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
  • C08F220/22—Esters containing halogen
  • C08F220/24—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
  • 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
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
• • 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

Definitions

• liquid crystal orientation In recent years, in an optically anisotropic layer formed by using a liquid crystal compound, further improvement in the orientation of the liquid crystal compound (hereinafter, also abbreviated as "liquid crystal orientation”) is required.
• the present inventors have studied the photo-oriented polymer described in Patent Document 1, and found that the liquid crystal alignment of the optically anisotropic layer provided on the upper layer of the layer formed by using the photo-oriented polymer. It was found that the sex meets the conventional demand level, but further improvement is needed to meet the higher demand level these days.
• the present invention relates to a photo-oriented polymer, a binder composition, a binder layer, an optical laminate, an optical laminate, and an image capable of improving the liquid crystal orientation of the optically anisotropic layer provided on the upper layer.
• An object is to provide a display device.
• a repeating unit A containing a photo-oriented group and It has a repeating unit D containing a cleaving group that decomposes to form a crosslinkable group by the action of at least one selected from the group consisting of light, heat, acid and base.
• the crosslinkable group is a self-crosslinkable crosslinkable group or a crosslinkable group that reacts with a hydroxyl group, an amino group, a carboxy group or an amide group to form a chemical bond.
• a photooriented polymer in which the repeating unit D has the cleaving group in the side chain and a fluorine atom or a silicon atom on the terminal side of the cleaving group in the side chain.
• [12] The photooriented polymer according to any one of [1] to [11], which has a weight average molecular weight of 10,000 to 500,000.
• a binder composition comprising the photo-oriented polymer according to any one of [1] to [12], a binder, and a photoacid generator.
• a binder layer formed by using the binder composition according to [13], the surface of which has an orientation control ability.
• a method for producing an optical laminate comprising 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.
• a photo-alignable polymer a binder composition, a binder layer, an optical laminate, a method for producing an optical laminate, and an image capable of improving the liquid crystal orientation of the optically anisotropic layer provided on the upper layer.
• a display device can be provided.
• the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
• a substance corresponding to each component may be used alone or in combination of two or more.
• the content of the component means the total content of the substances used in combination unless otherwise specified.
• (meth) acrylic is a notation representing "acrylic" or "methacryl”.
• 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".
• L 2 is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.
• the photo-oriented polymer of the present invention is a cleaving group that decomposes by the action of at least one selected from the group consisting of a repeating unit A containing a photo-oriented group and a group consisting of light, heat, acid and a base to form a crosslinkable group. It is a photo-oriented copolymer having a repeating unit D containing. Further, in the photoorientable polymer of the present invention, the crosslinkable group is a self-crosslinkable group or a crosslinkable group that reacts with a hydroxyl group, an amino group, a carboxy group or an amide group to form a chemical bond. Is.
• the repeating unit D is a repeating unit having the cleaving group in the side chain and having a fluorine atom or a silicon atom on the terminal side of the cleaving group in the side chain.
• liquid crystal orientation of the optically anisotropic layer provided on the upper layer
• a composition containing the photo-oriented polymer of the present invention is applied to form a layer such as a binder layer. It will be unevenly distributed on the side. Then, at least one selected from the group consisting of light, heat, acid and base is allowed to act on the photooriented polymer of the present invention unevenly distributed on the air interface side to decompose the cleaving group contained in the side chain.
• the photo-oriented polymer of the present invention has improved solvent resistance due to the presence of a crosslinkable group as a residue as compared with the photo-oriented polymer described in Patent Document 1, and as a result, the orientation is relaxed. Since it is suppressed, it is considered that the liquid crystal orientation of the optically anisotropic layer provided on the upper layer is improved.
• the photo-oriented polymer of the present invention has a repeating unit A containing a photo-oriented group.
• a photo-oriented group is a group having a photo-alignment function in which rearrangement or an heterogeneous chemical reaction is induced by irradiation with light having anisotropy (for example, planar polarization), and the uniformity of orientation.
• a photo-oriented group that produces at least one of dimerization and isomerization by the action of light is preferable because of its excellent thermal stability and good chemical stability.
• the photo-oriented group that dimerizes by the action of light for example, a group having a skeleton of at least one derivative selected from the group consisting of a lauric acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, and a benzophenone derivative. Etc. are preferably mentioned.
• the photo-oriented group that is isomerized by the action of light at least one selected from the group consisting of, for example, an azobenzene compound, a stilbene compound, a spiropyran compound, a cinnamic acid compound, and a hydrazono- ⁇ -ketoester compound.
• a group having a skeleton of a compound and the like are preferably mentioned.
• a group having a skeleton of at least one compound selected from the above is preferable, and 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 A containing a photo-oriented group is not particularly limited, and known structures can be mentioned.
• (meth) acrylic, styrene-based, siloxane-based, cycloolefin-based, methylpentene-based, and amide are examples.
• a skeleton selected from the group consisting of a system and an aromatic ester system is preferable.
• a skeleton selected from the group consisting of (meth) acrylic, siloxane, and cycloolefin is more preferable, and (meth) acrylic skeleton is even more preferable.
• the repeating unit A containing a photo-oriented group the repeating unit represented by the following formula (A) is preferable because the liquid crystal orientation becomes better.
• RA1 represents a hydrogen atom or a substituent.
• LA1 represents a single bond or a divalent linking group.
• RA2 , RA3 , RA4 , RA5 and RA6 each independently represent a hydrogen atom or a substituent. Of RA2 , RA3 , RA4 , RA5 and RA6 , two adjacent groups may be bonded to form a ring.
• RA1 represents a hydrogen atom or a substituent.
• the kind of the substituent represented by one embodiment of R A1 is not particularly limited, it includes known substituents.
• the substituent include a monovalent aliphatic hydrocarbon group and a monovalent aromatic hydrocarbon group, and more specifically, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and an amino group.
• LA1 represents a single bond or a divalent linking group.
• the divalent linking group represented by one embodiment of the L A1 for example, divalent or substituted hydrocarbon group, a divalent heterocyclic group, -O -, - S -, - N (Q)-, -CO-, or a group combining these can be mentioned.
• Q represents a hydrogen atom or a substituent.
• the divalent hydrocarbon group 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
• divalent heterocyclic group examples include a divalent aromatic heterocyclic group, and specific examples thereof include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, and thienylene (thiophene).
• pyridylene group pyridine-diyl group
• a pyridazine-diyl group an imidazole-diyl group
• thienylene thiophene
• Examples thereof include a group in which at least two or more kinds are combined selected from, for example, -O-2-valent hydrocarbon group-,-(O-2-valent hydrocarbon group) p- O- (p is 1 or more). (Representing an integer of), -2 valent hydrocarbon group-O-CO-, -CO-NH-2 valent hydrocarbon group-O-, and the like.
• the divalent linking group represented by one embodiment of the L A1 the liquid crystal reasons orientation becomes better, linear alkylene group having optionally ⁇ carbon atoms 1 be 10 substituted , A branched alkylene group having 3 to 10 carbon atoms which may have a substituent, a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, and a substituent.
• It is a divalent linking group that combines at least two or more groups selected from the group consisting of an arylene group having 6 to 12 carbon atoms, -O-, -CO-, and -N (Q)-. Is preferable.
• 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.
• a straight-chain alkylene group of having 1 carbon atoms which may 10 have a substituent 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.
• a group is more preferable, and an unsubstituted linear alkylene group having 2 to 6 carbon atoms or a divalent linking group containing an unsubstituted trans-1,4-cyclohexylene is even more 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.
• RA2 , RA3 , RA4 , RA5 and RA6 each independently represent a hydrogen atom or a substituent.
• Type of the substituent is not particularly limited, include known substituents, the groups exemplified in the substituents represented by the above embodiment of R A1, and the like.
• RA2 , RA3 , RA4 , RA5 and RA6 two adjacent groups may be bonded to form a ring.
• RA2 , RA3 , RA4 , RA5 and RA6 have a halogen atom, a linear alkyl group having 1 to 20 carbon atoms, and a carbon number of carbons, respectively, for the reason that the liquid crystal orientation is better.
• a aryloxy group, a hydroxy group, a cyano group, an amino group, or a group represented by the following formula (4) of 20 is preferable.
• the substituent may contain a linking group represented by ⁇ (CH 2 ) na ⁇ or —O— (CH 2 ) na ⁇ .
• na represents an integer from 1 to 10.
• * represents a bonding position.
• RA7 represents a monovalent organic group.
• 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.
• an alkyl group having 1 to 6 carbon atoms is preferable, and examples thereof include a methyl group, an ethyl group, and an 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, and 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.
• Examples of the monovalent organic group represented by RA7 in the above formula (4) include an alkyl group having 1 to 20 carbon atoms, which is a linear group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms.
• Alkyl group of is preferably mentioned.
• the linear alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group, and a methyl group or an ethyl group is used. preferable.
• the cyclic alkyl group having 3 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclohexyl group is preferable.
• the monovalent organic group represented by RA7 in the above formula (4) may be a combination of a plurality of the above-mentioned linear alkyl group and cyclic alkyl group directly or via a single bond. good.
• 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.
• repeating unit A including a photo-oriented group examples include the following.
• the content of the repeating unit A in the photo-oriented polymer of the present invention is not particularly limited, and 5 to 50% by mass is based on all the repeating units of the photo-oriented polymer for the reason that the liquid crystal orientation becomes better. It is preferable, 10 to 40% by mass is more preferable.
• the photo-oriented polymer of the present invention has a repeating unit D containing a cleaving group which is decomposed by the action of at least one selected from the group consisting of light, heat, acid and base to form a crosslinkable group.
• the repeating unit D is a repeating unit having the cleaving group in the side chain and having a fluorine atom or a silicon atom on the terminal side of the cleaving group in the side chain.
• crosslinkable group that forms a chemical bond.
• self-crosslinkable crosslinkable group refers to a group that can be bonded to each other to form a crosslinked structure, but groups having the same structure are bonded to each other to form a crosslinked structure. Not only the case but also the case where groups having different structures are bonded to each other to form a crosslinked structure is included.
• the cleavage group is a group containing a partial structure having an amide bond, a methylene group and an ether bond in this order.
• the bond between the methylene group and the ether bond is decomposed by the action of the acid, and the cross-linking group from which the ether bond is eliminated (hereinafter, abbreviated as "cross-linking group A” in this paragraph) and amide.
• the bond between the bond and the methylene group is decomposed to form a cross-linking group from which the methylene group and the ether bond are eliminated (hereinafter, abbreviated as "cross-linking group B" in this paragraph).
• cross-linking group A and the cross-linking group B can be bonded to each other to form a cross-linked structure, it can be said that they are self-cross-linking cross-linking groups. Further, since the cross-linking group A can also react with an alcohol to form a chemical bond, it can be said that the cross-linking group A is a cross-linking group that reacts with a hydroxyl group to form a chemical bond.
• the repeating unit D contains a group represented by the following formula (1).
• RD1 represents a hydrogen atom or an alkyl group.
• L D represents r + 1 valent connecting group.
• M represents a group containing a fluorine atom or a silicon atom.
• r represents an integer of 1 to 4, and when it is an integer of 2 to 4, the plurality of Ms may be the same or different. * Represents the bond position.
• RD1 represents a hydrogen atom or an alkyl group.
• the alkyl group represented by an embodiment of R D1 for example, straight-chain alkyl group having 1 to 18 carbon atoms, preferably branched or cyclic alkyl group having 3 to 18 carbon atoms, having 1 to 4 carbon atoms Linear alkyl groups are more preferred, and methyl or ethyl groups are even more preferred.
• L D represents r + 1 valent connecting group.
• the r + 1-valent linking group is an r + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent for the reason that the liquid crystal orientation becomes better, and constitutes a hydrocarbon group.
• a hydrocarbon group in which a part of the carbon 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 r + 1 valent linking group is not particularly limited, and 1 to 24 is preferable, and 1 to 10 is more preferable, for the reason that the liquid crystal orientation becomes better.
• a divalent linking group is preferable. Examples of the divalent linking group include the same as those exemplified for the divalent linking group represented by one aspect of LA1 in the above formula (A).
• M 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 is preferably 1 to 30 and more preferably 5 to 25 because the liquid crystal orientation is better. ⁇ 20 is more preferable.
• 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, 3 to 20 is more preferable, and 5 to 10 is further preferable, for the reason that the liquid crystal orientation becomes better.
• 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 (3) * -L D2 -Cf L D2 represents a single bond or a divalent linking group.
• the divalent linking group represented by one embodiment of the L D2 for example, it includes the same ones exemplified for the divalent linking group represented by one embodiment of L A1 in the formula (A).
• the divalent linking group represented by one embodiment of the L D2 linear alkylene group of having 1 carbon atoms which may 10 have a substituent, having 3 to 10 branched or carbon
• a cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, -O-, -CO-, -N (Q)-, or a group in which these are combined is preferable, and a substituent is preferable.
• a linear alkylene group having 1 to 10 carbon atoms and a branched or cyclic alkylene group having 3 to 10 carbon atoms are more preferable.
• 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, 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 alkyl group.
• the fluorine atom-containing alkyl group represents an alkyl group containing a fluorine atom, and a perfluoroalkyl 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, 3 to 20 is more preferable, and 5 to 10 is further preferable, because the liquid crystal orientation becomes better.
• the number of fluorine atoms contained in the fluorine atom-containing alkyl group is not particularly limited, and is preferably 1 to 30, more preferably 5 to 25, and even more preferably 10 to 20 for the reason that the liquid crystal orientation becomes better.
• r represents an integer of 1 to 4. Among them, 1 or 2 is preferable, and 1 is more preferable, from the viewpoint of synthetic suitability.
• the repeating unit D is preferably a repeating unit represented by the following formula (D).
• RD2 represents a hydrogen atom or a substituent.
• R D1, L D, M and r in the formula (D) is the same as the respective definitions of R D1, L D, M and r in the formula (1).
• examples of the substituent represented by one aspect of R D2 include the groups exemplified by the substituent represented by one aspect of RA1 in the above formula (A). Of these, an alkyl group is preferable, and a methyl group is more preferable.
• repeating unit D including a cleavage group include the following.
• R represents a linear alkyl group having 1 to 20 carbon atoms or a branched-chain alkyl group having 3 to 10 carbon atoms
• n represents 0 to 10. Represents an integer of.
• the content of the repeating unit D in the photo-oriented polymer of the present invention is not particularly limited, and 5 to 95% by mass is based on all the repeating units of the photo-oriented polymer for the reason that the liquid crystal orientation becomes better. It is preferably 20 to 90% by mass, more preferably 20 to 90% by mass.
• the photooriented polymer of the present invention preferably has a repeating unit B containing a group represented by the following formula (2). Since the polar group generated after the cleavage of the cleavage group contained in the group represented by the following formula (2) reacts with the above-mentioned repeating unit D to improve the cleavage rate, the lower layer and the upper layer are formed under a wider production condition. Even in this case, the upper layer coating property and the liquid crystal orientation are good.
• the group represented by the following formula (2) contains a predetermined cleaving group as described later, and is cleaved by the action of an acid to dissociate the group containing a fluorine atom or a silicon atom. As well as producing, it produces polar groups.
• L B represents a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group - some or all -CO- or It may be replaced with —O—.
• X represents a cleavage group represented by any of the formulas (B1) to (B3) described later.
• Y represents a group containing a fluorine atom or a silicon atom.
• n represents an integer of 1 or more, and when it is an integer of 2 or more, the plurality of Xs may be the same or different, and the plurality of Ys may be the same or different. You may.
• * represents a bond position.
• L B represents a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group - some or all -CO- or - It may be replaced with O ⁇ .
• the number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and 1 to 10 is preferable, 1 to 5 is more preferable, and 1 to 3 is further preferable because the liquid crystal orientation becomes better.
• 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, a linear shape is preferable because the liquid crystal orientation becomes better.
• "a part or all of -CH 2- constituting the aliphatic hydrocarbon group may be substituted with -CO- or -O-" means that, for example, the aliphatic hydrocarbon group is divalent.
• -CH 2- constituting the alkylene group for example, methylene group, ethylene group, propylene group, etc.
• -CO- or -O- a part or all of -CH 2- constituting the alkylene group (for example, methylene group, ethylene group, propylene group, etc.) is replaced with -CO- or -O-. It means that it may be done. That is, the (n + 1) -valent C 1 or more aliphatic hydrocarbon group having a carbon of, for example, -CO -, - O-CO -O -, - CH 2 -O -, - CH 2 -CH 2 -O -, - CH 2- CH 2- O-CO-, -CH 2 -CH 2 -O-CO-O- and the like are also included.
• X represents a cleavage group represented by any of the following formulas (B1) to (B3), and is represented by any of the following formulas (B1), (B2a) and (B3). It is preferable to represent a cleaving group.
• These cleaving groups are cleaving groups that are decomposed by the action of an acid to form polar groups.
• the "polar group” means a group having at least one hetero or halogen atom, and specifically, for example, a hydroxyl group, a carbonyl group, a carboxy group, an amino group, a nitro group, an ammonium group, or a cyano group. The group etc. can be mentioned.
• cleaving group that produces a polar group refers to a group that produces the above-mentioned polar group by cleavage, but in the present invention, it also includes a group that reacts with an oxygen molecule after radical cleavage to generate a polar group.
• * represents a bonding position.
• RB1 each independently represents a substituent, and two RB1s may be bonded to each other to form a ring.
• R B2 each independently represent a substituent, may form two R B2 are bonded to each other to form a ring.
• RB3 represents a substituent and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of RB3s may be the same or different.
• RB1 each independently represents a substituent, and two RB1s may be bonded to each other to form a ring.
• Kind of substituent represented by R B1 is not particularly limited, it includes known substituents. Examples of the substituent include the groups exemplified by the substituent represented by one aspect of RA1 in the above formula (A).
• the decomposition process of cleaving group, more stable and better degradation rate can be via a prone intermediate, because the upper layer coating property becomes better, as the substituent represented by R B1 Is preferably a cyclic substituent, and more preferably a cyclic aliphatic (alicyclic) hydrocarbon group having 3 or more carbon atoms or an aromatic hydrocarbon group having 6 or more carbon atoms. Further, for the same reason, it is preferable that the two RB1s are bonded to each other to form a ring.
• examples of the alicyclic hydrocarbon group having 3 or more 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 an ethyl.
• Monocyclic saturated hydrocarbon groups such as cyclohexyl groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, and , Cyclodecadien group and other monocyclic unsaturated hydrocarbon groups; 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 .
• Dodecyl group and polycyclic saturated hydrocarbon group such as adamantyl group
• examples of the aromatic hydrocarbon group having 6 or more 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 (particularly). Phenyl group) is preferred.
• R B2 each independently represent a substituent, may form two R B2 are bonded to each other to form a ring.
• Kind of substituent represented by R B2 is not particularly limited, include known substituents, the groups exemplified in the substituents represented by an embodiment of R A1 in the formula (A).
• the number 1 or more aliphatic hydrocarbon group having a carbon or an aromatic hydrocarbon group having 6 or more carbon atoms Is more preferable.
• the aliphatic hydrocarbon group having 1 or more carbon atoms for example, an 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.
• Groups, n-butyl groups, isobutyl groups, sec-butyl groups, and t-butyl groups) are more preferable, and alkyl groups having 1 to 4 carbon atoms are even more preferable.
• the aromatic hydrocarbon group having 6 or more carbon atoms the group exemplified as a preferable example of the above-mentioned RB1 can be mentioned.
• RB3 represents a substituent and m represents an integer of 0 to 3.
• m represents 2 or 3
• the plurality of RB3s may be the same or different.
• the type of the substituent represented by RB3 is not particularly limited, and known substituents can be mentioned, such as the group exemplified by the substituent represented by one aspect of RA1 in the above formula (A), or a fluorine atom-containing alkyl. The group is mentioned.
• m is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
• 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 is preferably 1 to 30 and more preferably 5 to 25 because the liquid crystal orientation is better. ⁇ 20 is more preferable.
• 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, 3 to 20 is more preferable, and 5 to 10 is further preferable, for the reason that the liquid crystal orientation becomes better.
• 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.
• Examples of the group containing a fluorine atom or a silicon atom include the same group as the group represented by the above formula (3) for the reason that the liquid crystal orientation becomes better.
• 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, for the reason that the liquid crystal orientation becomes better.
• the group represented by any of the following formulas (B4) to (B8) is preferable because the liquid crystal orientation becomes better.
• examples of the divalent linking group represented by one embodiment of the L B2 include the same ones exemplified for the divalent linking group represented by one embodiment of L A1 in the formula (A) .
• the definition and example of Cf are the same as the definition and example of Cf in the above formula (3).
• the group represented by any of the following formulas (B9) to (B16) is preferable because the liquid crystal orientation becomes better.
• L B2 represents a single bond or a divalent linking group
• L B3 represents a divalent aliphatic hydrocarbon group having a single bond or a C 1-10
• definition of R B2 is the same as the definition of R B2 in the formula (B2).
• n represents an integer of 0 to 10
• n represents an integer of 0 to 10
• LB21 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
• the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by LB21 may be linear or branched.
• the divalent aliphatic hydrocarbon group having 1 or more carbon atoms may have a cyclic structure.
• divalent aliphatic hydrocarbon group examples include a linear alkylene group, a branched chain alkylene group, and a cyclic alkylene group.
• linear alkylene group examples 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 examples 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.
• the structure of the main chain of the repeating unit containing the group represented by the above formula (2) is not particularly limited, and known structures can be mentioned.
• (meth) acrylic, styrene, siloxane, cycloolefin, and the like A skeleton selected from the group consisting of methylpentenes, amides, and aromatic esters is preferred.
• a skeleton selected from the group consisting of (meth) acrylic, siloxane, and cycloolefin is more preferable, and (meth) acrylic skeleton is even more preferable.
• the repeating unit represented by the following formula (B) is preferable because the liquid crystal orientation becomes better.
• R B represents a hydrogen atom or a substituent
• A represents, -O- or -NR Z - represents
• R Z represents a hydrogen atom or a substituent.
• L B, X, definitions of Y and n in the formula (B) is the same as the respective definitions of L B, X, Y and n in the formula (2).
• the kind of the substituent represented by R B is not particularly limited, include known substituents, include the groups exemplified in the substituents represented by an embodiment of R A1 in the formula (A) .. Of these, an alkyl group is preferable.
• the type of the substituent represented by R Z is not particularly limited, and examples thereof include known substituents, and examples thereof include the groups exemplified by the substituent represented by one aspect of RA1 in the above formula (A). Of these, an alkyl group is preferable.
• repeating unit including the group represented by the above formula (2) include the following.
• the content of any repeating unit B in the photoalignable polymer of the present invention is not particularly limited, and for the reason that the liquid crystal orientation becomes better, 3% by mass or more with respect to all the repeating units of the photoaligning polymer. 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 more preferable, 80% by mass or less is more preferable, and 60% by mass or less is further preferable. 50% by mass or less is particularly preferable, and 30% by mass or less is most preferable.
• the photo-oriented polymer of the present invention preferably has a repeating unit C containing a crosslinkable group because the liquid crystal orientation becomes better due to the effect of suppressing orientation relaxation by improving solvent resistance.
• the type of the crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups. Among them, 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 the following formulas (C1) to (C3) is preferable. * In the following equations (C1) to (C3) represents the bonding position.
• 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 following formula (C4) is preferable. * In the following 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 C containing a crosslinkable 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, siloxane, and cycloolefin is more preferable, and (meth) acrylic skeleton is even more preferable.
• the repeating unit C containing a crosslinkable group the repeating unit represented by the following formula (C) is preferable because the liquid crystal orientation becomes better.
• RC1 represents a hydrogen atom or a substituent.
• LC1 represents a single bond or a divalent linking group.
• LC2 represents a linking group having an m + 1 valence.
• Z represents a crosslinkable group.
• m represents an integer of 1 or more, and when it is an integer of 2 or more, the plurality of Zs may be the same or different.
• RC1 represents a hydrogen atom or a substituent.
• Kind of substituent represented by R C1 is not particularly limited, include known substituents, the groups exemplified in the substituents represented by an embodiment of R A1 in the formula (A). Of these, an alkyl group represented by 1 to 6 carbon atoms is preferable.
• Q represents a hydrogen atom or a substituent. Definition of each group are the same as the definition of each group described in the divalent linking group represented by L A1 described above.
• the LC2 represents a linking group of m + 1 valence.
• the m + 1-valent linking group is an m + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent for the reason that the liquid crystal orientation becomes better, and constitutes a hydrocarbon group.
• a hydrocarbon group in which a part of the carbon 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, for the reason that the liquid crystal orientation becomes better.
• a divalent linking group is preferable. Examples of the divalent linking group include the same as those exemplified for the divalent linking group represented by one aspect of LA1 in the above formula (A).
• Z represents a crosslinkable group.
• the definition of a 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 even more preferable, for the reason that the liquid crystal orientation becomes better.
• repeating unit including a crosslinkable group examples include the following.
• the content of any repeating unit C in the photo-oriented polymer of the present invention is not particularly limited, and 10 to 60 mass by mass with respect to all the repeating units of the photo-oriented polymer for the reason that the liquid crystal orientation becomes better. % Is preferable, and 10 to 40% by mass is more preferable.
• the photooriented polymer of the present invention may have other repeating units other than the above.
• 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 acid anhydrides, and styrene compounds. And vinyl compounds can be mentioned.
• the method for synthesizing the photoorientable polymer of the present invention is not particularly limited, and for example, the above-mentioned monomer forming the repeating unit A, the above-mentioned monomer forming the repeating unit D, and the monomer forming any other repeating unit.
• the weight average molecular weight (Mw) of the photooriented polymer of the present invention is not particularly limited, and is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and even more preferably 30,000 to 150,000 because the liquid crystal orientation is better. ..
• the weight average molecular weight and the number average molecular weight in the present invention are values measured by a gel permeation chromatograph (GPC) method under the conditions shown below.
• TOSOH HLC-8320GPC -Column Use by connecting three TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm)-Column temperature: 40 ° C.
• the binder composition of the present invention is a composition containing the photo-oriented 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 only of 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 chloride polyethylene 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. Further, as the polymerizable compound, a polymerizable liquid crystal compound or a urethane acrylate monomer may be used.
• 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, oil ring 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).
• Modified triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate is particularly useful as the (meth) acrylic monomer, the acrylate-based monomer and the methacrylate-based monomer, 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 tetramethacrylate, 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 homeotropic orientation, homogeneous orientation, hybrid orientation, and cholesteric orientation.
• liquid crystal compounds can be classified into a rod-shaped type and a disk-shaped type according to their shapes.
• 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).
• 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 degree of polymerization of less than 100 and has a relatively low molecular weight is preferable.
• the polymerizable group of 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 [0098] 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-2010-244033 are preferable.
• a liquid crystal compound having a reverse wavelength dispersibility can be used as the polymerizable liquid crystal compound.
• the liquid crystal compound having "reverse wavelength dispersibility" in the present specification the in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced by using the liquid crystal compound is measured. In this case, it means that 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 dispersible 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 compound represented by the general formula (1) described in JP-A-2016-081035 (particularly, the compound 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.
• a photoacid generator that is not directly sensitive to active light with a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that is sensitive to active light with 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 or 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 can 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 photooriented 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. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No.
• Examples thereof include phosphine oxide compounds (described in Japanese Patent Publication No. 63-040799, Japanese Patent Application Laid-Open No. 5-209234, Japanese Patent Application Laid-Open No. 10-095788, and Japanese Patent Application Laid-Open No. 10-029997).
• the binder composition of the present invention preferably contains a solvent from the viewpoint of workability for forming the binder layer.
• the solvent include ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclopentanone, and cyclohexanone), ethers (eg, dioxane, and tetrahydrofuran), and aliphatic hydrocarbons (eg, eg).
• alicyclic hydrocarbons eg, cyclohexane
• aromatic hydrocarbons eg, toluene, xylene, and trimethylbenzene
• carbon halides eg, dichloromethane, dichloroethane, dichlorobenzene, and chloro
• Toluene esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methylserosolves, and ethyl).
• Serosolves Serosolves
• cellosolve acetates eg, cellosolve acetates
• sulfoxides eg, dimethylsulfoxides
• amides eg, dimethylformamides, and dimethylacetamides
• 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 above-mentioned binder composition of the present invention, 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, an acid is generated from the photoacid generator in the coating film obtained by using the above binder composition, and then 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 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 performing 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 exposed by the photoacid generator contained in the binder composition.
• the light irradiation treatment carried out in the above treatment may be any treatment as long as it is a 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 performed after the curing treatment, or the curing treatment and the acid generation treatment may be performed 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 surface of the coating film. 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 the non-polarized film 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. However, it is preferable that ⁇ is 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 exposed, 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 rays 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 for 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 present invention is not limited to this embodiment, and the curing treatment is performed at the same time as the photo-alignment treatment. And acid generation treatment may be carried out.
• the thickness of the binder layer is not particularly limited, and is preferably 0.1 to 10 ⁇ m, more preferably 0.3 to 3 ⁇ m, because the liquid crystal orientation is better.
• 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.
• the 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 polymers such as phthalate; styrene polymers such as polystyrene and acrylonitrile styrene copolymers; polyolefin polymers such as polyethylene, polypropylene, and ethylene / propylene copolymers; vinyl chloride 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. Further, it is preferable that the support can be peeled off.
• the binder layer is the binder layer of the present invention described above.
• the optically anisotropic layer is preferably formed by 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 above-mentioned optical laminate of the present invention, and generates an acid from a photoacid generator in a coating film obtained by using the binder composition.
• the coating film is subjected to a 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 subjecting the coating film to a photoalignment treatment 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 application 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 curing treatment are performed separately, but a method of performing the curing treatment under heating conditions may also be used. If the orientation is performed without heat treatment depending on the type of the polymerizable liquid crystal compound, 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 more preferably 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.
• EL organic electroluminescence
• 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 cell used in the liquid crystal display device is a VA (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Tw) mode.
• VA Vertical Alignment
• OCB Optically Compensated Bend
• IPS In-Plane-Switching
• FFS Frringe-Field-Switching
• Tw TN
• the Nematic) mode is preferred, but is not limited to these.
• 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 polarizing element, 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 above-mentioned polarizing element 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 polarizing elements and reflection type polarizing elements can be used.
• the absorption type polarizing element include an iodine-based polarizing element, a dye-based polarizing element using a dichroic dye, and a polyene-based polarizing element.
• the iodine-based polarizing element and the dye-based polarizing element include a coating type polarizing element and a stretching type polarizing element, and both of them can be applied.
• Japanese Patent No. 5048120 Japanese Patent No. 5143918, Japanese Patent No. 4691020, and the like. Examples thereof include the methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486.
• the reflective polarizing element include a polarizing element in which thin films having different birefringences are laminated, a wire grid type polarizing element, and a modulator in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined.
• polyvinyl alcohol-based resin polymer containing as a repeating unit -CH 2 -CHOH- particular, polyvinyl alcohol and ethylene -. At least selected from the group consisting of vinyl alcohol copolymer A polarizing element containing 1) is preferable.
• the thickness of the polarizing element 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, and is a hole injection layer, a hole transport layer, and an electron injection in addition to the light emitting layer. 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.
• the reaction mixture was cooled to room temperature (23 ° C.), washed separately with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. 8.0 g of the monomer mb-6 represented by the formula mb-6 as a colorless liquid was obtained (yield 40%).
• the following monomer mb-6 corresponds to a monomer forming a repeating unit represented by the following formula B-6.
• Example 1 Synthesis of photo-oriented polymer
• 2-butanone 23 parts by mass
• the following monomer mA-18 (2.75 parts by mass
• the following monomer MB-0 (2.25 parts by mass)
• the following monomer mC-4Cl (2.25 parts by mass)
• the following monomer mD-6 (2.75 parts by mass)
• 2,2'-azobis isobutyronitrile
• Examples 2 to 11 and Comparative Examples 1 to 2 (synthesis of photo-oriented polymer)] Instead of the various monomers used in Example 1, the monomers forming the repeating units shown in Table 1 below were used, and the photo-orientations synthesized in Example 1 were used except for the contents shown in Table 1 below. A photo-oriented polymer was synthesized in the same manner as the sex polymer P-1.
• the weight average molecular weight of the synthesized photooriented polymer was measured by the method described above. The results are shown in Table 1 below.
• Example 1 Preparation of optical laminate
• a cellulose acylate film (ZRD40, manufactured by FUJIFILM Corporation) was prepared as a support. Further, as the composition for forming the binder layer, the following rod-shaped liquid crystal compound A (83 parts by mass), the following rod-shaped liquid crystal compound C (15 parts by mass), the following rod-shaped liquid crystal compound D (2 parts by mass), urethane acrylate (EBECRYL1290, Dycel.
• the obtained film was annealed at 110 ° C., 120 ° C. or 135 ° C. for 1 minute to form a binder layer.
• the thickness of the binder layer was 0.5 ⁇ m.
• the obtained binder layer is irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) 7.9 mJ / cm 2 (wavelength: 313 nm) through a wire grid type polarizing element at room temperature to impart an orientation function. bottom.
• UV light ultraviolet light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) 7.9 mJ / cm 2 (wavelength: 313 nm) through a wire grid type polarizing element at room temperature to impart an orientation function. bottom.
• optically anisotropic layer The following polymerizable liquid crystal compound A (65 parts by mass), the following polymerizable liquid crystal compound B (35 parts by mass), a photopolymerization initiator (Irgacure 907, manufactured by BASF) (3 parts by mass), a sensitizer (Kayacure DETX, Japan).
• a solution for forming an optically anisotropic layer was prepared by dissolving (1 part by mass) (1 part by mass) manufactured by Kayaku Co., Ltd. and the following horizontal orienting agent (0.3 part by mass) in methyl ethyl ketone (193 part by mass).
• the above solution for forming an optically anisotropic layer is applied onto the binder layer with a wire bar coater # 7, heated at 60 ° C. for 2 minutes, and the oxygen concentration is 1.0% by volume or less while maintaining the temperature at 60 ° C.
• a wire bar coater # 7 heated at 60 ° C. for 2 minutes, and the oxygen concentration is 1.0% by volume or less while maintaining the temperature at 60 ° C.
• an air-cooled metal halide lamp manufactured by Eye Graphics Co., Ltd.
• an optically anisotropic layer thickness: 2.5 ⁇ m
• Example 2 to 11 and Comparative Examples 1 to 2 manufactured of optical laminate
• An optical laminate was prepared in the same manner as in Example 1 except that the photo-aligned polymers P-2 to P-11 and H-1 to H-2 were used instead of the photo-aligned polymers P-1. ..
• the cleavage rate was evaluated by the difference between the surface energy of the binder layer forming composition and the surface energy of the binder layer after heating after irradiation with UV-LED at 365 nm (measured at 110 ° C./120 ° C./135 ° C., respectively).
• the evaluation criteria are as follows.
• the surface energy was measured by the following method using a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.]. ⁇ Measurement method of surface energy>
• the measurement target was spin-coated on a quartz substrate. When a solvent was contained, the film was dried to prepare a film.
• Example 5 From the comparison between Example 5 and Example 8, it was found that the cleavage rate is increased when the photooriented polymer has the repeating unit B containing the group represented by the above formula (2). .. Further, from the comparison between Example 3 and Example 6 and the comparison between Example 4 and Example 7, when the photo-oriented polymer has the repeating unit C having a crosslinkable group, the liquid crystal alignment is determined. It was found that the sex was better.

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