WO2015080218A1 - 重合性化合物、組成物、重合体、光学異方体、液晶表示素子及び有機el素子 - Google Patents
重合性化合物、組成物、重合体、光学異方体、液晶表示素子及び有機el素子 Download PDFInfo
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- WO2015080218A1 WO2015080218A1 PCT/JP2014/081441 JP2014081441W WO2015080218A1 WO 2015080218 A1 WO2015080218 A1 WO 2015080218A1 JP 2014081441 W JP2014081441 W JP 2014081441W WO 2015080218 A1 WO2015080218 A1 WO 2015080218A1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/24—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/02—Liquid crystal materials characterised by optical, electrical or physical properties of the components, in general
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3441—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having nitrogen as hetero atom
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Definitions
- the present invention relates to a polymerizable compound, a composition, a polymer, an optical anisotropic body, a liquid crystal display element, and an organic EL element.
- Optical anisotropic bodies such as retardation films and polarizing plates used in liquid crystal displays are solutions that contain a polymerizable liquid crystal material on a base material that has been subjected to a rubbing treatment or a photo-alignment film that has been photo-aligned. Can be produced by applying UV light and drying the solvent, followed by polymerization with ultraviolet light or heat.
- the retardation film in order to improve the viewing angle of the liquid crystal display, it is required to reduce or reverse the wavelength dispersion of the birefringence ( ⁇ n). In order to realize this characteristic, reverse dispersion type polymerizable liquid crystal compounds have been developed (for example, Patent Document 1).
- the wavelength dispersion of the birefringence index is reversed, or the polymerizable liquid crystal compound constituting the retardation film is a reverse dispersion type.
- the present invention has been made in view of the above circumstances, and a polymerizable compound suitable as an optically anisotropic material having excellent optical properties, a composition containing the polymerizable compound, and the polymerizable compound are polymerized. It is an object of the present invention to provide an obtained polymer, an optical anisotropic body composed of the polymer, and a liquid crystal display device including the optical anisotropic body.
- the first aspect of the present invention is the following polymerizable compound.
- Formula (1-0) is the following polymerizable compound.
- P represents a polymerizable functional group
- Sp represents a spacer group or a single bond
- a 1 , A 2 , A 3 , A 4 each independently represents a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group
- X 1 , X 2 , X 3 and X 4 each independently represent a divalent linking group or a single bond
- R 1 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group or “* -Sp—P” (* represents binding to A 4 or A 3 )
- m and n each independently represents an integer of 0 to 4 (where m + n is an integer of 2 or more)
- Z represents a naphthalene ring together with C—C ⁇ C—C in the formula, and two hydrogen atoms bonded to the naphthalene ring are each substituted with a group containing X 2 and a group containing X 3 in the formula.
- T 1 and T 2 are each independently —S—, —O—, —NR 2 —, —CH 2 —, —NH—, —C ( ⁇ O) —, —S ( ⁇ O) — or —C.
- S)- R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group or a hydroxyl group
- R 3 and R 4 each independently represent a monovalent substituent, or form a ring via Y connecting R 3 and R 4 .
- Y represents 2 to 4 atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16, and forms a 5- to 7-membered ring together with R 3 —C—R 4 in the formula.
- a monovalent substituent may be bonded to the hydrogen atom bonded to the 5- to 7-membered ring.
- T 1 and R 3 , and T 2 and R 4 are the same, and the case where T 1 and R 4 , and T 2 and R 3 are the same are excluded.
- the second aspect of the present invention is a composition containing the polymerizable compound of the first aspect.
- the third aspect of the present invention is a polymer obtained by polymerizing the composition of the second aspect.
- the fourth aspect of the present invention is an optical anisotropic body using the polymer of the third aspect.
- a fifth aspect of the present invention is a liquid crystal display element using the optical anisotropic body of the fourth aspect.
- the sixth aspect of the present invention is an organic EL element using the optical anisotropic body of the fourth aspect.
- an optical anisotropic body excellent in optical characteristics can be produced.
- a liquid crystal display element with an improved viewing angle can be manufactured.
- the polymerizable compound of the first embodiment of the present invention is a compound represented by the following general formula (1-0).
- P represents a polymerizable functional group
- Sp represents a spacer group or a single bond
- a 1 , A 2 , A 3 , A 4 each independently represents a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group
- X 1 , X 2 , X 3 and X 4 each independently represent a divalent linking group or a single bond
- R 1 represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group or “* -Sp—P” (* represents binding to A 4 or A 3 )
- m and n each independently represents an integer of 0 to 4 (where m + n is an integer of 2 or more)
- Z represents a naphthalene ring together with C—C ⁇ C—C in the formula, and two hydrogen atoms bonded to the naphthalene ring are each substituted with a group containing X 2 and a group containing X 3 in the formula.
- T 1 and T 2 are each independently —S—, —O—, —NR 2 —, —CH 2 —, —NH—, —C ( ⁇ O) —, —S ( ⁇ O) — or —C.
- S)- R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group or a hydroxyl group
- R 3 and R 4 each independently represent a monovalent substituent, or form a ring via Y connecting R 3 and R 4 .
- Y represents 2 to 4 atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16, and forms a 5- to 7-membered ring together with R 3 —C—R 4 in the formula.
- a monovalent substituent may be bonded to the hydrogen atom bonded to the 5- to 7-membered ring.
- T 1 and R 3 , and T 2 and R 4 are the same, and the case where T 1 and R 4 , and T 2 and R 3 are the same are excluded.
- the compound represented by the general formula (1-0) preferably has liquid crystallinity before polymerization. That is, the compound represented by the general formula (1-0) is preferably a polymerizable liquid crystal compound.
- P> As the polymerizable functional group represented by P in the general formula (1-0), groups used in conventional polymerizable liquid crystal compounds can be applied without limitation, and examples thereof include vinyl groups, p-stilbene groups, acrylic groups.
- Suitable polymerizable functional group P includes a substituent selected from the group consisting of substituents represented by the following general formula (II-c), general formula (II-d) and general formula (II-e). .
- R 21 , R 22 , R 23 , R 32 , R 33 , R 41 , R 42 and R 43 are: Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1.
- R 31 in the general formula (II-d) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms.
- the left end of the polymerizable functional group represented by the above general formula is bonded to Sp in the general formula (1-0).
- the alkyl group is preferably a linear or branched alkyl group, and more preferably a linear alkyl group.
- polymerizable functional groups represented by the above general formula from the viewpoint of enhancing the polymerizability and the storage stability, selected from the group consisting of groups represented by the general formula (II-c) and general formula (II-d) And a group selected from the group consisting of groups represented by formula (II-d) is more preferable.
- Examples of the polymerizable functional group represented by the general formula (II-c), general formula (II-d), or general formula (II-e) include the following reactive functional groups (P-1) to (P- 8). Of these reactive functional groups, the following (P-1) or (P-2) is preferred, and the following (P-1) is more preferred from the viewpoint of enhancing the polymerizability and storage stability.
- the right ends of the polymerizable functional groups represented by the following (P-1) to (P-8) are bonded to Sp in the general formula (1).
- ⁇ Sp> Sp in the general formula (1-0) represents a spacer group or a single bond.
- the spacer group is a divalent linking group capable of linking the polymerizable functional group P and A 1 or A 2, and is a compound represented by the general formula (1-0) (compound (1- A linking group that does not impair the liquid crystallinity of 0) is sometimes preferred.
- Suitable Sp includes, for example, a linear alkylene group having 1 to 20 carbon atoms or a single bond. Independently of each two or more CH 2 groups not one CH 2 group or adjacent existing in the alkylene group each other, between an oxygen atom, together sulfur atom, and to and from an oxygen atom and a sulfur atom In a form that is not directly bonded, —O—, —S—, —NH—, —N (CH 3 ) —, —CO—, —COO—, —OCO—, —OCOO—, —SCO—, —COS—, It may be replaced by —CH ⁇ CH— or —C ⁇ C—.
- the number of carbon atoms of the alkylene group is preferably 2 to 10, more preferably 3 to 8, and further preferably 3 to 6, from the viewpoint of improving liquid crystallinity.
- cyclic groups A 1 , A 2 , A 3 and A 4 each independently represent a divalent alicyclic hydrocarbon group or an aromatic hydrocarbon group.
- the cyclic group may be an aromatic heterocyclic group.
- cyclic group examples include 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group, pyridine-2,5-diyl group , Pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7- Diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a-
- One or more hydrogen atoms include F, Cl, CF 3 , OCF 3 , a cyano group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms, An alkanoyloxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms
- the cyclic groups A 1 , A 2 , A 3 and A 4 in the general formula (1-0) are preferably each independently the above-mentioned 1,4-phenylene group or 1,4-cyclohexylene group. When these cyclic groups are used, it becomes easy to improve the liquid crystallinity of the polymerizable compound of the present embodiment and improve the orientation of the polymer.
- ⁇ Linking group or a single bond X 1, X 2, X 3, X 4> X 1 , X 2 , X 3 and X 4 in the general formula (1-0) each independently represent a divalent linking group or a single bond.
- the divalent linking group include —CH 2 CH 2 —, —CH ⁇ CH—, —C ⁇ C—, —CH ⁇ CHCOO—, —OCO—CH ⁇ CH—, — (CH 2 ) u.
- u represents an integer of 0 to 2, and when u is 0, — (CH 2 ) u —COO— and —COO— (CH 2 ) u — represent —COO—, (CH 2 ) u -OCO- and -OCO- (CH 2 ) u- represent -OCO-.
- m and n each independently represents an integer of 0 to 4, and m + n is an integer of 2 or more.
- m and n are each independently preferably 0 to 3, more preferably 0 to 2, and even more preferably 1 or 2. Further, m and n are preferably the same integer.
- R 1 > The terminal group R 1 in the general formula (1-0) represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or “* -Sp—P”.
- “*” represents binding to A 4 when n is an integer of 1 or more, and binding to A 3 when n is 0.
- Sp and the polymerizable functional group P of “* -Sp-P” are the same as described above.
- they may be the same or different and are preferably the same.
- numerator they may be the same or different and it is preferable that they are the same.
- the alkyl group may be a linear, branched, or cyclic alkyl group, preferably a linear or branched alkyl group, and more preferably a linear alkyl group. preferable.
- the number of carbon atoms of the alkyl group is more preferably 2 to 10, more preferably 3 to 8, and further preferably 3 to 6.
- the alkyl group constituting the alkoxy group can be exemplified by the same group as the alkyl group.
- the number of carbon atoms of the alkyl group constituting the alkoxy group is preferably 1-8, more preferably 1-6, and still more preferably 1-3.
- the terminal group R 1 is “* -Sp— P ”is preferred.
- two Sp present in the molecule may be the same or different, and preferably the same, and two P present in the molecule may be the same or different. Often the same.
- Z represents a naphthalene ring together with C—C ⁇ C—C in the formula.
- the hydrogen atoms bonded to the naphthalene ring two hydrogen atoms are each substituted with a group containing X 2 and a group containing X 3 in the formula.
- the polymerizable compound represented by the general formula (1-0) include polymerizable compounds represented by the following general formulas (1-1), (1-2), and (1-3). .
- P, Sp, A 1 , A 2 , A 3 , A 4 , X 1 , X 2 , X 3 , X 4 , R 1 , m, n, T 1 , T 2 , R 2 , R 3 , and R 4 are P, Sp, A 1 , A 2 , A 3 , A 4 , X 1 , X 2 , X 3 , in the formula (1-0), X 4 is the same as R 1 , m, n, T 1 , T 2 , R 2 , R 3 , and R 4 . ]
- R 2 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group, a nitro group, or a hydroxyl group.
- T 1 and T 2 may be the same or different.
- the two R 2 may be the same or different from each other.
- T 1 is -O -, - NR 2 - or is preferably -S-, -NR 2 - or more preferably from -S-, and further preferably -S-.
- T 2 are -O -, - NR 2 - or is preferably -S-, -NR 2 - or more preferably from -S-, and further preferably -S-.
- R 2 is an alkyl group or an alkoxy group
- examples of the alkyl group and the alkyl group constituting the alkoxy group of R 2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, sec- Examples thereof include a butyl group, a tert-butyl group, a pentyl group, and a hexyl group.
- the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 or 2, and still more preferably 1.
- R 2 is a halogen atom, it is preferably a fluorine atom or a chlorine atom.
- T 1 and T 2 are represented by the following general formulas (2-1) to (2-5).
- R 3 and R 4 each independently represent a monovalent substituent, or form a ring via Y connecting R 3 and R 4 .
- Examples of monovalent substituents for R 3 and R 4 are independently an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, an alkynyl group, an aryl group, and a heterocyclic ring.
- cyano group carboxyl group, hydroxyl group, nitro group, halogen atom, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, Amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocycle Thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, carb
- Preferred monovalent substituents for R 3 and R 4 are preferably monovalent organic groups containing at least one carbon atom, and specifically include, for example, the aforementioned alkyl groups, alkenyl groups, and aryl groups.
- An amino group having a substituent containing an atom is exemplified. Further, it may be a halogen atom or a hydroxy group.
- a cyano group, an alkyl carboxylate (the alkyl group has 1 to 3 carbon atoms, for example), an alkyl group, and an alkoxy group are more preferable.
- R 3 and R 4 More preferably, at least one is a cyano group, or R 3 or R 4 is an alkyl carboxylate.
- R 3 and R 4 may be a divalent group excluding one hydrogen atom to form a ring in which the divalent groups are bonded to each other. This ring is formed without Y in the general formula (1-0).
- alkyl group examples include linear, branched substituted or unsubstituted alkyl groups having 1 to 30 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl group, and a 2-ethylhexyl group.
- cycloalkyl group include substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms.
- Specific examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group.
- Examples of the bicycloalkyl group include substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms.
- Examples of the unsubstituted bicycloalkyl group include a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms.
- Specific examples include a bicyclo [1,2,2] heptan-2-yl group and a bicyclo [2,2,2] octan-3-yl group.
- Examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms. Specific examples include a vinyl group and an allyl group. Examples of the cycloalkenyl group include substituted or unsubstituted cycloalkenyl groups having 3 to 30 carbon atoms. Examples of the unsubstituted cycloalkenyl group include a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Specific examples include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl groups.
- Examples of the bicycloalkenyl group include substituted or unsubstituted bicycloalkenyl groups having 5 to 30 carbon atoms.
- Examples of the unsubstituted bicycloalkenyl group include a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. Specific examples include a bicyclo [2,2,1] hept-2-en-1-yl group and a bicyclo [2,2,2] oct-2-en-4-yl group.
- alkynyl group examples include substituted or unsubstituted alkynyl groups having 2 to 30 carbon atoms. Specific examples include an ethynyl group and a propargyl group.
- aryl group examples include substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. Specific examples include a phenyl group, a p-tolyl group, and a naphthyl group.
- heterocyclic group examples include monovalent groups in which one hydrogen atom is removed from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound.
- it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.
- Specific examples include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.
- Examples of the alkoxy group include substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms. Specific examples include a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group, an n-octyloxy group, and a 2-methoxyethoxy group.
- Examples of the aryloxy group include substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms. Specific examples include a phenoxy group, a 2-methylphenoxy group, a 4-tert-butylphenoxy group, a 3-nitrophenoxy group, and a 2-tetradecanoylaminophenoxy group.
- Examples of the silyloxy group include silyloxy groups having 3 to 20 carbon atoms. Specific examples include a trimethylsilyloxy group and a tert-butyldimethylsilyloxy group.
- heterocyclic oxy group examples include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms. Specific examples include a 1-phenyltetrazol-5-oxy group and a 2-tetrahydropyranyloxy group.
- acyloxy group examples include a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Specific examples include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, and p-methoxyphenylcarbonyloxy group.
- carbamoyloxy group examples include substituted or unsubstituted carbamoyloxy groups having 1 to 30 carbon atoms.
- alkoxycarbonyloxy group examples include substituted or unsubstituted alkoxycarbonyloxy groups having 2 to 30 carbon atoms. Specific examples include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.
- aryloxycarbonyloxy group examples include substituted or unsubstituted aryloxycarbonyloxy groups having 7 to 30 carbon atoms. Specific examples include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyloxy group.
- amino group examples include an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted anilino group having 6 to 30 carbon atoms.
- Specific examples include an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, and a diphenylamino group.
- acylamino group examples include a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Specific examples include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, and benzoylamino group.
- Examples of the aminocarbonylamino group include substituted or unsubstituted aminocarbonylamino groups having 1 to 30 carbon atoms. Specific examples include a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, and a morpholinocarbonylamino group. Examples of the alkoxycarbonylamino group include substituted or unsubstituted alkoxycarbonylamino groups having 2 to 30 carbon atoms.
- Specific examples include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.
- Examples of the aryloxycarbonylamino group include substituted or unsubstituted aryloxycarbonylamino groups having 7 to 30 carbon atoms. Specific examples include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, and an mn-octyloxyphenoxycarbonylamino group.
- Examples of the sulfamoylamino group include substituted or unsubstituted sulfamoylamino groups having 0 to 30 carbon atoms. Specific examples include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.
- alkyl or arylsulfonylamino group examples include a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms.
- Specific examples include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group.
- alkylthio group examples include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.
- arylthio group examples include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms. Specific examples include a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.
- heterocyclic thio group examples include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms. Specific examples include 2-benzothiazolylthio group and 1-phenyltetrazol-5-ylthio group.
- sulfamoyl group examples include substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms. Specifically, for example, N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa And a moyl group and an N- (N′-phenylcarbamoyl) sulfamoyl group.
- alkyl or arylsulfinyl group examples include a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms.
- Specific examples include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.
- alkyl or arylsulfonyl group examples include a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, and a p-methylphenylsulfonyl group.
- acyl group examples include a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms.
- Specific examples include an acetyl group and a pivaloylbenzoyl group.
- Examples of the aryloxycarbonyl group include substituted or unsubstituted aryloxycarbonyl groups having 7 to 30 carbon atoms. Specific examples include a phenoxycarbonyl group, an o-chlorophenoxycarbonyl group, an m-nitrophenoxycarbonyl group, and a p-tert-butylphenoxycarbonyl group.
- Examples of the alkoxycarbonyl group include substituted or unsubstituted alkoxycarbonyl groups having 2 to 30 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.
- Examples of the carbamoyl group include substituted or unsubstituted carbamoyl groups having 1 to 30 carbon atoms. Specific examples include a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, and an N- (methylsulfonyl) carbamoyl group.
- Examples of the aryl or heterocyclic azo group include a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms and a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms. Specific examples include a phenylazo group, a p-chlorophenylazo group, and a 5-ethylthio-1,3,4-thiadiazol-2-ylazo group.
- Examples of the imide group include an N-succinimide group and an N-phthalimide group.
- Examples of the phosphino group include substituted or unsubstituted phosphino groups having 2 to 30 carbon atoms. Specific examples include a dimethylphosphino group, a diphenylphosphino group, and a methylphenoxyphosphino group. Examples of the phosphinyl group include substituted or unsubstituted phosphinyl groups having 2 to 30 carbon atoms. Specific examples include a phosphinyl group, a dioctyloxyphosphinyl group, and a diethoxyphosphinyl group.
- Examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 2 to 30 carbon atoms. Specific examples include a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.
- Examples of the phosphinylamino group include substituted or unsubstituted phosphinylamino groups having 2 to 30 carbon atoms. Specific examples include a dimethoxyphosphinylamino group and a dimethylaminophosphinylamino group.
- silyl group examples include substituted or unsubstituted silyl groups having 3 to 30 carbon atoms. Specific examples include a trimethylsilyl group, a tert-butyldimethylsilyl group, and a phenyldimethylsilyl group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- a group in which the hydrogen atom of the monovalent substituent exemplified above is further substituted with the above monovalent substituent can also be exemplified.
- Specific examples include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specifically, examples include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.
- the monovalent substituents exemplified above can be arbitrarily combined with the above-described preferred combinations of Z, T 1 and T 2 , and preferred combinations of the group containing X 2 and the group containing X 3 .
- R is a monovalent substituent
- examples of the monovalent substituent include the case where R 3 and R 4 described above are monovalent substituents.
- Y represents 2 to 4 atoms selected from the group consisting of carbon atoms and non-metal atoms of Groups 14 to 16, and R 3 —C—R described in the general formula (1-0-0) above. Forms a 5- to 7-membered ring together with 4 (hereinafter sometimes referred to as ring Y).
- R represents a hydrogen atom or a monovalent substituent.
- the monovalent substituent include the case where R 3 and R 4 described above are monovalent substituents. When there are a plurality of R, they may be the same or different.
- R in the formula (Y-1) examples include —N (Ph) 2 .
- Ph is a phenyl group.
- R substituted for N in the formula (Y-3) examples include a substituted or unsubstituted phenyl group.
- R bonded to C examples include about 1 to 3 carbon atoms such as a methyl group.
- Examples of R bonded to two N in the formula (Y-4) examples include an alkyl group having about 1 to 3 carbon atoms such as an ethyl group and a substituted or unsubstituted phenyl group.
- R bonded to N in the formulas (Y-5) and (Y-8) include an alkyl group having about 1 to 3 carbon atoms such as an ethyl group.
- R bonded to N in the formula (Y-10) include a substituted or unsubstituted phenyl group.
- R bonded to N in formulas (Y-11) to (Y-13) includes, for example, an alkyl group having about 1 to 3 carbon atoms such as an ethyl group.
- R bonded to C in the formula (Y-14) include a substituted or unsubstituted phenyl group.
- R bonded to two N in the formula (Y-15) include an alkyl group having about 1 to 3 carbon atoms such as a methyl group and a substituted or unsubstituted phenyl group.
- R bonded to N in the formula (Y-16) examples include an alkyl group having about 1 to 3 carbon atoms such as an ethyl group.
- R bonded to N in the formulas (Y-18) and (Y-20) examples include a substituted or unsubstituted phenyl group.
- R bonded to N in the formulas (Y-21) and (Y-22) includes an alkyl group having about 1 to 3 carbon atoms such as a methyl group and an ethyl group.
- R bonded to N in the formula (Y-23) examples include a substituted or unsubstituted phenyl group.
- R bonded to C examples include, for example, a hydrogen atom, —OH, and ester.
- R is an alkyl group having about 1 to 3 carbon atoms such as an ethyl group).
- R bonded to N in the formula (Y-24) include alkyl groups having about 1 to 3 carbon atoms such as a methyl group.
- S represents a sulfur atom
- the ring Y exemplified above can be arbitrarily combined with the above-mentioned preferred combinations of Z, T 1 and T 2 , and preferred combinations of the group containing X 2 and the group containing X 3 .
- the polymerizable compound represented by the general formula (1-0) is a long axis of a molecule composed of a group containing X 2 , a naphthalene ring, and a group containing X 3 in an optical anisotropic body such as a retardation film. The molecules are oriented to align the direction. As a result, refractive index anisotropy is exhibited, and the dipole moment is oriented in the lateral direction of the molecular long axis, so that the birefringence is considered to be small or reversed.
- composition The composition of the second embodiment of the present invention is a composition containing the polymerizable compound of the first embodiment.
- 1 type of polymeric compounds represented by general formula (1-0) may be contained, and 2 or more types may be contained.
- 1 to 4 types are preferably contained, more preferably 1 to 3 types are contained, still more preferably 1 or 2 types are contained.
- composition of the present embodiment may contain a known polymerizable compound in addition to the polymerizable compound of the first embodiment.
- known polymerizable compounds include polymerizable compounds represented by the following general formulas (A1) to (A24).
- P 0 is a polymerizable group having one of the meanings given above for P, independently of each other when multiple occurrences, preferably acrylic, methacrylic, oxetane, 3-ethyloxetane, epoxy, vinyloxy or styrene Group
- Sp 0 is a spacer group or single bond having one of the meanings given to Sp above
- X 0 represents —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 0 —, —NR 0 —CO—, —NR 0 —CO—.
- R 0 is an alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy having 1 to 20, preferably 1 to 15 C atoms (even if the group is fluorinated).
- Y 0 is F, Cl, CN, NO 2 , OCH 3 , OCN, SCN, SF 5 , 1 to 4 C atoms, and optionally fluorinated alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy Or alkoxycarbonyloxy, or monofluorinated, oligofluorinated or polyfluorinated alkyl or alkoxy having 1 to 4 C atoms
- X 00 represents —O—, —S—, —CO—, —COO—, —OCO—, —O—COO—, —CO—NR 01 —, —NR 01 —CO—, —NR 01 —CO—.
- R 01 is H or alkyl having 1 to 12 C atoms; L is the same or different when multiple occurrences, F, Cl, CN, SCN, SF 5 , or 1 to 12 C atoms, linear or branched, monofluorinated or polyvalent Optionally fluorinated alkyl, alkoxy, alkenyl, alkynyl,
- the total weight of the polymerizable compounds contained in the composition of the present embodiment is 100 parts by weight
- the total content of the polymerizable compounds represented by the general formula (1-0) is 10 to 100 parts by weight. It is preferably 30 to 100 parts by weight, more preferably 50 to 100 parts by weight.
- the composition of this embodiment contains the bifunctional compound which has two polymerizable functional groups in a molecule
- a bifunctional compound By containing a bifunctional compound, excellent orientation, optical properties, and the like can be imparted when used for applications of a polymer substrate and a laminate thereof.
- Specific examples of the application include use of optical anisotropic bodies such as a retardation film, a retardation patterning film, and a homogeneous alignment (horizontal alignment) liquid crystal film in the field of liquid crystal displays.
- the substrate on which the solution containing the composition of the present embodiment is applied is a substrate that is usually used for liquid crystal devices, displays, optical components and optical films, and is dried after application of the composition of the present embodiment. Or if it is the material which has heat resistance which can endure the heating at the time of liquid crystal device manufacture, there will be no restriction
- a substrate include organic materials such as a glass substrate, a metal substrate, a ceramic substrate, and a polymer substrate.
- the polymer base material is preferable because it can be produced by roll-to-roll and is easy to handle as compared with a glass substrate or the like.
- the base material (polymer base material) made of a polymer compound has excellent affinity with the polymerizable compound of the first embodiment, and after applying and drying a solution containing the polymerizable compound to the polymer base material.
- the polymerizable compound of the present embodiment is also suitable for applications that are laminated on a polymer substrate from the viewpoint that it is easy to impart excellent orientation.
- Examples of the polymer compound constituting such a preferable polymer substrate include cellulose derivatives, polyolefin-based, polyester-based, polyethylene terephthalate, polycarbonate, polyacrylate-based, polyarylate, polyethersulfone, polyimide, polyphenylene sulfide, and polyphenylene ether. , Nylon, or polystyrene. Particularly preferred are cycloolefin polymer, triacetyl cellulose, and polymethyl methacrylate resin.
- the substrate may be subjected to an alignment treatment so that the polymerizable compound is easily aligned when the composition of the present embodiment is applied and dried.
- the alignment treatment may be performed by applying an alignment film used in a general liquid crystal device.
- a particularly preferable method is a publicly known method using a photo-alignment film. When the photo-alignment film is used, a patterned retardation film can be produced.
- Organic solvent constituting the composition of the present embodiment is not particularly limited as long as the polymerizable compound represented by the general formula (1-0) can be dissolved.
- the organic solvent is volatilized at a temperature of 100 ° C. or lower to obtain the composition. It is preferable that it is a solvent which can dry a thing, and it is preferable not to corrode the base material to be used.
- solvents examples include aromatic hydrocarbons such as toluene, xylene, cumene, and mesitylene, ester solvents such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane, and the like.
- Ketone solvents such as pentanone, ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane and anisole, amide solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, Examples include diethylene glycol monomethyl ether acetate, ⁇ -butyrolactone, chlorobenzene, and chloroform. These organic solvents can be used alone or in combination of two or more.
- the polymerizable compound represented by the general formula (1-0) is excellent in solubility, the film obtained by polymerizing the composition is also excellent in orientation, and is dried at 100 ° C. or lower.
- chloroform, toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, propylene glycol monomethyl ether acetate, and N-methyl-2-pyrrolidone are more preferable.
- the content of the organic solvent relative to the total weight of the composition of the present embodiment may be adjusted to a content that makes it easy to apply the composition to a substrate. Is more preferable.
- the composition of the present embodiment preferably contains at least one polymerization initiator.
- the polymerization initiator is a useful compound for efficiently polymerizing the polymerizable compound of the first embodiment.
- a photopolymerization initiator is preferable, and specifically, the following compounds are preferable. Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 127, Irgacure 369, Irgacure 379, Irgacure 819, Irgacure OXE01, Irgacure OXE02, Lucyrin TPO, Darocur 1173 manufactured by BASF.
- the content of the polymerization initiator with respect to the total weight of the solid content of the composition of the present embodiment is, for example, preferably 0.1 to 10% by weight, more preferably 1.0 to 7.0% by weight, and 3.0 to 6%. Even more preferred is 0.0 wt%.
- composition of the present embodiment preferably contains a surfactant or a compound having a repeating unit represented by the following general formula (VI) and having a weight average molecular weight of 100 or more.
- R 11 , R 12 , R 13 and R 14 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and one or more hydrogen atoms in the hydrocarbon group The atom may be substituted with a halogen atom.
- the surfactant and the compound represented by the general formula (VI) impart an effect of reducing the tilt angle of the liquid crystal compound at the air interface.
- the surfactant include alkyl carboxylates, alkyl phosphates, alkyl sulfonates, fluoroalkyl carboxylates, fluoroalkyl phosphates, fluoroalkyl sulfonates, polyoxyethylene derivatives, fluoroalkylethylene oxide derivatives, Examples include polyethylene glycol derivatives, alkyl ammonium salts, fluoroalkyl ammonium salts, silicone derivatives, and the like. Of these, fluorine-containing surfactants and silicone derivatives are particularly preferable.
- MEGAFAC F-110 “MEGAFACCF-113”, “MEGAFAC F-120”, “MEGAFAC F-812”, “MEGAFAC F-142D”, “MEGAFAC F-144D”, “MEGAFAC F-” 150 “,” MEGAFAC F-171 “,” MEGAFACF-173 “,” MEGAFAC F-177 “,” MEGAFAC F-183 “,” MEGAFAC F-195 “,” MEGAFAC F-824 “,” MEGAFAC F-833 “ , “MEGAFAC F-114”, “MEGAFAC F-410”, “MEGAFAC F-493”, “MEGAFAC F-494”, “MEGAFAC F-443”, “MEGAFAC F-444”, “MEGAFAC F-445”, “ME “GAFAC F-446”, “MEGAFAC F-470”, “MEGAFAC F-471”, “MEGAFAC F-474”, “MEGAFAC F-475”, “MEGAFAC F-477”, “MEGAFAC F-110
- the weight average molecular weight of the compound represented by the general formula (VI) is preferably 200 to 100,000, more preferably 300 to 10,000, and further preferably 500 to 5,000.
- the surfactant and the compound represented by the general formula (VI) may be used alone or in combination of two or more. Further, the surfactant and the compound represented by the general formula (VI) may be used in combination.
- the total content of the surfactant and the compound represented by the general formula (VI) with respect to the total weight of the solid content of the polymerizable liquid crystal composition of the present embodiment is preferably 0.01 to 1% by weight, More preferably, it is 0.04 to 0.4% by weight.
- a chain transfer agent is preferably added to the composition of the present embodiment as another component in order to further improve the adhesion to the substrate.
- the chain transfer agent is preferably a thiol compound, more preferably a monothiol, dithiol, trithiol, or tetrathiol compound, and even more preferably a trithiol compound.
- compounds represented by the following general formulas (5-1) to (5-12) are preferable.
- the content of these thiol compounds is preferably 0.5 to 7.0% by weight, and 1.0 to 5.0% by weight, based on the total weight of the solid content of the composition. Is more preferable.
- R 66 is a carbon Represents an alkylene group having 2 to 18 atoms, and one or more methylene groups in the alkylene group are oxygen atoms, sulfur atoms, —CO—, —OCO on the assumption that an oxygen atom and a sulfur atom are not directly bonded to each other. It may be substituted with —, —COO—, or —CH ⁇ CH—.
- a polymerization inhibitor an antioxidant or the like in order to enhance storage stability.
- examples of such compounds include hydroquinone derivatives and hindered phenol antioxidants. More specifically, p-methoxyphenol, IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1098, IRGANOX1135, IRGANOX1325, IRGANOX1520, IRGANOX2457, IRGANOX3957, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX3590, IRGANOX
- the content of the polymerization inhibitor and the antioxidant is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.2% by mass, based on the total weight of the solid content of the composition. preferable.
- a non-polymerizable liquid crystal compound, a non-liquid crystalline polymerizable compound, or the like may be added as necessary.
- the content of these compounds is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5% by weight or less based on the total weight of the solid content of the composition.
- the polymer of the third embodiment can be obtained by polymerizing the polymerizable compound of the first embodiment contained in the composition of the second embodiment by a known method.
- This polymer is suitable for the production of optical anisotropic bodies such as retardation films, retardation patterning films, homogeneous alignment liquid crystal films and the like in the field of liquid crystal displays, and is also suitable as an antireflection film for organic EL displays.
- the polymerizable compound of the first embodiment is used in a solution state dissolved in a solvent. After applying this solution to the above-mentioned substrate (base material) or the like, it is dried and polymerized by ultraviolet irradiation or heat treatment to obtain a retardation film. Further, in order to facilitate the orientation of the polymerizable compound, the substrate may be subjected to an orientation treatment in advance. In particular, when a photo-alignment film is used as the alignment treatment material, a retardation film can be easily produced. It is also possible to change the phase difference pattern by changing the temperature at which the solution applied to the substrate is heated.
- the liquid crystal display element of the fifth embodiment including the optical anisotropic body of the fourth embodiment can be manufactured by incorporating the optical anisotropic body of the fourth embodiment into the liquid crystal display element by a known method.
- Example 1 A polymerizable compound represented by the following formula (1-1-15) was synthesized by the method shown below.
- the upper limit temperature of the phase sequence of the polymerizable compound (1-1-15) was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. 180 Iso ”.
- Compound (2) was prepared by reacting for 30 minutes under ice-cooling, and then a solution of 22.8 g (100 mmol) of ammonium peroxodisulfate and 50 ml of water was added dropwise while keeping the internal temperature at 10 ° C. or lower. The reaction was further carried out at 50 ° C. for 2 hours. The resulting solid was filtered, washed with 100 ml of water and 100 ml of methanol, and dried to obtain 19.2 g of Compound (3) (yield 63%).
- the said coating liquid was apply
- the retardation value of the produced optical film is measured using a measuring instrument (RET-100, manufactured by Otsuka Electronics Co., Ltd.), and the retardation value Re (450) at a wavelength of 450 nm is measured with a program attached to the apparatus.
- the retardation value Re (550) at a wavelength of 550 nm and the retardation value Re (650) at a wavelength of 650 nm were calculated. The results are shown in Table 1.
- the upper limit temperature of the phase sequence of the polymerizable compound (1-1-16) was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. 183 Iso ”.
- a coating solution was prepared in the same manner as in Example 1 except that the polymerizable compound (1-1-16) was used in the same amount instead of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the upper limit temperature of the above-described polymerizable compound (Ref1) phase sequence was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. there were.
- a coating solution was prepared in the same manner as in Example 1 except that the polymerizable compound (Ref1) was used in the same amount in place of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the upper limit temperature of the phase sequence of the polymerizable compound (1-1-17) was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. 94 Iso ”.
- a coating solution was prepared in the same manner as in Example 1 except that the polymerizable compound (1-1-17) was used in the same amount in place of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the upper limit temperature of the above-described polymerizable compound (Ref2) phase sequence was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. there were.
- a coating solution was prepared in the same manner as in Example 1 except that the polymerizable compound (Ref2) was used in the same amount in place of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the upper limit temperature of the phase sequence of the polymerizable compound (1-1-18) was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. 137 Iso ”.
- a coating solution was prepared in the same manner as in Example 1, except that the polymerizable compound (1-1-18) was used in the same amount in place of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the upper limit temperature of the above-mentioned polymerizable compound (Ref3) phase sequence was determined by differential scanning calorimetry and observation of the liquid crystal phase with a polarizing microscope equipped with a temperature variable device. there were.
- a coating solution was prepared in the same manner as in Example 1 except that the polymerizable compound (Ref3) was used in the same amount in place of the polymerizable compound (1-1-15) used in Example 1.
- the said coating liquid was apply
- the polymerizable compounds of Examples 1 to 4 have improved reverse wavelength dispersion as compared with the polymerizable compound of Comparative Example. Therefore, it is clear that optical anisotropic bodies having excellent optical properties can be produced by using the polymerizable compounds of Examples 1 to 4.
- the optical films of Examples 1 to 4 have excellent characteristics is that when the vertical unit has a naphthalene ring, the wavelength dispersibility in the molecular minor axis direction is increased. It is estimated that it contributes to the improvement of
- the polymerizable compound according to the present invention is widely applicable in the field of liquid crystal displays.
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Abstract
Description
一般式(1-0)
A1、A2、A3、A4はそれぞれ独立に二価の脂環式炭化水素基又は芳香族炭化水素基を表し、
X1、X2、X3、X4はそれぞれ独立に二価の連結基又は単結合を表し、
R1は炭素原子数1~12のアルキル基、アルコキシ基又は「*-Sp-P」を表し(*はA4又はA3に結合することを表す。)、
m、nはそれぞれ独立に0~4の整数を表し(ただし、m+nは2以上の整数である。)、
Zは式中のC-C=C-Cとともにナフタレン環を表し、このナフタレン環に結合する水素原子のうち2つが式中のX2を含む基及びX3を含む基にそれぞれ置換されており、
T1、T2はそれぞれ独立に、-S-、-O-、-NR2-、-CH2-、-NH-、-C(=O)-、-S(=O)-又は-C(=S)-を表し、
R2は水素原子、ハロゲン原子、炭素原子数1~6のアルキル基、炭素原子数1~6のアルコキシ基、シアノ基、ニトロ基又は水酸基を表し、
R3、R4は、それぞれ独立して一価の置換基を表すか、又は、R3とR4を連結するYを介して環を形成する。この環を形成する場合には、R3及びR4 はそれぞれ独立して、-O-、-S-、-SO-、-SO2-、-NR-(Rは水素原子又は一価の置換基を表す。)、=N-、=N(+)R-(Rは水素原子又は一価の置換基を表す。)、-C(=O)-、-C (=S)-及び=CR-(Rは水素原子又は一価の置換基を表す。)からなる群から選ばれる基を表す。
Yは炭素原子及び第14~16族の非金属原子からなる群から選択される2~4個の原子を表し、式中のR3-C-R4と共に5~7員環を形成する。この5~7員環に結合する水素原子には一価の置換基が結合してもよい。ただし、T1とR3、及びT2とR4が同じである場合、並びに、T1とR4、及びT2とR3が同じである場合は除く。]
で表される、重合性化合物。
本発明の第三態様は、第二態様の組成物を重合することにより得られる重合体である。
本発明の第四態様は、第三態様の重合体を用いた光学異方体である。
本発明の第五態様は、第四態様の光学異方体を用いた液晶表示素子である。
本発明の第六態様は、第四態様の光学異方体を用いた有機EL素子である。
本発明の第一実施形態の重合性化合物は、下記一般式(1-0)で表される化合物である。
A1、A2、A3、A4はそれぞれ独立に二価の脂環式炭化水素基又は芳香族炭化水素基を表し、
X1、X2、X3、X4はそれぞれ独立に二価の連結基又は単結合を表し、
R1は炭素原子数1~12のアルキル基、アルコキシ基又は「*-Sp-P」を表し(*はA4又はA3に結合することを表す。)、
m、nはそれぞれ独立に0~4の整数を表し(ただし、m+nは2以上の整数である。)、
Zは式中のC-C=C-Cとともにナフタレン環を表し、このナフタレン環に結合する水素原子のうち2つが式中のX2を含む基及びX3を含む基にそれぞれ置換されており、
T1、T2はそれぞれ独立に、-S-、-O-、-NR2-、-CH2-、-NH-、-C(=O)-、-S(=O)-又は-C(=S)-を表し、
R2は水素原子、ハロゲン原子、炭素原子数1~6のアルキル基、炭素原子数1~6のアルコキシ基、シアノ基、ニトロ基又は水酸基を表し、
R3、R4は、それぞれ独立して一価の置換基を表すか、又は、R3とR4を連結するYを介して環を形成する。この環を形成する場合には、R3及びR4 はそれぞれ独立して、-O-、-S-、-SO-、-SO2-、-NR-(Rは水素原子又は一価の置換基を表す。)、=N-、=N(+)R-(Rは水素原子又は一価の置換基を表す。)、-C(=O)-、-C (=S)-及び=CR-(Rは水素原子又は一価の置換基を表す。)からなる群から選ばれる基を表す。
Yは炭素原子及び第14~16族の非金属原子からなる群から選択される2~4個の原子を表し、式中のR3-C-R4と共に5~7員環を形成する。この5~7員環に結合する水素原子には一価の置換基が結合してもよい。ただし、T1とR3、及びT2とR4が同じである場合、並びに、T1とR4、及びT2とR3が同じである場合は除く。
一般式(1-0)中のPで表される重合性官能基は、従来の重合性液晶化合物に使用される基が制限なく適用可能であり、例えば、ビニル基、p-スチルベン基、アクリル基(アクリロイル基)、メタクリル基(メタクロイル基)、アクリロイルオキシ基、メタクロイルオキシ基、カルボキシル基、メチルカルボニル基、水酸基、アミド基、炭素数1~4のアルキルアミノ基、アミノ基、エポキシ基、オキセタニル基、アルデヒド基、イソシアネート基又はチオイソシアネート基などが挙げられる。
上記一般式で表される重合性官能基は、その左端が一般式(1-0)のSpに結合する。
前記アルキル基は直鎖又は分岐鎖アルキル基であることが好ましく、直鎖アルキル基であることがより好ましい。前記アルキル基に結合する水素原子の一部又は全部がハロゲン原子によって置換されていてもよい。
一般式(1-0)中のSpはスペーサー基又は単結合を表す。該スペーサー基は、重合性官能基PとA1又はA2とを連結可能な二価の連結基であり、一般式(1-0)で表される化合物(本明細書において化合物(1-0)と呼ぶことがある。)の液晶性を損なわない連結基が好ましい。
一般式(1-0)中の環式基A1、A2、A3、A4は、それぞれ独立に二価の脂環式炭化水素基、又は芳香族炭化水素基を表す。また、上記環式基は芳香族複素環式基であっても構わない。
前記環式基としては、例えば、1,4-フェニレン基、1,4-シクロヘキシレン基、1,4-シクロヘキセニル基、テトラヒドロピラン-2,5-ジイル基、1,3-ジオキサン-2,5-ジイル基、テトラヒドロチオピラン-2,5-ジイル基、1,4-ビシクロ(2,2,2)オクチレン基、デカヒドロナフタレン-2,6-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、1,2,3,4-テトラヒドロナフタレン-2,6-ジイル基、2,6-ナフチレン基、フェナントレン-2,7-ジイル基、9,10-ジヒドロフェナントレン-2,7-ジイル基、1,2,3,4,4a,9,10a-オクタヒドロフェナントレン2,7-ジイル基又はフルオレン2,7-ジイル基などが挙げられる。
一般式(1-0)中のX1、X2、X3、X4は、それぞれ独立に二価の連結基又は単結合を表す。前記二価の連結基としては、例えば、-CH2CH2-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCO-CH=CH-、-(CH2)u-O-COO-、-(CH2)u-OCO-、-(CH2)u-COO-、-(CH2)u-O -、-O-COO-(CH2)u-、-OCO-(CH2)u-、-COO-(CH2)u-、-O-(CH2)u-が挙げられ、-COO-及び-OCO-が好ましい。
ここで、uは0~2の何れかの整数を表し、uが0である場合、-(CH2)u -COO-及び-COO-(CH2)u-は-COO-を表し、-(CH2) u -OCO-及び-OCO-(CH2)u-は-OCO-を表す。
一般式(1-0)中のm、nは、それぞれ独立に0~4の整数を表し、且つ、m+nは2以上の整数である。
本実施形態の重合性化合物の液晶性を向上させる観点から、m、nはそれぞれ独立に、0~3が好ましく、0~2がより好ましく、1又は2が更に好ましい。また、mとnは同じ整数であることが好ましい。
一般式(1-0)中の末端基R1は、炭素原子数1~12のアルキル基、炭素原子数1~12アルコキシ基又は「*-Sp-P」を表す。ここで、「*」は、nが1以上の整数の場合にはA4に結合することを表し、nが0の場合にはA3に結合することを表す。
「*-Sp-P」のSp及び重合性官能基Pは、前述と同じである。分子内にSpが2個存在する場合、それらは同一であっても異なっていてもよく、同一であることが好ましい。また、分子内にPが2個存在する場合、それらは同一であっても異なっていてもよく、同一であることが好ましい。
一般式(1-0)中、Zは式中のC-C=C-Cとともにナフタレン環を表す。このナフタレン環に結合する水素原子のうち2つの水素原子が式中のX2を含む基及びX3を含む基にそれぞれ置換されている。一般式(1-0)で表される重合性化合物の好適な例として、下記の一般式(1-1)、(1-2)及び(1-3)で表さる重合性化合物が挙げられる。
一般式(1-0)中、T1、T2はそれぞれ独立に、-S-、-O-、-NR2-、-CH2-、-NH-、-C(=O)-、-S(=O)-又は-C(=S)-を表す。ここで、R2は水素原子、ハロゲン原子、炭素原子数1~6のアルキル基、炭素原子数1~6のアルコキシ基、シアノ基、ニトロ基又は水酸基を表す。T1とT2とは同じであってもよいし、異なっていてもよい。T1及びT2がともに-NR2-である場合には、2つのR2は互いに同じであってもよいし、異なっていてもよい。
T1は-O-、-NR2-又は-S-であることが好ましく、-NR2-又は-S-であることがより好ましく、-S-であることが更に好ましい。
T2は-O-、-NR2-又は-S-であることが好ましく、-NR2-又は-S-であることがより好ましく、-S-であることが更に好ましい。
R2がハロゲン原子である場合、フッ素原子又は塩素原子であることが好ましい。
一般式(1-0)中、R3、R4はそれぞれ独立して一価の置換基を表すか、又は、R3とR4を連結するYを介して環を形成する。
前記アルキル基としては、例えば、炭素数1~30の直鎖、分岐の置換又は無置換のアルキル基が挙げられる。具体的には、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、tert-ブチル基、n-オクチル基、2-エチルヘキシル基が挙げられる。
前記シクロアルキル基としては、例えば、炭素数3~30の置換または無置換のシクロアルキル基が挙げられる。具体的には、例えば、シクロヘキシル基、シクロペンチル基、4-n-ドデシルシクロヘキシル基が挙げられる。
前記ビシクロアルキル基としては、例えば、炭素数5~30の置換または無置換のビシクロアルキル基が挙げられる。ここで無置換のビシクロアルキル基としては、例えば、炭素数5~30のビシクロアルカンから水素原子を一個除いた一価の基が挙げられる。具体的には、例えば、ビシクロ[1,2,2]ヘプタン-2-イル基、ビシクロ[2,2,2]オクタン-3-イル基が挙げられる。
前記シクロアルケニル基としては、例えば、炭素数3~30の置換または無置換のシクロアルケニル基が挙げられる。ここで無置換のシクロアルケニル基としては、例えば、炭素数3~30のシクロアルケンの水素原子を一個除いた一価の基が挙げられる。具体的には、例えば、2-シクロペンテン-1-イル、2-シクロヘキセン-1-イル基が挙げられる。
前記ビシクロアルケニル基としては、例えば、炭素数5~30の置換または無置換のビシクロアルケニル基が挙げられる。ここで無置換のビシクロアルケニル基としては、二重結合を一個持つビシクロアルケンの水素原子を一個除いた一価の基が挙げられる。具体的には、例えば、ビシクロ[2,2,1]ヘプト-2-エン-1-イル基、ビシクロ[2,2,2]オクト-2-エン-4-イル基が挙げられる。
前記アリール基としては、例えば、炭素数6~30の置換または無置換のアリール基が挙げられる。具体的には、例えばフェニル基、p-トリル基、ナフチル基が挙げられる。
前記ヘテロ環基としては、例えば、5又は6員の置換または無置換の、芳香族または非芳香族のヘテロ環化合物から一個の水素原子を除いた一価の基が挙げられる。より好ましくは、炭素数3~30の5又は6員の芳香族のヘテロ環基である。具体的には、例えば、2-フリル基、2-チエニル基、2-ピリミジニル基、2-ベンゾチアゾリル基が挙げられる。
前記アリールオキシ基としては、例えば、炭素数6~30の置換または無置換のアリールオキシ基が挙げられる。具体的には、例えば、フェノキシ基、2-メチルフェノキシ基、4-tert-ブチルフェノキシ基、3-ニトロフェノキシ基、2-テトラデカノイルアミノフェノキシ基が挙げられる。
前記シリルオキシ基としては、例えば、炭素数3~20のシリルオキシ基が挙げられる。具体的には、例えば、トリメチルシリルオキシ基、tert-ブチルジメチルシリルオキシ基が挙げられる。
前記カルバモイルオキシ基としては、例えば、炭素数1~30の置換または無置換のカルバモイルオキシ基が挙げられる。具体的には、例えば、N,N-ジメチルカルバモイルオキシ基、N,N-ジエチルカルバモイルオキシ基、モルホリノカルボニルオキシ基、N,N-ジ-n-オクチルアミノカルボニルオキシ基、N-n-オクチルカルバモイルオキシ基が挙げられる。
前記アリールオキシカルボニルオキシ基としては、例えば、炭素数7~30の置換または無置換のアリールオキシカルボニルオキシ基が挙げられる。具体的には、例えば、フェノキシカルボニルオキシ基、p-メトキシフェノキシカルボニルオキシ基、p-n-ヘキサデシルオキシフェノキシカルボニルオキシ基が挙げられる。
前記アシルアミノ基としては、例えば、ホルミルアミノ基、炭素数1~30の置換または無置換のアルキルカルボニルアミノ基、炭素数6~30の置換または無置換のアリールカルボニルアミノ基が挙げられる。具体的には、例えば、ホルミルアミノ基、アセチルアミノ基、ピバロイルアミノ基、ラウロイルアミノ基、ベンゾイルアミノ基が挙げられる。
前記アルコキシカルボニルアミノ基としては、例えば、炭素数2~30の置換または無置換アルコキシカルボニルアミノ基が挙げられる。具体的には、例えば、メトキシカルボニルアミノ基、エトキシカルボニルアミノ基、tert-ブトキシカルボニルアミノ基、n-オクタデシルオキシカルボニルアミノ基、N-メチル-メトキシカルボニルアミノ基が挙げられる。
前記スルファモイルアミノ基としては、例えば、炭素数0~30の置換または無置換のスルファモイルアミノ基が挙げられる。具体的には、例えば、スルファモイルアミノ基、N,N-ジメチルアミノスルホニルアミノ基、N-n-オクチルアミノスルホニルアミノ基が挙げられる。
前記アリールチオ基としては、例えば、炭素数6~30の置換または無置換のアリールチオ基が挙げられる。具体的には、例えば、フェニルチオ基、p-クロロフェニルチオ基、m-メトキシフェニルチオ基が挙げられる。
前記ヘテロ環チオ基としては、例えば、炭素数2~30の置換または無置換のヘテロ環チオ基が挙げられる。具体的には、例えば、2-ベンゾチアゾリルチオ基、1-フェニルテトラゾール-5-イルチオ基が挙げられる。
前記アルキル又はアリールスルフィニル基としては、例えば、炭素数1~30の置換または無置換のアルキルスルフィニル基、炭素数6~30の置換または無置換のアリールスルフィニル基が挙げられる。具体的には、例えば、メチルスルフィニル基、エチルスルフィニル基、フェニルスルフィニル基、p-メチルフェニルスルフィニル基が挙げられる。
前記アシル基としては、例えば、ホルミル基、炭素数2~30の置換または無置換のアルキルカルボニル基、炭素数7~30の置換または無置換のアリールカルボニル基が挙げられる。具体的には、例えば、アセチル基、ピバロイルベンゾイル基が挙げられる。
前記アルコキシカルボニル基としては、例えば、炭素数2~30の置換または無置換アルコキシカルボニル基が挙げられる。具体的には、例えば、メトキシカルボニル基、エトキシカルボニル基、tert-ブトキシカルボニル基、n-オクタデシルオキシカルボニル基が挙げられる。
前記アリール又はヘテロ環アゾ基としては、例えば、炭素数6~30の置換または無置換のアリールアゾ基、炭素数3~30の置換または無置換のヘテロ環アゾ基が挙げられる。具体的には、例えば、フェニルアゾ基、p-クロロフェニルアゾ基、5-エチルチオ-1,3,4-チアジアゾール-2-イルアゾ基が挙げられる。
前記ホスフィノ基としては、例えば、炭素数2~30の置換または無置換のホスフィノ基が挙げられる。具体的には、例えば、ジメチルホスフィノ基、ジフェニルホスフィノ基、メチルフェノキシホスフィノ基が挙げられる。
前記ホスフィニル基としては、例えば、炭素数2~30の置換または無置換のホスフィニル基が挙げられる。具体的には、例えば、ホスフィニル基、ジオクチルオキシホスフィニル基、ジエトキシホスフィニル基が挙げられる。
前記ホスフィニルアミノ基としては、例えば、炭素数2~30の置換または無置換のホスフィニルアミノ基が挙げられる。具体的には、例えば、ジメトキシホスフィニルアミノ基、ジメチルアミノホスフィニルアミノ基が挙げられる。
一般式(1-0)中、R3及びR4がYを介して環を形成する下記一般式(1-0-0)の場合、
以下に好ましい環Yの構造の例を示す。構造式において波線を引いた=Cは、T1及びT2を含む5員環と連結する部位を表す。
本発明の第二実施形態の組成物は、第一実施形態の重合性化合物を含有する組成物である。本実施形態の組成物においては、一般式(1-0)で表される重合性化合物を1種のみ含有してもよいし、2種以上含有してもよい。通常、1~4種含有することが好ましく、1~3種含有することがより好ましく、1又は2種含有することが更に好ましい。
P0は、複数出現する場合は互いに独立に、上でPに与えられる意味の1つを有する重合性基であり、好ましくは、アクリル、メタクリル、オキセタン、3-エチルオキセタン、エポキシ、ビニルオキシまたはスチレン基であり、
Sp0は、上でSpに与えられる意味の1つを有するスペーサー基又は単結合であり、
X0は、-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR0-、-NR0-CO-、-NR0-CO-NR0-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR0-、-CY1=CY2-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-または単結合であり、
Sp0-X0は、好ましくは、-(CH2)p1-、-(CH2)p1-O-、-(CH2)p1-CO-O-および-(CH2)p1-O-CO-O-より選択され、ただし、p1は1~12の整数であり、ただし、これらの基は、存在しているのであれば、O原子を介して隣接する環に連結されており、
A0およびB0は、複数出現する場合は互いに独立に、1,4-フェニレン(該基は、1個、2個、3個または4個の基Lで置換されていてもよい。)またはトランス-1,4-シクロヘキシレンであり、
Hは、トランス-1,4-シクロヘキシレンであり、
Z0は、複数出現する場合は互いに独立に、-COO-、-OCO-、-CH2CH2-、-C≡C-、-CH=CH-、-CH=CH-COO-、-OCO-CH=CH-または単結合であり、
R0は、1~20個、好ましくは、1~15個のC原子を有するアルキル、アルコキシ、チオアルキル、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ(該基はフッ素化されていてもよい。)であるか、または、Y0またはP-Sp0-X0-を表し、
Y0は、F、Cl、CN、NO2、OCH3、OCN、SCN、SF5、1~4個のC原子を有し、フッ素化されていてもよいアルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ、または、1~4個のC原子を有し、一フッ素化、オリゴフッ素化またはポリフッ素化されたアルキルまたはアルコキシであり、
X00は、-O-、-S-、-CO-、-COO-、-OCO-、-O-COO-、-CO-NR01-、-NR01-CO-、-NR01-CO-NR01-、-OCH2-、-CH2O-、-SCH2-、-CH2S-、-CF2O-、-OCF2-、-CF2S-、-SCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-、-CH=N-、-N=CH-、-N=N-、-CH=CR01-、-CF=CF-、-C≡C-、-CH=CH-COO-、-OCO-CH=CH-または単結合であり、
R01は、Hまたは1~12個のC原子を有するアルキルであり、
Lは、複数出現する場合は同一または異なって、F、Cl、CN、SCN、SF5、または、1~12個のC原子を有し、直鎖状または分岐状で、一フッ素化または多フッ素化されていてもよいアルキル、アルコキシ、アルケニル、アルキニル、アルキルカルボニル、アルコキシカルボニル、または、アルキルカルボニルオキシまたはアルコキシカルボニルオキシ(ただし、アルキルおよびアルコキシと異なる基は少なくとも2個のC原子を含有し、分岐状の基は少なくとも3個のC原子を含有する。)、または、1~5個のC原子を有し、ハロゲン化されていてもよいアルキル、アルコキシ、アルキルカルボニル、アルコキシカルボニル、アルキルカルボニルオキシまたはアルコキシカルボニルオキシであり、
rは、0、1、2、3または4であり、
gは、0または1であり、
vおよびwは、それぞれ互いに独立に、0、1または2であり、
ただし、ベンゼンおよびナフタレン環は、1個以上の同一または異なる基Lで追加的に置換されていてもよい。
また、一般式(A1)~(A24)中、「-OOC-」は「-O-C(=O)-」を表し、「-OCO-」と同義である。
前記用途の具体例として、例えば、液晶ディスプレイの分野における位相差膜、位相差パターニング膜及びホモジニアス配向(水平配向)液晶フィルム等の光学異方体の用途が挙げられる。
本実施形態の組成物を構成する有機溶媒は、一般式(1-0)で表される重合性化合物を溶解可能であれば特に制限されないが、100℃以下の温度で揮発させて、当該組成物を乾燥できる溶媒であることが好ましく、用いる基材を侵食しないことが好ましい。そのような溶剤としては、例えば、トルエン、キシレン、クメン、メシチレン等の芳香族系炭化水素、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン等のケトン系溶剤、テトラヒドロフラン、1,2-ジメトキシエタン、アニソール等のエーテル系溶剤、N,N-ジメチルホルムアミド、N-メチル-2-ピロリドン等のアミド系溶剤、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、γ-ブチロラクトン、クロロベンゼン、クロロホルム等が挙げられる。これらの有機溶媒は、1種を単独で使用することもできるし、2種類以上を混合して使用することもできる。
本実施形態の組成物は、重合開始剤を少なくとも1種類以上含有することが好ましい。
重合開始剤は、第一実施形態の重合性化合物を効率よく重合させるために有用な化合物である。重合開始剤としては、光重合開始剤が好ましく、具体的には以下の化合物が好ましい。BASF社製のイルガキュア651、イルガキュア184、イルガキュア907、イルガキュア127、イルガキュア369、イルガキュア379、イルガキュア819、イルガキュアOXE01、イルガキュアOXE02、ルシリンTPO、ダロキュア1173。LAMBSON社製のエサキュア1001M、エサキュアKIP150、スピードキュアBEM、スピードキュアBMS、スピードキュアPBZ、ベンゾフェノン。
これらの重合開始剤は、1種類を単独で使用してもよく、2種類以上を併用してもよく、更に増感剤等を添加してもよい。
本実施形態の組成物は、界面活性剤、又は下記一般式(VI)で表される繰り返し単位を有する重量平均分子量が100以上である化合物を含有することが好ましい。
「フタージェント100」、「フタージェント100C」、「フタージェント110」、「フタージェント150」、「フタージェント150CH」、「フタージェントA」、「フタージェント100A-K」、「フタージェント501」、「フタージェント300」、「フタージェント310」、「フタージェント320」、「フタージェント400SW」、「FTX-400P」、「フタージェント251」、「フタージェント215M」、「フタージェント212MH」、「フタージェント250」、「フタージェント222F」、「フタージェント212D」、「FTX-218」、「FTX-209F」、「FTX-213F」、「FTX-233F」、「フタージェント245F」、「FTX-208G」、「FTX-240G」、「FTX-206D」、「FTX-220D」、「FTX-230D」、「FTX-240D」、「FTX-207S」、「FTX-211S」、「FTX-220S」、「FTX-230S」、「FTX-750FM」、「FTX-730FM」、「FTX-730FL」、「FTX-710FS」、「FTX-710FM」、「FTX-710FL」、「FTX-750LL」、「FTX-730LS」、「FTX-730LM」、「FTX-730LL」、「FTX-710LL」(以上、ネオス社製)、
「BYK-300」、「BYK-302」、「BYK-306」、「BYK-307」、「BYK-310」、「BYK-315」、「BYK-320」、「BYK-322」、「BYK-323」、「BYK-325」、「BYK-330」、「BYK-331」、「BYK-333」、「BYK-337」、「BYK-340」、「BYK-344」、「BYK-370」、「BYK-375」、「BYK-377」、「BYK-350」、「BYK-352」、「BYK-354」、「BYK-355」、「BYK-356」、「BYK-358N」、「BYK-361N」、「BYK-357」、「BYK-390」、「BYK-392」、「BYK-UV3500」、「BYK-UV3510」、「BYK-UV3570」、「BYK-Silclean3700」(以上、ビックケミー・ジャパン社製)、
「TEGO Rad2100」、「TEGO Rad2200N」、「TEGO Rad2250」、「TEGO Rad2300」、「TEGO Rad2500」、「TEGO Rad2600」、「TEGO Rad2700」(以上、テゴ社製)等の例を挙げることができる。
本実施形態の組成物には、その他の成分として、基材との密着性をより向上させるため、連鎖移動剤を添加することが好ましい。連鎖移動剤としては、チオール化合物が好ましく、モノチオール、ジチオール、トリチオール、テトラチオール化合物がより好ましく、トリチオール化合物が更により好ましい。具体的には下記一般式(5-1)~(5-12)で表される化合物が好ましい。
これらのチオール化合物の含有量としては、当該組成物の固形分の全重量に対して、0.5~7.0重量%であることが好ましく、1.0~5.0重量%であることがより好ましい。
これらの化合物の含有量としては、当該組成物の固形分の全重量に対して、20重量%以下が好ましく、10重量%以下がより好ましく、5重量%以下が更に好ましい。
第二実施形態の組成物に含まれる第一実施形態の重合性化合物を公知の手法により重合させることによって第三実施形態の重合体を得ることができる。この重合体は、液晶ディスプレイの分野における位相差膜、位相差パターニング膜、ホモジニアス配向液晶フィルム等の光学異方体の製造に好適であり、有機ELディスプレイの反射防止膜としても好適である。
第四実施形態の光学異方体を備えた第五実施形態の液晶表示素子は、公知の手法により第四実施形態の光学異方体を液晶表示素子に組み込むことによって製造できる。
以下に示す方法により、下記式(1-1-15)で表される重合性化合物を合成した。
上記の重合性化合物(1-1-15)は以下に示すスキームで合成した。
窒素雰囲気下、300mlの4ツ口フラスコにジエチルジチオカルバミン酸ナトリウム三水和物22.5g(100mmol)、水10mlおよびメタノール100mlを加え均一に溶解した。内温10℃以下に保ちながら、1,4-ナフトキノン(化合物(1))15.8g(100mmol)、酢酸17ml(300mmol)およびメタノール50mlの溶液を滴下した。氷冷下で30分間反応させ化合物(2)を調製した後、そのままペルオキソ二硫酸アンモニウム22.8g(100mmol)と水50mlとの溶液を内温10℃以下に保ちながら滴下した。さらに50℃で2時間反応させた。生じた固体をろ過し、水100mlおよびメタノール100mlで洗浄し、乾燥させることで化合物(3)が19.2g得られた(収率63%)。
窒素雰囲気下、300mlの4ツ口フラスコに化合物(3)15.3g(50mmol)、マロノニトリル4.0g(60mmol)、Irganox1010(商品名、チバ・スペシャルティ・ケミカルズ社製)50mgおよびN-メチル-2-ピロリドン(NMP)100mlを加え、撹拌下80℃まで加熱した。懸濁溶液が均一溶液となった後、さらに3時間攪拌した。室温に冷却後、酢酸エチルおよび水を加えて分液し、有機層を水飽和食塩水で順次洗浄した。有機層を硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、溶媒を減圧下濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィで精製し、化合物(4)が8.4g得られた(収率56%)。
窒素雰囲気下、1000mlの4ツ口フラスコに化合物(5-1)58.1g(500mmol)、パラトルエンスルホン酸ピリジニウム(PPTS)6.3g(25mmol)及びジクロロメタン600mlを加え均一に撹拌した。内温を10℃以下に保ちながら、3,4-ジヒドロ-2H-ピラン(DHP)21.0g(250mmol)を1時間かけて滴下した。さらに室温で6時間攪拌した。反応液を飽和炭酸水素ナトリウム水溶液で洗浄後、硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、減圧下濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、化合物(5-2)が42.1g得られた(DHP基準で収率84%)。
窒素雰囲気下、1000mlの4ツ口フラスコにジメチルホルムアミド(DMF)300mlと水素化ナトリウム (60%, 流動パラフィンに分散)12.0gを加え攪拌した。化合物(5-3)70.9g(600mmol)を溶解したDMF溶液200mlを、内温を10℃以下に保ちながら滴下した。水素の発生が終了した後、臭化ベンジル51.4g(300mmol)を室温で滴下した。さらに60℃で6時間反応させた。室温に冷却後、反応液を酢酸エチル1000mlと水1000mlに投入し分液した。有機層を水と飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、減圧下濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、化合物(5-4)が48.7g得られた(臭化ベンジル基準で収率78%)。
窒素雰囲気下、1000mlの4ツ口フラスコに化合物(5-4)45.0g(216mmol)、ピリジン18.8g(238mmol)及びジクロロメタン500mlを加え均一に攪拌した。塩化チオニル27.0g(227mmol)を内温を10℃以下に保ちながら滴下した。滴下後室温で6時間反応させた。反応液に水500mlを投入し分液した。有機層を水と飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、減圧下濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、化合物(5-5)が47.5g得られた(収率97%)。
窒素雰囲気下、500mlの4ツ口フラスコにジメチルホルムアミド(DMF)300mlと水素化ナトリウム (60%, 流動パラフィンに分散)8.9gを加え攪拌した。化合物(5-2)40.7g(203mmol)を溶解したDMF溶液100mlを、内温を10℃以下に保ちながら滴下した。水素の発生が終了した後、化合物(5-5)46.0g(203mmol)を室温で滴下した。さらに60℃で6時間反応させた。室温に冷却後、反応液を酢酸エチル500mlと水500mlに投入し分液した。有機層を水と飽和食塩水で順次洗浄し、硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、減圧下濃縮した。濃縮残渣をシリカゲルカラムクロマトグラフィーで精製し、化合物(5-6)が65.2g得られた(収率82%)。
500ml四つ口フラスコに化合物(5-6)63.0g(161mmol)、テトラヒドロフラン(THF)250ml及びメタノール50mlを加え攪拌した。混合液に濃硫酸1.0gを加え室温で5時間反応した。反応液を酢酸エチル500mlに投入し、飽和炭酸水素ナトリウム水溶液と飽和食塩水で順次洗浄した。有機層を濃縮し、得られた残渣をシリカゲルカラムクロマトグラフィで精製し、化合物(5-7)が45.3g得られた(収率92%)。
化合物(5-8)は以下に示す方法で合成した。
四つ口フラスコ(1l)に、トランス-1,4-シクロヘキサンジカルボン酸ジメチルエステル(5-8-1)100.0g(500mmol)とメタノール1000mlを加え攪拌した。水酸化カリウム16.8g(300mmol)を加えた後、還流下に6時間反応した。冷却後、反応液を濃縮し残渣に水500mlを加えた。希塩酸をpH2になるまで加え、析出した結晶をろ過した。結晶を水で洗浄後、減圧乾燥した。化合物(5-8-2)が54.0g(収率58.0%)得られた。
窒素雰囲気下、300ml四つ口フラスコに化合物(5-8-2)49.5g(266mmol)、N,N-ジメチル-4-アミノピリジン(DMAP)3.3g(26.7mmol)、tert-ブチルアルコール150mlおよびテトラヒドロフラン150mlを加え均一に撹拌した。氷冷下、N,N‘-ジイソプロピルカルボジイミド(DIC)50.4g(399mmol)を滴下した。室温で6時間反応した。水15mlを加えさらに1時間撹拌した。不溶物をろ過後、減圧下で反応液を濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィ(ジクロロメタン)で精製した。化合物(5-8-3)が51.9g得られた(収率80.6%)。
四つ口フラスコ(300ml)に化合物(5-8-3)48.0g(198mmol)、メタノール150mlおよびテトラヒドロフラン150mlを加え撹拌した。氷冷下、水酸化ナトリウム24.0g(600mmol)を加え、5℃以下で3時間撹拌した。水1000mlに投入し、ジクロロメタンで洗浄した。水層に希塩酸をpH2になるまで加えた。析出した結晶をろ過し、水で洗浄後減圧乾燥した。化合物(5-8)が41.4g得られた(収率91.6%)。
窒素雰囲気下、300ml四つ口フラスコに化合物(5-7)44.0g(144mmol)、化合物(5-8)32.8g(144mmol)、N,N-ジメチル-4-アミノピリジン(DMAP)1.8g(14.4mmol)およびテトラヒドロフラン500mlを加え均一に撹拌した。氷冷下、N,N‘-ジイソプロピルカルボジイミド(DIC)20.0g(158mmol)を滴下した。室温で6時間反応した。水15mlを加えさらに1時間撹拌した。不溶物をろ過後、減圧下で反応液を濃縮した。得られた残渣をシリカゲルカラムクロマトグラフィ(ジクロロメタン)で精製し、化合物(5-9)が69.2g得られた(収率93%)。
化合物(5-9)68.0g(132mmol)、触媒(5%Pd/C)2.8g及び酢酸エチル400mlを1lオートクレーブに加えた。水素圧0.3MPaを維持しながら室温で3時間反応させた。触媒をろ過し減圧下濃縮した。化合物(5-10)が56.3g得られた(定量的)。
乾燥空気雰囲気下、500ml四つ口フラスコに化合物(5-10)55.0g(129mmol)、トリエチルアミン(TEA)14.4g(142mmol)及びジクロロメタン300mlを加え攪拌した。アクリロイルクロリド12.3g(135mmol)を5℃以下で滴下し、室温で3時間反応した。反応液を水、希塩酸、飽和炭酸水素ナトリウム及び飽和食塩水で順次洗浄した。有機層を硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ過し、減圧下濃縮した。化合物(5-11)が62.0g得られた(定量的)。
乾燥空気雰囲気下、2000ml四つ口フラスコに化合物(5-11)60.0g(125mmol)、ジクロロメタン1000mlを加え撹拌した。氷冷下、トリフルオロ酢酸(TFA)142g(1250mmol)を滴下し、室温で8時間反応した。ヘキサン1000mlを加え、減圧下でジクロロメタンを留去した。析出した結晶をろ過し、水とヘキサンで順次洗浄した。結晶を減圧下乾燥し、化合物(5)が51.0g得られた(収率96.1%)。
窒素雰囲気下、300ml四つ口フラスコに、化合物(4)3.3g(11mmol)、化合物(5)10.2g(24mmol)、N,N-ジメチル-4-アミノピリジン(DMAP)0.28g(2mmol)及びジクロロメタン80mlを加え攪拌した。得られた混合液にジイソプロピルカルボジイミド(DIC)3.2g(25mmol)を溶解したジクロロメタン溶液20mlを5℃以下で滴下した。滴下後、室温で4時間反応させた。水を1ml添加しさらに1時間攪拌した。不溶物をろ過後、ろ液を水洗し、硫酸ナトリウムで乾燥した。硫酸ナトリウムをろ別後、減圧濃縮した。残渣にメタノール200mlを加えて氷冷下で沈殿させた。沈殿をろ過し、メタノールとn-ヘキサンで順次洗浄した。減圧下で乾燥して化合物(1-15-1)が8.8g得られた(収率72%)。
上記のように合成した重合性化合物(1-1-15)を19.32重量%、重合開始剤であるイルガキュア907(チバ・スペシャルティ・ケミカルズ株式会社製)を0.60重量%、重合禁止剤であるp-メトキシフェノール(MEHQ)を0.04重量%、界面活性剤であるBYK-361N(ビックケミージャパン製)を0.04重量%、溶剤であるクロロホルムを80.00重量%の配合で含む塗布液を調製した。
450nmから700nmの波長範囲において、作製した光学フィルムの位相差値を、測定機(RET-100、大塚電子社製)を用いて測定し、装置付属プログラムで波長450nmの位相差値Re(450)、波長550nmの位相差値Re(550)、波長650nmの位相差値Re(650)を算出した。その結果を表1に示す。
以下に示す方法により、下記式(1-1-16)で表される重合性化合物を合成した。
[化合物(1-1-16)の合成]
化合物(5-3)(1、6-ヘキサンジオール)を1、3-プロパンジオールに変えて合成を行った以外は、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(1-1-16)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに170℃で1分乾燥し、160℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
以下に示す方法により、下記式(Ref1)で表される重合性化合物を合成した。
[比較例1(Ref1)の合成]
化合物(1)(1、4-ナフトキノン)を1、4-ベンゾキノンに変えて合成を行った以外は、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(Ref1)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに200℃で1分乾燥し、190℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
以下に示す方法により、下記式(1-1-17)で表される重合性化合物を合成した。
[化合物(1-1-17)の合成]
化合物(4)の合成例で使用したマロノニトリルをシアノ酢酸エチルに変えて合成を行った以外は、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(1-1-17)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに90℃で1分乾燥し、90℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
以下に示す方法により、下記式(Ref2)で表される重合性化合物を合成した。
[比較例2(Ref2)の合成]
化合物(1)(1、4-ナフトキノン)を1、4-ベンゾキノンに変え、化合物(4)の合成例で使用したマロノニトリルをシアノ酢酸エチルに変えて合成を行った以外は、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(Ref2)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに110℃で1分乾燥し、110℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
以下に示す方法により、下記式(1-1-18)で表される重合性化合物を合成した。
[化合物(1-1-18)の合成]
化合物(4)の合成例で使用したマロノニトリルを5-オキソ-1-フェニル-2-ピラゾリン-3-カルボン酸エチルに変えて合成を行った以外は、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(1-1-18)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに130℃で1分乾燥し、130℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
以下に示す方法により、下記式(Ref3)で表される重合性化合物を合成した。
[比較例3(Ref3)の合成]
化合物(1)(1、4-ナフトキノン)を1、4-ベンゾキノンに変え、化合物(4)の合成例で使用したマロノニトリルを5-オキソ-1-フェニル-2-ピラゾリン-3-カルボン酸エチルに変え、且つ化合物(5-3)(1、6-ヘキサンジオール)を1、3-プロパンジオールに変えて、化合物(1-1-15)の合成例と同様に合成を行った。
実施例1で使用した重合性化合物(1-1-15)に代えて重合性化合物(Ref3)を同量で使用した以外は、実施例1と同様に塗布液を作製した。
次に、ラビング処理が施されたポリイミド付のガラス基板上に、前記塗布液をスピンコート法により塗布した。ホットプレート上において80℃で1分間乾燥した後、さらに150℃で1分乾燥し、150℃で1000mJ/cm2の紫外線を照射して、光学フィルム(光学異方体)を作製した。
作製した光学フィルムについて、実施例1と同様に光学特性を測定した。その結果を表1に併記した。
Claims (13)
- 一般式(1-0)
A1、A2、A3、A4はそれぞれ独立に二価の脂環式炭化水素基又は芳香族炭化水素基を表し、
X1、X2、X3、X4はそれぞれ独立に二価の連結基又は単結合を表し、
R1は炭素原子数1~12のアルキル基、アルコキシ基又は「*-Sp-P」を表し(*はA4又はA3に結合することを表す。)、
m、nはそれぞれ独立に0~4の整数を表し(ただし、m+nは2以上の整数である。)、
Zは式中のC-C=C-Cとともにナフタレン環を表し、このナフタレン環に結合する水素原子のうち2つが式中のX2を含む基及びX3を含む基にそれぞれ置換されており、
T1、T2はそれぞれ独立に、-S-、-O-、-NR2-、-CH2-、-NH-、-C(=O)-、-S(=O)-又は-C(=S)-を表し、
R2は水素原子、ハロゲン原子、炭素原子数1~6のアルキル基、炭素原子数1~6のアルコキシ基、シアノ基、ニトロ基又は水酸基を表し、
R3、R4は、それぞれ独立して一価の置換基を表すか、又は、R3とR4を連結するYを介して環を形成する。この環を形成する場合には、R3及びR4 はそれぞれ独立して、-O-、-S-、-SO-、-SO2-、-NR-(Rは水素原子又は一価の置換基を表す。)、=N-、=N(+)R-(Rは水素原子又は一価の置換基を表す。)、-C(=O)-、-C (=S)-及び=CR-(Rは水素原子又は一価の置換基を表す。)からなる群から選ばれる基を表す。
Yは炭素原子及び第14~16族の非金属原子からなる群から選択される2~4個の原子を表し、式中のR3-C-R4と共に5~7員環を形成する。この5~7員環に結合する水素原子には一価の置換基が結合してもよい。ただし、T1とR3、及びT2とR4が同じである場合、並びに、T1とR4、及びT2とR3が同じである場合は除く。]
で表される、重合性化合物。 - R3及びR4がそれぞれ独立に一価の置換基であり、R3及びR4のうち少なくとも一方がシアノ基である、請求項1~4の何れか一項に記載の重合性化合物。
- R3及びR4がそれぞれ独立に一価の置換基であり、R3又はR4が炭素原子数1~3のアルキル基を有するカルボン酸アルキルである、請求項1~5の何れか一項に記載の重合性化合物。
- X1、X2、X3、及びX4は、それぞれ独立に、単結合、-CH2CH2-、-CH=CH-、-C≡C-、-CH=CHCOO-、-OCO-CH=CH-、-(CH2)u-O-COO-、-(CH2)u-OCO-、-(CH2)u-COO-、-(CH2)u-O -、-O-COO-(CH2)u-、-OCO-(CH2)u-、-COO-(CH2)u-、又は-O-(CH2)u-である(ただし、uは0~2の何れかの整数を表す。)請求項1~7の何れか一項に記載の重合性化合物。
- 請求項1~8の何れか一項に記載の重合性化合物を含有する組成物。
- 請求項9に記載の組成物を重合することにより得られる重合体。
- 請求項10に記載の重合体を用いた光学異方体。
- 請求項11に記載の光学異方体を用いた液晶表示素子。
- 請求項11に記載の光学異方体を用いた有機EL素子。
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