup.18, Z.sup.19, Z.sup.20 and Z.sup.21 are independently a single bond, CH.sub.2CH.sub.2, COO, CH.sub.2O, OCF.sub.2 or OCF.sub.2CH.sub.2CH.sub.2;

[0084] L.sup.15 and L.sup.16 are independently fluorine or chlorine;

[0085] S.sup.11 is hydrogen or methyl;

[0086] X is CHF or CF.sub.2; and

[0087] j, k, m, n, p, q, r and s are independently 0 or 1, a sum of k, m, n and p is 1 or 2, a sum of q, r and s is 0, 1, 2 or 3, and t is 1, 2 or 3.

[0088] Item 10. The liquid crystal composition according to any one of items 5 to 9, containing a polymerizable compound represented by formula (16):

##STR00016##

wherein, in formula (16),

[0089] ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen;

[0090] ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen;

[0091] Z.sup.22 and Z.sup.23 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO or OCO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, C(CH.sub.3)CH, CHC(CH.sub.3), or C(CH.sub.3)C(CH.sub.3), and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0092] P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group;

[0093] Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine;

[0094] d is 0, 1 or 2; and

[0095] e, f and g are independently 0, 1, 2, 3 or 4, and a sum of e, f and g is 2 or more.

[0096] Item 11. The liquid crystal composition according to item 10, wherein in formula (16), P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group selected from the group of groups represented by any one of formulas (P-1) to (P-5):

##STR00017##

wherein in formulas (P-1) to (P-5), M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen.

[0097] Item 12. The liquid crystal composition according to any one of items 5 to 11, containing at least one polymerizable compound selected from the group of polymerizable compounds represented by any one of formulas (16-1) to (16-7):

##STR00018##

wherein, in formulas (16-1) to (16-7), P.sup.4, P.sup.5 and P.sup.6 are independently a polymerizable group selected from the group of groups represented by any one of formulas (P-1) to (P-3), in which M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen:

##STR00019##

wherein, L.sup.21, L.sup.22, L.sup.23, L.sup.24, L.sup.25, L.sup.26, L.sup.27 and L.sup.28 are independently hydrogen, fluorine or methyl; and

[0098] Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0099] Item 13. The liquid crystal composition according to any one of items 5 to 12, further containing at least one of any other polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer and an antifoaming agent.

[0100] Item 14. A liquid crystal display device, including at least one liquid crystal composition according to any one of items 5 to 13.

[0101] The invention further includes the following items:

(a) the liquid crystal composition, further containing at least two of additives such as a polymerizable compound, a polymerization initiator, a polymerization inhibitor, an optically active compound, an antioxidant, an ultraviolet light absorber, a light stabilizer, a heat stabilizer and an antifoaming agent;
(b) a polymerizable composition prepared by adding any other polymerizable compound different from compound (1) or compound (16) to the liquid crystal composition;
(c) the polymerizable composition prepared by adding compound (1) and compound (16) to the liquid crystal composition;
(d) a liquid crystal composite prepared by polymerizing the polymerizable composition;
(e) a device that has a polymer sustained alignment mode, and contains the liquid crystal composite; and
(f) a device having a polymer sustained alignment mode, wherein a polymerizable composition is prepared by adding compound (1), compound (16) and any other polymerizable compound different from compound (1) or compound (16) to the liquid crystal composition, and the device is prepared by using the polymerizable composition.

[0102] Next, an aspect of compound (1), synthesis of compound (1), the liquid crystal composition and the liquid crystal display device will be described in the order.

1. Aspect of Compound (1)

[0103] Compound (1) of the invention has features of having a mesogen moiety formed of at least one ring and a plurality of polar groups. The polar group noncovalently interacts with a substrate surface of glass (or metal oxide), and therefore compound (1) is useful. One of applications is as an additive for the liquid crystal composition used in the liquid crystal display device. Compound (1) is added for the purpose of controlling alignment of liquid crystal molecules. Such an additive preferably has chemical stability under conditions in which the additive is sealed in the device, high solubility in the liquid crystal composition, and a large voltage holding ratio when the compound is used in the liquid crystal display device. Compound (1) satisfies such characteristics to a significant extent.

[0104] Preferred examples of compound (1) will be described. Preferred examples of R.sup.1, Z.sup.1, Z.sup.4, Z.sup.5, A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.5, Sp.sup.2, Sp.sup.3, P.sup.2 and P.sup.3 in compound (1) apply also to a subordinate formula of formula (1) for compound (1). In compound (1), characteristics can be arbitrarily adjusted by suitably combining kinds of the groups. Compound (1) may contain a larger amount of isotope such as .sup.2H (deuterium) and .sup.13C than an amount of natural abundance because no significant difference exists in the characteristics of the compound.

##STR00020##

[0105] In formula (1), R.sup.1 is hydrogen, -Sp.sup.2-P.sup.2, -Sp.sup.3-P.sup.3 or alkyl having 1 to 15 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, S or NH, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen. In addition, Sp.sup.2, P.sup.2, Sp.sup.3 and P.sup.3 will be describe later.

[0106] Preferred R.sup.1 is alkyl having 1 to 15 carbons, alkenyl having 2 to 15 carbons, alkoxy having 1 to 14 carbons or alkenyloxy having 2 to 14 carbons. Further preferred R.sup.1 is alkyl having 1 to 10 carbons, alkenyl having 2 to 10 carbons or alkoxy having 1 to 9 carbons. Particularly preferred R.sup.1 is alkyl having 1 to 10 carbons.

[0107] In formula (1), ring A.sup.1, ring A.sup.4 and ring A.sup.5 are independently cyclohexylene, cyclohexenylene, phenylene, naphthylene, decahydronaphthylene, tetrahydronaphthylene, tetrahydropyrandiyl, 1,3-dioxanediyl, pyrimidinediyl or pyridinediyl, and in the rings, at least one hydrogen may be replace by halogen (particularly by fluorine or chlorine), alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyloxy having 2 to 11 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen. In addition, in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0108] Preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, cyclohexenylene, phenylene, naphthylene, tetrahydropyrandiyl or 1,3-dioxanediyl, and in the rings, at least one hydrogen may be replaced by fluorine, chlorine, alkyl having 1 to 5 carbons or alkoxy having 1 to 4 carbons. Further preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, phenylene, phenylene in which at least one hydrogen is replaced by fluorine, or phenylene in which at least one hydrogen is replaced by alkyl having 1 to 3 carbons. Particularly preferred ring A.sup.1, ring A.sup.4 or ring A.sup.5 is cyclohexylene, phenylene, phenylene in which at least one hydrogen is replaced by a methyl group, or phenylene in which at least one hydrogen is replaced by an ethyl group.

[0109] In formula (1), ring A.sup.2 and ring A.sup.3 are independently cyclohexylene or phenylene, and in the rings, at least one hydrogen may be replaced by halogen (particularly by fluorine or chlorine), alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyloxy having 2 to 11 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen. In addition, in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0110] In formula (1), Z.sup.1, Z.sup.4 and Z.sup.5 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0111] Preferred Z.sup.1, Z.sup.4 and Z.sup.5 are a single bond, CH.sub.2CH.sub.2, CHCH, CC, CO, COO, OCO, CF.sub.2O, OCF.sub.2, CH.sub.2O, OCH.sub.2 or CFCF. Further preferred Z.sup.1, Z.sup.4 and Z.sup.5 are a single bond.

[0112] In formula (1), Sp.sup.2 or Sp.sup.3 is independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine.

[0113] Preferred Sp.sup.2 or Sp.sup.3 is a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one piece of CH.sub.2 is replaced by O. Further preferred Sp.sup.2 or Sp.sup.3 is a single bond, alkylene having 1 to 3 carbons, or alkylene having 1 to 3 carbons in which one piece of CH.sub.2 is replaced by O. Particularly preferred Sp.sup.2 or Sp.sup.3 is CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or O(CH.sub.2).sub.2.

[0114] In formula (1), P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1).

##STR00021##

[0115] In formula (P-1), M.sup.1 and M.sup.2 are independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1 or M.sup.2 is hydrogen or methyl for increasing reactivity. Further preferred M.sup.1 and M.sup.2 are hydrogen.

[0116] R.sup.4 is a group represented by groups represented by any one of formulas (1a), (1b) and (1c). Preferred R.sup.4 is a group represented by formula (1a) or formula (1b). Further preferred R.sup.4 is a group represented by formula (1a).

##STR00022##

[0117] In formulas (1a), (1b) and (1c), Sp.sup.5 and Sp.sup.6 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen, particularly by fluorine or chlorine.

[0118] Preferred Sp.sup.5 and Sp.sup.6 are a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one piece of CH.sub.2 is replaced by O. Further preferred Sp.sup.5 and Sp.sup.6 are a single bond, alkylene having 1 to 5 carbons, or alkylene having 1 to 5 carbons in which one piece of CH.sub.2 is replaced by O. Particularly preferred Sp.sup.5 and Sp.sup.6 are a single bond, CH.sub.2, (CH.sub.2).sub.2, (CH.sub.2).sub.3 or O(CH.sub.2).sub.2.

[0119] In formulas (1a) to (1c), S.sup.1 is >CH or >N; and S.sup.2 is >C< or >Si<. Preferred S.sup.1 is >CH or >N, and preferred S.sup.2 is >C<.

[0120] In formulas (1a) to (1c), X.sup.1 is a group represented by OH, NH.sub.2, OR.sup.5, N(R.sup.5).sub.2, COOH, SH, B(OH).sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is hydrogen or alkyl having 1 to 10 carbons, and in the alkyl, at least one piece of CH.sub.2 may be replaced by O, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, and in the groups, at least one hydrogen may be replaced by halogen, particularly by fluorine or chlorine.

[0121] Preferred X.sup.1 is a group represented by OH, NH.sub.2 or Si(R.sup.5).sub.3, in which R.sup.5 is alkyl having 1 to 5 carbons or alkoxy having 1 to 4 carbons. Further preferred X.sup.1 is OH, NH.sub.2, Si(OCH.sub.3).sub.3 or Si(OC.sub.2H.sub.5).sub.3. Particularly preferred X.sup.1 is OH.

[0122] In formula (1), a, b and c are independently 0, 1, 2, 3 or 4. Preferred a, b and C are 0 to 3.

[0123] In formula (1), d and e are independently 0, 1, 2, 3 or 4. Preferred d and e are 1.

[0124] Particularly preferred examples of compound (1) are a compound represented by formula (1-1):

##STR00023##

[0125] In formula (1-1), P.sup.2 and P.sup.3 are independently a polymerizable group represented by formula (P-1-1);

##STR00024##

[0126] In formula (P-1-1),

[0127] M.sup.1 and M.sup.2 are independently hydrogen, fluorine or methyl;

[0128] Sp.sup.5 is independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, NH, CO, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by halogen;

[0129] Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 3 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O; and

[0130] R.sup.1, ring A.sup.1, ring A.sup.2, ring A.sup.3, Z.sup.1 and a are defined as described above.

2. Synthesis of Compound (1)

[0131] A synthesis method of compound (1) will be described. Compound (1) can be prepared by suitably combining methods in synthetic organic chemistry. Any compounds whose synthetic methods are not described above are prepared according to methods described in books such as Organic Syntheses (John Wiley & Sons, Inc.), Organic Reactions (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Shin Jikken Kagaku Koza in Japanese) (Maruzen Co., Ltd.).

2-1. Formation of a Bonding Group

[0132] An example of a method for forming a bonding group in compound (1) is as described in a scheme below. In the scheme, MSG.sup.1 (or MSG.sup.2) is a monovalent organic group having at least one ring. Monovalent organic groups represented by a plurality of MSG.sup.1 (or MSG.sup.2) may be identical or different. Compounds (1A) to (1G) correspond to compound (1) or an intermediate of compound (1).

##STR00025##

(I) Formation of a Single Bond

[0133] Compound (1A) is prepared by allowing aryl boronic acid (21) to react with compound (22) in the presence of carbonate and a tetrakis(triphenylphosphine)palladium catalyst. Compound (1A) is also prepared by allowing compound (23) to react with n-butyllithium and subsequently with zinc chloride, and further with compound (22) in the presence of a dichlorobis(triphenylphosphine)palladium catalyst.

(II) Formation of COO and OCO

[0134] Carboxylic acid (24) is obtained by allowing compound (23) to react with n-butyllithium and subsequently with carbon dioxide. Compound (1B) having COO is prepared by dehydration of carboxylic acid (24) and phenol (25) derived from compound (21) in the presence of 1,3-dicyclohexylcarbodiimide (DCC) and 4-dimethylaminopyridine (DMAP). A compound having OCO is also prepared according to the method.

(III) Formation of CF.sub.2O and OCF.sub.2

[0135] Compound (26) is obtained by sulfurizing compound (1B) with Lawesson's reagent. Compound (1C) having CF.sub.2O is prepared by fluorinating compound (26) with a hydrogen fluoride-pyridine complex and N-bromosuccinimide (NBS). Refer to M. Kuroboshi et al., Chem. Lett., 1992, 827. Compound (1C) is also prepared by fluorinating compound (26) with (diethylamino) sulfur trifluoride (DAST). Refer to W. H. Bunnelle et al., J. Org. Chem. 1990, 55, 768. A compound having OCF.sub.2 is also prepared according to the method.

(IV) Formation of CHCH

[0136] Aldehyde (27) is obtained by allowing compound (22) to react with n-butyllithium and subsequently with N,N-dimethylformamide (DMF). Compound (1D) is prepared by allowing phosphorus ylide generated by allowing phosphonium salt (28) to react with potassium t-butoxide to react with aldehyde (27). A cis isomer may be formed depending on reaction conditions, and therefore the cis isomer is isomerized into a trans isomer according to a publicly known method when necessary.

(V) Formation of CH.sub.2CH.sub.2

[0137] Compound (1E) is prepared by hydrogenating compound (1D) in the presence of a palladium on carbon catalyst.

(VI) Formation of CC

[0138] Compound (29) is obtained by allowing compound (23) to react with 2-methyl-3-butyn-2-ol in the presence of a catalyst of dichloropalladium and copper iodide, and then performing deprotection under basic conditions. Compound (1F) is prepared by allowing compound (29) to react with compound (22) in the presence of a catalyst of dichlorobis(triphenylphosphine)palladium and copper halide.

(VII) Formation of CH.sub.2O and OCH.sub.2

[0139] Compound (30) is obtained by reducing compound (27) with sodium borohydride. Compound (31) is obtained by brominating the obtained compound with hydrobromic acid. Compound (1G) is prepared by allowing compound (25) to react with compound (31) in the presence of potassium carbonate. A compound having OCH.sub.2 is also prepared according to the method.

(VIII) Formation of CFCF

[0140] Compound (32) is obtained by treating compound (23) with n-butyllithium, and then allowing the treated material to react with tetrafluoroethylene. Compound (1H) is prepared by treating compound (22) with n-butyllithium, and then allowing the treated material to react with compound (32).

2-2. Formation of Ring A.SUP.1 .and Ring A.SUP.2

[0141] A starting material is commercially available or a synthetic method is well known with regard to a ring such as 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2-methyl-1,4-phenylene, 2-ethyl-1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl and 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl.

2-3. Synthesis Example

[0142] An example of a method for preparing compound (1) is as described below.

[0143] For example, compound (1-71) described below can be synthesized as described below. Compound (52) is obtained by allowing compound (51) to react with formaldehyde in the presence of 1,4-diazabicyclo[2.2.2]octane (DABCO). Next, compound (53) is obtained by allowing t-butyldimethylsilyl chloride to react with imidazole, and then compound (54) is obtained by hydrolyzing compound (53) with a base such as lithium hydroxide. Compound (57) is obtained by allowing compound (56) to react with phenol in the presence of hydrochloric acid. Compound (58) is obtained by allowing compound (57) to react with compound (54) in the presence of DCC and DMAP, and then compound (1-71) can be introduced by performing deprotection of compound (58) using tetrabutylammonium fluoride (TBAF).

##STR00026##

3. Liquid Crystal Composition

[0144] A liquid crystal composition of the invention contains compound (1) as component A. Compound (1) can control alignment of liquid crystal molecules by non-covalent interaction with a substrate of the device. The composition contains compound (1) as component A, and preferably further contains a liquid crystal compound selected from components B, C, D and E described below.

[0145] Component B includes compounds (2) to (4). Compounds (2) to (4) have small dielectric anisotropy.

[0146] Component C includes compounds (5) to (7). Compounds (5) to (7) have large positive dielectric anisotropy.

[0147] Component D includes compound (8). Compound (8) has a cyano group, and therefore has large positive dielectric anisotropy.

[0148] Component E includes compounds (9) to (15). Compounds (9) to (15) have large negative dielectric anisotropy.

[0149] The composition may contain any other liquid crystal compound different from compounds (2) to (15). When the composition is prepared, components B, C, D and E are preferably selected by taking into account magnitude of positive or negative dielectric anisotropy or the like. A composition in which the components are suitably selected has high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy (more specifically, large optical anisotropy or small optical anisotropy), large positive or negative dielectric anisotropy, large specific resistance, stability to heat or ultraviolet light and a suitable elastic constant (more specifically, a large elastic constant or a small elastic constant), and the characteristics can be adjusted by suitable combination of components B, C, D and E and other liquid crystal compounds.

[0150] A preferred proportion of compound (1) that is component A is about 0.01% by weight or more for maintaining high stability to ultraviolet light, and about 5% by weight or less for dissolution in the liquid crystal composition. A further preferred proportion is in the range of about 0.05% by weight to about 2% by weight. A most preferred proportion is in the range of about 0.05% by weight to about 1% by weight.

Compound of Component B

[0151] Component B includes a compound in which two terminal groups are alkyl or the like.

##STR00027##

[0152] Component B has a small absolute value of dielectric anisotropy, and therefore is a compound close to neutrality. Compound (2) is mainly effective in decreasing the viscosity or adjusting the optical anisotropy. Compounds (3) and (4) are effective in extending a temperature range of a nematic phase by increasing the maximum temperature, or in adjusting the optical anisotropy.

[0153] As a content of component B is increased, the dielectric anisotropy of the composition is decreased, but the viscosity is decreased. Thus, as long as a desired value of threshold voltage of a device is met, the content is preferably as large as possible. When a composition for the IPS mode, the VA mode or the like is prepared, the content of component B is preferably 30% by weight or more, and further preferably 40% by weight or more, based on the weight of the liquid crystal composition.

[0154] Preferred examples of component B include compounds (2-1) to (2-11), compounds (3-1) to (3-19) and compounds (4-1) to (4-7). In the preferred compounds, R.sup.11 and R.sup.12 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl or the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine.

##STR00028## ##STR00029##

Compound of Component C

[0155] Component C is a compound having a halogen-containing group or a fluorine-containing group at a right terminal.

##STR00030##

[0156] Component C has positive dielectric anisotropy, and superb stability to heat, light and so forth, and therefore is used when a composition for the IPS mode, the FFS mode, the OCB mode or the like is prepared. A content of component C is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component C is added to a composition having negative dielectric anisotropy, the content of component C is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component C allows adjustment of the elastic constant of the composition and adjustment of a voltage-transmittance curve of the device.

[0157] Preferred examples of component C include compounds (5-1) to (5-16), compounds (6-1) to (6-113) and compounds (7-1) to (7-57). In the preferred compounds, R.sup.13 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and X.sup.11 is fluorine, chlorine, OCF.sub.3, OCHF.sub.2, CF.sub.3, CHF.sub.2, CH.sub.2F, OCF.sub.2CHF.sub.2 or OCF.sub.2CHFCF.sub.3.

##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050##

Compound of Component D

[0158] Component D is compound (8) in which a right-terminal group is CN or CCCN.

##STR00051##

[0159] Component D has positive dielectric anisotropy and a value thereof is large, and therefore is mainly used when a composition for the TN mode or the like is prepared. Addition of component D can increase the dielectric anisotropy of the composition. Component D is effective in extending a temperature range of a liquid crystal phase, adjusting the viscosity or adjusting the optical anisotropy. Component D is also useful for adjustment of the voltage-transmittance curve of the device.

[0160] When the composition for the TN mode or the like is prepared, a content of component D is suitably in the range of 1% by weight to 99% by weight, preferably in the range of 10% by weight to 97% by weight, and further preferably in the range of 40% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component D is added to a composition having negative dielectric anisotropy, the content of component D is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component D allows adjustment of the elastic constant of the composition and adjustment of the voltage-transmittance curve of the device.

[0161] Preferred examples of component D include compounds (8-1) to (8-64) In the preferred compounds, R.sup.14 is alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and X.sup.12 is CN or CCCN.

##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058##

Compound of Component E

[0162] Component E includes compounds (9) to (15). The compounds have phenylene in which hydrogen in lateral positions are replaced by two halogens, such as 2,3-difluoro-1,4-phenylene.

##STR00059##

[0163] Component E has large negative dielectric anisotropy. Component E is used when a composition for the IPS mode, the VA mode, the PSA mode or the like is prepared. As a content of component E is increased, the dielectric anisotropy of the composition is negatively increased, but the viscosity is increased. Thus, as long as a desired value of threshold voltage of the device is met, the content is preferably as small as possible. When the dielectric anisotropy at a degree of 5 is taken into account, the content is preferably 40% by weight or more in order to allow a sufficient voltage driving.

[0164] Among types of component E, compound (9) is a bicyclic compound, and therefore is mainly effective in decreasing the viscosity, adjusting the optical anisotropy or increasing the dielectric anisotropy. Compounds (10) and (11) are a tricyclic compound, and therefore are effective in increasing the maximum temperature, the optical anisotropy or the dielectric anisotropy. Compounds (12) to (15) are effective in increasing the dielectric anisotropy.

[0165] When a composition for the IPS mode, the VA mode, the PSA mode or the like is prepared, the content of component E is preferably 40% by weight or more, and further preferably in the range of 50% by weight to 95% by weight, based on the weight of the liquid crystal composition. When component E is added to a composition having positive dielectric anisotropy, the content of component E is preferably 30% by weight or less based on the weight of the liquid crystal composition. Addition of component E allows adjustment of the elastic constant of the composition and adjustment of the voltage-transmittance curve of the device.

[0166] Preferred examples of component E include compounds (9-1) to (9-8), compounds (10-1) to (10-17), compound (11-1), compounds (12-1) to (12-3), compounds (13-1) to (13-11), compounds (14-1) to (14-3) and compounds (15-1) to (15-3). In the preferred compounds, R.sup.15 and R.sup.16 are independently alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine; and R.sup.17 is hydrogen, fluorine, alkyl having 1 to 10 carbons or alkenyl having 2 to 10 carbons, and in the alkyl and the alkenyl, at least one piece of CH.sub.2 may be replaced by O, and at least one hydrogen may be replaced by fluorine.

##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065##

Polymerizable Compound of Formula (16)

[0167] The liquid crystal composition may contain a liquid crystal compound represented by formula (16). The compound has a polymerizable group.

##STR00066##

[0168] In compound (16), P.sup.1, P.sup.2 and P.sup.3 are independently a polymerizable group. Preferred P.sup.1, P.sup.2 or P.sup.3 is a polymerizable group selected from the group of groups represented by any one of formulas (P-1) to (P-5). Further preferred P.sup.1, P.sup.2 or P.sup.3 is group (P-1) or group (P-2). Particularly preferred group (P-1) is OCOCHCH.sub.2 or OCOC(CH.sub.3)CH.sub.2. A wavy line in group (P-1) to group (P-5) represents a site to form a bonding.

##STR00067##

[0169] In group (P-1) to group (P-5), M.sup.1, M.sup.2 and M.sup.3 are independently hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced by halogen. Preferred M.sup.1, M.sup.2 or M.sup.3 is hydrogen or methyl for increasing reactivity. Further preferred M.sup.1 is methyl, and further preferred M.sup.2 or M.sup.3 is hydrogen.

[0170] Sp.sup.1, Sp.sup.2 and Sp.sup.3 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, COO, OCO or OCOO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH or CC, and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Sp.sup.1, Sp.sup.2 or Sp.sup.3 is a single bond.

[0171] Ring F and ring I are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2-yl, pyrimidine-2-yl or pyridine-2-yl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen. Preferred ring F or ring I is phenyl.

[0172] Ring G is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, and in the rings, at least one hydrogen may be replaced by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or alkyl having 1 to 12 carbons in which at least one hydrogen is replaced by halogen. Particularly preferred ring G is 1,4-phenylene or 2-fluoro-1,4-phenylene.

[0173] Z.sup.22 and Z.sup.23 are independently a single bond or alkylene having 1 to 10 carbons, and in the alkylene, at least one piece of CH.sub.2 may be replaced by O, CO, COO or OCO, and at least one piece of CH.sub.2CH.sub.2 may be replaced by CHCH, C(CH.sub.3)CH, CHC(CH.sub.3) or C(CH.sub.3)C(CH.sub.3), and in the groups, at least one hydrogen may be replaced by fluorine or chlorine. Preferred Z.sup.22 and Z.sup.23 are a single bond, CH.sub.2CH.sub.2, CH.sub.2O, OCH.sub.2, COO or OCO. Further preferred Z.sup.22 or Z.sup.23 is a single bond.

[0174] Then, d is 0, 1 or 2. Preferred d is 0 or 1. Then, e, f and g are independently 0, 1, 2, 3 or 4, and a sum of e, f and g is 1 or more. Preferred e, f or g is 1 or 2.

Other Additives

[0175] A liquid crystal composition is prepared according to a publicly known method. For example, the component compounds are mixed and dissolved in each other by heating. According to an application, an additive may be added to the composition. Specific examples of the additives include any other polymerizable compound other than formula (1) and formula (16), the polymerization initiator, the polymerization inhibitor, the optically active compound, the antioxidant, the ultraviolet light absorber, the light stabilizer, the heat stabilizer and the antifoaming agent. Such additives are well known to those skilled in the art, and described in literature.

[0176] The polymerizable compound is added for the purpose of forming a polymer in the liquid crystal composition. The polymerizable compound and compound (1) are copolymerized by irradiation with ultraviolet light while voltage is applied between electrodes, and thus the polymer is formed in the liquid crystal composition. On the occasion, compound (1) is immobilized in a state in which the polar group noncovalently interacts with the substrate surface of glass (or metal oxide). Thus, capability of controlling alignment of liquid crystal molecules is further improved, and simultaneously the polar compound no longer leaks into the liquid crystal composition. Moreover, suitable pretilt can be obtained even in the substrate surface of glass (or metal oxide), and therefore a liquid crystal display device in which a response time is shortened and the voltage holding ratio is large can be obtained. Preferred examples of the polymerizable compound include acrylate, methacrylate, a vinyl compound, a vinyloxy compound, propenyl ether, an epoxy compound (oxirane, oxetane) and vinyl ketone. Further preferred examples include a compound having at least one acryloyloxy, and a compound having at least one methacryloyloxy. Still further preferred examples also include a compound having both acryloyloxy and methacryloyloxy.

[0177] Further preferred examples thereof include compounds (16-1-1) to (16-16). In compounds (16-1-1) to (16-16), R.sup.25 to R.sup.31 are independently hydrogen or methyl; v and x are independently 0 or 1; t and u are independently an integer from 1 to 10; and L.sup.31 to L.sup.36 are independently hydrogen or fluorine, and L.sup.37 and L.sup.38 are independently hydrogen, fluorine or methyl.

##STR00068## ##STR00069## ##STR00070##

[0178] The polymerizable compound can be rapidly polymerized by adding the polymerization initiator. An amount of a remaining polymerizable compound can be decreased by optimizing a reaction temperature. Examples of a photoradical polymerization initiator include TPO, 1173 and 4265 from Darocur series of BASF SE, and 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800, 1850 and 2959 from Irgacure series thereof.

[0179] Additional examples of the photoradical polymerization initiator include 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10-benzphenazine, a benzophenone-Michler's ketone mixture, a hexaarylbiimidazole-mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, a mixture of 2,4-diethylxanthone and methyl p-dimethylaminobenzoate, and a mixture of benzophenone and methyltriethanolamine.

[0180] After the photoradical polymerization initiator is added to the liquid crystal composition, polymerization can be performed by irradiation with ultraviolet light while an electric field is applied. However, an unreacted polymerization initiator or a decomposition product of the polymerization initiator may cause poor display such as image persistence in the device. In order to prevent such an event, photopolymerization may be performed with no addition of the polymerization initiator. A preferred wavelength of irradiation light is in the range of 150 nanometers to 500 nanometers. A further preferred wavelength is in the range of 250 nanometers to 450 nanometers, and a most preferred wavelength is in the range of 300 nanometers to 400 nanometers.

[0181] Upon storing the polymerizable compound, the polymerization inhibitor may be added thereto for preventing polymerization. The polymerizable compound is ordinarily added to the composition without removing the polymerization inhibitor. Specific examples of the polymerization inhibitor include hydroquinone, a hydroquinone derivative such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol and phenothiazine.

[0182] The optically active compound is effective in inducing helical structure in liquid crystal molecules to give a required twist angle, thereby preventing a reverse twist. A helical pitch can be adjusted by adding the optically active compound thereto. Two or more optically active compounds may be added for the purpose of adjusting temperature dependence of the helical pitch. Specific examples of a preferred optically active compound include compounds (Op-1) to (Op-18) described below. In compound (Op-18), ring J is 1,4-cyclohexylene or 1,4-phenylene, and R.sup.28 is alkyl having 1 to 10 carbons.

##STR00071## ##STR00072##

[0183] The antioxidant is effective for maintaining the large voltage holding ratio. Preferred examples of an antioxidant include compounds (AO-1) and (AO-2) described below; and Irganox 415, Irganox 565, Irganox 1010, Irganox 1035, Irganox 3114 and Irganox 1098 (trade names; BASF SE). The ultraviolet light absorber is effective for preventing a decrease of the maximum temperature. Preferred examples of an ultraviolet light absorber are a benzophenone derivative, a benzoate derivative, a triazole derivative or the like. Specific examples thereof include compounds (AO-3) and (AO-4) described below; Tinuvin 329, Tinuvin P, Tinuvin 326, Tinuvin 234, Tinuvin 213, Tinuvin 400, Tinuvin 328 and Tinuvin 99-2 (trade names; BASF SE); and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0184] The light stabilizer such as an amine having steric hindrance is preferred for maintaining the large voltage holding ratio. Specific examples of a preferred light stabilizer include compounds (AO-5) and (AO-6) described below; and Tinuvin 144, Tinuvin 765 and Tinuvin 770DF (trade names: BASF SE). The heat stabilizer is also effective for maintaining the large voltage holding ratio, and specific preferred examples include Irgafos 168 (trade name; BASF SE). The antifoaming agent is effective for preventing foam formation. Preferred examples of the antifoaming agent include dimethyl silicone oil and methylphenyl silicone oil.

##STR00073##

[0185] In compound (AO-1), R.sup.40 is alkyl having 1 to 20 carbons, alkoxy having 1 to 20 carbons, COOR.sup.41 or CH.sub.2CH.sub.2COOR.sup.41, in which R.sup.41 is alkyl having 1 to 20 carbons. In compounds (AO-2) and (AO-5), R.sup.42 is alkyl having 1 to 20 carbons. In compound (AO-5), R.sup.43 is hydrogen, methyl or O. (oxygen radical), ring G is 1,4-cyclohexylene or 1,4-phenylene, and z is 1, 2 or 3.

4. Liquid Crystal Display Device

[0186] The liquid crystal composition can be used in a liquid crystal display device having an operating mode such as the PC mode, the TN mode, the STN mode, the OCB mode and the PSA mode, and driven by an active matrix mode. The composition can also be used in a liquid crystal display device having the operating mode such as the PC mode, the TN mode, the STN mode, the OCB mode, the VA mode and the IPS mode, and driven by a passive matrix mode. The devices can be applied to any of a reflective type, a transmissive type and a transflective type.

[0187] The composition can also be used in a nematic curvilinear aligned phase (NCAP) device prepared by microencapsulating a nematic liquid crystal, and a polymer dispersed liquid crystal display device (PDLCD) and a polymer network liquid crystal display device (PNLCD), in which a three-dimensional network-polymer is formed in the liquid crystal. When an amount of adding the polymerizable compound is about 10% by weight or less based on the weight of the liquid crystal composition, a liquid crystal display device having the PSA mode is prepared. A preferred proportion thereof is in the range of about 0.1% by weight to about 2% by weight. A further preferred proportion is in the range of about 0.2% by weight to about 1.0% by weight. The device having the PSA mode can be driven by a driving mode such as the active matrix mode and the passive matrix mode. Such devices can be applied to any of the reflective type, the transmissive type and the transflective type. A device having a polymer dispersed mode can also be prepared by increasing the amount of adding the polymerizable compound.

[0188] In a device having a polymer sustained alignment mode, a polymer contained in a composition aligns the liquid crystal molecules. The polar compound assists alignment of the liquid crystal molecules. More specifically, the polar compound can be used in place of an alignment film. One example of a method for manufacturing such a device is as described below. A device having two substrates referred to as an array substrate and a color filter substrate is arranged. The substrate has no the alignment film. At least one of the substrates has an electrode layer. The liquid crystal composition is prepared by mixing the liquid crystal compounds. The polymerizable compound and the polar compound are added to the composition. The additive may be further added thereto when necessary. The composition is injected into the device. The device is irradiated with light in a state in which voltage is applied thereto. Ultraviolet light is preferred. The polymerizable compound is polymerized by irradiation with the light. The composition containing the polymer is formed by the polymerization to prepare the device having the PSA mode.

[0189] In the procedure, the polar compound is arranged on the substrate because the polar group interacts with the surface of the substrate. The polar compound aligns the liquid crystal molecules. When voltage is applied thereto, alignment of the liquid crystal molecules is further promoted by action of an electric field. The polymerizable compound is also aligned according to the alignment. The polymerizable compound is polymerized by ultraviolet light in the above state, and therefore a polymer maintaining the alignment is formed. The alignment of the liquid crystal molecules is additionally stable by an effect of the polymer, and therefore the response time in the device is shortened. The image persistence is caused due to poor operation in the liquid crystal molecules, and therefore the persistence is also simultaneously improved by the effect of the polymer. In particular, compound (1) of the invention is a polymerizable polar compound, and therefore aligns liquid crystal molecules, and also is copolymerized with any other polymerizable compound. Thus, the polar compound is no longer leaked into the liquid crystal composition, and therefore the liquid crystal display device having a large voltage holding ratio can be obtained.

EXAMPLES

[0190] Hereinafter, the invention will be described in greater detail by way of Examples (including Synthesis Examples and Use Examples). However, the invention is not limited by the Examples. The invention includes a mixture of a composition in Use Example 1 and a composition in Use Example 2. The invention also includes a mixture prepared by mixing at least two of the compositions in each Use Example.

1. Example of Compound (1)

[0191] Unless otherwise specified, a reaction was performed under a nitrogen atmosphere. Compound (1) was prepared according to procedures shown in Example 1 or the like. The thus prepared compound was identified by methods such as an NMR analysis. Characteristics of compound (1), the liquid crystal compound, the composition and the device were measured by methods described below.

[0192] Nmr Analysis:

[0193] For measurement, DRX-500 made by Bruker BioSpin Corporation was used. In .sup.1H-NMR measurement, a sample was dissolved in a deuterated solvent such as CDCl.sub.3, and measurement was carried out under conditions of room temperature, 500 MHz and 16 times of accumulation. Tetramethylsilane was used as an internal standard. In .sup.19F-NMR measurement, CFCl.sub.3 was used as an internal standard, and measurement was carried out under conditions of 24 times of accumulation. In explaining nuclear magnetic resonance spectra obtained, s, d, t, q, quin, sex and m stand for a singlet, a doublet, a triplet, a quartet, a quintet, a sextet and a multiplet, and br being broad, respectively.

[0194] Gas Chromatographic Analysis:

[0195] For measurement, GC-2010 Gas Chromatograph made by Shimadzu Corporation was used. As a column, a capillary column DB-1 (length 60 m, bore 0.25 mm, film thickness 0.25 m) made by Agilent Technologies, Inc. was used. As a carrier gas, helium (1 mL/minute) was used. A temperature of a sample vaporizing chamber and a temperature of a detector (FID) part were set to 300 C. and 300 C., respectively. A sample was dissolved in acetone and prepared to be a 1 weight % solution, and then 1 microliter of the solution obtained was injected into the sample vaporizing chamber. As a recorder, GC Solution System made by Shimadzu Corporation or the like was used.

[0196] HPLC Analysis:

[0197] For measurement, Prominence (LC-20AD; SPD-20A) made by Shimadzu Corporation was used. As a column, YMC-Pack ODS-A (length 150 mm, bore 4.6 mm, particle diameter 5 m) made by YMC Co., Ltd. was used. As an eluate, acetonitrile and water were appropriately mixed and used. As a detector, a UV detector, an RI detector, a CORONA detector or the like was appropriately used. When the UV detector was used, a detection wavelength was set to 254 nanometers. A sample was dissolved in acetonitrile and prepared to be a 0.1 weight % solution, and then 1 microliter of the solution was introduced into a sample chamber. As a recorder, C-R7Aplus made by Shimadzu Corporation was used.

[0198] Ultraviolet-Visible Spectrophotometry:

[0199] For measurement, PharmaSpec UV-1700 made by Shimadzu Corporation was used. A detection wavelength was adjusted in the range of 190 nanometers to 700 nanometers. A sample was dissolved in acetonitrile and prepared to be a 0.01 mmol/L solution, and measurement was carried out by putting the solution in a quartz cell (optical path length: 1 cm).

[0200] Sample for Measurement:

[0201] Upon measuring phase structure and a transition temperature (a clearing point, a melting point, a polymerization starting temperature or the like), the compound itself was used as a sample.

[0202] Measuring Method:

[0203] Measurement of characteristics was carried out by the methods described below. Most of the measuring methods are applied as described in the Standard of the Japan Electronics and Information Technology Industries Association (JEITA) (JEITA EIAJ ED-2521B) discussed and established by JEITA, or modified thereon. No thin film transistor (TFT) was attached to a TN device used for measurement.

(1) Phase Structure

[0204] A sample was placed on a hot plate in a melting point apparatus (FP-52 Hot Stage made by Mettler-Toledo International Inc.) equipped with a polarizing microscope. A state of phase and a change thereof were observed with the polarizing microscope while the sample was heated at a rate of 3 C. per minute, and a kind of the phase was specified.

(2) Transition Temperature ( C.)

[0205] For measurement, a differential scanning calorimeter, Diamond DSC System, made by PerkinElmer, Inc., or a high sensitivity differential scanning calorimeter, X-DSC7000, made by SSI NanoTechnology Inc. was used. A sample was heated and then cooled at a rate of 3 C. per minute, and a starting point of an endothermic peak or an exothermic peak caused by a phase change of the sample was determined by extrapolation, and thus a transition temperature was determined. A melting point and a polymerization starting temperature of a compound were also measured using the apparatus. Temperature at which a compound undergoes transition from a solid to a liquid crystal phase such as the smectic phase and the nematic phase may be occasionally abbreviated as minimum temperature of the liquid crystal phase. Temperature at which the compound undergoes transition from the liquid crystal phase to liquid may be occasionally abbreviated as clearing point.

[0206] A crystal was expressed as C. When the kind of crystals were distinguishable, each of the crystals was expressed as C.sub.1 or C.sub.2. The smectic phase or the nematic phase was expressed as S or N. In the smectic phase, when smectic A phase, smectic B phase, smectic C phase or smectic F phase was distinguishable, the phases were expressed as S.sub.A, S.sub.B, S.sub.C or S.sub.F, respectively. A liquid (isotropic) was expressed as I. A transition temperature was expressed as C 50.0 N 100.0 I, for example. The expression indicates that a transition temperature from the crystals to the nematic phase is 50.0 C., and a transition temperature from the nematic phase to the liquid is 100.0 C.

(3) Maximum Temperature of Nematic Phase (T.SUB.NI .or NI; C.)

[0207] A sample was placed on a hot plate in a melting point apparatus equipped with a polarizing microscope, and heated at a rate of 1 C. per minute. Temperature when part of the sample began to change from a nematic phase to an isotropic liquid was measured. A maximum temperature of the nematic phase may be occasionally abbreviated as maximum temperature. When the sample was a mixture of compound (1) and the base liquid crystal, the maximum temperature was expressed in terms of a symbol T.sub.NI. When the sample was a mixture of compound (1) and a compound such as components B, C and D, the maximum temperature was expressed in terms of a symbol NI.

(4) Minimum Temperature of Nematic Phase (T.SUB.C.; C.)

[0208] Samples each having a nematic phase were kept in freezers at temperatures of 0 C., 10 C., 20 C., 30 C. and 40 C. for 10 days, and then liquid crystal phases were observed. For example, when the sample maintained the nematic phase at 20 C. and changed to crystals or a smectic phase at 30 C., T.sub.C was expressed as T.sub.C20 C. A minimum temperature of the nematic phase may be occasionally abbreviated as minimum temperature.

(5) Viscosity (Bulk Viscosity; ; Measured at 20 C.; mPa.Math.s)

[0209] For measurement, a cone-plate (E type) rotational viscometer made by Tokyo Keiki Inc. was used.

(6) Optical Anisotropy (Refractive Index Anisotropy; Measured at 25 C.; n)

[0210] Measurement was carried out by an Abbe refractometer with a polarizing plate mounted on an ocular, using light at a wavelength of 589 nanometers. A surface of a main prism was rubbed in one direction, and then a sample was added dropwise onto the main prism. A refractive index (n) was measured when a direction of polarized light was parallel to a direction of rubbing. A refractive index (n) was measured when the direction of polarized light was perpendicular to the direction of rubbing. A value of optical anisotropy (n) was calculated from an equation: n=n|n.

(7) Specific Resistance (; Measured at 25 C.; cm)

[0211] Into a vessel equipped with electrodes, 1.0 milliliter of sample was injected. A direct current voltage (10V) was applied to the vessel, and a direct current after 10 seconds was measured. Specific resistance was calculated from the following equation: (specific resistance)={(voltage)(electric capacity of a vessel)}/{(direct current)(dielectric constant of vacuum)}.

(8) To (12) Viscosity, Dielectric Anisotropy, Elastic Constant, Threshold Voltage and Response Time

[0212] The measuring method of the characteristics may be different between a sample having positive dielectric anisotropy and a sample having negative dielectric anisotropy. When the dielectric anisotropy was positive, the measuring methods were described in sections (8a) to (12a). When the dielectric anisotropy was negative, the measuring methods were described in sections (8b) to (12b).

(8a) Viscosity (Rotational Viscosity; 1; Measured at 25 C.; mPa.Math.s)

[0213] Sample having positive dielectric anisotropy: Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was put in a TN device in which a twist angle was 0 degrees and a distance (cell gap) between two glass substrates was 5 micrometers. Voltage was applied stepwise to the device in the range of 16 V to 19.5 V at an increment of 0.5 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. A value of dielectric anisotropy required for the calculation was determined using the device by which the rotational viscosity was measured and by a method described below.

(8b) Viscosity (Rotational Viscosity; 1; Measured at 25 C.; mPa.Math.s)

[0214] Sample having negative dielectric anisotropy: Measurement was carried out according to a method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, p. 37 (1995). A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 20 micrometers. Voltage was applied stepwise to the device in the range of 39 V to 50 V at an increment of 1 V. After a period of 0.2 second with no voltage application, voltage was repeatedly applied under conditions of only one rectangular wave (rectangular pulse; 0.2 second) and no voltage application (2 seconds). A peak current and a peak time of transient current generated by the applied voltage were measured. A value of rotational viscosity was obtained from the measured values and calculation equation (8) described on page 40 of the paper presented by M. Imai et al. In dielectric anisotropy required for the calculation, a value measured according to items of dielectric anisotropy described below was used.

(9a) Dielectric Anisotropy (; Measured at 25 C.)

[0215] Sample having positive dielectric anisotropy: A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (10 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured. A value of dielectric anisotropy was calculated from an equation: =.

(9b) Dielectric Anisotropy (; Measured at 25 C.)

[0216] Sample having negative dielectric anisotropy: A value of dielectric anisotropy was calculated from an equation: =. A dielectric constant ( and ) was measured as described below.

(1) Measurement of dielectric constant (): an ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL) was applied to a well-cleaned glass substrate. After rotating the glass substrate with a spinner, the glass substrate was heated at 150 C. for 1 hour. A sample was put in a VA device in which a distance (cell gap) between two glass substrates was 4 micrometers, and the device was sealed with an ultraviolet-curable adhesive. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a major axis direction was measured.
(2) Measurement of dielectric constant (): a polyimide solution was applied to a well-cleaned glass substrate. After calcining the glass substrate, rubbing treatment was applied to the alignment film obtained. A sample was put in a TN device in which a distance (cell gap) between two glass substrates was 9 micrometers and a twist angle was 80 degrees. Sine waves (0.5 V, 1 kHz) were applied to the device, and after 2 seconds, a dielectric constant () of liquid crystal molecules in a minor axis direction was measured.

(10a) Elastic Constant (K; Measured at 25 C.; pN)

[0217] Sample having positive dielectric anisotropy: For measurement, HP4284A LCR Meter made by Yokogawa-Hewlett-Packard Co. was used. A sample was put in a horizontal alignment device in which a distance (cell gap) between two glass substrates was 20 micrometers. An electric charge of 0 V to 20 V was applied to the device, and electrostatic capacity and applied voltage were measured. The measured values of electrostatic capacity (C) and applied voltage (V) were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku in Japanese; Nikkan Kogyo Shimbun, Ltd.), and values of K.sub.11 and K.sub.33 were obtained from equation (2.99). Next, K.sub.22 was calculated using the previously determined values of K.sub.11 and K.sub.33 in equation (3.18) on page 171. Elastic constant K was expressed in terms of a mean value of the thus determined K.sub.11, K.sub.22 and K.sub.33.

(10b) Elastic Constant (K.sub.11 and K.sub.33; Measured at 25 C.; pN)

[0218] Sample having negative dielectric anisotropy: For measurement, Elastic Constant Measurement System Model EC-1 made by TOYO Corporation was used. A sample was put in a vertical alignment device in which a distance (cell gap) between two glass substrates was 20 micrometers. An electric charge of 20 V to 0 V was applied to the device, and electrostatic capacity and applied voltage were measured. Values of electrostatic capacity (C) and applied voltage (V) were fitted to equation (2.98) and equation (2.101) on page 75 of Liquid Crystal Device Handbook (Ekisho Debaisu Handobukku in Japanese; Nikkan Kogyo Shimbun, Ltd.), and a value of elastic constant was obtained from equation (2.100).

(11a) Threshold Voltage (Vth; Measured at 25 C.; V)

[0219] Sample having positive dielectric anisotropy: For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 0.45/n (m) and a twist angle was 80 degrees. A voltage (32 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 10 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of voltage at 90% transmittance.

(11b) Threshold Voltage (Vth; Measured at 25 C.; V)

[0220] Sample having negative dielectric anisotropy: For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A sample was put in a normally black mode VA device in which a distance (cell gap) between two glass substrates was 4 micrometers and a rubbing direction was anti-parallel, and the device was sealed with an ultraviolet-curable adhesive. A voltage (60 Hz, rectangular waves) to be applied to the device was stepwise increased from 0 V to 20 V at an increment of 0.02 V. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared, in which the maximum amount of light corresponds to 100% transmittance and the minimum amount of light corresponds to 0% transmittance. A threshold voltage is expressed in terms of voltage at 10% transmittance.

(12a) Response Time (T; Measured at 25 C.; ms)

[0221] Sample having positive dielectric anisotropy: For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A low-pass filter was set to 5 kHz. A sample was put in a normally white mode TN device in which a distance (cell gap) between two glass substrates was 5.0 micrometers and a twist angle was 80 degrees. A voltage (rectangular waves; 60 Hz, 5 V, 0.5 second) was applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. A rise time (r; millisecond) was expressed in terms of time required for a change from 90% transmittance to 10% transmittance. A fall time (f; millisecond) was expressed in terms of time required for a change from 10% transmittance to 90% transmittance. A response time was expressed by a sum of the rise time and the fall time thus determined.

(12b) Response Time (T; Measured at 25 C.; ms)

[0222] Sample having negative dielectric anisotropy: For measurement, an LCD-5100 luminance meter made by Otsuka Electronics Co., Ltd. was used. A light source was a halogen lamp. A low-pass filter was set to 5 kHz. A sample was put in a normally black mode PVA device in which a distance (cell gap) between two glass substrates was 3.2 micrometers, and a rubbing direction was anti-parallel. The device was sealed with an ultraviolet-curable adhesive. The device was applied with a voltage of a little exceeding a threshold voltage for 1 minute, and then was irradiated with ultraviolet light of 23.5 mW/cm.sup.2 for 8 minutes, while applying a voltage of 5.6 V. A voltage (rectangular waves; 60 Hz, 10 V, 0.5 second) was applied to the device. On the occasion, the device was irradiated with light from a direction perpendicular to the device, and an amount of light transmitted through the device was measured. The maximum amount of light corresponds to 100% transmittance, and the minimum amount of light corresponds to 0% transmittance. A response time was expressed in terms of time required for a change from 90% transmittance to 10% transmittance (fall time; millisecond).

(13) Voltage Holding Ratio

[0223] The polymerizable compound was polymerized by irradiating the device prepared as described above with ultraviolet light using Blacklight F40T10/BL (peak wavelength of 369 nm) made by Eye Graphics Co., Ltd. The device was charged by applying a pulse voltage (60 microseconds at 1 V) at 60 C. A decaying voltage was measured for 1.67 seconds with a high-speed voltmeter, and area A between a voltage curve and a horizontal axis in a unit cycle was determined. Area B is an area without decay. A voltage holding ratio is expressed in terms of a percentage of area A to area B.

Synthesis of Compound (1)

[0224] Next, a synthetic method of compound (1) will be described.

[0225] Raw material: Solmix (registered trademark) A-11 is a mixture of ethanol (85.5%), methanol (13.4%) and isopropanol (1.1%), and was purchased from Japan Alcohol Trading Co., Ltd.

Synthesis Example 1

Synthesis of Compound (T-4)

[0226] ##STR00074##

First Step

[0227] Paraformaldehyde (60.0 g), DABCO (56.0 g) and water (200 mL) were put in a reaction vessel, and the resulting mixture was stirred at room temperature for 15 minutes. A THF (400 mL) solution of compound (T-1) (50.0 g) was added dropwise thereto, and the resulting mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=2:1 (volume ratio)) to obtain compound (T-2) (44.1 g; 68%).

Second Step

[0228] Compound (T-2) (44.1 g), imidazole (25.0 g) and dichloromethane (400 mL) were put in a reaction vessel, and the resulting mixture was cooled to 0 C. A dichloromethane solution (200 mL) of tert-buthyldimethyl chlorosilane (53 g) was added dropwise thereto, and the resulting mixture was stirred for 4 hours while warming to room temperature. The reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The resulting solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (heptane:ethyl acetate=9:1 (volume ratio)) to obtain compound (T-3) (105 g; 84%).

Third Step

[0229] Compound (T-3) (105 g), THF (600 mL), methanol (150 mL) and water (100 mL) were put in a reaction vessel, and the resulting mixture was cooled to 0 C. Lithium hydroxide monohydrate (17.4 g) was added thereto, and the resulting mixture was stirred for 12 hours while returning to room temperature. The reaction mixture was poured into water, and 6 N hydrochloric acid (20 mL) was slowly added to be acidified, and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-4) (34.0 g; 35%).

Synthesis Example 2

Synthesis of Compound (No. 16)

[0230] ##STR00075##

First Step

[0231] Compound (T-5) (14.2 g), (T-6) (25 g) and calcium chloride (11.3) were put in a reaction vessel, and 10 mL of 6 N hydrochloric acid was slowly added thereto. The resulting mixture was stirred overnight, and then poured into water, and subjected to extraction with ethyl acetate. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the resulting residue was recrystallized by heptane to obtain compound (T-7) (20 g).

Second Step

[0232] Compound (T-7) (3.0 g), compound (T-4) (6.0 g), DMAP (0.15 g) and dichloromethane (150 mL) were put in a reaction vessel, and the resulting mixture was cooled to 0 C. while stirring thereof. A dichloromethane solution (150 mL) of DCC (4.0 g) was added dropwise thereto. The resulting mixture was stirred for 5 hours while warming to room temperature. The reaction mixture was poured into water, and an aqueous layer was subjected to extraction with dichloromethane. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=9:1 (volume ratio)) to obtain compound (T-8) (4.4).

Third Step

[0233] Compound (T-8) (4.4 g), pyridinium para-toluenesulfonate (2.9 g) and THF (100 mL) were put in a reaction vessel, and the resulting mixture was cooled to 0 C. while stirring thereof. TBAF (1 N, THF solution) (30 mL) was added dropwise thereto, and the resulting mixture was stirred for 3 hours while warming to room temperature. The reaction mixture was poured into water and an aqueous layer was subjected to extraction with ethyl acetate. A combined organic layer was washed with water, and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (toluene:ethyl acetate=1:1 (volume ratio)), and further purified by recrystallization from heptane to obtain compound (No. 16) (2 g).

[0234] An NMR analysis value of the resulting compound (No. 16) was as described below.

[0235] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.23 (d, 1H), 7.20 (dd, 1H), 7.08 (d, 1H), 7.02 (d, 1H), 6.99 (dd, 1H), 6.88 (d, 1H), 6.49 (d, 2H), 6.03 (d, 2H), 4.44 (dd, 4H), 2.62 (s, 2H), 2.52 (q, 2H), 2.46 (q, 2H), 2.23 (q, 2H), 1.94 (t, 2H), 1.80-0.80 (m, 36H).

[0236] Physical properties of compound (No. 16) were as described below.

[0237] Transition temperature: C 36.0 I.

Synthesis Example 3

Synthesis of Compound (No. 11)

[0238] Compound (No. 11) was prepared by performing an operation in a manner similar to Synthesis Example 2 in which phenol was used in place of (T-6).

##STR00076##

[0239] An NMR analysis value of the resulting compound (No. 11) was as described below.

[0240] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.37 (d, 2H), 7.19 (d, 2H), 7.09 (d, 2H), 6.97 (d, 2H), 6.48 (d, 2H), 6.02 (d, 2H), 4.42 (dd, 4H), 2.62 (d, 2H), 2.28 (d, 2H), 1.94 (t, 2H), 1.80-0.80 (m, 30H).

[0241] Physical properties of compound (No. 11) were as described below.

[0242] Transition temperature: C 44.0 I.

Synthesis of Comparative Compound

Comparative Example 1

[0243] Compound (S-1) was prepared as a comparative compound, and characteristics thereof were measured. The reason of selecting the compound as a comparative example is that the compound is described in WO 2014/090362 A, and similar to the compound of the invention.

##STR00077##

[0244] An NMR analysis value of the resulting comparative compound (S-1) was as described below.

[0245] .sup.1H-NMR: chemical shift (ppm; CDCl.sub.3): 7.57-7.52 (m, 2H), 7.45-7.42 (m, 2H), 7.36-7.30 (m, 1H), 7.04-6.95 (m, 2H), 4.75 (d, 6.0 Hz, 2H), 2.62 (t, J=7.8 Hz, 2H), 1.75-1.64 (m, 3H), 0.98 (t, J=7.4 Hz, 3H).

Comparative Measurement of Vertical Alignment Properties

[0246] Comparison was made on vertical alignment properties between compound (No. 16) and comparative compound (S-1). In addition, composition (i) and polymerizable compound (M-1-1) were used for evaluation.

[0247] A proportion of a component of composition (i) is expressed in terms of % by weight.

##STR00078##

[0248] Polymerizable compound (M-1-1) is shown below.

##STR00079##

[0249] Polymerizable compound (M-1-1) was added to composition (i) in a proportion of 0.4% by weight. Compound (No. 16) or comparative compound (S-1) was added thereto in a proportion of 0.5% to 3.0%. The resulting mixture was injected into a device having no alignment film in which a distance (cell gap) between two glass substrates was 3.5 micrometers. The device was set to a polarizing microscope, and irradiated with light from below, and presence or absence of light leakage was observed. When liquid crystal molecules were sufficiently aligned and no light passed through the device, the vertical alignment properties were judged to be Good. When light passing through the device was observed, the vertical alignment properties were expressed by Poor.

[0250] In comparative compound (S-1), vertical alignment properties were confirmed only in the case where the proportion is 3.0%. On the other hand, in the case where compound (No. 16) was used, vertical alignment was confirmed by addition thereof in 0.5%, and good vertical alignment was exhibited in the low concentration in comparison with comparative compound (S-1). The reason is that compound (No. 16) has a plurality of OH groups that induce vertical alignment, and therefore vertical alignment properties was enhanced. Accordingly, compound (No. 16) is reasonably a superior compound exhibiting the good vertical alignment properties in a low concentration.

Synthesis of Other Compound (1)

[0251] Compounds (No. 1) to (No. 20) described below can be prepared in accordance with the synthesis method described in Example 1 described above.

TABLE-US-00002 No. Formula 71 [00080] 1 [00081] 2 [00082] 3 [00083] 4 [00084] 5 Formula 72 [00085] 6 [00086] 7 [00087] 8 [00088] 9 [00089] 10 Formula 73 [00090] 11 [00091] 12 [00092] 13 [00093] 14 [00094] 15 Formula 74 [00095] 16 [00096] 17 [00097] 18 [00098] 19 [00099] 20

2. Examples of Composition

[0252] The compounds in Examples were represented using symbols according to definitions in Table 2 described below. In Table 2, the configuration of 1,4-cyclohexylene is trans. A parenthesized number next to a symbolized compound in Examples corresponds to the number of the compound. A symbol (-) means any other liquid crystal compound. A proportion (percentage) of the liquid crystal compound is expressed in terms of weight percent (% by weight) based on the weight of the liquid crystal composition. Values of the characteristics of the liquid crystal composition are summarized in a last part. Characteristics were measured according to the methods described above, and measured values were directly described (without extrapolation)

TABLE-US-00003 TABLE 2 Method for description of compounds using symbols R(A.sub.1)Z.sub.1 . . . Z.sub.n(A.sub.n)R 1) Left-terminal group R Symbol C.sub.nH.sub.2n+1 n- C.sub.nH.sub.2n+1O nO C.sub.mH.sub.2m+1OC.sub.nH.sub.2n mOn CH.sub.2CH V C.sub.nH.sub.2n+1CHCH nV CH.sub.2CHC.sub.nH.sub.2n Vn C.sub.mH.sub.2m+1CHCHC.sub.nH.sub.2n mVn CF.sub.2CH VFF CF.sub.2CHC.sub.nH.sub.2n VFFn 2) Right-terminal group R Symbol C.sub.nH.sub.2n+1 -n OC.sub.nH.sub.2n+1 On COOCH.sub.3 EMe CHCH.sub.2 V CHCHC.sub.nH.sub.2n+1 Vn C.sub.nH.sub.2nCHCH.sub.2 nV C.sub.mH.sub.2mCHCHC.sub.nH.sub.2n+1 mVn CHCF.sub.2 VFF F F Cl CL OCF.sub.3 OCF3 OCF.sub.2H OCF2H CF.sub.3 CF3 OCHCHCF.sub.3 OVCF3 CN C 3) Bonding group Z.sub.n Symbol C.sub.nH.sub.2n n COO E CHCH V CH.sub.2O 1O OCH.sub.2 O1 CF.sub.2O X CC T 4) Ring structure A.sub.n Symbol [00100] H [00101] B [00102] B(F) [00103] B(2F) [00104] B(F,F) [00105] B(2F,5F) [00106] B(2F,3F) [00107] Py [00108] G [00109] ch 5) Examples of description Example 1 3-HBCL [00110] Example 2 5-HHBB(F,F)F [00111] Example 3 3-HBO2 [00112] Example 4 3-HBB(F,F)F [00113]

Use Example 1

[0253]

TABLE-US-00004 2-HB-C (8-1) 6% 3-HB-C (8-1) 12% 3-HB-O2 (2-5) 15% 2-BTB-1 (2-10) 5% 3-HHB-F (6-1) 4% 3-HHB-1 (3-1) 7% 3-HHB-O1 (3-1) 5% 3-HHB-3 (3-1) 12% 3-HHEB-F (6-10) 3% 5-HHEB-F (6-10) 6% 2-HHB(F)-F (6-2) 6% 3-HHB(F)-F (6-2) 6% 5-HHB(F)-F (6-2) 6% 3-HHB(F,F)-F (6-3) 7%

[0254] Compound (No. 16) described below was added to the composition described above in a proportion of 0.05% by weight.

##STR00114##

[0255] NI=97.3 C.; =18.3 mPa.Math.s; n=0.103; =4.7.

Use Example 2

[0256]

TABLE-US-00005 3-HB-CL (5-2) 13% 3-HH-4 (2-1) 15% 3-HB-O2 (2-5) 8% 3-HHB(F,F)-F (6-3) 6% 3-HBB(F,F)-F (6-24) 24% 5-HBB(F,F)-F (6-24) 22% 5-HBB(F)B-2 (4-5) 6% 5-HBB(F)B-3 (4-5) 6%

[0257] Compound (No. 11) described below was added to the composition described above in a proportion of 0.3% by weight.

##STR00115##

[0258] NI=75.1 C.; =17.6 mPa.Math.s; n=0.115; =4.9.

Use Example 3

[0259]

TABLE-US-00006 7-HB(F,F)-F (5-4) 6% 3-HB-O2 (2-5) 7% 2-HHB(F)-F (6-2) 10% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 10% 2-HBB(F)-F (6-23) 9% 3-HBB(F)-F (6-23) 10% 5-HBB(F)-F (6-23) 14% 2-HBB-F (6-22) 4% 3-HBB-F (6-22) 5% 5-HBB-F (6-22) 5% 3-HBB(F,F)-F (6-24) 4% 5-HBB(F,F)-F (6-24) 8%

[0260] Compound (No. 16) described below was added to the composition described above in a proportion of 1% by weight.

##STR00116##

[0261] NI=82.1 C.; =24.0 mPa.Math.s; n=0.113; =5.2.

Use Example 4

[0262]

TABLE-US-00007 5-HB-CL (5-2) 13% 3-HH-4 (2-1) 15% 3-HH-5 (2-1) 4% 3-HHB-F (6-1) 5% 3-HHB-CL (6-1) 3% 4-HHB-CL (6-1) 4% 3-HHB(F)-F (6-2) 9% 4-HHB(F)-F (6-2) 9% 5-HHB(F)-F (6-2) 8% 7-HHB(F)-F (6-2) 8% 5-HBB(F)-F (6-23) 5% 1O1-HBBH-5 (4-1) 3% 3-HHBB(F,F)-F (7-6) 3% 4-HHBB(F,F)-F (7-6) 3% 5-HHBB(F,F)-F (7-6) 2% 3-HH2BB(F,F)-F (7-15) 3% 4-HH2BB(F,F)-F (7-15) 3%

[0263] Compound (No. 11) described below was added to the composition described above in a proportion of 3% by weight.

##STR00117##

[0264] NI=118.1 C.; =19.6 mPa.Math.s; n=0.091; =3.6.

Use Example 5

[0265]

TABLE-US-00008 3-HHB(F,F)-F (6-3) 11% 3-H2HB(F,F)-F (6-15) 8% 4-H2HB(F,F)-F (6-15) 7% 5-H2HB(F,F)-F (6-15) 7% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F)-F (6-24) 20% 3-H2BB(F,F)-F (6-27) 13% 5-HHBB(F,F)-F (7-6) 3% 5-HHEBB-F (7-17) 2% 3-HH2BB(F,F)-F (7-15) 3% 1O1-HBBH-4 (4-1) 3% 1O1-HBBH-5 (4-1) 3%

[0266] Compound (No. 16) described below was added to the composition described above in a proportion of 5% by weight.

##STR00118##

[0267] NI=93.9 C.; =34.3 mPa.Math.s; n=0.115; =9.2.

Use Example 6

[0268]

TABLE-US-00009 5-HB-F (5-2) 15% 6-HB-F (5-2) 7% 7-HB-F (5-2) 7% 2-HHB-OCF3 (6-1) 6% 3-HHB-OCF3 (6-1) 7% 4-HHB-OCF3 (6-1) 6% 5-HHB-OCF3 (6-1) 5% 3-HH2B-OCF3 (6-4) 6% 5-HH2B-OCF3 (6-4) 4% 3-HHB(F,F)-OCF2H (6-3) 4% 3-HHB(F,F)-OCF3 (6-3) 5% 3-HH2B(F)-F (6-5) 3% 3-HBB(F)-F (6-23) 8% 5-HBB(F)-F (6-23) 10% 5-HBBH-3 (4-1) 4% 3-HB(F)BH-3 (4-2) 3%

[0269] Compound (No. 11) described below was added to the composition described above in a proportion of 0.1% by weight.

##STR00119##

[0270] NI=87.5 C.; =14.9 mPa.Math.s; n=0.092; =4.4.

Use Example 7

[0271]

TABLE-US-00010 5-HB-CL (5-2) 15% 3-HH-4 (2-1) 5% 3-HHB-1 (3-1) 5% 3-HHB(F,F)-F (6-3) 5% 3-HBB(F,F)-F (6-24) 20% 5-HBB(F,F)-F (6-24) 15% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F)-F (6-12) 3% 5-HHEB(F,F)-F (6-12) 5% 2-HBEB(F,F)-F (6-39) 3% 3-HBEB(F,F)-F (6-39) 5% 5-HBEB(F,F)-F (6-39) 5% 3-HHBB(F,F)-F (7-6) 4%

[0272] Compound (No. 16) described below was added to the composition described above in a proportion of 0.5% by weight.

##STR00120##

[0273] NI=75.8 C.; =22.3 mPa.Math.s; n=0.103; =9.0.

Use Example 8

[0274]

TABLE-US-00011 3-HB-CL (5-2) 4% 5-HB-CL (5-2) 4% 3-HHB-OCF3 (6-1) 5% 3-H2HB-OCF3 (6-13) 5% 5-H4HB-OCF3 (6-19) 15% V-HHB(F)-F (6-2) 6% 3-HHB(F)-F (6-2) 5% 5-HHB(F)-F (6-2) 5% 3-H4HB(F,F)-CF3 (6-21) 8% 5-H4HB(F,F)-CF3 (6-21) 10% 5-H2HB(F,F)-F (6-15) 4% 5-H4HB(F,F)-F (6-21) 7% 2-H2BB(F)-F (6-26) 5% 3-H2BB(F)-F (6-26) 11% 3-HBEB(F,F)-F (6-39) 6%

[0275] Compound (No. 16) described below was added to the composition described above in a proportion of 2% by weight.

##STR00121##

[0276] NI=71.9 C.; =26.3 mPa.Math.s; n=0.098; =8.5.

Use Example 9

[0277]

TABLE-US-00012 5-HB-CL (5-2) 14% 7-HB(F,F)-F (5-4) 4% 3-HH-4 (2-1) 10% 3-HH-5 (2-1) 4% 3-HB-O2 (2-5) 14% 3-HHB-1 (3-1) 8% 3-HHB-O1 (3-1) 5% 2-HHB(F)-F (6-2) 8% 3-HHB(F)-F (6-2) 8% 5-HHB(F)-F (6-2) 8% 3-HHB(F,F)-F (6-3) 6% 3-H2HB(F,F)-F (6-15) 6% 4-H2HB(F,F)-F (6-15) 5%

[0278] Compound (No. 11) described below was added to the composition described above in a proportion of 1.5% by weight.

##STR00122##

[0279] NI=72.9 C.; =15.1 mPa.Math.s; n=0.074; =3.0.

Use Example 10

[0280]

TABLE-US-00013 5-HB-CL (5-2) 6% 7-HB(F)-F (5-3) 6% 3-HH-4 (2-1) 7% 3-HH-5 (2-1) 10% 3-HB-O2 (2-5) 11% 3-HHEB-F (6-10) 8% 5-HHEB-F (6-10) 10% 3-HHEB(F,F)-F (6-12) 10% 4-HHEB(F,F)-F (6-12) 5% 3-GHB(F,F)-F (6-109) 6% 4-GHB(F,F)-F (6-109) 5% 5-GHB(F,F)-F (6-109) 5% 2-HHB(F,F)-F (6-3) 7% 3-HHB(F,F)-F (6-3) 4%

[0281] Compound (No. 16) described below was added to the composition described above in a proportion of 0.5% by weight.

##STR00123##

[0282] NI=72.6 C.; r=19.1 mPa.Math.s; n=0.069; =5.9.

Use Example 11

[0283]

TABLE-US-00014 1V2-BEB(F,F)-C (8-15) 10% 3-HB-C (8-1) 13% 2-BTB-1 (2-10) 8% 5-HH-VFF (2-1) 30% 3-HHB-1 (3-1) 5% VFF-HHB-1 (3-1) 8% VFF2-HHB-1 (3-1) 11% 3-H2BTB-2 (3-17) 5% 3-H2BTB-3 (3-17) 5% 3-H2BTB-4 (3-17) 5%

[0284] Compound (No. 16) described below was added to the composition described above in a proportion of 1% by weight.

##STR00124##

[0285] NI=84.1 C.; r=13.9 mPa.Math.s; n=0.131; =8.8.

Use Example 12

[0286]

TABLE-US-00015 5-HB(F)B(F,F)XB(F,F)-F (7-41) 6% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 8% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 3-HH-V (2-1) 38% 3-HH-V1 (2-1) 5% 3-HHEH-5 (3-13) 3% 3-HHB-1 (3-1) 5% V-HHB-1 (3-1) 4% V2-BB(F)B-1 (3-6) 5% 1V2-BB-F (5-1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 10% 3-HHBB(F,F)-F (7-6) 3%

[0287] Compound (No. 11) described below was added to the composition described above in a proportion of 3% by weight.

##STR00125##

[0288] NI=84.7 C.; =17.0 mPa.Math.s; n=0.113; =8.0.

Use Example 13

[0289]

TABLE-US-00016 3-GB(F)B(F,F)XB(F,F)-F (7-75) 6% 5-HB(F)B(F,F)XB(F,F)-F (7-41) 3% 3-BB(F)B(F,F)XB(F,F)-F (7-47) 4% 4-BB(F)B(F,F)XB(F,F)-F (7-47) 5% 5-BB(F)B(F,F)XB(F,F)-F (7-47) 4% 3-HH-V (2-1) 35% 3-HH-V1 (2-1) 7% 3-HHEH-5 (3-13) 3% 3-HHB-1 (3-1) 3% V-HHB-1 (3-1) 5% V2-BB(F)B-1 (3-6) 5% 1V2-BB-F (5-1) 3% 3-BB(F,F)XB(F,F)-F (6-97) 7% 3-GB(F,F)XB(F,F)-F (6-113) 6% 3-HHBB(F,F)-F (7-6) 4%

[0290] Compound (No. 16) described below was added to the composition described above in a proportion of 0.05% by weight.

##STR00126##

[0291] NI=82.5 C.; =18.3 mPa.Math.s; n=0.109; =9.4.

INDUSTRIAL APPLICABILITY

[0292] Compound (1) has high chemical stability, high capability of aligning liquid crystal molecules and high solubility in a liquid crystal composition, and has a large voltage holding ratio when the compound is used in a liquid crystal display device. A liquid crystal composition containing compound (1) satisfies at least one of characteristics such as high maximum temperature, low minimum temperature, small viscosity, suitable optical anisotropy, large positive or negative dielectric anisotropy, large specific resistance, high stability to ultraviolet light, high stability to heat and a large elastic constant. A liquid crystal display device including the composition has characteristics such as a wide temperature range in which the device can be used, a short response time, a large voltage holding ratio, low threshold voltage, a large contrast ratio and a long service life, and therefore can be used in a liquid crystal projector, a liquid crystal television and so forth.