WO2018021328A1 - Polymer composition - Google Patents

Polymer composition Download PDF

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Publication number
WO2018021328A1
WO2018021328A1 PCT/JP2017/026900 JP2017026900W WO2018021328A1 WO 2018021328 A1 WO2018021328 A1 WO 2018021328A1 JP 2017026900 W JP2017026900 W JP 2017026900W WO 2018021328 A1 WO2018021328 A1 WO 2018021328A1
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Prior art keywords
group
hydrogen atom
carbon atoms
ring
substituent
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PCT/JP2017/026900
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French (fr)
Japanese (ja)
Inventor
伊藤　潤
裕太 菅野
真 畑中
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日産化学工業株式会社
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Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to KR1020187037257A priority Critical patent/KR102345838B1/en
Priority to JP2018529921A priority patent/JP7029111B2/en
Priority to CN201780044750.0A priority patent/CN109476926B/en
Publication of WO2018021328A1 publication Critical patent/WO2018021328A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

Definitions

  • the present invention relates to a polymer composition having a dichroic dye useful for forming an alignment layer for aligning a polymerizable liquid crystal composition to be a polarizing layer in forming a polarizing element.
  • iodine has been widely used as a dichroic dye for polarizing plates used in liquid crystal displays and the like.
  • iodine-based polarizing films have a problem that heat resistance, light resistance, etc. are inferior, attempts have been made to use organic dichroic substances, that is, dichroic dyes.
  • a dichroic dye for the purpose of obtaining high dichroism, a dye having an azo skeleton as a basic skeleton (Patent Documents 1 and 2), a dye having an anthraquinone skeleton, and the like are often used.
  • a dye serving as a guest material was mixed with a liquid crystal compound serving as a host material as a coating type polarizing plate.
  • a method of applying a liquid crystal composition to a substrate is known (Patent Document 3).
  • Patent Document 4 a method using a mixture of a crosslinkable liquid crystal and a polymerizable dichroic dye
  • adding a polymerizable non-liquid crystal solvent to the polymerizable liquid crystal compound A method for producing an optical anisotropic body in which a non-liquid crystal solvent is left in the coating film to improve adhesion with other optical films (Patent Document 5); and a polymerization property including a polymerizable mesogenic compound and a dichroic dye
  • Patent Document 6 a method in which a mesogen preparation is prepared and a polarizer is effectively prepared using the mesogen preparation in terms of time and cost.
  • the present invention provides a polymer composition having a dichroic dye useful for forming an alignment layer for aligning a polymerizable liquid crystal composition to be a novel polarizing layer.
  • A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
  • S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
  • T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
  • Y 1 is a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, and a monovalent substitution obtained by removing one hydrogen atom from a biphenyl ring.
  • a monovalent substituent formed by removing hydrogen, or a monovalent substituent formed by bonding two or six different substituents selected from these substituents through a linking group defined by B Represents a substituent, and hydrogen atoms bonded to carbon atoms in all these substituents are each independently —COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH C (CN) 2 , —CH ⁇ CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; Y 2 is a divalent substituent obtained by removing two hydrogen atoms
  • divalent substituents from which two hydrogen atoms have been removed from the furan ring divalent substituents from which two hydrogens have been removed from the pyrrole ring, and two hydrogen atoms from alicyclic hydrocarbons having 5 to 8 carbon atoms
  • R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —CH ⁇ CH—, —C ⁇ C—, * 1-CH ⁇ CH—CO—O— * 2, or * 1- O—CO—CH ⁇ CH— * 2;
  • * 1 represents a bonding position with P in the above formulas (1) to (6);
  • * 2 represents Q and Q in the above formulas (1) to (6).
  • the X may be the same or different;
  • Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring.
  • Divalent substituents divalent substituents from which two hydrogen atoms have been removed from a furan ring, divalent substituents from which two hydrogen atoms have been removed from a pyrrole ring, alicyclic carbonization having 5 to 8 carbon atoms Represents a divalent substituent obtained by removing two hydrogen atoms from hydrogen, and a divalent substituent selected from the group consisting of combinations thereof; provided that X is * 1-CH ⁇ CH—CO—O— * 2 or * 1-O—CO—CH ⁇ CH— * 2, * 1 represents the bonding position with P in the above formulas (1) to (6), and * 2 represents the above formulas (1) to (6).
  • ⁇ 4> The component according to any one of ⁇ 1> to ⁇ 3>, wherein the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Combined composition.
  • A, B, q1 and q2 have the same definition as above;
  • Y 3 is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, and a monovalent substitution in which one hydrogen atom is removed from a biphenyl ring.
  • R 3 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, naphthalene A monovalent substituent with one hydrogen atom removed from the ring, a monovalent substituent with one hydrogen atom removed from the biphenyl ring, a monovalent substituent with one hydrogen atom removed from the furan ring, a nitrogen-containing complex A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from an alicyclic hydrocarbon having from 5 to 8 carbon atoms, an alkyl group having from 1 to 12 carbon
  • any three to five of R 101 , R 102 , R 103 , R 104 and R 105 are each independently a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, C 3 to C 8 cycloalkyl group, C 3 to C 8 halocycloalkyl group, C 2 to C 6 alkenyl group, C 2 To C 6 haloalkenyl group, C 3 to C 8 cycloalkenyl group, C 3 to C 8 halocycloalkenyl group, C 2 to C 6 alkynyl group, C 2 to C 6 haloalkynyl group, (C 1 to C 1 to C 1 to C 6 haloalkynyl group, (C 1 to C 1 to C 1 to C 6 haloalkynyl group, (C 1 to C 1 to C
  • a divalent substituent in which two hydrogen atoms have been removed from a heterocyclic compound in the alkylene group, in a phenylene group or in a divalent substituent in which two hydrogen atoms have been removed from a carbocyclic compound, or
  • One or more hydrogen atoms in the divalent substituent obtained by removing two hydrogen atoms from the heterocyclic compound may be replaced with a fluorine atom or an organic group, and —CH 2 in R 106 CH 2 — may be replaced by —CH ⁇ CH—, and —CH 2 — in R 106 is a phenylene group, a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound, or a heterocyclic group.
  • Cyclization May be replaced with divalent substituent obtained by removing two hydrogen atoms from an object, further, -CH 2 in R 106 - is, -O -, - NHCO -, - CONH -, - COO-, Unless a divalent group selected from the group consisting of —OCO—, —NH—, —NHCONH—, and —CO— is adjacent to each other, these divalent groups may be substituted.
  • R107 is a hydrogen atom or a methyl group.
  • n represents 0 or 1.
  • the polymer composition used in the production method of the present invention has a dichroic dye in the side chain, and is a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter also simply referred to as a side chain polymer).
  • the coating film obtained using the polymer composition is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth an orientation layer) to which the orientation control ability was given through the process of heating the side chain type polymer film.
  • the polymer composition of the present invention is an alignment layer forming composition for orienting a polarizing layer containing a liquid crystalline composition and, if necessary, a dichroic dye, when forming the polarizing layer. Useful as.
  • the component (A) is a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range.
  • the side chain polymer preferably reacts with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 60 ° C to 300 ° C.
  • the side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
  • the (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in a temperature range of 60 ° C to 300 ° C.
  • the side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light.
  • the structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time.
  • the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.
  • the structure of the polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain has a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene group, and a tip.
  • a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene group, and a tip.
  • the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, It has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6) A structure is preferred.
  • A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH ⁇ CH—CO—.
  • S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
  • T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
  • Y 1 is a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, and a monovalent substitution obtained by removing one hydrogen atom from
  • a monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a pyrrole ring, or an alicyclic hydrocarbon having 5 to 8 carbon atoms 1 represents a monovalent substituent from which a hydrogen atom has been removed, or a monovalent group in which 2 to 6 identical or different substituents selected from these substituents are bonded via a linking group defined by B
  • hydrogen atoms bonded to carbon atoms are each independently —COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).
  • Y 2 is a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a divalent substituent obtained by removing two hydrogen atoms from a naphthalene ring, and a divalent substituent obtained by removing two hydrogen atoms from a biphenyl ring.
  • a divalent substituent from which two hydrogen atoms have been removed from a furan ring, a divalent substituent from which two hydrogen atoms have been removed from a pyrrole ring, and two hydrogens from an alicyclic hydrocarbon having 5 to 8 carbon atoms This represents a divalent substituent selected from the group consisting of a divalent substituent from which atoms have been removed, and combinations thereof, and hydrogen atoms bonded to carbon atoms in all these substituents are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms good; R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
  • X is a single bond, —COO—, —OCO—, —N ⁇ N—, —
  • the X may be the same or different;
  • Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH— May be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms; one of q1 and q2 is 1 and the other is 0; q3 is 0 or 1; P and Q each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring.
  • Divalent substituents divalent substituents from which two hydrogen atoms have been removed from a furan ring, divalent substituents from which two hydrogen atoms have been removed from a pyrrole ring, alicyclic carbonization having 5 to 8 carbon atoms Represents a divalent substituent obtained by removing two hydrogen atoms from hydrogen, and a divalent substituent selected from the group consisting of combinations thereof; provided that X is * 1-CH ⁇ CH—CO—O— * 2 or * 1-O—CO—CH ⁇ CH— * 2, * 1 represents the bonding position with P in the above formulas (1) to (6), and * 2 represents the above formulas (1) to (6).
  • the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
  • the side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
  • A, X, l, m, m1 and R have the same definition as above.
  • the side chain may be a photosensitive side chain represented by the following formula (14) or (15).
  • A, Y 1 , X, 1, m1, and m2 have the same definition as above.
  • the side chain may be a photosensitive side chain represented by the following formula (16) or (17).
  • A, X, l and m have the same definition as above.
  • the side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
  • A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
  • R 1 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents an alkyloxy group.
  • the side chain is preferably a photosensitive side chain represented by the following formula (20).
  • A, Y 1 , X, l and m have the same definition as above.
  • the (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
  • A, B, q1 and q2 have the same definition as above;
  • Y 3 is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, and a monovalent substitution in which one hydrogen atom is removed from a biphenyl ring.
  • R 3 represents a hydrogen atom, —NO 2 , —CN, —CH ⁇ C (CN) 2 , —CH ⁇ CH—CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, naphthalene A monovalent substituent with one hydrogen atom removed from the ring, a monovalent substituent with one hydrogen atom removed from the biphenyl ring, a monovalent substituent with one hydrogen atom removed from the furan ring, a nitrogen-containing complex A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from an alicyclic hydrocarbon having from 5 to 8 carbon atoms, an alkyl group having from 1 to 12 carbon
  • the above photosensitive side chain polymer capable of exhibiting liquid crystallinity is obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain, the liquid crystalline side chain monomer, and the dichroic dye monomer. Obtainable.
  • the photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
  • the photoreactive group possessed by the side chain the following structures and derivatives thereof are preferred.
  • photoreactive side chain monomer examples include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene, etc. And a polymerizable group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10) at least one photosensitive side chain, the above formulas (11) to (13) at least one photosensitive side chain, and the above formula (14) or (15).
  • sex A structure having a side chain is preferred.
  • photoreactive side chain monomers examples include monomers selected from the following formulas M1-1 to M1-7 and M1-17 to M1-20.
  • M1 is a hydrogen atom or a methyl group
  • s1 represents the number of methylene groups, and is a natural number of 2 to 9.
  • R is OH or NH 2
  • s1 represents the number of methylene groups, and is a natural number of 2 to 9.
  • Examples of the photoreactive side chain monomer represented by the above formula (M1-1) include 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl-1- (Oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, and the like ( 1) wherein R is OH, and 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-acryloxyhexyl-1-oxy) cinnamamide, 4- (3-methacryloxypropyl) And those wherein R in formula (M1-1) is NH 2 , such as (-1-oxy) cinnamamide.
  • the liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
  • a mesogenic group having a side chain even if it is a group having a mesogen structure alone, such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good.
  • the mesogenic group possessed by the side chain the following structure is preferable.
  • liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups
  • a structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.
  • liquid crystalline monomers as a monomer having a carboxyl group or an amide group, a monomer represented by a formula selected from the group consisting of the following formulas M2-1 to M2-9 can also be used.
  • R is OH or NH 2
  • M1 is a hydrogen atom or a methyl group
  • s1 represents the number of methylene groups is a natural number of 2 to 9.
  • a monomer having a substituent that exhibits liquid crystallinity which is an example of the other monomer
  • a monomer represented by a formula selected from the group consisting of the following formulas M2-10 to M2-16 can also be used.
  • M1 is a hydrogen atom or a methyl group
  • s1 represents the number of methylene groups, and is a natural number of 2 to 9.
  • a dichroic dye monomer is a monomer capable of forming a polymer having a dichroic dye at the side chain portion of the polymer when the polymer is formed, and is a hydrogen atom of the dichroic dye. Is a compound substituted with a polymerizable group.
  • the said polymeric group may be couple
  • Examples of the spacer include a divalent substituent obtained by removing two hydrogen atoms from an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a carbocyclic compound, or two hydrogen atoms removed from a heterocyclic compound.
  • a divalent substituent which is a divalent substituent in which two hydrogen atoms have been removed from an alkylene group, a phenylene group or a carbocyclic compound, or two hydrogen atoms have been removed from a heterocyclic compound.
  • One or more hydrogen atoms in the substituent may be replaced with a fluorine atom or an organic group.
  • —CH 2 CH 2 — in the spacer may be replaced with —CH ⁇ CH—, and —CH 2 — in the spacer removes two hydrogen atoms from the phenylene group or carbocyclic compound. May be replaced by a divalent substituent or a divalent substituent obtained by removing two hydrogen atoms from a heterocyclic compound, and when any of the following groups are not adjacent to each other, And —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  • a dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction.
  • the dichroic dye preferably has an absorption maximum wavelength ( ⁇ max) in the range of 300 to 700 nm.
  • dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, and among them, azo dyes are preferable.
  • the azo dye include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and bisazo dyes and trisazo dyes are preferable.
  • Examples of the azo dye include a compound represented by the formula (b) (hereinafter sometimes referred to as “compound (b)”).
  • a 1 (-N NA 2 )
  • a 2 represents a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent which may have a substituent. Represents a heterocyclic group.
  • p represents an integer of 1 to 4. When p is an integer of 2 or more, the plurality of A 2 may be the same or different independently of each other. ]
  • Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and benzoxazole.
  • Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the heterocyclic compound.
  • a phenyl group, a naphthyl group, and a monovalent heterocyclic group in A 1 and A 3 and a 1,4-phenylene group, a naphthalene-1,4-diyl group, and a divalent heterocyclic group in A 2 are optionally substituted
  • the group includes an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; a fluorinated alkyl having 1 to 4 carbon atoms such as a trifluoromethyl group A cyano group; a nitro group; a halogen atom; a substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (the substituted amino group has one or two alkyl groups having 1 to 6 carbon atoms)
  • the alkyl group having 1 to 6 carbon atoms may be linear or branched, and may be a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group.
  • B 1 to B 20 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group).
  • Group and unsubstituted amino group are as defined above), and represents a chlorine atom or a trifluoromethyl group.
  • n1 to n4 each independently represents an integer of 0 to 3.
  • the plurality of B 2 when n1 is 2 or more, the plurality of B 2 may be the same or different independently of each other; when n2 is 2 or more, the plurality of B 6 may be the same or different independently of each other; when n3 is 2 or more, the plurality of B 9 may be the same or different independently of each other; When n4 is 2 or more, the plurality of B 14 may be the same or different independently of each other.
  • the anthraquinone dye is preferably a compound represented by the formula (2-7).
  • R 1 to R 8 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the oxazone dye is preferably a compound represented by the formula (2-8).
  • R 9 to R 15 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • the acridine dye is preferably a compound represented by the formula (2-9).
  • R 16 to R 23 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
  • R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R x in the formula (2-7), the formula (2-8) and the formula (2-9) include a methyl group, an ethyl group, a propyl group, and a butyl group. Group, pentyl group, hexyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, toluyl group, xylyl group and naphthyl group.
  • the cyanine dye is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).
  • D 1 and D 2 each independently represent any group of formulas (2-10a) to (2-10d).
  • n5 represents an integer of 1 to 3.
  • D 3 and D 4 each independently represent any group of formulas (2-11a) to (2-11h).
  • n6 represents an integer of 1 to 3.
  • dichroic dye monomer examples include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, ⁇ -methylene- ⁇ -butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups.
  • a structure having a polymerizable group composed of at least one selected from the group consisting of siloxane and the above-described dichroic dye is preferable.
  • disperse thread 1 acrylate disperse thread 1 methacrylate
  • disperse yellow 7 methacrylate manufactured by ALDRICH
  • the side chain type polymer can be obtained by a copolymerization reaction of the above-described photoreactive side chain monomer exhibiting liquid crystallinity and a dichroic dye monomer. Further, copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity, a liquid crystalline side chain monomer, and a dichroic dye monomer, a photoreactive side chain monomer that exhibits liquid crystallinity, a liquid crystalline side chain monomer, and It can be obtained by copolymerization of a dichroic dye monomer. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
  • Examples of other monomers include industrially available monomers capable of radical polymerization reaction. Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
  • unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
  • acrylic ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl.
  • vinyl compound examples include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
  • styrene compound examples include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
  • maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
  • the content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 95 mol%, more preferably 30 mol% to 30 mol% based on the total amount of the side chain. 90 mol% is more preferable.
  • the coating film formed from the polymer composition of the present invention has an effect as a liquid crystal alignment film. There is a possibility of not playing enough.
  • the content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, more preferably 10 mol% to 70 mol% based on the total amount of sidechains. Further preferred.
  • the content of liquid crystalline side chains in the side chain polymer is higher than 90 mol% based on the total amount of side chains, the content of photoreactive side chains is less than 10 mol% based on the total amount of side chains, There is a possibility that the coating film formed from the polymer composition of the present invention does not sufficiently exhibit the effect as a liquid crystal alignment film.
  • the content of the dichroic dye side chain in the side chain polymer of the present invention is preferably 0.2 mol% to 20 mol%, more preferably 0.5 mol% to 15 mol% based on the total amount of the side chain. 1 mol% to 10 mol% is more preferable.
  • the coating film formed from the polymer composition of the present invention is used as the liquid crystal alignment film. There is a possibility that the effect of will not be fully achieved.
  • the side chain polymer of the present invention may contain other side chains other than the photoreactive side chain, liquid crystalline side chain, and dichroic dye side chain.
  • the content is the remaining portion when the total content of the photoreactive side chain, liquid crystalline side chain, and dichroic dye side chain is less than 100%.
  • the production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
  • RAFT reversible addition-cleavage chain transfer
  • a radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher.
  • radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation).
  • the radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation.
  • examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (
  • the radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
  • the organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
  • organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer
  • the polymerization temperature at the time of radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C.
  • the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass.
  • the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
  • the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is
  • the content is preferably 0.1 mol% to 10 mol% based on the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
  • the polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating.
  • impurities in the polymer can be reduced.
  • the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
  • the molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film.
  • the weight average molecular weight obtained in terms of polystyrene is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
  • the polymer composition of this invention can also contain the compound represented by a following formula (c) as (B) component.
  • formula (c) any three to five of R 101 , R 102 , R 103 , R 104 and R 105 are each independently a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, C 3 to C 8 cycloalkyl group, C 3 to C 8 halocycloalkyl group, C 2 to C 6 alkenyl group, C 2 To C 6 haloalkenyl group, C 3 to C 8 cycloalkenyl group, C 3 to C 8 halocycloalkenyl group, C 2 to C 6 alkynyl group, C 2 to C 6 haloalkynyl group, (C 1 to C 6 alkyl) ) Carbonyl
  • a divalent substituent from which two hydrogen atoms have been removed from a heterocyclic compound in a divalent substituent in which two hydrogen atoms have been removed from the alkylene group, phenylene group or carbocyclic compound, or
  • One or more hydrogen atoms in the divalent substituent obtained by removing two hydrogen atoms from the cyclic compound may be replaced with a fluorine atom or an organic group, and —CH 2 CH in R 106 2 — may be replaced by —CH ⁇ CH—, and —CH 2 — in R 106 represents a phenylene group, or a divalent substituent or heterocyclic ring in which two hydrogen atoms have been removed from a carbocyclic compound.
  • Formula May be replaced with divalent substituent obtained by removing two hydrogen atoms from further, -CH in R 106 2 - is, -O -, - NHCO -, - CONH -, - COO -, - OCO -, - NH -, - NHCONH-, and unless divalent radical selected from the group consisting of -CO- is not adjacent each other, these divalent good .R 107 be replaced based on the hydrogen An atom or a methyl group), and n represents 0 or 1. )
  • examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the notation “halo” also represents these halogen atoms.
  • C a to C b alkyl group in the present specification represents a linear or branched hydrocarbon group having a to b carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group.
  • the C a to C b haloalkyl group is represented by a linear or branched chain in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom and the number of carbon atoms is a to b And when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other.
  • fluoromethyl group chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fl group, 2-chloro-2,2-
  • the C a to C b cycloalkyl group represents a cyclic hydrocarbon group having a to b carbon atoms, and represents a monocyclic or complex ring structure having 3 to 6 members. Can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms.
  • cyclopropyl group 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group and the like. , Each selected range of carbon atoms.
  • a C a to C b halocycloalkyl group is a cyclic hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. It is possible to form a monocyclic or complex ring structure from 3 to 6-membered rings. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
  • 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like can be mentioned as specific examples, and each is selected within the range of the designated number of carbon atoms.
  • the C a to C b alkenyl groups are linear or branched having a carbon number of a to b and have one or more double bonds in the molecule.
  • Represents an unsaturated hydrocarbon group for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl group, 2- Specific examples include methyl-2-pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group, etc. Selected.
  • a C a to C b haloalkenyl group is a linear or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom. And an unsaturated hydrocarbon group having one or more double bonds in the molecule.
  • the halogen atoms may be the same as or different from each other.
  • C a to C b cycloalkenyl group in the present specification represents a cyclic unsaturated hydrocarbon group having 1 to 2 carbon atoms and having 1 to 2 carbon atoms
  • a monocyclic or complex ring structure from a 3-membered ring to a 6-membered ring can be formed.
  • Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-.
  • 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-hepten-2- Specific examples include yl groups and the like, and each is selected within the range of the designated number of carbon atoms.
  • a C a to C b halocycloalkenyl group has a cyclic structure in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom, the number of which is a to b, and 1 It represents an unsaturated hydrocarbon group having one or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members.
  • Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-.
  • substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other.
  • a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like are given as specific examples, and each group is selected within the range of the designated number of carbon atoms.
  • the C a to C b alkynyl group is a linear or branched chain having a carbon number of a to b, and has one or more triple bonds in the molecule.
  • Represents a saturated hydrocarbon group for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2-butynyl group, 1
  • Specific examples include a 1-dimethyl-2-propynyl group, a 2-hexynyl group, and the like, and each is selected within the range of the designated number of carbon atoms.
  • a C a to C b haloalkynyl group is a linear or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon group having one or more triple bonds in the molecule.
  • the halogen atoms when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other.
  • Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.
  • C a to C b alkoxy group in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group Specific examples include i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, etc. Selected in the range of the number of carbon atoms.
  • C a to C b haloalkoxy group in the present specification represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as difluoromethoxy group, trifluoromethoxy group, chloro Difluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro- 1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group, 2, 2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group, 2,2,3,3-tetra
  • (C a to C b alkyl) carbonyl group in the present specification represents an alkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, for example, acetyl group, propionyl group
  • Specific examples include butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, and the like, and each is selected within the range of the number of carbon atoms specified.
  • the notation of (C a to C b haloalkyl) carbonyl group in the present specification represents a haloalkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as fluoroacetyl group, chloro Acetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2-dimethyl
  • Specific examples include a propanoyl group and the like, and each is selected within the range of the designated number of carbon atoms.
  • (C a to C b alkoxy) carbonyl group in the present specification represents an alkyl-OC (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxycarbonyl group, ethoxy
  • Specific examples include a carbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, and the like. Selected by range.
  • the notation of (C a to C b haloalkoxy) carbonyl group in the present specification represents a haloalkyl-OC (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as 2-chloroethoxy
  • Specific examples include a carbonyl group, a 2,2-difluoroethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and the like. Selected by range.
  • the notation of (C a to C b alkylamino) carbonyl group in this specification represents a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of a to b carbon atoms.
  • Specific examples include methylcarbamoyl group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, t-butylcarbamoyl group, etc. Each of which is selected for each specified number of carbon atoms.
  • the notation of (C a to C b haloalkylamino) carbonyl group represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group having the above-mentioned meaning consisting of a to b carbon atoms.
  • Specific examples include 2-fluoroethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group, etc. Selected in a range of numbers.
  • the notation of a di (C a to C b alkyl) aminocarbonyl group means that the number of carbon atoms that may be the same or different from each other is a to b.
  • a carbamoyl group substituted by an alkyl group such as N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di-n-propylcarbamoyl
  • Specific examples include a group, an N, N-di-n-butylcarbamoyl group, and the like, which are selected in the range of the respective designated number of carbon atoms.
  • the substituents R 101 , R 102 , R 103 , R 104 and R 105 in the cinnamic acid or benzoic acid derivative having the structure represented by the formula (c) are each independently a hydrogen atom, a halogen atom, C 1 to A substituent selected from a C 6 alkyl group, a C 1 to C 6 haloalkyl group, a C 1 to C 6 alkoxy group, a C 1 to C 6 haloalkoxy group, a cyano group, and a nitro group is preferable.
  • R 103 is preferably a substituent other than a hydrogen atom in the above preferred definitions of R 101 , R 102 , R 103 , R 104 and R 105 from the viewpoint of orientation sensitivity, and preferably a halogen atom, C 1 to C 66 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, a substituent selected from cyano group and a nitro group more preferred.
  • R 101, R 102, R 103 , R 104 and R 105 is a group represented by the formula (c-2), among others, R 103 is A group represented by the formula (c-2) is preferable.
  • R 103 is A group represented by the formula (c-2) is preferable.
  • monomers include monomers selected from the formulas M1-1 to M1-7 and M1-17 to M1-21 as monomers having a cinnamic acid group.
  • Examples of the monomer having a benzoic acid group include monomers selected from the formulas M2-1 to M2-9.
  • Examples of such cinnamic acid and derivatives thereof include cinnamic acid, 4-methoxycinnamic acid, 4-ethoxy cinnamic acid, 4-propoxy cinnamic acid, 4-fluoro cinnamic acid, and the like.
  • monomers having a cinnamic acid group such as 4- (4- (6- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.
  • benzoic acid and derivatives thereof include benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, 4-fluorobenzoic acid; 4- (6- Methacryloxyhexyl-1-oxy) benzoic acid, 4- (6-acryloxyhexyl-1-oxy) benzoic acid, 4- (3-methacryloxypropyl-1-oxy) benzoic acid, 4- (4- (6 And monomers having a benzoic acid group such as methacryloxyhexyl-1-oxy) benzoyloxy) benzoic acid.
  • benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, 4-fluorobenzoic acid
  • 4- (6- Methacryloxyhexyl-1-oxy) benzoic acid 4- (6-acryloxyhexyl-1-oxy) benzoic acid, 4- (3-methacryloxypropyl-1-oxy)
  • the content when the component (B) is contained, the content is preferably 3 parts by mass to 100 parts by mass per 100 parts by mass of the side chain polymer of the component (A).
  • the content of the component (B) is 3 parts by mass or less, the irradiation margin is not improved.
  • the solvent tolerance of the cured film obtained may fall that content of (B) component exceeds 100 mass parts and is excessive.
  • the organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone,
  • the polymer composition of the present invention contains (A) a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent. Moreover, the compound represented by the said Formula (c) is contained as (B) component as needed.
  • the polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming an alignment layer. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent.
  • the resin component is a resin component containing a photosensitive side chain polymer having a dichroic dye in the side chain already described and capable of exhibiting liquid crystallinity.
  • the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
  • the resin component described above may be a photosensitive side chain polymer that has a dichroic dye in the side chain and can exhibit liquid crystallinity.
  • other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired.
  • the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
  • examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
  • the polymer composition used in the present invention may contain components other than the above (A) and organic solvent.
  • examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the alignment layer and the substrate, and the like. It is not limited.
  • Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done.
  • the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer
  • the compound that improves the adhesion between the alignment layer and the substrate include the following functional silane-containing compounds.
  • additives such as the following phenoplasts and epoxy group-containing compounds may be included in the polymer composition for the purpose of imparting heat resistance.
  • Specific phenoplast additives are shown below, but are not limited to this structure.
  • Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodip
  • the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
  • a photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
  • photosensitizers aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl- ⁇ -naphthothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- ( ⁇ -naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-b
  • Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
  • this invention relates to the manufacturing method of the board
  • a method for producing a substrate having a liquid crystal alignment film formed from the polymer composition of the present invention [I] (A) A polymer composition containing a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent on a substrate A step of applying a coating to form a coating film; [II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II]; Have Through the above steps, a liquid crystal alignment film having alignment control ability can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
  • the manufacturing method of the polarizing element is as follows: [IV] A step of preparing a substrate having the alignment layer obtained above; and a step selected from the following [V-1] and [V-2].
  • [V-1] A polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal is applied on the alignment layer of the substrate having the alignment layer, and the coating film is formed by heating and drying. And irradiating the obtained coating film with ultraviolet rays;
  • [V-2] On the alignment layer of the substrate having the alignment layer, (D) a polarizing layer-forming composition containing a dye having lyotropic liquid crystallinity is applied and heated to dry to form a coating film. Process. Thereby, a polarizing element can be obtained.
  • the combined composition is applied to form a coating film.
  • the substrate is usually a transparent substrate.
  • a transparent substrate When the substrate of the polarizing plate of the present invention (hereinafter sometimes referred to as the present polarizing plate) is not installed on the display surface of the display element, for example, a polarizing film obtained by removing the substrate from the polarizing plate is used as the display surface of the display element. In the case of installation, the substrate may not be transparent.
  • the transparent substrate means a substrate having transparency capable of transmitting light, particularly visible light, and the transparency means a characteristic that the transmittance with respect to a light beam having a wavelength of 380 to 780 nm is 80% or more.
  • a specific example of the transparent substrate is a translucent resin substrate.
  • polyolefin such as polyethylene and polypropylene
  • cyclic olefin resin such as norbornene polymer
  • polyvinyl alcohol polyethylene terephthalate
  • polymethacrylate ester polyacrylate ester
  • triacetylcellulose diacetyl Cellulose esters such as cellulose and cellulose acetate propionate
  • polyethylene naphthalate polycarbonate
  • polysulfone polyethersulfone
  • polyetherketone polyphenylene sulfide and polyphenylene oxide
  • polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin-based resin or polycarbonate is preferable.
  • Cellulose ester is obtained by esterifying part or all of hydroxyl groups contained in cellulose, and can be easily obtained from the market. Cellulose ester base materials can also be easily obtained from the market. Examples of commercially available cellulose ester substrates include “Fujitac Film” (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.).
  • Cyclic olefin resin can be easily obtained from the market.
  • Commercially available cyclic olefin resins include “Topas” [Ticona (Germany)], “Arton” [JSR Corporation], “ZEONOR” [Nippon Zeon Corporation], and “ZEONEX”. [Nippon Zeon Co., Ltd.] and “Apel” [Mitsui Chemicals Co., Ltd.].
  • Such a cyclic olefin resin can be formed into a substrate by, for example, forming a film by a known means such as a solvent casting method or a melt extrusion method.
  • a commercially available cyclic olefin resin substrate can also be used.
  • cyclic olefin resin base materials include “Essina” [Sekisui Chemical Co., Ltd.], “SCA40” [Sekisui Chemical Co., Ltd.], “Zeonor Film” [Optes Co., Ltd.], and “Arton Film”. [JSR Corporation].
  • the cyclic olefin-based resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group
  • the content ratio of the structural unit derived from the cyclic olefin is the total structural unit of the copolymer. On the other hand, it is usually 50 mol% or less, preferably 15 to 50 mol%.
  • chain olefins include ethylene and propylene
  • examples of aromatic compounds having a vinyl group include styrene, ⁇ -methylstyrene, and alkyl-substituted styrene.
  • the cyclic olefin-based resin is a ternary copolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group
  • the content ratio of the structural unit derived from the chain olefin is that of the copolymer.
  • the content of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol% based on the total structural unit, and the content of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol%. It is.
  • Such a terpolymer has the advantage that the amount of expensive cyclic olefin used can be relatively reduced in its production.
  • the characteristics required of the substrate vary depending on the configuration of the polarizing plate, but usually a substrate having as small a retardation as possible is preferable.
  • the substrate having as little retardation as possible include cellulose ester films having no phase difference, such as zero tack (Konica Minolta Opto Co., Ltd.), Z tack (Fuji Film Co., Ltd.), and the like.
  • an unstretched cyclic olefin resin substrate is also preferable.
  • the surface of the substrate on which the polarizing layer is not formed may be subjected to a hard coat treatment, an antireflection treatment, an antistatic treatment, or the like.
  • the hard coat layer may contain additives such as an ultraviolet absorber as long as the performance is not affected.
  • the thickness of the substrate is usually 5 to 300 ⁇ m, and preferably 20 to 200 ⁇ m, because if it is too thin, the strength tends to decrease and the workability tends to be poor.
  • the method for applying the polymer composition described above on the substrate is not particularly limited.
  • the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like.
  • Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
  • the polymer composition After the polymer composition is applied on the substrate, it is heated to 50 to 230 ° C., preferably 50 to 200 ° C. for 0.4 minutes to 60 minutes by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven.
  • the coating film can be obtained by evaporating the solvent for 1 minute, preferably 0.5 to 10 minutes.
  • the drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
  • the thickness of the coating film is too thick, it is disadvantageous in terms of anisotropy, and if it is too thin, there is a problem with polarization properties, so it is usually in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm. More preferably, it is 500 nm or less, and more preferably in the range of 10 nm to 300 nm.
  • step [II] the coating film obtained in step [I] is irradiated with polarized ultraviolet rays.
  • the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction.
  • ultraviolet rays to be used ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used.
  • the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used.
  • ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high-pressure mercury lamp can be used.
  • the irradiation amount of polarized ultraviolet rays depends on the coating film used.
  • the amount of irradiation is polarized ultraviolet light that realizes the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light.
  • the amount is preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.
  • step [III] the ultraviolet-irradiated coating film polarized in step [II] is heated.
  • An orientation control ability can be imparted to the coating film by heating.
  • a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used.
  • the heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
  • the heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature).
  • the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk.
  • the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C.
  • the liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
  • the thickness of the coating film formed after heating is preferably 5 nm to 500 nm, more preferably 50 nm to 300 nm, for the same reason described in the step [I].
  • substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply
  • the coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. .
  • polarized ultraviolet rays are formed. After irradiation and then heating, a polarizing element is prepared.
  • the coating film used in the method of the present invention is an alignment layer in which anisotropy is introduced with high efficiency and alignment control ability is excellent by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment. be able to.
  • the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
  • the optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film.
  • the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating.
  • the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating.
  • the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much.
  • the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.
  • the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferable to make it 0.1 mol% thru
  • the coating film used in the method of the present invention by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
  • the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured.
  • ⁇ A which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays.
  • the maximum value of ⁇ A ( ⁇ Amax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained.
  • a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ⁇ Amax.
  • the irradiation amount of the polarized ultraviolet light on the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet light that realizes ⁇ Amax. More preferably, it is within the range of 50%.
  • the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays realizing ⁇ Amax is 0. 0% of the entire photosensitive group of the side chain type polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
  • a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 60 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 50 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
  • the polarizing element provided by the present invention exhibits high reliability against external stresses such as light and heat.
  • the composition for forming a polarizing layer used for forming the polarizing element of the present invention contains a dichroic dye and (C) a polymerizable liquid crystal, or (D) a composition containing a dye having lyotropic liquid crystallinity. It is.
  • the composition for forming a polarizing layer containing a dichroic dye and (C) a polymerizable liquid crystal usually contains a solvent, and examples of the solvent include the same solvents as those contained in the above-mentioned oriented polymer composition. (C) It can be appropriately selected according to the solubility of the polymerizable liquid crystal.
  • the composition containing ⁇ (D) a dye having lyotropic liquid crystallinity usually contains a solvent, and the solvent is not particularly limited, and a conventionally known solvent can be used, but an aqueous solvent is preferable.
  • the aqueous solvent include water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like.
  • the hydrophilic solvent is a solvent that dissolves substantially uniformly in water.
  • hydrophilic solvent examples include alcohols such as methanol and isopropyl alcohol; glycols such as ethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methylethylketone; esters such as ethyl acetate; Is mentioned.
  • aqueous solvent water or a mixed solvent of water and a hydrophilic solvent is preferably used.
  • the dichroic dye the compounds shown in the above component (A) are used, but a dichroic dye having no polymerizable group may be used.
  • Examples of commercially available dichroic dyes having no polymerizable group include G-207, G-241, G-470 (manufactured by Hayashibara), Yellow-8, KRD-901, and KRD-902 (Showa Chemical). Kogyo Co., Ltd.) and SI-486 (Mitsui Chemicals Co., Ltd.).
  • the polymerizable liquid crystal is a compound having a polymerizable group and exhibiting liquid crystallinity.
  • the polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group.
  • the photopolymerizable group refers to a group capable of undergoing a polymerization reaction with an active radical or an acid generated from a photopolymerization initiator described later.
  • Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
  • the compound exhibiting liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and may be a nematic liquid crystal or a smectic liquid crystal in the thermotropic liquid crystal.
  • the polymerizable liquid crystal is preferably a smectic liquid crystal compound and more preferably a higher order smectic liquid crystal compound in that higher polarization characteristics can be obtained.
  • higher-order smectic liquid crystal compounds that form a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, or a smectic L phase.
  • higher order smectic liquid crystal compounds that form a smectic B phase, a smectic F phase, or a smectic I phase.
  • the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher order smectic phase
  • a polarizing film having a higher degree of alignment order can be produced.
  • such a long polarizing film having a high degree of orientational order can obtain a Bragg peak derived from a higher order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement.
  • the Bragg peak is a peak derived from a periodic structure of molecular orientation, and when the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher order smectic phase, the periodic interval is 3.0 to 6.06.
  • a membrane can be obtained.
  • Specific examples of such a compound include a compound represented by the following formula (d) (hereinafter sometimes referred to as compound (d)).
  • the polymerizable liquid crystal compounds may be used alone or in combination.
  • X 1 , X 2 and X 3 each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, at least one of X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent.
  • —CH 2 — constituting the cyclohexane-1,4-diyl group may be replaced by —O—, —S— or —NR—.
  • R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • U 1 represents a hydrogen atom or a polymerizable group.
  • U 2 represents a polymerizable group.
  • W 1 and W 2 each independently represent a single bond, —O—, —S—, —COO— or —OCOO—.
  • V 1 and V 2 each independently represents an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, -S- or -NH- may be substituted.
  • At least one of X 1 , X 2 and X 3 is preferably a 1,4-phenylene group which may have a substituent.
  • the 1,4-phenylene group which may have a substituent is preferably unsubstituted.
  • the cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent. It is preferable that the trans-cyclohexane-1,4-diyl group which may have a non-substituted group.
  • the optionally substituted 1,4-phenylene group or optionally substituted cyclohexane-1,4-diyl group includes a methyl group, an ethyl group, and a butyl group. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group, a cyano group, and a halogen atom.
  • Y 1 is preferably —CH 2 CH 2 —, —COO— or a single bond
  • Y 2 is preferably —CH 2 CH 2 — or —CH 2 O—.
  • U 2 is a polymerizable group.
  • U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group.
  • U 1 and U 2 are preferably both polymerizable groups, and both are preferably photopolymerizable groups.
  • the polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under a lower temperature condition.
  • the polymerizable groups represented by U 1 and U 2 may be different from each other independently, but are preferably the same.
  • the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group.
  • acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
  • alkanediyl group represented by V 1 and V 2 examples include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Group and icosane-1,20-diyl group and the like.
  • V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
  • substituents which the alkanediyl group having 1 to 20 carbon atoms which may have a substituent optionally include a cyano group and a halogen atom the alkanediyl group should be unsubstituted. It is more preferable that it is an unsubstituted and linear alkanediyl group.
  • W 1 and W 2 are independently of each other preferably a single bond or —O—.
  • the compound (d) include compounds represented by the formulas (1-1) to (1-23).
  • the cyclohexane-1,4-diyl group is preferably a trans isomer.
  • the exemplified compound (d) can be used alone or in combination for a long polarizing film. Moreover, when combining 2 or more types of polymeric liquid crystal compounds, it is preferable that at least 1 type is a compound (c), and it is more preferable that 2 or more types are a compound (d). In combination, the liquid crystallinity may be temporarily maintained even at a temperature lower than the liquid crystal-crystal phase transition temperature.
  • the mixing ratio when combining two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, more preferably 10:90 to 50:50. is there.
  • Compound (d) is, for example, Lub et al. Trav. Chim. It is manufactured by a known method described in Pays-Bas, 115, ⁇ 321-328 (1996), or Japanese Patent No. 4719156.
  • the polarizing layer contains (D) a dye having lyotropic liquid crystallinity
  • the dye is not particularly limited as long as it has lyotropic liquid crystallinity and can form a supramolecular aggregate.
  • lyotropic liquid crystalline dyes include azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, merocyanine compounds, and the like.
  • An azo compound is preferably used because it exhibits good lyotropic liquid crystallinity.
  • the azo compound is preferably an azo compound having a polar group in the molecule.
  • An azo compound having a polar group is soluble in an aqueous solvent, and is easily dissolved in an aqueous solvent to form a supramolecular aggregate. For this reason, the coating liquid containing an azo compound having a polar group exhibits particularly good lyotropic liquid crystallinity.
  • the polar group means a functional group having polarity. Examples of the polar group include functional groups containing oxygen and / or nitrogen having a relatively high electronegativity such as OH group, COOH group, NH 2 group, NO 2 group, and CN group.
  • an aromatic disazo compound represented by the following general formula (D-1) is preferable.
  • Q 1 represents a substituted or unsubstituted aryl group
  • Q 2 represents a substituted or unsubstituted arylene group
  • R D independently represents a hydrogen atom
  • a substituted or Represents an unsubstituted alkyl group a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenyl group
  • M represents a counter ion
  • m7 represents an integer of 0 to 2.
  • N7 represents an integer of 0 to 6.
  • m7 and n7 are not 0 but 1 ⁇ m7 + n7 ⁇ 6.
  • each RD is the same or different.
  • OH, (NHR D ) m7 , and (SO 3 M) n7 shown in the general formula (D-1) may be bonded to any of the seven substitution sites of the naphthyl ring.
  • substituted or unsubstituted means “substituted with a substituent or not substituted with a substituent”.
  • the bonding position of the naphthyl group and the azo group (—N ⁇ N—) in the general formula (D-1) is not particularly limited.
  • the naphthyl group refers to a naphthyl group represented on the right side in the formula (D-1).
  • the naphthyl group and the azo group are bonded at the 1-position or 2-position of the naphthyl group.
  • R D is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, and more preferably a hydrogen atom.
  • R D is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, and more preferably a hydrogen atom.
  • the substituted or unsubstituted alkyl group include substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  • M (counter ion) of the general formula (D-1) is preferably a hydrogen ion; an alkali metal ion such as Li, Na, K, or Cs; an alkaline earth metal ion such as Ca, Sr, or Ba; Metal ions; ammonium ions optionally substituted with alkyl groups or hydroxyalkyl groups; salts of organic amines, and the like.
  • the metal ions include Ni + , Fe 3+ , Cu 2+ , Ag + , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Sn 2+ , Co 2+ , Mn 2+ , Ce 3+ and the like can be mentioned.
  • Examples of the organic amine include alkylamines having 1 to 6 carbon atoms, alkylamines having 1 to 6 carbon atoms having a hydroxyl group, and alkylamines having 1 to 6 carbon atoms having a carboxyl group.
  • each M may be the same or different.
  • M of SO 3 M is a cation having a valence of 2 or more, it is bonded to SO 3 ⁇ of another adjacent azo compound of the general formula (D-1).
  • supramolecular aggregates can be formed.
  • M7 in the general formula (D-1) is preferably 1.
  • n7 is preferably 1 or 2.
  • Specific examples of the naphthyl group of the general formula (D-1) include the following formulas (Da) to (Dl).
  • R D and M in the formulas (Da) to (Dl) are the same as those in the general formula (D-1).
  • examples of the aryl group represented by Q 1 include a phenyl group and a condensed ring group in which two or more benzene rings are condensed, such as a naphthyl group.
  • examples of the arylene group represented by Q 2 include a condensed ring group in which two or more benzene rings are condensed, such as a naphthylene group, in addition to a phenylene group.
  • the aryl group of Q 1 or the arylene group of Q 2 may have a substituent, or may not have a substituent. Regardless of whether the aryl group or arylene group is substituted or unsubstituted, the aromatic disazo compound of the general formula (D-1) having a polar group is excellent in solubility in an aqueous solvent.
  • substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylamino group having 1 to 6 carbon atoms.
  • the substituent is one selected from an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group, a sulfonic acid group, and a nitro group.
  • An aromatic disazo compound having such a substituent is particularly excellent in water solubility.
  • These substituents may be substituted alone or in combination of two or more. Moreover, the said substituent may be substituted by arbitrary ratios.
  • Q 1 in the general formula (D-1) is preferably a substituted or unsubstituted phenyl group, more preferably a phenyl group having the substituent.
  • Q 2 is preferably a substituted or unsubstituted naphthylene group, more preferably a naphthylene group having the substituent, and particularly preferably a 1,4-naphthylene group having the substituent.
  • An aromatic disazo compound in which Q 1 in the general formula (D-1) is a substituted or unsubstituted phenyl group and Q 2 is a substituted or unsubstituted 1,4-naphthylene group has the following general formula (D -2).
  • R D , M, m7 and n7 are the same as those in the general formula (D-1).
  • a D and B D represent substituents, and a7 and b7 represent the number of substitutions.
  • a D and B D are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a phenylamino group, or a carbon atom.
  • the a7 is an integer from 0 to 5
  • the b7 is an integer from 0 to 4. However, at least one of a7 and b7 is not zero.
  • the substituents A D may be the same or different.
  • b7 is 2 or more, the substituents B D may be the same or different.
  • aromatic disazo compounds included in the general formula (D-2) it is preferable to use an aromatic disazo compound represented by the following general formula (D-3).
  • the aromatic disazo compound of the general formula (D-3) the substituent A D is bonded to the para position on the basis of the azo group (—N ⁇ N—). Further, in the aromatic disazo compound of the general formula (D-3), the OH group of the naphthyl group is bonded to the position adjacent to the azo group (ortho position). If such an aromatic disazo compound of the general formula (D-3) is used, a polarizing plate having a high degree of polarization can be obtained.
  • R D , M, m7 and n7 are the same as those in the general formula (D-1), and A D is the same as that in the general formula (D-2).
  • p7 represents an integer of 0 to 4. The p7 is preferably 1 or 2, and more preferably 1.
  • the aromatic disazo compounds represented by the above general formulas (D-1) to (D-3) are, for example, Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry (5th Edition)” (published on July 15, 1968 by Gihodo, 135 to 152).
  • the aromatic disazo compound of the general formula (D-3) is obtained by diazotizing and coupling an aniline derivative and a naphthalenesulfonic acid derivative to obtain a monoazo compound, and then diazotizing the monoazo compound. It can be synthesized by a coupling reaction with a 1-amino-8-naphtholsulfonic acid derivative.
  • the content of the (C) polymerizable liquid crystal compound or (D) lyotropic liquid crystal pigment in the composition for forming a polarizing layer is a solid content of the composition for forming a polarizing layer.
  • the amount is usually 70 to 99.9 parts by mass, preferably 80 to 99.9 parts by mass, more preferably 85 to 99 parts by mass, and still more preferably 90 to 99 parts by mass.
  • [IV] A step of preparing a substrate having the above alignment layer; and a step selected from the following [V-1] and [V-2].
  • [V-1] A polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal is applied on the alignment layer of the substrate having the alignment layer, and the coating film is formed by heating and drying. And irradiating the obtained coating film with ultraviolet rays;
  • [V-2] On the alignment layer of the substrate having the alignment layer, (D) a polarizing layer-forming composition containing a dye having lyotropic liquid crystallinity is applied and heated to dry to form a coating film. Process.
  • the application of the composition for forming a polarizing layer usually includes a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method, and a printing method such as a flexo method. This is done by known methods.
  • a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method
  • a printing method such as a flexo method.
  • the composition for forming a polarizing layer contains (C) polymerizable liquid crystal, by removing the solvent under the condition that (C) polymerizable liquid crystal contained in the obtained coating film is not normally polymerized after coating, A dry film is formed.
  • the drying method include natural drying, ventilation drying, heat drying, and reduced pressure drying.
  • the polymerizable liquid crystal (C) is polymerized by a known method of polymerizing a compound having a polymerizable functional group. be able to. Specific examples include thermal polymerization and photopolymerization, and photopolymerization is preferred from the viewpoint of ease of polymerization.
  • a composition containing a photopolymerization initiator to a polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal and drying it. It is preferable that the polymerizable liquid crystal in the dry film to be obtained is made into a liquid crystal phase and then photopolymerized while maintaining the liquid crystal state.
  • Fluorescence polymerization is usually carried out by irradiating the dry film with light.
  • the type of (C) polymerizable liquid crystal (particularly, the type of photopolymerizable group (C) polymerizable liquid crystal has), and the amount thereof, Specific examples include light selected from the group consisting of visible light, ultraviolet light, and laser light, and active electron beams.
  • ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a photopolymerization apparatus widely used in this field can be used, so that photopolymerization can be performed by ultraviolet light.
  • the polymerization temperature can be controlled by irradiating light while cooling the dry film by an appropriate cooling means.
  • a polarizing layer-forming composition containing a pigment having lyotropic liquid crystallinity is applied, and coating in the step of forming a coating film by heating and drying is performed, Usually, it is carried out by a known method including a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexographic method.
  • the drying method is not particularly limited, and natural drying or forced drying can be performed. Examples of forced drying include reduced-pressure drying, heat drying, and reduced-pressure heat drying. Preferably, natural drying is used.
  • the drying time can be appropriately selected depending on the drying temperature and the type of solvent. For example, in the case of natural drying, the drying time is preferably 1 second to 120 minutes, more preferably 10 seconds to 5 minutes.
  • the drying temperature is not particularly limited, but is preferably lower than the glass transition temperature (Tg) of the substrate. If the drying temperature exceeds the glass transition temperature of the substrate, the properties (such as mechanical strength and optical properties) of the substrate may be altered. Specifically, the drying temperature is preferably 10 ° C. to 100 ° C., more preferably 10 ° C. to 90 ° C., and particularly preferably 10 ° C. to 80 ° C.
  • the drying temperature means the temperature of the atmosphere in which the coating film is dried, not the surface or internal temperature of the coating film containing the pigment having (D) lyotropic liquid crystallinity.
  • the total thickness of the alignment layer and the polarizing layer in the Enomoto polarizing element is 10 ⁇ m or less.
  • the thickness of the alignment layer is preferably 0.5 ⁇ m or more and 9.5 ⁇ m or less, and more preferably 1 ⁇ m or more and 5 ⁇ m or less.
  • the thickness of the polarizing layer is preferably from 0.5 ⁇ m to 9.5 ⁇ m, and more preferably from 1 ⁇ m to 5 ⁇ m.
  • the thickness of the alignment layer and the polarizing layer can be usually determined by measurement with an interference film thickness meter, a laser microscope or a stylus thickness meter.
  • the obtained polarizing element can be widely applied to various display elements that require polarized light by using a known technique.
  • an antireflection film such as a liquid crystal display element or an organic EL. (Circularly polarizing plate), optical switches, optical filters, and various optical measuring instruments having them as constituent elements.
  • the molecular weight of the acrylic copolymer in the polymerization example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co. And measured.
  • the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
  • the acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P2).
  • Mn of the obtained acrylic copolymer was 12,000 and Mw was 28,000.
  • the acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P3).
  • Mn of the obtained acrylic copolymer was 11,000 and Mw was 21,000.
  • Examples 1 to 4> and ⁇ Comparative Examples 1 to 2> Compositions for forming alignment layers of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared with the compositions shown in Table 1. An alignment layer was formed using each composition for forming an alignment layer, and the dichroic ratio was measured for each alignment layer. Next, a polarizing element was formed using the composition for forming a polarizing layer. For each of the obtained polarizing elements, evaluation of orientation, polarization degree measurement, and dichroic ratio measurement were performed.
  • Example 1 [Formation of alignment layer]
  • the composition for forming an alignment layer shown in Table 1 was spin-coated on a quartz substrate, dried on a hot plate at 55 ° C. for 60 seconds, and then a coating film having a thickness of 200 nm was formed. Subsequently, 313 nm linearly polarized light was irradiated perpendicularly
  • the dichroic ratio of the obtained alignment layer was measured as follows.
  • the absorbance in the direction of the transmission axis (A1) and the absorbance in the direction of the absorption axis (A2) were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (Shimadzu Corporation UV-3600).
  • the dichroic ratio was calculated from the measured absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction using the following formula.
  • the measurement results are shown in Table 2.
  • Dichroic ratio (A2) / (A1)
  • the composition for forming a polarizing layer was spin-coated at 2000 rpm ⁇ 30 sec and dried on a hot plate at 65 ° C. for 60 sec to form a coating film. Next, this coating film was exposed at 500 mJ / cm 2 to obtain a polarizing element.
  • the polarization degree of the obtained polarizing element was measured as follows.
  • the transmittance (T1) in the transmission axis direction and the transmittance (T2) in the absorption axis direction were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation).
  • the degree of polarization was calculated from the measured transmission axis direction transmittance (T1) and absorption axis direction transmittance (T2) using the following equation.
  • the measurement results are shown in Table 2.
  • Polarization degree (%) ⁇ (T1 ⁇ T2) / (T1 + T2) ⁇ 1/2 ⁇ 100
  • the dichroic ratio of the obtained polarizing element was measured as follows.
  • the absorbance in the direction of the transmission axis (A1) and the absorbance in the direction of the absorption axis (A2) were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (Shimadzu Corporation UV-3600).
  • the dichroic ratio was calculated from the measured absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction using the following formula.
  • the measurement results are shown in Table 2.
  • Dichroic ratio (A2) / (A1)
  • Example 2 A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 150 ° C. The results are summarized in Table 2.
  • Example 3 A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 110 ° C. The results are summarized in Table 2.
  • Example 4 A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 150 ° C. The results are summarized in Table 2.
  • the polarizers obtained in Examples 1 to 4 were able to express a higher degree of polarization and dichroic ratio than Comparative Examples 1 and 2.

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Abstract

[Problem] The present invention addresses the problem of providing a polymer composition for a liquid crystal orientation film in which a polymerizable crystal composition can be oriented when a polarizing element having high dichroism is to be obtained. [Solution] The present invention provides a polymer composition containing (A) a photosensitive side-chain polymer that has a dichroic pigment in a side chain and develops liquid crystallinity at a predetermined temperature range, and an organic solvent. In a substrate having a liquid crystal orientation membrane formed from the polymer composition, a polymerizable liquid crystal composition is applied onto the orientation film, heating and drying are subsequently performed, and UV ray irradiation is also performed as needed, thereby making it possible to yield a polarizing element having high dichroism.

Description

重合体組成物Polymer composition
  本発明は、偏光素子の形成において偏光層となる重合性液晶組成物を配向させるための配向層形成に有用な二色性色素を有する重合体組成物に関する。 The present invention relates to a polymer composition having a dichroic dye useful for forming an alignment layer for aligning a polymerizable liquid crystal composition to be a polarizing layer in forming a polarizing element.
　液晶ディスプレイなどに使用される偏光板としては、従来、二色性色素としてヨウ素が広く使用されてきた。しかしながら、ヨウ素系の偏光フィルムは耐熱性や耐光性等が劣るという問題があるため、有機系の二色性物質、すなわち二色性色素を利用する試みが行われている。 Conventionally, iodine has been widely used as a dichroic dye for polarizing plates used in liquid crystal displays and the like. However, since iodine-based polarizing films have a problem that heat resistance, light resistance, etc. are inferior, attempts have been made to use organic dichroic substances, that is, dichroic dyes.
　従来、二色性色素としては、高い二色性を得る目的で、基本骨格としてアゾ骨格を有する色素（特許文献１乃び２）や、アントラキノン骨格等を有する色素が多く用いられている。 Conventionally, as a dichroic dye, for the purpose of obtaining high dichroism, a dye having an azo skeleton as a basic skeleton (Patent Documents 1 and 2), a dye having an anthraquinone skeleton, and the like are often used.
　また、偏光板の製造方法としては、ヨウ素や二色性色素などを含むポリマーフィルムを延伸する方法のほか、塗布型偏光板として、ホスト材料となる液晶化合物にゲスト材料となる色素を混合させた液晶組成物を基板に塗布する方法が知られている（特許文献３）。さらには、より安定な偏光フィルムを提供するために、架橋性液晶と重合性二色性染料の混合物を用いる方法（特許文献４）；重合性液晶化合物に重合性非液晶溶媒を加え、重合性非液晶溶媒を塗膜中に残存させて他の光学フィルム等との密着性を改善した光学異方体の製造方法（特許文献５）；ならびに重合性メソゲン化合物と二色性色素を含む重合性メソゲン製剤を調製し、これを用いて時間およびコストの点で効果的に偏光子を調製する方法（特許文献６）も提案されている。 Moreover, as a manufacturing method of a polarizing plate, in addition to a method of stretching a polymer film containing iodine, a dichroic dye, or the like, a dye serving as a guest material was mixed with a liquid crystal compound serving as a host material as a coating type polarizing plate. A method of applying a liquid crystal composition to a substrate is known (Patent Document 3). Furthermore, in order to provide a more stable polarizing film, a method using a mixture of a crosslinkable liquid crystal and a polymerizable dichroic dye (Patent Document 4); adding a polymerizable non-liquid crystal solvent to the polymerizable liquid crystal compound, A method for producing an optical anisotropic body in which a non-liquid crystal solvent is left in the coating film to improve adhesion with other optical films (Patent Document 5); and a polymerization property including a polymerizable mesogenic compound and a dichroic dye There has also been proposed a method (Patent Document 6) in which a mesogen preparation is prepared and a polarizer is effectively prepared using the mesogen preparation in terms of time and cost.
特開２０１１－２１３６１０号公報JP 2011-213610 A 特表２００６－５２５３８２号公報Special table 2006-525382 gazette 特表２００８－５４７０６２号公報Special table 2008-547062 gazette 特表２００４－５３５４８３号公報JP-T-2004-535483 特開２００４－１９８４８０号公報JP 2004-198480 A 特表２００６－１６１０５１号公報JP 2006-161051 Gazette
　現在、可視光領域における吸収特性を高めるため、吸収特性に優れる二色性色素を液晶性組成物に高配合することが検討されている。しかしながら、そのような二色性色素は、一般に、溶媒に対する溶解性が低いため、液晶性組成物に高配合することが困難であるという問題があった。 Currently, in order to enhance the absorption characteristics in the visible light region, it has been studied to highly blend a dichroic dye having excellent absorption characteristics into a liquid crystalline composition. However, such dichroic dyes generally have a low solubility in a solvent, and thus there is a problem that it is difficult to blend them in a liquid crystal composition.
　上記背景のもと、本発明は、新規な偏光層となる重合性液晶組成物を配向させるための配向層形成に有用な二色性色素を有する重合体組成物を提供する。 Based on the above background, the present invention provides a polymer composition having a dichroic dye useful for forming an alignment layer for aligning a polymerizable liquid crystal composition to be a novel polarizing layer.
　本発明者らは、上記課題を達成するべく鋭意検討を行った結果、以下の発明を見出した。
　＜１＞　［Ｉ］　（Ａ）側鎖に二色性色素を有し且つ所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び有機溶媒を含有する重合体組成物。
　＜２＞　（Ａ）成分が、光架橋、光異性化、または光フリース転移を起こす感光性側鎖を有する上記＜１＞記載の重合体組成物。 As a result of intensive studies to achieve the above problems, the present inventors have found the following invention.
<1> [I] (A) A polymer composition containing a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent.
<2> The polymer composition according to <1>, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
　＜３＞　（Ａ）成分が、下記式（１）乃至（６）からなる群から選ばれるいずれか１種の感光性側鎖を有する上記＜１＞記載の重合体組成物。
Figure JPOXMLDOC01-appb-C000005
 　式中、Ａ、Ｂ及びＤはそれぞれ独立に、単結合、－Ｏ－、－ＣＨ2－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯ－Ｏ－、又は－Ｏ－ＣＯ－ＣＨ＝ＣＨ－を表す；
　Ｓは、炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子に結合する水素原子はハロゲン原子に置き換えられていてもよい；
　Ｔは、単結合または炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子にに結合する水素原子はハロゲン原子に置き換えられていてもよい；
　Ｙ1は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、ピロール環から一つの水素原子を取り去った１価の置換基、もしくは炭素原子数５乃至８の脂環式炭化水素から一つの水素を取り去った１価の置換基を表すか、又はそれらの置換基から選ばれる同一又は相異なった２乃至６つの置換基がＢで定義される結合基を介して結合してなる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＣＯＯＲ0（式中、Ｒ0は水素原子又は炭素原子数１乃至５のアルキル基を表す）、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｙ2は、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｒは、ヒドロキシ基、炭素原子数１乃至６のアルコキシ基を表すか、又はＹ1と同じ定義を表す；
　Ｘは、単結合、－ＣＯＯ－、－ＯＣＯ－、－Ｎ＝Ｎ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２を表し、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
　Ｃｏｕは、クマリン－６－イル基またはクマリン－７－イル基を表し、それらに結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　ｑ１とｑ２は、一方が１で他方が０である；
　ｑ３は０または１である；
　Ｐ及びＱは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し；ただし、Ｘが※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２である場合、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、－ＣＨ＝ＣＨ－が結合する側のＰ又はＱは芳香環から二つの水素原子を取り去った２価の置換基を表す；
　ｌ１は０または１である；
　ｌ２は０乃至２の整数である；
　ｌ１とｌ２がともに０であるとき、かつＴが単結合であるときはＡも単結合を表す；
　ｌ１が１であるとき、かつＴが単結合であるときはＢも単結合を表す；
　Ｈ及びＩは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、およびそれらの組み合わせから選ばれる２価の置換基を表す。 <3> The polymer composition according to <1>, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
Figure JPOXMLDOC01-appb-C000005
 In the formula, A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
Y 1 is a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, and a monovalent substitution obtained by removing one hydrogen atom from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a pyrrole ring, or an alicyclic hydrocarbon having 5 to 8 carbon atoms A monovalent substituent formed by removing hydrogen, or a monovalent substituent formed by bonding two or six different substituents selected from these substituents through a linking group defined by B Represents a substituent, and hydrogen atoms bonded to carbon atoms in all these substituents are each independently —COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), -NO 2 , -CN, -CH = C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
Y 2 is a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a divalent substituent obtained by removing two hydrogen atoms from a naphthalene ring, and a divalent substituent obtained by removing two hydrogen atoms from a biphenyl ring. Groups, divalent substituents from which two hydrogen atoms have been removed from the furan ring, divalent substituents from which two hydrogens have been removed from the pyrrole ring, and two hydrogen atoms from alicyclic hydrocarbons having 5 to 8 carbon atoms And a divalent substituent selected from the group consisting of combinations thereof, wherein hydrogen atoms bonded to carbon atoms in all these substituents are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms. ;
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, * 1-CH═CH—CO—O— * 2, or * 1- O—CO—CH═CH— * 2; * 1 represents a bonding position with P in the above formulas (1) to (6); * 2 represents Q and Q in the above formulas (1) to (6). When the number of X is 2, the X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. Divalent substituents, divalent substituents from which two hydrogen atoms have been removed from a furan ring, divalent substituents from which two hydrogen atoms have been removed from a pyrrole ring, alicyclic carbonization having 5 to 8 carbon atoms Represents a divalent substituent obtained by removing two hydrogen atoms from hydrogen, and a divalent substituent selected from the group consisting of combinations thereof; provided that X is * 1-CH═CH—CO—O— * 2 or * 1-O—CO—CH═CH— * 2, * 1 represents the bonding position with P in the above formulas (1) to (6), and * 2 represents the above formulas (1) to (6). Represents the bonding position with Q in (6), and —CH═CH— P or Q of the binding side represents a divalent substituent obtained by removing two hydrogen atoms from an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, and T is a single bond, A also represents a single bond;
when l1 is 1 and T is a single bond, B also represents a single bond;
H and I each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. A divalent substituent selected by removing two hydrogen atoms from the furan ring, a divalent substituent removing two hydrogen atoms from the pyrrole ring, and combinations thereof. Represents a group.
　＜４＞　（Ａ）成分が、下記式（２１）乃至（３１）からなる群から選ばれるいずれか１種の液晶性側鎖を有する上記＜１＞乃至＜３＞のいずれかに記載の重合体組成物。
Figure JPOXMLDOC01-appb-C000006
 　式中、Ａ、Ｂ、ｑ１及びｑ２は上記と同じ定義を有する；
　Ｙ3は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、および、それらの組み合わせからなる群から選ばれる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｒ3は、水素原子、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、炭素原子数１乃至１２のアルキル基、又は炭素原子数１乃至１２のアルコキシ基を表す；
　ｌは１乃至１２の整数を表し、ｍは０乃至２の整数を表し、但し、式（２３）および式（２４）において、全てのｍの合計は２以上であり、式（２５）および式（２６）において、全てのｍの合計は１以上であり、ｍ１、ｍ２およびｍ３は、それぞれ独立に１乃至３の整数を表す；
　Ｒ2は、水素原子、－ＮＯ2、－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、アルキル基、又はアルキルオキシ基を表す；
　Ｚ1及びＺ2は単結合、－ＣＯ－、－ＣＨ2Ｏ－、－ＣＨ＝Ｎ－、又は－ＣＦ2－を表す。 <4> The component according to any one of <1> to <3>, wherein the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). Combined composition.
Figure JPOXMLDOC01-appb-C000006
 In which A, B, q1 and q2 have the same definition as above;
Y 3 is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, and a monovalent substitution in which one hydrogen atom is removed from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. Represents a monovalent substituent selected from the group consisting of a monovalent substituent from which two hydrogen atoms have been removed, and a combination thereof, and each of these substituents independently represents a hydrogen atom bonded to a carbon atom. May be substituted with —NO 2 , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, naphthalene A monovalent substituent with one hydrogen atom removed from the ring, a monovalent substituent with one hydrogen atom removed from the biphenyl ring, a monovalent substituent with one hydrogen atom removed from the furan ring, a nitrogen-containing complex A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from an alicyclic hydrocarbon having from 5 to 8 carbon atoms, an alkyl group having from 1 to 12 carbon atoms Or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formula (23) and formula (24), the sum of all m is 2 or more, and formula (25) and formula In (26), the sum of all m is 1 or more, and m1, m2, and m3 each independently represents an integer of 1 to 3;
R 2 represents a hydrogen atom, —NO 2 , —CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, biphenyl A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, carbon Represents a monovalent substituent, an alkyl group, or an alkyloxy group in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 atoms;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, or —CF 2 —.
　　＜５＞　（Ｂ）成分として、下記式（ｃ）で表される化合物を含有することを特徴とする上記＜１＞乃至＜４＞のいずれかに記載の重合体組成物。
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至５つは、それぞれ独立に水素原子、ハロゲン原子、Ｃ1乃至Ｃ6アルキル基、Ｃ1乃至Ｃ6ハロアルキル基、Ｃ1乃至Ｃ6アルコキシ基、Ｃ1乃至Ｃ6ハロアルコキシ基、Ｃ3乃至Ｃ8シクロアルキル基、Ｃ3乃至Ｃ8ハロシクロアルキル基、Ｃ2乃至Ｃ6アルケニル基、Ｃ2乃至Ｃ6ハロアルケニル基、Ｃ3乃至Ｃ8シクロアルケニル基、Ｃ3乃至Ｃ8ハロシクロアルケニル基、Ｃ2乃至Ｃ6アルキニル基、Ｃ2乃至Ｃ6ハロアルキニル基、（Ｃ1乃至Ｃ6アルキル）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）カルボニル基、（Ｃ1乃至Ｃ6アルコキシ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルコキシ）カルボニル基、（Ｃ1乃至Ｃ6アルキルアミノ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）アミノカルボニル基、ジ(Ｃ1乃至Ｃ6アルキル)アミノカルボニル基、シアノ基及びニトロ基から選ばれる置換基を表し、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至４つが上記の定義である場合、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちの残り１つ又は２つは下記式（ｃ－２）
Figure JPOXMLDOC01-appb-C000008
 （式（ｃ－２）中、破線は結合手を表し、Ｒ106は炭素原子数１乃至３０のアルキレン基、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基を表し、このアルキレン基中、フェニレン基中または炭素環式化合物から二つの水素原子を取り去った２価の置換基中、若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基中の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ106中の－ＣＨ2ＣＨ2－が－ＣＨ＝ＣＨ－に置き換えられていてもよく、Ｒ106中の－ＣＨ2－は、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基に置き換えられていてもよく、さらに、Ｒ106中の－ＣＨ2－は、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－、及び－ＣＯ－からなる群から選ばれた２価の基が互いに隣り合わない限り、これら２価の基に置き換えられていてもよい。
Ｒ107は水素原子又はメチル基である。）で表される基を表し、ｎは０または１を表す。） <5> The polymer composition as described in any one of <1> to <4> above, which contains a compound represented by the following formula (c) as the component (B).
Figure JPOXMLDOC01-appb-C000007
 (In the formula, any three to five of R 101 , R 102 , R 103 , R 104 and R 105 are each independently a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, C 3 to C 8 cycloalkyl group, C 3 to C 8 halocycloalkyl group, C 2 to C 6 alkenyl group, C 2 To C 6 haloalkenyl group, C 3 to C 8 cycloalkenyl group, C 3 to C 8 halocycloalkenyl group, C 2 to C 6 alkynyl group, C 2 to C 6 haloalkynyl group, (C 1 to C 6 alkyl) ) Carbonyl group, (C 1 to C 6 haloalkyl) carbonyl group, (C 1 to C 6 alkoxy) carbonyl group, (C 1 to C 6 haloalkoxy) carbonyl group, (C 1 to C 6 alkylamino) carbonyl group, (C 1 through C 6 halo Alkyl) aminocarbonyl group, di (C 1 to C 6 alkyl) aminocarbonyl group, a substituent selected from cyano group and a nitro group, any one of R 101, R 102, R 103 , R 104 and R 105 When three to four are defined as above, the remaining one or two of R 101 , R 102 , R 103 , R 104 and R 105 are represented by the following formula (c-2)
Figure JPOXMLDOC01-appb-C000008
 (In the formula (c-2), the broken line represents a bond, and R 106 represents an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound. Or a divalent substituent in which two hydrogen atoms have been removed from a heterocyclic compound, in the alkylene group, in a phenylene group or in a divalent substituent in which two hydrogen atoms have been removed from a carbocyclic compound, or One or more hydrogen atoms in the divalent substituent obtained by removing two hydrogen atoms from the heterocyclic compound may be replaced with a fluorine atom or an organic group, and —CH 2 in R 106 CH 2 — may be replaced by —CH═CH—, and —CH 2 — in R 106 is a phenylene group, a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound, or a heterocyclic group. Cyclization May be replaced with divalent substituent obtained by removing two hydrogen atoms from an object, further, -CH 2 in R 106 - is, -O -, - NHCO -, - CONH -, - COO-, Unless a divalent group selected from the group consisting of —OCO—, —NH—, —NHCONH—, and —CO— is adjacent to each other, these divalent groups may be substituted.
R107 is a hydrogen atom or a methyl group. ), And n represents 0 or 1. )
　本発明によれば、液晶性組成物に二色性色素を高配合することなく、高い偏光性能を有する偏光板を得ることができる新規な重合体組成物を提供することができる。 According to the present invention, it is possible to provide a novel polymer composition capable of obtaining a polarizing plate having high polarization performance without highly blending a dichroic dye into the liquid crystalline composition.
　本発明者は、鋭意研究を行った結果、以下の知見を得て本発明を完成するに至った。
　本発明の製造方法において用いられる重合体組成物は、側鎖に二色性色素を有し、液晶性を発現し得る感光性の側鎖型高分子（以下、単に側鎖型高分子とも呼ぶ）を含有しており、前記重合体組成物を用いて得られる塗膜は、液晶性を発現し得る感光性の側鎖型高分子を有する膜である。この塗膜にはラビング処理を行うこと無く、偏光照射によって配向処理を行う。そして、偏光照射の後、その側鎖型高分子膜を加熱する工程を経て、配向制御能が付与された塗膜（以下、配向層とも称する）となる。このとき、偏光照射によって発現した僅かな異方性がドライビングフォースとなり、液晶性の側鎖型高分子自体が自己組織化により効率的に再配向する。その結果、配向層として高効率な配向処理が実現し、高い配向制御能が付与された配向層を得ることができる。ここで、側鎖型高分子の側鎖に二色性色素を含有することにより、高い二色性比を有する配向層を得ることができる。従って、本発明の重合体組成物は、偏光層を形成する際に、液晶性組成物と必要に応じて二色性色素とを含有する偏光層を配向させるための、配向層形成用組成物として有用である。 As a result of intensive studies, the inventor has obtained the following knowledge and completed the present invention.
The polymer composition used in the production method of the present invention has a dichroic dye in the side chain, and is a photosensitive side chain polymer that can exhibit liquid crystallinity (hereinafter also simply referred to as a side chain polymer). The coating film obtained using the polymer composition is a film having a photosensitive side chain polymer that can exhibit liquid crystallinity. This coating film is subjected to orientation treatment by irradiation with polarized light without being rubbed. And after polarized light irradiation, it will become the coating film (henceforth an orientation layer) to which the orientation control ability was given through the process of heating the side chain type polymer film. At this time, the slight anisotropy developed by the irradiation of polarized light becomes a driving force, and the liquid crystalline side chain polymer itself is efficiently reoriented by self-organization. As a result, a highly efficient alignment process can be realized as the alignment layer, and an alignment layer with high alignment control ability can be obtained. Here, an alignment layer having a high dichroic ratio can be obtained by containing a dichroic dye in the side chain of the side chain polymer. Therefore, the polymer composition of the present invention is an alignment layer forming composition for orienting a polarizing layer containing a liquid crystalline composition and, if necessary, a dichroic dye, when forming the polarizing layer. Useful as.
　以下、本発明の実施形態について詳しく説明する。 Hereinafter, embodiments of the present invention will be described in detail.
＜＜（Ａ）側鎖型高分子＞＞
　（Ａ）成分は、側鎖に二色性色素を有し、所定の温度範囲で液晶性を発現する感光性の側鎖型高分子である。
　（Ａ）側鎖型高分子は、２５０ｎｍ乃至４００ｎｍの波長範囲の光で反応し、かつ６０℃乃至３００℃の温度範囲で液晶性を示すのがよい。
　（Ａ）側鎖型高分子は、２５０ｎｍ乃至４００ｎｍの波長範囲の光に反応する感光性側鎖を有することが好ましい。
　（Ａ）側鎖型高分子は、６０℃乃至３００℃の温度範囲で液晶性を示すためメソゲン基を有することが好ましい。 << (A) Side chain polymer >>
The component (A) is a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range.
(A) The side chain polymer preferably reacts with light in a wavelength range of 250 nm to 400 nm and exhibits liquid crystallinity in a temperature range of 60 ° C to 300 ° C.
(A) The side chain polymer preferably has a photosensitive side chain that reacts with light in the wavelength range of 250 nm to 400 nm.
The (A) side chain polymer preferably has a mesogenic group in order to exhibit liquid crystallinity in a temperature range of 60 ° C to 300 ° C.
　（Ａ）側鎖型高分子は、主鎖に感光性を有する側鎖が結合しており、光に感応して架橋反応、異性化反応、または光フリース転位を起こすことができる。感光性を有する側鎖の構造は特に限定されないが、光に感応して架橋反応、または光フリース転位を起こす構造が望ましく、架橋反応を起こすものがより望ましい。この場合、熱などの外部ストレスに曝されたとしても、実現された配向制御能を長期間安定に保持することができる。液晶性を発現し得る感光性の側鎖型高分子膜の構造は、そうした特性を満足するものであれば特に限定されないが、側鎖構造に剛直なメソゲン成分を有することが好ましい。この場合、該側鎖型高分子を液晶配向膜とした際に、安定な液晶配向を得ることができる。 (A) The side chain type polymer has a photosensitive side chain bonded to the main chain, and can cause a crosslinking reaction, an isomerization reaction, or a light fleece rearrangement in response to light. The structure of the side chain having photosensitivity is not particularly limited, but a structure that undergoes a crosslinking reaction or photofleece rearrangement in response to light is desirable, and a structure that causes a crosslinking reaction is more desirable. In this case, even if exposed to external stress such as heat, the achieved orientation control ability can be stably maintained for a long period of time. The structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such characteristics, but it is preferable to have a rigid mesogenic component in the side chain structure. In this case, stable liquid crystal alignment can be obtained when the side chain polymer is used as a liquid crystal alignment film.
　上記高分子の構造は、例えば、主鎖とそれに結合する側鎖を有し、その側鎖が、ビフェニル基、ターフェニル基、フェニルシクロヘキシル基、フェニルベンゾエート基、アゾベンゼン基などのメソゲン成分と、先端部に結合された、光に感応して架橋反応や異性化反応をする感光性基とを有する構造や、主鎖とそれに結合する側鎖を有し、その側鎖がメソゲン成分ともなり、かつ光フリース転位反応をするフェニルベンゾエート基を有する構造とすることができる。 The structure of the polymer has, for example, a main chain and a side chain bonded to the main chain, and the side chain has a mesogenic component such as a biphenyl group, a terphenyl group, a phenylcyclohexyl group, a phenylbenzoate group, an azobenzene group, and a tip. A structure having a photosensitive group bonded to a moiety, which undergoes a crosslinking reaction or an isomerization reaction in response to light, or a main chain and a side chain bonded to the main chain, and the side chain also serves as a mesogenic component, and A structure having a phenylbenzoate group that undergoes a photo-Fries rearrangement reaction can be obtained.
　液晶性を発現し得る感光性の側鎖型高分子膜の構造のより具体的な例としては、炭化水素、（メタ）アクリレート、イタコネート、フマレート、マレエート、α－メチレン－γ－ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン等のラジカル重合性基およびシロキサンからなる群から選択される少なくとも１種から構成された主鎖と、下記式（１）から（６）の少なくとも１種からなる側鎖を有する構造であることが好ましい。
Figure JPOXMLDOC01-appb-C000009
 　式中、Ａ、Ｂ及びＤはそれぞれ独立に、単結合、－Ｏ－、－ＣＨ2－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯ－Ｏ－、又は－Ｏ－ＣＯ－ＣＨ＝ＣＨ－を表す；
　Ｓは、炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子に結合する水素原子はハロゲン原子に置き換えられていてもよい；
　Ｔは、単結合または炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子に結合する水素原子はハロゲン原子に置き換えられていてもよい；
　Ｙ1は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、ピロール環から一つの水素原子を取り去った１価の置換基、もしくは炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基を表すか、又はそれらの置換基から選ばれる同一又は相異なった２乃至６つの置換基がＢで定義される結合基を介して結合してなる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＣＯＯＲ0（式中、Ｒ0は水素原子又は炭素原子数１乃至５のアルキル基を表す）、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｙ2は、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｒは、ヒドロキシ基、炭素原子数１乃至６のアルコキシ基を表すか、又はＹ1と同じ定義を表す；
　Ｘは、単結合、－ＣＯＯ－、－ＯＣＯ－、－Ｎ＝Ｎ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２を表し、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
　Ｃｏｕは、クマリン－６－イル基またはクマリン－７－イル基を表し、それらに結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　ｑ１とｑ２は、一方が１で他方が０である；
　ｑ３は０または１である；
　Ｐ及びＱは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し；ただし、Ｘが※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２である場合、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、－ＣＨ＝ＣＨ－が結合する側のＰ又はＱは芳香環から二つの水素原子を取り去った２価の置換基を表す；
　ｌ１は０または１である；
　ｌ２は０乃至２の整数である；
　ｌ１とｌ２がともに０であるとき、かつＴが単結合であるときはＡも単結合を表す；
　ｌ１が１であるとき、かつＴが単結合であるときはＢも単結合を表す；
　Ｈ及びＩは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、およびそれらの組み合わせから選ばれる２価の置換基を表す。 More specific examples of the structure of the photosensitive side chain polymer film capable of exhibiting liquid crystallinity include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, It has a main chain composed of at least one selected from the group consisting of radically polymerizable groups such as vinyl, maleimide, norbornene and siloxane, and a side chain composed of at least one of the following formulas (1) to (6) A structure is preferred.
Figure JPOXMLDOC01-appb-C000009
 In the formula, A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
Y 1 is a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, and a monovalent substitution obtained by removing one hydrogen atom from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a pyrrole ring, or an alicyclic hydrocarbon having 5 to 8 carbon atoms 1 represents a monovalent substituent from which a hydrogen atom has been removed, or a monovalent group in which 2 to 6 identical or different substituents selected from these substituents are bonded via a linking group defined by B In these substituents, hydrogen atoms bonded to carbon atoms are each independently —COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). , -NO 2 , -CN, -C H═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
Y 2 is a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a divalent substituent obtained by removing two hydrogen atoms from a naphthalene ring, and a divalent substituent obtained by removing two hydrogen atoms from a biphenyl ring. A divalent substituent from which two hydrogen atoms have been removed from a furan ring, a divalent substituent from which two hydrogen atoms have been removed from a pyrrole ring, and two hydrogens from an alicyclic hydrocarbon having 5 to 8 carbon atoms This represents a divalent substituent selected from the group consisting of a divalent substituent from which atoms have been removed, and combinations thereof, and hydrogen atoms bonded to carbon atoms in all these substituents are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms good;
R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, * 1-CH═CH—CO—O— * 2, or * 1- O—CO—CH═CH— * 2; * 1 represents a bonding position with P in the above formulas (1) to (6); * 2 represents Q and Q in the above formulas (1) to (6). When the number of X is 2, the X may be the same or different;
Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
one of q1 and q2 is 1 and the other is 0;
q3 is 0 or 1;
P and Q each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. Divalent substituents, divalent substituents from which two hydrogen atoms have been removed from a furan ring, divalent substituents from which two hydrogen atoms have been removed from a pyrrole ring, alicyclic carbonization having 5 to 8 carbon atoms Represents a divalent substituent obtained by removing two hydrogen atoms from hydrogen, and a divalent substituent selected from the group consisting of combinations thereof; provided that X is * 1-CH═CH—CO—O— * 2 or * 1-O—CO—CH═CH— * 2, * 1 represents the bonding position with P in the above formulas (1) to (6), and * 2 represents the above formulas (1) to (6). Represents the bonding position with Q in (6), and —CH═CH— P or Q of the binding side represents a divalent substituent obtained by removing two hydrogen atoms from an aromatic ring;
l1 is 0 or 1;
l2 is an integer from 0 to 2;
when l1 and l2 are both 0, and T is a single bond, A also represents a single bond;
when l1 is 1 and T is a single bond, B also represents a single bond;
H and I each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. A divalent substituent selected by removing two hydrogen atoms from the furan ring, a divalent substituent removing two hydrogen atoms from the pyrrole ring, and combinations thereof. Represents a group.
　側鎖は、下記式（７）乃至（１０）からなる群から選ばれるいずれか１種の感光性側鎖であるのがよい。
　式中、Ａ、Ｂ、Ｄ、Ｙ1、Ｘ、Ｙ2、及びＲは、上記と同じ定義を有する；
　ｌは１乃至１２の整数を表す；
　ｍは、０乃至２の整数を表し、ｍ１、ｍ２は１乃至３の整数を表す；
　ｎは０乃至１２の整数（ただしｎ＝０のときＢは単結合である）を表す。
Figure JPOXMLDOC01-appb-C000010
 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (7) to (10).
In which A, B, D, Y 1 , X, Y 2 and R have the same definition as above;
l represents an integer of 1 to 12;
m represents an integer of 0 to 2, and m1 and m2 represent an integer of 1 to 3;
n represents an integer of 0 to 12 (however, when n = 0, B is a single bond).
Figure JPOXMLDOC01-appb-C000010
　側鎖は、下記式（１１）乃至（１３）からなる群から選ばれるいずれか１種の感光性側鎖であるのがよい。
　式中、Ａ、Ｘ、ｌ、ｍ、ｍ１及びＲは、上記と同じ定義を有する。
Figure JPOXMLDOC01-appb-C000011
 The side chain may be any one type of photosensitive side chain selected from the group consisting of the following formulas (11) to (13).
In the formula, A, X, l, m, m1 and R have the same definition as above.
Figure JPOXMLDOC01-appb-C000011
　側鎖は、下記式（１４）又は（１５）で表される感光性側鎖であるのがよい。
　式中、Ａ、Ｙ1、Ｘ、ｌ、ｍ１及びｍ２は上記と同じ定義を有する。
Figure JPOXMLDOC01-appb-C000012
 The side chain may be a photosensitive side chain represented by the following formula (14) or (15).
In the formula, A, Y 1 , X, 1, m1, and m2 have the same definition as above.
Figure JPOXMLDOC01-appb-C000012
　側鎖は、下記式（１６）又は（１７）で表される感光性側鎖であるのがよい。
　式中、Ａ、Ｘ、ｌ及びｍは、上記と同じ定義を有する。
Figure JPOXMLDOC01-appb-C000013
 The side chain may be a photosensitive side chain represented by the following formula (16) or (17).
In the formula, A, X, l and m have the same definition as above.
Figure JPOXMLDOC01-appb-C000013
　また、側鎖は、下記式（１８）又は（１９）で表される感光性側鎖であるのがよい。
　式中、Ａ、Ｂ、Ｙ1、ｑ１、ｑ２、ｍ１、及びｍ２は、上記と同じ定義を有する。
　Ｒ1は、水素原子、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基を表す。
Figure JPOXMLDOC01-appb-C000014
 The side chain is preferably a photosensitive side chain represented by the following formula (18) or (19).
In the formula, A, B, Y 1 , q1, q2, m1, and m2 have the same definition as above.
R 1 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. Represents an alkyloxy group.
Figure JPOXMLDOC01-appb-C000014
　側鎖は、下記式（２０）で表される感光性側鎖であるのがよい。
　式中、Ａ、Ｙ1、Ｘ、ｌ及びｍは上記と同じ定義を有する。
Figure JPOXMLDOC01-appb-C000015
 The side chain is preferably a photosensitive side chain represented by the following formula (20).
In the formula, A, Y 1 , X, l and m have the same definition as above.
Figure JPOXMLDOC01-appb-C000015
　また、（Ａ）側鎖型高分子は、下記式（２１）乃至（３１）からなる群から選ばれるいずれか１種の液晶性側鎖を有するのがよい。
　式中、Ａ、Ｂ、ｑ１及びｑ２は上記と同じ定義を有する；
　Ｙ3は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、および、それらの組み合わせからなる群から選ばれる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
　Ｒ3は、水素原子、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、炭素原子数１乃至１２のアルキル基、又は炭素原子数１乃至１２のアルコキシ基を表す；
　ｌは１乃至１２の整数を表し、ｍは０乃至２の整数を表し、但し、式（２３）および式（２４）において、全てのｍの合計は２以上であり、式（２５）および式（２６）において、全てのｍの合計は１以上であり、ｍ１、ｍ２およびｍ３は、それぞれ独立に１乃至３の整数を表す；
　Ｒ2は、水素原子、－ＮＯ2、－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、アルキル基、又はアルキルオキシ基を表す；
　Ｚ1及びＺ2は単結合、－ＣＯ－、－ＣＨ2Ｏ－、－ＣＨ＝Ｎ－、又は－ＣＦ2－を表す。
Figure JPOXMLDOC01-appb-C000016
 The (A) side chain polymer preferably has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31).
In which A, B, q1 and q2 have the same definition as above;
Y 3 is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, and a monovalent substitution in which one hydrogen atom is removed from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. Represents a monovalent substituent selected from the group consisting of a monovalent substituent from which two hydrogen atoms have been removed, and a combination thereof, and each of these substituents independently represents a hydrogen atom bonded to a carbon atom. May be substituted with —NO 2 , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
R 3 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, naphthalene A monovalent substituent with one hydrogen atom removed from the ring, a monovalent substituent with one hydrogen atom removed from the biphenyl ring, a monovalent substituent with one hydrogen atom removed from the furan ring, a nitrogen-containing complex A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from an alicyclic hydrocarbon having from 5 to 8 carbon atoms, an alkyl group having from 1 to 12 carbon atoms Or an alkoxy group having 1 to 12 carbon atoms;
l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formula (23) and formula (24), the sum of all m is 2 or more, and formula (25) and formula In (26), the sum of all m is 1 or more, and m1, m2, and m3 each independently represents an integer of 1 to 3;
R 2 represents a hydrogen atom, —NO 2 , —CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, biphenyl A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, carbon Represents a monovalent substituent, an alkyl group, or an alkyloxy group in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 atoms;
Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, or —CF 2 —.
Figure JPOXMLDOC01-appb-C000016
＜＜側鎖に二色性色素を有する感光性の側鎖型高分子の製法＞＞
　上記の液晶性を発現し得る感光性の側鎖型高分子は、上記の感光性側鎖を有する光反応性側鎖モノマー、液晶性側鎖モノマー、および二色性色素モノマーを重合することによって得ることができる。 << Method for Producing Photosensitive Side Chain Polymer Having Dichroic Dye in Side Chain >>
The above photosensitive side chain polymer capable of exhibiting liquid crystallinity is obtained by polymerizing the photoreactive side chain monomer having the above photosensitive side chain, the liquid crystalline side chain monomer, and the dichroic dye monomer. Obtainable.
［光反応性側鎖モノマー］
　光反応性側鎖モノマーとは、高分子を形成した場合に、高分子の側鎖部位に感光性側鎖を有する高分子を形成することができるモノマーのことである。
　側鎖の有する光反応性基としては下記の構造およびその誘導体が好ましい。
Figure JPOXMLDOC01-appb-C000017
 [Photoreactive side chain monomer]
The photoreactive side chain monomer is a monomer capable of forming a polymer having a photosensitive side chain at the side chain portion of the polymer when the polymer is formed.
As the photoreactive group possessed by the side chain, the following structures and derivatives thereof are preferred.
Figure JPOXMLDOC01-appb-C000017
　光反応性側鎖モノマーのより具体的な例としては、炭化水素、（メタ）アクリレート、イタコネート、フマレート、マレエート、α－メチレン－γ－ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン等のラジカル重合性基およびシロキサンからなる群から選択される少なくとも１種から構成された重合性基と、上記式（１）乃至（６）の少なくとも１種からなる感光性側鎖、好ましくは、例えば、上記式（７）乃至（１０）の少なくとも１種からなる感光性側鎖、上記式（１１）乃至（１３）の少なくとも１種からなる感光性側鎖、上記式（１４）又は（１５）で表される感光性側鎖、上記式（１６）又は（１７）で表される感光性側鎖、上記式（１８）又は（１９）で表される感光性側鎖、上記式（２０）で表される感光性側鎖を有する構造であることが好ましい。 More specific examples of the photoreactive side chain monomer include radical polymerizable groups such as hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, etc. And a polymerizable group composed of at least one selected from the group consisting of siloxane and a photosensitive side chain composed of at least one of the above formulas (1) to (6), preferably, for example, the above formula (7 ) To (10) at least one photosensitive side chain, the above formulas (11) to (13) at least one photosensitive side chain, and the above formula (14) or (15). A photosensitive side chain, a photosensitive side chain represented by the above formula (16) or (17), a photosensitive side chain represented by the above formula (18) or (19), and a photosensitivity represented by the above formula (20). sex A structure having a side chain is preferred.
　このような光反応性側鎖モノマーとしては、例えば、下記式Ｍ１－１乃至Ｍ１－７およびＭ１－１７乃至Ｍ１－２０から選ばれるモノマーが挙げられる。
Figure JPOXMLDOC01-appb-C000018
 Examples of such photoreactive side chain monomers include monomers selected from the following formulas M1-1 to M1-7 and M1-17 to M1-20.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
 （式中、Ｍ１は水素原子又はメチル基であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。）
Figure JPOXMLDOC01-appb-C000020
 (In the formula, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number of 2 to 9.)
Figure JPOXMLDOC01-appb-C000021
 （式中、ＲはＯＨまたはＮＨ2であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。）
Figure JPOXMLDOC01-appb-C000021
 (In the formula, R is OH or NH 2 , s1 represents the number of methylene groups, and is a natural number of 2 to 9.)
　上記式（Ｍ１－１）で表される光反応性側鎖モノマーとしては、例えば、４－（６－メタクリルオキシヘキシル－１－オキシ）けい皮酸、４－（６－アクリルオキシヘキシル－１－オキシ）けい皮酸、４－（３－メタクリルオキシプロピル－１－オキシ）けい皮酸、４－（４－（６－メタクリルオキシヘキシル－１－オキシ）ベンゾイルオキシ）けい皮酸等の、式（１）におけるＲがＯＨであるもの、並びに、４－（６－メタクリルオキシヘキシル－１－オキシ）シンナムアミド、４－（６－アクリルオキシヘキシル－１－オキシ）シンナムアミド、４－（３－メタクリルオキシプロピル－１－オキシ）シンナムアミド等の、式（Ｍ１－１）におけるＲがＮＨ2であるものなどが挙げられる。 Examples of the photoreactive side chain monomer represented by the above formula (M1-1) include 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl-1- (Oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, and the like ( 1) wherein R is OH, and 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-acryloxyhexyl-1-oxy) cinnamamide, 4- (3-methacryloxypropyl) And those wherein R in formula (M1-1) is NH 2 , such as (-1-oxy) cinnamamide.
［液晶性側鎖モノマー］
　液晶性側鎖モノマーとは、該モノマー由来の高分子が液晶性を発現し、該高分子が側鎖部位にメソゲン基を形成することができるモノマーのことである。
　側鎖の有するメソゲン基として、ビフェニルやフェニルベンゾエートなどの単独でメソゲン構造となる基であっても、安息香酸などのように側鎖同士が水素結合することでメソゲン構造となる基であってもよい。側鎖の有するメソゲン基としては下記の構造が好ましい。
Figure JPOXMLDOC01-appb-C000022
 [Liquid crystal side chain monomer]
The liquid crystalline side chain monomer is a monomer in which a polymer derived from the monomer exhibits liquid crystallinity and the polymer can form a mesogenic group at a side chain site.
As a mesogenic group having a side chain, even if it is a group having a mesogen structure alone, such as biphenyl or phenylbenzoate, or a group having a mesogen structure by hydrogen bonding between side chains such as benzoic acid Good. As the mesogenic group possessed by the side chain, the following structure is preferable.
Figure JPOXMLDOC01-appb-C000022
　液晶性側鎖モノマーのより具体的な例としては、炭化水素、（メタ）アクリレート、イタコネート、フマレート、マレエート、α－メチレン－γ－ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン等のラジカル重合性基およびシロキサンからなる群から選択される少なくとも１種から構成された重合性基と、上記式（２１）乃至（３１）の少なくとも1種からなる側鎖を有する構造であることが好ましい。 More specific examples of liquid crystalline side chain monomers include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups A structure having a polymerizable group composed of at least one selected from the group consisting of siloxanes and a side chain composed of at least one of the above formulas (21) to (31) is preferable.
　このような液晶性モノマーのうち、カルボキシル基又はアミド基を有するモノマーとしては、下記式Ｍ２－１乃至Ｍ２－９からなる群から選ばれる式で表されるモノマーを用いることもできる。
Figure JPOXMLDOC01-appb-C000023
 Among such liquid crystalline monomers, as a monomer having a carboxyl group or an amide group, a monomer represented by a formula selected from the group consisting of the following formulas M2-1 to M2-9 can also be used.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000024
 （式中、ＲはＯＨまたはＮＨ2であり、Ｍ１は水素原子又はメチル基であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。）
Figure JPOXMLDOC01-appb-C000024
 (Wherein, R is OH or NH 2, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups is a natural number of 2 to 9.)
　また、当該その他モノマーの一例である液晶性を発現する置換基を有するモノマーとして、下記式Ｍ２－１０乃至Ｍ２－１６からなる群から選ばれる式で表されるモノマーを用いることもできる。
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｍ１は水素原子又はメチル基であり、ｓ１はメチレン基の数を表し、２乃至９の自然数である。） In addition, as a monomer having a substituent that exhibits liquid crystallinity, which is an example of the other monomer, a monomer represented by a formula selected from the group consisting of the following formulas M2-10 to M2-16 can also be used.
Figure JPOXMLDOC01-appb-C000025
 (In the formula, M1 is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number of 2 to 9.)
［二色性色素モノマー］
　二色性色素モノマーとは、高分子を形成した場合に、高分子の側鎖部位に二色性色素を有する高分子を形成することができるモノマーのことであり、二色性色素の水素原子が重合性基で置換された化合物である。なお、当該重合性基は、スペーサーを介して二色性色素に結合していてもよい。 [Dichroic dye monomer]
A dichroic dye monomer is a monomer capable of forming a polymer having a dichroic dye at the side chain portion of the polymer when the polymer is formed, and is a hydrogen atom of the dichroic dye. Is a compound substituted with a polymerizable group. In addition, the said polymeric group may be couple | bonded with the dichroic dye through the spacer.
　上記スペーサーとしては、炭素原子数１乃至３０のアルキレン基、フェニレン基または炭素環式化合物から二つの水素原子を取り去った２価の置換基、若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基であり、このアルキレン基中、フェニレン基中または炭素環式化合物から二つの水素原子を取り去った２価の置換基中、若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基中の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、上記スペーサー中の－ＣＨ2ＣＨ2－が－ＣＨ＝ＣＨ－に置き換えられていてもよく、上記スペーサー中の－ＣＨ2－は、フェニレン基または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、これらの基に置き換えられていてもよい；－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－、－ＣＯ－。 Examples of the spacer include a divalent substituent obtained by removing two hydrogen atoms from an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a carbocyclic compound, or two hydrogen atoms removed from a heterocyclic compound. A divalent substituent, which is a divalent substituent in which two hydrogen atoms have been removed from an alkylene group, a phenylene group or a carbocyclic compound, or two hydrogen atoms have been removed from a heterocyclic compound. One or more hydrogen atoms in the substituent may be replaced with a fluorine atom or an organic group. In addition, —CH 2 CH 2 — in the spacer may be replaced with —CH═CH—, and —CH 2 — in the spacer removes two hydrogen atoms from the phenylene group or carbocyclic compound. May be replaced by a divalent substituent or a divalent substituent obtained by removing two hydrogen atoms from a heterocyclic compound, and when any of the following groups are not adjacent to each other, And —O—, —NHCO—, —CONH—, —COO—, —OCO—, —NH—, —NHCONH—, —CO—.
  二色性色素とは、分子の長軸方向における吸光度と、短軸方向における吸光度とが異なる性質を有する色素をいう。 A dichroic dye refers to a dye having a property that the absorbance in the major axis direction of the molecule is different from the absorbance in the minor axis direction.
  二色性色素は、３００乃至７００ｎｍの範囲に吸収極大波長（λmax）を有するものが好ましい。このような二色性色素は、例えば、アクリジン色素、オキサジン色素、シアニン色素、ナフタレン色素、アゾ色素及びアントラキノン色素などが挙げられるが、中でもアゾ色素が好ましい。アゾ色素は、モノアゾ色素、ビスアゾ色素、トリスアゾ色素、テトラキスアゾ色素及びスチルベンアゾ色素などが挙げられ、好ましくはビスアゾ色素及びトリスアゾ色素である。 The dichroic dye preferably has an absorption maximum wavelength (λmax) in the range of 300 to 700 nm. Examples of such dichroic dyes include acridine dyes, oxazine dyes, cyanine dyes, naphthalene dyes, azo dyes and anthraquinone dyes, and among them, azo dyes are preferable. Examples of the azo dye include monoazo dyes, bisazo dyes, trisazo dyes, tetrakisazo dyes, and stilbene azo dyes, and bisazo dyes and trisazo dyes are preferable.
  アゾ色素は、例えば、式（ｂ）で表される化合物（以下、場合により「化合物（ｂ）」という。）が挙げられる。
    Ａ1（－Ｎ＝Ｎ－Ａ2）p－Ｎ＝Ｎ－Ａ3        （ｂ）
［式（ｂ）中、
  Ａ1及びＡ3は、互いに独立に、置換基を有していてもよいフェニル基、置換基を有していてもよいナフチル基又は置換基を有していてもよい１価の複素環基を表す。Ａ2は、置換基を有していてもよい１，４－フェニレン基、置換基を有していてもよいナフタレン－１，４－ジイル基又は置換基を有していてもよい２価の複素環基を表す。ｐは１乃至４の整数を表す。ｐが２以上の整数である場合、複数のＡ2は互いに独立して同一でも異なっていてもよい。］ Examples of the azo dye include a compound represented by the formula (b) (hereinafter sometimes referred to as “compound (b)”).
A 1 (-N = NA 2 ) p -N = NA 3 (b)
[In the formula (b),
A 1 and A 3 are each independently a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. Represents. A 2 represents a 1,4-phenylene group which may have a substituent, a naphthalene-1,4-diyl group which may have a substituent, or a divalent which may have a substituent. Represents a heterocyclic group. p represents an integer of 1 to 4. When p is an integer of 2 or more, the plurality of A 2 may be the same or different independently of each other. ]
  １価の複素環基としては、キノリン、チアゾール、ベンゾチアゾール、チエノチアゾール、イミダゾール、ベンゾイミダゾール、オキサゾール及びベンゾオキサゾールなどの複素環化合物から１個の水素原子を除いた基が挙げられる。２価の複素環基としては、前記複素環化合物から２個の水素原子を除いた基が挙げられる。 Examples of the monovalent heterocyclic group include groups in which one hydrogen atom has been removed from a heterocyclic compound such as quinoline, thiazole, benzothiazole, thienothiazole, imidazole, benzimidazole, oxazole and benzoxazole. Examples of the divalent heterocyclic group include groups in which two hydrogen atoms have been removed from the heterocyclic compound.
  Ａ1及びＡ3におけるフェニル基、ナフチル基及び１価の複素環基、並びにＡ2における１，４－フェニレン基、ナフタレン－１，４－ジイル基及び２価の複素環基が任意に有する置換基としては、炭素原子数１乃至４のアルキル基；メトキシ基、エトキシ基及びブトキシ基などの炭素原子数１乃至４のアルコキシ基；トリフルオロメチル基などの炭素原子数１乃至４のフッ化アルキル基；シアノ基；ニトロ基；ハロゲン原子；アミノ基、ジエチルアミノ基及びピロリジノ基などの置換又は無置換アミノ基（置換アミノ基とは、炭素原子数１乃至６のアルキル基を１つ又は２つ有するアミノ基、あるいは２つの置換アルキル基が互いに結合して炭素原子数２乃至８のアルカンジイル基を形成しているアミノ基を意味する。無置換アミノ基は、－ＮＨ2である。）が挙げられる。 A phenyl group, a naphthyl group, and a monovalent heterocyclic group in A 1 and A 3 and a 1,4-phenylene group, a naphthalene-1,4-diyl group, and a divalent heterocyclic group in A 2 are optionally substituted The group includes an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group and a butoxy group; a fluorinated alkyl having 1 to 4 carbon atoms such as a trifluoromethyl group A cyano group; a nitro group; a halogen atom; a substituted or unsubstituted amino group such as an amino group, a diethylamino group and a pyrrolidino group (the substituted amino group has one or two alkyl groups having 1 to 6 carbon atoms) An amino group or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. Is H 2.) Can be mentioned.
　炭素原子数１乃至６のアルキル基としては、直鎖状、分岐状のいずれであってもよく、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｓ－ブチル基、ｔ－ブチル基、ｎ－ペンチル基、１－メチルブチル基、２－メチルブチル基、３－メチルブチル基、１，１－ジメチルプロピル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、１－メチルペンチル基、２－メチルペンチル基、１，１－ジメチルブチル基、１－エチルブチル基、１，１，２－トリメチルプロピル基等が挙げられる。 The alkyl group having 1 to 6 carbon atoms may be linear or branched, and may be a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group. Group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1- Examples include methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, and the like.
  化合物（ｂ）のなかでも、以下の式（２－１）乃至式（２－６）でそれぞれ表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000026
 Of the compounds (b), compounds represented by the following formulas (2-1) to (2-6) are preferable.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
 ［式（２－１）乃至（２－６）中、
  Ｂ1乃至Ｂ20は、互いに独立に、水素原子、炭素原子数１乃至６のアルキル基、炭素原子数１乃至４のアルコキシ基、シアノ基、ニトロ基、置換若しくは無置換のアミノ基（置換アミノ基及び無置換アミノ基の定義は前記のとおり）、塩素原子又はトリフルオロメチル基を表す。
  ｎ１乃至ｎ４は、互いに独立に０乃至３の整数を表す。
  ｎ１が２以上である場合、複数のＢ2は互いに独立して同一でも異なっていてもよく、
  ｎ２が２以上である場合、複数のＢ6は互いに独立して同一でも異なっていてもよく、
  ｎ３が２以上である場合、複数のＢ9は互いに独立して同一でも異なっていてもよく、
  ｎ４が２以上である場合、複数のＢ14は互いに独立して同一でも異なっていてもよい。］
Figure JPOXMLDOC01-appb-C000027
 [In the formulas (2-1) to (2-6),
B 1 to B 20 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a substituted or unsubstituted amino group (substituted amino group). Group and unsubstituted amino group are as defined above), and represents a chlorine atom or a trifluoromethyl group.
n1 to n4 each independently represents an integer of 0 to 3.
when n1 is 2 or more, the plurality of B 2 may be the same or different independently of each other;
when n2 is 2 or more, the plurality of B 6 may be the same or different independently of each other;
when n3 is 2 or more, the plurality of B 9 may be the same or different independently of each other;
When n4 is 2 or more, the plurality of B 14 may be the same or different independently of each other. ]
  前記アントラキノン色素は、式（２－７）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000028
 ［式（２－７）中、
  Ｒ1乃至Ｒ8は、互いに独立に、水素原子、－Ｒx、－ＮＨ2、－ＮＨＲx、－ＮＲx 2、－ＳＲx又はハロゲン原子を表す。
  Ｒxは、炭素原子数１乃至４のアルキル基又は炭素原子数６乃至１２のアリール基を表す。］ The anthraquinone dye is preferably a compound represented by the formula (2-7).
Figure JPOXMLDOC01-appb-C000028
 [In the formula (2-7),
R 1 to R 8 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
  前記オキサゾン色素は、式（２－８）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000029
 ［式（２－８）中、
  Ｒ9乃至Ｒ15は、互いに独立に、水素原子、－Ｒx、－ＮＨ2、－ＮＨＲx、－ＮＲx 2、－ＳＲx又はハロゲン原子を表す。
  Ｒxは、炭素原子数１乃至４のアルキル基又は炭素原子数６乃至１２のアリール基を表す。］ The oxazone dye is preferably a compound represented by the formula (2-8).
Figure JPOXMLDOC01-appb-C000029
 [In the formula (2-8),
R 9 to R 15 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms. ]
  前記アクリジン色素は、式（２－９）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000030
 ［式（２－９）中、
  Ｒ16乃至Ｒ23は、互いに独立に、水素原子、－Ｒx、－ＮＨ2、－ＮＨＲx、－ＮＲx 2、－ＳＲx又はハロゲン原子を表す。
  Ｒxは、炭素原子数１乃至４のアルキル基又は炭素原子数６乃至１２のアリール基を表す。 The acridine dye is preferably a compound represented by the formula (2-9).
Figure JPOXMLDOC01-appb-C000030
 [In the formula (2-9),
R 16 to R 23 each independently represent a hydrogen atom, —R x , —NH 2 , —NHR x , —NR x 2 , —SR x, or a halogen atom.
R x represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 12 carbon atoms.
  式（２－７）、式（２－８）及び式（２－９）における、Ｒxで表される炭素原子数１乃至６のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基及びヘキシル基などが挙げられ、炭素原子数６乃至１２のアリール基としては、フェニル基、トルイル基、キシリル基及びナフチル基などが挙げられる。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R x in the formula (2-7), the formula (2-8) and the formula (2-9) include a methyl group, an ethyl group, a propyl group, and a butyl group. Group, pentyl group, hexyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, toluyl group, xylyl group and naphthyl group.
  前記シアニン色素は、式（２－１０）で表される化合物及び式（２－１１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000031
 ［式（２－１０）中、
  Ｄ1及びＤ2は、互いに独立に、式（２－１０ａ）乃至式（２－１０ｄ）のいずれかの基を表す。
Figure JPOXMLDOC01-appb-C000032
   ｎ５は１乃至３の整数を表す。］ The cyanine dye is preferably a compound represented by the formula (2-10) and a compound represented by the formula (2-11).
Figure JPOXMLDOC01-appb-C000031
 [In the formula (2-10),
D 1 and D 2 each independently represent any group of formulas (2-10a) to (2-10d).
Figure JPOXMLDOC01-appb-C000032
 n5 represents an integer of 1 to 3. ]
Figure JPOXMLDOC01-appb-C000033
 ［式（２－１１）中、
  Ｄ3及びＤ4は、互いに独立に、式（２－１１ａ）乃至式（２－１１ｈ）のいずれかの基を表す。
Figure JPOXMLDOC01-appb-C000034
   ｎ６は１乃至３の整数を表す。］
Figure JPOXMLDOC01-appb-C000033
 [In the formula (2-11),
D 3 and D 4 each independently represent any group of formulas (2-11a) to (2-11h).
Figure JPOXMLDOC01-appb-C000034
 n6 represents an integer of 1 to 3. ]
　二色性色素モノマーのより具体的な例としては、炭化水素、（メタ）アクリレート、イタコネート、フマレート、マレエート、α－メチレン－γ－ブチロラクトン、スチレン、ビニル、マレイミド、ノルボルネン等のラジカル重合性基およびシロキサンからなる群から選択される少なくとも１種から構成された重合性基と、上述した二色性色素を有する構造であることが好ましい。 More specific examples of the dichroic dye monomer include hydrocarbon, (meth) acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene and other radical polymerizable groups. A structure having a polymerizable group composed of at least one selected from the group consisting of siloxane and the above-described dichroic dye is preferable.
　また、二色性色素モノマーの市販品としては、例えば、ジスパースレッド１アクリラート、ジスパースレッド１メタクリラート、ジスパースイエロー７メタクリラート（ＡＬＤＲＩＣＨ社製）が挙げられる。 Moreover, as a commercial item of a dichroic dye monomer, for example, disperse thread 1 acrylate, disperse thread 1 methacrylate, disperse yellow 7 methacrylate (manufactured by ALDRICH) may be mentioned.
　（Ａ）側鎖型高分子は、上述した液晶性を発現する光反応性側鎖モノマーと二色性色素モノマーの共重合反応により得ることができる。また、液晶性を発現しない光反応性側鎖モノマー、液晶性側鎖モノマー、および二色性色素モノマーの共重合や、液晶性を発現する光反応性側鎖モノマー、液晶性側鎖モノマー、および二色性色素モノマーの共重合によって得ることができる。さらに、液晶性の発現能を損なわない範囲でその他のモノマーと共重合することができる。 (A) The side chain type polymer can be obtained by a copolymerization reaction of the above-described photoreactive side chain monomer exhibiting liquid crystallinity and a dichroic dye monomer. Further, copolymerization of a photoreactive side chain monomer that does not exhibit liquid crystallinity, a liquid crystalline side chain monomer, and a dichroic dye monomer, a photoreactive side chain monomer that exhibits liquid crystallinity, a liquid crystalline side chain monomer, and It can be obtained by copolymerization of a dichroic dye monomer. Furthermore, it can be copolymerized with other monomers as long as the liquid crystallinity is not impaired.
　その他のモノマーとしては、例えば工業的に入手できるラジカル重合反応可能なモノマーが挙げられる。
　その他のモノマーの具体例としては、不飽和カルボン酸、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド化合物、アクリロニトリル、マレイン酸無水物、スチレン化合物及びビニル化合物等が挙げられる。 Examples of other monomers include industrially available monomers capable of radical polymerization reaction.
Specific examples of the other monomer include unsaturated carboxylic acid, acrylic ester compound, methacrylic ester compound, maleimide compound, acrylonitrile, maleic anhydride, styrene compound and vinyl compound.
　不飽和カルボン酸の具体例としてはアクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸などが挙げられる。 Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.
　アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、及び、８－エチル－８－トリシクロデシルアクリレート等が挙げられる。 Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. Acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, Beauty, etc. 8-ethyl-8-tricyclodecyl acrylate.
　メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、及び、８－エチル－８－トリシクロデシルメタクリレート等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-me Le -8- tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.
　ビニル化合物としては、例えば、ビニルエーテル、メチルビニルエーテル、ベンジルビニルエーテル、２－ヒドロキシエチルビニルエーテル、フェニルビニルエーテル、及び、プロピルビニルエーテル等が挙げられる。 Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.
　スチレン化合物としては、例えば、スチレン、メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of the styrene compound include styrene, methyl styrene, chlorostyrene, bromostyrene, and the like.
　マレイミド化合物としては、例えば、マレイミド、Ｎ－メチルマレイミド、Ｎ－フェニルマレイミド、及びＮ－シクロヘキシルマレイミド等が挙げられる。 Examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.
　本発明の側鎖型高分子における光反応性側鎖の含有量は、側鎖全量に基づいて１０モル％乃至１００モル％が好ましく、２０モル％乃至９５モル％がより好ましく、３０モル％乃至９０モル％が更に好ましい。
　側鎖型高分子における光反応性側鎖の含有量が側鎖全量に基づいて１０モル％未満の場合、本発明の重合体組成物から形成される塗膜が、液晶配向膜としての効果を十分に奏さない可能性がある。 The content of the photoreactive side chain in the side chain polymer of the present invention is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 95 mol%, more preferably 30 mol% to 30 mol% based on the total amount of the side chain. 90 mol% is more preferable.
When the content of the photoreactive side chain in the side chain polymer is less than 10 mol% based on the total amount of the side chain, the coating film formed from the polymer composition of the present invention has an effect as a liquid crystal alignment film. There is a possibility of not playing enough.
　本発明の側鎖型高分子における液晶性側鎖の含有量は、側鎖全量に基づいて９０モル％以下が好ましく、５モル％乃至８０モル％がより好ましく、１０モル％乃至７０モル％が更に好ましい。
　側鎖型高分子における液晶性側鎖の含有量が側鎖全量に基づいて９０モル％より高い場合、光反応性側鎖の含有量が側鎖全量に基づいて１０モル％未満となるので、本発明の重合体組成物から形成される塗膜が、液晶配向膜としての効果を十分に奏さない可能性がある。 The content of the liquid crystalline side chain in the side chain polymer of the present invention is preferably 90 mol% or less, more preferably 5 mol% to 80 mol%, more preferably 10 mol% to 70 mol% based on the total amount of sidechains. Further preferred.
When the content of liquid crystalline side chains in the side chain polymer is higher than 90 mol% based on the total amount of side chains, the content of photoreactive side chains is less than 10 mol% based on the total amount of side chains, There is a possibility that the coating film formed from the polymer composition of the present invention does not sufficiently exhibit the effect as a liquid crystal alignment film.
　本発明の側鎖型高分子における二色性色素側鎖の含有量は、側鎖全量に基づいて０．２モル％乃至２０モル％が好ましく、０．５モル％乃至１５モル％がより好ましく、１モル％乃至１０モル％が更に好ましい。
　側鎖型高分子における二色性色素側鎖の含有量が側鎖全量に基づいて０．２モル％未満の場合、本発明の重合体組成物から形成される塗膜が、液晶配向膜としての効果を十分に奏さない可能性がある。 The content of the dichroic dye side chain in the side chain polymer of the present invention is preferably 0.2 mol% to 20 mol%, more preferably 0.5 mol% to 15 mol% based on the total amount of the side chain. 1 mol% to 10 mol% is more preferable.
When the content of the dichroic dye side chain in the side chain polymer is less than 0.2 mol% based on the total amount of the side chain, the coating film formed from the polymer composition of the present invention is used as the liquid crystal alignment film. There is a possibility that the effect of will not be fully achieved.
　本発明の側鎖型高分子は、上記光反応性側鎖、液晶性側鎖及び二色性色素側鎖以外のその他側鎖を含有していてもよい。その含有量は、上記光反応性側鎖、液晶性側鎖及び二色性色素側鎖の含有量の合計が１００％に満たない場合に、その残りの部分である。 The side chain polymer of the present invention may contain other side chains other than the photoreactive side chain, liquid crystalline side chain, and dichroic dye side chain. The content is the remaining portion when the total content of the photoreactive side chain, liquid crystalline side chain, and dichroic dye side chain is less than 100%.
　本実施の形態の側鎖型高分子の製造方法については、特に限定されるものではなく、工業的に扱われている汎用な方法が利用できる。具体的には、液晶性側鎖モノマーや光反応性側鎖モノマーのビニル基を利用したカチオン重合やラジカル重合、アニオン重合により製造することができる。これらの中では反応制御のしやすさなどの観点からラジカル重合が特に好ましい。 The production method of the side chain polymer of the present embodiment is not particularly limited, and a general-purpose method that is handled industrially can be used. Specifically, it can be produced by cationic polymerization, radical polymerization, or anionic polymerization using a vinyl group of a liquid crystalline side chain monomer or photoreactive side chain monomer. Among these, radical polymerization is particularly preferable from the viewpoint of ease of reaction control.
　ラジカル重合の重合開始剤としては、ラジカル重合開始剤や、可逆的付加－開裂型連鎖移動（ＲＡＦＴ）重合試薬等の公知の化合物を使用することができる。 As the polymerization initiator for radical polymerization, a known compound such as a radical polymerization initiator or a reversible addition-cleavage chain transfer (RAFT) polymerization reagent can be used.
　ラジカル熱重合開始剤は、分解温度以上に加熱することにより、ラジカルを発生させる化合物である。このようなラジカル熱重合開始剤としては、例えば、ケトンパーオキサイド類（メチルエチルケトンパーオキサイド、シクロヘキサノンパーオキサイド等）、ジアシルパーオキサイド類（アセチルパーオキサイド、ベンゾイルパーオキサイド等）、ハイドロパーオキサイド類（過酸化水素、ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド等）、ジアルキルパーオキサイド類（ジ－ｔｅｒｔ－ブチルパーオキサイド、ジクミルパーオキサイド、ジラウロイルパーオキサイド等）、パーオキシケタール類（ジブチルパーオキシシクロヘキサン等）、アルキルパーエステル類（パーオキシネオデカン酸－ｔｅｒｔ－ブチルエステル、パーオキシピバリン酸－ｔｅｒｔ－ブチルエステル、パーオキシ２－エチルシクロヘキサン酸－ｔｅｒｔ－アミルエステル等）、過硫酸塩類（過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等）、アゾ系化合物（アゾビスイソブチロニトリル、および２，２’－ジ（２－ヒドロキシエチル）アゾビスイソブチロニトリル等）が挙げられる。このようなラジカル熱重合開始剤は、１種を単独で使用することもできるし、あるいは２種以上を組み合わせて使用することもできる。 A radical thermal polymerization initiator is a compound that generates radicals when heated to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (peroxidation). Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (dibutyl peroxycyclohexane) Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethylcyclohex Acid-tert-amyl ester), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, and 2,2′-di (2-hydroxyethyl) And azobisisobutyronitrile). Such radical thermal polymerization initiators can be used singly or in combination of two or more.
　ラジカル光重合開始剤は、ラジカル重合を光照射によって開始する化合物であれば特に限定されない。このようなラジカル光重合開始剤としては、ベンゾフェノン、ミヒラーズケトン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、キサントン、チオキサントン、イソプロピルキサントン、２，４－ジエチルチオキサントン、２－エチルアントラキノン、アセトフェノン、２－ヒドロキシ－２－メチルプロピオフェノン、２－ヒドロキシ－２－メチル－４’－イソプロピルプロピオフェノン、１－ヒドロキシシクロヘキシルフェニルケトン、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、２，２－ジエトキシアセトフェノン、２，２－ジメトキシ－２－フェニルアセトフェノン、カンファーキノン、ベンズアントロン、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸イソアミル、４，４’－ジ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，４，４’－トリ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、２，４，６－トリメチルベンゾイルジフェニルフォスフィンオキサイド、２－（４’－メトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（３’，４’－ジメトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（２’，４’－ジメトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（２’－メトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４’－ペンチルオキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、４－［ｐ－Ｎ，Ｎ－ジ（エトキシカルボニルメチル）］－２，６－ジ（トリクロロメチル）－ｓ－トリアジン、１，３－ビス（トリクロロメチル）－５－（２’－クロロフェニル）－ｓ－トリアジン、１，３－ビス（トリクロロメチル）－５－（４’－メトキシフェニル）－ｓ－トリアジン、２－（ｐ－ジメチルアミノスチリル）ベンズオキサゾール、２－（ｐ－ジメチルアミノスチリル）ベンズチアゾール、２－メルカプトベンゾチアゾール、３，３’－カルボニルビス（７－ジエチルアミノクマリン）、２－（ｏ－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラキス（４－エトキシカルボニルフェニル）－１，２’－ビイミダゾール、２，２’－ビス（２，４－ジクロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、２，２’－ビス（２，４－ジブロモフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、２，２’－ビス（２，４，６－トリクロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、３－（２－メチル－２－ジメチルアミノプロピオニル）カルバゾール、３，６－ビス（２－メチル－２－モルホリノプロピオニル）－９－ｎ－ドデシルカルバゾール、１－ヒドロキシシクロヘキシルフェニルケトン、ビス（５－２，４－シクロペンタジエン－１－イル）－ビス（２，６－ジフルオロ－３－（１Ｈ－ピロール－１－イル）－フェニル）チタニウム、３，３’，４，４’－テトラ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，３’，４，４’－テトラ（ｔ－ヘキシルペルオキシカルボニル）ベンゾフェノン、３，３’－ジ（メトキシカルボニル）－４，４’－ジ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、３，４’－ジ（メトキシカルボニル）－４，３’－ジ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、４，４’－ジ（メトキシカルボニル）－３，３’－ジ（ｔ－ブチルペルオキシカルボニル）ベンゾフェノン、２－（３－メチル－３Ｈ－ベンゾチアゾール－２－イリデン）－１－ナフタレン－２－イル－エタノン、又は２－（３－メチル－１，３－ベンゾチアゾール－２（３Ｈ）－イリデン）－１－（２－ベンゾイル）エタノン等を挙げることができる。これらの化合物は単独で使用してもよく、２つ以上を混合して使用することもできる。 The radical photopolymerization initiator is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photopolymerization initiators include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2 -Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- N-di-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4′-di (t-butylperoxycarbonyl) benzophenone 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -S-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2', 4'-dimethoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (2′-methoxystyryl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (4′-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 4- [pN, N-di (ethoxycarbonylmethyl)]-2, 6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2′-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4 ′ -Methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2-mercaptobenzothiazole, 3,3′-carbonylbis (7-diethylamino) Coumarin), 2- (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bi (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4, 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl- 2-dimethylaminopropionyl) carbazole, 3,6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (5-2,4-cyclopenta En-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone 3,3 ′, 4,4′-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3′-di (methoxycarbonyl) -4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4 '-Di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxycarbonyl) -3,3'-di (t-butylperoxycarbonyl) benzophenone, 2 -(3-methyl-3H-benzothiazol-2-ylidene) -1-naphthalen-2-yl-ethanone or 2- (3-methyl- , 3-benzothiazol -2 (3H) - ylidene) -1- (2-benzoyl) ethanone, and the like. These compounds may be used alone or in combination of two or more.
　ラジカル重合法は、特に制限されるものでなく、乳化重合法、懸濁重合法、分散重合法、沈殿重合法、塊状重合法、溶液重合法等を用いることができる。 The radical polymerization method is not particularly limited, and an emulsion polymerization method, suspension polymerization method, dispersion polymerization method, precipitation polymerization method, bulk polymerization method, solution polymerization method and the like can be used.
　液晶性を発現し得る感光性の側鎖型高分子の重合反応に用いる有機溶媒としては、生成した高分子が溶解するものであれば特に限定されない。その具体例を以下に挙げる。 The organic solvent used for the polymerization reaction of the photosensitive side chain polymer capable of exhibiting liquid crystallinity is not particularly limited as long as the generated polymer is soluble. Specific examples are given below.
　Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、イソプロピルアルコール、メトキシメチルペンタノール、ジペンテン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、メチルセルソルブ、エチルセルソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、ジオキサン、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド等が挙げられる。 N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene Glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropiate Lenglycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropio Acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3- Examples thereof include ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like.
　これら有機溶媒は単独で使用しても、混合して使用してもよい。さらに、生成する高分子を溶解させない溶媒であっても、生成した高分子が析出しない範囲で、上述の有機溶媒に混合して使用してもよい。
　また、ラジカル重合において有機溶媒中の酸素は重合反応を阻害する原因となるので、有機溶媒は可能な程度に脱気されたものを用いることが好ましい。 These organic solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve the polymer | macromolecule to produce | generate, you may mix and use the above-mentioned organic solvent in the range which the polymer | macromolecule produced | generated does not precipitate.
In radical polymerization, oxygen in the organic solvent becomes a cause of inhibiting the polymerization reaction. Therefore, it is preferable to use an organic solvent that has been deaerated to the extent possible.
　ラジカル重合の際の重合温度は３０℃乃至１５０℃の任意の温度を選択することができるが、好ましくは５０℃乃至１００℃の範囲である。また、反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応液の粘性が高くなり過ぎて均一な攪拌が困難となるので、モノマー濃度が、好ましくは１質量％乃至５０質量％、より好ましくは５質量％乃至３０質量％である。反応初期は高濃度で行い、その後、有機溶媒を追加することができる。 The polymerization temperature at the time of radical polymerization can be selected from 30 ° C. to 150 ° C., but is preferably in the range of 50 ° C. to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the monomer concentration is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
　上述のラジカル重合反応においては、ラジカル重合開始剤の比率がモノマーに対して多いと得られる高分子の分子量が小さくなり、少ないと得られる高分子の分子量が大きくなるので、ラジカル開始剤の比率は重合させるモノマーに対して０．１モル％乃至１０モル％であることが好ましい。また重合時には各種モノマー成分や溶媒、開始剤などを追加することもできる。 In the above-mentioned radical polymerization reaction, the molecular weight of the obtained polymer is decreased when the ratio of the radical polymerization initiator is large relative to the monomer, and the molecular weight of the obtained polymer is increased when the ratio is small, the ratio of the radical initiator is The content is preferably 0.1 mol% to 10 mol% based on the monomer to be polymerized. Further, various monomer components, solvents, initiators and the like can be added during the polymerization.
［重合体の回収］
　上述の反応により得られた、液晶性を発現し得る感光性の側鎖型高分子の反応溶液から、生成した高分子を回収する場合には、反応溶液を貧溶媒に投入して、それら重合体を沈殿させれば良い。沈殿に用いる貧溶媒としては、メタノール、アセトン、ヘキサン、ヘプタン、ブチルセルソルブ、ヘプタン、メチルエチルケトン、メチルイソブチルケトン、エタノール、トルエン、ベンゼン、ジエチルエーテル、メチルエチルエーテル、水等を挙げることができる。貧溶媒に投入して沈殿させた重合体は、濾過して回収した後、常圧あるいは減圧下で、常温あるいは加熱して乾燥することができる。また、沈殿回収した重合体を、有機溶媒に再溶解させ、再沈殿回収する操作を２回乃至１０回繰り返すと、重合体中の不純物を少なくすることができる。この際の貧溶媒として、例えば、アルコール類、ケトン類、炭化水素等が挙げられ、これらの中から選ばれる３種類以上の貧溶媒を用いると、より一層精製の効率が上がるので好ましい。 [Recovery of polymer]
When recovering the produced polymer from the reaction solution of the photosensitive side chain polymer capable of exhibiting liquid crystallinity obtained by the above reaction, the reaction solution is put into a poor solvent, The coalescence can be precipitated. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer deposited in a poor solvent and precipitated can be recovered by filtration and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent and reprecipitation recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
　本発明の（Ａ）側鎖型高分子の分子量は、得られる塗膜の強度、塗膜形成時の作業性、および塗膜の均一性を考慮した場合、ＧＰＣ（Gel Permeation Chromatography）法で測定したポリスチレン換算で得られる重量平均分子量が、２０００乃至１００００００が好ましく、より好ましくは、５０００乃至１０００００である。 The molecular weight of the (A) side chain polymer of the present invention is measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, workability at the time of forming the coating film, and uniformity of the coating film. The weight average molecular weight obtained in terms of polystyrene is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000.
＜（Ｂ）成分＞
　本発明の重合体組成物は、（Ｂ）成分として、下記式（ｃ）で表される化合物を含有させることもできる。
Figure JPOXMLDOC01-appb-C000035
 （式中、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至５つは、それぞれ独立に水素原子、ハロゲン原子、Ｃ1乃至Ｃ6アルキル基、Ｃ1乃至Ｃ6ハロアルキル基、Ｃ1乃至Ｃ6アルコキシ基、Ｃ1乃至Ｃ6ハロアルコキシ基、Ｃ3乃至Ｃ8シクロアルキル基、Ｃ3乃至Ｃ8ハロシクロアルキル基、Ｃ2乃至Ｃ6アルケニル基、Ｃ2乃至Ｃ6ハロアルケニル基、Ｃ3乃至Ｃ8シクロアルケニル基、Ｃ3乃至Ｃ8ハロシクロアルケニル基、Ｃ2乃至Ｃ6アルキニル基、Ｃ2乃至Ｃ6ハロアルキニル基、（Ｃ1乃至Ｃ6アルキル）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）カルボニル基、（Ｃ1乃至Ｃ6アルコキシ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルコキシ）カルボニル基、（Ｃ1乃至Ｃ6アルキルアミノ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）アミノカルボニル基、ジ(Ｃ1乃至Ｃ6アルキル)アミノカルボニル基、シアノ基及びニトロ基から選ばれる置換基を表し、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至４つが上記の定義である場合、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちの残り１つ又は２つは下記式（ｃ－２）
Figure JPOXMLDOC01-appb-C000036
 （式（ｃ－２）中、破線は結合手を表し、Ｒ106は炭素原子数１乃至３０のアルキレン基、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基であり、このアルキレン基中、フェニレン基中または炭素環式化合物から二つの水素原子を取り去った２価の置換基中若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基中の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ106中の－ＣＨ2ＣＨ2－が－ＣＨ＝ＣＨ－に置き換えられていてもよく、Ｒ106中の－ＣＨ2－は、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基に置き換えられていてもよく、さらに、Ｒ106中の－ＣＨ2－は、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－、及び－ＣＯ－からなる群から選ばれた２価の基が互いに隣り合わない限り、これら２価の基に置き換えられていてもよい。Ｒ107は水素原子又はメチル基である。）で表される基を表し、ｎは０または１を表す。） <(B) component>
The polymer composition of this invention can also contain the compound represented by a following formula (c) as (B) component.
Figure JPOXMLDOC01-appb-C000035
 (In the formula, any three to five of R 101 , R 102 , R 103 , R 104 and R 105 are each independently a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, C 3 to C 8 cycloalkyl group, C 3 to C 8 halocycloalkyl group, C 2 to C 6 alkenyl group, C 2 To C 6 haloalkenyl group, C 3 to C 8 cycloalkenyl group, C 3 to C 8 halocycloalkenyl group, C 2 to C 6 alkynyl group, C 2 to C 6 haloalkynyl group, (C 1 to C 6 alkyl) ) Carbonyl group, (C 1 to C 6 haloalkyl) carbonyl group, (C 1 to C 6 alkoxy) carbonyl group, (C 1 to C 6 haloalkoxy) carbonyl group, (C 1 to C 6 alkylamino) carbonyl group, (C 1 through C 6 halo Alkyl) aminocarbonyl group, di (C 1 to C 6 alkyl) aminocarbonyl group, a substituent selected from cyano group and a nitro group, any one of R 101, R 102, R 103 , R 104 and R 105 When three to four are defined as above, the remaining one or two of R 101 , R 102 , R 103 , R 104 and R 105 are represented by the following formula (c-2)
Figure JPOXMLDOC01-appb-C000036
 (In the formula (c-2), the broken line represents a bond, and R 106 represents an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound. Or a divalent substituent from which two hydrogen atoms have been removed from a heterocyclic compound, in a divalent substituent in which two hydrogen atoms have been removed from the alkylene group, phenylene group or carbocyclic compound, or One or more hydrogen atoms in the divalent substituent obtained by removing two hydrogen atoms from the cyclic compound may be replaced with a fluorine atom or an organic group, and —CH 2 CH in R 106 2 — may be replaced by —CH═CH—, and —CH 2 — in R 106 represents a phenylene group, or a divalent substituent or heterocyclic ring in which two hydrogen atoms have been removed from a carbocyclic compound. Formula May be replaced with divalent substituent obtained by removing two hydrogen atoms from further, -CH in R 106 2 - is, -O -, - NHCO -, - CONH -, - COO -, - OCO -, - NH -, - NHCONH-, and unless divalent radical selected from the group consisting of -CO- is not adjacent each other, these divalent good .R 107 be replaced based on the hydrogen An atom or a methyl group), and n represents 0 or 1. )
　本明細書におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。尚、本明細書中「ハロ」の表記もこれらのハロゲン原子を表す。 In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present specification, the notation “halo” also represents these halogen atoms.
　本明細書におけるＣa乃至Ｃbアルキル基の表記は、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状の炭化水素基を表し、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、s-ブチル基、t-ブチル基、n-ペンチル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルプロピル基、1,1-ジメチルプロピル基、1,2-ジメチルプロピル基、2,2-ジメチルプロピル基、n-ヘキシル基、1-メチルペンチル基、2-メチルペンチル基、1,1-ジメチルブチル基、1,3-ジメチルブチル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of a C a to C b alkyl group in the present specification represents a linear or branched hydrocarbon group having a to b carbon atoms, such as a methyl group, an ethyl group, or an n-propyl group. I-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group Group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group Specific examples include 1,3-dimethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and the like, and each is selected within the range of the designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbハロアルキル基の表記は、炭素原子に結合した水素原子が、ハロゲン原子によって任意に置換された、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状の炭化水素基を表し、このとき、２個以上のハロゲン原子によって置換されている場合、それらのハロゲン原子は互いに同一でも、または互いに相異なっていてもよい。例えばフルオロメチル基、クロロメチル基、ブロモメチル基、ヨードメチル基、ジフルオロメチル基、クロロフルオロメチル基、ジクロロメチル基、ブロモフルオロメチル基、トリフルオロメチル基、クロロジフルオロメチル基、ジクロロフルオロメチル基、トリクロロメチル基、ブロモジフルオロメチル基、ブロモクロロフルオロメチル基、ジブロモフルオロメチル基、2-フルオロエチル基、2-クロロエチル基、2-ブロモエチル基、2,2-ジフルオロエチル基、2-クロロ-2-フルオロエチル基、2,2-ジクロロエチル基、2-ブロモ-2-フルオロエチル基、2,2,2-トリフルオロエチル基、2-クロロ-2,2-ジフルオロエチル基、2,2-ジクロロ-2-フルオロエチル基、2,2,2-トリクロロエチル基、2-ブロモ-2,2-ジフルオロエチル基、2-ブロモ-2-クロロ-2-フルオロエチル基、2-ブロモ-2,2-ジクロロエチル基、1,1,2,2-テトラフルオロエチル基、ペンタフルオロエチル基、1-クロロ-1,2,2,2-テトラフルオロエチル基、2-クロロ-1,1,2,2-テトラフルオロエチル基、1,2-ジクロロ-1,2,2-トリフルオロエチル基、2-ブロモ-1,1,2,2-テトラフルオロエチル基、2-フルオロプロピル基、2-クロロプロピル基、2-ブロモプロピル基、2-クロロ-2-フルオロプロピル基、2,3-ジクロロプロピル基、2-ブロモ-3-フルオロプロピル基、3-ブロモ-2-クロロプロピル基、2,3-ジブロモプロピル基、3,3,3-トリフルオロプロピル基、3-ブロモ-3,3-ジフルオロプロピル基、2,2,3,3-テトラフルオロプロピル基、2-クロロ-3,3,3-トリフルオロプロピル基、2,2,3,3,3-ペンタフルオロプロピル基、1,1,2,3,3,3-ヘキサフルオロプロピル基、ヘプタフルオロプロピル基、2,3-ジクロロ-1,1,2,3,3-ペンタフルオロプロピル基、2-フルオロ-1-メチルエチル基、2-クロロ-1-メチルエチル基、2-ブロモ-1-メチルエチル基、2,2,2-トリフルオロ-1-(トリフルオロメチル)エチル基、1,2,2,2-テトラフルオロ-1-(トリフルオロメチル)エチル基、2,2,3,3,4,4-ヘキサフルオロブチル基、2,2,3,4,4,4-ヘキサフルオロブチル基、2,2,3,3,4,4,4-ヘプタフルオロブチル基、1,1,2,2,3,3,4,4-オクタフルオロブチル基、ノナフルオロブチル基、4-クロロ-1,1,2,2,3,3,4,4-オクタフルオロブチル基、2-フルオロ-2-メチルプロピル基、2-クロロ-1,1-ジメチルエチル基、2-ブロモ-1,1-ジメチルエチル基、5-クロロ-2,2,3,4,4,5,5-ヘプタフルオロペンチル基、トリデカフルオロヘキシル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the C a to C b haloalkyl group is represented by a linear or branched chain in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom and the number of carbon atoms is a to b And when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, chlorofluoromethyl group, dichloromethyl group, bromofluoromethyl group, trifluoromethyl group, chlorodifluoromethyl group, dichlorofluoromethyl group, trichloromethyl Group, bromodifluoromethyl group, bromochlorofluoromethyl group, dibromofluoromethyl group, 2-fluoroethyl group, 2-chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2-chloro-2-fluoroethyl Group, 2,2-dichloroethyl group, 2-bromo-2-fluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2-dichloro-2 -Fluoroethyl group, 2,2,2-trichloroethyl group, 2-bromo-2,2-difluoroethyl group, 2-bromo-2-chloro-2-fluoroethyl group, 2-butyl Lomo-2,2-dichloroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 1-chloro-1,2,2,2-tetrafluoroethyl group, 2-chloro-1 1,2,2-tetrafluoroethyl group, 1,2-dichloro-1,2,2-trifluoroethyl group, 2-bromo-1,1,2,2-tetrafluoroethyl group, 2-fluoropropyl Group, 2-chloropropyl group, 2-bromopropyl group, 2-chloro-2-fluoropropyl group, 2,3-dichloropropyl group, 2-bromo-3-fluoropropyl group, 3-bromo-2-chloropropyl group Group, 2,3-dibromopropyl group, 3,3,3-trifluoropropyl group, 3-bromo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2-chloro- 3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2, 3-dichloro-1,1,2,3,3-pentaph Oropropyl group, 2-fluoro-1-methylethyl group, 2-chloro-1-methylethyl group, 2-bromo-1-methylethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl Groups, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,4,4, 4-hexafluorobutyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl Group, 4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl group, 2-fluoro-2-methylpropyl group, 2-chloro-1,1-dimethylethyl group, 2 Specific examples include -bromo-1,1-dimethylethyl group, 5-chloro-2,2,3,4,4,5,5-heptafluoropentyl group, tridecafluorohexyl group, etc. In the range of the number of carbon atoms.
　本明細書におけるＣa乃至Ｃbシクロアルキル基の表記は、炭素原子数がａ乃至ｂ個よりなる環状の炭化水素基を表し、３員環から６員環までの単環又は複合環構造を形成することが出来る。また、各々の環は指定の炭素原子数の範囲でアルキル基によって任意に置換されていてもよい。例えばシクロプロピル基、1-メチルシクロプロピル基、2-メチルシクロプロピル基、2,2-ジメチルシクロプロピル基、2,2,3,3-テトラメチルシクロプロピル基、シクロブチル基、シクロペンチル基、2-メチルシクロペンチル基、3-メチルシクロペンチル基、シクロヘキシル基、2-メチルシクロヘキシル基、3-メチルシクロヘキシル基、4-メチルシクロヘキシル基、ビシクロ[2.2.1]ヘプタン-2-イル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the C a to C b cycloalkyl group represents a cyclic hydrocarbon group having a to b carbon atoms, and represents a monocyclic or complex ring structure having 3 to 6 members. Can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. For example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, 2,2,3,3-tetramethylcyclopropyl group, cyclobutyl group, cyclopentyl group, 2- Specific examples include methylcyclopentyl group, 3-methylcyclopentyl group, cyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, bicyclo [2.2.1] heptan-2-yl group and the like. , Each selected range of carbon atoms.
　本明細書におけるＣa乃至Ｃbハロシクロアルキル基の表記は、炭素原子に結合した水素原子が、ハロゲン原子によって任意に置換された、炭素原子数がａ乃至ｂ個よりなる環状の炭化水素基を表し、３員環から６員環までの単環又は複合環構造を形成することが出来る。また、各々の環は指定の炭素原子数の範囲でアルキル基によって任意に置換されていてもよく、ハロゲン原子による置換は環構造部分であっても、側鎖部分であっても、或いはそれらの両方であってもよく、さらに、２個以上のハロゲン原子によって置換されている場合、それらのハロゲン原子は互いに同一でも、または互いに相異なっていてもよい。例えば2,2-ジフルオロシクロプロピル基、2,2-ジクロロシクロプロピル基、2,2-ジブロモシクロプロピル基、2,2-ジフルオロ-1-メチルシクロプロピル基、2,2-ジクロロ-1-メチルシクロプロピル基、2,2-ジブロモ-1-メチルシクロプロピル基、2,2,3,3-テトラフルオロシクロブチル基、2-(トリフルオロメチル)シクロヘキシル基、3-(トリフルオロメチル)シクロヘキシル基、4-(トリフルオロメチル)シクロヘキシル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, a C a to C b halocycloalkyl group is a cyclic hydrocarbon group having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. It is possible to form a monocyclic or complex ring structure from 3 to 6-membered rings. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, 2- (trifluoromethyl) cyclohexyl group, 3- (trifluoromethyl) cyclohexyl group , 4- (trifluoromethyl) cyclohexyl group and the like can be mentioned as specific examples, and each is selected within the range of the designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbアルケニル基の表記は、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状で、且つ分子内に１個又は２個以上の二重結合を有する不飽和炭化水素基を表し、例えばビニル基、1-プロペニル基、2-プロペニル基、1-メチルエテニル基、2-ブテニル基、1-メチル-2-プロペニル基、2-メチル-2-プロペニル基、2-ペンテニル基、2-メチル-2-ブテニル基、3-メチル-2-ブテニル基、2-エチル-2-プロペニル基、1,1-ジメチル-2-プロペニル基、2-ヘキセニル基、2-メチル-2-ペンテニル基、2,4-ジメチル-2,6-ヘプタジエニル基、3,7-ジメチル-2,6-オクタジエニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the C a to C b alkenyl groups are linear or branched having a carbon number of a to b and have one or more double bonds in the molecule. Represents an unsaturated hydrocarbon group, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 2-pentenyl group, 2-methyl-2-butenyl group, 3-methyl-2-butenyl group, 2-ethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2-hexenyl group, 2- Specific examples include methyl-2-pentenyl group, 2,4-dimethyl-2,6-heptadienyl group, 3,7-dimethyl-2,6-octadienyl group, etc. Selected.
　本明細書におけるＣa乃至Ｃbハロアルケニル基の表記は、炭素原子に結合した水素原子が、ハロゲン原子によって任意に置換された、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状で、且つ分子内に１個又は２個以上の二重結合を有する不飽和炭化水素基を表す。このとき、２個以上のハロゲン原子によって置換されている場合、それらのハロゲン原子は互いに同一でも、または互いに相異なっていてもよい。例えば2,2-ジクロロビニル基、2-フルオロ-2-プロペニル基、2-クロロ-2-プロペニル基、3-クロロ-2-プロペニル基、2-ブロモ-2-プロペニル基、3-ブロモ-2-プロペニル基、3,3-ジフルオロ-2-プロペニル基、2,3-ジクロロ-2-プロペニル基、3,3-ジクロロ-2-プロペニル基、2,3-ジブロモ-2-プロペニル基、2,3,3-トリフルオロ-2-プロペニル基、2,3,3-トリクロロ-2-プロペニル基、1-(トリフルオロメチル)エテニル基、3-クロロ-2-ブテニル基、3-ブロモ-2-ブテニル基、4,4-ジフルオロ-3-ブテニル基、3,4,4-トリフルオロ-3-ブテニル基、3-クロロ-4,4,4-トリフルオロ-2-ブテニル基、3-ブロモ-2-メチル-2-プロペニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, a C a to C b haloalkenyl group is a linear or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom. And an unsaturated hydrocarbon group having one or more double bonds in the molecule. At this time, when substituted with two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3-bromo-2 -Propenyl group, 3,3-difluoro-2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3-dibromo-2-propenyl group, 2, 3,3-trifluoro-2-propenyl group, 2,3,3-trichloro-2-propenyl group, 1- (trifluoromethyl) ethenyl group, 3-chloro-2-butenyl group, 3-bromo-2- Butenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4-trifluoro-2-butenyl group, 3-bromo- A 2-methyl-2-propenyl group or the like is given as a specific example, and is selected within the range of each designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbシクロアルケニル基の表記は、炭素原子数がａ乃至ｂ個よりなる環状の、且つ１個又は２個以上の二重結合を有する不飽和炭化水素基を表し、３員環から６員環までの単環又は複合環構造を形成することが出来る。また、各々の環は指定の炭素原子数の範囲でアルキル基によって任意に置換されていてもよく、さらに、二重結合はendo-又はexo-のどちらの形式であってもよい。例えば2-シクロペンテン-1-イル基、3-シクロペンテン-1-イル基、2-シクロヘキセン-1-イル基、3-シクロヘキセン-1-イル基、ビシクロ[2.2.1]-5-ヘプテン-2-イル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of a C a to C b cycloalkenyl group in the present specification represents a cyclic unsaturated hydrocarbon group having 1 to 2 carbon atoms and having 1 to 2 carbon atoms, A monocyclic or complex ring structure from a 3-membered ring to a 6-membered ring can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. For example, 2-cyclopenten-1-yl group, 3-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, bicyclo [2.2.1] -5-hepten-2- Specific examples include yl groups and the like, and each is selected within the range of the designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbハロシクロアルケニル基の表記は、炭素原子に結合した水素原子が、ハロゲン原子によって任意に置換された、炭素原子数がａ乃至ｂ個よりなる環状の、且つ１個又は２個以上の二重結合を有する不飽和炭化水素基を表し、３員環から６員環までの単環又は複合環構造を形成することが出来る。また、各々の環は指定の炭素原子数の範囲でアルキル基によって任意に置換されていてもよく、さらに、二重結合はendo-又はexo-のどちらの形式であってもよい。また、ハロゲン原子による置換は環構造部分であっても、側鎖部分であっても、或いはそれらの両方であってもよく、２個以上のハロゲン原子によって置換されている場合、それらのハロゲン原子は互いに同一でも、または互いに相異なっていても良い。例えば2-クロロビシクロ[2.2.1]-5-ヘプテン-2-イル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, a C a to C b halocycloalkenyl group has a cyclic structure in which a hydrogen atom bonded to a carbon atom is arbitrarily substituted with a halogen atom, the number of which is a to b, and 1 It represents an unsaturated hydrocarbon group having one or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. In addition, the substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other. For example, a 2-chlorobicyclo [2.2.1] -5-hepten-2-yl group and the like are given as specific examples, and each group is selected within the range of the designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbアルキニル基の表記は、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状で、且つ分子内に１個又は２個以上の三重結合を有する不飽和炭化水素基を表し、例えばエチニル基、1-プロピニル基、2-プロピニル基、2-ブチニル基、1-メチル-2-プロピニル基、2-ペンチニル基、1-メチル-2-ブチニル基、1,1-ジメチル-2-プロピニル基、2-ヘキシニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the C a to C b alkynyl group is a linear or branched chain having a carbon number of a to b, and has one or more triple bonds in the molecule. Represents a saturated hydrocarbon group, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, 1-methyl-2-propynyl group, 2-pentynyl group, 1-methyl-2-butynyl group, 1 Specific examples include a 1-dimethyl-2-propynyl group, a 2-hexynyl group, and the like, and each is selected within the range of the designated number of carbon atoms.
　本明細書におけるＣa乃至Ｃbハロアルキニル基の表記は、炭素原子に結合した水素原子が、ハロゲン原子によって任意に置換された、炭素原子数がａ乃至ｂ個よりなる直鎖状又は分岐鎖状で、且つ分子内に１個又は２個以上の三重結合を有する不飽和炭化水素基を表す。このとき、２個以上のハロゲン原子によって置換されている場合、それらのハロゲン原子は互いに同一でも、または互いに相異なっていても良い。例えば2-クロロエチニル基、2-ブロモエチニル基、2-ヨードエチニル基、3-クロロ-2-プロピニル基、3-ブロモ-2-プロピニル基、3-ヨード-2-プロピニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, a C a to C b haloalkynyl group is a linear or branched chain having a to b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon group having one or more triple bonds in the molecule. At this time, when substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.
　本明細書におけるＣa乃至Ｃbアルコキシ基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル-O-基を表し、例えばメトキシ基、エトキシ基、n-プロピルオキシ基、i-プロピルオキシ基、n-ブチルオキシ基、i-ブチルオキシ基、s-ブチルオキシ基、t-ブチルオキシ基、n-ペンチルオキシ基、n-ヘキシルオキシ基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of C a to C b alkoxy group in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group Specific examples include i-propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, etc. Selected in the range of the number of carbon atoms.
　本明細書におけるＣa乃至Ｃbハロアルコキシ基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるハロアルキル-O-基を表し、例えばジフルオロメトキシ基、トリフルオロメトキシ基、クロロジフルオロメトキシ基、ブロモジフルオロメトキシ基、2-フルオロエトキシ基、2-クロロエトキシ基、2,2,2-トリフルオロエトキシ基、1,1,2,2,-テトラフルオロエトキシ基、2-クロロ-1,1,2-トリフルオロエトキシ基、2-ブロモ-1,1,2-トリフルオロエトキシ基、ペンタフルオロエトキシ基、2,2-ジクロロ-1,1,2-トリフルオロエトキシ基、2,2,2-トリクロロ-1,1-ジフルオロエトキシ基、2-ブロモ-1,1,2,2-テトラフルオロエトキシ基、2,2,3,3-テトラフルオロプロピルオキシ基、1,1,2,3,3,3-ヘキサフルオロプロピルオキシ基、2,2,2-トリフルオロ-1-(トリフルオロメチル)エトキシ基、ヘプタフルオロプロピルオキシ基、2-ブロモ-1,1,2,3,3,3-ヘキサフルオロプロピルオキシ基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of C a to C b haloalkoxy group in the present specification represents a haloalkyl-O— group having the above-mentioned meaning consisting of a to b carbon atoms, such as difluoromethoxy group, trifluoromethoxy group, chloro Difluoromethoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro- 1,1,2-trifluoroethoxy group, 2-bromo-1,1,2-trifluoroethoxy group, pentafluoroethoxy group, 2,2-dichloro-1,1,2-trifluoroethoxy group, 2, 2,2-trichloro-1,1-difluoroethoxy group, 2-bromo-1,1,2,2-tetrafluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 1,1,2 , 3,3,3-hexafluoropropyloxy group, 2,2,2-trifluoro-1- (trifluoromethyl) eth Specific examples include Si group, heptafluoropropyloxy group, 2-bromo-1,1,2,3,3,3-hexafluoropropyloxy group, etc. The
　本明細書における（Ｃa乃至Ｃbアルキル）カルボニル基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル-C(O)-基を表し、例えばアセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、2-メチルブタノイル基、ピバロイル基、ヘキサノイル基、ヘプタノイル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of (C a to C b alkyl) carbonyl group in the present specification represents an alkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, for example, acetyl group, propionyl group Specific examples include butyryl group, isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, and the like, and each is selected within the range of the number of carbon atoms specified.
　本明細書における（Ｃa乃至Ｃbハロアルキル）カルボニル基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるハロアルキル-C(O)-基を表し、例えばフルオロアセチル基、クロロアセチル基、ジフルオロアセチル基、ジクロロアセチル基、トリフルオロアセチル基、クロロジフルオロアセチル基、ブロモジフルオロアセチル基、トリクロロアセチル基、ペンタフルオロプロピオニル基、ヘプタフルオロブタノイル基、3-クロロ-2,2-ジメチルプロパノイル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of (C a to C b haloalkyl) carbonyl group in the present specification represents a haloalkyl-C (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as fluoroacetyl group, chloro Acetyl group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2-dimethyl Specific examples include a propanoyl group and the like, and each is selected within the range of the designated number of carbon atoms.
　本明細書における（Ｃa乃至Ｃbアルコキシ）カルボニル基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル-O-C(O)-基を表し、例えばメトキシカルボニル基、エトキシカルボニル基、n-プロピルオキシカルボニル基、i-プロピルオキシカルボニル基、n-ブトキシカルボニル基、i-ブトキシカルボニル基、t-ブトキシカルボニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of (C a to C b alkoxy) carbonyl group in the present specification represents an alkyl-OC (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as methoxycarbonyl group, ethoxy Specific examples include a carbonyl group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, t-butoxycarbonyl group, and the like. Selected by range.
　本明細書における（Ｃa乃至Ｃbハロアルコキシ）カルボニル基の表記は、炭素原子数がａ乃至ｂ個よりなる前記の意味であるハロアルキル-O-C(O)-基を表し、例えば2-クロロエトキシカルボニル基、2,2-ジフルオロエトキシカルボニル基、2,2,2-トリフルオロエトキシカルボニル基、2,2,2-トリクロロエトキシカルボニル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of (C a to C b haloalkoxy) carbonyl group in the present specification represents a haloalkyl-OC (O) — group having the above-mentioned meaning consisting of a to b carbon atoms, such as 2-chloroethoxy Specific examples include a carbonyl group, a 2,2-difluoroethoxycarbonyl group, a 2,2,2-trifluoroethoxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and the like. Selected by range.
　本明細書における（Ｃa乃至Ｃbアルキルアミノ）カルボニル基の表記は、水素原子の一方が、炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル基によって置換されたカルバモイル基を表し、例えばメチルカルバモイル基、エチルカルバモイル基、n-プロピルカルバモイル基、i-プロピルカルバモイル基、n-ブチルカルバモイル基、i-ブチルカルバモイル基、s-ブチルカルバモイル基、t-ブチルカルバモイル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 The notation of (C a to C b alkylamino) carbonyl group in this specification represents a carbamoyl group in which one of the hydrogen atoms is substituted with an alkyl group having the above-mentioned meaning consisting of a to b carbon atoms. Specific examples include methylcarbamoyl group, ethylcarbamoyl group, n-propylcarbamoyl group, i-propylcarbamoyl group, n-butylcarbamoyl group, i-butylcarbamoyl group, s-butylcarbamoyl group, t-butylcarbamoyl group, etc. Each of which is selected for each specified number of carbon atoms.
　本明細書における（Ｃa乃至Ｃbハロアルキルアミノ）カルボニル基の表記は、水素原子の一方が、炭素原子数がａ乃至ｂ個よりなる前記の意味であるハロアルキル基によって置換されたカルバモイル基を表し、例えば2-フルオロエチルカルバモイル基、2-クロロエチルカルバモイル基、2,2-ジフルオロエチルカルバモイル基、2,2,2-トリフルオロエチルカルバモイル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the notation of (C a to C b haloalkylamino) carbonyl group represents a carbamoyl group in which one of the hydrogen atoms is substituted with a haloalkyl group having the above-mentioned meaning consisting of a to b carbon atoms. Specific examples include 2-fluoroethylcarbamoyl group, 2-chloroethylcarbamoyl group, 2,2-difluoroethylcarbamoyl group, 2,2,2-trifluoroethylcarbamoyl group, etc. Selected in a range of numbers.
　本明細書におけるジ(Ｃa乃至Ｃbアルキル)アミノカルボニル基の表記は、水素原子が両方とも、それぞれ同一でも又は互いに相異なっていてもよい炭素原子数がａ乃至ｂ個よりなる前記の意味であるアルキル基によって置換されたカルバモイル基を表し、例えばN,N-ジメチルカルバモイル基、N-エチル-N-メチルカルバモイル基、N,N-ジエチルカルバモイル基、N,N-ジ-n-プロピルカルバモイル基、N,N-ジ-n-ブチルカルバモイル基等が具体例として挙げられ、各々の指定の炭素原子数の範囲で選択される。 In the present specification, the notation of a di (C a to C b alkyl) aminocarbonyl group means that the number of carbon atoms that may be the same or different from each other is a to b. A carbamoyl group substituted by an alkyl group such as N, N-dimethylcarbamoyl group, N-ethyl-N-methylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di-n-propylcarbamoyl Specific examples include a group, an N, N-di-n-butylcarbamoyl group, and the like, which are selected in the range of the respective designated number of carbon atoms.
式（ｃ）で表される構造の桂皮酸又は安息香酸誘導体における置換基Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105としては、中でも、それぞれ独立に水素原子、ハロゲン原子、Ｃ1乃至Ｃ6アルキル基、Ｃ1乃至Ｃ6ハロアルキル基、Ｃ1乃至Ｃ6アルコキシ基、Ｃ1乃至Ｃ6ハロアルコキシ基、シアノ基及びニトロ基から選ばれる置換基であることが好ましい。 The substituents R 101 , R 102 , R 103 , R 104 and R 105 in the cinnamic acid or benzoic acid derivative having the structure represented by the formula (c) are each independently a hydrogen atom, a halogen atom, C 1 to A substituent selected from a C 6 alkyl group, a C 1 to C 6 haloalkyl group, a C 1 to C 6 alkoxy group, a C 1 to C 6 haloalkoxy group, a cyano group, and a nitro group is preferable.
また、Ｒ103としては上記好ましいＲ101、Ｒ102、Ｒ103、Ｒ104及びＲ105の定義の中で水素原子以外の置換基であることが、配向感度の点から好ましく、ハロゲン原子、Ｃ1乃至Ｃ66アルキル基、Ｃ1乃至Ｃ6ハロアルキル基、Ｃ1乃至Ｃ6アルコキシ基、Ｃ1乃至Ｃ6ハロアルコキシ基、シアノ基及びニトロ基から選ばれる置換基がさらに好ましい。 In addition, R 103 is preferably a substituent other than a hydrogen atom in the above preferred definitions of R 101 , R 102 , R 103 , R 104 and R 105 from the viewpoint of orientation sensitivity, and preferably a halogen atom, C 1 to C 66 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, a substituent selected from cyano group and a nitro group more preferred.
また、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のいずれか１又は２の置換基が上記式（ｃ－２）で表される基であることも好ましく、なかでも、Ｒ103が式（ｃ－２）で表される基であることが好ましい。そのようなモノマーとしては、桂皮酸基を有するモノマーとして、前記式Ｍ１－１乃至Ｍ１－７およびＭ１－１７乃至Ｍ１－２１から選ばれるモノマーが挙げられる。また、安息香酸基を有するモノマーとしては、前記式Ｍ２－１乃至Ｍ２－９から選ばれるモノマーが挙げられる。 It is also preferable either 1 or 2 substituents R 101, R 102, R 103 , R 104 and R 105 is a group represented by the formula (c-2), among others, R 103 is A group represented by the formula (c-2) is preferable. Examples of such monomers include monomers selected from the formulas M1-1 to M1-7 and M1-17 to M1-21 as monomers having a cinnamic acid group. Examples of the monomer having a benzoic acid group include monomers selected from the formulas M2-1 to M2-9.
このようなけい皮酸及びその誘導体としては、けい皮酸、４－メトキシけい皮酸、４－エトキシけい皮酸、４－プロポキシけい皮酸、４－フルオロけい皮酸、等のけい皮酸誘導体；４－（６－メタクリルオキシヘキシル－１－オキシ）けい皮酸、４－（６－アクリルオキシヘキシル－１－オキシ）けい皮酸、４－（３－メタクリルオキシプロピル－１－オキシ）けい皮酸、４－（４－（６－メタクリルオキシヘキシル－１－オキシ）ベンゾイルオキシ）けい皮酸等のけい皮酸基を有するモノマーなどが挙げられる。 Examples of such cinnamic acid and derivatives thereof include cinnamic acid, 4-methoxycinnamic acid, 4-ethoxy cinnamic acid, 4-propoxy cinnamic acid, 4-fluoro cinnamic acid, and the like. 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic And monomers having a cinnamic acid group such as 4- (4- (6- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.
また、このような安息香酸及びその誘導体としては、安息香酸、４－メトキシ安息香酸、４－エトキシ安息香酸、４－プロポキシ安息香酸、４－フルオロ安息香酸等の安息香酸誘導体；４－（６－メタクリルオキシヘキシル－１－オキシ）安息香酸、４－（６－アクリルオキシヘキシル－１－オキシ）安息香酸、４－（３－メタクリルオキシプロピル－１－オキシ）安息香酸、４－（４－（６－メタクリルオキシヘキシル－１－オキシ）ベンゾイルオキシ）安息香酸等の安息香酸基を有するモノマーなどが挙げられる。 Examples of such benzoic acid and derivatives thereof include benzoic acid derivatives such as benzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-propoxybenzoic acid, 4-fluorobenzoic acid; 4- (6- Methacryloxyhexyl-1-oxy) benzoic acid, 4- (6-acryloxyhexyl-1-oxy) benzoic acid, 4- (3-methacryloxypropyl-1-oxy) benzoic acid, 4- (4- (6 And monomers having a benzoic acid group such as methacryloxyhexyl-1-oxy) benzoyloxy) benzoic acid.
　本発明の重合体組成物において（Ｂ）成分を含有させる場合の含有量は、（Ａ）成分の側鎖型高分子の１００質量部あたり、３質量部乃至１００質量部であることが好ましい。（Ｂ）成分の含有量が３質量部以下であると、照射量マージンの向上が見られない。また、（Ｂ）成分の含有量が１００質量部を超えて過大なものであると、得られる硬化膜の溶剤耐性が低下する場合がある。 In the polymer composition of the present invention, when the component (B) is contained, the content is preferably 3 parts by mass to 100 parts by mass per 100 parts by mass of the side chain polymer of the component (A). When the content of the component (B) is 3 parts by mass or less, the irradiation margin is not improved. Moreover, the solvent tolerance of the cured film obtained may fall that content of (B) component exceeds 100 mass parts and is excessive.
＜有機溶媒＞
　本発明に用いられる重合体組成物に用いる有機溶媒は、樹脂成分を溶解させる有機溶媒であれば特に限定されない。その具体例を以下に挙げる。
　Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチル－２－ピロリドン、Ｎ－メチルカプロラクタム、２－ピロリドン、Ｎ－エチルピロリドン、Ｎ－ビニルピロリドン、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、γ－ブチロラクトン、３－メトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－エトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、３－ブトキシ－Ｎ，Ｎ－ジメチルプロパンアミド、１，３－ジメチル－イミダゾリジノン、エチルアミルケトン、メチルノニルケトン、メチルエチルケトン、メチルイソアミルケトン、メチルイソプロピルケトン、シクロヘキサノン、エチレンカーボネート、プロピレンカーボネート、ジグライム、４－ヒドロキシ－４－メチル－２－ペンタノン、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、イソプロピルアルコール、メトキシメチルペンタノール、メチルセロソルブ、エチルセロソルブ、ブチルセロソルブ、メチルセロソルブアセテート、エチルセロソルブアセテート、ブチルカルビトール、エチルカルビトール、エチルカルビトールアセテート、エチレングリコール、エチレングリコールモノアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコール、プロピレングリコールモノアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコール－ｔｅｒｔ－ブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコール、ジエチレングリコールモノアセテート、ジエチレングリコールジメチルエーテル、ジプロピレングリコールモノアセテートモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノアセテートモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノアセテートモノプロピルエーテル、３－メチル－３－メトキシブチルアセテート、トリプロピレングリコールメチルエーテル、３－メチル－３－メトキシブタノール、ジイソプロピルエーテル、エチルイソブチルエーテル、ジイソブチレン、アミルアセテート、ブチルブチレート、ブチルエーテル、ジイソブチルケトン、メチルシクロへキセン、プロピルエーテル、ジヘキシルエーテル、１－ヘキサノール、ｎ－へキサン、ｎ－ペンタン、ｎ－オクタン、ジエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸ｎ－ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸メチルエチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸、３－メトキシプロピオン酸、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、１－ブトキシ－２－プロパノール、１－フェノキシ－２－プロパノール、プロピレングリコールモノアセテート、プロピレングリコールジアセテート、プロピレングリコール－１－モノメチルエーテル－２－アセテート、プロピレングリコール－１－モノエチルエーテル－２－アセテート、ジプロピレングリコール、２－（２－エトキシプロポキシ）プロパノール、乳酸メチルエステル、乳酸エチルエステル、乳酸ｎ－プロピルエステル、乳酸ｎ－ブチルエステル、乳酸イソアミルエステル等が挙げられる。これらは単独で使用しても、混合して使用してもよい。 <Organic solvent>
The organic solvent used for the polymer composition used in the present invention is not particularly limited as long as it is an organic solvent that dissolves the resin component. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Methyl-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, Isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether , Ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol Cole monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3- Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether 1-hexanol, n-hexane, n-pentane, n-octane, diethyl Ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, 3 -Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1- Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-mono Examples include ethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, and lactate isoamyl ester. These may be used alone or in combination.
＜重合体組成物＞
　本発明の重合体組成物は、（Ａ）側鎖に二色性色素を有し且つ所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び有機溶媒を含有する。また、必要に応じて（Ｂ）成分として、上記式（ｃ）で表される化合物を含有する。 <Polymer composition>
The polymer composition of the present invention contains (A) a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent. Moreover, the compound represented by the said Formula (c) is contained as (B) component as needed.
［重合体組成物の調製］
　本発明に用いられる重合体組成物は、配向層の形成に好適となるように塗布液として調製されることが好ましい。すなわち、本発明に用いられる重合体組成物は、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液として調製されることが好ましい。ここで、その樹脂成分とは、既に説明した側鎖に二色性色素を有し、液晶性を発現し得る感光性の側鎖型高分子を含む樹脂成分である。その際、樹脂成分の含有量は、１質量％乃至２０質量％が好ましく、より好ましくは３質量％乃至１５質量％、特に好ましくは３質量％乃至１０質量％である。 [Preparation of polymer composition]
The polymer composition used in the present invention is preferably prepared as a coating solution so as to be suitable for forming an alignment layer. That is, the polymer composition used in the present invention is preferably prepared as a solution in which a resin component for forming a resin film is dissolved in an organic solvent. Here, the resin component is a resin component containing a photosensitive side chain polymer having a dichroic dye in the side chain already described and capable of exhibiting liquid crystallinity. At that time, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
　本発明の重合体組成物において、前述の樹脂成分は、全てが上述した側鎖に二色性色素を有し、液晶性を発現し得る感光性の側鎖型高分子であってもよいが、液晶発現能および感光性能を損なわない範囲でそれら以外の他の重合体が混合されていてもよい。その際、樹脂成分中における他の重合体の含有量は、０．５質量％乃至８０質量％、好ましくは１質量％乃至５０質量％である。
　そのような他の重合体は、例えば、ポリ（メタ）アクリレートやポリアミック酸やポリイミド等からなり、液晶性を発現し得る感光性の側鎖型高分子ではない重合体等が挙げられる。 In the polymer composition of the present invention, the resin component described above may be a photosensitive side chain polymer that has a dichroic dye in the side chain and can exhibit liquid crystallinity. In addition, other polymers may be mixed as long as the liquid crystal expression ability and the photosensitive performance are not impaired. At that time, the content of the other polymer in the resin component is 0.5% by mass to 80% by mass, preferably 1% by mass to 50% by mass.
Examples of such other polymers include polymers that are made of poly (meth) acrylate, polyamic acid, polyimide, and the like and are not a photosensitive side chain polymer that can exhibit liquid crystallinity.
　本発明に用いられる重合体組成物は、上記（Ａ）及び有機溶媒以外の成分を含有してもよい。その例としては、重合体組成物を塗布した際の、膜厚均一性や表面平滑性を向上させる化合物、配向層と基板との密着性を向上させる化合物等を挙げることができるが、これに限定されない。 The polymer composition used in the present invention may contain components other than the above (A) and organic solvent. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, compounds that improve the adhesion between the alignment layer and the substrate, and the like. It is not limited.
　膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤およびノ二オン系界面活性剤等が挙げられる。
　より具体的には、例えば、エフトップ（登録商標）３０１、ＥＦ３０３、ＥＦ３５２（トーケムプロダクツ社製）、メガファック（登録商標）Ｆ１７１、Ｆ１７３、Ｒ－３０（ＤＩＣ社製）、フロラードＦＣ４３０、ＦＣ４３１（住友スリーエム社製）、アサヒガード（登録商標）ＡＧ７１０（旭硝子社製）、サーフロン（登録商標）Ｓ－３８２、ＳＣ１０１、ＳＣ１０２、ＳＣ１０３、ＳＣ１０４、ＳＣ１０５、ＳＣ１０６（ＡＧＣセイミケミカル社製）等が挙げられる。これらの界面活性剤の使用割合は、重合体組成物に含有される樹脂成分の１００質量部に対して、好ましくは０．０１質量部乃至２質量部、より好ましくは０．０１質量部乃至１質量部である。 Examples of the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
More specifically, for example, Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), MegaFac (registered trademark) F171, F173, R-30 (manufactured by DIC), Florard FC430, FC431 (Manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 (manufactured by Asahi Glass Company), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.) It is done. The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. Part by mass.
　配向層と基板との密着性を向上させる化合物の具体例としては、次に示す官能性シラン含有化合物などが挙げられる。
　例えば、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、２－アミノプロピルトリメトキシシラン、２－アミノプロピルトリエトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルトリメトキシシラン、Ｎ－（２－アミノエチル）－３－アミノプロピルメチルジメトキシシラン、３－ウレイドプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリメトキシシラン、Ｎ－エトキシカルボニル－３－アミノプロピルトリエトキシシラン、Ｎ－トリエトキシシリルプロピルトリエチレントリアミン、Ｎ－トリメトキシシリルプロピルトリエチレントリアミン、１０－トリメトキシシリル－１，４，７－トリアザデカン、１０－トリエトキシシリル－１，４，７－トリアザデカン、９－トリメトキシシリル－３，６－ジアザノニルアセテート、９－トリエトキシシリル－３，６－ジアザノニルアセテート、Ｎ－ベンジル－３－アミノプロピルトリメトキシシラン、Ｎ－ベンジル－３－アミノプロピルトリエトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリエトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリメトキシシラン、Ｎ－ビス（オキシエチレン）－３－アミノプロピルトリエトキシシラン等が挙げられる。 Specific examples of the compound that improves the adhesion between the alignment layer and the substrate include the following functional silane-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Examples thereof include propyltrimethoxysilane and N-bis (oxyethylene) -3-aminopropyltriethoxysilane.
　さらに、基板と配向層の密着性の向上に加え、耐熱性を付与する目的で、以下のようなフェノプラスト系やエポキシ基含有化合物の添加剤を、重合体組成物中に含有させても良い。具体的なフェノプラスト系添加剤を以下に示すが、この構造に限定されない。 Furthermore, in addition to improving the adhesion between the substrate and the alignment layer, additives such as the following phenoplasts and epoxy group-containing compounds may be included in the polymer composition for the purpose of imparting heat resistance. . Specific phenoplast additives are shown below, but are not limited to this structure.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　具体的なエポキシ基含有化合物としては、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、２，２－ジブロモネオペンチルグリコールジグリシジルエーテル、１，３，５，６－テトラグリシジル－２，４－ヘキサンジオール、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－４、４’－ジアミノジフェニルメタンなどが例示される。 Specific epoxy group-containing compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N ′,-tetraglycidyl- , 4'-diaminodiphenylmethane and the like.
　基板との密着性を向上させる化合物を使用する場合、その使用量は、重合体組成物に含有される樹脂成分の１００質量部に対して０．１質量部乃至３０質量部であることが好ましく、より好ましくは１質量部乃至２０質量部である。使用量が０．１質量部未満であると密着性向上の効果は期待できず、３０質量部よりも多くなると液晶の配向性が悪くなる場合がある。 When using a compound that improves adhesion to the substrate, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the polymer composition. More preferably, it is 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
　添加剤として、光増感剤を用いることもできる。無色増感剤および三重項増感剤が好ましい。
　光増感剤としては、芳香族ニトロ化合物、クマリン（７－ジエチルアミノ－４－メチルクマリン、７－ヒドロキシ４－メチルクマリン）、ケトクマリン、カルボニルビスクマリン、芳香族２－ヒドロキシケトン、およびアミノ置換された、芳香族２－ヒドロキシケトン（２－ヒドロキシベンゾフェノン、モノ－もしくはジ－ｐ－（ジメチルアミノ）－２－ヒドロキシベンゾフェノン）、アセトフェノン、アントラキノン、キサントン、チオキサントン、ベンズアントロン、チアゾリン（２－ベンゾイルメチレン－３－メチル－β－ナフトチアゾリン、２－（β－ナフトイルメチレン）－３－メチルベンゾチアゾリン、２－（α－ナフトイルメチレン）－３－メチルベンゾチアゾリン、２－（４－ビフェノイルメチレン）－３－メチルベンゾチアゾリン、２－（β－ナフトイルメチレン）－３－メチル－β－ナフトチアゾリン、２－（４－ビフェノイルメチレン）－３－メチル－β－ナフトチアゾリン、２－（ｐ－フルオロベンゾイルメチレン）－３－メチル－β－ナフトチアゾリン）、オキサゾリン（２－ベンゾイルメチレン－３－メチル－β－ナフトオキサゾリン、２－（β－ナフトイルメチレン）－３－メチルベンゾオキサゾリン、２－（α－ナフトイルメチレン）－３－メチルベンゾオキサゾリン、２－（４－ビフェノイルメチレン）－３－メチルベンゾオキサゾリン、２－（β－ナフトイルメチレン）－３－メチル－β－ナフトオキサゾリン、２－（４－ビフェノイルメチレン）－３－メチル－β－ナフトオキサゾリン、２－（ｐ－フルオロベンゾイルメチレン）－３－メチル－β－ナフトオキサゾリン）、ベンゾチアゾール、ニトロアニリン（ｍ－もしくはｐ－ニトロアニリン、２，４，６－トリニトロアニリン）またはニトロアセナフテン（５－ニトロアセナフテン）、（２－［（ｍ－ヒドロキシ－ｐ－メトキシ）スチリル］ベンゾチアゾール、ベンゾインアルキルエーテル、Ｎ－アルキル化フタロン、アセトフェノンケタール（２，２－ジメトキシフェニルエタノン）、ナフタレン、アントラセン（２－ナフタレンメタノール、２－ナフタレンカルボン酸、９－アントラセンメタノール、および９－アントラセンカルボン酸）、ベンゾピラン、アゾインドリジン、メロクマリン等がある。
　好ましくは、芳香族２－ヒドロキシケトン（ベンゾフェノン）、クマリン、ケトクマリン、カルボニルビスクマリン、アセトフェノン、アントラキノン、キサントン、チオキサントン、およびアセトフェノンケタールである。 A photosensitizer can also be used as an additive. Colorless and triplet sensitizers are preferred.
As photosensitizers, aromatic nitro compounds, coumarins (7-diethylamino-4-methylcoumarin, 7-hydroxy4-methylcoumarin), ketocoumarins, carbonyl biscoumarins, aromatic 2-hydroxyketones, and amino-substituted Aromatic 2-hydroxyketones (2-hydroxybenzophenone, mono- or di-p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thioxanthone, benzanthrone, thiazoline (2-benzoylmethylene-3 -Methyl-β-naphthothiazoline, 2- (β-naphthoylmethylene) -3-methylbenzothiazoline, 2- (α-naphthoylmethylene) -3-methylbenzothiazoline, 2- (4-biphenoylmethylene)- 3-methylbenzothia Phosphorus, 2- (β-naphthoylmethylene) -3-methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene)- 3-methyl-β-naphthothiazoline), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2- (β-naphthoylmethylene) -3-methylbenzoxazoline, 2- (α-naphthoylmethylene) ) -3-methylbenzoxazoline, 2- (4-biphenoylmethylene) -3-methylbenzoxazoline, 2- (β-naphthoylmethylene) -3-methyl-β-naphthoxazoline, 2- (4-biphenoyl) Methylene) -3-methyl-β-naphthoxazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β- Ftoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline) or nitroacenaphthene (5-nitroacenaphthene), (2-[(m-hydroxy-p -Methoxy) styryl] benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene, anthracene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, 9-anthracenemethanol And 9-anthracenecarboxylic acid), benzopyran, azoindolizine, melocoumarin and the like.
Aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonyl biscoumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.
　また、本発明は、上記重合体組成物を用いた液晶配向膜を有する基板及び偏光素子の製造方法に関する。
　本発明の重合体組成物から形成された液晶配向膜を有する基板の製造方法は、
　［Ｉ］　（Ａ）側鎖に二色性色素を有し且つ所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び有機溶媒を含有する重合体組成物を、基板上に塗布して塗膜を形成する工程；
　［ＩＩ］　［Ｉ］で得られた塗膜に偏光した紫外線を照射する工程；及び
　［ＩＩＩ］　［ＩＩ］で得られた塗膜を加熱する工程；
を有する。
　上記工程により、配向制御能が付与された液晶配向膜を得ることができ、該液晶配向膜を有する基板を得ることができる。 Moreover, this invention relates to the manufacturing method of the board | substrate which has a liquid crystal aligning film using the said polymer composition, and a polarizing element.
A method for producing a substrate having a liquid crystal alignment film formed from the polymer composition of the present invention,
[I] (A) A polymer composition containing a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent on a substrate A step of applying a coating to form a coating film;
[II] a step of irradiating the coating film obtained in [I] with polarized ultraviolet rays; and [III] a step of heating the coating film obtained in [II];
Have
Through the above steps, a liquid crystal alignment film having alignment control ability can be obtained, and a substrate having the liquid crystal alignment film can be obtained.
　偏光素子の製造方法は、
　［ＩＶ］上記で得られた配向層を有する基板を準備する工程；及び下記［Ｖ－１］及び［Ｖ－２］から選ばれる工程を有する。
　［Ｖ－１］前記配向層を有する基板の配向層上に、二色性色素と（Ｃ）重合性液晶とを含有する偏光層形成用組成物を塗付し、加熱乾燥することにより塗膜を形成し、得られた塗膜に紫外線を照射する工程；
　［Ｖ－２］前記配向層を有する基板の配向層上に、（Ｄ）リオトロピック液晶性を有する色素を含有する偏光層形成用組成物を塗付し、加熱乾燥することにより塗膜を形成する工程。
これにより偏光素子を得ることができる。 The manufacturing method of the polarizing element is as follows:
[IV] A step of preparing a substrate having the alignment layer obtained above; and a step selected from the following [V-1] and [V-2].
[V-1] A polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal is applied on the alignment layer of the substrate having the alignment layer, and the coating film is formed by heating and drying. And irradiating the obtained coating film with ultraviolet rays;
[V-2] On the alignment layer of the substrate having the alignment layer, (D) a polarizing layer-forming composition containing a dye having lyotropic liquid crystallinity is applied and heated to dry to form a coating film. Process.
Thereby, a polarizing element can be obtained.
　以下、本発明の製造方法の有する［Ｉ］乃至［ＩＩＩ］、および[ＩＶ]の各工程について説明する。
＜工程［Ｉ］＞
　工程［Ｉ］では、基板上に、（Ａ）側鎖に二色性色素を有し且つ所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び有機溶媒を含有する重合体組成物を塗布して塗膜を形成する。 The steps [I] to [III] and [IV] of the production method of the present invention will be described below.
<Process [I]>
In the step [I], a heavy polymer containing (A) a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range and an organic solvent on the substrate. The combined composition is applied to form a coating film.
＜基板＞
　基板は通常透明基板である。なお、本発明の偏光板（以下、本偏光板ということがある）の基板が表示素子の表示面に設置されないとき、例えば、本偏光板から基板を取り除いた偏光フィルムを表示素子の表示面に設置する場合は、基板は透明でなくてもよい。透明基板とは、光、特に可視光を透過し得る透明性を有する基板を意味し、透明性とは、波長３８０乃至７８０ｎｍにわたる光線に対しての透過率が８０％以上となる特性をいう。具体的な透明基板としては、透光性樹脂基板が挙げられる。透光性樹脂基板を構成する樹脂としては、ポリエチレン、ポリプロピレンなどのポリオレフィン；ノルボルネン系ポリマーなどの環状オレフィン系樹脂；ポリビニルアルコール；ポリエチレンテレフタレート；ポリメタクリル酸エステル；ポリアクリル酸エステル；トリアセチルセルロース、ジアセチルセルロース、セルロースアセテートプロピオネートなどのセルロースエステル；ポリエチレンナフタレート；ポリカーボネート；ポリスルホン；ポリエーテルスルホン；ポリエーテルケトン；ポリフェニレンスルフィドおよびポリフェニレンオキシドが挙げられる。入手のしやすさや透明性の観点から、ポリエチレンテレフタレート、ポリメタクリル酸エステル、セルロースエステル、環状オレフィン系樹脂またはポリカーボネートが好ましい。 <Board>
The substrate is usually a transparent substrate. When the substrate of the polarizing plate of the present invention (hereinafter sometimes referred to as the present polarizing plate) is not installed on the display surface of the display element, for example, a polarizing film obtained by removing the substrate from the polarizing plate is used as the display surface of the display element. In the case of installation, the substrate may not be transparent. The transparent substrate means a substrate having transparency capable of transmitting light, particularly visible light, and the transparency means a characteristic that the transmittance with respect to a light beam having a wavelength of 380 to 780 nm is 80% or more. A specific example of the transparent substrate is a translucent resin substrate. As the resin constituting the translucent resin substrate, polyolefin such as polyethylene and polypropylene; cyclic olefin resin such as norbornene polymer; polyvinyl alcohol; polyethylene terephthalate; polymethacrylate ester; polyacrylate ester; triacetylcellulose, diacetyl Cellulose esters such as cellulose and cellulose acetate propionate; polyethylene naphthalate; polycarbonate; polysulfone; polyethersulfone; polyetherketone; polyphenylene sulfide and polyphenylene oxide. From the viewpoint of availability and transparency, polyethylene terephthalate, polymethacrylic acid ester, cellulose ester, cyclic olefin-based resin or polycarbonate is preferable.
  セルロースエステルは、セルロースに含まれる水酸基の一部または全部が、エステル化されたものであり、市場から容易に入手することができる。また、セルロースエステル基材も市場から容易に入手することができる。市販のセルロースエステル基板としては、例えば、“フジタックフィルム”（富士写真フイルム（株））；“ＫＣ８ＵＸ２Ｍ”、“ＫＣ８ＵＹ”及び“ＫＣ４ＵＹ”（コニカミノルタオプト（株））などが挙げられる。 Cellulose ester is obtained by esterifying part or all of hydroxyl groups contained in cellulose, and can be easily obtained from the market. Cellulose ester base materials can also be easily obtained from the market. Examples of commercially available cellulose ester substrates include “Fujitac Film” (Fuji Photo Film Co., Ltd.); “KC8UX2M”, “KC8UY” and “KC4UY” (Konica Minolta Opto Co., Ltd.).
  環状オレフィン系樹脂は、市場から容易に入手できる。市販の環状オレフィン系樹脂としては、“Ｔｏｐａｓ”［Ｔｉｃｏｎａ社（独）］、“アートン”［ＪＳＲ（株）］、“ゼオノア（ＺＥＯＮＯＲ）”［日本ゼオン（株）］、“ゼオネックス（ＺＥＯＮＥＸ）”［日本ゼオン（株）］および“アペル”［三井化学（株）製］が挙げられる。このような環状オレフィン系樹脂を、例えば、溶剤キャスト法、溶融押出法などの公知の手段により製膜して、基板とすることができる。また、市販されている環状オレフィン系樹脂基板を用いることもできる。市販の環状オレフィン系樹脂基材としては、“エスシーナ”［積水化学工業（株）］、“ＳＣＡ４０”［積水化学工業（株）］、“ゼオノアフィルム”［オプテス（株）］および“アートンフィルム”［ＪＳＲ（株）］が挙げられる。 Cyclic olefin resin can be easily obtained from the market. Commercially available cyclic olefin resins include “Topas” [Ticona (Germany)], “Arton” [JSR Corporation], “ZEONOR” [Nippon Zeon Corporation], and “ZEONEX”. [Nippon Zeon Co., Ltd.] and “Apel” [Mitsui Chemicals Co., Ltd.]. Such a cyclic olefin resin can be formed into a substrate by, for example, forming a film by a known means such as a solvent casting method or a melt extrusion method. A commercially available cyclic olefin resin substrate can also be used. Commercially available cyclic olefin resin base materials include “Essina” [Sekisui Chemical Co., Ltd.], “SCA40” [Sekisui Chemical Co., Ltd.], “Zeonor Film” [Optes Co., Ltd.], and “Arton Film”. [JSR Corporation].
  環状オレフィン系樹脂が、環状オレフィンと、鎖状オレフィンやビニル基を有する芳香族化合物との共重合体である場合、環状オレフィンに由来する構造単位の含有割合は、共重合体の全構造単位に対して、通常５０モル％以下、好ましくは１５乃至５０モル％の範囲である。鎖状オレフィンとしては、エチレンおよびプロピレンが挙げられ、ビニル基を有する芳香族化合物としては、スチレン、α－メチルスチレンおよびアルキル置換スチレンが挙げられる。環状オレフィン系樹脂が、環状オレフィンと、鎖状オレフィンと、ビニル基を有する芳香族化合物との三元共重合体である場合、鎖状オレフィンに由来する構造単位の含有割合は、共重合体の全構造単位に対して、通常５乃至８０モル％であり、ビニル基を有する芳香族化合物に由来する構造単位の含有割合は、共重合体の全構造単位に対して、通常５乃至８０モル％である。このような三元共重合体は、その製造において、高価な環状オレフィンの使用量を比較的少なくすることができるという利点がある。 When the cyclic olefin-based resin is a copolymer of a cyclic olefin and an aromatic compound having a chain olefin or a vinyl group, the content ratio of the structural unit derived from the cyclic olefin is the total structural unit of the copolymer. On the other hand, it is usually 50 mol% or less, preferably 15 to 50 mol%. Examples of chain olefins include ethylene and propylene, and examples of aromatic compounds having a vinyl group include styrene, α-methylstyrene, and alkyl-substituted styrene. When the cyclic olefin-based resin is a ternary copolymer of a cyclic olefin, a chain olefin, and an aromatic compound having a vinyl group, the content ratio of the structural unit derived from the chain olefin is that of the copolymer. The content of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol% based on the total structural unit, and the content of the structural unit derived from the aromatic compound having a vinyl group is usually 5 to 80 mol%. It is. Such a terpolymer has the advantage that the amount of expensive cyclic olefin used can be relatively reduced in its production.
  基板に求められる特性は、偏光板の構成によって異なるが、通常、位相差性ができるだけ小さい基板が好ましい。位相差性ができるだけ小さい基板としては、ゼロタック（コニカミノルタオプト株式会社）、Zタック（富士フィルム株式会社）などの位相差を有しないセルロースエステルフィルムが挙げられる。また、未延伸の環状オレフィン系樹脂基材も好ましい。 The characteristics required of the substrate vary depending on the configuration of the polarizing plate, but usually a substrate having as small a retardation as possible is preferable. Examples of the substrate having as little retardation as possible include cellulose ester films having no phase difference, such as zero tack (Konica Minolta Opto Co., Ltd.), Z tack (Fuji Film Co., Ltd.), and the like. Further, an unstretched cyclic olefin resin substrate is also preferable.
  基板上に、配向膜を介して偏光層が形成されている偏光板の場合、偏光層が形成されていない基板の面に、ハードコート処理、反射防止処理、帯電防止処理等がなされてもよい。また、性能に影響しない範囲で、紫外線吸収剤などの添加剤をハードコート層は含んでいてもよい。 In the case of a polarizing plate in which a polarizing layer is formed on the substrate via an alignment film, the surface of the substrate on which the polarizing layer is not formed may be subjected to a hard coat treatment, an antireflection treatment, an antistatic treatment, or the like. . In addition, the hard coat layer may contain additives such as an ultraviolet absorber as long as the performance is not affected.
  基板の厚みは、薄すぎると強度が低下し、加工性に劣る傾向があるため、通常５乃至３００μmであり、好ましくは２０乃至２００μmである。 The thickness of the substrate is usually 5 to 300 μm, and preferably 20 to 200 μm, because if it is too thin, the strength tends to decrease and the workability tends to be poor.
　上述した重合体組成物を基板上に塗布する方法は特に限定されない。
　塗布方法は、工業的には、スクリーン印刷、オフセット印刷、フレキソ印刷またはインクジェット法などで行う方法が一般的である。その他の塗布方法としては、ディップ法、ロールコータ法、スリットコータ法、スピンナ法（回転塗布法）またはスプレー法などがあり、目的に応じてこれらを用いてもよい。 The method for applying the polymer composition described above on the substrate is not particularly limited.
In general, the application method is generally performed by screen printing, offset printing, flexographic printing, an inkjet method, or the like. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method (rotary coating method), or a spray method, and these may be used depending on the purpose.
　基板上に重合体組成物を塗布した後は、ホットプレート、熱循環型オーブンまたはＩＲ（赤外線）型オーブンなどの加熱手段により５０乃至２３０℃、好ましくは５０乃至２００℃で０．４分間乃至６０分間、好ましくは０．５分間乃至１０分間溶媒を蒸発させて塗膜を得ることができる。このときの乾燥温度は、側鎖型高分子の液晶相発現温度よりも低いことが好ましい。 After the polymer composition is applied on the substrate, it is heated to 50 to 230 ° C., preferably 50 to 200 ° C. for 0.4 minutes to 60 minutes by a heating means such as a hot plate, a thermal circulation oven or an IR (infrared) oven. The coating film can be obtained by evaporating the solvent for 1 minute, preferably 0.5 to 10 minutes. The drying temperature at this time is preferably lower than the liquid crystal phase expression temperature of the side chain polymer.
　塗膜の厚みは、厚すぎると異方性の発現の面で不利となり、薄すぎると偏光特性に問題があるので、通常１０ｎｍ乃至１００００ｎｍの範囲であり、好ましくは１０ｎｍ乃至１０００ｎｍの範囲であり、より好ましくは５００ｎｍ以下であり、さらに好ましくは１０ｎｍ乃至３００ｎｍの範囲である。 If the thickness of the coating film is too thick, it is disadvantageous in terms of anisotropy, and if it is too thin, there is a problem with polarization properties, so it is usually in the range of 10 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm. More preferably, it is 500 nm or less, and more preferably in the range of 10 nm to 300 nm.
　尚、［Ｉ］工程の後、続く［ＩＩ］工程の前に塗膜の形成された基板を室温にまで冷却する工程を設けることも可能である。 In addition, it is also possible to provide the process of cooling the board | substrate with which the coating film was formed to room temperature after the [I] process and before the following [II] process.
＜工程［ＩＩ］＞
　工程［ＩＩ］では、工程［Ｉ］で得られた塗膜に、偏光した紫外線を照射する。塗膜の膜面に偏光した紫外線を照射する場合、基板に対して一定の方向から偏光板を介して偏光された紫外線を照射する。使用する紫外線としては、波長１００ｎｍ乃至４００ｎｍの範囲の紫外線を使用することができる。好ましくは、使用する塗膜の種類によりフィルター等を介して最適な波長を選択する。そして、例えば、選択的に光架橋反応を誘起できるように、波長２９０ｎｍ乃至４００ｎｍの範囲の紫外線を選択して使用することができる。紫外線としては、例えば、高圧水銀灯から放射される光を用いることができる。 <Process [II]>
In step [II], the coating film obtained in step [I] is irradiated with polarized ultraviolet rays. When irradiating the surface of the coating film with polarized ultraviolet rays, the substrate is irradiated with polarized ultraviolet rays through a polarizing plate from a certain direction. As the ultraviolet rays to be used, ultraviolet rays having a wavelength in the range of 100 nm to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 nm to 400 nm can be selected and used so that the photocrosslinking reaction can be selectively induced. As the ultraviolet light, for example, light emitted from a high-pressure mercury lamp can be used.
　偏光した紫外線の照射量は、使用する塗膜に依存する。照射量は、該塗膜における、偏光した紫外線の偏光方向と平行な方向の紫外線吸光度と垂直な方向の紫外線吸光度との差であるΔＡの最大値（以下、ΔＡｍａｘとも称する）を実現する偏光紫外線の量の１％乃至７０％の範囲内とすることが好ましく、１％乃至５０％の範囲内とすることがより好ましい。 The irradiation amount of polarized ultraviolet rays depends on the coating film used. The amount of irradiation is polarized ultraviolet light that realizes the maximum value of ΔA (hereinafter also referred to as ΔAmax), which is the difference between the ultraviolet light absorbance in a direction parallel to the polarization direction of polarized ultraviolet light and the ultraviolet light absorbance in a direction perpendicular to the polarization direction of the polarized ultraviolet light. The amount is preferably in the range of 1% to 70%, and more preferably in the range of 1% to 50%.
＜工程［ＩＩＩ］＞
　工程［ＩＩＩ］では、工程［ＩＩ］で偏光した紫外線の照射された塗膜を加熱する。加熱により、塗膜に配向制御能を付与することができる。
　加熱は、ホットプレート、熱循環型オーブンまたはＩＲ（赤外線）型オーブンなどの加熱手段を用いることができる。加熱温度は、使用する塗膜の液晶性を発現させる温度を考慮して決めることができる。 <Step [III]>
In step [III], the ultraviolet-irradiated coating film polarized in step [II] is heated. An orientation control ability can be imparted to the coating film by heating.
For heating, a heating means such as a hot plate, a heat circulation type oven, or an IR (infrared) type oven can be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystallinity of the coating film used is developed.
　加熱温度は、側鎖型高分子が液晶性を発現する温度（以下、液晶発現温度という）の温度範囲内であることが好ましい。塗膜のような薄膜表面の場合、塗膜表面の液晶発現温度は、液晶性を発現し得る感光性の側鎖型高分子をバルクで観察した場合の液晶発現温度よりも低いことが予想される。このため、加熱温度は、塗膜表面の液晶発現温度の温度範囲内であることがより好ましい。すなわち、偏光紫外線照射後の加熱温度の温度範囲は、使用する側鎖型高分子の液晶発現温度の温度範囲の下限より１０℃低い温度を下限とし、その液晶温度範囲の上限より１０℃低い温度を上限とする範囲の温度であることが好ましい。加熱温度が、上記温度範囲よりも低いと、塗膜における熱による異方性の増幅効果が不十分となる傾向があり、また加熱温度が、上記温度範囲よりも高すぎると、塗膜の状態が等方性の液体状態（等方相）に近くなる傾向があり、この場合、自己組織化によって一方向に再配向することが困難になることがある。
　なお、液晶発現温度は、側鎖型高分子または塗膜表面が固体相から液晶相に相転移がおきるガラス転移温度（Ｔｇ）以上であって、液晶相からアイソトロピック相（等方相）に相転移を起こすアイソトロピック相転移温度（Ｔｉｓｏ）以下の温度をいう。 The heating temperature is preferably within the temperature range of the temperature at which the side chain polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the liquid crystal expression temperature on the coating film surface is expected to be lower than the liquid crystal expression temperature when a photosensitive side chain polymer that can exhibit liquid crystallinity is observed in bulk. The Therefore, the heating temperature is more preferably within the temperature range of the liquid crystal expression temperature on the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is 10 ° C. lower than the lower limit of the temperature range of the liquid crystal expression temperature of the side chain polymer used, and 10 ° C. lower than the upper limit of the liquid crystal temperature range. It is preferable that it is the temperature of the range which makes an upper limit. If the heating temperature is lower than the above temperature range, the anisotropic amplification effect due to heat in the coating film tends to be insufficient, and if the heating temperature is too higher than the above temperature range, the state of the coating film Tends to be close to an isotropic liquid state (isotropic phase), and in this case, reorientation in one direction may be difficult due to self-organization.
The liquid crystal expression temperature is not less than the glass transition temperature (Tg) at which the side chain polymer or coating film surface undergoes a phase transition from the solid phase to the liquid crystal phase, and from the liquid crystal phase to the isotropic phase (isotropic phase). It means a temperature below the isotropic phase transition temperature (Tiso) that causes a phase transition.
　加熱後に形成される塗膜の厚みは、工程［Ｉ］で記した同じ理由から、好ましくは５ｎｍ乃至５００ｎｍ、より好ましくは５０ｎｍ乃至３００ｎｍであるのがよい。
　以上の工程を有することにより、本発明の製造方法では、高効率な、塗膜への異方性の導入を実現することができる。そして、高効率に配向層付基板を製造することができる。 The thickness of the coating film formed after heating is preferably 5 nm to 500 nm, more preferably 50 nm to 300 nm, for the same reason described in the step [I].
By having the above steps, the production method of the present invention can realize highly efficient introduction of anisotropy into the coating film. And the board | substrate with an alignment layer can be manufactured highly efficiently.
　本発明の塗膜付基板の製造方法は、重合体組成物を基板上に塗布し塗膜を形成した後、偏光した紫外線を照射する。次いで、加熱を行うことにより側鎖型高分子膜への高効率な異方性の導入を実現し、液晶の配向制御能を備えた液晶配向膜付基板を製造する。
　本発明に用いる塗膜では、側鎖の光反応と液晶性に基づく自己組織化によって誘起される分子再配向の原理を利用して、塗膜への高効率な異方性の導入を実現する。本発明の製造方法では、側鎖型高分子に光反応性基として光架橋性基を有する構造の場合、側鎖型高分子を用いて基板上に塗膜を形成した後、偏光した紫外線を照射し、次いで、加熱を行った後、偏光素子を作成する。 The manufacturing method of the board | substrate with a coating film of this invention irradiates the polarized ultraviolet-ray, after apply | coating a polymer composition on a board | substrate and forming a coating film. Next, by heating, high-efficiency anisotropy is introduced into the side chain polymer film, and a substrate with a liquid crystal alignment film having a liquid crystal alignment control ability is manufactured.
The coating film used in the present invention realizes the introduction of highly efficient anisotropy into the coating film by utilizing the principle of molecular reorientation induced by the side chain photoreaction and liquid crystallinity. . In the production method of the present invention, in the case of a structure having a photocrosslinkable group as a photoreactive group in the side chain polymer, after forming a coating film on the substrate using the side chain polymer, polarized ultraviolet rays are formed. After irradiation and then heating, a polarizing element is prepared.
　したがって、本発明の方法に用いる塗膜は、塗膜への偏光した紫外線の照射と加熱処理を順次行うことにより、高効率に異方性が導入され、配向制御能に優れた配向層とすることができる。 Therefore, the coating film used in the method of the present invention is an alignment layer in which anisotropy is introduced with high efficiency and alignment control ability is excellent by sequentially irradiating the coating film with polarized ultraviolet rays and heat treatment. be able to.
　そして、本発明の方法に用いる塗膜では、塗膜への偏光した紫外線の照射量と、加熱処理における加熱温度を最適化する。それにより高効率な、塗膜への異方性の導入を実現することができる。 And in the coating film used for the method of the present invention, the irradiation amount of polarized ultraviolet rays to the coating film and the heating temperature in the heat treatment are optimized. Thereby, introduction of anisotropy into the coating film with high efficiency can be realized.
　本発明に用いられる塗膜への高効率な異方性の導入に最適な偏光紫外線の照射量は、その塗膜において感光性基が光架橋反応や光異性化反応、若しくは光フリース転位反応する量を最適にする偏光紫外線の照射量に対応する。本発明に用いられる塗膜に対して偏光した紫外線を照射した結果、光架橋反応や光異性化反応、若しくは光フリース転位反応する側鎖の感光性基が少ないと、十分な光反応量とならない。その場合、その後に加熱しても十分な自己組織化は進行しない。一方、本発明に用いられる塗膜で、光架橋性基を有する構造に対して偏光した紫外線を照射した結果、架橋反応する側鎖の感光性基が過剰となると側鎖間での架橋反応が進行しすぎることになる。その場合、得られる膜は剛直になって、その後の加熱による自己組織化の進行の妨げとなることがある。また、本発明に用いられる塗膜で、光フリース転位基を有する構造に対して偏光した紫外線を照射した結果、光フリース転位反応する側鎖の感光性基が過剰となると、塗膜の液晶性が低下しすぎることになる。その場合、得られる膜の液晶性も低下し、その後の加熱による自己組織化の進行の妨げとなることがある。さらに、光フリース転位基を有する構造に対して偏光した紫外線を照射する場合、紫外線の照射量が多すぎると、側鎖型高分子が光分解し、その後の加熱による自己組織化の進行の妨げとなることがある。 The optimum irradiation amount of polarized ultraviolet rays for introducing highly efficient anisotropy into the coating film used in the present invention is such that the photosensitive group undergoes photocrosslinking reaction, photoisomerization reaction, or photofries rearrangement reaction in the coating film. Corresponds to the irradiation amount of polarized ultraviolet rays to optimize the amount. As a result of irradiating the coating film used in the present invention with polarized ultraviolet rays, if the photo-crosslinking reaction, photoisomerization reaction, or photo-fleece rearrangement reaction has few photosensitive groups in the side chain, the amount of photoreaction will not be sufficient. . In that case, sufficient self-organization does not proceed even after heating. On the other hand, as a result of irradiating polarized ultraviolet rays to the structure having a photocrosslinkable group in the coating film used in the present invention, the crosslinking reaction between the side chains is caused when the photosensitive group of the side chain undergoing the crosslinking reaction becomes excessive. Too much progress. In that case, the resulting film may become rigid and hinder the progress of self-assembly by subsequent heating. In addition, when the coating film used in the present invention is irradiated with polarized ultraviolet rays to the structure having the light Fleece rearrangement group, if the photosensitive group of the side chain that undergoes the light Fleece rearrangement reaction becomes excessive, the liquid crystallinity of the coating film Will drop too much. In that case, the liquid crystallinity of the obtained film is also lowered, which may hinder the progress of self-assembly by subsequent heating. Furthermore, when irradiating polarized ultraviolet light to a structure having a photo-fleece rearrangement group, if the amount of ultraviolet light irradiation is too large, the side-chain polymer is photodegraded, preventing the subsequent self-organization by heating. It may become.
　したがって、本発明に用いられる塗膜において、偏光紫外線の照射によって側鎖の感光性基が光架橋反応や光異性化反応、若しくは光フリース転位反応する最適な量は、その側鎖型高分子膜の有する感光性基の０．１モル％乃至４０モル％にすることが好ましく、０．１モル％乃至２０モル％にすることがより好ましい。光反応する側鎖の感光性基の量をこのような範囲にすることにより、その後の加熱処理での自己組織化が効率良く進み、膜中での高効率な異方性の形成が可能となる。 Therefore, in the coating film used in the present invention, the optimum amount of the photopolymerization reaction, photoisomerization reaction, or photofleece rearrangement reaction of the side chain photosensitive group by irradiation with polarized ultraviolet rays is the side chain polymer film. It is preferable to make it 0.1 mol% thru | or 40 mol% of the photosensitive group which it has, and it is more preferable to make it 0.1 mol% thru | or 20 mol%. By making the amount of the photo-reactive side chain photosensitive group within such a range, the self-organization in the subsequent heat treatment proceeds efficiently, and the formation of highly efficient anisotropy in the film is possible. Become.
　本発明の方法に用いる塗膜では、偏光した紫外線の照射量の最適化により、側鎖型高分子膜の側鎖における、感光性基の光架橋反応や光異性化反応、または光フリース転位反応の量を最適化する。そして、その後の加熱処理と併せて、高効率な、本発明に用いられる塗膜への異方性の導入を実現する。その場合、好適な偏光紫外線の量については、本発明に用いられる塗膜の紫外吸収の評価に基づいて行うことが可能である。 In the coating film used in the method of the present invention, by optimizing the irradiation amount of polarized ultraviolet rays, photocrosslinking reaction or photoisomerization reaction of photosensitive groups or photofleece rearrangement reaction in the side chain of the side chain polymer film Optimize the amount of. Then, in combination with the subsequent heat treatment, highly efficient introduction of anisotropy into the coating film used in the present invention is realized. In that case, a suitable amount of polarized ultraviolet rays can be determined based on the evaluation of ultraviolet absorption of the coating film used in the present invention.
　すなわち、本発明に用いられる塗膜について、偏光紫外線照射後の、偏光した紫外線の偏光方向と平行な方向の紫外線吸収と、垂直な方向の紫外線吸収とをそれぞれ測定する。紫外吸収の測定結果から、その塗膜における、偏光した紫外線の偏光方向と平行な方向の紫外線吸光度と垂直な方向の紫外線吸光度との差であるΔＡを評価する。そして、本発明に用いられる塗膜において実現されるΔＡの最大値（ΔＡｍａｘ）とそれを実現する偏光紫外線の照射量を求める。本発明の製造方法では、このΔＡｍａｘを実現する偏光紫外線照射量を基準として、液晶配向膜の製造において照射する、好ましい量の偏光した紫外線量を決めることができる。 That is, with respect to the coating film used in the present invention, the ultraviolet absorption in the direction parallel to the polarization direction of the polarized ultraviolet ray and the ultraviolet absorption in the vertical direction after the irradiation with the polarized ultraviolet ray are measured. From the measurement result of ultraviolet absorption, ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarization direction of the polarized ultraviolet rays, is evaluated. Then, the maximum value of ΔA (ΔAmax) realized in the coating film used in the present invention and the irradiation amount of polarized ultraviolet light that realizes it are obtained. In the production method of the present invention, a preferable amount of polarized ultraviolet rays to be irradiated in the production of the liquid crystal alignment film can be determined on the basis of the amount of polarized ultraviolet rays to realize this ΔAmax.
　本発明の製造方法では、本発明に用いられる塗膜への偏光した紫外線の照射量を、ΔＡｍａｘを実現する偏光紫外線の量の１％乃至７０％の範囲内とすることが好ましく、１％乃至５０％の範囲内とすることがより好ましい。本発明に用いられる塗膜において、ΔＡｍａｘを実現する偏光紫外線の量の１％乃至５０％の範囲内の偏光紫外線の照射量は、その側鎖型高分子膜の有する感光性基全体の０．１モル％乃至２０モル％を光架橋反応させる偏光紫外線の量に相当する。 In the production method of the present invention, the irradiation amount of the polarized ultraviolet light on the coating film used in the present invention is preferably in the range of 1% to 70% of the amount of polarized ultraviolet light that realizes ΔAmax. More preferably, it is within the range of 50%. In the coating film used in the present invention, the irradiation amount of polarized ultraviolet rays within the range of 1% to 50% of the amount of polarized ultraviolet rays realizing ΔAmax is 0. 0% of the entire photosensitive group of the side chain type polymer film. 1 mol% to 20 mol% corresponds to the amount of polarized ultraviolet light that undergoes a photocrosslinking reaction.
　以上より、本発明の製造方法では、塗膜への高効率な異方性の導入を実現するため、その側鎖型高分子の液晶温度範囲を基準として、上述したような好適な加熱温度を定めるのがよい。したがって、例えば、本発明に用いられる側鎖型高分子の液晶温度範囲が６０℃乃至２００℃である場合、偏光紫外線照射後の加熱の温度を５０℃乃至１９０℃とすることが望ましい。こうすることにより、本発明に用いられる塗膜において、より大きな異方性が付与されることになる。 From the above, in the production method of the present invention, in order to achieve highly efficient anisotropy introduction into the coating film, a suitable heating temperature as described above is set based on the liquid crystal temperature range of the side chain polymer. It is good to decide. Therefore, for example, when the liquid crystal temperature range of the side chain polymer used in the present invention is 60 ° C. to 200 ° C., the heating temperature after irradiation with polarized ultraviolet light is desirably 50 ° C. to 190 ° C. By doing so, greater anisotropy is imparted to the coating film used in the present invention.
　こうすることにより、本発明によって提供される偏光素子は光や熱などの外部ストレスに対して高い信頼性を示すことになる。 By doing so, the polarizing element provided by the present invention exhibits high reliability against external stresses such as light and heat.
＜偏光層形成用組成物＞
  本発明の偏光素子の形成に用いられる偏光層形成用組成物は、二色性色素と（Ｃ）重合性液晶とを含有するか、または（Ｄ）リオトロピック液晶性を有する色素を含有する組成物である。二色性色素と（Ｃ）重合性液晶とを含有する偏光層形成用組成物は、通常溶剤を含み、溶剤としては、上述の配向性重合体組成物に含まれる溶剤と同様のものが挙げられ、（Ｃ）重合性液晶の溶解性に応じて適宜選択することができる。 <Polarizing layer forming composition>
The composition for forming a polarizing layer used for forming the polarizing element of the present invention contains a dichroic dye and (C) a polymerizable liquid crystal, or (D) a composition containing a dye having lyotropic liquid crystallinity. It is. The composition for forming a polarizing layer containing a dichroic dye and (C) a polymerizable liquid crystal usually contains a solvent, and examples of the solvent include the same solvents as those contained in the above-mentioned oriented polymer composition. (C) It can be appropriately selected according to the solubility of the polymerizable liquid crystal.
  （Ｄ）リオトロピック液晶性を有する色素を含有する組成物は、通常溶剤を含み、前記溶剤は、特に限定されず、従来公知の溶媒を用いることができるが、水系溶媒が好ましい。水系溶媒としては、水、親水性溶媒、水と親水性溶媒の混合溶媒などが挙げられる。前記親水性溶媒は、水に略均一に溶解する溶媒である。親水性溶媒としては、例えば、メタノール、イソプロピルアルコールなどのアルコール類；エチレングリコールなどのグリコール類；メチルセロソルブ、エチルセロソルブなどのセロソルブ類；アセトン、メチルエチルケトンなどのケトン類；酢酸エチルなどのエステル類；などが挙げられる。上記水系溶媒は、好ましくは、水、又は、水と親水性溶媒の混合溶媒が用いられる。 The composition containing 組成 (D) a dye having lyotropic liquid crystallinity usually contains a solvent, and the solvent is not particularly limited, and a conventionally known solvent can be used, but an aqueous solvent is preferable. Examples of the aqueous solvent include water, a hydrophilic solvent, a mixed solvent of water and a hydrophilic solvent, and the like. The hydrophilic solvent is a solvent that dissolves substantially uniformly in water. Examples of the hydrophilic solvent include alcohols such as methanol and isopropyl alcohol; glycols such as ethylene glycol; cellosolves such as methyl cellosolve and ethyl cellosolve; ketones such as acetone and methylethylketone; esters such as ethyl acetate; Is mentioned. As the aqueous solvent, water or a mixed solvent of water and a hydrophilic solvent is preferably used.
  二色性色素としては前述の（Ａ）成分に示した化合物が用いられるが、重合性基を有さない二色性色素でもよい。 As the dichroic dye, the compounds shown in the above component (A) are used, but a dichroic dye having no polymerizable group may be used.
　重合性基を有さない二色性色素の市販品としては、例えば、Ｇ－２０７、Ｇ－２４１、Ｇ－４７０（林原社製）、Ｙｅｌｌｏｗ－８、ＫＲＤ－９０１、ＫＲＤ－９０２（昭和化学工業株式会社製）、ＳＩ－４８６（三井化学株式会社製）が挙げられる。 Examples of commercially available dichroic dyes having no polymerizable group include G-207, G-241, G-470 (manufactured by Hayashibara), Yellow-8, KRD-901, and KRD-902 (Showa Chemical). Kogyo Co., Ltd.) and SI-486 (Mitsui Chemicals Co., Ltd.).
＜（Ｃ）重合性液晶＞
  （Ｃ）重合性液晶とは、重合性基を有し、かつ、液晶性を示す化合物である。
  重合性基とは、重合反応に関与する基を意味し、光重合性基であることが好ましい。ここで、光重合性基とは、後述する光重合開始剤から発生した活性ラジカルや酸などによって重合反応し得る基のことをいう。重合性基としては、ビニル基、ビニルオキシ基、１－クロロビニル基、イソプロペニル基、４－ビニルフェニル基、アクリロイルオキシ基、メタクリロイルオキシ基、オキシラニル基、オキセタニル基等が挙げられる。中でも、アクリロイルオキシ基、メタクリロイルオキシ基、ビニルオキシ基、オキシラニル基及びオキセタニル基が好ましく、アクリロイルオキシ基がより好ましい。液晶性を示す化合物は、サーモトロピック性液晶でもリオトロピック液晶でもよく、また、サーモトロピック液晶における、ネマチック液晶でもスメクチック液晶でもよい。 <(C) Polymerizable liquid crystal>
(C) The polymerizable liquid crystal is a compound having a polymerizable group and exhibiting liquid crystallinity.
The polymerizable group means a group involved in the polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group capable of undergoing a polymerization reaction with an active radical or an acid generated from a photopolymerization initiator described later. Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable. The compound exhibiting liquid crystallinity may be a thermotropic liquid crystal or a lyotropic liquid crystal, and may be a nematic liquid crystal or a smectic liquid crystal in the thermotropic liquid crystal.
  重合性液晶は、より高い偏光特性が得られるという点でスメクチック液晶化合物が好ましく、高次スメクチック液晶化合物がより好ましい。中でも、スメクチックＢ相、スメクチックＤ相、スメクチックＥ相、スメクチックＦ相、スメクチックＧ相、スメクチックＨ相、スメクチックＩ相、スメクチックＪ相、スメクチックＫ相またはスメクチックＬ相を形成する高次スメクチック液晶化合物がより好ましく、スメクチックＢ相、スメクチックＦ相またはスメクチックＩ相を形成する高次スメクチック液晶化合物がより好ましい。重合性液晶化合物が形成する液晶相がこれらの高次スメクチック相であると、配向秩序度のより高い偏光膜を製造することができる。また、このように配向秩序度の高い長尺偏光膜はＸ線回折測定においてヘキサチック相やクリスタル相といった高次構造由来のブラッグピークが得られる。当該ブラッグピークは、分子配向の周期構造に由来するピークであり、重合性液晶化合物が形成する液晶相がこれらの高次スメクチック相であると、その周期間隔が３．０乃至６．０Åである膜を得ることができる。
このような化合物は、具体的には、下記式（ｄ）で表される化合物（以下、化合物（ｄ）ということがある。）等が挙げられる。当該重合性液晶化合物は、単独で用いてもよいし、組み合わせてもよい。 The polymerizable liquid crystal is preferably a smectic liquid crystal compound and more preferably a higher order smectic liquid crystal compound in that higher polarization characteristics can be obtained. Among these, higher-order smectic liquid crystal compounds that form a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, a smectic J phase, a smectic K phase, or a smectic L phase. More preferred are higher order smectic liquid crystal compounds that form a smectic B phase, a smectic F phase, or a smectic I phase. When the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher order smectic phase, a polarizing film having a higher degree of alignment order can be produced. Further, such a long polarizing film having a high degree of orientational order can obtain a Bragg peak derived from a higher order structure such as a hexatic phase or a crystal phase in X-ray diffraction measurement. The Bragg peak is a peak derived from a periodic structure of molecular orientation, and when the liquid crystal phase formed by the polymerizable liquid crystal compound is a higher order smectic phase, the periodic interval is 3.0 to 6.0６. A membrane can be obtained.
Specific examples of such a compound include a compound represented by the following formula (d) (hereinafter sometimes referred to as compound (d)). The polymerizable liquid crystal compounds may be used alone or in combination.
    Ｕ1－Ｖ1－Ｗ1－Ｘ1－Ｙ1－Ｘ2－Ｙ2－Ｘ3－Ｗ2－Ｖ2－Ｕ2    （ｄ）
［式（ｄ）中、
  Ｘ1、Ｘ2及びＸ3は、互いに独立に、置換基を有していてもよい１，４－フェニレン基又は置換基を有していてもよいシクロヘキサン－１，４－ジイル基を表す。ただし、Ｘ1、Ｘ2及びＸ3のうち少なくとも１つは、置換基を有していてもよい１，４－フェニレン基である。シクロへキサン－１，４－ジイル基を構成する－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＮＲ－に置き換わっていてもよい。Ｒは、炭素原子数１乃至６のアルキル基又はフェニル基を表す。
  Ｙ1及びＹ2は、互いに独立に、－ＣＨ2ＣＨ2－、－ＣＨ2Ｏ－、－ＣＯＯ－、－ＯＣＯＯ－、単結合、－Ｎ＝Ｎ－、－ＣＲa＝ＣＲb－、－Ｃ≡Ｃ－又は－ＣＲa＝Ｎ－を表す。Ｒa及びＲbは、互いに独立に、水素原子又は炭素原子数１乃至４のアルキル基を表す。
  Ｕ1は、水素原子又は重合性基を表す。
  Ｕ2は、重合性基を表す。
  Ｗ1及びＷ2は、互いに独立に、単結合、－Ｏ－、－Ｓ－、－ＣＯＯ－又は－ＯＣＯＯ－を表す。
  Ｖ1及びＶ2は、互いに独立に、置換基を有していてもよい炭素原子数１乃至２０のアルカンジイル基を表し、該アルカンジイル基を構成する－ＣＨ2－は、－Ｏ－、－Ｓ－又は－ＮＨ－に置き換わっていてもよい。］ U 1 −V 1 −W 1 −X 1 −Y 1 −X 2 −Y 2 −X 3 −W 2 −V 2 −U 2 (d)
[In the formula (d),
X 1 , X 2 and X 3 each independently represent a 1,4-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, at least one of X 1 , X 2 and X 3 is a 1,4-phenylene group which may have a substituent. —CH 2 — constituting the cyclohexane-1,4-diyl group may be replaced by —O—, —S— or —NR—. R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.
Y 1 and Y 2, independently of one another, -CH 2 CH 2 -, - CH 2 O -, - COO -, - OCOO-, a single bond, -N = N -, - CR a = CR b -, - C≡C— or —CR a ═N— is represented. R a and R b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
U 1 represents a hydrogen atom or a polymerizable group.
U 2 represents a polymerizable group.
W 1 and W 2 each independently represent a single bond, —O—, —S—, —COO— or —OCOO—.
V 1 and V 2 each independently represents an optionally substituted alkanediyl group having 1 to 20 carbon atoms, and —CH 2 — constituting the alkanediyl group is —O—, -S- or -NH- may be substituted. ]
  化合物（ｄ）において、Ｘ1、Ｘ2及びＸ3のうち少なくとも１つは、置換基を有していてもよい１，４－フェニレン基であることが好ましい。
  置換基を有していてもよい１，４－フェニレン基は、無置換であることが好ましい。置換基を有していてもよいシクロへキサン－１，４－ジイル基は、置換基を有していてもよいトランス－シクロへキサン－１，４－ジイル基であることが好ましく、置換基を有していてもよいトランス－シクロへキサン－１，４－ジイル基は無置換であることが好ましい。 In the compound (d), at least one of X 1 , X 2 and X 3 is preferably a 1,4-phenylene group which may have a substituent.
The 1,4-phenylene group which may have a substituent is preferably unsubstituted. The cyclohexane-1,4-diyl group which may have a substituent is preferably a trans-cyclohexane-1,4-diyl group which may have a substituent. It is preferable that the trans-cyclohexane-1,4-diyl group which may have a non-substituted group.
  置換基を有していてもよい１，４－フェニレン基又は置換基を有していてもよいシクロへキサン－１，４－ジイル基が任意に有する置換基は、メチル基、エチル基及びブチル基などの炭素原子数１乃至４のアルキル基、シアノ基およびハロゲン原子などが挙げられる。 The optionally substituted 1,4-phenylene group or optionally substituted cyclohexane-1,4-diyl group includes a methyl group, an ethyl group, and a butyl group. Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a group, a cyano group, and a halogen atom.
  Ｙ1は、－ＣＨ2ＣＨ2－、－ＣＯＯ－又は単結合であると好ましく、Ｙ2は、－ＣＨ2ＣＨ2－又は－ＣＨ2Ｏ－であると好ましい。 Y 1 is preferably —CH 2 CH 2 —, —COO— or a single bond, and Y 2 is preferably —CH 2 CH 2 — or —CH 2 O—.
  Ｕ2は、重合性基である。Ｕ1は、水素原子又は重合性基であり、好ましくは重合性基である。Ｕ1及びＵ2は、ともに重合性基であると好ましく、ともに光重合性基であると好ましい。光重合性基を有する重合性液晶化合物は、より低温条件下で重合できる点で有利である。 U 2 is a polymerizable group. U 1 is a hydrogen atom or a polymerizable group, preferably a polymerizable group. U 1 and U 2 are preferably both polymerizable groups, and both are preferably photopolymerizable groups. The polymerizable liquid crystal compound having a photopolymerizable group is advantageous in that it can be polymerized under a lower temperature condition.
  Ｕ1及びＵ2で表される重合性基は互いに独立して異なっていてもよいが、同一であると好ましい。重合性基としては、ビニル基、ビニルオキシ基、１－クロロビニル基、イソプロペニル基、４－ビニルフェニル基、アクリロイルオキシ基、メタクリロイルオキシ基、オキシラニル基、オキセタニル基等が挙げられる。中でも、アクリロイルオキシ基、メタクリロイルオキシ基、ビニルオキシ基、オキシラニル基及びオキセタニル基が好ましく、アクリロイルオキシ基がより好ましい。 The polymerizable groups represented by U 1 and U 2 may be different from each other independently, but are preferably the same. Examples of the polymerizable group include a vinyl group, vinyloxy group, 1-chlorovinyl group, isopropenyl group, 4-vinylphenyl group, acryloyloxy group, methacryloyloxy group, oxiranyl group, and oxetanyl group. Among them, acryloyloxy group, methacryloyloxy group, vinyloxy group, oxiranyl group and oxetanyl group are preferable, and acryloyloxy group is more preferable.
  Ｖ1及びＶ2で表されるアルカンジイル基としては、メチレン基、エチレン基、プロパン－１，３－ジイル基、ブタン－１，３－ジイル基、ブタン－１，４－ジイル基、ペンタン－１，５－ジイル基、ヘキサン－１，６－ジイル基、ヘプタン－１，７－ジイル基、オクタン－１，８－ジイル基、デカン－１，１０－ジイル基、テトラデカン－１，１４－ジイル基及びイコサン－１，２０－ジイル基などが挙げられる。Ｖ1及びＶ2は、好ましくは炭素原子数２乃至１２のアルカンジイル基であり、より好ましくは炭素原子数６乃至１２のアルカンジイル基である。
  置換基を有していてもよい炭素原子数１乃至２０のアルカンジイル基が任意に有する置換基としては、シアノ基及びハロゲン原子などが挙げられるが、該アルカンジイル基は、無置換であることが好ましく、無置換且つ直鎖状のアルカンジイル基であることがより好ましい。 Examples of the alkanediyl group represented by V 1 and V 2 include methylene group, ethylene group, propane-1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane- 1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, decane-1,10-diyl group, tetradecane-1,14-diyl Group and icosane-1,20-diyl group and the like. V 1 and V 2 are preferably alkanediyl groups having 2 to 12 carbon atoms, and more preferably alkanediyl groups having 6 to 12 carbon atoms.
Examples of the substituent which the alkanediyl group having 1 to 20 carbon atoms which may have a substituent optionally include a cyano group and a halogen atom, the alkanediyl group should be unsubstituted. It is more preferable that it is an unsubstituted and linear alkanediyl group.
  Ｗ1及びＷ2は、互いに独立に、好ましくは単結合又は－Ｏ－である。 W 1 and W 2 are independently of each other preferably a single bond or —O—.
  化合物（ｄ）の具体例は、式（１－１）乃至式（１－２３）で表される化合物などが挙げられる。化合物（ｄ）が、シクロヘキサン－１，４－ジイル基を有する場合、そのシクロヘキサン－１，４－ジイル基は、トランス体であることが好ましい。
Figure JPOXMLDOC01-appb-C000038
 Specific examples of the compound (d) include compounds represented by the formulas (1-1) to (1-23). When the compound (d) has a cyclohexane-1,4-diyl group, the cyclohexane-1,4-diyl group is preferably a trans isomer.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
  例示した化合物（ｄ）の中でも、式（１－２）、式（１－３）、式（１－４）、式（１－６）、式（１－７）、式（１－８）、式（１－１３）、式（１－１４）及び式（１－１５）でそれぞれ表される化合物からなる群より選ばれる少なくとも１種が好ましい。 Among the exemplified compounds (d), formula (1-2), formula (1-3), formula (1-4), formula (1-6), formula (1-7), formula (1-8) At least one selected from the group consisting of compounds represented by formula (1-13), formula (1-14) and formula (1-15) is preferred.
  例示した化合物（ｄ）は、単独又は組み合わせて、長尺偏光膜に用いることができる。
また、２種以上の重合性液晶化合物を組み合わせる場合には、少なくとも１種が化合物（ｃ）であると好ましく、２種以上が化合物（ｄ）であるとより好ましい。組み合わせることにより、液晶－結晶相転移温度以下の温度でも一時的に液晶性を保持することができる場合がある。２種類の重合性液晶化合物を組み合わせる場合の混合比は、通常、１：９９乃至５０：５０であり、好ましくは５：９５乃至５０：５０であり、より好ましくは１０：９０乃至５０：５０である。 The exemplified compound (d) can be used alone or in combination for a long polarizing film.
Moreover, when combining 2 or more types of polymeric liquid crystal compounds, it is preferable that at least 1 type is a compound (c), and it is more preferable that 2 or more types are a compound (d). In combination, the liquid crystallinity may be temporarily maintained even at a temperature lower than the liquid crystal-crystal phase transition temperature. The mixing ratio when combining two kinds of polymerizable liquid crystal compounds is usually 1:99 to 50:50, preferably 5:95 to 50:50, more preferably 10:90 to 50:50. is there.
  化合物（ｄ）は、例えば、Ｌｕｂ  eｔ  aｌ.  Ｒｅｃｌ．Ｔｒａｖ．Ｃｈｉｍ．Ｐａｙｓ－Ｂａｓ，１１５,  ３２１－３２８（１９９６）、又は特許第４７１９１５６号などに記載の公知方法で製造される。 Compound (d) is, for example, Lub et al. Trav. Chim. It is manufactured by a known method described in Pays-Bas, 115, 特許 321-328 (1996), or Japanese Patent No. 4719156.
＜（Ｄ）リオトロピック液晶性を有する色素＞
  偏光層に（Ｄ）リオトロピック液晶性を有する色素を含有させる場合は、当該色素はリオトロピック液晶性を有し、且つ、超分子会合体を形成し得るものであれば特に限定されない。
  このようなリオトロピック液晶性を有する色素としては、例えば、アゾ系化合物、アントラキノン系化合物、ペリレン系化合物、キノフタロン系化合物、ナフトキノン系化合物、メロシアニン系化合物などが挙げられる。良好なリオトロピック液晶性を示すことから、アゾ系化合物を用いることが好ましい。 <(D) Dye having lyotropic liquid crystal properties>
When the polarizing layer contains (D) a dye having lyotropic liquid crystallinity, the dye is not particularly limited as long as it has lyotropic liquid crystallinity and can form a supramolecular aggregate.
Examples of such lyotropic liquid crystalline dyes include azo compounds, anthraquinone compounds, perylene compounds, quinophthalone compounds, naphthoquinone compounds, merocyanine compounds, and the like. An azo compound is preferably used because it exhibits good lyotropic liquid crystallinity.
  アゾ系化合物の中では、分子中に芳香環を有するアゾ化合物が好ましく、ナフタレン環を有するジスアゾ化合物がより好ましい。このようなアゾ系化合物を含むコーティング液を塗布・乾燥することにより、偏光特性に優れた偏光層を得ることができる。
  また、アゾ系化合物は、その分子中に極性基を有するアゾ系化合物が好ましい。極性基を有するアゾ系化合物は、水系溶媒に可溶であり、水系溶媒に溶解して超分子会合体を形成し易い。このため、極性基を有するアゾ系化合物を含むコーティング液は、特に良好なリオトロピック液晶性を示す。
  なお、極性基とは、極性を持つ官能基を意味する。極性基としては、ＯＨ基、ＣＯＯＨ基、ＮＨ2基、ＮＯ2基、ＣＮ基のような比較的電気陰性度の大きい酸素及び／又は窒素を含む官能基が挙げられる。 Among the azo compounds, azo compounds having an aromatic ring in the molecule are preferable, and disazo compounds having a naphthalene ring are more preferable. By applying and drying a coating solution containing such an azo compound, a polarizing layer having excellent polarization characteristics can be obtained.
The azo compound is preferably an azo compound having a polar group in the molecule. An azo compound having a polar group is soluble in an aqueous solvent, and is easily dissolved in an aqueous solvent to form a supramolecular aggregate. For this reason, the coating liquid containing an azo compound having a polar group exhibits particularly good lyotropic liquid crystallinity.
The polar group means a functional group having polarity. Examples of the polar group include functional groups containing oxygen and / or nitrogen having a relatively high electronegativity such as OH group, COOH group, NH 2 group, NO 2 group, and CN group.
  極性基を有するアゾ系化合物としては、例えば、下記一般式（Ｄ－１）で表される芳香族ジスアゾ化合物が好ましい。
Figure JPOXMLDOC01-appb-C000042
 As the azo compound having a polar group, for example, an aromatic disazo compound represented by the following general formula (D-1) is preferable.
Figure JPOXMLDOC01-appb-C000042
  一般式（Ｄ－１）において、Ｑ1は、置換若しくは無置換のアリール基を表し、Ｑ2は、置換若しくは無置換のアリーレン基を表し、ＲDは、独立して、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアセチル基、置換若しくは無置換のベンゾイル基、置換若しくは無置換のフェニル基を表し、Ｍは、対イオンを表し、ｍ７は、０乃至２の整数を表し、ｎ７は、０乃至６の整数を表す。ただし、ｍ７及びｎ７の少なくとも何れか一方は、０でなく、１≦ｍ７＋ｎ７≦６である。前記ｍ７が２である場合、各ＲDは、同一又は異なる。
  一般式（Ｄ－１）に示されたＯＨ、（ＮＨＲD）m7、及び（ＳＯ3Ｍ）n7は、それぞれナフチル環の７つの置換部位のいずれに結合していてもよい。
  なお、本明細書において、「置換若しくは無置換」とは、「置換基で置換されている、又は、置換基で置換されていない」ことを意味する。 In the general formula (D-1), Q 1 represents a substituted or unsubstituted aryl group, Q 2 represents a substituted or unsubstituted arylene group, and R D independently represents a hydrogen atom, a substituted or Represents an unsubstituted alkyl group, a substituted or unsubstituted acetyl group, a substituted or unsubstituted benzoyl group, a substituted or unsubstituted phenyl group, M represents a counter ion, and m7 represents an integer of 0 to 2. , N7 represents an integer of 0 to 6. However, at least one of m7 and n7 is not 0 but 1 ≦ m7 + n7 ≦ 6. When m7 is 2, each RD is the same or different.
OH, (NHR D ) m7 , and (SO 3 M) n7 shown in the general formula (D-1) may be bonded to any of the seven substitution sites of the naphthyl ring.
In the present specification, “substituted or unsubstituted” means “substituted with a substituent or not substituted with a substituent”.
  前記一般式（Ｄ－１）のナフチル基とアゾ基（－Ｎ＝Ｎ－）の結合位置は、特に限定されない。前記ナフチル基は、式（Ｄ－１）において右側に表されているナフチル基を指す。好ましくは、前記ナフチル基とアゾ基は、前記ナフチル基の１位又は２位で結合されている。 (2) The bonding position of the naphthyl group and the azo group (—N═N—) in the general formula (D-1) is not particularly limited. The naphthyl group refers to a naphthyl group represented on the right side in the formula (D-1). Preferably, the naphthyl group and the azo group are bonded at the 1-position or 2-position of the naphthyl group.
  前記一般式（Ｄ－１）のＲDのアルキル基、アセチル基、ベンゾイル基、又はフェニル基が置換基を有する場合、その置換基としては、下記アリール基又はアリーレン基において例示する、各置換基が挙げられる。
  前記ＲDは、好ましくは、水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアセチル基であり、より好ましくは水素原子である。
  前記置換若しくは無置換のアルキル基としては、置換若しくは無置換の炭素原子数１乃至６のアルキル基が挙げられる。 In the case where the alkyl group, acetyl group, benzoyl group, or phenyl group of R D in the general formula (D-1) has a substituent, the substituent is exemplified by the following aryl groups or arylene groups. Is mentioned.
R D is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acetyl group, and more preferably a hydrogen atom.
Examples of the substituted or unsubstituted alkyl group include substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms.
  前記一般式（Ｄ－１）のＭ（対イオン）は、好ましくは、水素イオン；Ｌｉ、Ｎａ、Ｋ、Ｃｓなどのアルカリ金属イオン；Ｃａ、Ｓｒ、Ｂａなどのアルカリ土類金属イオン；その他の金属イオン；アルキル基若しくはヒドロキシアルキル基で置換されていてもよいアンモニウムイオン；有機アミンの塩などが挙げられる。前記金属イオンとしては、例えば、Ｎｉ+、Ｆｅ3+、Ｃｕ2+、Ａｇ+、Ｚｎ2+、Ａｌ3+、Ｐｄ2+、Ｃｄ2+、Ｓｎ2+、Ｃｏ2+、Ｍｎ2+、Ｃｅ3+などが挙げられる。有機アミンとしては、炭素原子数１乃至６のアルキルアミン、ヒドロキシル基を有する炭素原子数１乃至６のアルキルアミン、カルボキシル基を有する炭素原子数１乃至６のアルキルアミンなどが挙げられる。上記一般式（Ｄ－１）において、ＳＯ3Ｍが２つ以上である場合、各Ｍは、同一又は異なっていてもよい。また、前記一般式（Ｄ－１）において、ＳＯ3ＭのＭが２価以上の陽イオンである場合、隣接する他の一般式（Ｄ－１）のアゾ系化合物のＳＯ3 -と結合して超分子会合体を形成し得る。 M (counter ion) of the general formula (D-1) is preferably a hydrogen ion; an alkali metal ion such as Li, Na, K, or Cs; an alkaline earth metal ion such as Ca, Sr, or Ba; Metal ions; ammonium ions optionally substituted with alkyl groups or hydroxyalkyl groups; salts of organic amines, and the like. Examples of the metal ions include Ni + , Fe 3+ , Cu 2+ , Ag + , Zn 2+ , Al 3+ , Pd 2+ , Cd 2+ , Sn 2+ , Co 2+ , Mn 2+ , Ce 3+ and the like can be mentioned. Examples of the organic amine include alkylamines having 1 to 6 carbon atoms, alkylamines having 1 to 6 carbon atoms having a hydroxyl group, and alkylamines having 1 to 6 carbon atoms having a carboxyl group. In the general formula (D-1), when there are two or more SO 3 Ms, each M may be the same or different. In the general formula (D-1), when M of SO 3 M is a cation having a valence of 2 or more, it is bonded to SO 3 − of another adjacent azo compound of the general formula (D-1). Thus, supramolecular aggregates can be formed.
  前記一般式（Ｄ－１）のｍ７は、好ましくは１である。また、一般式（Ｄ－１）のｎ７は、好ましくは１又は２である。
  一般式（Ｄ－１）のナフチル基の具体例としては、例えば、下記式（Ｄ－ａ）乃至式（Ｄ－ｌ）などが挙げられる。式（Ｄ－ａ）乃至式（Ｄ－ｌ）のＲD及びＭは、一般式（Ｄ－１）と同様である。
Figure JPOXMLDOC01-appb-C000043
 M7 in the general formula (D-1) is preferably 1. In the general formula (D-1), n7 is preferably 1 or 2.
Specific examples of the naphthyl group of the general formula (D-1) include the following formulas (Da) to (Dl). R D and M in the formulas (Da) to (Dl) are the same as those in the general formula (D-1).
Figure JPOXMLDOC01-appb-C000043
  前記一般式（Ｄ－１）において、前記Ｑ1で表されるアリール基は、フェニル基の他、ナフチル基などのようなベンゼン環が２以上縮合した縮合環基が挙げられる。
  前記Ｑ2で表されるアリーレン基は、フェニレン基の他、ナフチレン基などのようなベンゼン環が２以上縮合した縮合環基が挙げられる。 In the general formula (D-1), examples of the aryl group represented by Q 1 include a phenyl group and a condensed ring group in which two or more benzene rings are condensed, such as a naphthyl group.
Examples of the arylene group represented by Q 2 include a condensed ring group in which two or more benzene rings are condensed, such as a naphthylene group, in addition to a phenylene group.
  Ｑ1のアリール基又はＱ2のアリーレン基は、それぞれ置換基を有していてもよいし、又は、置換基を有していなくてもよい。前記アリール基又はアリーレン基が、置換若しくは無置換のいずれの場合でも、極性基を有する一般式（Ｄ－１）の芳香族ジスアゾ化合物は、水系溶媒に対する溶解性に優れている。 The aryl group of Q 1 or the arylene group of Q 2 may have a substituent, or may not have a substituent. Regardless of whether the aryl group or arylene group is substituted or unsubstituted, the aromatic disazo compound of the general formula (D-1) having a polar group is excellent in solubility in an aqueous solvent.
  前記アリール基又はアリーレン基が置換基を有する場合、その置換基としては、例えば、炭素原子数１乃至６のアルキル基、炭素原子数１乃至６のアルコキシ基、炭素原子数１乃至６のアルキルアミノ基、フェニルアミノ基、炭素原子数１乃至６のアシルアミノ基、ジヒドロキシプロピル基等の炭素原子数１乃至６のヒドロキシアルキル基、ＣＯＯＭ基などのカルボキシル基、ＳＯ3Ｍ基などのスルホン酸基、水酸基、シアノ基、ニトロ基、アミノ基、ハロゲノ基などが挙げられる。好ましくは、前記置換基は、炭素原子数１乃至６のアルコキシ基、炭素原子数１乃至６のヒドロキシアルキル基、カルボキシル基、スルホン酸基、及びニトロ基から選ばれる１つである。このような置換基を有する芳香族ジスアゾ化合物は、特に水溶性に優れている。これらの置換基は、１種又は２種以上置換されていてもよい。また、前記置換基は、任意の比率で置換されていてもよい。 When the aryl group or arylene group has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and an alkylamino group having 1 to 6 carbon atoms. Group, phenylamino group, acylamino group having 1 to 6 carbon atoms, hydroxyalkyl group having 1 to 6 carbon atoms such as dihydroxypropyl group, carboxyl group such as COOM group, sulfonic acid group such as SO 3 M group, hydroxyl group , Cyano group, nitro group, amino group, halogeno group and the like. Preferably, the substituent is one selected from an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a carboxyl group, a sulfonic acid group, and a nitro group. An aromatic disazo compound having such a substituent is particularly excellent in water solubility. These substituents may be substituted alone or in combination of two or more. Moreover, the said substituent may be substituted by arbitrary ratios.
  前記一般式（Ｄ－１）のＱ1は、好ましくは置換若しくは無置換のフェニル基であり、より好ましくは前記置換基を有するフェニル基である。
  前記Ｑ2は、好ましくは置換若しくは無置換のナフチレン基であり、より好ましくは前記置換基を有するナフチレン基であり、特に好ましくは前記置換基を有する１，４－ナフチレン基である。 Q 1 in the general formula (D-1) is preferably a substituted or unsubstituted phenyl group, more preferably a phenyl group having the substituent.
Q 2 is preferably a substituted or unsubstituted naphthylene group, more preferably a naphthylene group having the substituent, and particularly preferably a 1,4-naphthylene group having the substituent.
  一般式（Ｄ－１）のＱ1が置換若しくは無置換のフェニル基で、且つ、Ｑ2が置換若しくは無置換の１，４－ナフチレン基である芳香族ジスアゾ系化合物は、下記一般式（Ｄ－２）で表される。
Figure JPOXMLDOC01-appb-C000044
   一般式（Ｄ－２）において、ＲD、Ｍ、ｍ７及びｎ７は、上記一般式（Ｄ－１）のそれらと同様である。
  一般式（Ｄ－２）において、ＡD及びＢDは、置換基を表し、ａ７及びｂ７は、その置換数を表す。前記ＡD及びＢDは、それぞれ独立して、炭素原子数１乃至６のアルキル基、炭素原子数１乃至６のアルコキシ基、炭素原子数１乃至６のアルキルアミノ基、フェニルアミノ基、炭素原子数１乃至６のアシルアミノ基、ジヒドロキシプロピル基等の炭素原子数１乃至６のヒドロキシアルキル基、ＣＯＯＭ基などのカルボキシル基、ＳＯ3Ｍ基などのスルホン酸基、水酸基、シアノ基、ニトロ基、アミノ基、ハロゲノ基を表す。前記ａ７は、０乃至５の整数であり、前記ｂ７は、０乃至４の整数を表す。ただし、ａ７及びｂ７の少なくとも何れか一方は０でない。前記ａ７が２以上の場合、前記置換基ＡDは、同じでもよいし、又は、異なっていてもよい。前記ｂ７が２以上の場合、前記置換基ＢDは、同じでもよいし、又は、異なっていてもよい。 An aromatic disazo compound in which Q 1 in the general formula (D-1) is a substituted or unsubstituted phenyl group and Q 2 is a substituted or unsubstituted 1,4-naphthylene group has the following general formula (D -2).
Figure JPOXMLDOC01-appb-C000044
 In the general formula (D-2), R D , M, m7 and n7 are the same as those in the general formula (D-1).
In the general formula (D-2), A D and B D represent substituents, and a7 and b7 represent the number of substitutions. A D and B D are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylamino group having 1 to 6 carbon atoms, a phenylamino group, or a carbon atom. number 1-6 acylamino group, a hydroxyalkyl group having 1 to 6 carbon atoms, such as dihydroxypropyl group, a carboxyl group, such as COOM group, a sulfonic acid group such as SO 3 M group, a hydroxyl group, a cyano group, a nitro group, an amino Represents a halogeno group. The a7 is an integer from 0 to 5, and the b7 is an integer from 0 to 4. However, at least one of a7 and b7 is not zero. When the a7 is 2 or more, the substituents A D may be the same or different. When b7 is 2 or more, the substituents B D may be the same or different.
  一般式（Ｄ－２）に含まれる芳香族ジスアゾ化合物の中では、下記一般式（Ｄ－３）で表される芳香族ジスアゾ化合物を用いることが好ましい。一般式（Ｄ－３）の芳香族ジスアゾ化合物は、置換基ＡDがアゾ基（－Ｎ＝Ｎ－）を基準にしてパラ位に結合している。さらに、一般式（Ｄ－３）の芳香族ジスアゾ化合物は、そのナフチル基のＯＨ基がアゾ基に隣接した位置（オルト位）に結合している。かかる一般式（Ｄ－３）の芳香族ジスアゾ化合物を用いれば、偏光度の高い偏光板を得ることができる。
Figure JPOXMLDOC01-appb-C000045
   一般式（Ｄ－３）において、ＲD、Ｍ、ｍ７及びｎ７は、上記一般式（Ｄ－１）のそれらと同様であり、ＡDは、一般式（Ｄ－２）のそれと同様である。
  一般式（Ｄ－３）において、ｐ７は、０乃至４の整数を表す。前記ｐ７は、好ましくは１又は２であり、より好ましくは１である。 Among the aromatic disazo compounds included in the general formula (D-2), it is preferable to use an aromatic disazo compound represented by the following general formula (D-3). In the aromatic disazo compound of the general formula (D-3), the substituent A D is bonded to the para position on the basis of the azo group (—N═N—). Further, in the aromatic disazo compound of the general formula (D-3), the OH group of the naphthyl group is bonded to the position adjacent to the azo group (ortho position). If such an aromatic disazo compound of the general formula (D-3) is used, a polarizing plate having a high degree of polarization can be obtained.
Figure JPOXMLDOC01-appb-C000045
 In the general formula (D-3), R D , M, m7 and n7 are the same as those in the general formula (D-1), and A D is the same as that in the general formula (D-2). .
In the general formula (D-3), p7 represents an integer of 0 to 4. The p7 is preferably 1 or 2, and more preferably 1.
  上記一般式（Ｄ－１）乃至（Ｄ－３）で表される芳香族ジスアゾ化合物は、例えば、細田豊著「理論製造  染料化学（５版）」（昭和４３年７月１５日技報堂発行、１３５頁乃至１５２頁）に従って合成できる。
  例えば、一般式（Ｄ－３）の芳香族ジスアゾ化合物は、アニリン誘導体とナフタレンスルホン酸誘導体をジアゾ化及びカップリング反応させてモノアゾ化合物を得た後、このモノアゾ化合物をジアゾ化した後、さらに、１－アミノ－８－ナフトールスルホン酸誘導体とカップリング反応させることによって合成できる。 The aromatic disazo compounds represented by the above general formulas (D-1) to (D-3) are, for example, Yutaka Hosoda “Theoretical Manufacturing Dye Chemistry (5th Edition)” (published on July 15, 1968 by Gihodo, 135 to 152).
For example, the aromatic disazo compound of the general formula (D-3) is obtained by diazotizing and coupling an aniline derivative and a naphthalenesulfonic acid derivative to obtain a monoazo compound, and then diazotizing the monoazo compound. It can be synthesized by a coupling reaction with a 1-amino-8-naphtholsulfonic acid derivative.
  偏光層形成用組成物における（Ｃ）重合性液晶化合物または（Ｄ）リオトロピック液晶性を有する色素の含有割合は、液晶化合物の配向性を高くするという観点から、当該偏光層形成用組成物の固形分に対して、通常７０乃至９９．９質量部であり、好ましくは８０乃至９９．９質量部であり、より好ましくは８５乃至９９質量部であり、さらに好ましくは９０乃至９９質量部である。 From the viewpoint of increasing the orientation of the liquid crystal compound, the content of the (C) polymerizable liquid crystal compound or (D) lyotropic liquid crystal pigment in the composition for forming a polarizing layer is a solid content of the composition for forming a polarizing layer. The amount is usually 70 to 99.9 parts by mass, preferably 80 to 99.9 parts by mass, more preferably 85 to 99 parts by mass, and still more preferably 90 to 99 parts by mass.
［ＩＶ］上記の配向層を有する基板を準備する工程であり；及び下記［Ｖ－１］及び［Ｖ－２］から選ばれる工程である。
　［Ｖ－１］前記配向層を有する基板の配向層上に、二色性色素と（Ｃ）重合性液晶とを含有する偏光層形成用組成物を塗付し、加熱乾燥することにより塗膜を形成し、得られた塗膜に紫外線を照射する工程；
　［Ｖ－２］前記配向層を有する基板の配向層上に、（Ｄ）リオトロピック液晶性を有する色素を含有する偏光層形成用組成物を塗付し、加熱乾燥することにより塗膜を形成する工程。 [IV] A step of preparing a substrate having the above alignment layer; and a step selected from the following [V-1] and [V-2].
[V-1] A polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal is applied on the alignment layer of the substrate having the alignment layer, and the coating film is formed by heating and drying. And irradiating the obtained coating film with ultraviolet rays;
[V-2] On the alignment layer of the substrate having the alignment layer, (D) a polarizing layer-forming composition containing a dye having lyotropic liquid crystallinity is applied and heated to dry to form a coating film. Process.
  偏光層形成用組成物の塗布は、通常、スピンコ－ティング法、エクストルージョン法、グラビアコーティング法、ダイコーティング法、バーコーティング法、アプリケータ法などの塗布法や、フレキソ法などの印刷法を含んだ公知の方法によって行われる。偏光層形成用組成物が（Ｃ）重合性液晶を含む場合は、塗布後、通常、得られた塗布膜中に含まれる（Ｃ）重合性液晶が重合しない条件で溶剤を除去することにより、乾燥被膜が形成される。乾燥方法としては、自然乾燥法、通風乾燥法、加熱乾燥および減圧乾燥法が挙げられる。 The application of the composition for forming a polarizing layer usually includes a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, and an applicator method, and a printing method such as a flexo method. This is done by known methods. When the composition for forming a polarizing layer contains (C) polymerizable liquid crystal, by removing the solvent under the condition that (C) polymerizable liquid crystal contained in the obtained coating film is not normally polymerized after coating, A dry film is formed. Examples of the drying method include natural drying, ventilation drying, heat drying, and reduced pressure drying.
  二色性色素と（Ｃ）重合性液晶とを含有する塗膜に紫外線を照射する工程において、（Ｃ）重合性液晶の重合は、重合性官能基を有する化合物を重合させる公知の方法により行うことができる。具体的には、熱重合および光重合が挙げられ、重合の容易さの観点から、光重合が好ましい。光重合により重合性液晶を重合させる場合、二色性色素と（Ｃ）重合性液晶とを含有する偏光層形成用組成物にさらに光重合開始剤を含有した組成物を塗布、乾燥して得られる乾燥被膜中の重合性液晶を液晶相状態にした後、該液晶状態を保持したまま、光重合させることが好ましい。 In the step of irradiating the coating film containing the dichroic dye and the polymerizable liquid crystal (C) with ultraviolet rays, the polymerizable liquid crystal (C) is polymerized by a known method of polymerizing a compound having a polymerizable functional group. be able to. Specific examples include thermal polymerization and photopolymerization, and photopolymerization is preferred from the viewpoint of ease of polymerization. When polymerizing a polymerizable liquid crystal by photopolymerization, it is obtained by applying a composition containing a photopolymerization initiator to a polarizing layer-forming composition containing a dichroic dye and (C) a polymerizable liquid crystal and drying it. It is preferable that the polymerizable liquid crystal in the dry film to be obtained is made into a liquid crystal phase and then photopolymerized while maintaining the liquid crystal state.
  光重合は、通常、乾燥被膜に光を照射することにより実施される。照射する光としては、乾燥被膜に含まれる光重合開始剤の種類、（Ｃ）重合性液晶の種類（特に、（Ｃ）重合性液晶が有する光重合基の種類）およびその量に応じて、適宜選択され、具体的には、可視光、紫外光およびレーザー光からなる群より選択される光、活性電子線が挙げられる。中でも、重合反応の進行を制御し易い点、および、光重合装置として当分野で広範に用いられているものが使用できるという点で、紫外光が好ましく、紫外光によって光重合可能なように、（Ｃ）重合性液晶や光重合開始剤の種類を選択することが好ましい。また、重合時に、適切な冷却手段により乾燥被膜を冷却しながら、光照射することで、重合温度を制御することもできる。このような冷却手段の採用により、より低温で（Ｃ）重合性液晶の重合を実施すれば、基材が比較的耐熱性が低いものを用いたとしても、適切に偏光層を形成できる。 Fluorescence polymerization is usually carried out by irradiating the dry film with light. As the light to be irradiated, depending on the type of photopolymerization initiator contained in the dry film, the type of (C) polymerizable liquid crystal (particularly, the type of photopolymerizable group (C) polymerizable liquid crystal has), and the amount thereof, Specific examples include light selected from the group consisting of visible light, ultraviolet light, and laser light, and active electron beams. Among them, ultraviolet light is preferable in that it is easy to control the progress of the polymerization reaction and that a photopolymerization apparatus widely used in this field can be used, so that photopolymerization can be performed by ultraviolet light. (C) It is preferable to select the kind of polymerizable liquid crystal or photopolymerization initiator. Further, at the time of polymerization, the polymerization temperature can be controlled by irradiating light while cooling the dry film by an appropriate cooling means. By adopting such a cooling means, if the polymerization of the polymerizable liquid crystal (C) is carried out at a lower temperature, the polarizing layer can be appropriately formed even if the substrate has a relatively low heat resistance.
　前記配向層を有する基板の配向層上に、（Ｄ）リオトロピック液晶性を有する色素を含有する偏光層形成用組成物を塗付し、加熱乾燥することにより塗膜を形成する工程における塗布は、通常、スピンコ－ティング法、エクストルージョン法、グラビアコーティング法、ダイコーティング法、バーコーティング法、アプリケータ法などの塗布法や、フレキソ法などの印刷法を含んだ公知の方法によって行われる。乾燥方法は特に限定されず、自然乾燥や強制的な乾燥を実施できる。強制的な乾燥としては、例えば、減圧乾燥、加熱乾燥、減圧加熱乾燥などが挙げられる。好ましくは、自然乾燥が用いられる。
 乾燥時間は、乾燥温度や溶媒の種類によって、適宜、選択され得る。例えば、自然乾燥の場合には、乾燥時間は、好ましくは１秒乃至１２０分であり、より好ましくは１０秒乃至５分である。 On the alignment layer of the substrate having the alignment layer, (D) a polarizing layer-forming composition containing a pigment having lyotropic liquid crystallinity is applied, and coating in the step of forming a coating film by heating and drying is performed, Usually, it is carried out by a known method including a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method, an applicator method, or a flexographic method. The drying method is not particularly limited, and natural drying or forced drying can be performed. Examples of forced drying include reduced-pressure drying, heat drying, and reduced-pressure heat drying. Preferably, natural drying is used.
The drying time can be appropriately selected depending on the drying temperature and the type of solvent. For example, in the case of natural drying, the drying time is preferably 1 second to 120 minutes, more preferably 10 seconds to 5 minutes.
  また、乾燥温度は特に限定されないが、基板のガラス転移温度（Ｔｇ）よりも低いことが好ましい。乾燥温度が基板のガラス転移温度を超えると、基板の性質（機械的強度や光学特性等）が変質する虞がある。具体的には、乾燥温度は、好ましくは１０℃乃至１００℃であり、より好ましくは１０℃乃至９０℃であり、特に好ましくは１０℃乃至８０℃である。
  なお、乾燥温度とは、（Ｄ）リオトロピック液晶性を有する色素を含有する塗膜の表面や内部の温度ではなく、塗膜を乾燥する雰囲気の温度を意味する。 The drying temperature is not particularly limited, but is preferably lower than the glass transition temperature (Tg) of the substrate. If the drying temperature exceeds the glass transition temperature of the substrate, the properties (such as mechanical strength and optical properties) of the substrate may be altered. Specifically, the drying temperature is preferably 10 ° C. to 100 ° C., more preferably 10 ° C. to 90 ° C., and particularly preferably 10 ° C. to 80 ° C.
The drying temperature means the temperature of the atmosphere in which the coating film is dried, not the surface or internal temperature of the coating film containing the pigment having (D) lyotropic liquid crystallinity.
  本偏光素子における、配向層と偏光層の厚さの合計は１０μｍ以下である。配向層の厚さは、０．５μｍ以上９．５μｍ以下が好ましく、１μｍ以上５μｍ以下がより好ましい。偏光層の厚さは、０．５μｍ以上９．５μｍ以下が好ましく、１μｍ以上５μｍ以下がより好ましい。配向層および偏光層の厚さは、通常、干渉膜厚計、レーザー顕微鏡または触針式膜厚計による測定によって求めることができる。 The total thickness of the alignment layer and the polarizing layer in the Enomoto polarizing element is 10 μm or less. The thickness of the alignment layer is preferably 0.5 μm or more and 9.5 μm or less, and more preferably 1 μm or more and 5 μm or less. The thickness of the polarizing layer is preferably from 0.5 μm to 9.5 μm, and more preferably from 1 μm to 5 μm. The thickness of the alignment layer and the polarizing layer can be usually determined by measurement with an interference film thickness meter, a laser microscope or a stylus thickness meter.
　以上のようにして、得られた偏光素子は、公知の手法を用いて、偏光を必要とする各種表示素子に広範囲に応用することができ、例えば、液晶表示素子、有機ＥＬ等の反射防止膜（円偏光板）、光スイッチおよび光学フィルターならびにそれらを構成要素とする各種光学測定機器等に利用することができる。 As described above, the obtained polarizing element can be widely applied to various display elements that require polarized light by using a known technique. For example, an antireflection film such as a liquid crystal display element or an organic EL. (Circularly polarizing plate), optical switches, optical filters, and various optical measuring instruments having them as constituent elements.
以下、本発明の実施例を挙げて、本発明を具体的に説明するが、本発明はこれらに限定して解釈されるものではない。
＜溶剤＞
実施例及び比較例の各配向層形成用組成物は溶剤を含有し、その溶剤として、プロピレングリコールモノメチルエーテル（ＰＭ）、シクロヘキサノン（ＣＹＨ）、メチルイソブチルケトン（ＭＩＢＫ）を用いた。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited thereto.
<Solvent>
Each alignment layer forming composition of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), cyclohexanone (CYH), and methyl isobutyl ketone (MIBK) were used as the solvent.
＜重合体の分子量の測定＞
重合例におけるアクリル共重合体の分子量は、（株）Ｓｈｏｄｅｘ社製常温ゲル浸透クロマトグラフィー（ＧＰＣ）装置（ＧＰＣ－１０１）、Ｓｈｏｄｅｘ社製カラム（ＫＤ―８０３、ＫＤ－８０５）を用い以下のようにして測定した。
なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表した。
カラム温度：５０℃
溶離液：Ｎ，Ｎ－ジメチルホルムアミド（添加剤として、臭化リチウム－水和物（ＬｉＢｒ・Ｈ2Ｏ）が３０ｍｍｏｌ／Ｌ、リン酸・無水結晶（ｏ―リン酸）が３０ｍｍｏｌ／Ｌ、テトラヒドロフラン（ＴＨＦ）が１０ｍＬ／Ｌ）
流速：１．０ｍＬ／分
検量線作成用標準サンプル：東ソー社製　ＴＳＫ　標準ポリエチレンオキサイド（分子量　約９００，０００、１５０，０００、１００，０００、３０，０００）、及び、ポリマーラボラトリー社製　ポリエチレングリコール（分子量　約１２，０００、４，０００、１，０００）。 <Measurement of molecular weight of polymer>
The molecular weight of the acrylic copolymer in the polymerization example was as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co. And measured.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) is 10 mL / L)
Flow rate: 1.0 mL / minute standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories ( Molecular weight about 12,000, 4,000, 1,000).
＜合成例１＞
４－ヒドロキシシンナミックアシッドと１－ブロモ－６－ヘキサノールをアルカリ条件下で加熱することにより４－（６－ヒドロキシヘキシルオキシ）シンナミックアシッドを合成した。この生成物にメタクリル酸クロライドを塩基性条件下で反応させ、下記式（ＥＸ－１）に示される化合物（Ｍ１）を得た。 <Synthesis Example 1>
4- (6-hydroxyhexyloxy) cinnamic acid was synthesized by heating 4-hydroxycinnamic acid and 1-bromo-6-hexanol under alkaline conditions. This product was reacted with methacrylic acid chloride under basic conditions to obtain a compound (M1) represented by the following formula (EX-1).
＜合成例２＞
４－ヒドロキシ安息香酸と１－ブロモ－６－ヘキサノールをアルカリ条件下で加熱することにより４－（６－ヒドロキシヘキシルオキシ）安息香酸を合成した。この生成物にメタクリル酸クロライドを塩基性条件下で反応させ、化合物（ＥＸ－Ａ）で表される化合物（以下、化合物（ＥＸ－Ａ）ともいう。）を得た。この化合物（ＥＸ－Ａ）をＤＣＣとＤＭＡＰ存在下でメトキシフェノールと反応させることで、下記式（ＥＸ－２）に示される化合物を得た。
Figure JPOXMLDOC01-appb-C000046
 <Synthesis Example 2>
4- (6-Hydroxyhexyloxy) benzoic acid was synthesized by heating 4-hydroxybenzoic acid and 1-bromo-6-hexanol under alkaline conditions. This product was reacted with methacrylic acid chloride under basic conditions to obtain a compound represented by compound (EX-A) (hereinafter also referred to as compound (EX-A)). This compound (EX-A) was reacted with methoxyphenol in the presence of DCC and DMAP to obtain a compound represented by the following formula (EX-2).
Figure JPOXMLDOC01-appb-C000046
＜合成例４＞
上記式（ＥＸ－１）で示されるメタクリル酸エステル　１８．０ｇ、二色性色素ジスパースレッド１メタクリラート　１．０ｇ、重合触媒としてα、α’－アゾビスイソブチロニトリル　０．３ｇを１、４－ジオキサン　１７０．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をジエチルエーテル　１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで残モノマーを除去し、アクリル重合体（Ｐ１）を得た。得られたアクリル共重合体のＭｎは１０，０００、Ｍｗは２２，０００であった。 <Synthesis Example 4>
18.0 g of the methacrylic acid ester represented by the above formula (EX-1), 1.0 g of dichroic dye disperse thread 1 methacrylate, 0.3 g of α, α′-azobisisobutyronitrile as a polymerization catalyst 4-Dioxane was dissolved in 170.0 g and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic polymer (P1). Mn of the obtained acrylic copolymer was 10,000 and Mw was 22,000.
＜合成例５＞
上記式（ＥＸ－１）で示されるメタクリル酸エステル　９．６ｇ、上記式（ＥＸ－Ａ）で示されるメタクリル酸エステル　８．０ｇ、二色性色素ジスパースレッド１メタクリラート　１．０ｇ、重合触媒としてα、α’－アゾビスイソブチロニトリル　０．３ｇを１、４－ジオキサン　１７０．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をジエチルエーテル　１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで残モノマーを除去し、アクリル共重合体（Ｐ２）を得た。得られたアクリル共重合体のＭｎは１２，０００、Ｍｗは２８，０００であった。 <Synthesis Example 5>
9.6 g of a methacrylic acid ester represented by the above formula (EX-1), 8.0 g of a methacrylic acid ester represented by the above formula (EX-A), 1.0 g of a dichroic dye disperse thread 1 methacrylate, a polymerization catalyst As a result, 0.3 g of α, α′-azobisisobutyronitrile was dissolved in 170.0 g of 1,4-dioxane and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P2). Mn of the obtained acrylic copolymer was 12,000 and Mw was 28,000.
＜合成例６＞
上記式（ＥＸ－１）で示されるメタクリル酸エステル　９．５ｇ、上記式（ＥＸ－２）で示されるメタクリル酸エステル　１０．６ｇ、二色性色素ジスパースレッド１メタクリラート　１．０ｇ、重合触媒としてα、α’－アゾビスイソブチロニトリル　０．３ｇを１、４－ジオキサン　１９０．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をジエチルエーテル　１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで残モノマーを除去し、アクリル共重合体（Ｐ３）を得た。得られたアクリル共重合体のＭｎは１１，０００、Ｍｗは２１，０００であった。 <Synthesis Example 6>
9.5 g of methacrylic acid ester represented by the above formula (EX-1), 10.6 g of methacrylic acid ester represented by the above formula (EX-2), 1.0 g of dichroic dye disperse thread 1 methacrylate, polymerization catalyst As a result, 0.3 g of α, α′-azobisisobutyronitrile was dissolved in 190.0 g of 1,4-dioxane and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P3). Mn of the obtained acrylic copolymer was 11,000 and Mw was 21,000.
＜合成例７＞
上記式（ＥＸ－１）で示されるメタクリル酸エステル　１６．０ｇ、重合触媒としてα、α’－アゾビスイソブチロニトリル　０．４ｇを１、４－ジオキサン　１８０．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をジエチルエーテル　１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで残モノマーを除去し、アクリル重合体（Ｐ４）を得た。得られたアクリル共重合体のＭｎは９，３００、Ｍｗは１６，０００であった。 <Synthesis Example 7>
16.0 g of the methacrylic acid ester represented by the formula (EX-1) and 0.4 g of α, α′-azobisisobutyronitrile as a polymerization catalyst were dissolved in 180.0 g of 1,4-dioxane, and the mixture was heated to 80 ° C. For 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic polymer (P4). Mn of the obtained acrylic copolymer was 9,300 and Mw was 16,000.
＜合成例８＞
上記式（ＥＸ－１）で示されるメタクリル酸エステル　８．０ｇ、上記式（ＥＸ－２）で示されるメタクリル酸エステル　９．８ｇ、重合触媒としてα、α’－アゾビスイソブチロニトリル　０．２ｇを１、４－ジオキサン　１８０．０ｇに溶解し、８０℃にて２０時間反応させることによりアクリル共重合体溶液を得た。アクリル共重合体溶液をジエチルエーテル　１０００．０ｇに徐々に滴下して固体を析出させ、ろ過および減圧乾燥することで残モノマーを除去し、アクリル共重合体（Ｐ５）を得た。得られたアクリル共重合体のＭｎは１４，０００、Ｍｗは２４，０００であった。 <Synthesis Example 8>
8.0 g of the methacrylic acid ester represented by the above formula (EX-1), 9.8 g of the methacrylic acid ester represented by the above formula (EX-2), and α, α′-azobisisobutyronitrile as the polymerization catalyst. 2 g was dissolved in 180.0 g of 1,4-dioxane and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of diethyl ether to precipitate a solid, and the residual monomer was removed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P5). Mn of the obtained acrylic copolymer was 14,000 and Mw was 24,000.
＜製造例１＞
重合性液晶（ＲＭＭ１４１Ｃ、メルク社製）１４．６ｇ、二色性色素（ジスパースレッド１メタクリラート、ＡＬＤＲＩＣＨ社製）０．４４ｇをＭＩＢＫ　３５．０ｇに溶解し、固形分濃度３０質量％の偏光層形成用組成物を調製した。 <Production Example 1>
14.6 g of polymerizable liquid crystal (RMM141C, manufactured by Merck & Co., Inc.) and 0.44 g of dichroic dye (Disperthread 1 methacrylate, manufactured by ALDRICH) are dissolved in 35.0 g of MIBK, and a polarized light having a solid content concentration of 30% by mass. A layer forming composition was prepared.
＜実施例１乃至４＞及び＜比較例１乃至２＞
表１に示す組成にて実施例１乃至４および比較例１乃至２の各配向層形成用組成物を調製した。各配向層形成用組成物を用いて配向層を形成し、配向層それぞれについて、二色性比測定を行った。次に、偏光層形成用組成物を用いて偏光素子を形成した。得られた偏光素子それぞれについて、配向性の評価、偏光度測定、二色比測定を行った。 <Examples 1 to 4> and <Comparative Examples 1 to 2>
Compositions for forming alignment layers of Examples 1 to 4 and Comparative Examples 1 to 2 were prepared with the compositions shown in Table 1. An alignment layer was formed using each composition for forming an alignment layer, and the dichroic ratio was measured for each alignment layer. Next, a polarizing element was formed using the composition for forming a polarizing layer. For each of the obtained polarizing elements, evaluation of orientation, polarization degree measurement, and dichroic ratio measurement were performed.
Figure JPOXMLDOC01-appb-T000047
Figure JPOXMLDOC01-appb-T000047
＜実施例１＞
［配向層の形成］
表１に示す配向層形成用組成物を石英基板上にスピンコートし、５５℃のホットプレート上で６０秒間乾燥後、膜厚２００ｎｍの塗膜を形成した。次いで、塗膜面に偏光板を介して３１３ｎｍの直線偏光を２ｍＪ／ｃｍ2の露光量で垂直に照射した。次いで、ホットプレートにて１７０℃で５分間加熱して、配向層を形成した。 <Example 1>
[Formation of alignment layer]
The composition for forming an alignment layer shown in Table 1 was spin-coated on a quartz substrate, dried on a hot plate at 55 ° C. for 60 seconds, and then a coating film having a thickness of 200 nm was formed. Subsequently, 313 nm linearly polarized light was irradiated perpendicularly | vertically with the exposure amount of 2 mJ / cm < 2 > through the polarizing plate to the coating-film surface. Subsequently, it heated at 170 degreeC for 5 minute (s) with the hotplate, and formed the alignment layer.
［配向層の二色性比測定］
得られた配向層の二色性比は、以下のようにして測定した。透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）を、分光光度計（島津製作所株式会社製　ＵＶ－３６００）に偏光子付フォルダーをセットした装置を用いて測定した。測定された透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）の値から、下記式を用いて二色性比を算出した。測定結果を表２に示す。
二色性比＝（Ａ２）／（Ａ１） [Dichroic ratio measurement of alignment layer]
The dichroic ratio of the obtained alignment layer was measured as follows. The absorbance in the direction of the transmission axis (A1) and the absorbance in the direction of the absorption axis (A2) were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (Shimadzu Corporation UV-3600). The dichroic ratio was calculated from the measured absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction using the following formula. The measurement results are shown in Table 2.
Dichroic ratio = (A2) / (A1)
［偏光層の形成］
得られた配向層の上に、偏光層形成用組成物を、２０００ｒｐｍ・３０ｓｅｃにてスピンコートし、６５℃のホットプレート上で６０秒間乾燥し、塗膜を形成した。次いで、この塗膜を５００ｍＪ／ｃｍ2で露光することで、偏光素子を得た。 [Formation of polarizing layer]
On the obtained alignment layer, the composition for forming a polarizing layer was spin-coated at 2000 rpm · 30 sec and dried on a hot plate at 65 ° C. for 60 sec to form a coating film. Next, this coating film was exposed at 500 mJ / cm 2 to obtain a polarizing element.
［配向性の評価］
得られた偏光素子の配向性を偏光顕微鏡観察によって確認した。偏光顕微鏡クロスニコ
ルの間に０°および４５°の方向にサンプルを挿入し、光抜けの状態の観察を実施した。配向している場合、０°では光抜けは発生せずに暗視野の状態が観察され、４５°では光抜けが発生して明視野の状態で観察される。０°で暗視野、４５°で明視野が得られた場合は「○」、得られなかった場合は「×」とした。これらの測定結果を表２に示す。 [Evaluation of orientation]
The orientation of the obtained polarizing element was confirmed by observation with a polarizing microscope. Samples were inserted in the directions of 0 ° and 45 ° between polarization microscope crossed Nicols, and observation of light leakage was performed. In the case of orientation, no light omission occurs at 0 °, and a dark field state is observed. At 45 °, light omission occurs and a bright field state is observed. When a dark field was obtained at 0 ° and a bright field at 45 °, “◯” was obtained, and when it was not obtained, “X” was given. These measurement results are shown in Table 2.
［偏光度測定］
得られた偏光素子の偏光度は、以下のようにして測定した。透過軸方向の透過率（Ｔ１）及び吸収軸方向の透過率（Ｔ２）を、分光光度計（島津製作所（株）製　ＵＶ－３６００）に偏光子付フォルダーをセットした装置を用いて測定した。測定された透過軸方向の透過率（Ｔ１）及び吸収軸方向の透過率（Ｔ２）の値から、下記式を用いて偏光度を算出した。測定結果を表２に示す。
偏光度（％）＝｛（Ｔ１－Ｔ２）／（Ｔ１＋Ｔ２）｝1/2×１００ [Polarization measurement]
The polarization degree of the obtained polarizing element was measured as follows. The transmittance (T1) in the transmission axis direction and the transmittance (T2) in the absorption axis direction were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (UV-3600, manufactured by Shimadzu Corporation). The degree of polarization was calculated from the measured transmission axis direction transmittance (T1) and absorption axis direction transmittance (T2) using the following equation. The measurement results are shown in Table 2.
Polarization degree (%) = {(T1−T2) / (T1 + T2)} 1/2 × 100
［偏光素子の二色性比測定］
得られた偏光素子の二色性比は、以下のようにして測定した。透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）を、分光光度計（島津製作所株式会社製　ＵＶ－３６００）に偏光子付フォルダーをセットした装置を用いて測定した。測定された透過軸方向の吸光度（Ａ１）及び吸収軸方向の吸光度（Ａ２）の値から、下記式を用いて二色性比を算出した。測定結果を表２に示す。
二色性比＝（Ａ２）／（Ａ１） [Dichroic ratio measurement of polarizing element]
The dichroic ratio of the obtained polarizing element was measured as follows. The absorbance in the direction of the transmission axis (A1) and the absorbance in the direction of the absorption axis (A2) were measured using an apparatus in which a folder with a polarizer was set in a spectrophotometer (Shimadzu Corporation UV-3600). The dichroic ratio was calculated from the measured absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction using the following formula. The measurement results are shown in Table 2.
Dichroic ratio = (A2) / (A1)
＜実施例２＞
配向層形成時の偏光露光後の加熱温度を１５０℃とした以外は、実施例１と同様にして偏光素子を作成した。結果を表２にまとめる。 <Example 2>
A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 150 ° C. The results are summarized in Table 2.
＜実施例３＞
配向層形成時の偏光露光後の加熱温度を１１０℃とした以外は、実施例１と同様にして偏光素子を作成した。結果を表２にまとめる。 <Example 3>
A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 110 ° C. The results are summarized in Table 2.
＜実施例４＞
配向層形成時の偏光露光後の加熱温度を１５０℃とした以外は、実施例１と同様にして偏光素子を作成した。結果を表２にまとめる。 <Example 4>
A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 150 ° C. The results are summarized in Table 2.
＜比較例１＞
実施例１と同様にして偏光素子を作成した。結果を表２にまとめる。 <Comparative Example 1>
A polarizing element was produced in the same manner as in Example 1. The results are summarized in Table 2.
＜比較例２＞
配向層形成時の偏光露光後の加熱温度を１１０℃とした以外は、実施例１と同様にして偏光素子を作成した。結果を表２にまとめる。 <Comparative example 2>
A polarizing element was prepared in the same manner as in Example 1 except that the heating temperature after the polarization exposure at the time of forming the alignment layer was 110 ° C. The results are summarized in Table 2.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
配向層に二色性色素を含有していないアクリル共重合体を用いた比較例１乃至２では、配向層の二色性比は０であった。それに対して、配向層に二色性色素を含有するアクリル共重合体を用いた実施例１乃至４では、二色性比が得られ、配向層中で二色性色素を配向させることが可能であった。 In Comparative Examples 1 and 2 using an acrylic copolymer containing no dichroic dye in the alignment layer, the dichroic ratio of the alignment layer was 0. On the other hand, in Examples 1 to 4 using an acrylic copolymer containing a dichroic dye in the alignment layer, a dichroic ratio is obtained, and the dichroic dye can be aligned in the alignment layer. Met.
実施例１乃至４で得られた偏光子は、比較例１乃至２と比較して、高い偏光度と二色性比を発現することが可能であった。 The polarizers obtained in Examples 1 to 4 were able to express a higher degree of polarization and dichroic ratio than Comparative Examples 1 and 2.

Claims (5)

  1. （Ａ）側鎖に二色性色素を有し且つ所定の温度範囲で液晶性を発現する感光性の側鎖型高分子、及び有機溶媒を含有する重合体組成物。 (A) A polymer composition comprising a photosensitive side chain polymer having a dichroic dye in the side chain and exhibiting liquid crystallinity in a predetermined temperature range, and an organic solvent.
  2. （Ａ）成分が、光架橋、光異性化、または光フリース転移を起こす感光性側鎖を有する請求項１記載の重合体組成物。 The polymer composition according to claim 1, wherein the component (A) has a photosensitive side chain that undergoes photocrosslinking, photoisomerization, or photofleece transition.
  3. （Ａ）成分が、下記式（１）乃至（６）からなる群から選ばれるいずれか１種の感光性側鎖を有する請求項１記載の重合体組成物。
    Figure JPOXMLDOC01-appb-C000001
     　式中、Ａ、Ｂ及びＤはそれぞれ独立に、単結合、－Ｏ－、－ＣＨ2－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－ＣＯ－Ｏ－、又は－Ｏ－ＣＯ－ＣＨ＝ＣＨ－を表す；
    　Ｓは、炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子に結合する水素原子はハロゲン原子に置き換えられていてもよい；
    　Ｔは、単結合または炭素原子数１乃至１２のアルキレン基を表し、該アルキレン基中の炭素原子に結合する水素原子はハロゲン原子に置き換えられていてもよい；
    　Ｙ1は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、ピロール環から一つの水素原子を取り去った１価の置換基、もしくは炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基を表すか、又はそれらの置換基から選ばれる同一又は相異なった２乃至６つの置換基がＢで定義される結合基を介して結合してなる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＣＯＯＲ0（式中、Ｒ0は水素原子又は炭素原子数１乃至５のアルキル基を表す）、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
    　Ｙ2は、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
    　Ｒは、ヒドロキシ基、炭素原子数１乃至６のアルコキシ基を表すか、又はＹ1と同じ定義を表す；
    　Ｘは、単結合、－ＣＯＯ－、－ＯＣＯ－、－Ｎ＝Ｎ－、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２を表し、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、Ｘの数が２となるときは、Ｘ同士は同一でも異なっていてもよい；
    　Ｃｏｕは、クマリン－６－イル基またはクマリン－７－イル基を表し、それらに結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
    　ｑ１とｑ２は、一方が１で他方が０である；
    　ｑ３は０または１である；
    　Ｐ及びＱは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、炭素原子数５乃至８の脂環式炭化水素から二つの水素原子を取り去った２価の置換基、および、それらの組み合わせからなる群から選ばれる２価の置換基を表し；ただし、Ｘが※１－ＣＨ＝ＣＨ－ＣＯ－Ｏ－※２、又は※１－Ｏ－ＣＯ－ＣＨ＝ＣＨ－※２である場合、※１は上記式（１）乃至（６）におけるＰとの結合位置を表し、※２は上記式（１）乃至（６）におけるＱとの結合位置を表し、－ＣＨ＝ＣＨ－が結合する側のＰ又はＱは芳香環から二つの水素原子を取り去った２価の置換基を表す；
    　ｌ１は０または１である；
    　ｌ２は０乃至２の整数である；
    　ｌ１とｌ２がともに０であるとき、かつＴが単結合であるときはＡも単結合を表す；
    　ｌ１が１であるとき、かつＴが単結合であるときはＢも単結合を表す；
    　Ｈ及びＩは、各々独立に、ベンゼン環から二つの水素原子を取り去った２価の置換基、ナフタレン環から二つの水素原子を取り去った２価の置換基、ビフェニル環から二つの水素原子を取り去った２価の置換基、フラン環から二つの水素原子を取り去った２価の置換基、ピロール環から二つの水素原子を取り去った２価の置換基、およびそれらの組み合わせから選ばれる２価の置換基を表す。     The polymer composition according to claim 1, wherein the component (A) has any one photosensitive side chain selected from the group consisting of the following formulas (1) to (6).
    Figure JPOXMLDOC01-appb-C000001
     In the formula, A, B and D are each independently a single bond, —O—, —CH 2 —, —COO—, —OCO—, —CONH—, —NH—CO—, —CH═CH—CO—. Represents O— or —O—CO—CH═CH—;
    S represents an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
    T represents a single bond or an alkylene group having 1 to 12 carbon atoms, and a hydrogen atom bonded to a carbon atom in the alkylene group may be replaced by a halogen atom;
    Y 1 is a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, and a monovalent substitution obtained by removing one hydrogen atom from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a pyrrole ring, or an alicyclic hydrocarbon having 5 to 8 carbon atoms 1 represents a monovalent substituent from which a hydrogen atom has been removed, or a monovalent group in which 2 to 6 identical or different substituents selected from these substituents are bonded via a linking group defined by B In these substituents, hydrogen atoms bonded to carbon atoms are each independently —COOR 0 (wherein R 0 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). , -NO 2 , -CN, -C H═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
    Y 2 is a divalent substituent obtained by removing two hydrogen atoms from a benzene ring, a divalent substituent obtained by removing two hydrogen atoms from a naphthalene ring, and a divalent substituent obtained by removing two hydrogen atoms from a biphenyl ring. A divalent substituent from which two hydrogen atoms have been removed from a furan ring, a divalent substituent from which two hydrogen atoms have been removed from a pyrrole ring, and two hydrogens from an alicyclic hydrocarbon having 5 to 8 carbon atoms This represents a divalent substituent selected from the group consisting of a divalent substituent from which atoms have been removed, and combinations thereof, and hydrogen atoms bonded to carbon atoms in all these substituents are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms good;
    R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y 1 ;
    X is a single bond, —COO—, —OCO—, —N═N—, —CH═CH—, —C≡C—, * 1-CH═CH—CO—O— * 2, or * 1- O—CO—CH═CH— * 2; * 1 represents a bonding position with P in the above formulas (1) to (6); * 2 represents Q and Q in the above formulas (1) to (6). When the number of X is 2, the X may be the same or different;
    Cou represents a coumarin-6-yl group or a coumarin-7-yl group, and the hydrogen atoms bonded thereto are independently —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH— May be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
    one of q1 and q2 is 1 and the other is 0;
    q3 is 0 or 1;
    P and Q each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. Divalent substituents, divalent substituents from which two hydrogen atoms have been removed from a furan ring, divalent substituents from which two hydrogen atoms have been removed from a pyrrole ring, alicyclic carbonization having 5 to 8 carbon atoms Represents a divalent substituent obtained by removing two hydrogen atoms from hydrogen, and a divalent substituent selected from the group consisting of combinations thereof; provided that X is * 1-CH═CH—CO—O— * 2 or * 1-O—CO—CH═CH— * 2, * 1 represents the bonding position with P in the above formulas (1) to (6), and * 2 represents the above formulas (1) to (6). Represents the bonding position with Q in (6), and —CH═CH— P or Q of the binding side represents a divalent substituent obtained by removing two hydrogen atoms from an aromatic ring;
    l1 is 0 or 1;
    l2 is an integer from 0 to 2;
    when l1 and l2 are both 0, and T is a single bond, A also represents a single bond;
    when l1 is 1 and T is a single bond, B also represents a single bond;
    H and I each independently remove a divalent substituent from which two hydrogen atoms have been removed from a benzene ring, a divalent substituent from which two hydrogen atoms have been removed from a naphthalene ring, and two hydrogen atoms from a biphenyl ring. A divalent substituent selected by removing two hydrogen atoms from the furan ring, a divalent substituent removing two hydrogen atoms from the pyrrole ring, and combinations thereof. Represents a group.
  4. （Ａ）成分が、下記式（２１）乃至（３１）からなる群から選ばれるいずれか１種の液晶性側鎖を有する請求項１乃至請求項３のいずれか一項に記載の重合体組成物。
    Figure JPOXMLDOC01-appb-C000002
     　式中、Ａ、Ｂ、ｑ１及びｑ２は上記と同じ定義を有する；
    　Ｙ3は、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、および、それらの組み合わせからなる群から選ばれる１価の置換基を表し、これら全ての置換基中の、炭素原子に結合する水素原子はそれぞれ独立に－ＮＯ2、－ＣＮ、ハロゲン原子、炭素原子数１乃至５のアルキル基、又は炭素原子数１乃至５のアルキルオキシ基で置換されても良い；
    　Ｒ3は、水素原子、－ＮＯ2、－ＣＮ、－ＣＨ＝Ｃ（ＣＮ）2、－ＣＨ＝ＣＨ－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、炭素原子数１乃至１２のアルキル基、又は炭素原子数１乃至１２のアルコキシ基を表す；
    　ｌは１乃至１２の整数を表し、ｍは０乃至２の整数を表し、但し、式（２３）および式（２４）において、全てのｍの合計は２以上であり、式（２５）および式（２６）において、全てのｍの合計は１以上であり、ｍ１、ｍ２およびｍ３は、それぞれ独立に１乃至３の整数を表す；
    　Ｒ2は、水素原子、－ＮＯ2、－ＣＮ、ハロゲン原子、ベンゼン環から一つの水素原子を取り去った１価の置換基、ナフタレン環から一つの水素原子を取り去った１価の置換基、ビフェニル環から一つの水素原子を取り去った１価の置換基、フラン環から一つの水素原子を取り去った１価の置換基、窒素含有複素環から一つの水素原子を取り去った１価の置換基、炭素原子数５乃至８の脂環式炭化水素から一つの水素原子を取り去った１価の置換基、アルキル基、又はアルキルオキシ基を表す；
    　Ｚ1及びＺ2は単結合、－ＣＯ－、－ＣＨ2Ｏ－、－ＣＨ＝Ｎ－、又は－ＣＦ2－を表す。     The polymer composition according to any one of claims 1 to 3, wherein the component (A) has any one liquid crystalline side chain selected from the group consisting of the following formulas (21) to (31). object.
    Figure JPOXMLDOC01-appb-C000002
     In which A, B, q1 and q2 have the same definition as above;
    Y 3 is a monovalent substituent in which one hydrogen atom is removed from a benzene ring, a monovalent substituent in which one hydrogen atom is removed from a naphthalene ring, and a monovalent substitution in which one hydrogen atom is removed from a biphenyl ring. A monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms. Represents a monovalent substituent selected from the group consisting of a monovalent substituent from which two hydrogen atoms have been removed, and a combination thereof, and each of these substituents independently represents a hydrogen atom bonded to a carbon atom. May be substituted with —NO 2 , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyloxy group having 1 to 5 carbon atoms;
    R 3 represents a hydrogen atom, —NO 2 , —CN, —CH═C (CN) 2 , —CH═CH—CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, naphthalene A monovalent substituent with one hydrogen atom removed from the ring, a monovalent substituent with one hydrogen atom removed from the biphenyl ring, a monovalent substituent with one hydrogen atom removed from the furan ring, a nitrogen-containing complex A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from an alicyclic hydrocarbon having from 5 to 8 carbon atoms, an alkyl group having from 1 to 12 carbon atoms Or an alkoxy group having 1 to 12 carbon atoms;
    l represents an integer of 1 to 12, m represents an integer of 0 to 2, provided that in formula (23) and formula (24), the sum of all m is 2 or more, and formula (25) and formula In (26), the sum of all m is 1 or more, and m1, m2, and m3 each independently represents an integer of 1 to 3;
    R 2 represents a hydrogen atom, —NO 2 , —CN, a halogen atom, a monovalent substituent obtained by removing one hydrogen atom from a benzene ring, a monovalent substituent obtained by removing one hydrogen atom from a naphthalene ring, biphenyl A monovalent substituent from which one hydrogen atom has been removed from a ring, a monovalent substituent from which one hydrogen atom has been removed from a furan ring, a monovalent substituent from which one hydrogen atom has been removed from a nitrogen-containing heterocyclic ring, carbon Represents a monovalent substituent, an alkyl group, or an alkyloxy group in which one hydrogen atom is removed from an alicyclic hydrocarbon having 5 to 8 atoms;
    Z 1 and Z 2 each represents a single bond, —CO—, —CH 2 O—, —CH═N—, or —CF 2 —.
  5. （Ｂ）成分として、下記式（ｃ）で表される化合物を含有することを特徴とする請求項１乃至請求項４のいずれか一項に記載の重合体組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至５つは、それぞれ独立に水素原子、ハロゲン原子、Ｃ1乃至Ｃ6アルキル基、Ｃ1乃至Ｃ6ハロアルキル基、Ｃ1乃至Ｃ6アルコキシ基、Ｃ1乃至Ｃ6ハロアルコキシ基、Ｃ3乃至Ｃ8シクロアルキル基、Ｃ3乃至Ｃ8ハロシクロアルキル基、Ｃ2乃至Ｃ6アルケニル基、Ｃ2乃至Ｃ6ハロアルケニル基、Ｃ3乃至Ｃ8シクロアルケニル基、Ｃ3乃至Ｃ8ハロシクロアルケニル基、Ｃ2乃至Ｃ6アルキニル基、Ｃ2乃至Ｃ6ハロアルキニル基、（Ｃ1乃至Ｃ6アルキル）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）カルボニル基、（Ｃ1乃至Ｃ6アルコキシ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルコキシ）カルボニル基、（Ｃ1乃至Ｃ6アルキルアミノ）カルボニル基、（Ｃ1乃至Ｃ6ハロアルキル）アミノカルボニル基、ジ(Ｃ1乃至Ｃ6アルキル)アミノカルボニル基、シアノ基及びニトロ基から選ばれる置換基を表し、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちいずれか３つ乃至４つが上記の定義である場合、Ｒ101、Ｒ102、Ｒ103、Ｒ104及びＲ105のうちの残り１つ又は２つは下記式（ｃ－２）
    Figure JPOXMLDOC01-appb-C000004
     （式（ｃ－２）中、破線は結合手を表し、Ｒ106は炭素原子数１乃至３０のアルキレン基、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基を表し、このアルキレン基中、フェニレン基中または炭素環式化合物から二つの水素原子を取り去った２価の置換基中、若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基中の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ106中の－ＣＨ2ＣＨ2－が－ＣＨ＝ＣＨ－に置き換えられていてもよく、Ｒ106中の－ＣＨ2－は、フェニレン基、または炭素環式化合物から二つの水素原子を取り去った２価の置換基若しくは複素環式化合物から二つの水素原子を取り去った２価の置換基に置き換えられていてもよく、さらに、Ｒ106中の－ＣＨ2－は、－Ｏ－、－ＮＨＣＯ－、－ＣＯＮＨ－、－ＣＯＯ－、－ＯＣＯ－、－ＮＨ－、－ＮＨＣＯＮＨ－、及び－ＣＯ－からなる群から選ばれた２価の基が互いに隣り合わない限り、これら２価の基に置き換えられていてもよい。Ｒ107は水素原子又はメチル基である。）で表される基を表し、ｎは０または１を表す。）     (B) As a component, the compound represented by following formula (c) is contained, The polymer composition as described in any one of the Claims 1 thru | or 4 characterized by the above-mentioned.
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, any three to five of R 101 , R 102 , R 103 , R 104 and R 105 are each independently a hydrogen atom, a halogen atom, a C 1 to C 6 alkyl group, C 1 to C 6 haloalkyl group, C 1 to C 6 alkoxy group, C 1 to C 6 haloalkoxy group, C 3 to C 8 cycloalkyl group, C 3 to C 8 halocycloalkyl group, C 2 to C 6 alkenyl group, C 2 To C 6 haloalkenyl group, C 3 to C 8 cycloalkenyl group, C 3 to C 8 halocycloalkenyl group, C 2 to C 6 alkynyl group, C 2 to C 6 haloalkynyl group, (C 1 to C 6 alkyl) ) Carbonyl group, (C 1 to C 6 haloalkyl) carbonyl group, (C 1 to C 6 alkoxy) carbonyl group, (C 1 to C 6 haloalkoxy) carbonyl group, (C 1 to C 6 alkylamino) carbonyl group, (C 1 through C 6 halo Alkyl) aminocarbonyl group, di (C 1 to C 6 alkyl) aminocarbonyl group, a substituent selected from cyano group and a nitro group, any one of R 101, R 102, R 103 , R 104 and R 105 When three to four are defined as above, the remaining one or two of R 101 , R 102 , R 103 , R 104 and R 105 are represented by the following formula (c-2)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (c-2), the broken line represents a bond, and R 106 represents an alkylene group having 1 to 30 carbon atoms, a phenylene group, or a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound. Or a divalent substituent in which two hydrogen atoms have been removed from a heterocyclic compound, in the alkylene group, in a phenylene group or in a divalent substituent in which two hydrogen atoms have been removed from a carbocyclic compound, or One or more hydrogen atoms in the divalent substituent obtained by removing two hydrogen atoms from the heterocyclic compound may be replaced with a fluorine atom or an organic group, and —CH 2 in R 106 CH 2 — may be replaced by —CH═CH—, and —CH 2 — in R 106 is a phenylene group, a divalent substituent obtained by removing two hydrogen atoms from a carbocyclic compound, or a heterocyclic group. Cyclization May be replaced with divalent substituent obtained by removing two hydrogen atoms from an object, further, -CH 2 in R 106 - is, -O -, - NHCO -, - CONH -, - COO-, -OCO -, - NH -, - NHCONH-, and unless divalent radical selected from the group consisting of -CO- is not adjacent to each other, these divalent good .R 107 be replaced based on the A hydrogen atom or a methyl group), and n represents 0 or 1. )
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