WO2020110818A1 - 光配向性共重合体、バインダー組成物、バインダー層、光学積層体および画像表示装置 - Google Patents
光配向性共重合体、バインダー組成物、バインダー層、光学積層体および画像表示装置 Download PDFInfo
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- WO2020110818A1 WO2020110818A1 PCT/JP2019/045171 JP2019045171W WO2020110818A1 WO 2020110818 A1 WO2020110818 A1 WO 2020110818A1 JP 2019045171 W JP2019045171 W JP 2019045171W WO 2020110818 A1 WO2020110818 A1 WO 2020110818A1
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Classifications
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Definitions
- the present invention relates to a photo-alignable copolymer, a binder composition, a binder layer, an optical laminate and an image display device.
- Optical films such as an optical compensation sheet and a retardation film are used in various image display devices from the viewpoints of eliminating image coloring and enlarging a viewing angle.
- a stretched birefringent film has been used as the optical film, but in recent years, it has been proposed to use an optically anisotropic layer using a liquid crystal compound instead of the stretched birefringent film.
- Such an optically anisotropic layer is known to be provided with an alignment film on a support forming the optically anisotropic layer in order to align the liquid crystal compound, and as the alignment film, a rubbing treatment is performed.
- a photo-alignment film which has been subjected to a photo-alignment treatment instead of.
- Patent Document 1 discloses a composition for a photo-alignment film containing a polymer A having a structural unit a1 containing a cinnamate group and a low molecular weight compound B having a cinnamate group and having a smaller molecular weight than the polymer A.
- the polymer A has a structural unit a2 containing a crosslinkable group such as an epoxy group or an oxetanyl group ([0024] to [0028]).
- Patent Document 2 a photoalignable copolymer having a repeating unit A containing a predetermined photoalignable group and a repeating unit B containing a predetermined crosslinkable group, and this photoalignable copolymer A photo-alignment film formed using a composition for a photo-alignment film containing is described ([claim 1] [claim 13]).
- the present inventors examined the copolymers described in Patent Documents 1 and 2, and found that when forming an optically anisotropic layer on the obtained photo-alignment film, a composition for the optically anisotropic layer was obtained. It was clarified that the coating property (hereinafter, also referred to as “upper layer coating property”) may be inferior.
- the present invention aims to provide a photo-alignable copolymer, a binder composition, a binder layer, an optical laminate and an image display device capable of improving the upper layer coatability after being formed as a layer.
- a repeating unit A containing a photoalignable group and a crosslinking reaction by the action of at least one selected from the group consisting of light, heat, acid and base A repeating unit B containing a crosslinkable group that gives rise to, and a repeating unit C containing a cleavage group that decomposes to produce a polar group by the action of at least one selected from the group consisting of light, heat, acid and base.
- the inventors have found that the use of a binder composition containing a copolymer contained in a predetermined mass ratio improves the coatability of the upper layer after being formed as a layer, and completed the present invention. That is, the present inventors have found that the above problems can be achieved by the following configurations.
- the repeating unit C has a cleavage group in the side chain, and has an atomic group capable of unevenly distributing the photoalignable copolymer to the air interface side, on the terminal side of the side chain cleavage group,
- the content of each repeating unit with respect to the sum of the content a of the repeating unit A, the content b of the repeating unit B, and the content c of the repeating unit C is represented by the following formulas (W1) to (W3) in mass ratio.
- each repeating unit with respect to the sum of the content a of the repeating unit A, the content b of the repeating unit B, and the content c of the repeating unit C is represented by the following formula (W4) to (The photoalignable copolymer according to [1], which satisfies W6).
- the repeating unit C is a repeating unit represented by the following formula (C1) or a repeating unit represented by the following formula (C2-1) or (C2-2), [1] to [5 ]
- R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a plurality of R 11 in the formula (C1) are the same. It may or may not be.
- X 11 and X 12 each independently represent a single bond or a divalent linking group
- RK represents a cleavage group
- RL represents a monovalent organic group containing a fluorine atom or a silicon atom.
- RK in the above formulas (C1), (C2-1) and (C2-2) is a cleavage group represented by any of the following formulas (rk-1) to (rk-13), The photo-alignable copolymer according to [6].
- *1 is any one of X 11 and X 12 in the formulas (C1), (C2-1) and (C2-2).
- R's each independently represent a hydrogen atom or a monovalent organic group.
- L 1 in the above formula (A) represents a divalent linking group containing a nitrogen atom and a cycloalkane ring, and some of the carbon atoms constituting the cycloalkane ring are formed from nitrogen, oxygen and sulfur.
- L 1 in the above formula (A) is a divalent linking group represented by any of the above formulas (2), (3), (7) and (8).
- the substituents represented by R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) are each independently a halogen atom, a straight chain having 1 to 20 carbon atoms, a branched chain or Cyclic alkyl group, linear halogenated alkyl 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
- * represents a bonding position with the benzene ring in the above formula (A)
- R 9 represents a monovalent organic group.
- a repeating unit B is a repeating unit in which X in the above formula (B) is a crosslinkable group represented by any of the above formulas (X1) to (X3), and X in the above formula (B). Is a crosslinkable group represented by the above formula (X4), and the photoalignable copolymer according to [18].
- L 2 in the above formula (B) each independently has a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent, and a substituent.
- the photoalignable copolymer according to any one of [17] to [19], which is a linking group.
- a binder layer formed using the binder composition according to [23].
- An image display device comprising the binder layer according to [24] or the optical layered body according to [25].
- a photo-alignable copolymer a binder composition, a binder layer, an optical laminate and an image display device that can improve the coating property of the upper layer after being formed as a layer. ..
- a numerical range represented by “to” means a range including the numerical values before and after “to” as a lower limit value and an upper limit value.
- the photo-alignable copolymer of the present invention comprises a repeating unit A containing a photo-alignable group and a cross-linkable group which causes a cross-linking reaction by the action of at least one selected from the group consisting of light, heat, acid and base. And a repeating unit C containing a cleavage group that decomposes to form a polar group by the action of at least one selected from the group consisting of light, heat, acid, and base. It is united.
- the repeating unit C has a cleavage group in the side chain, and the photoalignment copolymer is provided on the air interface side closer to the terminal side than the side chain cleavage group. It has an atomic group that can be unevenly distributed.
- the photoalignable copolymer of the present invention has a content of each repeating unit with respect to the total of the content a of the repeating unit A, the content b of the repeating unit B, and the content c of the repeating unit C, They satisfy the following formulas (W1) to (W3) in terms of mass ratio. 0.03 ⁇ a/(a+b+c) ⁇ 0.75 (W1) 0.20 ⁇ b/(a+b+c) ⁇ 0.90 (W2) 0.03 ⁇ c/(a+b+c) ⁇ 0.70 (W3)
- the coatability of the upper layer becomes good after being formed as a layer. ..
- the present inventors presume as follows. That is, the composition containing the photoalignable copolymer of the present invention is applied, and after being formed as a layer such as a binder layer, with respect to the photoalignable copolymer of the present invention unevenly distributed on the air interface side.
- the action of at least one selected from the group consisting of:, light, heat, acid and base decomposes the cleavage group contained in the side chain to form a polar group, which is considered to have improved the upper layer coatability. Be done.
- the repeating units A, B and C are described in detail below.
- the repeating unit A contained in the photoalignable copolymer of the present invention is a repeating unit containing a photoalignable group.
- the “photo-alignment group” means a group having a photo-alignment function in which rearrangement or an anisotropic chemical reaction is induced by irradiation with light having anisotropy (for example, plane polarized light).
- a photo-alignment group that causes at least one of dimerization and isomerization by the action of light is preferable because it has excellent alignment uniformity and also has good thermal stability and chemical stability.
- photoalignable group that dimerizes by the action of light
- the photoalignable group that dimerizes by the action of light include, for example, cinnamic acid derivatives (M. Schadt et al., J. Appl. Phys., vol. 31, No. 7, page 2155 ( 1992)), coumarin derivatives (M. Schadt et al., Nature., vol. 381, page 212 (1996)), chalcone derivatives (Toshihiro Ogawa et al., Proceedings of Liquid Crystal Conference, 2AB03 (1997)), maleimide derivatives.
- a group having a skeleton of at least one derivative selected from the group consisting of benzophenone derivatives YK Jang et al., SID Int.
- photo-orienting group that is isomerized by the action of light specifically, for example, azobenzene compound (K. Ichimura et al., Mol.Cryst.Liq.Cryst ., 298,221 (1997)), stilbene compound (JGVictor and JM Torkelson, 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)), cinnamic acid compound (K.
- the photo-alignment group is a group having a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives and maleimide derivatives, azobenzene compounds, stilbene compounds and spiropyran compounds.
- a group having a cinnamic acid derivative or a coumarin derivative skeleton is more preferable.
- the repeating unit A is preferably a repeating unit represented by the following formula (A).
- R 1 represents a hydrogen atom or a methyl group
- L 1 represents a divalent linking group.
- R 2, R 3, R 4, R 5 and R 6 each independently represent a hydrogen atom or a substituent, R 2, R 3, R 4, of R 5 and R 6, two adjacent radicals May combine with each other to form a ring.
- divalent linking group represented by L 1 in the above formula (A) will be described.
- examples of the divalent linking group include the same as those described for L 2 in the formula (B) described below, but a composition containing the photoalignable copolymer of the present invention is applied.
- the orientation of the optically anisotropic layer formed by using a liquid crystal compound on the formed layer (hereinafter, also referred to as “liquid crystal orientation”) is better.
- liquid crystal orientation a divalent linking group containing a nitrogen atom and a cycloalkane ring is preferred.
- a part of carbon atoms constituting the cycloalkane ring may be substituted with a hetero atom selected from the group consisting of nitrogen, oxygen and sulfur.
- the nitrogen atom may not be present separately from the cycloalkane ring.
- the cycloalkane ring is preferably a cycloalkane ring having 6 or more carbon atoms, and specific examples thereof include a cyclohexane ring, a cyclopeptane ring, a cyclooctane ring, a cyclododecane ring, a cyclodocosane ring and the like.
- L 1 in the above formula (A) is a divalent linking group represented by any one of the following formulas (1) to (10) for the reason that the liquid crystal orientation is better. It is preferable.
- *1 represents a bonding position with a carbon atom constituting the main chain in the above formula (A)
- *2 represents a carbonyl group in the above formula (A). It represents the bond position with the constituent carbon atom.
- divalent linking group represented by any one of the above formulas (1) to (10) the solubility in a solvent used when forming a layer such as a binder layer and the solvent resistance of the obtained layer. From the reason of good balance, a divalent linking group represented by any of the above formulas (2), (3), (7) and (8) is preferable.
- R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) will be described.
- R 2 , R 3 , R 4 , R 5 and R 6 in the formula (A) may be hydrogen atoms instead of substituents.
- R 2 , R 3 , R 4 , R 5 and R 6 in the above formula (A) makes it easier for the photo-alignment group to interact with the liquid crystal compound and has better liquid crystal alignment.
- a halogen atom a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear halogenated alkyl group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms.
- * represents a bonding position with the benzene ring in the formula (A)
- R 9 represents a monovalent organic group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
- the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, specifically, for example, methyl group, ethyl group. Group, n-propyl group and the like.
- the branched alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include an isopropyl group and a tert-butyl group.
- the cyclic alkyl group is preferably an alkyl group having 3 to 6 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group and a cyclohexyl group.
- the linear halogenated alkyl group having 1 to 20 carbon atoms is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group and a perfluoropropyl group. , A perfluorobutyl group, and the like, among which 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 6 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 14 carbon atoms is further preferable.
- Preferred examples thereof include groups, and among them, an n-hexyloxy group, an n-octyloxy group, an n-decyloxy group, an n-dodecyloxy group and an n-tetradecyloxy group are more preferred.
- the aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group and a naphthyl group. preferable.
- the aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include a phenyloxy group and a 2-naphthyloxy group. Is preferred.
- 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, a nitrogen-containing heterocyclic compound (eg, pyrrolidine , Piperidine, piperazine, etc.) and a tertiary amino group such as a group having a nitrogen atom as a bond.
- a primary amino group —NH 2
- secondary amino group such as a methylamino group
- a dimethylamino group a diethylamino group
- a dibenzylamino group examples include a nitrogen-containing heterocyclic compound (eg, pyrrolidine , Piperidine, piperazine, etc.) and a tertiary amino group such as a group having a nitrogen atom as a bond.
- a nitrogen-containing heterocyclic compound eg, pyrrolidine , Piperidine
- examples of the monovalent organic group represented by R 9 in the above formula (11) include a linear or cyclic alkyl group having 1 to 20 carbon atoms. ..
- the linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and an n-propyl group. Among them, a methyl group or an ethyl group is preferable. preferable.
- the cyclic alkyl group is preferably an alkyl group having a carbon number of 3 to 6, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and among them, a cyclohexyl group is preferable.
- the monovalent organic group represented by R 9 in the above formula (11) may be a combination of a plurality of the above linear alkyl groups and cyclic alkyl groups directly or through a single bond. Good.
- R 2 , R 3 , R 4 , R 5 and R in the above formula (A) are used because the photo-alignment group easily interacts with the liquid crystal compound and the liquid crystal alignment becomes better.
- R 4 it is preferable that at least R 4 is a substituent as described above, further, improves the linearity of the resulting photoorientable copolymer tends to interact with the liquid crystal compound, liquid crystal orientation is For the reason of further improvement, it is more preferable that R 2 , R 3 , R 5 and R 6 all represent a hydrogen atom.
- R 4 in the above formula (A) is preferably an electron-donating substituent because the reaction efficiency is improved when the resulting binder layer or other layer is irradiated with light.
- the electron-donating substituent refers to a substituent having a Hammett value (Hammett substituent constant ⁇ p) of 0 or less.
- an alkyl group examples thereof include halogenated alkyl groups and alkoxy groups.
- an alkoxy group is preferable, and when formed as a layer such as a binder layer, uneven film thickness (hereinafter, also referred to as “wind unevenness”) caused by dry air during drying can be suppressed, and liquid crystal From the reason of better orientation, an alkoxy group having 6 to 16 carbon atoms is more preferable, and an alkoxy group having 7 to 10 carbon atoms is further preferable.
- repeating unit A represented by the above formula (A) include repeating units A-1 to A-56 shown below.
- Me represents a methyl group
- Et represents an ethyl group.
- the “1,4-cyclohexyl group” contained in the divalent linking group of the repeating units A-1 to A-10 may be either a cis form or a trans form. It is preferably a trans form.
- the repeating unit B contained in the photoalignable copolymer of the present invention is a repeating unit containing a crosslinkable group which causes a crosslinking reaction by the action of at least one selected from the group consisting of light, heat, acid and base. ..
- the repeating unit B is preferably a repeating unit represented by the following formula (B) for the reason that the liquid crystal orientation is better.
- R 7 represents a hydrogen atom or a methyl group
- L 2 represents a divalent linking group
- X represents a crosslinkable group.
- a linear group having 1 to 18 carbon atoms, which may have a substituent may be used because the photo-alignment group is likely to interact with the liquid crystal compound and the liquid crystal alignment becomes better.
- -, branched- or cyclic alkylene groups, optionally substituted arylene groups having 6 to 12 carbon atoms, ether groups (-O-), carbonyl groups (-C( O)-), and It is preferably a divalent linking group obtained by combining at least two groups selected from the group consisting of an imino group (—NH—) which may have a substituent.
- the substituent which the alkylene group, the arylene group and the imino group may have, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, a carboxy group, an alkoxycarbonyl group. And hydroxyl groups.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
- alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group. Is particularly preferable.
- an alkyl group having 1 to 8 carbon atoms eg, methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.
- an alkyl group having 1 to 4 carbon atoms
- an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable, and carbon group It is more preferably an alkoxy group of the formula 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
- the aryl group include an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group and a naphthyl group, and among them, a phenyl group is preferable.
- Examples of the aryloxy group include phenoxy, naphthoxy, imidazoyloxy, benzimidazoyloxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, thiophen-3-yloxy and the like.
- Examples of the alkoxycarbonyl group include methoxycarbonyl and ethoxycarbonyl.
- a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms a linear alkylene group having 1 to 6 carbon atoms, a branched alkylene group having 3 to 6 carbon atoms, or 3 to 6 carbon atoms
- the cyclic alkylene group of is preferable, and the linear alkylene group having 1 to 6 carbon atoms is more preferable.
- Specific examples of the linear alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group.
- branched alkylene group examples include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, a 2-ethyl-2-methylpropylene group and the like.
- cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group and a norbornane-diyl group.
- 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.
- the phenylene group is preferable. ..
- X (crosslinkable group) in the above formula (B) include an epoxy group, an epoxycyclohexyl group, an oxetanyl group, and a functional group having an ethylenically unsaturated double bond.
- at least one crosslinkable group selected from the group consisting of the following formulas (X1) to (X4) is preferable.
- * represents a bonding position with L 2 in the formula (B)
- R 8 represents any one of a hydrogen atom, a methyl group and an ethyl group.
- S represents a functional group having an ethylenically unsaturated double bond.
- specific examples of the functional group having an ethylenically unsaturated double bond include a vinyl group, an allyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group or a methacryloyl group. Is preferred.
- the repeating unit B is used for the reason that the strength of the optical layered body of the present invention described later becomes high and the handling property when forming other layers using the optical layered body of the present invention described later becomes good.
- X in (B) contains a repeating unit which is a crosslinkable group represented by the above formula (X4) (hereinafter, also abbreviated as “repeating unit B2”).
- repeating unit B (repeating unit B1) represented by the above formula (B) include repeating units B-1 to B-17 shown below.
- repeating unit B (repeating unit B2) represented by the above formula (B) include repeating units B-18 to B-47 shown below.
- the repeating unit C contained in the photoalignable copolymer of the present invention is a repeating unit containing a cleavage group that decomposes to produce a polar group by the action of at least one selected from the group consisting of light, heat, acid and base. is there. Further, the repeating unit C contained in the photoalignable copolymer of the present invention has the above-mentioned cleavage group in the side chain, and the photoalignable copolymer of the present invention is present at the terminal side of the side chain with respect to the above-mentioned cleavage group. It has an atomic group capable of unevenly distributing the coalescence on the air interface side.
- the “polar group” refers to a group having at least one atom of a hetero atom or a halogen atom, and specific examples thereof include a hydroxyl group, a carbonyl group, a carboxy group, an amino group, a nitro group, an ammonium group, and a cyano group. Groups and the like. Of these, a hydroxyl group and a carboxy group are preferable.
- the “cleavable 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 produce a polar group.
- an atomic group that can be unevenly distributed on the air interface side means that when a composition containing the photoalignable copolymer of the present invention is applied and formed as a layer such as a binder layer, A functional group capable of unevenly distributing the photoalignable copolymer of the present invention on the air interface side.
- a functional group capable of unevenly distributing the photoalignable copolymer of the present invention on the air interface side Specifically, for example, a fluorine atom, a silicon atom and a long chain alkyl group (for example, having 6 to 6 carbon atoms). 20 alkyl groups) and other atomic groups that can reduce the surface energy.
- the repeating unit C has a cleavage group in the side chain, and has a fluorine atom or a silicon atom on the terminal side of the side chain cleavage group. It is preferably a unit having.
- the repeating unit C is a repeating unit represented by the following formula (C1) or the following formula (C2-1) for the reason that the film thickness unevenness (wind unevenness) can be further suppressed.
- it is preferably a repeating unit represented by (C2-2).
- R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and a plurality of R 11 in formula (C1) may be the same as each other. It may be different.
- R 11 is preferably a hydrogen atom or a methyl group.
- X 11 and X 12 each independently represent a single bond or a divalent linking group
- RK represents a cleavage group
- RL represents a monovalent organic group containing a fluorine atom or a silicon atom.
- the divalent linking group represented by X 11 and X 12 in the above formulas (C1), (C2-1) and (C2-2) is, for example, 1 to 10 carbon atoms which may have a substituent.
- a linear, branched or cyclic alkylene group, an arylene group having 6 to 12 carbon atoms which may have a substituent, an ether group (-O-), a carbonyl group (-C( O)-) , And at least one group selected from the group consisting of an imino group (—NH—) which may have a substituent.
- examples of the substituent that the alkylene group, the arylene group and the imino group may have include an alkyl group, an alkoxy group, a halogen atom and a hydroxyl group.
- the alkyl group for example, a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, isopropyl group , N-butyl group, isobutyl group, sec-butyl group, t-butyl group, cyclohexyl group, etc.), more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group.
- alkoxy group for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, etc.) is more preferable, and carbon group It is more preferably an alkoxy group of the formula 1 to 4, and particularly preferably a methoxy group or an ethoxy group.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom and a chlorine atom are preferable.
- linear alkylene group having 1 to 10 carbon atoms specific examples include methylene group, ethylene group, propylene group, butylene group, pentylene group, Examples thereof include a hexylene group and a decylene group.
- branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, a 2-ethyl-2-methylpropylene group and the like.
- cyclic alkylene group examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group and a norbornane-diyl group.
- 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.
- a phenylene group is particularly preferable. preferable.
- Examples of the cleavage group represented by RK in the above formulas (C1), (C2-1) and (C2-2) include cleavage groups represented by any of the following formulas (rk-1) to (rk-13). A group (bond) is mentioned.
- *1 is a bond with any one of X 1 and X 2 in the above formulas (C1), (C2-1) and (C2-2).
- *2 represents a bonding position of X 1 and X 2 in the above formulas (C1), (C2-1) and (C2-2) to the side not bonded to *1,
- R Each independently represent a hydrogen atom or a monovalent organic group.
- examples of the monovalent organic group represented by R include a chain or cyclic alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, and the like. Can be mentioned.
- the anion part in the above formulas (rk-10) and (rk-11) is not particularly limited because it does not affect the cleavage, and an inorganic anion or an organic anion can be used.
- the inorganic anion include halide ions such as chloride ion and bromide ion; sulfonate anion; and the like.
- the organic anion include carboxylate anion such as acetate anion; organic sulfonate anion such as methanesulfonate anion and paratoluenesulfonate anion; and the like.
- the cleavage group represented by the above formula (rk-1) in the case of cleavage using light, from the viewpoint of quantum efficiency, the cleavage group represented by the above formula (rk-1) is preferable, and acid is used. In the case of the cleavage, the cleavage group represented by the above formula (rk-9) is preferable from the viewpoint of the cleavage rate.
- Examples of the monovalent organic group containing a fluorine atom or a silicon atom represented by RL in the above formulas (C1), (C2-1) and (C2-2) include, for example, at least one carbon atom substituted with a fluorine atom.
- Examples of the group include an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms.
- repeating unit C include the following repeating units C-1 to C-29.
- the photo-alignable copolymer of the present invention has a content of the repeating unit A, a content of the repeating unit B, and a content of the repeating unit C for the reason that the upper layer coatability and the liquid crystal aligning property are better.
- the content of each repeating unit with respect to the sum with c preferably satisfies the following formulas (W4) to (W6), and more preferably satisfies the following formulas (W7) to (W9). More preferably, the following formulas (W10) to (W12) are satisfied.
- the photoalignable copolymer of the present invention may have other repeating unit D in addition to the above-mentioned repeating unit A, repeating unit B and repeating unit C, as long as the effects of the present invention are not impaired.
- the repeating unit D is preferably a repeating unit represented by the following formula (D).
- R 8 represents a hydrogen atom or a methyl group
- L 3 is a linear, branched or cyclic alkylene group having 1 to 18 carbon atoms which may have a substituent
- Q represents any one of —OH, —COOH, and —COOtBu. Note that “tBu” is a notation indicating tert-butyl.
- the substituent, the linear, branched or cyclic alkylene group having 1 to 18 carbon atoms and the like are the same as those described for L 2 in the above formula (B).
- repeating unit D represented by the above formula (D) include repeating units D-1 to D-13 shown below.
- repeating unit D represented by a formula other than the above formula (D) include acrylic acid ester compounds, methacrylic acid ester compounds, repeating units D-14 shown below, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, Examples thereof include styrene compounds and vinyl compounds.
- the method for synthesizing the photoalignable copolymer of the present invention is not particularly limited, and examples thereof include a monomer forming the repeating unit A described above, a monomer forming the repeating unit B described above, a monomer forming the repeating unit C described above, Further, it can be synthesized by mixing any other monomer forming the repeating unit D and polymerizing it in an organic solvent using a radical polymerization initiator.
- the weight average molecular weight (Mw) of the photo-alignable copolymer of the present invention is preferably 10,000 to 500,000, and more preferably 30,000 to 300,000 because the liquid crystal alignment is further improved.
- the weight average molecular weight and the number average molecular weight in the present invention are values measured by a gel permeation chromatography (GPC) method under the following conditions.
- the binder composition of the present invention is a composition containing a binder and the photoalignable copolymer of the present invention.
- the content of the photoalignable copolymer contained in the binder composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder to be described later, and 0.5. It is more preferably about 5 parts by mass.
- the binder contained in the binder composition of the present invention is not particularly limited, and is a resin that is simply dried and solidified (hereinafter, also referred to as “resin binder”) such that it is composed only of a resin having no polymerization reactivity. It may be present or may be a polymerizable compound.
- resin binder a resin that is simply dried and solidified
- ⁇ Resin binder specifically, for example, 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, Acrylonitrile acrylate styrene copolymer resin, acrylonitrile styrene resin, acrylonitrile chloride polyethylene styrene copolymer resin, ethylene vinyl acetate resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride Resin, cellulose acetate resin, fluororesin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone resin
- polymerizable compound examples include an epoxy-based monomer, an acrylic-based monomer, an oxetanyl-based monomer, and the like. Among them, the epoxy-based monomer and the acrylic-based monomer are preferable. In the present invention, a polymerizable liquid crystal compound may be used as the polymerizable compound.
- epoxy group-containing monomer examples 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, 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, tetraphenylolethane type epoxy resin, Dicyclopentadiene phenol 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, glycidyl amine type epoxy resin, glyoxal type epoxy resin, alicyclic Type epoxy resin, heterocyclic epoxy resin and the like.
- acrylate and methacrylate monomers which are acrylic monomers
- trifunctional monomers such as trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, trimethylolpropane EO (ethylene oxide) modified triacrylate, and trifunctional Methylolpropane trimethacrylate and pentaerythritol triacrylate may be mentioned.
- tetrafunctional or higher functional monomers and oligomers examples include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. be able to.
- the polymerizable liquid crystal compound is not particularly limited, and for example, a compound capable of homeotropic alignment, homogeneous alignment, hybrid alignment and cholesteric alignment can be used.
- liquid crystal compounds can be classified into a rod-shaped type and a disc-shaped type according to their shapes.
- low-molecular type and high-molecular type respectively.
- a polymer generally refers to a polymer 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 (hereinafter also abbreviated as “CLC”) or a discotic liquid crystal compound (discotic liquid crystal compound) (hereinafter also abbreviated as “DLC”). It is preferable to use a liquid crystal compound which is a monomer or a relatively low molecular weight compound having a degree of polymerization of less than 100.
- Specific 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.
- rod-shaped liquid crystal compound for example, those described in claim 1 of JP-A-11-513019 or paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and are discotic.
- liquid crystal compound for example, those described in paragraphs [0020] to [0067] of JP2007-108732A and paragraphs [0013] to [0108] of JP2010-244038A can be preferably used. However, it is not limited to these.
- a reverse wavelength dispersion liquid crystal compound can be used as the polymerizable liquid crystal compound.
- the “reverse wavelength dispersion” liquid crystal compound means an in-plane retardation (Re) value at a specific wavelength (visible light range) of a retardation film produced using the liquid crystal compound. At that time, the Re value becomes equal or higher as the measurement wavelength becomes larger.
- the reverse wavelength dispersive 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, compounds described in paragraphs [0034] to [0039]) and compounds represented by the general formula (1) described in JP 2010-84032A (in particular, paragraphs [0067] to [0073] and the compounds represented by formula (1) described in JP-A-2016-081035 (particularly the compounds described in paragraphs [0043] to [0055]). be able to.
- paragraph numbers [0028] to [0115] of WO14/147904 can be used.
- the binder composition of the present invention preferably contains a polymerization initiator when a polymerizable compound is used as the binder.
- a polymerization initiator is not particularly limited, but examples thereof include a thermal polymerization initiator and a photopolymerization initiator depending on the type of polymerization reaction.
- a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
- the photopolymerization initiator for example, ⁇ -carbonyl compound (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No.
- acyloin compounds described in U.S. Pat. No. 2,722,512
- polynuclear quinone compounds described in U.S. Pat. Nos. 3,046,127 and 2,951,758
- combinations of triarylimidazole dimers and p-aminophenyl ketones U.S. Pat. No. 3549367
- acridine and phenazine compounds JP-A-60-105667, US Pat. No. 4,239,850
- oxadiazole compounds US Pat. No. 4,212,970
- acylphosphine examples thereof include oxide compounds (described in JP-B-63-40799, JP-B-5-29234, JP-A-10-95788, and JP-A-10-29997).
- photoacid generator In the binder composition of the present invention, when the above-mentioned photoalignable copolymer is a polymer having a monovalent specific group containing a cleavage group which decomposes by the action of an acid to generate a polar group, a photoacid generator It is preferable to contain
- the photo-acid generator is preferably a compound which reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm to generate an acid, but is not limited to its chemical structure. Further, as for a photo-acid generator which is not directly sensitive to actinic rays having a wavelength of 300 nm or more, when used in combination with a sensitizer, a compound which is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid is a It can be preferably used in combination.
- the photoacid generator used in the present invention is preferably a photoacid generator that generates an acid with a pKa of 4 or less, more preferably a photoacid generator that generates an acid with a pKa of 3 or less, and an acid of 2 or less.
- 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 Chemical Handbook or the like can be referred to.
- the acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
- photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. .. Among these, onium salt compounds, imide sulfonate compounds and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable.
- the photoacid generator may be used alone or in combination of two or more.
- the binder composition of the present invention preferably contains a solvent from the viewpoint of workability for forming a binder layer and the like.
- a solvent from the viewpoint of workability for forming a binder layer and the like.
- the solvent include ketones (eg, acetone, 2-butanone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (eg, dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (eg, hexane).
- Etc. alicyclic hydrocarbons (eg cyclohexane etc.), aromatic hydrocarbons (eg toluene, xylene, trimethylbenzene etc.), halogenated carbons (eg dichloromethane, dichloroethane, dichlorobenzene, chlorotoluene etc.) ), esters (eg, methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (eg, ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, etc.), cellosolve Examples thereof include acetates, sulfoxides (eg, dimethylsulfoxide, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.), and the like, which may be used alone or in combination of two or more kinds
- the binder layer of the present invention is a layer formed using the binder composition of the present invention described above, and is a layer having an orientation regulating force.
- the method for forming the binder layer is not particularly limited because it depends on the kind of the binder, but when a polymerizable compound is used as the binder, it can be formed by a conventionally known method such as photocationic polymerization and radical polymerization.
- having an alignment regulating force means having a function of aligning a liquid crystal compound arranged on the binder layer in a predetermined direction.
- the optical layered body of the present invention is an optical layered body having the 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 the binder layer and the optically anisotropic layer. And are stacked adjacent to each other.
- the optical layered body of the present invention preferably has a support for supporting 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-based polymers having acrylic ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalate, polyethylene naphthalate, etc.
- polyolefin polymer vinyl chloride polymer; nylon, aromatic polyamide Amide polymers such as; imide polymers; sulfone polymers; polyether sulfone polymers; polyether ether ketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol polymers; vinyl butyral polymers; arylate polymers A polyoxymethylene-based polymer; an epoxy-based polymer; or a polymer obtained by mixing these polymers.
- the thickness of the support is not particularly limited, but is preferably 5 to 200 ⁇ m, more preferably 10 to 100 ⁇ m, and further preferably 20 to 90 ⁇ m.
- the binder layer is the binder layer of the present invention described above.
- the thickness of the binder layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the optically anisotropic layer is formed using the polymerizable liquid crystal composition containing the polymerizable liquid crystal compound.
- the polymerizable liquid crystal composition for forming the optically anisotropic layer for example, a composition in which the polymerizable liquid crystal compound described as an optional component in the binder composition of the present invention, a polymerization initiator and a solvent are mixed. Things are listed.
- the thickness of the optically anisotropic layer is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the method for producing the optical layered body of the present invention is not particularly limited.
- the action step is a step performed between the binder layer forming step and the second applying step, or simultaneously with the binder layer forming step or the second applying step.
- the irradiation step is a step that is performed between the binder layer forming step and the second coating step, or simultaneously with the binder layer forming step or the second coating step.
- the first coating step is a step of coating the above-mentioned binder composition of the present invention on the above-mentioned support.
- the method for applying the binder composition of the present invention is not particularly limited, and specific examples of the application method include spin coating, air knife coating, curtain coating, roller coating, wire bar coating, A gravure coating method, a die coating method and the like can be mentioned.
- the binder layer forming step is a step of forming a binder layer after the first coating step, and the coating film obtained in the first coating step is subjected to a curing treatment (ultraviolet irradiation (light irradiation treatment) or heat treatment). Can be formed by applying.
- a curing treatment ultraviolet irradiation (light irradiation treatment) or heat treatment.
- the conditions of the curing treatment are not particularly limited, it is preferable to use ultraviolet rays in the polymerization by light irradiation.
- 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 to 1000 mJ/cm 2 is particularly preferable. Further, in order to accelerate the polymerization reaction, it may be carried out under heating conditions.
- the action step is a step of acting at least one selected from the group consisting of light, heat, acid and base.
- the action step is between the binder layer forming step and the second coating step, or the binder layer forming step or the second coating, from the viewpoint of ensuring coating properties when forming the optically anisotropic layer as the upper layer.
- This is a process performed at the same time as the process.
- “between the binder layer forming step and the second applying step” means that the binder layer formed in the binder layer forming step (for example, thermal polymerization) is subjected to the action step before the second applying step. (For example, a step of applying light) is performed.
- “simultaneously with the binder layer forming step” means a step of forming a binder layer, for example, a step of forming a binder layer by polymerization of an olefinic monomer by photoradical generation, and polymerization of an epoxy monomer by photoacid generation.
- the action step (for example, a step of applying light) are performed at the same time. That is, it means that the light used for polymerization of the binder layer and the light used for cleavage cause two effects at the same time.
- “simultaneously with the second coating step” means that when the second coating step is performed on the binder layer formed in the binder layer forming step (for example, photopolymerization), an action step (for example, heat is applied). Process) is performed at the same time. Among these, it is preferable from the viewpoint of process simplification that the process is performed by applying light and is performed at the same time as the binder layer forming process.
- a method of irradiating the binder layer with ultraviolet rays can be mentioned.
- the light source it is possible to use a lamp that emits ultraviolet rays such as a high pressure mercury lamp or a metal halide lamp.
- the irradiation dose 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. More preferably, it is particularly preferably 50 to 1000 mJ/cm 2 .
- Examples of the method of applying heat include a method of heating the binder layer.
- the heating temperature is preferably 50 to 200° C., more preferably 60 to 150° C., and particularly preferably 70 to 130° C.
- the method of causing the acid to act for example, a method of previously adding an acid to the binder layer, a method of adding a photo-acid generator to the binder layer and generating an acid by using light as a trigger, and a binder layer
- a method of adding a photo-acid generator to the binder layer and generating an acid by using light as a trigger, and a binder layer examples thereof include a method in which a thermal acid generator is added and heat is used as a trigger to generate an acid. Of these, the method using a photo acid generator and a thermal acid generator is preferable.
- a method of causing the base to act for example, a method of previously adding a base to the binder layer, a method of adding a photobase generator to the binder layer and generating a base by using light as a trigger, and a binder layer
- a method of adding a photobase generator to the binder layer and generating a base by using light as a trigger examples include a method in which a thermal base generator is added and heat is used as a trigger to generate a base.
- the method using a photobase generator and a thermal base generator is preferable.
- the irradiation step is a step of irradiating polarized light or non-polarized light, that is, a step of forming a binder layer having an alignment regulating force. Further, the irradiation step is performed between the binder layer forming step and the second coating step, or in the binder layer forming step or the second coating, from the viewpoint of ensuring coating properties when forming the optically anisotropic layer as the upper layer. This is a process performed at the same time as the process.
- between the binder layer forming step and the second coating step means that the binder layer formed in the binder layer forming step (for example, thermal polymerization) is irradiated with the irradiation step before the second coating step. (For example, a step of irradiating polarized light) is performed.
- “simultaneously with the binder layer forming step” means a step of forming a binder layer, for example, a step of forming a binder layer by polymerization of an olefinic monomer by photoradical generation, and polymerization of an epoxy monomer by photoacid generation.
- the irradiation step (for example, the step of irradiating polarized light) are performed at the same time. That is, it means that the light used for polymerization of the binder layer and the light used for orientation simultaneously cause two actions.
- “simultaneously with the second coating step” means that when the second coating step is performed on the binder layer formed in the binder layer forming step (for example, photopolymerization), the irradiation step (for example, polarized light is irradiated). Process) is performed at the same time. Among these, it is preferable that the process is performed between the binder layer forming process and the second coating process.
- 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.
- a method of irradiating for example, a method of irradiating with polarized light of ultraviolet rays is preferably mentioned, and specifically, a method of using a polarizing plate (for example, iodine polarizing plate, dichroic dye polarizing plate, wire grid polarizing plate, etc.); prism Examples include a method using a system element (for example, Glan-Thompson prism, etc.) and a reflective polarizer using Brewster's angle; a method using light emitted from a laser light source having polarization.
- a polarizing plate for example, iodine polarizing plate, dichroic dye polarizing plate, wire grid polarizing plate, etc.
- prism Examples include a method using a system element (for example, Glan-Thompson prism, etc.) and a reflective polarizer using Brewster's angle; a method using light emitted from a laser light source having polarization.
- the light source used for ultraviolet irradiation is not particularly limited as long as it is a light source that emits ultraviolet light, and examples thereof include a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, and a xenon lamp. Can be used.
- the second coating step is a step of directly coating the polymerizable liquid crystal composition forming the optically anisotropic layer on the binder layer.
- the method of applying the polymerizable liquid crystal composition for forming the optically anisotropic layer is not particularly limited, and the method similar to the method of the first application step can be mentioned.
- the optically anisotropic layer forming step is a step of forming an optically anisotropic layer after the second coating step, and the coating film obtained in the second coating step is subjected to a curing treatment (ultraviolet irradiation (light irradiation)). It can be formed by performing a treatment) or a heat treatment). Moreover, although the conditions of the curing treatment are not particularly limited, it is preferable to use ultraviolet rays in the polymerization by light irradiation.
- 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 to 1000 mJ/cm 2 is particularly preferable. Further, in order to accelerate 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 and an organic EL display panel are preferable, and a liquid crystal cell is more preferable.
- the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element and an organic EL display device using an organic EL display panel as a display element.
- a liquid crystal display device which is an example of the image display device of the present invention, is a liquid crystal display device including the above-described optically anisotropic layer of the present invention or the optical laminate of the present invention, and a liquid crystal cell.
- the liquid crystal cell that constitutes 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 (Vertical Alignment) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, or a TN (Twisted Nematic). It is not limited to.
- VA Vertical Alignment
- OCB Optically Compensated Bend
- IPS In-Plane-Switching
- TN Transmission Nematic
- rod-shaped liquid crystal molecules rod-shaped liquid crystal compounds
- the TN mode liquid crystal cell is most often used as a color TFT liquid crystal display device, and is described in many documents.
- VA mode liquid crystal cell rod-shaped liquid crystal molecules are aligned substantially vertically when no voltage is applied.
- the VA-mode liquid crystal cell includes (1) a VA-mode liquid crystal cell in a narrow sense in which rod-like liquid crystal molecules are aligned substantially vertically when no voltage is applied, and are aligned substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. HEI 2-200,600).
- the VA mode is multi-domain (for MVA (Multi-domain Vertical Alignment) mode) liquid crystal cell (SID97, Digest of tech.
- n-ASM mode (Axially symmetric aligned microcell)
- a liquid crystal cell (described in Proceedings 58-59 (1998) of the Japan Liquid Crystal Conference) and (4) SURVIVAL (Super Range Viewing by Vertical Alignment) mode liquid crystal cell (announced at LCD (liquid crystal display) International 98) are included.
- SURVIVAL Super Range Viewing by Vertical Alignment
- LCD liquid crystal display
- any of a PVA (Patterned Vertical Alignment) type, a photo-alignment type (Optical Alignment), and a PSA (Polymer-Sustained Alignment) may be used.
- JP-A-2006-215326 and JP-A-2008-538819 Details of these modes are described in JP-A-2006-215326 and JP-A-2008-538819.
- the liquid crystal cell of the IPS mode rod-shaped liquid crystalline molecules are oriented substantially parallel to the substrate, and the liquid crystalline molecules respond in a plane when an electric field parallel to the substrate surface is applied.
- 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.
- a method of reducing leakage light at the time of black display in an oblique direction and improving a viewing angle by using an optical compensation sheet is disclosed in JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522.
- Organic EL display As an organic EL display device which is an example of the image display device of the present invention, for example, a polarizer, an optically anisotropic layer of the present invention or an optical laminate of the present invention, and an organic EL display panel are provided from the viewing side. Preferred embodiments include those having the same order.
- the above-mentioned 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 polarizer include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers.
- the iodine-based polarizer and the dye-based polarizer include a coating-type polarizer and a stretch-type polarizer, both of which are applicable.
- Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 4691205, No. 4,751,481 and Japanese Patent No. 4,751,486 can be cited, and known techniques relating to these polarizers can also be preferably used.
- the reflection-type polarizer a polarizer in which thin films having different birefringence are laminated, a wire grid-type polarizer, a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1 ⁇ 4 wavelength plate are combined are used.
- a polyvinyl alcohol-based resin (a polymer containing —CH 2 —CHOH— as a repeating unit, in particular, at least selected from the group consisting of polyvinyl alcohol and an ethylene-vinyl alcohol copolymer, in view of better adhesion. It is preferable that the polarizer includes one).
- the thickness of the polarizer is not particularly limited, but is preferably 3 ⁇ m to 60 ⁇ m, more preferably 5 ⁇ m to 30 ⁇ m, and further preferably 5 ⁇ m to 15 ⁇ m.
- the organic EL display panel is a member in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes of an anode and a cathode, and in addition to the light emitting layer, a hole injection layer, a hole transport layer, and an electron injection layer. It may have a layer, an electron transporting layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.
- Example 1-1 A flask equipped with a cooling tube, a thermometer, and a stirrer was charged with 5 parts by mass of 2-butanone as a solvent, and refluxed by heating in a water bath while flowing 5 mL/min of nitrogen in the flask. 50 parts by mass of the following monomer mA-52, 20 parts by mass of the following monomer mB-2, 30 parts by mass of the following monomer mC-1 and 2,2′-azobis(isobutyronitrile) as a polymerization initiator were added. A solution obtained by mixing 1 part by mass and 5 parts by mass of 2-butanone as a solvent was added dropwise over 3 hours, and the mixture was stirred for 3 hours while maintaining a reflux state.
- Examples 1-2 to 1-11 and Comparative Example 1-1 Synthesized in Example 1 except that each of the synthesized monomers was used as the monomer forming the repeating unit shown in Table 1 below and the addition amount of the polymerization initiator was changed so as to obtain the weight average molecular weight shown in Table 1 below.
- a copolymer was synthesized in the same manner as the polymer P-1.
- Table 1 below the structures of the repeating unit A-9, repeating unit B-2, etc. are the same as those described in the above description of each repeating unit.
- Example 2-1 [Preparation of binder layer] Acrylic monomer (PET A, manufactured by Osaka Organic Chemical Industry Co., Ltd.) (100 parts by mass), photopolymerization initiator (IRGACURE819, manufactured by BASF) (3 parts by mass), photo acid generator (B-1-1) below ( 5.0 parts by mass) and copolymer P-4 (2.0 parts by mass) were dissolved in methyl ethyl ketone (300 parts by mass) to prepare a binder layer forming solution.
- the prepared solution for forming a binder layer was spin-coated on a cleaned glass substrate and irradiated with ultraviolet rays at a dose of 500 mJ/cm 2 at room temperature using a 365 nm UV-LED. Then, the binder layer was produced by annealing for 1 minute at 120 degreeC.
- the film thickness was about 3 ⁇ m.
- the surface energy of the binder layer was 50 mN/m.
- the obtained binder layer is irradiated with UV light (ultra-high pressure mercury lamp; UL750; made by HOYA) that has passed through a wire grid polarizer at room temperature at 25 mJ/cm 2 (wavelength: 313 nm) to have an alignment function (regulating force). Granted.
- UV light ultra-high pressure mercury lamp; UL750; made by HOYA
- the above-mentioned solution for forming an optically anisotropic layer was coated on the binder layer having the above-mentioned orientation function (regulating force) with a wire bar coater #2.2, heated at 60°C for 2 minutes, and maintained at 60°C.
- a wire bar coater #2.2 heated at 60°C for 2 minutes, and maintained at 60°C.
- an irradiation dose of 300 mJ/cm 2 of ultraviolet rays is applied. Irradiation was performed to form an optically anisotropic layer, and an optical layered body was produced.
- Example 2-2 An optical layered body was produced in the same manner as in Example 2-1, except that the copolymer P-9 was used instead of the copolymer P-4.
- Example 2-3 An optical layered body was produced in the same manner as in Example 2-2, except that 50 parts by mass of each of the following liquid crystal compound L-3 and the following liquid crystal compound L-4 were used instead of the rod-shaped liquid crystal compound.
- the group adjacent to the acryloyloxy group of the following liquid crystal compounds L-3 and L-4 represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and the following liquid crystal compounds L-3 and L-4 are It represents a mixture of regioisomers with different positions of the methyl group.
- Example 2-4 An optical layered body was produced in the same manner as in Example 2-2 except that 50 parts by mass of each of the following liquid crystal compound L-5 and the following liquid crystal compound L-6 was used instead of the rod-shaped liquid crystal compound.
- Example 2-5 An optical layered body was produced in the same manner as in Example 2-2 except that the following liquid crystal compound L-7 was used instead of the rod-shaped liquid crystal compound.
- Example 2-6 The copolymer P-11 was used in place of the copolymer P-9, and the following liquid crystal compound L-1 and the following liquid crystal compound L-2 were used instead of the acrylic monomer (PETA, manufactured by Osaka Organic Chemical Industry Co., Ltd.). In the same manner as in Example 2-3 except that the following vertical alignment agent S-1 (1.0 part by mass) and the following vertical alignment agent S-2 (1.0 part by mass) were added. A laminated body was produced.
- Example 2-7 The copolymer P-11 was used in place of the copolymer P-9, and the following liquid crystal compounds L-8 (83 parts by mass) and L were used instead of the acrylic monomer (PETA, manufactured by Osaka Organic Chemical Industry Co., Ltd.). -9 (15 parts by mass) and L-10 (2 parts by mass) were used, and the above vertical alignment agents S-1 (1.0 parts by mass) and S-2 (1.0 parts by mass) were added.
- An optical laminate was prepared in the same manner as in Example 2-3.
- Wind unevenness Two polarizing plates were placed in crossed Nicols, and a sample of the prepared binder layer was placed between them to observe the presence or absence of streaky unevenness, and the wind unevenness was evaluated according to the following criteria. The results are shown in Table 2 below. ⁇ Evaluation criteria> A: Unevenness is not visible. B: Almost no unevenness is visible. C: Unevenness is visible.
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Abstract
Description
光学フィルムとしては延伸複屈折フィルムが使用されていたが、近年、延伸複屈折フィルムに代えて、液晶化合物を用いた光学異方性層を使用することが提案されている。
また、特許文献2には、所定の光配向性基を含む繰り返し単位Aと、所定の架橋性基を含む繰り返し単位Bとを有する光配向性共重合体、および、この光配向性共重合体を含有する光配向膜用組成物を用いて形成した光配向膜が記載されている([請求項1][請求項13])。
すなわち、本発明者らは、以下の構成により上記課題を達成することができることを見出した。
光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により架橋反応を生起する架橋性基を含む繰り返し単位Bと、
光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により分解して極性基を生じる開裂基を含む繰り返し単位Cと、を有する光配向性共重合体であって、
繰り返し単位Cが、側鎖に開裂基を有し、かつ、側鎖の開裂基よりも末端側に、光配向性共重合体を空気界面側に偏在させることが可能な原子団を有し、
繰り返し単位Aの含有量aと、繰り返し単位Bの含有量bと、繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W1)~(W3)を満たす、光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.75 ・・・(W1)
0.20 ≦ b/(a+b+c) ≦ 0.90 ・・・(W2)
0.03 ≦ c/(a+b+c) ≦ 0.70 ・・・(W3)
0.03 ≦ a/(a+b+c) ≦ 0.45 ・・・(W4)
0.45 ≦ b/(a+b+c) ≦ 0.90 ・・・(W5)
0.03 ≦ c/(a+b+c) ≦ 0.50 ・・・(W6)
[3] 繰り返し単位Aの含有量aと、繰り返し単位Bの含有量bと、繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W7)~(W9)を満たす、[1]に記載の光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.40 ・・・(W7)
0.55 ≦ b/(a+b+c) ≦ 0.90 ・・・(W8)
0.03 ≦ c/(a+b+c) ≦ 0.40 ・・・(W9)
[4] 繰り返し単位Aの含有量aと、繰り返し単位Bの含有量bと、繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W10)~(W12)を満たす、[1]に記載の光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.20 ・・・(W10)
0.60 ≦ b/(a+b+c) ≦ 0.80 ・・・(W11)
0.15 ≦ c/(a+b+c) ≦ 0.35 ・・・(W12)
ここで、上記式(C1)および(C2-1)中、R11は、水素原子または炭素数1~3のアルキル基を表し、上記式(C1)中の複数のR11は、それぞれ同一であっても異なっていてもよい。
また、上記式(C1)、(C2-1)および(C2-2)中、X11およびX12は、それぞれ独立に単結合または2価の連結基を表し、RKは、開裂基を表し、RLは、フッ素原子またはケイ素原子を含む1価の有機基を表す。
ここで、上記式(rk-1)~(rk-13)中、*1は、上記式(C1)、(C2-1)および(C2-2)中のX11およびX12のいずれか一方との結合位置を表し、*2は、上記式(C1)、(C2-1)および(C2-2)中のX11およびX12のうち*1と結合していない側との結合位置を表し、Rは、それぞれ独立に水素原子または1価の有機基を表す。
上記式(A)中、R1は、水素原子またはメチル基を表し、L1は、2価の連結基を表す。R2、R3、R4、R5およびR6は、それぞれ独立に、水素原子または置換基を表し、R2、R3、R4、R5およびR6のうち、隣接する2つの基が結合して環を形成していてもよい。
上記式(1)~(10)中、*1は、上記式(A)中の主鎖を構成する炭素原子との結合位置を表し、*2は、上記式(A)中のカルボニル基を構成する炭素原子との結合位置を表す。
[12] 上記式(A)中のR2、R3、R4、R5およびR6のうち、少なくともR4が置換基を表す、[8]~[11]のいずれかに記載の光配向性共重合体。
[13] 上記式(A)中のR2、R3、R5およびR6がいずれも水素原子を表す、[12]に記載の光配向性共重合体。
[14] 上記式(A)中のR4が、電子供与性の置換基である、[12]または[13]に記載の光配向性共重合体。
[15] 上記式(A)中のR4が、炭素数が6~16のアルコキシ基である、[14]に記載の光配向性共重合体。
[16] 上記式(A)中のR2、R3、R4、R5およびR6が表す置換基が、それぞれ独立に、ハロゲン原子、炭素数1~20の直鎖状、分岐状もしくは環状のアルキル基、炭素数1~20の直鎖状のハロゲン化アルキル基、炭素数1~20のアルコキシ基、炭素数6~20のアリール基、炭素数6~20のアリールオキシ基、シアノ基、アミノ基、または、下記式(11)で表される基である、[8]~[15]のいずれかに記載の光配向性共重合体。
上記式(11)中、*は、上記式(A)中のベンゼン環との結合位置を表し、R9は、1価の有機基を表す。
上記式(B)中、R7は、水素原子またはメチル基を表し、L2は、2価の連結基を表し、Xは、架橋性基を表す。
[18] 上記式(B)中のXが、下記式(X1)~(X4)からなる群から選択される少なくとも1種の架橋性基である、[17]に記載の光配向性共重合体。
上記式(X1)~(X4)中、*は、上記式(B)中のL2との結合位置を表し、R8は、水素原子、メチル基およびエチル基のいずれかを表し、上記式(X4)中、Sは、エチレン性不飽和二重結合を有する官能基を表す。
[19] 繰り返し単位Bが、上記式(B)中のXが上記式(X1)~(X3)のいずれかで表される架橋性基である繰り返し単位と、上記式(B)中のXが上記式(X4)で表される架橋性基である繰り返し単位とを含む、[18]に記載の光配向性共重合体。
[20] 上記式(B)中のL2が、それぞれ独立に、置換基を有していてもよい炭素数1~18の直鎖状、分岐状または環状のアルキレン基、置換基を有していてもよい炭素数6~12のアリーレン基、エーテル基、カルボニル基、および、置換基を有していてもよいイミノ基からなる群から選択される少なくとも2以上の基を組み合わせた2価の連結基である、[17]~[19]のいずれかに記載の光配向性共重合体。
[22] 重量平均分子量が30000~300000である、[21]に記載の光配向性共重合体。
[24] [23]に記載のバインダー組成物を用いて形成される、バインダー層。
[25] [24]に記載のバインダー層と、バインダー層上に設けられる光学異方性層とを有する光学積層体であって、
光学異方性層が、重合性液晶化合物を含有する重合性液晶組成物を用いて形成され、
バインダー層と光学異方性層とが互いに隣接して積層されている、光学積層体。
[26] [24]に記載のバインダー層または[25]に記載の光学積層体を有する、画像表示装置。
以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。
なお、本願明細書において、「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明の光配向性共重合体は、光配向性基を含む繰り返し単位Aと、光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により架橋反応を生起する架橋性基を含む繰り返し単位Bと、光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により分解して極性基を生じる開裂基を含む繰り返し単位Cと、を有する光配向性共重合体である。
また、本発明の光配向性共重合体は、繰り返し単位Cが、側鎖に開裂基を有し、かつ、側鎖の開裂基よりも末端側に、光配向性共重合体を空気界面側に偏在させることが可能な原子団を有する。
更に、本発明の光配向性共重合体は、繰り返し単位Aの含有量aと、繰り返し単位Bの含有量bと、繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W1)~(W3)を満たすものである。
0.03 ≦ a/(a+b+c) ≦ 0.75 ・・・(W1)
0.20 ≦ b/(a+b+c) ≦ 0.90 ・・・(W2)
0.03 ≦ c/(a+b+c) ≦ 0.70 ・・・(W3)
これは、詳細には明らかではないが、本発明者らは以下のように推測している。
すなわち、本発明の光配向性共重合体を含有する組成物を塗布し、バインダー層などの層として形成された後において、空気界面側に偏在した本発明の光配向性共重合体に対して、光、熱、酸および塩基からなる群から選択される少なくとも1種を作用させることにより、側鎖に含まれる開裂基が分解して極性基を生じるため、上層塗布性が良好になったと考えられる。
以下に、繰り返し単位A、BおよびCについて詳述する。
本発明の光配向性共重合体が有する繰り返し単位Aは、光配向性基を含む繰り返し単位である。
ここで、「光配向性基」とは、異方性を有する光(例えば、平面偏光など)の照射により、再配列や異方的な化学反応が誘起される光配向機能を有する基をいい、配向の均一性に優れ、熱的安定性や化学的安定性も良好となる理由から、光の作用により二量化および異性化の少なくとも一方が生じる光配向性基が好ましい。
一方、光の作用により異性化する光配向性基としては、具体的には、例えば、アゾベンゼン化合物(K. Ichimura et al.,Mol.Cryst.Liq.Cryst .,298,221(1997))、スチルベン化合物(J.G.Victor and J.M.Torkelson,Macromolecules,20,2241(1987))、スピロピラン化合物(K. Ichimura et al., Chemistry Letters, page 1063 (1992) ;K.Ichimura et al., Thin Solid Films, vol. 235, page 101 (1993) )、桂皮酸化合物(K.Ichimura et al.,Macromolecules,30,903(1997))、および、ヒドラゾノ-β-ケトエステル化合物(S. Yamamura et al., Liquid Crystals, vol. 13, No. 2, page 189 (1993))からなる群から選択される少なくとも1種の化合物の骨格を有する基などが好適に挙げられる。
上記式(A)中、R1は、水素原子またはメチル基を表し、L1は、2価の連結基を表す。R2、R3、R4、R5およびR6は、それぞれ独立に、水素原子または置換基を表し、R2、R3、R4、R5およびR6のうち、隣接する2つの基が結合して環を形成していてもよい。
ここで、2価の連結基は、後述する式(B)中のL2で説明するものと同様のものが挙げられるが、本発明の光配向性共重合体を含有する組成物を塗布し、バインダー層などの層として形成された後において、形成された層上に液晶化合物を用いて形成される光学異方性層の配向性(以下、「液晶配向性」ともいう。)がより良好となる理由から、窒素原子とシクロアルカン環とを含む2価の連結基であることが好ましい。なお、本発明においては、上述した通り、シクロアルカン環を構成する炭素原子の一部は、窒素、酸素および硫黄からなる群から選択されるヘテロ原子で置換されていてもよい。また、シクロアルカン環を構成する炭素原子の一部が窒素原子で置換されている場合は、シクロアルカン環とは別に窒素原子を有していなくてもよい。
上記式(1)~(10)中、*1は、上記式(A)中の主鎖を構成する炭素原子との結合位置を表し、*2は、上記式(A)中のカルボニル基を構成する炭素原子との結合位置を表す。
ここで、上記式(11)中、*は、上記式(A)中のベンゼン環との結合位置を表し、R9は、1価の有機基を表す。
分岐状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、イソプロピル基、tert-ブチル基などが挙げられる。
環状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられる。
直鎖状のアルキル基としては、炭素数1~6のアルキル基が好ましく、具体的には、例えば、メチル基、エチル基、n-プロピル基などが挙げられ、中でも、メチル基またはエチル基が好ましい。
環状のアルキル基としては、炭素数3~6のアルキル基が好ましく、具体的には、例えば、シクロプロピル基、シクロペンチル基、シクロヘキシル基などが挙げられ、中でも、シクロヘキシル基が好ましい。
なお、上記式(11)中のR9が表す1価の有機基としては、上述した直鎖状のアルキル基および環状のアルキル基を直接または単結合を介して複数組み合わせたものであってもよい。
ここで、電子供与性の置換基(電子供与性基)とは、ハメット値(Hammett置換基定数σp)が0以下の置換基のことをいい、例えば、上述した置換基のうち、アルキル基、ハロゲン化アルキル基、アルコキシ基などが挙げられる。
これらのうち、アルコキシ基であることが好ましく、バインダー層などの層として形成する際に、乾燥時の乾燥風で引き起こされる膜厚ムラ(以下、「風ムラ」ともいう。)を抑制でき、液晶配向性がより良好となる理由から、炭素数が6~16のアルコキシ基であることがより好ましく、炭素数7~10のアルコキシ基であることが更に好ましい。
本発明の光配向性共重合体が有する繰り返し単位Bは、光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により架橋反応を生起する架橋性基を含む繰り返し単位である。
上記式(B)中、R7は、水素原子またはメチル基を表し、L2は、2価の連結基を表し、Xは、架橋性基を表す。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、中でも、フッ素原子、塩素原子であるのが好ましい。
アルキル基としては、例えば、炭素数1~18の直鎖状、分岐鎖状または環状のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、シクロヘキシル基等)がより好ましく、炭素数1~4のアルキル基であることが更に好ましく、メチル基またはエチル基であるのが特に好ましい。
アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、メトキシエトキシ基等)がより好ましく、炭素数1~4のアルコキシ基であることが更に好ましく、メトキシ基またはエトキシ基であるのが特に好ましい。
アリール基としては、例えば、炭素数6~12のアリール基が挙げられ、具体的には、例えば、フェニル基、α-メチルフェニル基、ナフチル基などが挙げられ、中でも、フェニル基が好ましい。
アリールオキシ基としては、例えば、フェノキシ、ナフトキシ、イミダゾイルオキシ、ベンゾイミダゾイルオキシ、ピリジン-4-イルオキシ、ピリミジニルオキシ、キナゾリニルオキシ、プリニルオキシ、チオフェン-3-イルオキシなどが挙げられる。
アルコキシカルボニル基としては、例えば、メトキシカルボニル、エトキシカルボニルなどが挙げられる。
また、分岐状のアルキレン基としては、具体的には、例えば、ジメチルメチレン基、メチルエチレン基、2,2-ジメチルプロピレン基、2-エチル-2-メチルプロピレン基などが挙げられる。
また、環状のアルキレン基としては、具体的には、例えば、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロオクチレン基、シクロデシレン基、アダマンタン-ジイル基、ノルボルナン-ジイル基、exo-テトラヒドロジシクロペンタジエン-ジイル基などが挙げられ、中でも、シクロヘキシレン基が好ましい。
上記式(X1)~(X4)中、*は、上記式(B)中のL2との結合位置を表し、R8は、水素原子、メチル基およびエチル基のいずれかを表し、上記式(X4)中、Sは、エチレン性不飽和二重結合を有する官能基を表す。
ここで、エチレン性不飽和二重結合を有する官能基としては、具体的には、例えば、ビニル基、アリル基、スチリル基、アクリロイル基、メタクリロイル基が挙げられ、アクリロイル基またはメタクリロイル基であることが好ましい。
本発明の光配向性共重合体が有する繰り返し単位Cは、光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により分解して極性基を生じる開裂基を含む繰り返し単位である。
また、本発明の光配向性共重合体が有する繰り返し単位Cは、側鎖に上記開裂基を有し、かつ、側鎖の上記開裂基よりも末端側に、本発明の光配向性共重合体を空気界面側に偏在させることが可能な原子団を有する。
ここで、「極性基」とは、ヘテロ原子またはハロゲン原子を少なくとも1原子以上有する基をいい、具体的には、例えば、水酸基、カルボニル基、カルボキシ基、アミノ基、ニトロ基、アンモニウム基、シアノ基などが挙げられる。なかでも、水酸基、カルボキシ基が好ましい。
また、「極性基を生じる開裂基」とは、開裂によって上述した極性基を生じる基をいうが、本発明においては、ラジカル開裂後に酸素分子と反応し、極性基を生成する基も含む。
更に、「空気界面側に偏在させることが可能な原子団」とは、本発明の光配向性共重合体を含有する組成物を塗布し、バインダー層などの層として形成した際に、層の空気界面側に本発明の光配向性共重合体を偏在させることが可能な官能基団をいい、具体的には、例えば、フッ素原子、ケイ素原子および長鎖アルキル基(例えば、炭素数6~20のアルキル基)などの表面エネルギーを低減可能な原子団が挙げられる。
R11としては、水素原子またはメチル基であることが好ましい。
アルキル基としては、例えば、炭素数1~18の直鎖状、分岐鎖状または環状のアルキル基が好ましく、炭素数1~8のアルキル基(例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、t-ブチル基、シクロヘキシル基等)がより好ましく、炭素数1~4のアルキル基であることが更に好ましく、メチル基またはエチル基であるのが特に好ましい。
アルコキシ基としては、例えば、炭素数1~18のアルコキシ基が好ましく、炭素数1~8のアルコキシ基(例えば、メトキシ基、エトキシ基、n-ブトキシ基、メトキシエトキシ基等)がより好ましく、炭素数1~4のアルコキシ基であることが更に好ましく、メトキシ基またはエトキシ基であるのが特に好ましい。
ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子などが挙げられ、なかでも、フッ素原子、塩素原子であるのが好ましい。
また、分岐状のアルキレン基としては、具体的には、例えば、ジメチルメチレン基、メチルエチレン基、2,2-ジメチルプロピレン基、2-エチル-2-メチルプロピレン基などが挙げられる。
また、環状のアルキレン基としては、具体的には、例えば、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロオクチレン基、シクロデシレン基、アダマンタン-ジイル基、ノルボルナン-ジイル基、exo-テトラヒドロジシクロペンタジエン-ジイル基などが挙げられ、なかでも、シクロヘキシレン基が好ましい。
ここで、Rが示す1価の有機基としては、例えば、炭素数1~20の鎖状または環状のアルキル基、置換基を有していていてもよい炭素数6~20のアリール基等が挙げられる。
無機のアニオンとしては、具体的には、例えば、塩化物イオン、臭化物イオンなどのハロゲン化物イオン;スルホン酸アニオン;等が挙げられる。
有機のアニオンとしては、具体的には、例えば、酢酸アニオンなどのカルボン酸アニオン;メタンスルホン酸アニオン、パラトルエンスルホン酸アニオンなどの有機スルホン酸アニオン;等を挙げることができる。
0.03 ≦ a/(a+b+c) ≦ 0.45 ・・・(W4)
0.45 ≦ b/(a+b+c) ≦ 0.90 ・・・(W5)
0.03 ≦ c/(a+b+c) ≦ 0.50 ・・・(W6)
0.03 ≦ a/(a+b+c) ≦ 0.40 ・・・(W7)
0.55 ≦ b/(a+b+c) ≦ 0.90 ・・・(W8)
0.03 ≦ c/(a+b+c) ≦ 0.40 ・・・(W9)
0.03 ≦ a/(a+b+c) ≦ 0.20 ・・・(W10)
0.60 ≦ b/(a+b+c) ≦ 0.80 ・・・(W11)
0.15 ≦ c/(a+b+c) ≦ 0.35 ・・・(W12)
本発明の光配向性共重合体は、本発明の効果を阻害しない限り、上述した繰り返し単位A、繰り返し単位Bおよび繰り返し単位C以外に、他の繰り返し単位Dを有していてもよい。
ここで、置換基、および、炭素数1~18の直鎖状、分岐状または環状のアルキレン基などについては、上記式(B)中のL2において説明したものと同様である。
ここで、本発明における重量平均分子量および数平均分子量は、以下に示す条件でゲル浸透クロマトグラフ(GPC)法により測定された値である。
・溶媒(溶離液):THF(テトラヒドロフラン)
・装置名:TOSOH HLC-8320GPC
・カラム:TOSOH TSKgel Super HZM-H(4.6mm×15cm
)を3本接続して使用
・カラム温度:40℃
・試料濃度:0.1質量%
・流速:1.0ml/min
・校正曲線:TOSOH製TSK標準ポリスチレン Mw=2800000~1050(Mw/Mn=1.03~1.06)までの7サンプルによる校正曲線を使用
本発明のバインダー組成物は、バインダーと本発明の光配向性共重合体とを含有する組成物である。
ここで、本発明のバインダー組成物中に含まれる光配向性共重合体の含有量は、後述するバインダー100質量部に対して、0.1~10質量部であることが好ましく、0.5~5質量部であることがより好ましい。
本発明のバインダー組成物に含まれるバインダーは、特に限定されず、それ自体は重合反応性のない樹脂のみから構成されるような単に乾燥固化する樹脂(以下、「樹脂バインダー」ともいう。)であってもよく、重合性化合物であってもよい。
樹脂バインダーとしては、具体的には、例えば、エポキシ樹脂、ジアリルフタレート樹脂、シリコーン樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ポリイミド樹脂、ポリウレタン樹脂、メラミン樹脂、ユリア樹脂、アイオノマー樹脂、エチレンエチルアクリレート樹脂、アクリロニトリルアクリレートスチレン共重合樹脂、アクリロニトリルスチレン樹脂、アクリロニトリル塩化ポリエチレンスチレン共重合樹脂、エチレン酢ビ樹脂、エチレンビニルアルコール共重合樹脂、アクリロニトリルブタジエンスチレン共重合樹脂、塩化ビニル樹脂、塩素化ポリエチレン樹脂、ポリ塩化ビニリデン樹脂、酢酸セルロース樹脂、フッ素樹脂、ポリオキシメチレン樹脂、ポリアミド樹脂、ポリアリレート樹脂、熱可塑性ポリウレタンエラストマー、ポリエーテルエーテルケトン樹脂、ポリエーテルスルホン樹脂、ポリエチレン、ポリプロピレン、ポリカーボネート樹脂、ポリスチレン、ポリスチレンマレイン酸共重合樹脂、ポリスチレンアクリル酸共重合樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンサルファイド樹脂、ポリブタジエン樹脂、ポリブチレンテレフタレート樹脂、アクリル樹脂、メタクリル樹脂、メチルペンテン樹脂、ポリ乳酸、ポリブチレンサクシネート樹脂、ブチラール樹脂、ホルマール樹脂、ポリビニルアルコール、ポリビニルピロリドン、エチルセルロース、カルボキシメチルセルロース、ゼラチン、および、これらの共重合樹脂などが挙げられる。
重合性化合物としては、例えば、エポキシ系モノマー、アクリル系モノマー、オキセタニル系モノマーなどが挙げられ、なかでも、エポキシ系モノマーおよびアクリル系モノマーが好ましい。
また、本発明においては、重合性化合物として、重合性液晶化合物を用いてもよい。
エポキシ系モノマーであるエポキシ基含有モノマーとしては、例えば、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ジフェニルエーテル型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビフェニル型エポキシ樹脂、フルオレン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂、トリスヒドロキシフェニルメタン型エポキシ樹脂、3官能型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、ジシクロペンタジエンフェノール型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールA含核ポリオール型エポキシ樹脂、ポリプロピレングリコール型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリオキザール型エポキシ樹脂、脂環型エポキシ樹脂、複素環型エポキシ樹脂などを挙げることができる。
アクリル系モノマーである、アクリレートモノマー及びメタクリレートモノマーとしては、3官能モノマーとして、トリメチロールプロパントリアクリレート、トリメチロールプロパンPO(プロピレンオキサイド)変性トリアクリレート、トリメチロールプロパンEO(エチレンオキサイド)変性トリアクリレート、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアクリレートが挙げられる。また、4官能以上のモノマー、オリゴマーとして、例えば、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート等を例示することができる。
重合性液晶化合物は、特に限定されず、例えば、ホメオトロピック配向、ホモジニアス配向、ハイブリッド配向およびコレステリック配向のいずれかの配向が可能な化合物を用いることができる。
ここで、一般的に、液晶化合物はその形状から、棒状タイプと円盤状タイプに分類できる。さらにそれぞれ低分子と高分子タイプがある。高分子とは一般に重合度が100以上のものを指す(高分子物理・相転移ダイナミクス,土井 正男 著,2頁,岩波書店,1992)。本発明では、いずれの液晶化合物を用いることもできるが、棒状液晶化合物(以下、「CLC」とも略す。)またはディスコティック液晶化合物(円盤状液晶化合物)(以下、「DLC」とも略す。)を用いることが好ましく、また、モノマーであるか、重合度が100未満の比較的低分子量な液晶化合物を用いることが好ましい。
また、重合性液晶化合物が有する重合性基としては、具体的には、例えば、アクリロイル基、メタクリロイル基、エポキシ基、ビニル基等が挙げられる。
このような重合性液晶化合物を重合させることにより、液晶化合物の配向を固定することができる。なお、液晶化合物が重合によって固定された後においては、もはや液晶性を示す必要はない。
ここで、本明細書において「逆波長分散性」の液晶化合物とは、これを用いて作製された位相差フィルムの特定波長(可視光範囲)における面内のレターデーション(Re)値を測定した際に、測定波長が大きくなるにつれてRe値が同等または高くなるものをいう。
更に、特開2011-6360号公報の段落番号[0027]~[0100]、特開2011-6361号公報の段落番号[0028]~[0125]、特開2012-207765号公報の段落番号[0034]~[0298]、特開2012-77055号公報の段落番号[0016]~[0345]、WO12/141245号公報の段落番号[0017]~[0072]、WO12/147904号公報の段落番号[0021]~[0088]、WO14/147904号公報の段落番号[0028]~[0115]に記載の化合物を用いることができる。
本発明のバインダー組成物は、バインダーとして重合性化合物を用いた場合には、重合開始剤を含有することが好ましい。
このような重合開始剤は特に限定されないが、重合反応の形式に応じて、熱重合開始剤および光重合開始剤が挙げられる。
本発明においては、紫外線照射によって重合反応を開始可能な光重合開始剤であることが好ましい。
光重合開始剤としては、例えば、α-カルボニル化合物(米国特許第2367661号、同2367670号の各明細書記載)、アシロインエーテル(米国特許第2448828号明細書記載)、α-炭化水素置換芳香族アシロイン化合物(米国特許第2722512号明細書記載)、多核キノン化合物(米国特許第3046127号、同2951758号の各明細書記載)、トリアリールイミダゾールダイマーとp-アミノフェニルケトンとの組み合わせ(米国特許第3549367号明細書記載)、アクリジンおよびフェナジン化合物(特開昭60-105667号公報、米国特許第4239850号明細書記載)およびオキサジアゾール化合物(米国特許第4212970号明細書記載)、アシルフォスフィンオキシド化合物(特公昭63-40799号公報、特公平5-29234号公報、特開平10-95788号公報、特開平10-29997号公報記載)等が挙げられる。
本発明のバインダー組成物は、上述した光配向性共重合体が、酸の作用により分解して極性基を生じる開裂基を含む1価の特定基を有する重合体である場合、光酸発生剤を含有していることが好ましい。
本発明のバインダー組成物は、バインダー層を形成する作業性等の観点から、溶媒を含有するのが好ましい。
溶媒としては、具体的には、例えば、ケトン類(例えば、アセトン、2-ブタノン、メチルイソブチルケトン、シクロヘキサノンなど)、エーテル類(例えば、ジオキサン、テトラヒドロフランなど)、脂肪族炭化水素類(例えば、ヘキサンなど)、脂環式炭化水素類(例えば、シクロヘキサンなど)、芳香族炭化水素類(例えば、トルエン、キシレン、トリメチルベンゼンなど)、ハロゲン化炭素類(例えば、ジクロロメタン、ジクロロエタン、ジクロロベンゼン、クロロトルエンなど)、エステル類(例えば、酢酸メチル、酢酸エチル、酢酸ブチルなど)、水、アルコール類(例えば、エタノール、イソプロパノール、ブタノール、シクロヘキサノールなど)、セロソルブ類(例えば、メチルセロソルブ、エチルセロソルブなど)、セロソルブアセテート類、スルホキシド類(例えば、ジメチルスルホキシドなど)、アミド類(例えば、ジメチルホルムアミド、ジメチルアセトアミドなど)等が挙げられ、これらを1種単独で用いてもよく、2種以上を併用してもよい。
本発明のバインダー層は、上述した本発明のバインダー組成物を用いて形成される層であり、配向規制力を有する層である。
バインダー層の形成方法は、バインダーの種類によって異なるため特に限定されないが、バインダーとして重合性化合物を用いた場合には、光カチオン重合、ラジカル重合など、従来公知の方法で形成することができる。
なお、配向規制力を有するとは、バインダー層上に配置される液晶化合物を所定の方向に配向させる機能を有することを意味する。
本発明の光学積層体は、本発明のバインダー層と、バインダー層上に設けられる光学異方性層とを有する光学積層体である。
本発明の光学積層体は、バインダー層上に設けられる光学異方性層が重合性液晶化合物を含有する重合性液晶組成物を用いて形成されており、また、バインダー層と光学異方性層とが互いに隣接して積層されている。
また、本発明の光学積層体は、バインダー層を支持する支持体を有していることが好ましい。
以下、本発明の光学積層体の好適態様について詳述する。
支持体としては、例えば、ガラス基板およびポリマーフィルムが挙げられる。
ポリマーフィルムの材料としては、セルロース系ポリマー;ポリメチルメタクリレート、ラクトン環含有重合体等のアクリル酸エステル重合体を有するアクリル系ポリマー;熱可塑性ノルボルネン系ポリマー;ポリカーボネート系ポリマー;ポリエチレンテレフタレート、ポリエチレンナフタレート等のポリエステル系ポリマー;ポリスチレン、アクリロニトリル・スチレン共重合体(AS樹脂)等のスチレン系ポリマー;ポリエチレン、ポリプロピレン、エチレン・プロピレン共重合体等のポリオレフィン系ポリマー;、塩化ビニル系ポリマー;ナイロン、芳香族ポリアミド等のアミド系ポリマー;イミド系ポリマー;スルホン系ポリマー;ポリエーテルスルホン系ポリマー;ポリエーテルエーテルケトン系ポリマー;ポリフェニレンスルフィド系ポリマー;塩化ビニリデン系ポリマー;ビニルアルコール系ポリマー;ビニルブチラール系ポリマー;アリレート系ポリマー;ポリオキシメチレン系ポリマー;エポキシ系ポリマー;またはこれらのポリマーを混合したポリマーが挙げられる。
バインダー層は、上述した本発明のバインダー層である。
本発明においては、上記バインダー層の厚みについては特に限定されないが、0.1~10μmであるのが好ましく、0.5~5μmであるのがより好ましい。
光学異方性層は、上述したように、重合性液晶化合物を含有する重合性液晶組成物を用いて形成される。
ここで、光学異方性層を形成するための重合性液晶組成物としては、例えば、本発明のバインダー組成物において任意成分として記載した重合性液晶化合物、重合開始剤および溶媒などを配合した組成物が挙げられる。
本発明の光学積層体を作製する方法は特に限定されず、例えば、上述した支持体上に、上述した本発明のバインダー組成物を塗布する第1塗布工程と、第1塗布工程の後に、バインダー層を形成するバインダー層形成工程と、光、熱、酸および塩基からなる群から選択される少なくとも1種を作用させる作用工程と、偏光または無偏光を照射する照射工程と、バインダー層上に、光学異方性層を形成する重合性液晶組成物を直接塗布する第2塗布工程と、第2塗布工程の後に、光学異方性層を形成する光学異方性層形成工程と、を有する方法により作製することができる。
また、作用工程は、バインダー層形成工程と第2塗布工程との間、または、バインダー層形成工程または第2塗布工程と同時、に行う工程である。
更に、照射工程は、バインダー層形成工程と第2塗布工程との間、または、バインダー層形成工程または第2塗布工程と同時、に行う工程である。
第1塗布工程は、上述した支持体上に、上述した本発明のバインダー組成物を塗布する工程である。
本発明のバインダー組成物を塗布する方法は特に限定されず、塗布方法としては、具体的には、例えば、スピンコート法、エアーナイフコート法、カーテンコート法、ローラーコート法、ワイヤーバーコート法、グラビアコート法、ダイコート法等が挙げられる。
バインダー層形成工程は、第1塗布工程の後に、バインダー層を形成する工程であり、第1塗布工程で得られた塗膜に対して硬化処理(紫外線の照射(光照射処理)または加熱処理)を施すことにより形成することができる。
また、硬化処理の条件は特に限定されないが、光照射による重合においては、紫外線を用いることが好ましい。照射量は、10mJ/cm2~50J/cm2であることが好ましく、20mJ/cm2~5J/cm2であることがより好ましく、30mJ/cm2~3J/cm2であることが更に好ましく、50~1000mJ/cm2であることが特に好ましい。また、重合反応を促進するため、加熱条件下で実施してもよい。
作用工程は、光、熱、酸および塩基からなる群から選択される少なくとも1種を作用させる工程である。
また、作用工程は、上層としての光学異方性層を形成する際の塗布性を担保する観点から、バインダー層形成工程と第2塗布工程との間、または、バインダー層形成工程または第2塗布工程と同時に行う工程である。
ここで、「バインダー層形成工程と第2塗布工程との間」とは、バインダー層形成工程(例えば、熱重合)で形成したバインダー層に対して、第2塗布工程を施す前に、作用工程(例えば、光を作用させる工程)を行うことをいう。
また、「バインダー層形成工程と同時」とは、バインダー層を形成する工程、例えば、光ラジカル発生によるオレフィン系モノマーの重合、および、光酸発生によるエポキシモノマーの重合などによりバインダー層を形成する工程と、作用工程(例えば、光を作用させる工程)とを同時に行うことをいう。すなわち、バインダー層の重合に用いる光と、開裂に用いる光が、同時に2つの作用を引き起こすことを意味する。
また、「第2塗布工程と同時」とは、バインダー層形成工程(例えば、光重合)で形成したバインダー層に対して、第2塗布工程を施す際に、作用工程(例えば、熱を作用させる工程)を同時に行うことをいう。
このうち、光を作用させ、バインダー層形成工程と同時に行う工程であることが、プロセス簡略化の観点から好ましい。
また、熱を作用させる方法としては、例えば、バインダー層を加熱する方法などが挙げられる。加熱する温度としては、50~200℃であることが好ましく、60~150℃であることがより好ましく、70~130℃であることが特に好ましい。
また、酸を作用させる方法としては、例えば、バインダー層に予め酸を添加しておく方法、バインダー層に光酸発生剤を添加しておき、光をトリガーとして酸を発生させる方法、バインダー層に熱酸発生剤を添加しておき、熱をトリガーとして酸を発生させる方法などが挙げられる。これらのうち、光酸発生剤および熱酸発生剤を用いる方法が好ましい。
また、塩基を作用させる方法としては、例えば、バインダー層に予め塩基を添加しておく方法、バインダー層に光塩基発生剤を添加しておき、光をトリガーとして塩基を発生させる方法、バインダー層に熱塩基発生剤を添加しておき、熱をトリガーとして塩基を発生させる方法などが挙げられる。これらのうち、光塩基発生剤および熱塩基発生剤を用いる方法が好ましい。
照射工程は、偏光または無偏光を照射する工程、すなわち、配向規制力が付与されたバインダー層を形成する工程である。
また、照射工程は、上層としての光学異方性層を形成する際の塗布性を担保する観点から、バインダー層形成工程と第2塗布工程との間、または、バインダー層形成工程または第2塗布工程と同時に行う工程である。
ここで、「バインダー層形成工程と第2塗布工程との間」とは、バインダー層形成工程(例えば、熱重合)で形成したバインダー層に対して、第2塗布工程を施す前に、照射工程(例えば、偏光を照射する工程)を行うことをいう。
また、「バインダー層形成工程と同時」とは、バインダー層を形成する工程、例えば、光ラジカル発生によるオレフィン系モノマーの重合、および、光酸発生によるエポキシモノマーの重合などによりバインダー層を形成する工程と、照射工程(例えば、偏光を照射する工程)とを同時に行うことをいう。すなわち、バインダー層の重合に用いる光と、配向に用いる光が、同時に2つの作用を引き起こすことを意味する。
また、「第2塗布工程と同時」とは、バインダー層形成工程(例えば、光重合)で形成したバインダー層に対して、第2塗布工程を施す際に、照射工程(例えば、偏光を照射する工程)を同時に行うことをいう。
このうち、バインダー層形成工程と第2塗布工程との間に行う工程であることが好ましい。
照射する方法としては、例えば、紫外線を偏光照射する方法が好ましく挙げられ、具体的には、偏光板(例えば、ヨウ素偏光板、二色色素偏光板、ワイヤーグリッド偏光板など)を用いる方法;プリズム系素子(例えば、グラントムソンプリズムなど)やブリュースター角を利用した反射型偏光子を用いる方法;偏光を有するレーザー光源から出射される光を用いる方法;などが挙げられる。
ここで、紫外線照射に用いる光源としては、紫外線を発生する光源であれば特に限定されず、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、カーボンアーク灯、メタルハライドランプ、キセノンランプ等を用いることができる。
第2塗布工程は、バインダー層上に、光学異方性層を形成する重合性液晶組成物を直接塗布する工程である。
光学異方性層を形成する重合性液晶組成物を塗布する方法は特に限定されず、第1塗布工程と同様方の方法が挙げられる。
光学異方性層形成工程は、第2塗布工程の後に、光学異方性層を形成する工程であり、第2塗布工程で得られた塗膜に対して硬化処理(紫外線の照射(光照射処理)または加熱処理)を施すことにより形成することができる。
また、硬化処理の条件は特に限定されないが、光照射による重合においては、紫外線を用いることが好ましい。照射量は、10mJ/cm2~50J/cm2であることが好ましく、20mJ/cm2~5J/cm2であることがより好ましく、30mJ/cm2~3J/cm2であることが更に好ましく、50~1000mJ/cm2であることが特に好ましい。また、重合反応を促進するため、加熱条件下で実施してもよい。
本発明の画像表示装置は、本発明の光学異方性層または本発明の光学積層体を有する、画像表示装置である。
本発明の画像表示装置に用いられる表示素子は特に限定されず、例えば、液晶セル、有機エレクトロルミネッセンス(以下、「EL」と略す。)表示パネル、プラズマディスプレイパネル等が挙げられる。
これらのうち、液晶セル、有機EL表示パネルであるのが好ましく、液晶セルであるのがより好ましい。すなわち、本発明の画像表示装置としては、表示素子として液晶セルを用いた液晶表示装置、表示素子として有機EL表示パネルを用いた有機EL表示装置であるのが好ましい。
本発明の画像表示装置の一例である液晶表示装置は、上述した本発明の光学異方性層または本発明の光学積層体と、液晶セルとを有する液晶表示装置である。
以下に、液晶表示装置を構成する液晶セルについて詳述する。
液晶表示装置に利用される液晶セルは、VA(Vertical Alignment)モード、OCB(Optically Compensated Bend)モード、IPS(In-Plane-Switching)モード、またはTN(Twisted Nematic)であることが好ましいが、これらに限定されるものではない。
TNモードの液晶セルでは、電圧無印加時に棒状液晶性分子(棒状液晶化合物)が実質的に水平配向し、更に60~120゜にねじれ配向している。TNモードの液晶セルは、カラーTFT液晶表示装置として最も多く利用されており、多数の文献に記載がある。
VAモードの液晶セルでは、電圧無印加時に棒状液晶性分子が実質的に垂直に配向している。VAモードの液晶セルには、(1)棒状液晶性分子を電圧無印加時に実質的に垂直に配向させ、電圧印加時に実質的に水平に配向させる狭義のVAモードの液晶セル(特開平2-176625号公報記載)に加えて、(2)視野角拡大のため、VAモードをマルチドメイン化した(MVA(Multi-domain Vertical Alignment)モードの)液晶セル(SID97、Digest of tech.Papers(予稿集)28(1997)845記載)、(3)棒状液晶性分子を電圧無印加時に実質的に垂直配向させ、電圧印加時にねじれマルチドメイン配向させるモード(n-ASMモード(Axially symmetric aligned microcell))の液晶セル(日本液晶討論会の予稿集58~59(1998)記載)および(4)SURVIVAL(Super Ranged Viewing by Vertical Alignment)モードの液晶セル(LCD(liquid crystal display)インターナショナル98で発表)が含まれる。また、PVA(Patterned Vertical Alignment)型、光配向型(Optical Alignment)、およびPSA(Polymer-Sustained Alignment)のいずれであってもよい。これらのモードの詳細については、特開2006-215326号公報、および特表2008-538819号公報に詳細な記載がある。
IPSモードの液晶セルは、棒状液晶性分子が基板に対して実質的に平行に配向しており、基板面に平行な電界が印加することで液晶性分子が平面的に応答する。IPSモードは電界無印加時で黒表示となり、上下一対の偏光板の吸収軸は直交している。光学補償シートを用いて、斜め方向での黒表示時の漏れ光を低減させ、視野角を改良する方法が、特開平10-54982号公報、特開平11-202323号公報、特開平9-292522号公報、特開平11-133408号公報、特開平11-305217号公報、特開平10-307291号公報などに開示されている。
本発明の画像表示装置の一例である有機EL表示装置としては、例えば、視認側から、偏光子、本発明の光学異方性層または本発明の光学積層体、および、有機EL表示パネルをこの順で有する態様が好適に挙げられる。
上記偏光子は、光を特定の直線偏光に変換する機能を有する部材であれば特に限定されず、従来公知の吸収型偏光子および反射型偏光子を利用することができる。
吸収型偏光子としては、ヨウ素系偏光子、二色性染料を利用した染料系偏光子、およびポリエン系偏光子などが用いられる。ヨウ素系偏光子および染料系偏光子には、塗布型偏光子と延伸型偏光子があり、いずれも適用できる。
また、基材上にポリビニルアルコール層を形成した積層フィルムの状態で延伸および染色を施すことで偏光子を得る方法として、特許第5048120号公報、特許第5143918号公報、特許第4691205号公報、特許第4751481号公報、特許第4751486号公報を挙げることができ、これらの偏光子に関する公知の技術も好ましく利用することができる。
反射型偏光子としては、複屈折の異なる薄膜を積層した偏光子、ワイヤーグリッド型偏光子、選択反射域を有するコレステリック液晶と1/4波長板とを組み合わせた偏光子などが用いられる。
これらのうち、密着性がより優れる点で、ポリビニルアルコール系樹脂(-CH2-CHOH-を繰り返し単位として含むポリマー。特に、ポリビニルアルコールおよびエチレン-ビニルアルコール共重合体からなる群から選択される少なくとも1つ)を含む偏光子であることが好ましい。
有機EL表示パネルは、陽極、陰極の一対の電極間に発光層もしくは発光層を含む複数の有機化合物薄膜を形成した部材であり、発光層のほか正孔注入層、正孔輸送層、電子注入層、電子輸送層、保護層などを有してもよく、またこれらの各層はそれぞれ他の機能を備えたものであってもよい。各層の形成にはそれぞれ種々の材料を用いることができる。
冷却管、温度計、および撹拌機を備えたフラスコに、溶媒として2-ブタノン5質量部を仕込み、フラスコ内に窒素を5mL/min流しながら、水浴加熱により還流させた。ここに、下記モノマーmA-52を50質量部、下記モノマーmB-2を20質量部、下記モノマーmC-1を30質量部、重合開始剤として2,2’-アゾビス(イソブチロニトリル)を1質量部と、溶媒として2-ブタノン5質量部を混合した溶液を、3時間かけて滴下し、さらに3時間還流状態を維持したまま撹拌した。反応終了後、室温まで放冷し、2-ブタノン30質量部を加えて希釈することで約20質量%の重合体溶液を得た。得られた重合体溶液を大過剰のメタノール中へ投入して重合体を沈殿させ、回収した沈殿物をろ別し、大量のメタノールで洗浄した後、50℃において12時間送風乾燥することにより、上述した繰り返し単位A-52、繰り返し単位B-2、および、繰り返し単位C-1を下記表1に示す質量部で有する共重合体P-1を得た。
下記表1に示す繰り返し単位を形成するモノマーとして、合成した各モノマーを用い、下記表1に示す重量平均分子量となるように重合開始剤の添加量を変更した以外は、実施例1で合成した重合体P-1と同様の方法で、共重合体を合成した。
なお、下記表1中、繰り返し単位A-9、繰り返し単位B-2などの構造は、上述した各繰り返し単位の説明において記載したものと同様である。
〔バインダー層の作製〕
アクリルモノマー(PETA、大阪有機化学工業(株)製)(100質量部)、光重合開始剤(IRGACURE819、BASF社製)(3質量部)、下記光酸発生剤(B-1-1)(5.0質量部)、および、共重合体P-4(2.0質量部)をメチルエチルケトン(300質量部)に溶解して、バインダー層形成用溶液を調製した。調製したバインダー層形成用溶液を、洗浄済みガラス基板上にスピンコートし、室温で、365nmのUV-LEDを用いて、照射量500mJ/cm2の紫外線を照射した。その後、120℃で1分アニリーリングすることで、バインダー層を作製した。膜厚は約3μmであった。また、バインダー層の表面エネルギーは、50mN/mであった。
得られたバインダー層に、室温で、ワイヤーグリッド偏光子を通したUV光(超高圧水銀ランプ;UL750;HOYA製)を25mJ/cm2(波長:313nm)照射し、配向機能(規制力)を付与した。
市販の液晶化合物(ZLI-4792、メルク社製)(100質量部)、光重合開始剤(イルガキュア907、BASF社製)(3質量部)、増感剤(カヤキュアーDETX、日本化薬(株)製)(1質量部)、および、下記水平配向剤(0.3質量部)をメチルエチルケトン(193質量部)に溶解して、光学異方性層形成用溶液を調製した。
上記配向機能(規制力)を付与したバインダー層上に、上記の光学異方性層形成用溶液をワイヤーバーコーター#2.2で塗布し、60℃で2分間加熱し、60℃に維持したまま、酸素濃度が1.0体積%以下の雰囲気になるように窒素パージしながら160W/cmの空冷メタルハライドランプ(アイグラフィックス(株)製)を用いて、照射量300mJ/cm2の紫外線を照射して光学異方性層を形成し、光学積層体を作製した。
共重合体P-4に代えて、共重合体P-9を用いた以外は、実施例2-1と同様の方法で、光学積層体を作製した。
棒状液晶化合物に代えて、下記液晶化合物L-3および下記液晶化合物L-4をそれぞれ50質量部用いた以外は、実施例2-2と同様の方法で、光学積層体を作製した。
なお、下記液晶化合物L-3およびL-4のアクリロイルオキシ基に隣接する基は、プロピレン基(メチル基がエチレン基に置換した基)を表し、下記液晶化合物L-3およびL-4は、メチル基の位置が異なる位置異性体の混合物を表す。
共重合体P-9に代えて、共重合体P-11を用い、アクリルモノマー(PETA、大阪有機化学工業(株)製)に代えて、下記液晶化合物L-1および下記液晶化合物L-2を用い、下記垂直配向剤S-1(1.0質量部)および下記垂直配向剤S-2(1.0質量部)を添加した以外は、実施例2-3と同様の方法で、光学積層体を作製した。
共重合体P-9に代えて、共重合体P-11を用い、アクリルモノマー(PETA、大阪有機化学工業(株)製)に代えて、下記液晶化合物L-8(83質量部)、L-9(15質量部)およびL-10(2質量部)を用い、上記垂直配向剤S-1(1.0質量部)およびS-2(1.0質量部)を添加した以外は、実施例2-3と同様の方法で、光学積層体を作製した。
2枚の偏光板をクロスニコルに設置し、その間に、作製したバインダー層のサンプルを設置してスジ状のムラの有無を観察し、以下の基準で風ムラの評価を行った。結果を下記表2に示す。
<評価基準>
A:ムラが視認できない。
B:ムラがほとんど視認できない。
C:ムラが視認できる。
作製したバインダー層の表面エネルギーを測定し、以下の基準で上層塗布性を評価した。結果を下記表2に示す。
<評価基準>
A:45mN/m以上
B:40mN/m以上、45mN/m未満
C:30mN/m以上、40mN/m未満
D:30mN/m未満
2枚の偏光板をクロスニコルに設置し、その間に得られたバインダー層および光学異方性層を積層したサンプルを設置して光漏れの程度を観察し、以下の基準で評価した。結果を下記表2に示す。
<評価基準>
A:光漏れがない。
B:光漏れがほとんどない。
C:光漏れが観察される。
これに対し、光などの作用により分解して極性基を生じる開裂基を側鎖に含む繰り返し単位Cを有する共重合体を用いると、バインダー層形成時の風ムラを抑制することができ、また、形成したバインダー層の上層塗布液に対する塗布性および液晶配向性も良好となることが分かった(実施例2-1~2-7)。
Claims (26)
- 光配向性基を含む繰り返し単位Aと、
光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により架橋反応を生起する架橋性基を含む繰り返し単位Bと、
光、熱、酸および塩基からなる群から選択される少なくとも1種の作用により分解して極性基を生じる開裂基を含む繰り返し単位Cと、を有する光配向性共重合体であって、
前記繰り返し単位Cが、側鎖に前記開裂基を有し、かつ、前記側鎖の前記開裂基よりも末端側に、前記光配向性共重合体を空気界面側に偏在させることが可能な原子団を有し、
前記繰り返し単位Aの含有量aと、前記繰り返し単位Bの含有量bと、前記繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W1)~(W3)を満たす、光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.75 ・・・(W1)
0.20 ≦ b/(a+b+c) ≦ 0.90 ・・・(W2)
0.03 ≦ c/(a+b+c) ≦ 0.70 ・・・(W3) - 前記繰り返し単位Aの含有量aと、前記繰り返し単位Bの含有量bと、前記繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W4)~(W6)を満たす、請求項1に記載の光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.45 ・・・(W4)
0.45 ≦ b/(a+b+c) ≦ 0.90 ・・・(W5)
0.03 ≦ c/(a+b+c) ≦ 0.50 ・・・(W6) - 前記繰り返し単位Aの含有量aと、前記繰り返し単位Bの含有量bと、前記繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W7)~(W9)を満たす、請求項1に記載の光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.40 ・・・(W7)
0.55 ≦ b/(a+b+c) ≦ 0.90 ・・・(W8)
0.03 ≦ c/(a+b+c) ≦ 0.40 ・・・(W9) - 前記繰り返し単位Aの含有量aと、前記繰り返し単位Bの含有量bと、前記繰り返し単位Cの含有量cとの合計に対する各繰り返し単位の含有量が、質量比で下記式(W10)~(W12)を満たす、請求項1に記載の光配向性共重合体。
0.03 ≦ a/(a+b+c) ≦ 0.20 ・・・(W10)
0.60 ≦ b/(a+b+c) ≦ 0.80 ・・・(W11)
0.15 ≦ c/(a+b+c) ≦ 0.35 ・・・(W12) - 前記繰り返し単位Cが、側鎖に前記開裂基を有し、かつ、前記側鎖の前記開裂基よりも末端側にフッ素原子またはケイ素原子を有する、請求項1~4のいずれか1項に記載の光配向性共重合体。
- 前記式(A)中のL1が、窒素原子とシクロアルカン環とを含む2価の連結基を表し、前記シクロアルカン環を構成する炭素原子の一部が、窒素、酸素および硫黄からなる群から選択されるヘテロ原子で置換されていてもよい、請求項8に記載の光配向性共重合体。
- 前記式(A)中のL1が、前記式(2)、(3)、(7)および(8)のいずれかで表される2価の連結基である、請求項10に記載の光配向性共重合体。
- 前記式(A)中のR2、R3、R4、R5およびR6のうち、少なくともR4が置換基を表す、請求項8~11のいずれか1項に記載の光配向性共重合体。
- 前記式(A)中のR2、R3、R5およびR6がいずれも水素原子を表す、請求項12に記載の光配向性共重合体。
- 前記式(A)中のR4が、電子供与性の置換基である、請求項12または13に記載の光配向性共重合体。
- 前記式(A)中のR4が、炭素数が6~16のアルコキシ基である、請求項14に記載の光配向性共重合体。
- 前記繰り返し単位Bが、前記式(B)中のXが前記式(X1)~(X3)のいずれかで表される架橋性基である繰り返し単位と、前記式(B)中のXが前記式(X4)で表される架橋性基である繰り返し単位とを含む、請求項18に記載の光配向性共重合体。
- 前記式(B)中のL2が、それぞれ独立に、置換基を有していてもよい炭素数1~18の直鎖状、分岐状または環状のアルキレン基、置換基を有していてもよい炭素数6~12のアリーレン基、エーテル基、カルボニル基、および、置換基を有していてもよいイミノ基からなる群から選択される少なくとも2以上の基を組み合わせた2価の連結基である、請求項17~19のいずれか1項に記載の光配向性共重合体。
- 重量平均分子量が10000~500000である、請求項1~20のいずれか1項に記載の光配向性共重合体。
- 重量平均分子量が30000~300000である、請求項21に記載の光配向性共重合体。
- バインダーと、請求項1~22のいずれか1項に記載の光配向性共重合体とを含有する、バインダー組成物。
- 請求項23に記載のバインダー組成物を用いて形成される、バインダー層。
- 請求項24に記載のバインダー層と、前記バインダー層上に設けられる光学異方性層とを有する光学積層体であって、
前記光学異方性層が、重合性液晶化合物を含有する重合性液晶組成物を用いて形成され、
前記バインダー層と前記光学異方性層とが互いに隣接して積層されている、光学積層体。 - 請求項24に記載のバインダー層または請求項25に記載の光学積層体を有する、画像表示装置。
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JP2015527459A (ja) * | 2012-08-27 | 2015-09-17 | エルジー・ケム・リミテッド | 光配向性共重合体、これを用いた光学異方性フィルムおよびその製造方法 |
WO2015199052A1 (ja) * | 2014-06-24 | 2015-12-30 | 日産化学工業株式会社 | 重合体組成物および横電界駆動型液晶表示素子用液晶配向膜 |
JP2017016116A (ja) * | 2015-06-30 | 2017-01-19 | 富士フイルム株式会社 | 感光性樹脂組成物、硬化膜の製造方法、硬化膜および液晶表示装置 |
WO2018173727A1 (ja) * | 2017-03-24 | 2018-09-27 | 富士フイルム株式会社 | 光配向性共重合体、光配向膜および光学積層体 |
WO2018216812A1 (ja) * | 2017-05-26 | 2018-11-29 | 富士フイルム株式会社 | 光配向性ポリマー、バインダー組成物、バインダー層、光学積層体、光学積層体の製造方法および画像表示装置 |
WO2018216806A1 (ja) * | 2017-05-26 | 2018-11-29 | 富士フイルム株式会社 | 重合性液晶組成物、光学異方性層、光学積層体、光学積層体の製造方法および画像表示装置 |
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WO2024177039A1 (ja) * | 2023-02-22 | 2024-08-29 | 富士フイルム株式会社 | 光配向膜、光学フィルム、円偏光板、画像表示装置および円偏光板の製造方法 |
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US20210292456A1 (en) | 2021-09-23 |
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CN113166336A (zh) | 2021-07-23 |
KR102505149B1 (ko) | 2023-02-28 |
KR20210082501A (ko) | 2021-07-05 |
JP7189232B2 (ja) | 2022-12-13 |
JPWO2020110818A1 (ja) | 2021-10-14 |
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