Classifications

• • 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
  • C08F20/22—Esters containing halogen
  • C08F20/24—Esters containing halogen containing perhaloalkyl radicals
• • 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
  • C08F20/22—Esters containing halogen
• • 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
  • C08F220/00—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
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
  • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
  • C09K19/38—Polymers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/30—Polarising elements
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/13363—Birefringent elements, e.g. for optical compensation

Definitions

• the present invention relates to a fluoropolymer, a composition, an optical film, a liquid crystal film, a hard coat film, and a polarizing plate.
• Polymer materials have been increasingly used in many fields in recent years. Along with this, the properties of the polymer as a matrix, as well as the properties of its surface and interface, have become important according to each field.
• Optical films such as optical compensation sheets and retardation films are used in various image display devices for eliminating image coloring or expanding the viewing angle.
• a stretched birefringence film has been used as the optical film, but in recent years, it has been proposed to use a film (liquid crystal film) having an optically anisotropic layer made of a liquid crystal compound instead of the stretched birefringence film. ..
• Patent Document 1 it has been proposed to use an optical film having an optically anisotropic layer containing a predetermined fluoroaliphatic group-containing copolymer in order to display an image having high display quality without causing unevenness.
• the optically anisotropic layer formed by using a liquid crystal compound there is a requirement to uniformly orient the liquid crystal compound so as not to cause an orientation defect (hereinafter, satisfying such a requirement is referred to as "orientation”. It is also called “excellent”.) There is also a demand for homogeneity without unevenness or defects.
• the present invention relates to a fluorine-containing polymer capable of forming a film having excellent orientation and homogeneity, a composition containing the fluorine-containing polymer, an optical film having a layer formed from the composition, and a liquid crystal.
• An object of the present invention is to provide a film, a hard coat film, and a polarizing plate.
• the problems of the present invention can be achieved by producing an optical film using a composition containing a predetermined fluorine-containing polymer. .. That is, it was found that the above problem can be achieved by the following configuration.
• L 1 represents a linking group of x + 1 valence.
• x represents an integer of 2 or more.
• L 2 to L 5 each independently represent a single bond or a divalent linking group.
• R 1 to R 7 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• Z 1 to Z 5 each independently represent a fluorine atom-containing aliphatic hydrocarbon group which may have an oxygen atom, and a plurality of Z 1 may be the same or different from each other.
• R 21 has a total number of carbon atoms in which a perfluoroalkyl group having 1 to 20 carbon atoms, a partially fluorinated alkyl group having 1 to 20 carbon atoms, and a perfluoroalkyl group are linked via an oxygen atom is 1. It represents a partially fluorinated alkyl group having a total number of carbon atoms of 1 to 20 to which a perfluoroalkyl group of ⁇ 20 or a partially fluorinated alkyl group is linked via an oxygen atom.
• R 22 represents the same group as R 21 , an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or a phenyl group.
• R 23 represents a hydrogen atom or a methyl group.
• A is, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (CH 3) -, or, -CH (CH 3) CH 2 - divalent represented
• X and Y independently represent divalent linking groups represented by the following structural formulas (a), (b) or (c).
• R 41 in the following structural formula (c) represents an alkyl group having 1 to 6 carbon atoms.
• R 8 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• P represents an aromatic ring which may have a substituent.
• L 6 represents a single bond or a divalent linking group.
• R 9 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• L 7 represents a single bond or a divalent linking group.
• Q 1 represents a group containing a polymerizable group selected from the group consisting of cationically polymerizable group and a radical polymerizable group.
• R 10 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• U 1 and U 2 independently represent -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO-, or -NH-, respectively.
• R 11 and R 12 independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, respectively, and R 11 and R 12 12 may be linked to each other via a linking group.
• L 8 represents a single bond or a divalent linking group.
• a partial structure obtained by radically polymerizing a mesogen group derived from at least one liquid crystal compound selected from the group consisting of a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound and a compound having two or more polymerizable groups.
• the fluorine-containing polymer according to [5], wherein the compound having a mesogen group and two or more polymerizable groups derived from the rod-shaped liquid crystal compound is a compound represented by the following general formula (X).
• Q X1 and Q X2 each independently represent a polymerizable group
• L X1 and L X4 each independently represent a divalent linking group
• L X 2 and L X 3 independently represent a single bond.
• it represents a divalent linking group
• Cy X1 , Cy X2 and Cy X3 each independently represent a divalent cyclic group
• nx represents an integer of 0 to 3.
• the fluorine-containing compound according to [5], wherein the compound having a mesogen group and two or more polymerizable groups derived from the disk-shaped liquid crystal compound is a compound represented by the following general formula (IX).
• Polymer in the general formula (IX), Y 11 , Y 12 and Y 13 each independently represent a potentially substituted methine or nitrogen atom, and L 1 , L 2 and L 3 are independent and single bonds, respectively.
• it represents a divalent linking group
• H 1 , H 2 and H 3 independently represent a group represented by the following general formula (IA) or a group represented by the following general formula (IB).
• Representing R 1 , R 2 and R 3 independently represent a group represented by the following general formula (IR).
• YA 1 and YA 2 each independently represent a methine or nitrogen atom which may have a substituent, and XA represents an oxygen atom, a sulfur atom, methylene or imino, *. represents a position bonding with L 1 ⁇ L 3 side in the above general formula (I-X), ** represents a position bonded with R 1 ⁇ R 3 side in the general formula (I-X).
• YB 1 and YB 2 each independently represent a methine or nitrogen atom which may have a substituent, and XB represents an oxygen atom, a sulfur atom, methylene or imino, *.
• [8] A composition containing the fluorine-containing polymer according to any one of [1] to [7]. [9] Further containing a polymerizable liquid crystal compound, The composition according to [8], wherein the content of the polymerizable liquid crystal compound is 40% by mass or more with respect to the total mass of the composition. [10] An optical film having a layer formed from the composition according to [8] or [9]. [11] A liquid crystal film having a layer formed from the composition according to [8] or [9]. [12] A hardcourt film having a layer formed from the composition according to [8] or [9]. [13] A polarizing plate having a layer formed from the composition according to [8] or [9].
• a fluoropolymer capable of forming a film having excellent orientation and homogeneity a composition containing the fluoropolymer, an optical film having a layer formed from the composition, and a hard film.
• a coated film and a polarizing plate can be provided.
• the bonding direction of the divalent group (for example, —CO—O—) described is not particularly limited, and for example, D1 in the general formula (W) described later is ⁇ CO—O—.
• D1 may be * 1-CO-O- * 2
• * 1 It may be -O-CO- * 2.
• (meth) acrylate represents acrylate and methacrylate.
• (meth) acrylic acid represents acrylic acid and methacrylic acid.
• the (meth) acryloyl group represents a methacryloyl group or an acryloyl group.
• the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent.
• the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• the "organic group” in the present specification means a group containing at least one carbon atom.
• the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent” are not particularly limited.
• the number of substituents may be, for example, one, two, three, or more.
• the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and for example, it can be selected from the following substituent group T.
• substituent T examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; a phenoxy group and a p-tolyloxy group.
• Aryloxy group alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy group such as acetoxy group, propionyloxy group, and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl Acrylic groups such as groups, methacryloyl groups, and metoxalyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfonyl groups; alkyl groups; cycloalkyl groups.
• the fluorine-containing polymer of the present invention has a branched structure in which a plurality of aliphatic hydrocarbon groups having a fluorine atom are branched.
• the fluorine moiety can be efficiently localized to the air interface side and the copolymerization component to the matrix resin forming component (curable component) side in the composition, and the fluorine-containing polymer of the present invention and the matrix resin can be formed.
• the compatibility with the ingredients is improved.
• the composition containing the fluorine-containing polymer of the present invention aggregation of the fluorine-containing polymer is less likely to occur, and the orientation of the liquid crystal compound is improved. Further, due to the branched structure, the transferability of the fluorine-containing polymer to the coating film surface is improved.
• the surface tension of the composition (coating film) is lowered, so that the wettability (homogeneous coating property) of the composition with respect to the substrate at the time of coating is improved. It is presumed that a film with improved homogeneity with less unevenness and defects was obtained.
• the fluorine-containing polymer of the present invention is a fluorine-containing polymer having a repeating unit represented by the following general formulas (I) to (III).
• L 1 represents an x + 1 valent linking group.
• x represents an integer of 2 or more.
• L 2 to L 5 each independently represent a single bond or a divalent linking group.
• R 1 to R 7 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms.
• Z 1 to Z 5 each independently represent a fluorine atom-containing aliphatic hydrocarbon group which may have an oxygen atom, and a plurality of Z 1 may be the same or different from each other.
• the general formula (I) does not include the unit represented by the following formula (Ie).
• R 21 has a total number of carbon atoms in which a perfluoroalkyl group having 1 to 20 carbon atoms, a partially fluorinated alkyl group having 1 to 20 carbon atoms, and a perfluoroalkyl group are linked via an oxygen atom is 1. It represents a partially fluorinated alkyl group having a total number of carbon atoms of 1 to 20 to which a perfluoroalkyl group of ⁇ 20 or a partially fluorinated alkyl group is linked via an oxygen atom.
• the perfluoroalkyl group is a kind of fluoroalkyl group, and means an alkyl group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and the partially fluorinated alkyl group is a fluoroalkyl group. It is a kind and means an alkyl group in which a part of the hydrogen atom of the alkyl group is replaced with a fluorine atom.
• R 22 represents the same group as R 21 , an alkyl group having 1 to 10 carbon atoms, an aralkyl group having 1 to 10 carbon atoms, or a phenyl group.
• R 23 represents a hydrogen atom or a methyl group.
• A is, -CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 CH (CH 3) -, or, -CH (CH 3) CH 2 - divalent represented
• X and Y independently represent divalent linking groups represented by the following structural formulas (a), (b) or (c).
• R 41 in the following structural formula (c) represents an alkyl group having 1 to 6 carbon atoms.
• R 1 to R 7 are preferably hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 4 carbon atoms, respectively, and are preferably hydrogen atoms or methyl groups. It is more preferable to have.
• L 1 represents an x + 1 valent linking group as described above, but it is preferable that x represents 2 or 3, that is, a trivalent or tetravalent linking group.
• L 2 ⁇ L 5 each independently represents a single bond or a divalent linking group, -O -, - CO-O -, - CO-NH -, - 2 divalent linking group having a O-CO- Is preferable.
• R 2 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms. Among them, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
• L 1A to L 1C each independently represent a single bond or a divalent group having 2 to 50 carbon atoms.
• the divalent group having 2 to 50 carbon atoms represented by one aspect of L 1A to L 1C may contain a hetero atom, and may contain an aromatic group, a hetero aromatic group, a hetero ring group, and an aliphatic group. , It may be an alicyclic group.
• Specific examples of L 1A to L 1C include the following groups, which may have a plurality of these groups.
• X is an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.) and an alkoxy group having 1 to 4 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy).
• 1,2-phenylene, 1,3-phenylene or 1,4-phenylene which may have the above-mentioned substituent is preferable, and 1,4-phenylene which may have the above-mentioned substituent is preferable. Especially preferable.
• Y represents —O—CO—, —CO—O ⁇ , —CONH— or —NHCO ⁇ .
• W represents a trivalent group.
• Examples of the trivalent group represented by W include a group derived by removing three hydrogen atoms contained in a carbon atom or a nitrogen atom.
• Z a and Z b each independently represent a fluorine atom-containing aliphatic hydrocarbon group which may have an oxygen atom. Specifically, the following groups can be mentioned.
• R 4 and R 5 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms. Among them, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
• L 2A to L 2C each independently represent a single bond or a divalent group having 2 to 50 carbon atoms, and may contain a hetero atom, and may contain an aromatic group or a hetero. It may be an aromatic group, a heterocyclic group, an aliphatic group, or an alicyclic group.
• a divalent group having 2 to 50 carbon atoms represented by one aspect of L 2A to L 2C the number of carbon atoms represented by one aspect of L 1A to L 1C of the general formula (VII) described above is used. Examples thereof include groups similar to divalent groups of 2 to 50.
• Z c and Z d each independently represent a fluorine atom-containing aliphatic hydrocarbon group which may have an oxygen atom, and specific examples thereof include the above-mentioned general formula (VII). ), The same group as Z a and Z b can be mentioned.
• R 6 and R 7 independently represent a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms. Among them, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
• L 3A to L 3C each independently represent a single bond or a divalent group having 2 to 50 carbon atoms, and may contain a hetero atom, and may contain an aromatic group or a hetero. It may be an aromatic group, a heterocyclic group, an aliphatic group, or an alicyclic group.
• a divalent group having 2 to 50 carbon atoms represented by one aspect of L 3A to L 3C the number of carbon atoms represented by one aspect of L 1A to L 1C of the general formula (VII) described above is used. Examples thereof include groups similar to divalent groups of 2 to 50.
• Ze and Z f each independently represent a fluorine atom-containing aliphatic hydrocarbon group which may have an oxygen atom, and specific examples thereof include the above-mentioned general formula (VII). ), The same group as Z a and Z b can be mentioned.
• the repeating unit represented by the general formula (II) or (III) is a dicarboxylic acid ester skeleton derived from an ethylenically unsaturated dicarboxylic acid or an anhydride thereof.
• the ethylenically unsaturated dicarboxylic acid or its anhydride is not particularly limited, but the ethylenically unsaturated dicarboxylic acid having 4 to 10 carbon atoms or its anhydride, particularly itaconic acid, fumaric acid, maleic acid, citraconic acid, Mesaconic acid, glutaconic acid and teraconic acid are suitable.
• R 8 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms. Among them, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
• P represents an aromatic ring which may have a substituent.
• aromatic ring group examples include aromatic hydrocarbon ring groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthroline ring group; a furan ring group, a pyrrole ring group, a thiophene ring group, and a pyridine ring.
• Aromatic heterocyclic groups such as groups, thiazole ring groups, and benzothiazole ring groups; Of these, a benzene ring group (for example, 1,4-phenyl group, etc.) is preferable.
• aromatic hydrocarbon ring groups such as a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthroline ring group
• a furan ring group such as a pyrrole ring group, a thiophene ring group, and a pyridine ring.
• L 6 represents a single bond or a divalent linking group.
• L 6 is preferably —C (O) —OL 61 ⁇ from the viewpoint that the effect of the present invention is more excellent.
• L 61 is an alkylene group having 1 to 10 carbon atoms, or a group represented by (L 62 O) m10 (in the formula, L 62 represents an alkylene group having 1 to 4 carbon atoms, and m10 is 1 to 1 to 4). Represents an integer of 10.).
• R 9 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group having 1 to 20 carbon atoms. Among them, a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms is preferable, and a hydrogen atom or a methyl group is more preferable.
• L 7 represents a single bond or a divalent linking group. L 7 is from the viewpoint of the effect of the present invention more excellent, -C (O) -O-L 71 - are preferred. L 71 represents an alkylene group having 1 to 5 carbon atoms which may have a substituent.
• Q 1 represents a group containing a polymerizable group selected from the group consisting of cationically polymerizable group and a radical polymerizable group.
• the cationically polymerizable group is not particularly limited, and for example, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, or a spiroorthoester group. , Vinyloxy group and the like.
• an alicyclic ether group or a vinyloxy group is preferable, an epoxy group, an oxetanyl group or a vinyloxy group is more preferable, an epoxy group or an oxetanyl group is further preferable, and an epoxy group is particularly preferable.
• the epoxy group is particularly preferably an alicyclic epoxy group.
• each group mentioned above may have a substituent.
• the radically polymerizable group is not particularly limited, and examples thereof include a group containing a polymerizable carbon-carbon double bond, and specifically, (meth). ) Acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, styryl group, allyl group and the like, and (meth) acryloyloxy group is preferable.
• each group mentioned above may have a substituent.
• R 10 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and among them, a hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferable. Alkyl groups are more preferred, and hydrogen atoms or methyl groups are even more preferred.
• U 1 and U 2 independently represent -O-, -S-, -COO-, -OCO-, -CONH-, -NHCOO-, -NH-, and -O- or -NH- are preferable. , —O— is even more preferred.
• R 11 and R 12 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, respectively, and R 11 And R 12 may be linked to each other via a linking group.
• Substituted or unsubstituted aliphatic hydrocarbon groups indicated by R 11 and R 12 include alkyl groups, alkenyl groups or alkynyl groups which may have a substituent.
• alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and a tridecyl group.
• alkenyl group examples include a linear group such as a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-methyl-1-propenyl group, a 1-cyclopentenyl group and a 1-cyclohexenyl group. , Branched or cyclic alkenyl groups.
• alkynyl group include an ethynyl group, a 1-propynyl group, a 1-butynyl group, a 1-octynyl group and the like.
• substituted or unsubstituted aryl group indicated by R 11 and R 12 for example, one to four benzene rings forming a fused ring, and a benzene ring and an unsaturated five-membered ring forming a fused ring.
• Specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, a pyrenyl group and the like.
• a hydrogen atom on a heteroaromatic ring containing one or more heteroatoms selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom is used.
• examples thereof include those obtained by removing one atom and using it as a heteroaryl group.
• Specific examples of the heteroaromatic ring containing one or more heteroatoms selected from the group consisting of nitrogen atom, oxygen atom and sulfur atom include, for example, pyrrole, furan, thiophene, pyrazole, imidazole, triazole, oxazole and isoxazole.
• R 11 and R 12 may have include monovalent non-metal atomic groups excluding hydrogen, and are selected from the following substituent group Y, for example.
• substituent group Y Halogen atom (-F, -Br, -Cl, -I), hydroxyl group, alkoxy group, allyloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group , N, N-dialkylamino group, N-arylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-ally Lucarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbam
• Diarylphosphonooxy groups (-OPO 3 (aryl) 2 ), alkylarylphosphonooxy groups (-OPO 3 (alkyl) (aryl)), monoalkylphosphonooxy groups (-OPO 3 H (alkyl)) and a conjugated base group thereof, monoarylphosphono group (-OPO 3 H (aryl)) and its conjugated base group, a cyano group, a nitro group, an aryl group, an alkenyl group and alkynyl group also, these substituents May form a ring by bonding substituents to each other or to a hydrocarbon group substituted, if possible.
• R 11 and R 12 in the above formula (IV) are preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group, and hydrogen. It is more preferred that they are linked to each other with an atom or an alkylene linking group.
• L 8 represents a single bond, or, -O -, - S -, - COO -, - OCO -, - CONR 13 -, - NR 13 COO -, - CR 13 N-, divalent substituted or unsubstituted aliphatic group, a substituted or unsubstituted divalent aromatic radical, and a divalent linking group selected from the group consisting of, R 10 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms Represents.
• L 8 is, -O -, - COO -, - OCO -, - CONR 13 -, - NR 13 COO-, a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group , And a divalent linking group selected from the group consisting of these combinations is preferable.
• L 8 contains a substituted or unsubstituted divalent aromatic group, the number of aromatic rings is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. Within this range, the orientation of the formed optically anisotropic layer can be improved.
• monomers forming the repeating unit represented by the above formula (VI) include monomers represented by the following formulas 3-1 to 3-26.
• the fluorine-containing polymer of the present invention preferably has a structure derived from a liquid crystal compound.
• the structure derived from the liquid crystal compound is a partial structure obtained by radically polymerizing a mesogen group derived from at least one liquid crystal compound selected from a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound and a compound having two or more polymerizable groups. Can be mentioned.
• the fluorinated polymer of the present invention has such a partial structure, the fluorinated polymer is branched. That is, the polymerizable group derived from the liquid crystal compound serves as a branch point.
• the partial structure is preferably introduced into the fluorine-containing polymer of the present invention as a repeating unit having a structure derived from a liquid crystal compound.
• the partial structure includes a mesogen structure derived from a liquid crystal compound. Therefore, when the fluorine-containing polymer of the present invention contains the above partial structure, the compatibility between the polymerizable liquid crystal compound and the fluorine-containing polymer in the liquid crystal composition is improved. As a result, the wettability of the liquid crystal composition with respect to the substrate is further improved, and repelling during application of the liquid crystal composition can be suppressed, so that a more homogeneous film can be obtained. In particular, when the content of the polymerizable liquid crystal compound in the liquid crystal composition is high, this effect is more remarkable.
• branched means that the polymer has a three-dimensional crosslinked structure and at least one polymerization initiator fragment is incorporated at the end.
• the polymerization initiator fragment differs depending on the polymerization initiator structure used when polymerizing the polymer, but it is possible to use a method such as NMR (nuclear magnetic resonance) spectrum measurement, IR (infrared) spectrum measurement, mass analysis measurement, or element analysis measurement. , It can be confirmed that the polymer fragment is incorporated in the polymer.
• Q X1 and Q X2 each independently represent a polymerizable group
• L X1 and L X4 each independently represent a divalent linking group
• L X 2 and LX 3 independently represent a single bond or divalent, respectively.
• Cy X1 , Cy X2 and Cy X3 each independently represent a divalent cyclic group
• nx represents an integer of 0 to 3.
• the rod-shaped liquid crystal compound represented by the general formula (X) will be further described below.
• Q X1 and Q X 2 are independently polymerizable groups.
• the polymerization reaction of the polymerizable group is preferably addition polymerization.
• the polymerizable group is preferably a functional group capable of an addition polymerization reaction. Examples of the polymerizable group include the following formulas (M-1) to (M-6).
• R m represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 7 carbon atoms, a hydrogen atom or a methyl group Most preferred.
• (M-1) to (M-6) (M-1) or (M-2) is preferable, and (M-1) is more preferable.
• L X1 and L X4 are independently divalent linking groups.
• R x1 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
• An example of a divalent linking group consisting of a combination is shown below. Here, the left side is connected to Q (Q X1 or Q X2 ), and the right side is connected to Cy (Cy X1 or Cy X3 ).
• the divalent chain group means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group.
• An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferable, and an alkylene group and an alkenylene group are more preferable.
• the alkylene group may have a branch.
• the alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
• the alkylene moiety of the substituted alkylene group is the same as the above-mentioned alkylene group.
• substituents include halogen atoms.
• the alkenylene group may have a branch.
• the number of carbon atoms of the alkenylene group is preferably 2 to 12, more preferably 2 to 10, and most preferably 2 to 8.
• the alkenylene moiety of the substituted alkenylene group is the same as the above alkenylene group.
• substituents include halogen atoms.
• the alkynylene group may have a branch.
• the alkynylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and most preferably 2 to 8 carbon atoms.
• the alkynylene moiety of the substituted alkynylene group is the same as the above alkynylene group.
• substituents include halogen atoms.
• divalent chain group include ethylene, trimethylene, propylene, tetramethylene, 2-methyl-tetramethylene, pentamethylene, hexamethylene, octamethylene, 2-butenylene and 2-butylenylene.
• divalent cyclic groups are similar to the definitions and examples of Cy X1 , Cy X2 and Cy X3 described below.
• L X2 or L X 3 are independently single-bonded or divalent linking groups, respectively.
• the R x2 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and may be a hydrogen atom, a methyl group, or an ethyl group. More preferably, it is most preferably a hydrogen atom.
• the divalent chain group and the divalent cyclic group are synonymous with the definitions in LX1 and LX4.
• R xa and R xb each independently represent a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, preferably a methyl group), and jx represents an integer of 1 or more and 1 to 3. It is preferably an integer in the range.
• nx represents 0, 1, 2, or 3.
• the plurality of LX3s may be the same or different, and the plurality of Cy X2s may be the same or different.
• nx is preferably 1 or 2, more preferably 1.
• Cy X1 , Cy X2 and Cy X3 are independently divalent cyclic groups.
• the ring contained in the divalent cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring. Most preferred.
• the ring contained in the cyclic group may be a fused ring. However, it is more preferable that it is a monocyclic ring rather than a fused ring.
• the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocycle.
• aromatic rings include benzene rings and naphthalene rings.
• aliphatic rings include cyclohexane rings.
• heterocycles include pyridine rings and pyrimidine rings.
• 1,4-phenylene is preferable.
• naphthalene-1,5-diyl and naphthalene-2,6-diyl are preferable.
• the cyclic group having a cyclohexane ring is preferably 1,4-cyclohexylene.
• pyridine-2,5-diyl is preferable.
• pyrimidine-2,5-diyl is preferable.
• the cyclic group may have a substituent.
• substituents are a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms, a halogen substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and a carbon number of carbon atoms.
• the structure derived from the compound represented by the general formula (X) is composed of a group consisting of a compound represented by the following general formula (XI) and a compound represented by the following general formula (X-II). Most preferably, it contains at least one selected.
• R 101 to R 104 each independently represent a polymerizable group
• X 101 and Y 101 independently represent a hydrogen atom, a methyl group, and an ethyl.
• Examples of the halogen group include a chlorine atom and a bromine atom.
• R xc and R xd each independently represent a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 3 carbon atoms, preferably a methyl group), and ny is preferably an integer of 2 to 8.
• X 101 and Y 101 represent a methyl group in the general formula (XI) or (X-II).
• ny is preferably an integer of 4 to 8.
• mesogen group derived from the disk-shaped liquid crystal compound it is also preferable to include a structure derived from the compound represented by the following general formula (IX).
• Y 11 , Y 12 and Y 13 each independently represent a methine or nitrogen atom which may have a substituent, and L 1 , L 2 and L 3 are independent, respectively.
• YA 1 and YA 2 each independently represent a methine or nitrogen atom which may have a substituent
• XA represents an oxygen atom, a sulfur atom, methylene or imino
• YB 1 and YB 2 represent a methine or nitrogen atom which may independently have a substituent
• XB represents an oxygen atom, a sulfur atom, methylene or an imino
• *. represents a position bonding with L 1 ⁇ L 3 side in the above general formula (I-X)
• ** represents a position bonding with R 1 ⁇ R 3 side in the general formula (I-X).
• R 1 , R 2 and R 3 independently represent the following general formula (IR).
• * represents the general formula (I-X) position for coupling with H 1 ⁇ H 3 side in
• L r1 represents a single bond or a divalent linking group
• Q 2 is A divalent group (cyclic group) having at least one kind of cyclic structure is represented
• n1 represents an integer of 0 to 4
• L r2 and L r3 each represent a divalent linking group independently
• Q 1 represents a divalent linking group.
• at least two for Q 1 existing in plural numbers represent a polymerizable group.
• Y 11 , Y 12 and Y 13 each represent a methine or a nitrogen atom which may independently have a substituent, and a methine which may have a substituent is preferable. Is more preferably unsubstituted.
• Substituents that methin may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom and A cyano group can be mentioned as a preferred example.
• an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number of carbon atoms. More preferably, an alkoxycarbonyl group of 2 to 12, an acyloxy group having 2 to 12 carbon atoms, a halogen atom and a cyano group.
• the R 7 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom, a methyl group or an ethyl group. It is preferably a hydrogen atom, most preferably a hydrogen atom.
• the divalent cyclic group in L 1 , L 2 and L 3 is a divalent linking group having at least one kind of cyclic structure (hereinafter, may be referred to as a cyclic group).
• the cyclic group is preferably a 5-membered ring, a 6-membered ring, or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.
• the ring contained in the cyclic group may be a fused ring. However, it is more preferable that it is a monocyclic ring rather than a fused ring.
• the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocycle.
• aromatic ring a benzene ring and a naphthalene ring are preferable examples.
• a cyclohexane ring is given as a preferable example.
• heterocycle a ring containing at least one sulfur atom, nitrogen atom or oxygen atom is preferable, and a pyridine ring, a pyrimidine ring and an oxadiazole ring are preferable examples.
• the cyclic group is more preferably an aromatic ring or a heterocycle.
• the divalent cyclic group in the present invention is more preferably a divalent linking group having only a cyclic structure (provided that it contains a substituent) (hereinafter, the same applies).
• the cyclic group having a benzene ring is preferably a 1,4-phenylene group.
• a naphthalene ring a naphthalene-1,5-diyl group and a naphthalene-2,6-diyl group are preferable.
• the cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group.
• a pyridine ring a pyridine-2,5-diyl group is preferable.
• cyclic group having a pyrimidine ring a pyrimidine-2,5-diyl group is preferable.
• cyclic group having an oxadiazole ring a 1,2,4-oxadiazole-3,5-diyl group is preferable.
• the divalent cyclic group represented by L 1 , L 2 and L 3 may have a substituent.
• substituents include a halogen atom (preferably a fluorine atom and a chlorine atom), a cyano group, a nitro group, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, and an alkynyl group having 2 to 16 carbon atoms.
• * represents a position in the general formula (IX) to be coupled to the 6-membered ring side including Y 11 , Y 12 and Y 13.
• H 1 , H 2 and H 3 independently represent the groups of the general formula (IA) or (IB), respectively.
• R 1 , R 2 and R 3 independently represent the following general formula (IR).
• * represents a position bonded with H 1 ⁇ H 3 side in formula (I-X).
• L r1 represents a single bond or a divalent linking group.
• Q 2 represents a divalent group having at least one cyclic structure (cyclic group).
• the R 7 is a hydrogen atom or an alkyl group having 1 to 7 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a methyl group. , Hydrogen atom is most preferable.
• Q 2 represents a divalent group having at least one cyclic structure (cyclic group).
• a cyclic group having a 5-membered ring, a 6-membered ring, or a 7-membered ring is preferable, a cyclic group having a 5-membered ring or a 6-membered ring is more preferable, and a cyclic group having a 6-membered ring is preferable.
• the cyclic structure contained in the cyclic group may be a fused ring. However, it is more preferable that it is a monocyclic ring rather than a fused ring.
• the ring contained in the cyclic group may be any of an aromatic ring, an aliphatic ring, and a heterocycle.
• Preferred examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring.
• a cyclohexane ring is given as a preferable example.
• the heterocycle preferably has at least one nitrogen atom or oxygen atom, and examples thereof include a pyridine ring, a pyrimidine ring, and an oxadiazole ring.
• the cyclic group having a benzene ring a 1,4-phenylene group is preferred.
• a naphthalene ring naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-2,5-diyl group, naphthalene-2,6 -Diylnaphthalene-2,7-Diyl group is preferable.
• the cyclic group having a cyclohexane ring is preferably a 1,4-cyclohexylene group.
• a pyridine-2,5-diyl group is preferable.
• a pyrimidine ring a pyrimidine-2,5-diyl group is preferable.
• the oxadiazole ring is preferably a 1,2,4-oxadiazole-3,5-diyl group. Among these, 1,4-phenylene group, naphthalene-2,6-diyl group, 1,4-cyclohexylene group and 1,2,4-oxadiazole-3,5-diyl group are particularly preferable.
• Q 2 may have a substituent.
• substituents include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 carbon atoms.
• alkynyl group alkyl group substituted with halogen with 1 to 16 carbon atoms, alkoxy group with 1 to 16 carbon atoms, acyl group with 2 to 16 carbon atoms, alkylthio group with 1 to 16 carbon atoms, 2 carbon atoms It contains an acyloxy group of up to 16; an alkoxycarbonyl group of 2 to 16 carbon atoms, a carbamoyl group, an alkyl substituted carbamoyl group of 2 to 16 carbon atoms and an acylamino group of 2 to 16 carbon atoms.
• a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom.
• Alkyl groups substituted with 4 to 4 halogens are more preferable, and halogen atoms, alkyl groups having 1 to 3 carbon atoms, and trifluoromethyl groups are even more preferable.
• N1 represents an integer from 0 to 4. As n1, an integer of 1 to 3 is preferable, and 1 or 2 is more preferable.
• L r2 is a group containing a hydrogen atom
• this hydrogen atom may be substituted with a substituent.
• substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of carbon atoms.
• Preferred examples include a group and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.
• a divalent linking group selected from the group is preferred.
• Such substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of carbon atoms.
• Preferred examples include a group and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable. By substituting with these substituents, the solubility in a solvent used when preparing a liquid crystal composition from the liquid crystal compound of the present invention can be improved.
• L r3 preferably contains 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms. Furthermore, L r3 is, -CH 2 - preferably contains 1 to 16 pieces of, -CH 2 - is more preferable that 2 to be 12 contains.
• Q 1 is represents a polymerizable group or a hydrogen atom, in the general formula (I-X), at least two for Q 1 existing in plural numbers represent a polymerizable group. Further, it is preferable Q 1 to plurality of are all polymerizable groups.
• the definition of Q 1 is synonymous with the definitions of Q X 1 and Q x 4 , and the preferred range is also the same.
• the compound represented by the following general formula (IX) is more preferable.
• Y 11, Y 12 and Y 13 have the same meanings as defined in formula Y 11 of (I-X) in, Y 12 and Y 13, R 11, R 12 and R 13 each It independently represents the following general formula (I'-A), the following general formula (I'-B), or the following general formula (I'-C).
• a 11 , A 12 , A 13 , A 14 , A 15 and A 16 each represent a methine or nitrogen atom which may independently have a substituent, and X 1 is.
• L 11 and L 12 each independently represent a divalent linking group
• Q 11 represents a polymerizable group or a hydrogen atom.
• a 21 , A 22 , A 23 , A 24 , A 25 and A 26 each represent a methine or nitrogen atom which may independently have a substituent, and X 2 is.
• L 21 and L 22 each independently represent a divalent linking group
• Q 21 represents a polymerizable group or a hydrogen atom.
• a 31 , A 32 , A 33 , A 34 , A 35 and A 36 each represent a methine or nitrogen atom which may independently have a substituent, and X 3 is.
• L 31 and L 32 each independently represent a divalent linking group
• Q 31 represents a polymerizable group or a hydrogen atom.
• Q 11 , Q 21 and Q 31 represent polymerizable groups.
• R 11 , R 12 and R 13 independently represent the following general formula (I'-A), the following general formula (I'-B) or the following general formula (I'-C), respectively.
• the general formula (I'-A) or the general formula (I'-C) is preferable, and the general formula (I'-A) is more preferable.
• a 11 , A 12 , A 13 , A 14 , A 15 and A 16 each represent a methine or nitrogen atom which may independently have a substituent. It is preferable that at least one of A 11 and A 12 is a nitrogen atom, and it is more preferable that both are nitrogen atoms.
• a 13 , A 14 , A 15 and A 16 are preferably methines in which at least three of them may have a substituent, and more preferably all of them are methines which may have a substituent. preferable. Furthermore, this methine is preferably unsubstituted.
• substituents in the case of methine where A 11 , A 12 , A 13 , A 14 , A 15 or A 16 may have substituents include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine).
• Atomic group cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, alkynyl group having 2 to 16 carbon atoms, alkyl group substituted with halogen having 1 to 16 carbon atoms, An alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, and carbon.
• X 1 represents an oxygen atom, a sulfur atom, methylene or imino, and an oxygen atom is preferable.
• a 21 , A 22 , A 23 , A 24 , A 25 and A 26 each represent a methine or nitrogen atom which may independently have a substituent. It is preferable that at least one of A 21 and A 22 is a nitrogen atom, and it is more preferable that both are nitrogen atoms.
• a 23 , A 24 , A 25 and A 26 are preferably methines in which at least three of them may have a substituent, and more preferably all of them are methines which may have a substituent. preferable. Furthermore, this methine is preferably unsubstituted.
• substituents in the case of methine where A 21 , A 22 , A 23 , A 24 , A 25 or A 26 may have a substituent include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine).
• Atomic group cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, alkynyl group having 2 to 16 carbon atoms, alkyl group substituted with halogen having 1 to 16 carbon atoms, An alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, and carbon.
• X 2 represents an oxygen atom, a sulfur atom, methylene or imino, and an oxygen atom is preferable.
• a 31 , A 32 , A 33 , A 34 , A 35 and A 36 each represent a methine or nitrogen atom which may independently have a substituent. It is preferable that at least one of A 31 and A 32 is a nitrogen atom, and it is more preferable that both are nitrogen atoms.
• a 33 , A 34 , A 35 and A 36 are preferably methines in which at least three may have a substituent, and more preferably all methines in which they may have a substituent. Furthermore, this methine is preferably unsubstituted. If A 31 , A 32 , A 33 , A 34 , A 35 or A 36 may have a substituent, the methine may have a substituent.
• substituents include halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, and 2 carbon atoms.
• alkynyl group alkyl group substituted with halogen with 1 to 16 carbon atoms, alkoxy group with 1 to 16 carbon atoms, acyl group with 2 to 16 carbon atoms, alkylthio group with 1 to 16 carbon atoms, 2 carbon atoms It contains an acyloxy group of up to 16; an alkoxycarbonyl group of 2 to 16 carbon atoms, a carbamoyl group, an alkyl substituted carbamoyl group of 2 to 16 carbon atoms and an acylamino group of 2 to 16 carbon atoms.
• a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom.
• Alkyl groups substituted with 4 to 4 halogens are more preferable, and halogen atoms, alkyl groups having 1 to 3 carbon atoms, and trifluoromethyl groups are even more preferable.
• X 3 represents an oxygen atom, a sulfur atom, a methylene group or an imino group, an oxygen atom is preferable.
• L 11 in the general formula (I'-A), L 21 in the general formula (I'-B), and L 31 in the general formula (I'-C) are independently -O- and -C, respectively.
• this hydrogen atom may be replaced with a substituent.
• substituents include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a carbon number of carbon atoms.
• Preferred examples include a group and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferable.
• L 12 in the general formula (I'-A), L 22 in the general formula (I'-B), and L 32 in the general formula (I'-C) are independently -O- and -S, respectively.
• Such substituents include a halogen atom, a cyano group, a nitro group, a hydroxyl group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and 1 to 6 carbon atoms.
• Preferred examples include a carbamoyl group substituted with, and an acylamino group having 2 to 6 carbon atoms, more preferably a halogen atom, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms, and particularly preferably a halogen atom, a methyl group, and an ethyl group. ..
• L 12 , L 22 and L 32 are each independently preferably having 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms. Preferably 2 to 14 carbon atoms, -CH 2 - is more preferable to have 1 to 16 pieces of, -CH 2 - is more preferred to have 2-12 a.
• the number of carbon atoms constituting L 12 , L 22 and L 32 affects the phase transition temperature of the liquid crystal and the solubility of the compound in the solvent. Generally the more increased the number of carbon atoms, transition temperature of the discotic nematic phase from (N D phase) to the isotropic liquid tends to decrease. In addition, the solubility in a solvent generally tends to improve as the number of carbon atoms increases.
• Q 11 in the general formula (I'-A), Q 21 in the general formula (I'-B), and Q 31 in the general formula (I'-C) independently have a polymerizable group or a hydrogen atom. At least two represent polymerizable groups. Further, it is preferable that Q 11 , Q 21 and Q 31 are all polymerizable groups.
• the example of the polymerizable group has the same meaning as the polymerizable group represented by Q X1 or Q X 2 in the general formula (X), and the same applies to the preferred example.
• Specific examples of the compound represented by the general formula (IX) include the exemplary compounds described in paragraphs [0068] to [0077] of JP-A-2010-244038, and paragraphs of JP-A-2007-2220.
• the exemplary compounds described in [0040] to [0063] are included.
• the present invention is not limited to these compounds.
• the above compound can be synthesized by various methods, for example, it can be synthesized by the methods described in [0064] to [0070] of JP-A-2007-2220.
• Discotic liquid crystal compound as a liquid phase, it is preferable to show a columnar phase and a discotic nematic phase (N D phase), among these liquid crystal phases, a discotic nematic phase having a good monodomain property (N D Phase) is preferred.
• the disk-shaped liquid crystal compound contains a structure derived from the compound represented by the following general formula (1).
• D 41 represents a disk-shaped core
• L 41 represents a divalent linking group
• Q 41 represents a polymerizable group
• n 41 represents an integer of 2 to 12.
• L represents a divalent linking group and Q represents a polymerizable group.
• the divalent linking group (L 41 ) is a group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O-, -S- and a combination thereof. It is preferably a divalent linking group more selected.
• the divalent linking group (L 41 ) is a combination of at least two divalent groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, -CO-, -NH-, -O- and -S-. It is more preferable that it is a base.
• the divalent linking group (L 41 ) is most preferably a group in which at least two divalent groups selected from the group consisting of an alkylene group, an alkenylene group, an arylene group, and -CO- and -O- are combined. ..
• the alkylene group preferably has 1 to 12 carbon atoms.
• the number of carbon atoms of the alkenylene group is preferably 2 to 12.
• the arylene group preferably has 6 to 10 carbon atoms.
• the alkylene group, alkenylene group and arylene group may have a substituent (eg, an alkyl group, a halogen atom, a cyano, an alkoxy group, an acyloxy group).
• L 41 An example of a divalent linking group (L 41 ) is shown below. * Bonds to the disc-shaped core (D 41 ) and ** binds to the polymerizable group (Q 41 ).
• AL means an alkylene group or an alkenylene group
• AR means an arylene group.
• L 41 -1 * - AL- CO-O-AL - ** L 41 -2: * - AL- CO-O-AL-O - ** L 41 -3: * -AL-CO-O-AL-O-AL-** L 41 -4: * -AL-CO-O-AL-O-CO-** L 41 -5: * - CO- AR-O-AL - ** L 41 -6: * - CO- AR-O-AL-O - ** L 41 -7: * - CO- AR-O-AL-O-CO - ** L 41 -8: * - CO- NH-AL - ** L 41 -9: * - NH- AL-O - ** L 41 -10: * - NH- AL-O-CO - ** L 41 -11: * - O- AL-O - ** L 41 -12: * - O- AL-O - ** L 41 -13: * - O- AL-O-CO - **
• Q 41 represents a polymerizable group and is synonymous with the polymerizable group represented by Q X1 or Q X 2 in the general formula (X).
• n41 is 2 or more, a plurality of combinations of L 41 and Q 41 may be different, but are preferably the same.
• Examples of the structure derived from the compound represented by the general formula (1) include triphenylene derivatives represented by the general formulas (1) to (3) described in JP-A-7-306317 and JP-A-7-309913.
• the triphenylene derivative represented by the general formula (I) described in Japanese Patent Application Laid-Open No. 2001-100028 and the triphenylene derivative represented by the general formula (I) described in JP-A-2001-100028 are preferable.
• the triphenylene derivatives the following compounds having a linking group between the triphenylene structure and the polymerizable group are most preferable.
• the fluorine-containing polymer of the present invention may have a structure derived from a liquid crystal compound other than the above.
• the fluorine-containing polymer of the present invention may have a partial structure derived from the polymerizable liquid crystal compound in the section of "composition" described later.
• the partial structure is preferably introduced into the fluorine-containing polymer of the present invention as a repeating unit having a structure derived from a liquid crystal compound.
• the partial structure includes a mesogen structure derived from a liquid crystal compound. Therefore, when the fluorine-containing polymer of the present invention contains the above partial structure, the compatibility between the polymerizable liquid crystal compound and the fluorine-containing polymer in the liquid crystal composition is improved.
• the wettability of the liquid crystal composition with respect to the substrate is further improved, and repelling during application of the liquid crystal composition can be suppressed, so that a more homogeneous film can be obtained.
• the content of the polymerizable liquid crystal compound in the liquid crystal composition is high, this effect is more remarkable.
• the fluorine-containing polymer of the present invention may further contain a repeating unit other than the above.
• a repeating unit include a repeating unit represented by the following formula (VI).
• R t1 represents a hydrogen atom or a methyl group.
• L t1 represents an alkylene group having 1 to 4 carbon atoms.
• t represents an integer from 0 to 20.
• the fluorine-containing polymer of the present invention is obtained by polymerizing a monomer for obtaining each repeating unit by a known method. At the time of producing the fluorine-containing polymer of the present invention, only one kind of monomer may be used for obtaining the repeating unit represented by the above formulas (I) to (III), or two or more kinds may be mixed. You may use it.
• fluorine-containing polymer of the present invention only one kind of monomer for obtaining the above repeating unit other than the repeating unit represented by the above formulas (I) to (III) may be used. Two or more kinds may be mixed and used.
• fluorine-containing polymer of the present invention Specific examples of the fluorine-containing polymer of the present invention are shown below, but the present invention is not limited thereto.
• the content of the repeating unit represented by the general formulas (I) to (III) is preferably 2 to 100% by mass, preferably 3 to 90% by mass, based on the total mass of the fluorine-containing polymer.
• the mass% is more preferable, and 5 to 80% by mass is further preferable.
• the content of the repeating unit in the general formula (II) is 1 to 95 with respect to the total mass of the fluorinated polymer.
• the mass% is preferable, 5 to 95% by mass is more preferable, and 10 to 90% by mass is further preferable.
• the content of the repeating unit in the general formula (III) is 0.1 with respect to the total mass of the fluorinated polymer. It is preferably ⁇ 95% by mass, more preferably 0.5 to 95% by mass, still more preferably 1 to 90% by mass.
• the content of the repeating unit in the general formula (IV) is 0.1 with respect to the total mass of the fluorinated polymer. It is preferably ⁇ 90% by mass, more preferably 0.5 to 80% by mass, still more preferably 1 to 70% by mass.
• the fluoropolymer of the present invention has a partial structure obtained by radically polymerizing a mesogen group derived from at least one liquid crystal compound selected from a rod-shaped liquid crystal compound and a disk-shaped liquid crystal compound and a compound having two or more polymerizable groups.
• the content of the repeating unit including this partial structure is preferably 1 to 95% by mass, more preferably 5 to 95% by mass, and 10 to 90% by mass with respect to the total mass of the fluoropolymer. More preferred.
• the fluorinated polymer of the present invention is a copolymer obtained by using two or more kinds of monomers
• the fluorinated polymer of the present invention may have a block structure, a graft structure, a branch structure or a star structure. preferable.
• the weight average molecular weight (Mw) of the fluorine-containing polymer of the present invention is preferably 1000 to 100,000, more preferably 1500 to 90,000, and even more preferably 2000 to 80,000.
• the number average molecular weight (Mn) of the fluorine-containing polymer of the present invention is preferably 500 to 40,000, more preferably 600 to 35,000, and even more preferably 600 to 30,000.
• the dispersity (Mw / Mn) of the fluorine-containing polymer of the present invention is preferably 1.00 to 12.00, more preferably 1.00 to 11.00, and even more preferably 1.00 to 10.00.
• the weight average molecular weight and the number average molecular weight are values measured by gel permeation chromatography (GPC) under the following conditions.
• composition of the present invention a composition containing the fluorine-containing polymer of the present invention (hereinafter, also abbreviated as "composition of the present invention”) will be described.
• the composition of the present invention may contain a component other than the fluorine-containing copolymer, and preferably contains a film-forming compound and a solvent in addition to the fluorine-containing polymer.
• a polymerizable liquid crystal compound as a compound for forming a film, it can be used as a composition (coating liquid) for forming an optically anisotropic layer.
• the liquid crystal composition which is one of the preferred embodiments of the composition of the present invention, contains at least the fluorine-containing polymer of the present invention and the polymerizable liquid crystal compound.
• the components contained in the liquid crystal composition will be described.
• the liquid crystal composition contains the fluorine-containing polymer of the present invention.
• the content of the fluorine-containing polymer of the present invention is preferably 0.003 to 10% by mass, more preferably 0.005 to 5% by mass, and 0.01 to 3% by mass with respect to the total mass of the liquid crystal composition. The above is more preferable.
• the content of the fluorine-containing polymer of the present invention is 0.003% by mass or more, a film having better homogeneity can be obtained.
• the content of the fluorine-containing polymer of the present invention is 10% by mass or less, the orientation of the liquid crystal component contained in the film is more excellent.
• the liquid crystal composition contains a polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound is a liquid crystal compound having at least one polymerizable group.
• liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shape. Furthermore, there are small molecule and high molecular types, respectively.
• a polymer generally refers to a molecule having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
• the polymerizable liquid crystal compound any liquid crystal compound can be used as long as it has a polymerizable group.
• a rod-shaped polymerizable liquid crystal compound or a disk-shaped polymerizable liquid crystal compound is preferably used, and a rod-shaped polymerizable liquid crystal compound is preferable. It is more preferable to use a compound.
• the liquid crystal composition may contain a liquid crystal compound other than the polymerizable liquid crystal compound.
• the polymerizable liquid crystal compound preferably has two or more polymerizable groups in one molecule.
• the layer thus formed may be referred to as a liquid crystal layer for convenience.
• the liquid crystal layer is preferably a layer in which the oriented liquid crystal compound is fixed while maintaining the oriented state.
• the type of the polymerizable group of the polymerizable liquid crystal compound is not particularly limited, a functional group capable of an addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring-polymerizable group is preferable. More specifically, a (meth) acryloyl group, a vinyl group, a styryl group, an allyl group, an epoxy group, or an oxetane group is preferable, and a (meth) acryloyl group is more preferable in that the polymerization reaction is fast.
• Examples of the rod-shaped polymerizable liquid crystal compound include the compound according to claim 1 of JP-A No. 11-513019 and the compounds according to paragraphs [0026] to [0098] of JP-A-2005-289980. Can be mentioned.
• Examples of the disk-shaped polymerizable liquid crystal compound include the compounds described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038. ], Examples thereof include the compounds described in.
• Examples of the rod-shaped polymerizable liquid crystal compound include liquid crystal compounds capable of expressing a smectic phase.
• liquid crystal compounds capable of expressing a smectic phase For example, JP-A-2016-51178, JP-A-2008-214269, JP-A-2008-19240, and JP-A-2008-19240. Examples thereof include the compounds described in JP-A-2006-276821.
• the rod-shaped polymerizable liquid crystal compound a polymerizable liquid crystal compound having a maximum absorption wavelength in the wavelength range of 330 to 380 nm is preferable.
• the rod-shaped polymerizable liquid crystal compound is preferably a reverse wavelength dispersible polymerizable liquid crystal compound.
• the "reverse wavelength dispersibility" polymerizable liquid crystal compound is in-plane in a specific wavelength (visible light range) of a retardation film (optically anisotropic layer or the like) produced by using the polymerizable liquid crystal compound. When the retardation value (Re) of is measured, Re becomes equal to or higher as the measurement wavelength becomes larger.
• a polymerizable liquid crystal compound capable of forming an optically anisotropic layer satisfying the following formula is preferable.
• Re (450) represents the in-plane retardation of the optically anisotropic layer at a wavelength of 450 nm
• Re (550) represents the in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm. ..
• the value of the in-plane retardation can be measured by using AxoScan OPMF-1 (manufactured by Optoscience) and using light having a measurement wavelength.
• the polymerizable liquid crystal compound is preferably a compound having a group selected from the group consisting of the groups represented by the general formulas (A1) to (A7). Having such a group makes it easy to introduce reverse wavelength dispersibility into the polymerizable liquid crystal compound.
• * 1 and * 2 represent the bonding position.
• Q 1 represents N or CH
• Q 2 represents -S-, -O-, or -N (J 5 )-
• J 5 is a hydrogen atom or the number of carbon atoms.
• It represents an alkyl group of 1 to 6
• Y 1 represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
• Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y 1 include an aryl group such as a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group.
• Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y 1 include heteroaryl groups such as a thienyl group, a thiazolyl group, a frill group, and a pyridyl group.
• examples of the substituent that Y 1 may have include an alkyl group, an alkoxy group, a halogen atom and the like.
• the alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group or an isopropyl group) is preferable.
• N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc. are more preferable, an alkyl group having 1 to 4 carbon atoms is further preferable, and a methyl group or an ethyl group is particularly preferable.
• an alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, a methoxyethoxy group, etc.) is more preferable.
• Alkoxy groups having 1 to 4 carbon atoms are more preferable, and methoxy groups or ethoxy groups are particularly preferable.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom or a chlorine atom is preferable.
• Z 1, Z 2 and Z 3 are each independently a hydrogen atom, monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, 3 carbon atoms Represents a monovalent alicyclic hydrocarbon group of 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NJ 6 J 7 or -SJ 8 .
• J 6 to J 8 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to each other to form an aromatic ring.
• an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and specifically, a methyl group and an ethyl group.
• Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and the like.
• Monocyclic saturated hydrocarbon group such as ethylcyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, And monocyclic unsaturated hydrocarbon groups such as cyclodecadien; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.2.10 2,6].
• Decyl group tricyclo [3.3.1.1 3,7 ] decyl group, tetracyclo [6.2.1.1 3,6 . 0 2,7 ]
• Dodecyl group polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
• the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and an aryl group having 6 to 12 carbon atoms. (Especially phenyl group) is preferable.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and among them, a fluorine atom, a chlorine atom or a bromine atom is preferable.
• alkyl groups having 1 to 6 carbon atoms indicated by J 6 to J 8 include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Examples include a group, an n-pentyl group, an n-hexyl group and the like.
• Z 1 and Z 2 may be bonded to each other to form an aromatic ring as described above.
• Z 1 and Z 2 in the above formula (A1) may be bonded to each other to form an aromatic ring.
• Examples of the structure of the case include a group represented by the following formula (Ar-1a).
• Ar-1a * represents a bonding position
• Q 1 , Q 2 and Y 1 are the same as those described in the above formula (A1).
• a 3 and A 4 are each independently, -O -, - N (J 9) -, - S-, and, from the group consisting of -CO- represents a group selected, J 9 represents a hydrogen atom or a substituent.
• Examples of the substituent represented by J 9 include the same substituents that Y 1 in the above general formula (A1) may have.
• X represents a non-metal atom of Group 14 to 16 to which a hydrogen atom or a substituent may be bonded.
• substituents include an alkyl group, an alkoxy group, an alkyl substituted alkoxy group, a cyclic alkyl group, an aryl group (for example, a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group.
• substituents include a carbonyl group, a sulfo group and a hydroxyl group.
• J 1 , J 2 , J 3 and J 4 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
• SP 3 and SP 4 are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a direct group having 1 to 12 carbon atoms.
• One or more of -CH 2- constituting the chain-shaped or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-.
• examples of the linear or branched alkylene group having 1 to 12 carbon atoms shown in one aspect of SP 3 and SP 4 include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. , Methylhexylene group, heptylene group and the like are preferable.
• E 3 and E 4 each independently represent a monovalent organic group.
• Examples of the monovalent organic group indicated by E 3 and E 4 include an alkyl group, an aryl group, and a heteroaryl group.
• the alkyl group may be linear, branched or cyclic, but linear is preferred.
• the number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10.
• the aryl group may be monocyclic or polycyclic, but monocyclic is preferable.
• the aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms.
• the heteroaryl group may be monocyclic or polycyclic.
• the number of heteroatoms constituting the heteroaryl group is preferably 1 to 3.
• a nitrogen atom, a sulfur atom and an oxygen atom are preferable.
• the heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms.
• the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y 1 in the above formula (Ar-1) may have.
• Ax is an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle.
• Ay is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic heterocycle. Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of.
• the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
• Q 3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
• Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of International Publication No. 2014/010325.
• the polymerizable liquid crystal compound is preferably a reverse wavelength dispersible polymerizable liquid crystal compound represented by the general formula (W).
• E 1- SP 1- A 1- D 3- G 1- D 1- Ar-D 2- G 2- D 4- A 2- SP 2- E 2 ... (W)
• Ar represents any group selected from the group consisting of the groups represented by the general formulas (A1) to (A7) described above.
• * 1 represents the bonding position with D 1
• * 2 represents the bonding position with D 2.
• J 1 , J 2 , J 3 and J 4 independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.
• G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and constitute an alicyclic hydrocarbon group-CH. 2 - of one or more -O -, - S- or -NH- with optionally substituted.
• a 1 and A 2 independently represent an aromatic ring group having 6 or more carbon atoms or a cycloalkylene ring group having 6 or more carbon atoms.
• SP 1 and SP 2 are independently single-bonded, a linear or branched alkylene group having 1 to 12 carbon atoms, or a direct chain having 1 to 12 carbon atoms.
• One or more of -CH 2- constituting the chain-shaped or branched alkylene group is substituted with -O-, -S-, -NH-, -N (Q)-, or -CO-.
• E 1 and E 2 each independently represent a monovalent organic group, and at least one of E 1 and E 2 represents a polymerizable group.
• Ar is a group represented by the above-mentioned general formula (A3)
• at least one of E 1 and E 2 and E 3 and E 4 in the above-mentioned general formula (A 3) has a polymerizable group. show.
• G 1 and G 2 each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms.
• the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms represented by G 1 and G 2 is preferably a 5-membered ring or a 6-membered ring.
• the alicyclic hydrocarbon group may be saturated or unsaturated, but a saturated alicyclic hydrocarbon group is preferable.
• the divalent alicyclic hydrocarbon group represented by G 1 and G 2 for example, the description in paragraph [0078] of JP2012-21068A can be referred to, and this content is incorporated in the present specification. ..
• a 1 and A 2 independently represent an aromatic ring group having 6 or more carbon atoms or a cycloalkylene ring group having 6 or more carbon atoms.
• Examples of the aromatic ring group having 6 or more carbon atoms indicated by A 1 and A 2 include an aromatic hydrocarbon ring group such as a benzene ring group, a naphthalene ring group, an anthracene ring group, and a phenanthroline ring group; a furan ring.
• Examples include aromatic heterocyclic groups such as a group, a pyrrole ring group, a thiophene ring group, a pyridine ring group, a thiazole ring group, and a benzothiazole ring group. Of these, a benzene ring group (for example, 1,4-phenyl group, etc.) is preferable.
• Examples of the cycloalkylene ring group having 6 or more carbon atoms shown by A 1 and A 2 include a cyclohexane ring group, a cyclohexene ring group, and the like, and among them, a cyclohexane ring (for example, cyclohexane-1,4). -Zyle group, etc.) is preferable.
• SP 1 and SP 2 each independently represent a linear or branched alkylene group having 1 to 12 carbon atoms.
• a linear or branched alkylene group having 1 to 12 carbon atoms indicated by SP 1 and SP 2 a methylene group, an ethylene group, a propylene group, or a butylene group is preferable.
• E 1 and E 2 each independently represent a monovalent organic group, and at least one of E 1 and E 2 represents a polymerizable group.
• examples of the monovalent organic group represented by E 1 and E 2 include those similar to those described in E 3 and E 4 in the above formula (A3).
• the polymerizable group represented by at least one of E 1 and E 2 is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
• the radically polymerizable group a generally known radically polymerizable group can be used, and an acryloyl group or a methacryloyl group is preferable.
• the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group can also be used as the polymerizable group of the highly birefringent liquid crystal.
• the cationically polymerizable group a generally known cationically polymerizable group can be used, and specifically, an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and the like. And vinyloxy group and the like.
• an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetane group, or a vinyloxy group is more preferable.
• particularly preferable polymerizable groups include polymerizable groups represented by any of the following formulas (P-1) to (P-20).
• both E 1 and E 2 in the above formula (I) are polymerizable groups for the reason that the durability is better, and the acryloyloxy group or the methacryloyloxy group is used. It is more preferable to have.
• liquid crystal compound represented by the above general formula (W) Preferred examples of the liquid crystal compound represented by the above general formula (W) are shown below, but the present invention is not limited to these liquid crystal compounds.
• the 1,4-cyclohexylene group in the following formula is a trans-1,4-cyclohexylene group.
• the group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is replaced with an ethylene group), and the positions of the methyl groups are different. Represents a mixture of bodies.
• K side chain structure
• Tables 1 to 3 below, "*" shown in the side chain structure of K represents the bonding position with the aromatic ring.
• the group adjacent to the acryloyloxy group and the methacryloyl group is a propylene group (methyl group becomes an ethylene group, respectively). Represents a substituted group) and represents a mixture of positional isomers with different methyl group positions.
• the polymerizable liquid crystal compound may be used alone or in combination of two or more. From the viewpoint of suppressing the crystallization of the polymerizable liquid crystal compound and achieving good solubility and liquid crystal property, it is preferable to use two or more kinds. Further, a polymerizable liquid crystal compound other than those described above may be used.
• a polymerizable liquid crystal compound published in the Liquid Crystal Handbook (edited by the Liquid Crystal Handbook Editorial Committee, published by Maruzen Co., Ltd., October 30, 2000) and a known polymerizable liquid crystal compound are used. May be good.
• the content of the polymerizable liquid crystal compound is preferably 20% by mass or more, more preferably 40% by mass or more, based on the total mass of the liquid crystal composition.
• the upper limit of the content of the polymerizable liquid crystal compound is preferably 60% by mass or less, more preferably 55% by mass or more, still more preferably 50% by mass or more, based on the total mass of the liquid crystal composition.
• the content of the polymerizable liquid crystal compound is preferably 50 to 99.99% by mass, more preferably 65 to 99.5% by mass, and further 70 to 99% by mass with respect to the total mass of the solid content of the liquid crystal composition.
• the polymerizable liquid crystal compound may be used alone or in combination of two or more. When two or more kinds of polymerizable liquid crystal compounds are used, the total content thereof is preferably within the above range.
• the solid content of the liquid crystal composition is a component capable of forming an optically anisotropic layer, and does not contain a solvent. Even if the properties of the above components are liquid, if an optically anisotropic layer can be formed, the solid content is calculated.
• a polymerizable liquid crystal compound having a reverse wavelength dispersibility preferably, a polymerizable liquid crystal compound represented by the general formula (W)
• the content thereof is optically different.
• 50 to 100% by mass is preferable, 65 to 95% by mass is more preferable, and 70 to 90% by mass is based on the total mass of the liquid crystal compound in the liquid crystal composition. Is even more preferable.
• the polymerizable liquid crystal compound having a reverse wavelength dispersity (preferably, the polymerizable liquid crystal compound represented by the general formula (W)) may be used alone or in combination of two or more.
• the total content thereof is preferably within the above range.
• the total mass of the liquid crystal compound is the total mass of the compounds showing liquid crystallinity in the liquid crystal composition, and when the liquid crystal composition also contains a non-polymerizable liquid crystal compound, not only the polymerizable liquid crystal compound but also the polymerizable liquid crystal compound. , The mass obtained by adding the mass of the non-polymerizable liquid crystal compound.
• the liquid crystal composition may contain a polymerization initiator.
• the polymerization initiator used is selected according to the type of polymerization reaction, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator.
• examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, oxime esters, onium salts and the like. If desired, it can be combined with a sensitizer and / or a chain transfer agent.
• the content of the polymerization initiator is 0.01 to 20% by mass with respect to the total content of the polymerizable liquid crystal compound and the non-liquid crystal polymerizable monomer described later. Is preferable, and 0.5 to 5% by mass is more preferable.
• the polymerization initiator may be used alone or in combination of two or more. When two or more kinds of polymerization initiators are used, the total content thereof is preferably within the above range.
• the liquid crystal composition may contain a non-liquid crystal polymerizable monomer from the viewpoint of the uniformity of the coating film and the strength of the film.
• the non-liquid crystalline polymerizable monomer include radically polymerizable or cationically polymerizable compounds.
• a polyfunctional radically polymerizable monomer can be used, and one that is copolymerizable with the above-mentioned liquid crystal compound containing a polymerizable group is preferable.
• esters of polyhydric alcohols with (meth) acrylic acid eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tri).
• 1,4-divinylbenzene 4-vinylbenzoic acid-2-acryloylethyl ester, 1,4-divinylcyclohexanone
• vinyl sulfone eg, 1,4-divinylbenzen
• the liquid crystal composition contains a non-liquid crystal polymerizable monomer
• the content of the non-liquid crystal polymerizable monomer is preferably 1 to 50% by mass based on the total mass of the polymerizable liquid crystal compound, and 2 to 30%. %% by mass is more preferable.
• the non-liquid crystalline polymerizable monomer may be used alone or in combination of two or more. When two or more kinds of non-liquid crystalline polymerizable monomers are used, the total content thereof is preferably within the above range.
• the liquid crystal composition may contain an organic solvent.
• the organic solvent is preferably one that can completely dissolve the above-mentioned polymerizable liquid crystal compound, and is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound.
• the organic solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, etc.
• Ester solvents such as ⁇ -butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methylisobutylketone; pentane, hexane, and heptane.
• aromatic hydrocarbon solvents such as toluene and xylene, nitrile solvents such as acetonitrile; ether solvents such as tetraethylene glycol dimethyl ether, tetrahydrofuran, and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; And so on.
• the content of the organic solvent in the liquid crystal composition is determined by the solubility of the solid content, the liquid viscosity, the pot life of the coating liquid, the suitability of the coating machine and the coating method, the uniformity and film thickness control of the coating film, and the orientation control. It can be adjusted as appropriate from the viewpoint.
• the content of the organic solvent in the liquid crystal composition is preferably, for example, an amount such that the solid content concentration of the liquid crystal composition is 13 to 50% by mass, preferably 15 to 40% by mass. Is more preferable.
• the organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used, the total content thereof is preferably within the above range.
• the liquid crystal composition may contain other components other than those described above.
• a surfactant, a chiral agent, or the like may be used from the viewpoint of adjusting the orientation of the optically anisotropic layer.
• a sub liquid crystal compound non-polymerizable liquid crystal compound
• the sub liquid crystal compound may be a small molecule liquid crystal compound.
• the sub liquid crystal compound may be a main chain type liquid crystal polymer or a side chain type liquid crystal polymer.
• a polymerization inhibitor from the viewpoint of imparting pot life to the liquid crystal composition and improving the durability of the optically anisotropic layer, a polymerization inhibitor, an antioxidant, an ultraviolet absorber and the like may be used.
• the optical film of the present invention is an optical film having a layer formed from the composition of the present invention described above.
• examples of such an optical film include an antireflection film, a brightness improving film, an antiglare film, a diffusion film, a light collecting film, and the like, and among them, it is preferable to use the antireflection film.
• the composition for forming the antireflection film for example, a known composition for forming an antireflection layer containing particles, a compound for forming a binder resin, and a solvent (for example, paragraph 17 of JP-A-2017-187584].
• the composition for forming an antireflection layer described in [0050] to [0072]), and the above-mentioned composition containing the fluoropolymer of the present invention is preferably mentioned.
• the liquid crystal film of the present invention is an optical film having a layer (optically anisotropic layer) formed from the above-mentioned liquid crystal composition.
• the method for forming the optically anisotropic layer using the liquid crystal composition described above is not particularly limited, and for example, the liquid crystal composition is directly applied onto the support to form a coating film, and the obtained coating film is used.
• a liquid crystal film having an optically anisotropic layer can be formed by subjecting an orientation forming treatment such as heating and / or cooling and a curing treatment (irradiation of ultraviolet rays (light irradiation treatment) or heat treatment). Further, the liquid crystal composition may be applied onto the alignment film described later and the same treatment as described above may be performed to form an optically anisotropic layer.
• the liquid crystal composition can be applied by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method).
• the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
• optically anisotropic layer can be oriented in various orientation states such as horizontal orientation, vertical orientation, tilt alignment, hybrid orientation, random homogenius orientation, and cholesteric orientation, and the optical anisotropy and orientation of the polymerizable liquid crystal compound can be obtained.
• Various optical characteristics can be imparted by appropriately selecting the state.
• the optically anisotropic layer may be used as a positive A plate.
• a positive A plate can be obtained by horizontally orienting a rod-shaped polymerizable liquid crystal compound.
• the in-plane retardation Re (550) is 100 to 160 nm (preferably 120 to 150 nm), it can be suitably used as a positive uniaxial ⁇ / 4 plate.
• Re (550) represents the in-plane retardation of the optically anisotropic layer at a wavelength of 550 nm.
• the value of the in-plane retardation can be measured using AxoScan OPMF-1 (manufactured by OptoScience).
• the optically anisotropic layer may be used as a positive C plate.
• a positive C plate can be obtained by vertically orienting a rod-shaped polymerizable liquid crystal compound.
• the thickness direction retardation Rth (550) is, for example, 20 to 200 nm, and is preferably 50 to 120 nm from the viewpoint of imparting various optical compensation functions and / or viewing angle improving functions.
• the optically anisotropic layer may be a negative A plate or a negative C plate. Further, by orienting the liquid crystal layer in a cholesteric manner, optical rotation, wavelength selective reflectivity, and the like can be imparted.
• the A plate is defined as follows. There are two types of A plates, a positive A plate (positive A plate) and a negative A plate (negative A plate), and the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized). ) Is nx, the refractive index in the direction orthogonal to the slow axis in the plane is ny, and the refractive index in the thickness direction is nz, the positive A plate satisfies the relationship of the equation (A1). The negative A plate satisfies the relation of the formula (A2). The positive A plate shows a positive value for Rth, and the negative A plate shows a negative value for Rth.
• Equation (A1) nx> ny ⁇ nz Equation (A2) ny ⁇ nx ⁇ nz
• ⁇ includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, “ny ⁇ nz” when (ny-nz) ⁇ d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. In the case where (nx-nz) ⁇ d is ⁇ 10 to 10 nm, preferably ⁇ 5 to 5 nm, it is also included in “nx ⁇ nz”.
• C plates There are two types of C plates, a positive C plate (positive C plate) and a negative C plate (negative C plate).
• the positive C plate satisfies the relationship of the formula (C1)
• the negative C plate is It satisfies the relation of the formula (C2).
• the positive C plate shows a negative value of Rth
• the negative C plate shows a positive value of Rth. Equation (C1) nz> nx ⁇ ny Equation (C2) nz ⁇ nx ⁇ ny
• ⁇ includes not only the case where both are completely the same, but also the case where both are substantially the same.
• substantially the same means, for example, that (nx-ny) x d (where d is the thickness of the film) is included in "nx ⁇ ny" even when it is 0 to 10 nm, preferably 0 to 5 nm. Is done.
• the wavelength dispersity of optical anisotropy can be appropriately adjusted.
• the optically anisotropic layer preferably exhibits reverse wavelength dispersibility.
• the optically anisotropic layer satisfies the following formula (II) as a uniaxial retardation layer. ⁇ n (450) / ⁇ n (550) ⁇ 1.00 ...
• ⁇ n (450) represents the difference between the maximum refractive index of the optically anisotropic layer at a wavelength of 450 nm and the refractive index in the direction orthogonal to the maximum refractive index
• ⁇ n (550) is the optically anisotropic layer. Represents the difference in refractive index between the maximum refractive index direction and the refractive index in the direction orthogonal to the maximum refractive index at a wavelength of 550 nm.
• the liquid crystal film of the present invention preferably has a support.
• the support is not particularly limited, and various known materials can be used. Above all, a long polymer film is preferable in terms of enabling continuous production.
• the polymer film include polypropylene and polyolefin / cyclic olefin resins such as norbornene polymers; polyvinyl alcohol; polyethylene terephthalates, polybutylene terephthalates, and polyester resins such as polyethylene naphthalate; polymethacrylic acid esters such as polymethylmethacrylate.
• -Polyacrylic acid esters cellulose esters such as triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate
• polyethylene naphthalate polycarbonate
• polymer films obtained by filming copolymers thereof and the like can be mentioned.
• These polymer films can be appropriately selected from the viewpoints of tensile elastic modulus, bending elastic modulus, parallel light transmittance, haze, optical anisotropy, optical isotropic property, easy peeling property, easy adhesiveness and the like.
• the coated surface of the support is smooth when the liquid crystal composition is directly applied to the support to form the optically anisotropic layer.
• the surface roughness Ra is preferably 3 to 50 nm.
• the surface of the alignment layer may be smooth as long as the surface roughness Ra thereof. Is preferably 3 to 50 nm. It is also possible to adjust the surface roughness of these by providing an intermediate layer or the like, which will be described later.
• the coated surface of the liquid crystal composition on the support is from the viewpoint of preventing shape transfer and blocking phenomenon between the film surfaces in the state of the wound body in which the manufactured liquid crystal film is wound.
• An anti-blocking treatment, a matte treatment, or the like can be applied to the surface on the opposite side. Further, knurling may be provided at the end of the film.
• the support is provided so as to be removable. That is, in the liquid crystal film, it is also preferable that the support is arranged so as to be peelable from the adjacent layer.
• the optically anisotropic layer when the optically anisotropic layer is directly arranged on the support, it is preferable that the optically anisotropic layer can be peeled off at the interface between the support and the optically anisotropic layer.
• an alignment layer and / or another layer (intermediate layer) described later is arranged between the support and the optically anisotropic layer, any arbitrary layer between the support and the optically anisotropic layer is arranged. It is preferable that it can be peeled off at the interface or in the layer.
• the liquid crystal film of the present invention may have an alignment layer, if necessary. From the viewpoint that it is easy to obtain an optically anisotropic layer having better orientation, it is preferable to provide an alignment layer on the support and further provide the above-mentioned optically anisotropic layer on the alignment layer. That is, the liquid crystal film of the present invention preferably has a photoalignment layer between the support and the optically anisotropic layer.
• a rubbing film made of an organic compound such as a polymer, an oblique vapor deposition film of an inorganic compound, a film having microgrooves, and a film.
• a film obtained by accumulating an LB film (Langmuir-Blogett film) formed by the Langmuir-Bloget method using an organic compound (for example, ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearate) is available.
• an organic compound for example, ⁇ -tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearate
• Examples of the rubbing alignment film include a coating film of polyimide, polyvinyl alcohol, a polymer having a polymerizable group described in JP-A-9-152509, and JP-A-2005-97377 and JP-A-2005-99228. Examples thereof include the alignment film described in Japanese Patent Application Laid-Open No. 2005-128503.
• composition for forming a photoalignment film used for forming the photoalignment film that can be used in the present invention has been described in many documents and the like.
• JP-A-2014-123091 and the photo-oriented polyorganosiloxane composite material described in JP-A-2015-26050; the katsura acid group-containing cellulose ester material described in JP-A-2012-234146; Materials using the optical fleece rearrangement reaction or a similar reaction described in JP-A-145660 and JP-A-2013-238717; JP-A-2016-71286, JP-A-2013-518296, JP-A-2014-533376. No., JP-A-2016-535158, WO10 / 150748, WO11 / 126022, WO13 / 054784, WO14 / 104320, and WO16 / 002722.
• a material in which a cinnamate compound, a chalcone compound, and / or a coumarin compound is pendant on various polymers can be used in the composition for forming a photoalignment film.
• a photoalignment film using a photoisomerization reaction of an azo group or a photoalignment film using a photoreaction of a cinnamate compound is preferable from the viewpoint of irradiation energy required for photoalignment, orientation control force, and the like.
• the composition for forming an alignment film (preferably a composition for forming a photoalignment film) used for forming an alignment film includes a cross-linking agent, a binder, a plasticizing agent, a sensitizer, a cross-linking catalyst, and an adhesion force, if necessary. Adjusting agents, leveling agents and the like can be added.
• the film thickness of the alignment layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 10 to 1000 nm is preferable, and 10 to 300 nm is more preferable.
• the surface roughness of the oriented layer is as described above.
• the liquid crystal film of the present invention may further contain other layers, if necessary.
• a smoothing layer, an easy-adhesion layer, an easy-release layer, a light-shielding layer, a colored layer, a fluorescent layer, an oxygen barrier layer, a water vapor barrier layer, and the like can be mentioned.
• Layers having one or more such layer functions are collectively referred to as an intermediate layer.
• the intermediate layer may be a layer having a function other than the above-mentioned functions.
• An intermediate layer can be provided, for example, between the support and the optically anisotropic layer and / or between the support and the above-mentioned alignment layer to exhibit various functions.
• the liquid crystal film of the present invention can be produced, for example, by sequentially laminating and coating a composition (liquid crystal composition or the like) for forming each layer on a support.
• a composition liquid crystal composition or the like
• steps (1) to (4) in order can be mentioned.
• (1) A step of applying a composition for forming an alignment film on a support to obtain a coating film (coating step).
• step (3) as a method of forming an optically anisotropic layer.
• the coating method in the coating step is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing.
• the application of the alignment film forming composition is preferably accompanied by a solvent removing step (drying step), and can be further accompanied by a post-baking step.
• the alignment regulating force applying step is a step of performing a rubbing treatment, a light irradiation treatment, or the like on a coating film formed by using the alignment film forming composition.
• the rubbing treatment can be performed by a conventionally known method.
• the light irradiation treatment for the coating film formed by using the composition for forming a photoalignment film it is preferable to irradiate with polarized light.
• the polarized light is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light. Among them, linearly polarized light is preferable.
• the wavelength in polarized light or non-polarized light is not particularly limited as long as the coating film formed from the composition for forming a photoalignment film can be imparted with an orientation control ability for a polymerizable liquid crystal compound or the like.
• Examples of the type of light used include ultraviolet rays, near-ultraviolet rays, and visible light. Of these, near-ultraviolet rays of 250 to 450 nm are preferable.
• the light source for irradiating polarized or unpolarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a laser, and an LED (light emitting dimension).
• the wavelength range of irradiation can be limited by using an interference filter, a color filter, or the like for ultraviolet rays and visible rays obtained from a light source. Further, linearly polarized light can be obtained by using a polarizing filter, a polarizing prism, or the like for the light from these light sources.
• the amount of polarized or unpolarized integrated light is not particularly limited as long as it can impart orientation control ability to a polymerizable liquid crystal compound or the like to the coating film of the composition for forming a photoalignment film, and is, for example, 1 to 300 mJ /. cm 2 is preferable, and 3 to 100 mJ / cm 2 is more preferable.
• the polarized or unpolarized illuminance is not particularly limited as long as it can impart the orientation control ability to the liquid crystal compound to the coating film of the composition for forming a photoalignment film, but is 0.1 to 300 mW / cm 2. Preferably, 1 to 100 mW / cm 2 is more preferable.
• the hardcourt film of the present invention is a hardcourt film having a layer formed from the composition of the present invention described above.
• a siloxane structural unit containing an epoxy group described in, for example, JP-A-2017-0081143, JP-A-2018-192704 and the like is used as a composition for forming such a hard coat film.
• a curable composition containing a polyorganosylsesquioxane containing the above-mentioned composition containing the fluorine-containing polymer of the present invention described above is preferably mentioned.
• such a hard coat film can be produced, for example, by applying the above-mentioned composition on a cellulose ester base material, drying it, and then irradiating it with ultraviolet rays to cure the coating layer.
• the polarizing plate of the present invention is a polarizing plate having a layer formed from the composition of the present invention described above.
• Examples of the structure of the polarizing plate of the present invention include a polarizing element and a hard coat film of the present invention provided as a protective film on at least one surface of the polarizing element.
• a polarizing element, a hard coat film of the present invention provided as a protective film on one surface of the polarizing element, and a hard coat film of the present invention provided on the other surface of the polarizing element are provided. It may include an optical compensation film having optical anisotropy.
• the optical compensation film in this case can be the same as the above-mentioned optically anisotropic layer.
• the polarizing plate of the present invention is preferably composed of a polarizing element and a protective film that protects both sides thereof. Further, a protective film is attached to one surface of the polarizing plate and separated on the opposite surface. It is more preferable that the films are laminated to each other.
• the protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate, at the time of product inspection, and the like.
• the protective film is attached for the purpose of protecting the surface of the polarizing plate, and is used on the opposite side of the surface on which the polarizing plate is attached to the liquid crystal plate. Further, the separate film is used for the purpose of covering the adhesive layer to be bonded to the liquid crystal plate, and is used on the surface side where the polarizing plate is bonded to the liquid crystal plate.
• the method for producing the polarizing plate of the present invention is not particularly limited, and the polarizing plate can be produced by a general method.
• a method of alkali-treating the obtained hard coat film, dipping and stretching the polyvinyl alcohol film in an iodine solution, and adhering the polyvinyl alcohol film to both sides of a polarizing element using a completely saponified polyvinyl alcohol aqueous solution and the like can be mentioned.
• an easy-adhesion process as described in JP-A-6-94915 and JP-A-6-118232 may be performed.
• the above surface treatment may be performed.
• the surface to be bonded to the polarizing element of the hard coat film may be a surface on which the hard coat layer is laminated or a surface on which the hard coat layer is not laminated.
• the adhesive used for adhering the protective film-treated surface and the polarizing element include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, vinyl-based latex such as butyl acrylate, and the like.
• the progress of the reaction was confirmed by 1H NMR, and the reaction rate was 99.9%.
• the temperature of the obtained reaction solution was set to 10 ° C. or lower again.
• 19.48 g (215.28 mmol) of acrylic acid chloride was added dropwise over 2 hours, and the mixture was reacted at room temperature for 2 hours.
• the reaction solution was transferred to a separating funnel, and the separating solution was carried out twice with 2N hydrochloric acid, and then twice with an aqueous solution of baking soda. Finally, the liquid was divided twice with water, and the organic layer was taken out and dried over magnesium sulfate.
• the weight average molecular weight of the obtained polymer is 22800, and the molecular weight distribution is 1.85 (gel permeation chromatography (EcoSEC HLC-8320GPC (manufactured by Tosoh Corporation)), eluent polystyrene, flow rate 0.35 ml / min, temperature 40 ° C. Calculated in terms of polystyrene under the measurement conditions, the columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, and TSKgel SuperHZ200 (manufactured by Tosoh Corporation).
• Synthesis Examples 2 to 25> The monomer and composition ratio used in Synthesis Example 1 were changed to the monomer and composition ratio forming the repeating unit of the fluorine-containing polymer having the structure shown in Table 4 below, and the same method as in Synthesis Example 1 was used. Fluoropolymers (Ia-2) to (Ia-8), (IIa-1) to (IIa-10), and (IIIa-1) to (IIIa-7) were obtained.
• Examples 1 to 25 and Comparative Examples 1 to 4 [Preparation of composition for forming a photoalignment film]
• the photoalignment film forming material described in Example 1 of WO2016 / 002722 was prepared and used for producing the liquid crystal film of the present invention.
• a liquid crystal composition having the following composition was prepared.
• the obtained film was further dried by transporting it between the rolls of the heat treatment apparatus to prepare an optical film having a thickness of 40 ⁇ m, which was used as a cellulose acylate film 1.
• the core layer of the cellulose acylate film 1 had a thickness of 36 ⁇ m, and the outer layers arranged on both sides of the core layer had a thickness of 2 ⁇ m, respectively.
• the in-plane retardation of the obtained cellulose acylate film 1 at a wavelength of 550 nm was 0 nm.
• the obtained cellulose acylate film 1 was used as a support.
• composition for forming a photoalignment film prepared above was applied to one side of the prepared cellulose acylate film 1 with a bar coater. After applying the composition for forming a photoalignment film, the obtained film was dried on a hot plate at 120 ° C. for 1 minute to remove the solvent, and a composition layer for forming a photoalignment film having a thickness of 0.3 ⁇ m was formed. .. The obtained composition layer for forming a photo-alignment film was irradiated with polarized ultraviolet rays (10 mJ / cm 2 , using an ultra-high pressure mercury lamp) to form a photo-alignment layer.
• liquid crystal compositions (Examples 1 to 25 and Comparative Examples 1 to 4) prepared above were applied onto the photo-alignment layer with a bar coater to form a liquid crystal composition layer.
• the formed liquid crystal composition layer was once heated to 110 ° C. on a hot plate and then cooled to 60 ° C. to stabilize the orientation.
• the orientation was fixed by UV irradiation (500 mJ / cm 2 , using an ultrahigh pressure mercury lamp) under a nitrogen atmosphere (oxygen concentration 100 ppm) at 60 ° C. to form an optically anisotropic layer with a thickness of 2.3 ⁇ m.
• a liquid crystal film was produced.
• the in-plane retardation of the obtained liquid crystal film at a wavelength of 550 nm was 140 nm.
• the number of repellents in the liquid crystal composition layer in each of the prepared liquid crystal films was counted.
• the evaluation was made according to the following criteria. If the evaluation standard A or B is used, the production efficiency is excellent and it can be suitably used, and the evaluation standard A is more preferable.
• the liquid crystal film having the fluorine-containing polymer of the present invention is a highly homogeneous film having excellent orientation and less interference unevenness, bumpy defects and cissing. (Examples 1 to 25). From the comparison of Examples 1 to 25, it was shown that the liquid crystal film formed by using the fluorine-containing polymer having a repeating unit derived from the liquid crystal compound can further suppress repelling (Examples 22 to 25).

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