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
  • 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
• • 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
  • G02F1/1334—Constructional arrangements; Manufacturing methods based on polymer dispersed liquid crystals, e.g. microencapsulated liquid crystals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/08—Cellulose derivatives
  • C08L1/10—Esters of organic acids, i.e. acylates
• • 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
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • 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
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133769—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers comprising an active, e.g. switchable, alignment layer
• • 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
  • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
• • 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
  • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
  • C09K2323/02—Alignment layer characterised by chemical composition

Definitions

• the present invention relates to a photo-oriented polymer, a binder composition, a binder layer, an optical laminate, a method for producing an optical laminate, and an image display device.
• Optical films such as optical compensation sheets and retardation films are used in various image display devices from the viewpoints of eliminating image coloring and expanding the viewing angle.
• a stretched birefringent film has been used as the optical film, but in recent years, an optically anisotropic layer formed by using a liquid crystal compound has been proposed in place of the stretched birefringent film.
• a photoalignment film obtained by performing a photoalignment treatment may be used in order to orient the liquid crystal compound.
• a photooriented polymer represented by the following formula is disclosed. This photo-oriented polymer contains a cleaving group that is decomposed by the action of an acid to form a polar group.
• an object of the present invention is to provide a photo-oriented polymer having excellent liquid crystal orientation. Another object of the present invention is to provide a binder composition, a binder layer, an optical laminate, a method for producing an optical laminate, and an image display device.
• the content a of the repeating unit having a photo-oriented group, the content b of the repeating unit having a group represented by the formula (1), and the content c of the repeating unit having a crosslinkable group are The photo-oriented polymer according to any one of (6) to (8), which satisfies the formula (D1) described later in terms of mass ratio.
• An image display device having the binder layer according to (12) or the optical laminate according to (13).
• the present invention it is possible to provide a photo-oriented polymer having excellent liquid crystal orientation. Further, according to the present invention, it is possible to provide a binder composition, a binder layer, an optical laminate, a method for producing an optical laminate, and an image display device.
• the bonding direction of the divalent group (for example, -O-CO-) described in the present specification is not particularly limited, and for example, L 2 is-in the bonding of "L 1- L 2- L 3". In the case of O-CO-, if the position bonded to the L 1 side is * 1 and the position bonded to the L 3 side is * 2, L 2 is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.
• the photooriented polymer of the present invention will be described in detail, and then the binder composition, the binder layer, the optical laminate, the method for producing the optical laminate, and the image display device will be described in detail.
• One of the features of the photooriented polymer of the present invention is that it has a repeating unit having a group represented by the formula (1).
• the acid resistance of the cleaving group which decomposes by the action of the acid contained in the photo-oriented polymer to generate a polar group is low, and a predetermined value is obtained. It was found that the cleavage of the cleavage group in the photo-oriented polymer may proceed before the layer is formed, and as a result, the liquid crystal orientation is lowered. More specifically, as the cleavage of the cleaving group progresses, the group containing a fluorine atom or a silicon atom in the photo-oriented polymer is eliminated.
• the polymer chain portion having the photo-oriented group is not unevenly distributed on the surface of the layer. A part of the layer moves inside the layer, and as a result, the orientation control ability of the formed layer is lowered, and the liquid crystal orientation is lowered.
• the acid resistance of the cleavage group is improved by binding an aliphatic hydrocarbon group having 1 or more carbon atoms to the cleavage group which is decomposed by the action of an acid to generate a polar group.
• the photo-oriented polymer of the present invention has a repeating unit having a photo-oriented group and a repeating unit having a group represented by the formula (1) described later.
• the repeating unit having a group represented by the formula (1) will be described in detail.
• the photo-oriented polymer of the present invention has a repeating unit having a group represented by the formula (1).
• the group represented by the formula (1) contains a predetermined cleaving group, which is cleaved by the action of an acid to cause elimination of a group containing a fluorine atom or a silicon atom, and at the same time. Produces a polar group.
• * represents the bond position.
• LB1 represents an aliphatic hydrocarbon group having n + 1 valence and having 1 or more carbon atoms.
• the number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and the liquid crystal orientation of the photo-oriented polymer is more excellent (hereinafter, also simply referred to as “the effect of the present invention is more excellent”). Is preferable, 1 to 5 is more preferable, and 1 to 3 is even more preferable.
• the aliphatic hydrocarbon group is n + 1 valent. For example, when n is 1, a divalent aliphatic hydrocarbon group (so-called alkylene group) is used, and when n is 2, a trivalent aliphatic hydrocarbon group is used.
• n 3
• n 3
• n 3
• n 3
• n 3
• aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may have a cyclic structure. Of these, linear is preferable because the effect of the present invention is more excellent.
• X represents a cleaving group that is decomposed by the action of an acid to form a polar group.
• the polar group include a carboxy group, a hydroxyl group, and a sulfonic acid group.
• the cleaving group a known cleaving group can be used. Among them, the group represented by any of the formulas (B1) to (B3) is preferable, and the group represented by the formula (B1) is more preferable, because the effect of the present invention is more excellent. Note that * in the equations (B1) to (B3) represents the coupling position.
• R B4 in the formula (B1) represents an alkyl group or an aryl group.
• the number of carbon atoms of the alkyl group is not particularly limited, and is preferably 1 to 10, and more preferably 1 to 6.
• the alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a cyclohexyl group. Examples of the aryl group include a phenyl group and a naphthyl group.
• R B2 in the formula (B2) represents a hydrogen atom or a substituent.
• Kind of substituent represented by R B2 is not particularly limited, it includes known substituents.
• Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an acyloxy group.
• the above-mentioned substituent may be further substituted with a substituent.
• substituent represented by R B2 alkyl groups are preferred.
• the alkyl group may be linear or branched. Further, the alkyl group may have a cyclic structure.
• an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group) is preferable.
• Groups, t-butyl groups, and cyclohexyl groups are more preferred, and alkyl groups having 1 to 4 carbon atoms are even more preferred.
• R B3 in the formula (B3) represents a substituent.
• Kind of substituent represented by R B3 is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R B2.
• As the substituent represented by RB3 an alkyl group is preferable. Further, as the substituent represented by RB3 , a group containing a fluorine atom or a silicon atom represented by Y, which will be described later, is also preferable.
• Y represents a group containing a fluorine atom or a silicon atom.
• the total number of fluorine atoms and silicon atoms contained in the group containing a fluorine atom or a silicon atom is not particularly limited, and 1 to 30 is preferable, 5 to 25 is more preferable, and 10 to 10 to more in that the effect of the present invention is more excellent. 20 is more preferred.
• the group containing a fluorine atom or a silicon atom is preferably a so-called organic group (a group containing a carbon atom).
• the number of carbon atoms contained in the group containing a fluorine atom and a silicon atom is not particularly limited, and 1 to 30 is preferable, 2 to 20 is more preferable, and 3 to 10 is further preferable, in that the effect of the present invention is more excellent.
• Examples of the group containing a fluorine atom or a silicon atom include a group containing a fluorine atom-containing alkyl group described later and a group containing a polydialkylsiloxane chain.
• Equation (2) * -L B3- Cf LB3 represents a single bond or a divalent linking group.
• Examples of the divalent linking group represented by LB3 include a divalent hydrocarbon group which may have a substituent, a divalent heterocyclic group, —O—, —S—, and —N ( Q)-, -CO-, or a group combining these can be mentioned.
• Q represents a hydrogen atom or a substituent.
• divalent hydrocarbon group examples include 2 such as an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5), an alkenylene group having 1 to 10 carbon atoms, and an alkynylene group having 1 to 10 carbon atoms.
• Valuable aliphatic hydrocarbon groups; divalent aromatic hydrocarbon groups such as arylene groups; can be mentioned.
• divalent heterocyclic group examples include a divalent aromatic heterocyclic group, specifically, a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, and thienylene (thiophene).
• -Diyl group quinolylene group (quinoline-diyl group) and the like.
• a linear group having 1 to 10 carbon atoms, a branched chain group having 3 to 10 carbon atoms, or a branched chain group having 3 to 10 carbon atoms which may have a substituent may be used as the divalent linking group represented by LB3 .
• a cyclic alkylene group of 10, an arylene group having 6 to 12 carbon atoms which may have a substituent, -O-, -CO-, -N (Q)-, or a group obtained by combining these is preferable.
• a linear alkylene group having 1 to 10 carbon atoms in which at least one -CH 2- is substituted with -O- is more preferable, and the linear group having 1 to 5 carbon atoms or 3 to 5 carbon atoms is preferable.
• a branched alkylene group of 1 to 10 or a linear alkylene group having 1 to 10 carbon atoms in which one -CH 2- is substituted with -O- is more preferable, and a linear alkylene group having 1 to 3 carbon atoms is more preferable.
• alkylene group is particularly preferred.
• linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.
• branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
• examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
• Examples of the substituent which the divalent hydrocarbon group (alkylene group, arylene group) may have and the substituent represented by Q include a halogen atom, an alkyl group, an alkoxy group, an aryl group and an aryl. Examples thereof include an oxy group, a cyano group, a carboxy group, an alkoxycarbonyl group, and a hydroxyl group.
• Cf represents a fluorine atom-containing organic group.
• the fluorine atom-containing organic group represents an organic group containing a fluorine atom.
• Examples of the fluorine atom-containing organic group include a fluorine atom-containing alkyl group which may contain —O— and a fluorine atom-containing alkenyl group which may contain —O—, and a fluorine atom-containing alkyl group or fluorine.
• Atom-containing alkenyl groups are preferred, and fluorine atom-containing alkyl groups are more preferred.
• the fluorine atom-containing alkyl group represents an alkyl group containing a fluorine atom, and a perfluoroalkyl group is preferable.
• the fluorine atom-containing alkenyl group represents an alkenyl group containing a fluorine atom, and a perfluoroalkenyl group is preferable.
• the number of carbon atoms of the fluorine atom-containing alkyl group is not particularly limited, and 1 to 30 is preferable, 2 to 20 is more preferable, and 3 to 10 is further preferable, in that the effect of the present invention is more excellent.
• the number of fluorine atoms contained in the fluorine atom-containing alkyl group is not particularly limited, and 1 to 30 is preferable, 5 to 25 is more preferable, and 10 to 20 is further preferable, in that the effect of the present invention is more excellent.
• the number of carbon atoms of the fluorine atom-containing alkenyl group is not particularly limited, and 1 to 30 is preferable, 2 to 20 is more preferable, and 3 to 10 is further preferable, in that the effect of the present invention is more excellent.
• the number of fluorine atoms contained in the fluorine atom-containing alkenyl group is not particularly limited, and 1 to 30 is preferable, 5 to 25 is more preferable, and 10 to 20 is further preferable, in that the effect of the present invention is more excellent.
• the number of double bonds contained in the fluorine atom-containing alkenyl group is not particularly limited, and is preferably 1 to 3, and more preferably 1.
• Examples of the fluorine atom-containing alkyl group that may contain —O— include a group represented by ⁇ (XO) m—R f.
• X represents a persfluoroalkylene group having 1 to 4 carbon atoms
• R f represents a perfluoroalkyl group having 1 to 4 carbon atoms.
• m represents an integer of 1 or more, preferably 2 to 10.
• N represents an integer of 1 or more. Among them, an integer of 1 to 10 is preferable, an integer of 1 to 5 is more preferable, and an integer of 1 to 3 is further preferable, in that the effect of the present invention is more excellent.
• the group represented by the formula (1) the group represented by any of the formulas (B4) to (B8) is preferable because the effect of the present invention is more excellent. * In the formulas (B4) to (B8) represents the bonding position.
• LB2 represents a divalent aliphatic hydrocarbon group having 1 or more carbon atoms.
• LB3 represents a single bond or a divalent linking group.
• Cf represents a fluorine atom-containing alkyl group. Defining L B3 and Cf are as described above.
• the number of carbon atoms included in the divalent aliphatic saturated hydrocarbon L B2 is 1 or more, in that the effect of the present invention is more excellent, preferably 1 to 10 carbon atoms, more preferably 1-5, 1-3 Is even more preferable.
• the divalent aliphatic hydrocarbon group having 1 or more carbon atoms may be linear or branched.
• the divalent aliphatic hydrocarbon group having 1 or more carbon atoms may have a cyclic structure.
• Specific examples of the divalent aliphatic hydrocarbon group include a linear alkylene group, a branched chain alkylene group, and a cyclic alkylene group.
• Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.
• Examples of the branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
• Examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-.
• Examples include the tetrahydrodicyclopentadiene-diyl group.
• LB2 represents a divalent aliphatic hydrocarbon group having 1 or more carbon atoms.
• RB2 represents a hydrogen atom or a substituent.
• LB3 represents a single bond or a divalent linking group.
• Cf represents a fluorine atom-containing alkyl group. Defining L B2, R B2, L B3 and Cf are as described above.
• LB2 represents a divalent aliphatic hydrocarbon group having 1 or more carbon atoms.
• LB3 each independently represents a single bond or a divalent linking group.
• Cf independently represents a fluorine atom-containing alkyl group. Defining L B2, L B3 and Cf are as described above.
• LB4 represents a single bond or a divalent aliphatic hydrocarbon group having 1 or more carbon atoms.
• LB3 each independently represents a single bond or a divalent linking group.
• Cf independently represents a fluorine atom-containing alkyl group.
• L B3, and Cf are as described above.
• LB4 represents a single bond or a divalent aliphatic hydrocarbon group having 1 or more carbon atoms. Defining divalent aliphatic hydrocarbon group having 1 or more carbon atoms represented by L B4 is the same as the definition of a divalent aliphatic hydrocarbon group having 1 or more carbon atoms represented by L B2.
• LB4 represents a single bond or a divalent aliphatic hydrocarbon group having 1 or more carbon atoms.
• LB3 each independently represents a single bond or a divalent linking group.
• Cf independently represents a fluorine atom-containing alkyl group. Defining L B3, L B4 and Cf are as described above.
• the structure of the main chain of the repeating unit having a group represented by the formula (1) is not particularly limited, and known structures can be mentioned.
• (meth) acrylic type, styrene type, siloxane type, cycloolefin type, and methyl A skeleton selected from the group consisting of penten-based, amide-based, and aromatic ester-based is preferred.
• a skeleton selected from the group consisting of (meth) acrylic type, siloxane type, and cycloolefin type is more preferable, and (meth) acrylic type skeleton is further preferable.
• (meth) acrylic is a general term for acrylic and methacrylic.
• the repeating unit represented by the formula (B) is preferable because the effect of the present invention is more excellent.
• RB1 represents a hydrogen atom or a substituent.
• Kind of substituent represented by R B1 is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R B2. Of these, an alkyl group having 1 to 3 carbon atoms is preferable.
• the definitions of LB1 , X, Y and n in the formula (B) are the same as the definitions of LB1 , X, Y and n in the formula (1).
• the repeating unit having a group represented by the formula (1) the repeating unit represented by the formula (E) is preferable.
• the definition of RB1 in the formula (E) is the same as the definition of LB1 in the formula (1).
• Z in the formula (E) represents a group represented by any of the formulas (B4) to (B8).
• repeating unit having a group represented by the formula (1) include the following.
• the content of the repeating unit having a group represented by the formula (1) in the photo-oriented polymer is not particularly limited, and the effect of the present invention is more excellent with respect to all the repeating units of the photo-oriented polymer.
• 3% by mass or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 20% by mass or more is particularly preferable, 95% by mass or less is preferable, 80% by mass or less is more preferable, and 60% by mass or less. Is more preferable, 50% by mass or less is particularly preferable, and 30% by mass or less is most preferable.
• Photo-oriented polymers have repeating units with photo-oriented groups.
• a photo-oriented group is a group having a photo-alignment function in which rearrangement or an anisotropic chemical reaction is induced by irradiation with anisotropic light (for example, planar polarization), and the uniformity of orientation.
• a photo-oriented group in which at least one of dimerization and anisotropy is generated by the action of light is preferable from the viewpoint of excellent thermal stability and good chemical stability.
• photo-oriented groups that dimerize by the action of light include cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., Vol. 31, No. 7, page 2155 (1992)) and coumarins. Derivatives (M. Schadt et al., Nature., Vol. 381, page 212 (1996)), coumarin derivatives (Toshihiro Ogawa et al., Proceedings of the LCD Discussion Meeting, 2AB03 (1997)), maleimide derivatives, and benzophenone derivatives.
• Preferred examples include groups having a skeleton of at least one derivative selected from the group consisting of (YK Jang et al., SID Int. Symposium Digest, P-53 (1997)).
• examples of photo-oriented groups that are isomerized by the action of light include azobenzene compounds (K. Ichimura et al., Mol. Cryst. Liq. Cryst., 298, 221 (1997)) and stillben compounds (JG Victor and). JMTorkelson, Macromolecules, 20, 2241 (1987)), Spiropyran compounds (K. Ichimura et al., Chemistry Letters, page 1063 (1992); K. Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993) )), Ceramic acid compounds (K.
• a group having a skeleton of at least one derivative selected from the group consisting of a cinnamic acid derivative, a coumarin derivative, a chalcone derivative and a maleimide derivative, an azobenzene compound, a stilben compound, and a spiropyran compound is preferable.
• a group having a cinnamic acid derivative skeleton or a coumarin derivative skeleton is more preferable.
• the structure of the main chain of the repeating unit having a photo-oriented group is not particularly limited, and known structures can be mentioned.
• a skeleton selected from the group consisting of aromatic esters are preferred.
• a skeleton selected from the group consisting of (meth) acrylic type, siloxane type, and cycloolefin type is more preferable, and (meth) acrylic type skeleton is further preferable.
• the repeating unit represented by the formula (A) is preferable because the effect of the present invention is more excellent.
• RA1 represents a hydrogen atom or a methyl group.
• LA1 represents a single bond or a divalent linking group.
• Definition of the divalent linking group represented by L A1 is the same as the definition of the divalent linking group represented by L B3 described above.
• the divalent linking group represented by L A1 in that the effect of the present invention is more excellent, linear and having 1 carbon atoms which may 10 have a substituent, 3 carbon atoms, A branched alkylene group of 10 or a cyclic alkylene group having 3 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms which may have a substituent, -O-, -CO-, and -N (Q). It is preferably a divalent linking group in which at least two or more groups selected from the group consisting of ⁇ are combined.
• Q represents a hydrogen atom or a substituent.
• Substituents that the alkylene group and arylene group may have, and the substituent represented by Q include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and a carboxy group. , Alkoxycarbonyl group, and hydroxyl group.
• the divalent linking group represented by A1 as mentioned above, linear and having 1 carbon atoms which may 10 have a substituent, having 3 to 10 branched or number of carbon-carbon
• a cyclic alkylene group of 3 to 10 and an arylene group having 6 to 12 carbon atoms which may have a substituent may be mentioned as a combination option.
• Examples of the linear alkylene group having 1 to 10 carbon atoms, a branched chain having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent are described above. Examples thereof include linear, branched, or cyclic alkylene groups described for divalent aliphatic hydrocarbon groups.
• Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and a phenylene group is preferable.
• a straight-chain alkylene group of having 1 carbon atoms which may 10 have a substituent have a substituent
• a divalent linking group containing at least one of a cyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms which may have a substituent is preferable.
• an unsubstituted linear alkylene group having 2 to 6 carbon atoms or a divalent linking group containing an unsubstituted trans-1,4-cyclohexylene is further preferable.
• a divalent linking group containing at least a linear alkylene group having 1 to 10 carbon atoms which may have a substituent and a cyclic cyclic group having 3 to 10 carbon atoms which may have a substituent may be used. Comparing with a divalent linking group containing at least an alkylene group, the effect is more excellent in the case of a divalent linking group containing at least a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent.
• R A2 , R A3 , R A4 , R A5 and R A6 each independently represent a hydrogen atom or a substituent.
• Type of the substituent is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R B2.
• R A2 , R A3 , R A4 , R A5 and R A6 two adjacent groups may be bonded to form a ring.
• the halogen atom and the linear, branched or cyclic group having 1 to 20 carbon atoms are independently provided in that the effect of the present invention is more excellent.
• Alkyl group, linear alkyl halide group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, cyano group, amino A group or a group represented by the following formula (3) is preferable.
• * represents a coupling position.
• RA7 represents a linear or cyclic alkyl group having 1 to 20 carbon atoms.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
• the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, for example, a methyl group, an ethyl group, and an alkyl group. , N-propyl group.
• an alkyl group having 3 to 6 carbon atoms is preferable, and examples thereof include an isopropyl group and a tert-butyl group.
• the cyclic alkyl group an alkyl group having 3 to 6 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.
• a fluoroalkyl group having 1 to 4 carbon atoms is preferable, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluoro group.
• a butyl group is mentioned, and a trifluoromethyl group is preferable.
• an alkoxy group having 1 to 20 carbon atoms an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 3 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 18 carbon atoms is further preferable.
• methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetradecyloxy group can be mentioned. Be done.
• the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
• the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group.
• amino group examples include a primary amino group (-NH 2 ); a secondary amino group such as a methylamino group; a dimethylamino group, a diethylamino group, a dibenzylamino group, and a nitrogen-containing heterocyclic compound (for example). , Pyrrolidine, piperidine, piperazine, etc.), such as a tertiary amino group having a nitrogen atom as a bond.
• Photoaligning group is likely to interact with the liquid crystal compound from the viewpoint of liquid crystal alignment property becomes excellent, among the R A2, R A3, R A4, R A5 and R A6 in the formula (A), at least R It is preferable that A4 represents the above-mentioned substituent (preferably an alkoxy group having 1 to 20 carbon atoms), and further, the linearity of the obtained photo-oriented polymer is improved, and it becomes easier to interact with the liquid crystal compound. , because the liquid crystal orientation becomes better, R A2, R A3, and more preferably R A5 and R A6 represents either hydrogen atoms.
• R A4 in the formula (A) is an electron donating substituent.
• the electron-donating substituent means a substituent having a Hammett value (Hammett substituent constant ⁇ p) of 0 or less, and for example, among the above-mentioned substituents, an alkyl group, Examples thereof include an alkyl halide group and an alkoxy group.
• an alkoxy group is preferable, an alkoxy group having 4 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 18 carbon atoms is further preferable, and an alkoxy group having 8 to 18 carbon atoms is preferable from the viewpoint of better liquid crystal orientation.
• Alkoxy groups are particularly preferred.
• the repeating unit having a photo-oriented group include the following.
• Me represents a methyl group and Et represents an ethyl group.
• the "1,4-cyclohexyl group" contained in the divalent linking group such as A-31 may be either a cis form or a trans form, but it must be a trans form. Is preferable.
• the content of the repeating unit having a photo-oriented group in the photo-oriented polymer is not particularly limited, and 5 to 60% by mass with respect to all the repeating units of the photo-oriented polymer in that the effect of the present invention is more excellent. Is preferable, 10 to 50% by mass is more preferable, and 15 to 40% by mass is further preferable.
• the photooriented polymer may have a repeating unit other than the repeating unit described above.
• the photooriented polymer may further have repeating units with crosslinkable groups.
• the type of the crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups. Of these, a cationically polymerizable group or a radically polymerizable group is preferable because it has excellent adhesion to the upper layer arranged on the binder layer.
• Examples of the cationically polymerizable group include an epoxy group, an epoxycyclohexyl group, and an oxetanyl group, and a group represented by any of formulas (C1) to (C3) is preferable. * In the formulas (C1) to (C3) represents the bonding position.
• RC2 represents a hydrogen atom, a methyl group, or an ethyl group.
• Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group, and a group represented by the formula (C4) is preferable. * In the formula (C4) represents the bonding position.
• RC3 represents a hydrogen atom or a methyl group.
• the structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and known structures can be mentioned.
• a skeleton selected from the group consisting of aromatic esters is preferred.
• a skeleton selected from the group consisting of (meth) acrylic type, siloxane type, and cycloolefin type is more preferable, and (meth) acrylic type skeleton is further preferable.
• the repeating unit represented by the formula (C) is preferable because the effect of the present invention is more excellent.
• RC1 represents a hydrogen atom or a substituent.
• Kind of substituent represented by R C1 is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R C1. Examples of the substituent represented by R C1, alkyl groups are preferred.
• LC1 represents a single bond or a divalent linking group.
• Definition of the divalent linking group represented by L C1 has the same definition of the divalent linking group represented by L B3 described above.
• the divalent linking group represented by L C1 in that the effect of the present invention is more excellent, linear and having 1 carbon atoms which may 10 have a substituent group, branched or At least two or more selected from the group consisting of a cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, -O-, -CO-, and -N (Q)-. It is preferably a divalent linking group in which groups are combined.
• the LC2 represents an m + 1 valent linking group.
• the m + 1-valent linking group is an m + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent and is a carbon constituting the hydrocarbon group because the effect of the present invention is more excellent.
• a hydrocarbon group in which a part of the atom may be substituted with a hetero atom is preferable, and an aliphatic hydrocarbon group which may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.
• the number of carbon atoms contained in the m + 1 valent linking group is not particularly limited, and 1 to 24 is preferable, and 1 to 10 is more preferable in that the effect of the present invention is more excellent.
• a divalent linking group is preferable.
• the definition of a divalent linking group is the same as the definition of a divalent linking group represented by LB3 described above.
• the divalent linking group is -CO-O- (which may have a substituent and has 1 to 10 carbon atoms (preferably 1 to 5).
• Z represents a crosslinkable group.
• the definition of the crosslinkable group is as described above.
• m represents an integer of 1 or more. Among them, an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 is further preferable, in that the effect of the present invention is more excellent.
• repeating unit having a crosslinkable group examples include the following.
• the content of the repeating unit having a crosslinkable group in the photo-oriented polymer is not particularly limited, and 10 to 60% by mass is added to all the repeating units of the photo-oriented polymer in that the effect of the present invention is more excellent. Preferably, 20 to 50% by mass is more preferable.
• the content a of the repeating unit having a group represented by the above formula (1), the content b of the repeating unit having the above-mentioned photooriented group, and the content c of the repeating unit having the above-mentioned crosslinkable group is satisfied in terms of mass ratio because the effect of the present invention is more excellent. 0.03 ⁇ a / (a + b + c) ⁇ 0.5 ... (D1)
• Examples of the monomer (radical polymerizable monomer) forming other repeating units other than the above include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and the like. And vinyl compounds.
• the method for synthesizing the photoalignable polymer is not particularly limited, and for example, a monomer forming a repeating unit having a group represented by the above formula (1), a monomer forming a repeating unit having a photoreactive group described above, and the like. It can also be synthesized by mixing monomers forming any other repeating unit and polymerizing them in an organic solvent with a radical polymerization initiator.
• the weight average molecular weight (Mw) of the photo-oriented copolymer of the present invention is not particularly limited, and is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and further 30,000 to 150,000 in that the effect of the present invention is more excellent. preferable.
• the weight average molecular weight and the number average molecular weight in the present invention are values measured by the gel permeation chromatography (GPC) method under the conditions shown below.
• the binder composition of the present invention is a composition containing the photooriented polymer of the present invention, a binder, and a photoacid generator.
• the content of the photooriented polymer contained in the binder composition of the present invention is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder described later. More preferred.
• the content of the photoacid generator contained in the binder composition of the present invention is preferably 0.5 to 50 parts by mass, more preferably 2.5 to 25 parts by mass with respect to 100 parts by mass of the binder described later. preferable.
• binder The type of binder contained in the binder composition of the present invention is not particularly limited, and a resin that simply dries and solidifies so as to be composed of only a resin that does not have a polymerization reactivity (hereinafter, also referred to as "resin binder"). It may be a polymerizable compound.
• resin binder examples include epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ethylene ethyl acrylate resin, and acrylonitrile acrylate styrene copolymer.
• acrylonitrile styrene resin acrylonitrile polyethylene chloride styrene copolymer resin, ethylene vinegar resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, cellulose acetate resin , Fluorine resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic Acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic resin, methylpentene resin,
• polymerizable compound examples include an epoxy-based monomer, a (meth) acrylic-based monomer, and an oxetanyl-based monomer, and an epoxy-based monomer or a (meth) acrylic-based monomer is preferable. Moreover, you may use a polymerizable liquid crystal compound as a polymerizable compound.
• Examples of the epoxy group-containing monomer which is an epoxy-based monomer include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, and hydroquinone type epoxy resin.
• Naphthalene type epoxy resin biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, Dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glioxal type epoxy resin, alicyclic Examples thereof include a type epoxy resin and a heterocyclic epoxy resin.
• the trifunctional monomer includes trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, and trimethylolpropane EO (ethylene oxide).
• tetrafunctional or higher functional monomer examples include pentaerythritol tetraacrylate, pentaerythritol tetramethritol, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. ..
• the polymerizable liquid crystal compound is not particularly limited, and examples thereof include compounds capable of any of homeotropic orientation, homogeneous orientation, hybrid orientation, and cholesteric orientation.
• liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes.
• a polymer generally refers to a polymer having a degree of polymerization of 100 or more (polymer physics / phase transition dynamics, by Masao Doi, p. 2, Iwanami Shoten, 1992).
• any liquid crystal compound can be used, but a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound) is preferable.
• a liquid crystal compound which is a monomer or has a relatively low molecular weight having a degree of polymerization of less than 100 is preferable.
• examples of the polymerizable group contained in the polymerizable liquid crystal compound include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.
• the rod-shaped liquid crystal compound for example, those described in claim 1 of JP-A No. 11-513019 or paragraphs [0026] to [00998] of JP-A-2005-289980 are preferable, and the discotic liquid crystal compound is preferably a discotic liquid crystal compound.
• the discotic liquid crystal compound is preferably a discotic liquid crystal compound.
• those described in paragraphs [0020] to [0067] of JP-A-2007-108732 or paragraphs [0013] to [0108] of JP-A-2010-2404038 are preferable.
• the polymerizable liquid crystal compound a liquid crystal compound having a reverse wavelength dispersion can be used.
• the liquid crystal compound having "reverse wavelength dispersibility" in the present specification is a retardation film produced using the liquid crystal compound, and the in-plane retardation (Re) value at a specific wavelength (visible light range) is measured. In this case, the Re value becomes equal or higher as the measurement wavelength becomes larger.
• the reverse wavelength dispersible liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersive film as described above, and is represented by, for example, the general formula (I) described in JP-A-2008-297210. (In particular, the compounds described in paragraphs [0034] to [0039]) and the compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraphs [0067] to [0073]. ], And the compounds represented by the general formula (1) described in JP-A-2016-081035 (particularly, the compounds described in paragraphs [0043] to [0055]).
• the binder composition of the present invention contains a photoacid generator.
• the photoacid generator is not particularly limited, and a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. Further, a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
• a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is more preferable.
• the agent is more preferred.
• pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured by changing to a solvent suitable for measurement. Specifically, pKa described in the Chemistry Handbook and the like can be referred to.
• As the acid having a pKa of 3 or less sulfonic acid or phosphonic acid is preferable, and sulfonic acid is more preferable.
• Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among them, an onium salt compound, an imide sulfonate compound, or an oxime sulfonate compound is preferable, and an onium salt compound or an oxime sulfonate compound is more preferable.
• the photoacid generator may be used alone or in combination of two or more.
• the binder composition of the present invention may contain components other than the above-mentioned photo-oriented polymer, binder, and photoacid generator.
• the binder composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator is not particularly limited, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator depending on the type of the polymerization reaction.
• a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
• the photopolymerization initiator include ⁇ -carbonyl compounds (described in US Pat. No. 2,376,661 and US Pat. No. 2,376,670), acidoin ether (described in US Pat. No.
• Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 35493667 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), and acyl. Examples thereof include phosphine oxide compounds (described in JP-A-63-040799, JP-A-5-209234, JP-A-10-095788, and JP-A-10-02997).
• the binder composition of the present invention preferably contains a solvent from the viewpoint of workability for forming the binder layer.
• Solvents include, for example, ketones (eg, acetone, 2-butanone, methylisobutylketone, and cyclohexanone), ethers (eg, dioxane, and tetrahydrofuran), aliphatic hydrocarbons (eg, hexane), fats.
• Cyclic hydrocarbons eg, cyclohexane
• aromatic hydrocarbons eg, toluene, xylene, and trimethylbenzene
• carbon halides eg, dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene
• esters Classes eg, methyl acetate, ethyl acetate, and butyl acetate
• water eg, ethanol, isopropanol, butanol, and cyclohexanol
• cellosolves eg, methyl cellosolve and ethyl cellosolve
• cellosolves eg, methyl cellosolve and ethyl cellosolve
• Examples thereof include acetates, sulfoxides (eg, dimethyl sulfoxide), and amides (eg, dimethylformamide, and dimethylacetamide).
• sulfoxides eg, dimethyl sulfoxide
• amides eg, dimethylformamide, and dimethylacetamide.
• One type of solvent may be used alone, or two or more types may be used in combination.
• the binder layer of the present invention is a layer formed by using the binder composition of the present invention described above, and the surface thereof has an orientation control ability. More specifically, the binder layer is a layer formed by generating an acid from a photoacid generator in a coating film of a binder composition and then performing a photoalignment treatment. That is, in the method of forming the binder layer, after generating an acid from the photoacid generator in the coating film obtained by using the above binder composition, the coating film is subjected to a photoalignment treatment to form the binder layer. It is preferable to have a step of forming (step 1).
• having an orientation control ability means having a function of orienting a liquid crystal compound arranged on a binder layer in a predetermined direction.
• the coating film obtained by using the above binder composition is subjected to a curing treatment, and then an acid is applied from the photoacid generator in the coating film. It is preferable to perform a treatment for generating the binder layer (hereinafter, also simply referred to as “acid generation treatment”) and then perform a photoalignment treatment to form a binder layer.
• the hardening treatment and the acid generation treatment may be carried out at the same time.
• the method of carrying out the above curing treatment will be described in detail.
• the method for forming the coating film of the binder composition is not particularly limited, and examples thereof include a method of applying the binder composition on the support and subjecting it to a drying treatment as necessary.
• the support will be described in detail later. Further, an orientation layer may be arranged on the support.
• the method of applying the binder composition is not particularly limited, and examples of the application method include a spin coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a die coating method. Can be mentioned.
• the coating film of the binder composition is subjected to a curing treatment and a treatment of generating an acid from the photoacid generator in the coating film (hereinafter, also referred to as "acid generation treatment").
• the curing treatment include light irradiation treatment and heat treatment.
• the conditions of the curing treatment are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. Irradiation dose is preferably 10mJ / cm 2 ⁇ 50J / cm 2, more preferably 20mJ / cm 2 ⁇ 5J / cm 2, more preferably 30mJ / cm 2 ⁇ 3J / cm 2, particularly 50 ⁇ 1000mJ / cm 2 preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.
• the treatment for generating an acid from the photoacid generator in the coating film is a treatment for generating the acid by irradiating the light that the photoacid generator contained in the binder composition is exposed to.
• the light irradiation treatment carried out in the above treatment may be any treatment in which the photoacid generator is exposed to light, and examples thereof include a method of irradiating ultraviolet rays.
• a lamp that emits ultraviolet rays such as a high-pressure mercury lamp and a metal halide lamp can be used.
• the irradiation amount is preferably 10mJ / cm 2 ⁇ 50J / cm 2, more preferably 20mJ / cm 2 ⁇ 5J / cm 2, more preferably 30mJ / cm 2 ⁇ 3J / cm 2, 50 ⁇ 1000mJ / cm 2 Is particularly preferable.
• the acid generation treatment may be carried out after the hardening treatment is carried out, or the hardening treatment and the acid generation treatment may be carried out at the same time.
• the photoacid generator and the polymerization initiator in the binder composition are exposed to light of the same wavelength, it is preferable to carry out the process at the same time from the viewpoint of productivity.
• the method of photoalignment treatment performed on the coating film of the binder composition formed above is not particularly limited, and known methods are available. Can be mentioned.
• the photoalignment treatment for example, the coating film of the binder composition (including the cured film of the binder composition that has been cured) is irradiated with polarized light or non-polarized light from an oblique direction with respect to the coating film surface. There is a way to do it.
• the polarized light to be irradiated is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light, and linearly polarized light is preferable.
• the "diagonal direction" for irradiating non-polarized light is not particularly limited as long as it is tilted by a polar angle ⁇ (0 ⁇ ⁇ 90 °) with respect to the normal direction of the coating film surface, depending on the purpose. It can be appropriately selected, but the ⁇ is preferably 20 to 80 °.
• the wavelength in polarized light or unpolarized light is not particularly limited as long as it is light to which the photoaligning group is sensitive, and examples thereof include ultraviolet rays, near-ultraviolet rays, and visible light, and near-ultraviolet rays having a diameter 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, and a metal halide lamp.
• an interference filter, a color filter, or the like for ultraviolet rays or visible light obtained from such a light source the wavelength range to be irradiated can be limited.
• linearly polarized light can be obtained by using a polarizing filter or a polarizing prism with respect to the light from these light sources.
• the amount of polarized or unpolarized integrated light is not particularly limited, and is preferably 1 to 300 mJ / cm 2 and more preferably 5 to 100 mJ / cm 2 .
• the illuminance of the polarized light or unpolarized light is not particularly limited, preferably 0.1 ⁇ 300mW / cm 2, more preferably 1 ⁇ 100mW / cm 2.
• the thickness of the binder layer is not particularly limited, and is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m, in that the effect of the present invention is more excellent.
• the optical laminate of the present invention has a binder layer of the present invention and an optically anisotropic layer provided on the binder layer.
• an optically anisotropic layer provided on the binder layer is formed by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and also.
• An embodiment in which the binder layer and the optically anisotropic layer are laminated adjacent to each other can be mentioned.
• the optical laminate of the present invention preferably has a support that supports the binder layer.
• Examples of the support include a glass substrate and a polymer film.
• Materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and polyethylene na.
• Polyester-based polymers such as phthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers; polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers;, vinyl chloride-based polymers; nylon, aromatic polyamides, etc.
• the thickness of the support is not particularly limited, and is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and even more preferably 20 to 90 ⁇ m.
• the binder layer is the binder layer of the present invention described above.
• the optically anisotropic layer is preferably formed using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.
• a polymerizable liquid crystal composition for forming the optically anisotropic layer for example, a composition containing the polymerizable liquid crystal compound described as an optional component in the binder composition of the present invention, a polymerization initiator, a solvent and the like. Things can be mentioned.
• the thickness of the optically anisotropic layer is not particularly limited, and is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
• the method for producing an optical laminate of the present invention is a method for producing a preferred embodiment of the optical laminate of the present invention described above, and generates acid from a photoacid generator in a coating film obtained by using the binder composition. After that, the coating film is subjected to photoalignment treatment to form a binder layer (step 1), and a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound is applied onto the binder layer to obtain optics. It has a step (step 2) of forming an anisotropic layer.
• Step 1 is a step of generating an acid from a photoacid generator in a coating film obtained by using the binder composition, and then performing a photoalignment treatment on the coating film to form a binder layer.
• the procedure of step 1 is as described above.
• Step 2 is a step of applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on the binder layer to form an optically anisotropic layer.
• the method for applying the polymerizable liquid crystal composition is not particularly limited, and examples thereof include the coating method exemplified in step 1.
• Examples of the method for forming the optically anisotropic layer include a method in which a coating film of a polymerizable liquid crystal composition is heat-treated and then cured.
• the polymerizable liquid crystal compound can be oriented by the above heat treatment.
• the heat treatment and the hardening treatment are carried out separately, but a method of carrying out the hardening treatment under heating conditions may also be used.
• the heat treatment may not be performed. After heating the coating film, if necessary, the coating film may be cooled before the curing treatment described later.
• the conditions of the heat treatment are not particularly limited, and may be any temperature as long as the polymerizable liquid crystal compound is oriented.
• the heating temperature is usually preferably 30 to 100 ° C, more preferably 50 to 80 ° C.
• the heating time is preferably 0.5 to 20 minutes, more preferably 1 to 5 minutes.
• the method of the curing treatment is not particularly limited, and examples thereof include light irradiation treatment and heat treatment, and light irradiation treatment is preferable. Ultraviolet rays are preferable as the light in the light irradiation treatment.
• the conditions for light irradiation are not particularly limited, and the irradiation amount is preferably 10 mJ / cm 2 to 50 J / cm 2, more preferably 20 mJ / cm 2 to 5 J / cm 2 , and 30 mJ / cm 2 to 3 J / cm. 2 is more preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.
• the image display device of the present invention is an image display device having the optically anisotropic layer of the present invention or the optical laminate of the present invention.
• the display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel. Of these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element or an organic EL display device using an organic EL display panel as a display element is preferable.
• the liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-mentioned optically anisotropic layer of the present invention or the optical laminate of the present invention and a liquid crystal cell.
• the liquid crystal cells constituting the liquid crystal display device will be described in detail below.
• the liquid crystal cell used in the liquid crystal display device is preferably a VA (Victorial Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic) mode. It is not limited to these.
• the rod-shaped liquid crystal molecules (rod-shaped liquid crystal compounds) are substantially horizontally oriented when no voltage is applied, and are further twisted to 60 to 120 °.
• the TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and has been described in many documents.
• the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied.
• VA mode liquid crystal cell (1) a VA mode liquid crystal cell in a narrow sense in which rod-shaped liquid crystal molecules are oriented substantially vertically when no voltage is applied and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. 2-). In addition to (described in Japanese Patent Application Laid-Open No. 176625), (2) a liquid crystal cell (SID97, Digist of technique.
• VA Multi-dominant Vertical Alginment
• n-ASM Analy cyclic aligned microcell
• the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a plane by applying an electric field parallel to the substrate surface.
• black is displayed when no electric field is applied, and the absorption axes of the pair of upper and lower polarizing plates are orthogonal to each other.
• JP-A-10-054982 JP-A-11-202323, and JP-A-9-292522. It is disclosed in JP-A-11-133408, JP-A-11-305217, and JP-A-10-307291.
• Organic EL display device As the organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, the polarizer, the optically anisotropic layer of the present invention or the optical laminate of the present invention, and the organic EL display panel are used. Aspects having in order are preferably mentioned.
• the polarizer is not particularly limited as long as it is a member having a function of converting light into specific linearly polarized light, and conventionally known absorption type polarizers and reflection type polarizers can be used.
• the absorption type polarizing element include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer.
• the iodine-based polarizing element and the dye-based polarizer include a coating type polarizing element and a stretching type polarizing element, and both can be applied.
• Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205 examples thereof include the methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486.
• the reflective polarizer examples include a polarizer in which thin films having different birefringence are laminated, a wire grid type polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined.
• a polymer containing a polyvinyl alcohol-based resin (-CH 2- CHOH- as a repeating unit.
• at least selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers in that the adhesion is more excellent.
• a polarizer containing (1) is preferable.
• the thickness of the polarizer is not particularly limited, and is preferably 3 to 60 ⁇ m, more preferably 5 to 30 ⁇ m, and even more preferably 5 to 15 ⁇ m.
• the organic EL display panel is a member in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode.
• a hole injection layer, a hole transport layer, and an electron injection It may have a layer, an electron transport layer, a protective layer, and the like, and each of these layers may have other functions.
• Various materials can be used to form each layer.
• Example 1 In a flask equipped with a cooling tube, a thermometer and a stirrer, 5.5 parts by mass of monomer mA-2 forming a repeating unit represented by the formula (A-2) described later, and 10 parts by mass of 2-butanone as a solvent. was charged, and the mixture was refluxed by heating in a water bath while flowing 5 mL / min of monomer into the flask.
• a solution prepared by mixing 0.062 parts by mass of azobis (isobutyronitrile) and 13 parts by mass of 2-butanone as a solvent was added dropwise over 3 hours, and the mixture was further stirred for 3 hours while maintaining the reflux state. After completion of the reaction, the mixture was allowed to cool to room temperature and diluted by adding 10 parts by mass of 2-butanone to obtain a polymer solution of about 20% by mass.
• the obtained polymer solution was poured into a large excess of methanol to precipitate the polymer, the recovered precipitate was filtered off, washed with a large amount of methanol, and then air-dried at 50 ° C. for 12 hours.
• a photo-oriented polymer P-1 was obtained.
• Examples 2-48 and Comparative Examples 1-2 As the monomers forming the repeating units shown in Tables 1 and 2 below, the same method as the photo-oriented polymer P-1 synthesized in Example 1 was used except that the following monomers capable of forming the repeating units were used. Photooriented polymers P-2-46 and H-1 to H-2 were synthesized. In addition, each symbol in Table 1 and Table 2 means the following. Further, n in B-14 represents 2.
• PETA Acrylic monomer (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• CEL2021P Epoxy monomer (manufactured by Daicel Corporation)
• Epolide GT401 manufactured by Daicel Corporation
• A-DPH Acrylic monomer (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• the weight average molecular weight of each of the synthesized polymers was measured by the method described above. The results are shown in Tables 1 and 2 below.
• a cellulose acylate film (TD40UL, manufactured by FUJIFILM Corporation) is passed through a dielectric heating roll having a temperature of 60 ° C. to raise the film surface temperature to 40 ° C., and then an alkaline solution having the following composition is applied to one side of the film. , The film was applied at a coating amount of 14 ml / m 2 using a bar coater, and heated to 110 ° C. Next, the obtained film was conveyed under a steam-type far-infrared heater manufactured by Noritake Co., Ltd. Limited for 10 seconds. Next, 3 ml / m 2 of pure water was applied to the obtained film using the same bar coater.
• the obtained film was washed with water by a fountain coater and drained with an air knife three times, and then transported to a drying zone at 70 ° C. for 10 seconds to be dried to prepare an alkali saponified cellulose acylate film.
• a drying zone at 70 ° C. for 10 seconds to be dried to prepare an alkali saponified cellulose acylate film.
• the alignment layer coating solution having the following composition was continuously applied to the long cellulose acetate film saponified as described above with a wire bar of # 14. After coating, the obtained film was dried with warm air at 60 ° C. for 60 seconds, and further dried with warm air at 100 ° C. for 120 seconds.
• polymerization initiator (IN1)" represents a photopolymerization initiator (IRGACURE2959, manufactured by BASF).
• the dried coating film was continuously subjected to a rubbing treatment to form an oriented layer. At this time, the longitudinal direction of the long film and the conveying direction were parallel, and the rotation axis of the rubbing roller with respect to the longitudinal direction of the film was set to a direction of 45 ° clockwise.
• the prepared binder composition was applied onto the alignment layer with a # 3.0 wire bar.
• the obtained coating film is heated at 70 ° C. for 2 minutes, cooled to 40 ° C., and then irradiated with a 365 nm UV-LED while purging nitrogen so that the oxygen concentration becomes 1.0% by volume or less. An amount of 500 mJ / cm 2 of ultraviolet rays was irradiated. Then, the obtained film was anilized at 120 ° C. for 1 minute to prepare a cured layer.
• the film thickness was about 1 ⁇ m.
• the surface energy of the cured layer was 50 mN / m.
• the obtained cured layer is irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) through a wire grid polarizer at room temperature at 25 mJ / cm 2 (wavelength: 313 nm) to impart an orientation function to the cured layer.
• UV light ultra-high pressure mercury lamp; UL750; manufactured by HOYA
• wire grid polarizer at room temperature at 25 mJ / cm 2 (wavelength: 313 nm) to impart an orientation function to the cured layer.
• a binder layer was formed.
• the above-mentioned solution for forming an optically anisotropic layer was applied with a wire bar coater # 2.2 on the binder layer to which the above-mentioned orientation function was imparted.
• the obtained coating film was heated at 60 ° C. for 2 minutes, and while maintaining the temperature at 60 ° C., a 160 W / cm air-cooled metal halide lamp (eye graphic) was purged with nitrogen so that the oxygen concentration became 1.0% by volume or less.
• An optically anisotropic layer was prepared by irradiating ultraviolet rays having an irradiation volume of 300 mJ / cm 2 using a product manufactured by Su Co., Ltd.
• photo-oriented polymers P-2 to P-46 and H-1 to H-2 are used instead of the photo-oriented polymers P-1, and the liquid crystal compounds L1 to L4 are substituted.
• the type of the liquid crystal compound in the binder layer forming composition was changed, and as shown in Tables 1 and 2, a cross-linking agent (polymerizable compound) was added to the binder composition as needed.
• An optical laminate was prepared according to the same procedure as above, except that it was further added to the product.
• the amount of the liquid crystal compound A used is 80 parts by mass and the amount of the liquid crystal compound B used is 20 parts by mass. It was. Further, when CEL2021P was used instead of the liquid crystal compounds L1 to L4 in the binder layer forming composition in Comparative Example 1, the amount of CEL2021P used was 100 parts by mass. The amount of the cross-linking agent (polymerizable compound) used in each example was 100 parts by mass.
• “Content a” in Tables 1 and 2 represents the content (mass%) of the repeating unit A with respect to all the repeating units of the photooriented polymer.
• “Content b” in Tables 1 and 2 represents the content (mass%) of the repeating unit B with respect to all the repeating units of the photooriented polymer.
• “Content c” in Tables 1 and 2 represents the content (mass%) of the repeating unit C with respect to all the repeating units of the photooriented polymer.
• the "binder” column in Tables 1 and 2 represents the type of binder contained in the binder layer forming composition.
• Example 49> In Example 1, instead of the liquid crystal compounds L1 to L4 in the composition for forming the binder layer, the liquid crystal compound A (80 parts by mass) and the liquid crystal compound B (20 parts by mass) are used for forming the optically anisotropic layer. Instead of liquid crystal compound A and liquid crystal compound B in the solution, liquid crystal compound L-1 (39 parts by mass), liquid crystal compound L-2 (39 parts by mass), liquid crystal compound L-3 (17 parts by mass), and liquid crystal. An optical laminate was prepared according to the same procedure as in each example except that the compound L-4 (5 parts by mass) was used. When the evaluation of the above ⁇ liquid crystal orientation> was carried out using the obtained optical laminate, "B" was obtained as a result similar to that of Example 1.
• Example 50> In Example 2, instead of the liquid crystal compounds L1 to L4 in the composition for forming the binder layer, the liquid crystal compound A (80 parts by mass) and the liquid crystal compound B (20 parts by mass) are used for forming the optically anisotropic layer. Instead of liquid crystal compound A and liquid crystal compound B in the solution, liquid crystal compound L-1 (39 parts by mass), liquid crystal compound L-2 (39 parts by mass), liquid crystal compound L-3 (17 parts by mass), and liquid crystal.
• An optical laminate was prepared according to the same procedure as in each example except that the compound L-4 (5 parts by mass) was used. When the evaluation of the above ⁇ liquid crystal orientation> was carried out using the obtained optical laminate, "A" was obtained as a result similar to that of Example 2.
• Examples 50 to 94> In Examples 4 to 9 and 11 to 48, liquid crystal compound A (80 parts by mass) and liquid crystal compound B (20 parts by mass) were used instead of the liquid crystal compounds L1 to L4 in the binder layer forming composition, and the optics were used. Instead of liquid crystal compound A and liquid crystal compound B in the solution for forming an anisotropic layer, liquid crystal compound L-1 (39 parts by mass), liquid crystal compound L-2 (39 parts by mass), liquid crystal compound L-3 (17 parts by mass). Parts) and the liquid crystal compound L-4 (5 parts by mass) were used, and optical laminates were prepared according to the same procedure as in each example. When the above-mentioned ⁇ liquid crystal orientation> was evaluated using the obtained optical laminate, the evaluation "AA" was obtained in all the examples.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Nonlinear Science (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Mathematical Physics (AREA)
• Crystallography & Structural Chemistry (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Dispersion Chemistry (AREA)
• Liquid Crystal (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Polarising Elements (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=74684835

Family Applications (1)

Country Status (5)

Cited By (3)

Citations (2)

Family Cites Families (4)

• 2020
  • 2020-08-25 CN CN202080060218.XA patent/CN114364711B/zh active Active
  • 2020-08-25 KR KR1020227005902A patent/KR102761797B1/ko active Active
  • 2020-08-25 WO PCT/JP2020/032063 patent/WO2021039803A1/ja not_active Ceased
  • 2020-08-25 JP JP2021542944A patent/JP7228049B2/ja active Active
• 2022
  • 2022-02-22 US US17/677,955 patent/US20220179250A1/en not_active Abandoned

Patent Citations (2)

Also Published As

Similar Documents

Legal Events