Monomer, liquid crystal composition, liquid crystal display device, and production method for liquid crystal display device
09719018 · 2017-08-01
Assignee
Inventors
- Masanobu Mizusaki (Osaka, JP)
- Youhei Nakanishi (Osaka, JP)
- Takeshi Noma (Osaka, JP)
- Satoshi Enomoto (Inzai, JP)
Cpc classification
C09K19/52
CHEMISTRY; METALLURGY
C09K19/2028
CHEMISTRY; METALLURGY
C09K19/20
CHEMISTRY; METALLURGY
C09K2019/0448
CHEMISTRY; METALLURGY
C07J17/00
CHEMISTRY; METALLURGY
G02F1/133788
PHYSICS
C09K3/10
CHEMISTRY; METALLURGY
C07J9/00
CHEMISTRY; METALLURGY
C07C69/54
CHEMISTRY; METALLURGY
International classification
C09K19/12
CHEMISTRY; METALLURGY
C09K19/20
CHEMISTRY; METALLURGY
G02F1/1337
PHYSICS
C07J17/00
CHEMISTRY; METALLURGY
C07C69/54
CHEMISTRY; METALLURGY
C07J9/00
CHEMISTRY; METALLURGY
Abstract
The present invention provides a liquid crystal composition for forming a polymer layer capable of keeping high voltage holding ratio. The liquid crystal composition in an aspect of the present invention contains a liquid crystal material and one or more kind monomers and, at least one of the monomers is a compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more.
Claims
1. A liquid crystal composition comprising a liquid crystal material and one or more kinds of monomers, the one or more monomers including: a first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more; and a second monomer having a structure for producing a radical by light irradiation; wherein the first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to the cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by the following formula (2): ##STR00032## in the formula, P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group; A.sup.3 denotes a trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group; the trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group is selected from the group consisting of benzene-1,2,3-triyl, benzene-1,2,4-triyl, benzene-1,3,5-triyl, pyridine-2,3,4-triyl, pyridine-2,3,5-triyl, pyridine-2,4,6-triyl, naphthalene-1,2,5-triyl, naphthalene-1,2,6-triyl, naphthalene-1,2,7-triyl, naphthalene-1,2,8-triyl, naphthalene-1,3,5-triyl, naphthalene-1,3,6-triyl, naphthalene-1,3,7-triyl, naphthalene-1,3,8-triyl, naphthalene-1,4,5-triyl, naphthalene-1,4,6-triyl, naphthalene-1,4,7-triyl, naphthalene-1,6,7-triyl, naphthalene-1,6,8-triyl, naphthalene-2,3,6-triyl, cyclohexane-1,2,3-triyl, cyclohexane-1,2,4-triyl, cyclohexane-1,3,5-triyl, decahydronaphthalene-1,2,5-triyl, decahydronaphthalene-1,2,6-triyl, decahydronaphthalene-1,2,7-triyl, decahydronaphthalene-1,2,8-triyl, decahydronaphthalene-1,3,5-triyl, decahydronaphthalene-1,3,6-triyl, decahydronaphthalene-1,3,7-triyl, decahydronaphthalene-1,3,8-triyl, decahydronaphthalene-1,4,5-triyl, decahydronaphthalene-1,4,6-triyl, decahydronaphthalene-1,4,7-triyl, decahydronaphthalene-1,6,7-triyl, decahydronaphthalene-1,6,8-triyl, decahydronaphthalene-2,3,6-triyl, indan-1,1,5-triyl, indan-1,1,6-triyl, indan-1,3,5-triyl, indan-1,3,6-triyl, phenanthrene-1,2,6-triyl, phenanthrene-1,2,7-triyl, phenanthrene-1,2,8-triyl, phenanthrene-1,2,9-triyl, phenanthrene-1,3,6-triyl, phenanthrene-1,3,7-triyl, phenanthrene-1,3,8-triyl, phenanthrene-1,3,9-triyl, phenanthrene-1,6,7-triyl, phenanthrene-1,6,9-triyl, phenanthrene-1,7,9-triyl, phenanthrene-1,8,9-triyl, phenanthrene-1,9,10-triyl, phenanthrene-2,3,6-triyl, phenanthrene-2,3,7-triyl, phenanthrene-2,3,9-triyl, phenanthrene-2,7,9-triyl, phenanthrene-2,9,10-triyl, phenanthrene-3,6,7-triyl, phenanthrene-3,6,9-triyl, phenanthrene-3,9,10-triyl, anthracene-1,2,5-triyl, anthracene-1,2,6-triyl, anthracene-1,2,7-triyl, anthracene-1,2,8-triyl, anthracene-1,2,9-triyl, anthracene-1,2,10-triyl, anthracene-1,3,5-triyl, anthracene-1,3,6-triyl, anthracene-1,3,7-triyl, anthracene-1,3,8-triyl, anthracene-1,3,9-triyl, anthracene-1,3,10-triyl, anthracene-1,4,5-triyl, anthracene-1,4,6-triyl, anthracene-1,4,8-triyl, anthracene-1,4,9-triyl, anthracene-1,5,9-triyl, anthracene-1,6,7-triyl, anthracene-1,6,9-triyl, anthracene-1,7,9-triyl, anthracene-1,8,9-triyl, anthracene-1,9,10-triyl, anthracene-2,3,6-triyl, anthracene-2,3,9-triyl, anthracene-2,6,9-triyl, anthracene-2,7,9-triyl, anthracene-2,7,10-triyl, and anthracene-2,9,10-triyl group; A.sup.4 denotes a phenylene group; a —CH.sub.2— group included in A.sup.3 and A.sup.4 may be substituted with an —O— or a —S— group unless neighboring each other; a —CH═ group included in A.sup.3 and A.sup.4 may be substituted with a —N═ group unless neighboring each other; a hydrogen atom included in A.sup.3 and A.sup.4 may be substituted with a fluorine atom, a chlorine atom, a —CN group, or a straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy group with 1 to 12 carbon atoms and further one or more of carbon atoms in these groups may be substituted with a silicon atom; Z.sup.4 and Z.sup.5 may be same or different, and denote —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —NHCO—, —N(CH.sub.3)CO—, —N(C.sub.2H.sub.5)CO—, —N(C.sub.3H.sub.7)CO—, —N(C.sub.4H.sub.9)CO—, —CONH—, —CON(CH.sub.3)—, —CON(C.sub.2H.sub.5)—, —CON(C.sub.3H.sub.7)—, —CON(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— group, or a direct bond; L.sup.3 denotes an alkyl, alkenyl, or aralkyl with 12 carbon atoms or more, or a monovalent monocyclic or polycyclic hydrocarbon group with 12 carbon atoms or more, or a biphenyl group; the alkyl and alkenyl groups may be straight or branched; one or more hydrogen atoms included in the aralkyl and the monovalent monocyclic or polycyclic hydrocarbon groups may be substituted with a straight or branched alkyl or alkenyl group with 1 to 8 carbon atoms; a —CH.sub.2— group included in the alkyl, the alkenyl, and the monovalent monocyclic or polycyclic hydrocarbon group for L.sup.3 may be substituted with —O—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless oxygen atoms neighbor each other; and n.sup.3 denotes 0 or 1; the second monomer having a structure for producing a radical by light irradiation is at least one of: a compound represented by the following formula (4) and having a structure for producing a radical by hydrogen abstraction reaction by light irradiation, and a compound represented by the following formula (5) and having a structure for producing a radical by self-cleavage reaction by light irradiation; the formula (4) being: ##STR00033## in the formula, A.sup.5 denotes an aromatic ring; A.sup.6 denotes an aromatic ring same as or different from A.sup.5, or a straight or branched alkyl or alkenyl group with 1 to 12 carbon atoms; at least one of A.sup.5 and A.sup.6 contains -Sp.sup.3-P group; an aromatic ring included in at least one of A.sup.5 and A.sup.6 is a benzene ring or a biphenyl ring; a hydrogen atom included in A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group, a halogen atom, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —SF.sub.5, or an alkyl, alkenyl or aralkyl group with 1 to 12 carbon atoms and the alkyl and alkenyl groups may be straight or branched; two neighboring hydrogen atoms included in A.sup.5 and A.sup.6 may be substituted with a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms to form a ring structure; a hydrogen atom included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; P denotes a radical polymerizable group; Sp.sup.3 denotes a straight, branched or cyclic alkylene or alkyleneoxy group with 1 to 6 carbon atoms, or a direct bond; m.sup.1 denotes 1 or 2; a dotted line part connecting A.sup.5 and Y and a dotted line part connecting A.sup.6 and Y represent that a bond through Y may exist between A.sup.5 and A.sup.6; and Y denotes —CH.sub.2—, —CH.sub.2CH.sub.2—, —CH═CH—, —O—, —S—, —NH—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3F.sub.17)—, —N(C.sub.4H.sub.9)—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S— group, or a direct bond; the formula (5) being: ##STR00034## in the formula, R.sup.3 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.6-P; R.sup.4 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.7-P; P denotes a same or different radical polymerizable group and a total number is 2 or more; Sp.sup.4 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.2 is 2 or more; Sp.sup.5 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.3 is 2 or more; Sp.sup.6 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; Sp.sup.7 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; L.sup.4 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.4 is 2 or more; in the case where two L.sup.4s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and two L.sup.4s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; L.sup.5 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.5 is 2 or more; in the case where two L.sup.5s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and the two L.sup.5s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; one or more hydrogen atoms included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —F or —OH group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, -Sp.sup.4-P, or -Sp.sup.5-P group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; m.sup.2 denotes an integer of 1 to 3; m.sup.3 denotes an integer of 0 to 3; n.sup.4 denotes an integer of 0 to 4; n.sup.5 denotes an integer of 0 to 4; a total of m.sup.2 and n.sup.4 is an integer of 1 to 5; a total of m.sup.3 and n.sup.5 is an integer of 0 to 5; and a total of m.sup.2 and m.sup.3 is an integer of 1 to 6.
2. The liquid crystal composition according to claim 1, wherein the first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by one of the following formulas (3-1) to (3-5): ##STR00035## in the formula, P and P are the same or different, and denote a radical polymerizable group.
3. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer sandwiched between the pair of the substrates and containing a liquid crystal material; and a polymer layer formed on at least one of the pair of the substrates and configured to control alignment of liquid crystal molecules, wherein the polymer layer is formed by polymerizing one or more kinds of monomers, and the one or more monomers includes: a first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more; and a second monomer having a structure for producing a radical by light irradiation; wherein the first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to the cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by the following formula (2): ##STR00036## in the formula, P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group; A.sup.3 denotes a trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group; the trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group is selected from the group consisting of benzene-1,2,3-triyl, benzene-1,2,4-triyl, benzene-1,3,5-triyl, pyridine-2,3,4-triyl, pyridine-2,3,5-triyl, pyridine-2,4,6-triyl, naphthalene-1,2,5-triyl, naphthalene-1,2,6-triyl, naphthalene-1,2,7-triyl, naphthalene-1,2,8-triyl, naphthalene-1,3,5-triyl, naphthalene-1,3,6-triyl, naphthalene-1,3,7-triyl, naphthalene-1,3,8-triyl, naphthalene-1,4,5-triyl, naphthalene-1,4,6-triyl, naphthalene-1,4,7-triyl, naphthalene-1,6,7-triyl, naphthalene-1,6,8-triyl, naphthalene-2,3,6-triyl, cyclohexane-1,2,3-triyl, cyclohexane-1,2,4-triyl, cyclohexane-1,3,5-triyl, decahydronaphthalene-1,2,5-triyl, decahydronaphthalene-1,2,6-triyl, decahydronaphthalene-1,2,7-triyl, decahydronaphthalene-1,2,8-triyl, decahydronaphthalene-1,3,5-triyl, decahydronaphthalene-1,3,6-triyl, decahydronaphthalene-1,3,7-triyl, decahydronaphthalene-1,3,8-triyl, decahydronaphthalene-1,4,5-triyl, decahydronaphthalene-1,4,6-triyl, decahydronaphthalene-1,4,7-triyl, decahydronaphthalene-1,6,7-triyl, decahydronaphthalene-1,6,8-triyl, decahydronaphthalene-2,3,6-triyl, indan-1,1,5-triyl, indan-1,1,6-triyl, indan-1,3,5-triyl, indan-1,3,6-triyl, phenanthrene-1,2,6-triyl, phenanthrene-1,2,7-triyl, phenanthrene-1,2,8-triyl, phenanthrene-1,2,9-triyl, phenanthrene-1,3,6-triyl, phenanthrene-1,3,7-triyl, phenanthrene-1,3,8-triyl, phenanthrene-1,3,9-triyl, phenanthrene-1,6,7-triyl, phenanthrene-1,6,9-triyl, phenanthrene-1,7,9-triyl, phenanthrene-1,8,9-triyl, phenanthrene-1,9,10-triyl, phenanthrene-2,3,6-triyl, phenanthrene-2,3,7-triyl, phenanthrene-2,3,9-triyl, phenanthrene-2,7,9-triyl, phenanthrene-2,9,10-triyl, phenanthrene-3,6,7-triyl, phenanthrene-3,6,9-triyl, phenanthrene-3,9,10-triyl, anthracene-1,2,5-triyl, anthracene-1,2,6-triyl, anthracene-1,2,7-triyl, anthracene-1,2,8-triyl, anthracene-1,2,9-triyl, anthracene-1,2,10-triyl, anthracene-1,3,5-triyl, anthracene-1,3,6-triyl, anthracene-1,3,7-triyl, anthracene-1,3,8-triyl, anthracene-1,3,9-triyl, anthracene-1,3,10-triyl, anthracene-1,4,5-triyl, anthracene-1,4,6-triyl, anthracene-1,4,8-triyl, anthracene-1,4,9-triyl, anthracene-1,5,9-triyl, anthracene-1,6,7-triyl, anthracene-1,6,9-triyl, anthracene-1,7,9-triyl, anthracene-1,8,9-triyl, anthracene-1,9,10-triyl, anthracene-2,3,6-triyl, anthracene-2,3,9-triyl, anthracene-2,6,9-triyl, anthracene-2,7,9-triyl, anthracene-2,7,10-triyl, and anthracene-2,9,10-triyl group; A.sup.4 denotes a phenylene group; a —CH.sub.2— group included in A.sup.3 and A.sup.4 may be substituted with an —O— or a —S— group unless neighboring each other; a —CH═ group included in A.sup.3 and A.sup.4 may be substituted with a —N═ group unless neighboring each other; a hydrogen atom included in A.sup.3 and A.sup.4 may be substituted with a fluorine atom, a chlorine atom, a —CN group, or a straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy group with 1 to 12 carbon atoms and further one or more of carbon atoms in these groups may be substituted with a silicon atom; Z.sup.4 and Z.sup.5 may be same or different, and denote —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —NHCO—, —N(CH.sub.3)CO—, —N(C.sub.2H.sub.5)CO—, —N(C.sub.3H.sub.7)CO—, —N(C.sub.4H.sub.9)CO—, —CONH—, —CON(CH.sub.3)—, —CON(C.sub.2H.sub.5)—, —CON(C.sub.3H.sub.7)—, —CON(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— group, or a direct bond; L.sup.3 denotes an alkyl, alkenyl, or aralkyl with 12 carbon atoms or more, or a monovalent monocyclic or polycyclic hydrocarbon group with 12 carbon atoms or more, or a biphenyl group; the alkyl and alkenyl groups may be straight or branched; one or more hydrogen atoms included in the aralkyl and the monovalent monocyclic or polycyclic hydrocarbon groups may be substituted with a straight or branched alkyl or alkenyl group with 1 to 8 carbon atoms; a —CH.sub.2— group included in the alkyl, the alkenyl, and the monovalent monocyclic or polycyclic hydrocarbon group for L.sup.3 may be substituted with —O—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless oxygen atoms neighbor each other; and n.sup.3 denotes 0 or 1; the second monomer having a structure for producing a radical by light irradiation is at least one of: a compound represented by the following formula (4) and having a structure for producing a radical by hydrogen abstraction reaction by light irradiation, and a compound represented by the following formula (5) and having a structure for producing a radical by self-cleavage reaction by light irradiation; the formula (4) being: ##STR00037## in the formula, A.sup.5 denotes an aromatic ring; A.sup.6 denotes an aromatic ring same as or different from A.sup.5, or a straight or branched alkyl or alkenyl group with 1 to 12 carbon atoms; at least one of A.sup.5 and A.sup.6 contains -Sp.sup.3-P group; an aromatic ring included in at least one of A.sup.5 and A.sup.6 is a benzene ring or a biphenyl ring; a hydrogen atom included in A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group, a halogen atom, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —SF.sub.5, or an alkyl, alkenyl or aralkyl group with 1 to 12 carbon atoms and the alkyl and alkenyl groups may be straight or branched; two neighboring hydrogen atoms included in A.sup.5 and A.sup.6 may be substituted with a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms to form a ring structure; a hydrogen atom included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; P denotes a radical polymerizable group; Sp.sup.3 denotes a straight, branched or cyclic alkylene or alkyleneoxy group with 1 to 6 carbon atoms, or a direct bond; m.sup.1 denotes 1 or 2; a dotted line part connecting A.sup.5 and Y and a dotted line part connecting A.sup.6 and Y represent that a bond through Y may exist between A.sup.5 and A.sup.6; and Y denotes —CH.sub.2—, —CH.sub.2CH.sub.2—, —CH═CH—, —O—, —S—, —NH—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3F.sub.17)—, —N(C.sub.4H.sub.9)—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S— group, or a direct bond; the formula (5) being: ##STR00038## in the formula, R.sup.3 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.6-P; R.sup.4 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.7-P; P denotes a same or different radical polymerizable group and a total number is 2 or more; Sp.sup.4 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.2 is 2 or more; Sp.sup.5 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.3 is 2 or more; Sp.sup.6 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; Sp.sup.7 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; L.sup.4 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.4 is 2 or more; in the case where two L.sup.4s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and two L.sup.4s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; L.sup.5 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.5 is 2 or more; in the case where two L.sup.5s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and the two L.sup.5s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; one or more hydrogen atoms included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —F or —OH group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, -Sp.sup.4-P, or -Sp.sup.5-P group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; m.sup.2 denotes an integer of 1 to 3; m.sup.3 denotes an integer of 0 to 3; n.sup.4 denotes an integer of 0 to 4; n.sup.5 denotes an integer of 0 to 4; a total of m.sup.2 and n.sup.4 is an integer of 1 to 5; a total of m.sup.3 and n.sup.5 is an integer of 0 to 5; and a total of m.sup.2 and m.sup.3 is an integer of 1 to 6.
4. The liquid crystal display device according to claim 3, wherein the first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by one of the following formulas (3-1) to (3-5): ##STR00039## in the formula, P and P are the same or different, and denote a radical polymerizable group.
5. A production method for a liquid crystal display device comprising: injecting a liquid crystal composition containing a liquid crystal material and one or more kinds of monomers between a pair of substrates; and forming a polymer layer for controlling alignment of liquid crystal molecules on a substrate by polymerizing the monomers by radiating the liquid crystal composition with light, the one or more monomers including: a first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more; and a second monomer having a structure for producing a radical by light irradiation, wherein the first monomer produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to the cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by the following formula (2): ##STR00040## in the formula, P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group; A.sup.3 denotes a trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group; the trivalent, alicyclic, aromatic monocyclic, or condensed polycyclic hydrocarbon group is selected from the group consisting of benzene-1,2,3-triyl, benzene-1,2,4-triyl, benzene-1,3,5-triyl, pyridine-2,3,4-triyl, pyridine-2,3,5-triyl, pyridine-2,4,6-triyl, naphthalene-1,2,5-triyl, naphthalene-1,2,6-triyl, naphthalene-1,2,7-triyl, naphthalene-1,2,8-triyl, naphthalene-1,3,5-triyl, naphthalene-1,3,6-triyl, naphthalene-1,3,7-triyl, naphthalene-1,3,8-triyl, naphthalene-1,4,5-triyl, naphthalene-1,4,6-triyl, naphthalene-1,4,7-triyl, naphthalene-1,6,7-triyl, naphthalene-1,6,8-triyl, naphthalene-2,3,6-triyl, cyclohexane-1,2,3-triyl, cyclohexane-1,2,4-triyl, cyclohexane-1,3,5-triyl, decahydronaphthalene-1,2,5-triyl, decahydronaphthalene-1,2,6-triyl, decahydronaphthalene-1,2,7-triyl, decahydronaphthalene-1,2,8-triyl, decahydronaphthalene-1,3,5-triyl, decahydronaphthalene-1,3,6-triyl, decahydronaphthalene-1,3,7-triyl, decahydronaphthalene-1,3,8-triyl, decahydronaphthalene-1,4,5-triyl, decahydronaphthalene-1,4,6-triyl, decahydronaphthalene-1,4,7-triyl, decahydronaphthalene-1,6,7-triyl, decahydronaphthalene-1,6,8-triyl, decahydronaphthalene-2,3,6-triyl, indan-1,1,5-triyl, indan-1,1,6-triyl, indan-1,3,5-triyl, indan-1,3,6-triyl, phenanthrene-1,2,6-triyl, phenanthrene-1,2,7-triyl, phenanthrene-1,2,8-triyl, phenanthrene-1,2,9-triyl, phenanthrene-1,3,6-triyl, phenanthrene-1,3,7-triyl, phenanthrene-1,3,8-triyl, phenanthrene-1,3,9-triyl, phenanthrene-1,6,7-triyl, phenanthrene-1,6,9-triyl, phenanthrene-1,7,9-triyl, phenanthrene-1,8,9-triyl, phenanthrene-1,9,10-triyl, phenanthrene-2,3,6-triyl, phenanthrene-2,3,7-triyl, phenanthrene-2,3,9-triyl, phenanthrene-2,7,9-triyl, phenanthrene-2,9,10-triyl, phenanthrene-3,6,7-triyl, phenanthrene-3,6,9-triyl, phenanthrene-3,9,10-triyl, anthracene-1,2,5-triyl, anthracene-1,2,6-triyl, anthracene-1,2,7-triyl, anthracene-1,2,8-triyl, anthracene-1,2,9-triyl, anthracene-1,2,10-triyl, anthracene-1,3,5-triyl, anthracene-1,3,6-triyl, anthracene-1,3,7-triyl, anthracene-1,3,8-triyl, anthracene-1,3,9-triyl, anthracene-1,3,10-triyl, anthracene-1,4,5-triyl, anthracene-1,4,6-triyl, anthracene-1,4,8-triyl, anthracene-1,4,9-triyl, anthracene-1,5,9-triyl, anthracene-1,6,7-triyl, anthracene-1,6,9-triyl, anthracene-1,7,9-triyl, anthracene-1,8,9-triyl, anthracene-1,9,10-triyl, anthracene-2,3,6-triyl, anthracene-2,3,9-triyl, anthracene-2,6,9-triyl, anthracene-2,7,9-triyl, anthracene-2,7,10-triyl, and anthracene-2,9,10-triyl group; A.sup.4 denotes a phenylene group; a —CH.sub.2— group included in A.sup.3 and A.sup.4 may be substituted with an —O— or a —S— group unless neighboring each other; a —CH═ group included in A.sup.3 and A.sup.4 may be substituted with a —N═ group unless neighboring each other; a hydrogen atom included in A.sup.3 and A.sup.4 may be substituted with a fluorine atom, a chlorine atom, a —CN group, or a straight or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, or alkylcarbonyloxy group with 1 to 12 carbon atoms and further one or more of carbon atoms in these groups may be substituted with a silicon atom; Z.sup.4 and Z.sup.5 may be same or different, and denote —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —NHCO—, —N(CH.sub.3)CO—, —N(C.sub.2H.sub.5)CO—, —N(C.sub.3H.sub.7)CO—, —N(C.sub.4H.sub.9)CO—, —CONH—, —CON(CH.sub.3)—, —CON(C.sub.2H.sub.5)—, —CON(C.sub.3H.sub.7)—, —CON(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH— group, or a direct bond; L.sup.3 denotes an alkyl, alkenyl, or aralkyl with 12 carbon atoms or more, or a monovalent monocyclic or polycyclic hydrocarbon group with 12 carbon atoms or more, or a biphenyl group; the alkyl and alkenyl groups may be straight or branched; one or more hydrogen atoms included in the aralkyl and the monovalent monocyclic or polycyclic hydrocarbon groups may be substituted with a straight or branched alkyl or alkenyl group with 1 to 8 carbon atoms; a —CH.sub.2— group included in the alkyl, the alkenyl, and the monovalent monocyclic or polycyclic hydrocarbon group for L.sup.3 may be substituted with —O—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless oxygen atoms neighbor each other; and n.sup.3 denotes 0 or 1; the second monomer having a structure for producing a radical by light irradiation is at least one of: a compound represented by the following formula (4) and having a structure for producing a radical by hydrogen abstraction reaction by light irradiation, and a compound represented by the following formula (5) and having a structure for producing a radical by self-cleavage reaction by light irradiation, the formula (4) being: ##STR00041## in the formula, A.sup.5 denotes an aromatic ring; A.sup.6 denotes an aromatic ring same as or different from A.sup.5, or a straight or branched alkyl or alkenyl group with 1 to 12 carbon atoms; at least one of A.sup.5 and A.sup.6 contains -Sp.sup.3-P group; an aromatic ring included in at least one of A.sup.5 and A.sup.6 is a benzene ring or a biphenyl ring; a hydrogen atom included in A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group, a halogen atom, —CN, —NO.sub.2, —NCO, —NCS, —OCN, —SCN, —SF.sub.5, or an alkyl, alkenyl or aralkyl group with 1 to 12 carbon atoms and the alkyl and alkenyl groups may be straight or branched; two neighboring hydrogen atoms included in A.sup.5 and A.sup.6 may be substituted with a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms to form a ring structure; a hydrogen atom included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with -Sp.sup.3-P group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of A.sup.5 and A.sup.6 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, or —OCO—CH═CH— group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; P denotes a radical polymerizable group; Sp.sup.3 denotes a straight, branched or cyclic alkylene or alkyleneoxy group with 1 to 6 carbon atoms, or a direct bond; m.sup.1 denotes 1 or 2; a dotted line part connecting A.sup.5 and Y and a dotted line part connecting A.sup.6 and Y represent that a bond through Y may exist between A.sup.5 and A.sup.6; and Y denotes —CH.sub.2—, —CH.sub.2CH.sub.2—, —CH═CH—, —O—, —S—, —NH—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S— group, or a direct bond; the formula (5) being: ##STR00042## in the formula, R.sup.3 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.6-P; R.sup.4 denotes a straight or branched alkyl or alkenyl group with 1 to 4 carbon atoms or -Sp.sup.7-P; P denotes a same or different radical polymerizable group and a total number is 2 or more; Sp.sup.4 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.2 is 2 or more; Sp.sup.5 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms, or a direct bond and may be same or different in the case where m.sup.3 is 2 or more; Sp.sup.6 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; Sp.sup.7 denotes a straight, branched, or cyclic alkylene, alkyleneoxy, or alkylenecarbonyloxy group with 1 to 6 carbon atoms; L.sup.4 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.4 is 2 or more; in the case where two L.sup.4s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and two L.sup.4s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; L.sup.5 denotes —F, —OH, or a straight or branched alkyl, straight or branched alkenyl, or aralkyl group with 1 to 12 carbon atoms and may be same or different in the case where n.sup.5 is 2 or more; in the case where two L.sup.5s are bonded to two neighboring carbon atoms in an aromatic ring, a ring structure may be formed by bonding each other and the two L.sup.5s may be same or different and be a straight or branched alkylene or alkenylene group with 1 to 12 carbon atoms; one or more hydrogen atoms included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —F or —OH group; a —CH.sub.2— group included in the alkyl, the alkenyl, the alkylene, the alkenylene or the aralkyl group of L.sup.4 and L.sup.5 may be substituted with —O—, —S—, —NH—, —CO—, —COO—, —OCO—, —O—COO—, —OCH.sub.2—, —CH.sub.2O—, —SCH.sub.2—, —CH.sub.2S—, —N(CH.sub.3)—, —N(C.sub.2H.sub.5)—, —N(C.sub.3H.sub.7)—, —N(C.sub.4H.sub.9)—, —CF.sub.2O—, —OCF.sub.2—, —CF.sub.2S—, —SCF.sub.2—, —N(CF.sub.3)—, —CH.sub.2CH.sub.2—, —CF.sub.2CH.sub.2—, —CH.sub.2CF.sub.2—, —CF.sub.2CF.sub.2—, —CH═CH—, —CF═CF—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, -Sp.sup.4-P, or -Sp.sup.5-P group unless an oxygen atom, a sulfur atom, and a nitrogen atom neighbor one another; m.sup.2 denotes an integer of 1 to 3; m.sup.3 denotes an integer of 0 to 3; n.sup.4 denotes an integer of 0 to 4; n.sup.5 denotes an integer of 0 to 4; a total of m.sup.2 and n.sup.4 is an integer of 1 to 5; a total of m.sup.3 and n.sup.5 is an integer of 0 to 5; and a total of m.sup.2 and m.sup.3 is an integer of 1 to 6.
6. The liquid crystal composition according to claim 1, wherein L.sup.3 in the formula (2) includes a cholesteryl group or a biphenyl group.
7. The liquid crystal display device according to claim 3, wherein L.sup.3 in the formula (2) includes a cholesteryl group or a biphenyl group.
8. The production method for a liquid crystal display device according to claim 5, wherein L.sup.3 in the formula (2) includes a cholesteryl group or a biphenyl group.
9. A liquid crystal composition comprising: a liquid crystal material; and one or more kinds of monomers, at least one of the monomers being a compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more, wherein the compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by one of the following formulas (3-1) to (3-5): ##STR00043## in the formula, P and P are the same or different, and denote a radical polymerizable group.
10. A liquid crystal display device comprising: a pair of substrates; a liquid crystal layer sandwiched between the pair of the substrates and containing a liquid crystal material; and a polymer layer formed on at least one of the pair of the substrates and configured to control alignment of liquid crystal molecules, wherein the polymer layer is formed by polymerizing one or more kind of monomers, at least one of the monomers being a compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more, the compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by one of the following formulas (3-1) to (3-5): ##STR00044## in the formula, P and P are the same or different, and denote a radical polymerizable group.
11. A production method for a liquid crystal display device comprising: injecting a liquid crystal composition containing a liquid crystal material and one or more kind of monomers between a pair of substrates; and forming a polymer layer for controlling alignment of liquid crystal molecules on a substrate by polymerizing the monomers by radiating the liquid crystal composition with light, at least one of the monomers being a compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more, wherein the compound produced by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound produced by bonding two polymerizable groups to a cyclic aliphatic compound or aromatic compound with 6 carbon atoms or more is a compound represented by one of the following formulas (3-1) to (3-5): ##STR00045## in the formula, P and P are the same or different, and denote a radical polymerizable group.
12. The liquid crystal composition according to claim 9, wherein P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group.
13. The liquid crystal display device according to claim 10, wherein P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group.
14. The production method for a liquid crystal display device according to claim 11, wherein P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group.
15. A monomer being a compound represented by the following formulas (3-1) to (3-5): ##STR00046## in the formula, P and P are the same or different, and denote a (meth)acryloyloxy, (meth)acryloylamino, vinyl, or vinyloxy group.
Description
BRIEF DESCRIPTION OF DRAWINGS
(1)
(2)
(3)
(4)
(5)
(6)
DESCRIPTION OF EMBODIMENTS
(7) Hereinafter, the present invention will be described in more detail referring to the drawings in the following embodiments, but is not limited to these embodiments.
Embodiment 1
(8) A liquid crystal display device produced by using a liquid crystal composition in an aspect of the present invention and a liquid crystal display device produced by the production method in an aspect of the present invention exhibit excellent display properties while being used for display devices, for example, a television, a personal computer, a mobile phone, an information display, etc.
(9) Hereinafter, one example of a production method of a liquid crystal display device of Embodiment 1 will be described.
(10) As illustrated in
(11) The radical polymerizable monomer 104 produces a radical by irradiating the liquid crystal layer 105 with light and using the radical as active species, the radical polymerizable group of the radical polymerizable monomer 104 successively starts and promotes chain polymerization to be polymerized. The polymer formed by the polymerization is deposited in the form of a polymer layer (PSA layer) 107 on the alignment film 108 formed on the substrates 110 and 120 as illustrated in
(12) In the case where a common polymerization initiator (e.g. Irgacure 651 or the like) is used, products formed by cleavage by ultraviolet irradiation float as impurities in a liquid crystal and consequently lower the voltage holding ratio (VHR). In Embodiment 1, since producing a radical by itself, the radical polymerizable monomer 104 does not require such a polymerization initiator and does not produce impurities derived from the polymerization initiator and consequently keeps high voltage holding ratio (VHR). Further, since having two polymerizable groups, the radical polymerizable monomer 104 is easy to be taken in a polymer layer 107 when the polymer layer 107 is formed and hardly remains as an impurity in the liquid crystal layer and consequently does not lower the voltage holding ratio (VHR).
(13) As illustrated in
(14) In Embodiment 1, at the time of carrying out the PSA polymerization step, a polymer layer can be produced and liquid crystal molecules can be aligned vertically to the substrate face without applying voltage not lower than the threshold value to the liquid crystal layer 105 in the case where one or more kind radical polymerizable monomers are used in Embodiment 1. Further, at the time of carrying out the PSA polymerization step, a polymer is formed following the liquid crystal molecules aligned in the state that voltage not lower than the threshold value is applied to the liquid crystal layer 105 by radiating the liquid crystal layer 105 with light in the state that voltage not lower than the threshold value is applied. In this case, the polymer layer to be formed is to have a structure for defining the pre-tilt angle to the liquid crystal molecules even in the state that no voltage is applied thereafter.
(15) In Embodiment 1, use of a compound formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more can keep high voltage holding ratio (VHR).
(16) Other constituent elements of a liquid crystal display device of Embodiment 1 will be described in detail.
(17) In the liquid crystal display device of Embodiment 1, the array substrate 110, the liquid crystal layer 105 and the color filter substrate 120 are layered in this order from the back side of the liquid crystal display device to the observation side. Polarizing plates are installed in the back side of the array substrate 110 and in the observation side of the color filter substrate 120. A retardation film may be arranged for these polarizing plates and the polarizing plates may be circular polarization plates.
(18) The liquid crystal display device of Embodiment 1 may be a transmission type, a reflection type, and a transmission/reflection combined type. In the case of a transmission type or a transmission/reflection combined type, the liquid crystal display device of Embodiment 1 is further equipped with a back light unit. The back light unit is arranged in the further back side of the array substrate 110 and arranged in a manner that light is transmitted through the array substrate 110, the liquid crystal layer 105, and the color filter substrate 120 in this order. In the case of a reflection type or a transmission/reflection combined type, the array substrate 110 is equipped with a reflector for reflecting outside light. Further, in a region in which at least the reflected light is used for display, the polarizing plate of the color filter substrate 120 is required to have a circular polarization plate equipped with so-called λ/4 retardation film.
(19) The liquid crystal layer 105 is filled with a liquid crystal material having a property of aligning in a specified direction by applying a certain voltage. The alignment property of the liquid crystal molecules in the liquid crystal layer 105 is controlled based on application of voltage not lower than the threshold value.
(20) Regarding the liquid crystal display device of Embodiment 1, the liquid crystal display device (e.g. a mobile phone, a monitor, a liquid crystal TV (television), and information display) is disassembled and the monomer components existing in the polymer layer are analyzed by carrying out chemical analysis using NMR (nuclear magnetic resonance), FT-IR (Fourier transform infrared spectroscopy), MS (mass spectrometry), etc. and thus the types of the monomer components can be determined.
Embodiment 2
(21) Embodiment 2 is same as Embodiment 1, except that a monomer having a structure for producing a radical by light irradiation is used in addition to the radical polymerizable monomer used in Embodiment 1.
(22) Hereinafter, one example of a production method of a liquid crystal display device of Embodiment 2 will be described.
(23) As illustrated in
(24) The second radical polymerizable monomer 206 is a monomer having a structure for producing a radical by light irradiation and may be a compound having a structure for producing a radical by hydrogen abstraction reaction by light irradiation and a compound having a structure for producing a radical by self-cleavage reaction by light irradiation. The compound having a structure for producing a radical by hydrogen abstraction reaction by light irradiation is practically a compound represented by the above-mentioned formula (4) and more practically a compound represented by one of the above-mentioned formulas (6-1) to (6-8). The compound having a structure for producing a radical by self-cleavage reaction by light irradiation is practically a compound represented by the above-mentioned formula (5) and more practically a compound represented by the above-mentioned formula (7).
(25) Both of the first radical polymerizable monomer 204 and the second radical polymerizable monomer 206 independently produce radicals by irradiating the liquid crystal layer 205 with light and using the radicals as active species, the radical polymerizable groups of the first radical polymerizable monomer 204 and the second radical polymerizable monomer 206 successively start and promote chain polymerization to be polymerized. The polymer formed by the polymerization is deposited in the form of a polymer layer (PSA layer) 207 on the alignment film 208 formed on the substrates 210 and 220 as illustrated in
(26) As illustrated in
(27) In Embodiment 2, use of a compound formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more and use of a monomer having a structure for producing a radical by light irradiation in combination can keep high voltage holding ratio (VHR) same as in Embodiment 1. The polymer layer by which vertical alignment of liquid crystal molecules can be induced can be formed so that liquid crystal molecules can be aligned vertically to the substrate face.
Embodiment 3
(28) Embodiment 3 is same as Embodiment 1, except that a monomer having a structure for producing a radical by light irradiation is used in addition to the radical polymerizable monomer used in Embodiment 1 and the outermost faces of the array substrate and the color filter substrate are substantially not composed of an alignment film.
(29) Hereinafter, one example of a production method of a liquid crystal display device of Embodiment 3 will be described.
(30) In this Embodiment, “alignment film” means a mono-layer film or a multilayer film formed by using a polyimide, a polyamic acid, a polyamide, a polymaleimide, a polysiloxane, or a their copolymer, or a film formed by oblique vapor deposition of a silicon oxide and is a film capable of controlling alignment of liquid crystal molecules. In a common liquid crystal display device, an alignment film is formed by directly applying an alignment film material (e.g. applying a polyimide or the like) to or carrying out vapor deposition (e.g. oblique vapor deposition of silicon oxide (SiO) on a substrate face in a display region. The display region means a region for forming images which an observer recognizes and the region excludes, for example, a peripheral region of terminal parts or the like. The above-mentioned alignment film is not limited to those which are subjected to an alignment treatment and is an applied film made of an already existing alignment film material such as a polyimide or the like.
(31) As illustrated in
(32) Both of the first radical polymerizable monomer 304 and the second radical polymerizable monomer 306 produce radicals by radiating the liquid crystal layer 305 with light and using the radicals as active species, the radical polymerizable groups of the first radical polymerizable monomer 304 and the second radical polymerizable monomer 306 successively start and promote chain polymerization to be polymerized. The polymer formed by the polymerization is deposited in the form of a polymer layer (PSA layer) 307 on the substrates 310 and 320 as illustrated in
(33) As illustrated in
(34) In Embodiment 3, even in the case where no alignment film is formed, use of a compound formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more and use of a monomer having a structure for producing a radical by light irradiation in combination can keep high voltage holding ratio (VHR). The polymer layer having high alignment controllability for liquid crystal molecules can be formed so that liquid crystal molecules can be aligned vertically to the substrate face.
(35) Hereinafter, described are synthesis Examples for actually synthesizing a compound formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more.
Synthesis Example 1
(36) In Synthesis Example 1, 3-hexadecanyl-4,4′-dimethacryloxybiphenyl was synthesized as a practical example of a compound represented by the above-mentioned formula (3-1).
(37) At first, as illustrated in the following formula (8), 3.0 g of 4,4′-biphenol (compound A) was dissolved in 18 g of acetonitrile and mixed with potassium carbonate and stirred for 10 minutes. Thereafter, 0.57 g of dimethyl sulfate was added and the resulting solution was heated until the temperature became 60° C. Successively, the solution was stirred for 15 hours and filtered and pure water was dropwise added to the filtrate to precipitate crystals. The obtained crystals were recovered by filtration and dried to obtain 4,4′-dimethoxybiphenyl (compound B) at 90% yield.
(38) ##STR00009##
(39) Next, as illustrated in the following formula (9), 3 g of compound B was dissolved in 90 g of methylene chloride and cooled until the solution temperature became 0° C. After 1.87 g of aluminum chloride was added to the resulting solution and stirred for 30 minutes, the solution was heated until the solution temperature became 25° C. and stirred further for 2 hours. Thereafter, the resulting solution was cooled until the temperature became 0° C. and mixed with 24 g of pure water. Successively, the organic layer was recovered and washed with pure water 3 times and further with saturated salt water and then the solvent was removed. Thereafter, the product was refined by silica gel column chromatography using an ethyl acetate/hexane (4/96) solution as an eluent to obtain 3-hexadecanyl-4,4′-dimethoxybiphenyl (compound C) at 63% yield.
(40) ##STR00010##
(41) Next, as illustrated in the following formula (10), 3 g of compound C was dissolved in 60 g methylene chloride and mixed with 1.7 g of triethylsilane. A solution obtained by dissolving 7.5 g of trifluoroacetic acid in 15 g of methylene chloride was dropwise added to the above-mentioned resulting solution in 30 minutes. On completion of the dropwise addition, the resulting solution was stirred for 1 hour and cooled until the temperature became 10° C. After 58 g of an aqueous 5% sodium hydroxide solution was added thereto and the obtained solution mixture was separated, was washed 3 times and washed with saturated salt water and the obtained solution was separated. Thereafter, the solvent was removed therefrom to obtain 3-hexadecanyl-4,4′-dimethoxybiphenyl (compound D) at 86% yield.
(42) ##STR00011##
(43) Next, as illustrated in the following formula (11), 2.8 g of a compound D was dissolved in 56 g of acetic acid and mixed with 10.8 g of an aqueous 48% HBr solution and thereafter heated until the solution temperature became 110° C. Successively, the solution was stirred for 15 hours, cooled, and mixed with 112 g of pure water to precipitate crystals. The crystals were recovered by filtration, sufficiently washed with pure water, re-dissolved in 56 g of ethyl acetate, and separated and washed with pure water 4 times. Thereafter, the solvent was removed therefrom to obtain 3-hexadecanyl-4,4′-dihydroxybiphenyl (compound E) at 86% yield.
(44) ##STR00012##
(45) As illustrated in the following formula (12), 2.2 g of the compound E was dissolved in 22 g of tetrahydrofuran (THF) and 1.27 g of triethylamine (TEA) and 0.033 g of 4-dimethylaminopyridine (DMAP) were added to the obtained solution and stirred. After 1.90 g of methacrylic anhydride was dropwise added in 10 minutes to the obtained solution and stirred for 2 hours, 30 g of an aqueous 1% HCl solution was added and stirred further for 10 minutes. Thereafter, extraction was carried out with 55 g of toluene and the extract was washed with pure water 4 times. Thereafter, the oily component obtained by removing the solvent was refined by silica gel column chromatography using an ethyl acetate/hexane (2/98) solution as an eluent to obtain a compound F at 63% yield.
(46) ##STR00013##
(47) The analysis result of the obtained compound F by .sup.1H-NMR (400 MHz) is as follows. .sup.1H-NMR (CDCl.sub.3, ppm): δ=0.88 (t, 3H, methyl group), 1.28 (m, 26H, methylene group), 1.58 (q, 2H, methylene group), 2.06 (s, 3H, methyl group), 2.10 (s, 3H, methyl group), 2.56 (t, 2H, methylene group), 5.78 (s, 2H, vinyl group), 6.38 (s, 2H, vinyl group), 7.13 (d, 1H, benzene ring), 7.18 (d, 2H, benzene ring), 7.41 (m, 2H, benzene ring), 7.57 (d, 2H, benzene ring)
(48) According to the above-mentioned analysis result, the obtained compound F was proved to be the aimed compound, 3-hexadecanyl-4,4′-dimethacryloxybiphenyl.
Synthesis Example 2
(49) In Synthesis Example 2, 3,5-dimethacryloxybenzoic acid n-dodecane ester was synthesized as a practical example of a compound represented by the above-mentioned formula (3-2).
(50) At first, as illustrated in the following formula (13), 3.0 g of 3,5-dihydroxybenzoic acid (compound G) was dispersed in 24 g of anisole. The obtained dispersion, 8.8 g of n-dodecanol, and 0.57 g of sulfuric acid were loaded to a reactor equipped with a Dean-Stark tube and refluxed at 75° C. and 4 Torr for 8 hours. Thereafter, the reaction system was cooled and mixed with 1.2 g of triethylamine and stirred for 10 minutes. The precipitate was filtered and the residue was washed with 21 g of toluene and mixed with the filtrate and the solvent was removed. Thereafter, after an oily component was separated by adding 100 g of hexane, hexane was removed by decantation, the remaining oily component was mixed with 100 g of hexane, and the mixture was subjected to decantation further 2 times. The remaining oily component in a lower layer was vacuum-dried to obtain 5.4 g of a mixture of 3,5-dihydroxybenzoic acid n-dodecane ester (compound H) and dodecanol.
(51) ##STR00014##
(52) Next, as illustrated in the following formula (14), the mixture of the compound H and dodecanol was subjected to methacryl-esterification by the same reaction step as the above-mentioned formula (12). Thereafter, the obtained product was refined by silica gel column chromatography using an ethyl acetate/hexane (4/96) solution as an eluent to obtain a compound I at 57% yield.
(53) ##STR00015##
(54) The analysis result of the obtained compound I by .sup.1H-NMR (400 MHz) is as follows. .sup.1H-NMR (CDCl.sub.3, ppm): δ=0.89 (t, 3H, methyl group), 1.39 (m, 18H, methylene group), 1.75 (q, 2H, methylene group), 2.06 (s, 6H, methyl group), 4.31 (t, 2H, methylene group), 5.79 (s, 2H, vinyl group), 6.36 (s, 2H, vinyl group), 7.23 (s, 1H, benzene ring), 7.70 (s, 2H, benzene ring)
(55) According to the above-mentioned analysis result, the obtained compound I was proved to be the aimed compound, 3,5-dimethacryloxybenzoic acid n-dodecane ester.
Synthesis Example 3
(56) In Synthesis Example 3, 3,5-dimethacryloxybenzoic acid n-hexadecane ester was synthesized as a practical example of a compound represented by the above-mentioned formula (3-3).
(57) Synthesis Example 3 was the same as represented by the above-mentioned formulas (13) and (14), except that n-dodecanol was replaced with n-hexadecanol. In Synthesis Example 3, as illustrated in the following chemical reaction formula (15), a compound J was obtained at 43% yield from 3.0 g of the compound G by the same reaction process as the above-mentioned formulas (13) and (14).
(58) ##STR00016##
(59) The analysis result of the obtained compound J by .sup.1H-NMR (400 MHz) is as follows. .sup.1H-NMR (CDCl.sub.3, ppm): δ=0.88 (t, 3H, methyl group), 1.34 (m, 26H, methylene group), 1.75 (q, 2H, methylene group), 2.06 (s, 6H, methyl group), 4.31 (t, 2H, methylene group), 5.79 (s, 2H, vinyl group), 6.36 (s, 2H, vinyl group), 7.23 (s, 1H, benzene ring), 7.69 (s, 2H, benzene ring)
(60) According to the above-mentioned analysis result, the obtained compound J was proved to be the aimed compound, 3,5-dimethacryloxybenzoic acid n-hexadecane ester.
Synthesis Example 4
(61) In Synthesis Example 4, 3,5-dimethacryloxybenzoic acid cholesterol was synthesized as a practical example of a compound represented by the above-mentioned formula (3-4).
(62) At first, as illustrated in the following formula (16), 8.00 g of methyl 3,5-dihydroxybenzoate (compound K) was dissolved in 56.0 g of THF. After 0.650 g of pyridinium p-toluenesulfonate (PPTS) was added to the obtained solution, the solution was heated until the solution temperature became 60° C. After 17.5 g of 3,4-dihydro-2H-pyran was dropwise added in 10 minutes to the solution and stirred for 15 hours and cooled until the solution temperature became 25° C., 0.52 g of TEA was added. Thereafter, a solution obtained by dissolving 1.04 g of NaOH in 8.0 g of pure water was added to the resulting solution and stirred, and the resulting solution was subjected to extraction by adding 160 g of cyclohexane, an organic layer was recovered therefrom by liquid separation and again the solution was extracted by adding 80 g of cyclohexane to the water layer. Those organic layers were mixed and the solvent was removed therefrom by distillation after washing with pure water 3 times to obtain methyl 3,5-di(tetrahydro-2H-pyran-2-yloxy)benzoate (compound L) at 64% yield.
(63) ##STR00017##
(64) Next, as illustrated in the following formula (17), 11.0 g of the compound L was dissolved in 55.0 g of THF and heated until the solution temperature became 60° C. After 22.3 g of an aqueous 10% NaOH solution was dropwise added in 30 minutes to the obtained solution and stirred for 15 hours, the solution was cooled. THF was removed by distillation by using an evaporator and 55 g of pure water was added. Thereafter, 20 g of cyclohexane was added and stirred and resulting solution was subjected to decantation further 2 times. After that, a solution obtained by dissolving 4.6 g of an aqueous 35% HCl solution in 69 g of pure water was dropwise added to the water layer and the resulting solution was extracted with 110 g of ethyl acetate to separate and the organic layer obtained by liquid separation was washed with 88 g of pure water 2 times. Successively, the solvent was removed therefrom by distillation to obtain 3,5-di(tetrahydro-2H-pyran-2-yloxy)benzoic acid (compound M) at 53% yield.
(65) ##STR00018##
(66) Next, as illustrated in the following formula (18), 1.3 g of the compound M was dissolved in 100 g of methylene chloride. Successively, 0.30 g of DMAP, 1.13 g of TEA and 3.07 g of cholesterol were added to the solution and dissolved. A solution obtained by dissolving 2.56 g of dicyclohexylcarbodiimide (DCC) in 12.8 g of methylene chloride was dropwise added to the resulting solution over 30 minutes. After stirred for 3 hours, the resulting solution was mixed with an 139 g of an aqueous 3% NaHCO.sub.3 solution and stirred further for 10 minutes. After the precipitated solid was recovered by filtration and the resulting solution was subjected to liquid separation, the recovered methylene chloride layer was removed by distillation and the obtained residue was re-dissolved in 60 g of cyclohexane. The precipitated solid was recovered by filtration and the filtered substance was subjected to washing with pure water 3 times and thereafter the solvent was removed therefrom by distillation. After that, the product was refined by silica gel column chromatography using an ethyl acetate/hexane (3/100) solution as an eluent to obtain 3,5-di(tetrahydro-2H-pyran-2-yloxy)benzoic acid cholesterol (compound N) at 31% yield.
(67) ##STR00019##
(68) Next, as illustrated in the following formula (19), 2.5 g of the compound N was dissolved in 25 g of ethanol, 0.045 g of PPTS was added thereto, to heat until the solution temperature became 60° C. After stirred for 24 hours, the resulting solution was cooled until the temperature became 25° C. and 0.40 g of TEA was added. After the solvent was removed by distillation, acetonitrile was added thereto and the obtained crystals were recovered by filtration. The crystals were vacuum-dried to obtain 3,5-dihydroxybenzoic acid cholesterol (compound O) at 74% yield.
(69) ##STR00020##
(70) Next, as illustrated in the following formula (20), the compound O was methacryl-esterified by the same reaction step as the above-mentioned formula (12). Thereafter, the obtained product was refined by silica gel column chromatography using an ethyl acetate/cyclohexane (5/95) solution as an eluent to obtain a compound P at 41% yield.
(71) ##STR00021##
(72) The analysis result of the obtained compound P by .sup.1H-NMR (400 MHz) is as follows. .sup.1H-NMR (CDCl.sub.3, ppm): δ=0.74 (s, 3H, methyl group), 0.88 (d, 6H, methylene group), 0.97 (d, 3H, methylene group), 1.03-2.09 (m, 35H, methyl group), 2.46 (d, 2H, methylene group), 4.81 (m, 1H, methine group), 5.44 (m, 1H, methine group), 5.89 (s, 2H, vinyl group), 6.36 (s, 2H, vinyl group), 7.37 (s, 1H, benzene ring), 7.73 (s, 2H, benzene ring)
(73) According to the above-mentioned analysis result, the obtained compound P was proved to be the aimed compound, 3,5-dimethacryloxybenzoic acid cholesterol.
Synthesis Example 5
(74) In Synthesis Example 5, 3,5-dimethacryloxybenzoic acid (12-biphenyloxy)-dodecyl ester was synthesized as a practical example of a compound represented by the above-mentioned formula (3-5).
(75) At first, 12-hydroxydodecyl biphenyl ether was obtained by using 1-bromododecanol as a raw material by the same reaction step as represented by the above-mentioned formula (8). Next, as illustrated in the following formula (21), the obtained 12-hydroxydodecyl biphenyl ether and 4-phenylphenol (compound Q) were tosylated using p-toluenesulfonic acid chloride by the same reaction step as represented by the above-mentioned formula (12) to obtain 12-p-toluenesulfonyloxy-dodecyl biphenyl ether (compound R) at 51% yield. Is in the following compound R denotes toluenesulfonyl group.
(76) ##STR00022##
(77) Next, as illustrated in the following formula (22), 2.0 g of the compound M obtained according to the above-mentioned formula (17) was dissolved in 20 g of DMF and 0.75 g of TEA was added thereto. After stirred for 10 minutes, the resulting solution was mixed with the compound R obtained according to the above-mentioned formula (21) and heated until the temperature became 70° C. After stirred for 15 hours, the resulting solution was cooled until the temperature became 25° C. and 80 g of pure water was added. Thereafter, the resulting solution was subjected to extraction with 30 g of toluene and the extract was washed with 15 g of pure water 3 times. Successively, toluene was removed therefrom by distillation to obtain 3,5-di(tetrahydro-2H-pyran-2-yloxy)benzoic acid (12-biphenyloxy)-dodecyl ester (compound S) at 60% yield.
(78) ##STR00023##
(79) Next, as illustrated in the following formula (23), 2.45 g of the compound S was subjected to deprotection reaction by the same reaction step as represented by the above-mentioned formula (19) to quantitatively obtain 3,5-dihydroxybenzoic acid (12-biphenyloxy)-dodecyl ester (compound T).
(80) ##STR00024##
(81) Next, as illustrated in the following formula (24), the compound T was methacryl-esterified by the same reaction step as the above-mentioned formula (12). Thereafter, the obtained product was refined by silica gel column chromatography using an ethyl acetate/cyclohexane (3/97) solution as an eluent to obtain a compound U at 58% yield.
(82) ##STR00025##
(83) The analysis result of the obtained compound U by .sup.1H-NMR (400 MHz) is as follows. .sup.1H-NMR (CDCl.sub.3, ppm): δ=1.40 (m, 16H, methylene group), 1.78 (m, 4H, methylene group), 2.06 (s, 6H, methyl group), 3.99 (t, 2H, methylene group), 4.31 (t, 2H, methylene group), 5.79 (s, 2H, vinyl group), 6.36 (s, 2H, vinyl group), 6.98 (d, 2H, benzene ring), 7.22 (s, 1H, benzene ring), 7.29 (t, 1H, benzene ring), 7.41 (t, 2H, benzene ring), 7.51 (d, 2H, benzene ring), 7.55 (d, 2H, benzene ring), 7.69 (s, 2H, benzene ring).
(84) According to the above-mentioned analysis result, the obtained compound U was proved to be the aimed compound, 3,5-dimethacryloxybenzoic acid (12-biphenyloxy)-dodecyl ester.
Example 1
(85) Hereinafter, a liquid crystal cell of Example 1 practically produced according to Embodiment 1 will be described.
(86) In the case where the initial alignment of liquid crystal molecules is orthogonal to a substrate face, a vertical alignment film is used preferably. An alignment film material to be used for a vertical alignment film may include those obtained by introducing a side chain showing a vertical alignment property into a polyamic acid and carrying out imidization. But such an alignment film material is poor in wettability and tends to be uneven when applied to a substrate and thus causes unevenness of alignment of liquid crystal molecules. As a method for improving the wettability of an alignment film material, an alignment film formed by using an alignment film material with a horizontally aligning property was used in Example 1.
(87) At first, a pair of substrates respectively having a transparent electrode on the surface were prepared and after the substrates were washed, an alignment film material having no vertically aligning property was applied to both substrates to form an alignment film. For example, a polyimide alignment film material showing a horizontally aligning property was used as the above-mentioned alignment film material. Use of such an alignment film material made it possible to form a uniform alignment film without coating unevenness. After the alignment film formation, the alignment film was pre-baked at 80° C. for 5 minutes and successively post-baked at 200° C. for 60 minutes.
(88) Thereafter, a sealing material was applied to one substrate and then a liquid crystal composition containing a liquid crystal material having negative anisotropy of dielectric constant and a radical polymerizable monomer was dropped thereon, and subsequently, beads were sprayed as spacers to a counter substrate and the substrates were stuck to each other.
(89) The liquid crystal cell produced in Example 1 was the following Sample A. For Sample A, the compound represented by the following formula (25) was added as a radical polymerizable monomer in an amount of 0.3 weight % in the entire liquid crystal composition. The compound represented by the following formula (25) was a compound F obtained in the above-mentioned Synthesis Example 1.
(90) ##STR00026##
(91) The liquid crystal cell produced in Comparative Example 1 was the following Sample B. For Sample B, a compound represented by the following formula (26) was added as a radical polymerizable monomer in an amount of 0.3 weight % in the entire liquid crystal composition.
(92) ##STR00027##
(93) In the state that no voltage was applied, Samples A and B were radiated with non-polarized ultraviolet rays (2.57 mW/cm.sup.2) from a normal direction to the substrates for 30 minutes to polymerize the radical polymerizable monomers and thus liquid crystal cells were completed. A black light FHF-32BLB (wavelength region: 300 to 370 nm) manufactured by TOSHIBA Lighting & Technology Corporation was used as a light source for the non-polarized ultraviolet rays.
(94) Regarding the completed respective liquid crystal cells, the alignment property of liquid crystal molecules was observed and initial voltage holding ratio (VHR) and voltage holding ratio (VHR) after an aging test were measured for the respective liquid crystal cells. The aging test was carried out by radiating each liquid crystal cell with backlight unit of a cold cathode fluorescent lamp for 1000 hours from the normal direction to the substrates.
(95) The voltage holding ratio (VHR) was measured by using a 6254 model liquid crystal physical property measurement system manufactured by TOYO Corporation. After each liquid crystal cell was put in an oven at 70° C. and pulsed voltage was applied, potential between electrodes was measured for 16.6 ms open period (period for applying no voltage).
(96) The following Table 1 represents the measurement results of the alignment property of liquid crystal molecules, the initial voltage holding ratio (initial VHR), and voltage holding ratio (VHR) after the aging test for Samples A and B.
(97) TABLE-US-00001 TABLE 1 Concentration of VHR monomer in entire Initial (%) after liquid crystal Alignment VHR aging composition property (%) test Example 1 Sam- Formula (25): Vertical 99.2 98.8 ple A 0.3(weight %) alignment Compar- Sam- Formula (26): Horizontal 99.1 98.6 ative ple B 0.3(weight %) alignment Example 1
(98) In Sample A, an example in an aspect of the present invention, the liquid crystal molecules were aligned vertically to the substrate face. The initial voltage holding ratio (VHR) was as high as 99% or higher and voltage holding ratio (VHR) was scarcely decreased even after the aging test. On the other hand, in Sample B, Comparative Example, the initial voltage holding ratio (initial VHR) and the voltage holding ratio (VHR) after the aging test were both high but the liquid crystal molecules were not aligned vertically to the substrate face.
(99) Based on investigations on the above-mentioned results, it is supposed that since the compound of Sample A represented by the formula (25) has a hydrocarbon group with 12 carbon atoms or more, liquid crystal molecules are aligned by strong intermolecular interaction with the hydrocarbon group and aligned vertically to the substrate face.
(100) On the other hand, since the compound of Sample B represented by the formula (26) does not have the hydrocarbon group included in the compound represented by the formula (25) has, intermolecular interaction with liquid crystal molecules is weak and the liquid crystal molecules cannot be aligned vertically to the substrate face.
(101) As described above, even in the case where a horizontal alignment film was used, use of a compound formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more and represented by the above-mentioned formula (25) could align liquid crystal molecules vertically to the substrate face by strong intermolecular interaction with the liquid crystal molecules. Further, with no need of a polymerization initiator, a polymer layer capable of controlling the alignment of liquid crystal molecules could be formed. Still further, it was made possible to keep a high voltage holding ratio and to obtain a highly reliable liquid crystal display device.
Example 2
(102) Hereinafter, a liquid crystal cell of Example 2 practically produced according to Embodiment 2 will be described. The production method for a liquid crystal cell employed in Example 2 was the same as that employed in Example 1, except that a vertically aligned film was formed using an alignment film material with a low imidization ratio and the time for light irradiation to polymerize the radical polymerizable monomer was changed to be 20 minutes.
(103) As a method for improving the wettability of the alignment film material, a polyimide alignment film material with imidization ratio of 50% or lower for polyamic acid was used as the alignment film material for the vertical alignment film in Example 2. Use of such an alignment film material made it possible to form a uniform alignment film without coating unevenness.
(104) Liquid crystal cells produced in Example 2 were the following Samples C to F. As a radical polymerizable monomer, a compound represented by the following formula (27) was added in an amount of 1.0 weight % for Sample C: a compound represented by the following formula (28) was added in an amount of 1.0 weight % for Sample D: a compound represented by the following formula (29) was added in an amount of 1.0 weight % for Sample E: and a compound represented by the following formula (30) was added in an amount of 1.0 weight % for Sample F in the entire liquid crystal compositions, respectively. The compound represented by the following formula (27) was the compound I obtained in the above-mentioned Synthesis Example 2: the compound represented by the following formula (28) was the compound J obtained in the above-mentioned Synthesis Example 3: the compound represented by the following formula (29) was the compound P obtained in the above-mentioned Synthesis Example 4: and the compound represented by the following formula (30) was the compound U obtained in the above-mentioned Synthesis Example 5.
(105) ##STR00028##
(106) Further, for Samples C to F, a compound represented by the following formula (33) was added as a monomer having a structure for producing a radical by light irradiation in an amount of 0.05 weight % in the entire liquid crystal composition. The compound represented by the following formula (33) was a compound having a structure for producing a radical by hydrogen abstraction reaction by light irradiation.
(107) ##STR00029##
(108) Liquid crystal cells produced in Comparative Example 2 were the following Samples G to I. In Sample G, no radical polymerizable monomer was added to the liquid crystal composition. A compound (dodecyl methacrylate) represented by the following formula (31) was added in an amount of 1.0 weight % for Sample H: and a compound represented by the following formula (32) was added in an amount of 1.0 weight % for Sample I in the entire liquid crystal compositions, respectively. Further, for Samples H and I, a compound represented by the above-mentioned formula (33) was added in an amount of 0.05 weight % in the entire liquid crystal composition.
(109) ##STR00030##
(110) Regarding the completed respective liquid crystal cells, the alignment property of liquid crystal molecules was observed and initial voltage holding ratio (VHR) and voltage holding ratio (VHR) after an aging test were measured for the respective liquid crystal cells. The measurement method for voltage holding ratio (VHR) and the method for aging test were same as those in Example 1.
(111) The following Table 2 represents the measurement results of the alignment property of liquid crystal molecules, the initial voltage holding ratio (initial VHR), and voltage holding ratio (VHR) after the aging test for Samples C to I.
(112) TABLE-US-00002 TABLE 2 Concentration of VHR monomer in entire Initial (%) after liquid crystal Alignment VHR aging composition property (%) test Exam- Sam- Formula (27): 1.0 Vertical 99.1 98.8 ple 2 ple C (weight %) + alignment Formula (33): 0.05 (weight %) Sam- Formula (28): 1.0 Vertical 99.2 99.0 ple D (weight %) + alignment Formula (33): 0.05 (weight %) Sam- Formula (29): 1.0 Vertical 99.1 98.9 ple E (weight %) + alignment Formula (33): 0.05 (weight %) Sam- Formula (30): 1.0 Vertical 99.2 98.8 ple F (weight %) + alignment Formula (33): 0.05 (weight %) Compar- Sam- No monomer Horizontal 98.1 94.0 ative ple G addition (no alignment Exam- polymer layer) ple 2 Sam- Formula (31): 1.0 Vertical 98.0 90.5 ple H (weight %) + alignment Formula (33): 0.05 (weight %) Sam- Formula (32): 1.0 Horizontal 99.0 98.7 ple I (weight %) + alignment Formula (33): 0.05 (weight %)
(113) In Samples C to F, Examples in an aspect of the present invention, the liquid crystal molecules were aligned vertically to the substrate face in all Samples. In all of Samples C to F, the initial voltage holding ratio (initial VHR) was as high as 99% or higher and the voltage holding ratio (VHR) after the aging test was scarcely lowered.
(114) Regarding Samples G to I, Comparative Examples, in Sample G and H, the initial voltage holding ratio (initial VHR) was about 98%, and slightly low, and the voltage holding ratio (VHR) after the aging test was so significantly lowered. In Sample I, the initial voltage holding ratio (initial VHR) was as high as 99% and the voltage holding ratio (VHR) after the aging test was scarcely lowered, but the liquid crystal molecules were not aligned vertically to the substrate face.
(115) The above-mentioned results were comprehensively concluded as follows. Since no radical polymerizable monomer was added in Sample G, no polymer layer (PSA layer) was formed on the alignment film. Therefore, it was supposed that the carboxylic acid in the polyamic acid of the alignment film absorbed light from backlight unit and as a result, deterioration was promoted to result in decrease of the voltage holding ratio (VHR) after the aging test.
(116) Since the compound represented by the above-mentioned formula (31) used for Sample H had one polymerizable group, the polymerization speed was so slow and the polymer was so hard to be taken in the polymer layer so that the radical generated in the polymerizable group at a polymerization terminal might remain in the liquid crystal layer and accordingly, it was supposed that the initial voltage holding ratio (initial VHR) was rather slightly lowered.
(117) Since the compound represented by the above-mentioned formula (32) used for Sample I had two polymerizable groups, the reaction speed was high and the polymer layer was formed on the alignment film within a short time so that it was supposed that the initial voltage holding ratio (initial VHR) was high. Further, it was supposed that the voltage holding ratio (VHR) after the aging test was not lowered owing to the formation of the polymer layer. However, since the compound represented by the formula (32) has the hydrocarbon group with carbon atoms as low as 8, it is supposed that intermolecular interaction with liquid crystal molecules is weak and the liquid crystal molecules cannot sufficiently be aligned vertically to the substrate face.
(118) As described above, even in the case where a vertical alignment film formed from the alignment film material with imidization ratio of 50% or lower was used, use of the compounds formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more and represented by the above-mentioned formulas (27) to (30) made it possible to form a polymer layer capable of controlling the alignment of the liquid crystal molecules. Further, use of a monomer represented by the above-mentioned formula (33) and having a structure for producing a radical by light irradiation in combination therewith made it possible to form the polymer layer with high alignment controllability for the liquid crystal molecules and to vertically align the liquid crystal molecules to the substrate face. Still further, it was made possible to keep a high voltage holding ratio and to obtain a highly reliable liquid crystal display device.
Example 3
(119) Hereinafter, a liquid crystal cell of Example 3 practically produced according to Embodiment 3 will be described. The production method for a liquid crystal cell employed in Example 3 was same as that employed in Example 1, except that the method did not have a step for forming an alignment film on the surface of a substrate of the liquid crystal cell and that the time for light irradiation to polymerize the radical polymerizable monomer was changed to be 20 minutes.
(120) Liquid crystal cells produced in Example 3 were the following Samples J to M. For Samples J to M, compounds represented by the above-mentioned formulas (27) to (30) were added as a radical polymerizable monomer in an amount of 1.0 weight % in the entire liquid crystal compositions, respectively, as same in Example 2. Further, for Samples J to M, a compound represented by the following formula (34) was added as a monomer having a structure for producing a radical by light irradiation in an amount of 0.05 weight % in the entire liquid crystal composition. The compound represented by the following formula (34) was a compound having a structure for producing a radical by self-cleavage reaction by light irradiation.
(121) ##STR00031##
(122) Liquid crystal cells produced in Comparative Example 3 were the following Samples N to P. In Sample N, no radical polymerizable monomer was added to the liquid crystal composition. A compound represented by the above-mentioned formula (31) was added in an amount of 1.0 weight % for Sample O: and a compound represented by the above-mentioned formula (32) was added in an amount of 1.0 weight % for Sample P in the entire liquid crystal compositions, respectively. Further, for Samples O and P, a compound represented by the above-mentioned formula (34) was added in an amount of 0.05 weight % in the entire liquid crystal composition.
(123) Regarding the completed respective liquid crystal cells, the alignment property of liquid crystal molecules was observed and initial voltage holding ratio (VHR) and voltage holding ratio (VHR) after an aging test were measured for the respective liquid crystal cells. The measurement method for voltage holding ratio (VHR) and the method for aging test were same as those in Example 1.
(124) The following Table 3 represents the measurement results of the alignment property of liquid crystal molecules, the initial voltage holding ratio (initial VHR), and voltage holding ratio (VHR) after the aging test for Samples J to P.
(125) TABLE-US-00003 TABLE 3 Concentration of VHR monomer in entire Initial (%) after liquid crystal Alignment VHR aging composition property (%) test Exam- Sam- Formula (27): 1.0 Vertical 99.4 99.5 ple 3 ple J (weight %) + alignment Formula (34): 0.05 (weight %) Sam- Formula (28): 1.0 Vertical 99.4 99.5 ple K (weight %) + alignment Formula (34): 0.05 (weight %) Sam- Formula (29): 1.0 Vertical 99.5 99.5 ple L (weight %) + alignment Formula (34): 0.05 (weight %) Sam- Formula (30): 1.0 Vertical 99.5 99.5 ple M (weight %) + alignment Formula (34): 0.05 (weight %) Compar- Sam- No monomer Horizontal 99.4 97.2 ative ple N addition (no alignment Exam- polymer layer) ple 3 Sam- Formula (31): 1.0 Vertical 98.5 92.3 ple O (weight %) + alignment Formula (34): 0.05 (weight %) Sam- Formula (32): 1.0 Horizontal 99.5 99.4 ple P (weight %) + alignment Formula (34): 0.05 (weight %)
(126) In Samples J to M, Examples in an aspect of the present invention, the liquid crystal molecules were aligned vertically to the substrate face in all Samples. In all of Samples J to M, the initial voltage holding ratio (initial VHR) was as high as 99% or higher and the voltage holding ratio (VHR) after the aging test was scarcely lowered.
(127) Regarding Samples N to P, Comparative Example, in Sample N, the liquid crystal molecules were not vertically aligned to the substrate face and although the initial voltage holding ratio (initial VHR) was high, the voltage holding ratio (VHR) after the aging test was lowered to 97% level. In Sample O, although the liquid crystal molecules were vertically aligned to the substrate face, the initial voltage holding ratio (initial VHR) was slightly low and the voltage holding ratio (VHR) after the aging test was lowered to 92% level. In Sample P, both of the initial voltage holding ratio (VHR) and the voltage holding ratio (VHR) after the aging test showed high values but the liquid crystal molecules were not aligned vertically to the substrate face.
(128) The above-mentioned results were comprehensively concluded as follows. In Sample N, no polymer layer was formed so that the liquid crystal molecules could not be aligned vertically to the substrate face. Since having only one polymerizable group, the compound represented by the above-mentioned formula (31) used for Sample O remained in the liquid crystal layer and thus it was supposed that the voltage holding ratio (VHR) after the aging test was considerably lowered. The compound represented by the formula (32) used for Sample P had the hydrocarbon group with small carbon atoms and it was supposed that intermolecular interaction with liquid crystal molecules was weak and the liquid crystal molecules could not sufficiently be aligned vertically to the substrate face.
(129) As described above, even in the case where no alignment film was formed, use of compounds represented by the above-mentioned formulas (27) to (30) and formed by further bonding a hydrocarbon group with 12 carbon atoms or more to a compound formed by bonding two polymerizable groups to a cyclic aliphatic compound or an aromatic compound with 6 carbon atoms or more and use of a monomer represented by the above-mentioned formula (34) and having a structure for producing a radical by light irradiation in combination made it possible to form a polymer layer with high alignment controllability for liquid crystal molecules and to align liquid crystal molecules vertically to the substrate face. Still further, in the same manner as that in Example 2, it was made possible to keep a high voltage holding ratio and to obtain a highly reliable liquid crystal display device.
(130) TABLE-US-00004 REFERENCE SIGNS LIST 103, 203, 303 Sealing material 104, 204, 304 (First) radical polymerizable monomer 105, 205, 305 Liquid crystal layer 206, 306 (Second) radical polymerizable monomer 107, 207, 307 Polymer layer (PSA layer) 108, 208 Alignment film 110, 210, 310 Array substrate 120, 220, 320 Color filter substrate