WO2021153402A1

WO2021153402A1 - Photo-alignment polymer, binder composition, binder layer, optical laminate, method for manufacturing optical laminate, and image display device

Info

Publication number: WO2021153402A1
Application number: PCT/JP2021/001972
Authority: WO
Inventors: 壮一郎渡邉; 寛野副; 隆史飯泉; 一茂中川; 匡広渥美; 西川　秀幸
Original assignee: 富士フイルム株式会社
Priority date: 2020-01-30
Filing date: 2021-01-21
Publication date: 2021-08-05
Also published as: KR20220088746A; JPWO2021153402A1; JP7303334B2

Abstract

The present invention addresses the problem of providing: a photo-alignment polymer with which upper layer-coating properties and liquid crystal alignment properties can be improved even when a lower layer and an upper layer are formed under a wider range of production conditions; a binder composition; a binder layer; an optical laminate; a method for manufacturing an optical laminate; and an image display device. A photo-alignment polymer according to the present invention has a repeating unit having a photo-alignment group and a repeating unit having a group represented by formula (1).

Description

Photo-oriented polymer, binder composition, binder layer, optical laminate, method for manufacturing the optical laminate, image display device

The present invention relates to a photo-oriented polymer, a binder composition, a binder layer, an optical laminate, a method for producing an optical laminate, and an image display device.

Optical films such as optical compensation sheets and retardation films are used in various image display devices from the viewpoints of eliminating image coloring and expanding the viewing angle.
A stretched birefringent film has been used as the optical film, but in recent years, an optically anisotropic layer formed by using a liquid crystal compound has been proposed in place of the stretched birefringent film.

When forming such an optically anisotropic layer, a photoalignment film obtained by subjecting a photoalignment treatment may be used in order to orient the liquid crystal compound.
For example, in the examples of Patent Document 1, a method of forming an optically anisotropic layer using a photo-oriented polymer represented by the following formula is disclosed. This photo-oriented polymer contains a cleaving group that is decomposed by the action of an acid to form a polar group.

International Publication No. 2018/216812

The present inventors have investigated a photo-oriented polymer containing a cleaving group that decomposes by the action of light to generate a polar group, which is specifically described in Patent Document 1, and found that the photo-orientation property. A composition for an optically anisotropic layer depending on the preparation conditions of a layer formed by using a polymer (hereinafter, also abbreviated as "lower layer") and the preparation conditions of an optically anisotropic layer formed on the upper layer of the lower layer. The coatability (hereinafter, also abbreviated as "upper layer coatability") may be inferior, or the orientation of the optically anisotropic layer to be formed (hereinafter, also abbreviated as "liquid crystal orientation") may be inferior. Clarified.

Therefore, according to the present invention, even when the lower layer and the upper layer are formed under a wider range of production conditions, the photo-oriented polymer, the binder composition, the binder layer, and the optics can improve the upper layer coating property and the liquid crystal orientation. An object of the present invention is to provide a laminate, a method for manufacturing an optical laminate, and an image display device.

As a result of diligent studies to achieve the above problems, the present inventors made a wider production by blending a repeating unit having a photo-oriented group and a photo-oriented polymer having a specific repeating unit containing a predetermined cleaving group. The present invention has been completed by finding that the upper layer coating property and the liquid crystal orientation are good even when the lower layer and the upper layer are formed under the conditions.
That is, the present inventors have found that the above-mentioned problems can be achieved by the following configurations.

[1] A repeating unit having a photo-oriented group and
A photo-oriented polymer having a repeating unit having a group represented by the following formula (1).

In the above formula (1),
L ^B represents a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group _- some or all may be substituted by -CO- or -O- May be good.
X represents a cleavage group represented by any of the following formulas (B1) to (B3).
Y represents a group containing a fluorine atom or a silicon atom.
n represents an integer of 1 or more.
* Represents the bond position.

In the above formulas (B1) to (B3), * represents a bonding position.
In the above formula (B1), ^RB1 independently represents a substituent, and two ^RB1s may be bonded to each other to form a ring.
In the above formula (B2), ^RB2 each independently represents a substituent, and two ^RB2s may be bonded to each other to form a ring.
In the above formula (B3), ^RB3 represents a substituent and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of ^RB3s may be the same or different.

[2] The photooriented polymer according to [1], wherein the repeating unit having a group represented by the above formula (1) is a repeating unit represented by the following formula (B).

In the formula (B), ^{R B} represents a hydrogen atom or a substituent, A represents, -O- or -NR ^Z - represents, ^{R Z} represents a hydrogen atom or a substituent.
^L B, X, definitions of Y and n in the formula (B) is the same as the respective definitions of ^L B, X, Y and n in the above formula (1).

[3] The photooriented polymer according to [1] or [2], wherein the group represented by the above formula (1) represents a group represented by any of the following formulas (B4) to (B8).

In the formula (B4) ~ (B8), * represents a bonding position, the definition of ^{L B} are as defined for ^{L B} in the formula ^{(1), L B2} represents a single bond or a divalent Cf represents a fluorine atom-containing alkyl group.
In the formula ^(B4), the definition of ^{R B1} is the same as the definition of ^{R B1} in the formula (B1).
In the above formula (B5) and ^(B6), the definition of ^{R B2} is the same as the definition of ^{R B2} in the formula (B2).
In the formula (B7) and ^(B8), of ^{R B3} and m definitions are the same as the respective definitions of ^{R B3} and m in the formula (B3).

[4] The photooriented polymer according to [1] or [2], wherein the group represented by the above formula (1) represents a group represented by any of the following formulas (B9) to (B16).

In the above formulas (B9) to (B16), * represents a bond position, and Cf represents a fluorine atom-containing alkyl group.
In the formula (B9) and (B10), the definition of ^{L B,} are as defined for ^{L B} in the above formula (1), n represents an integer of 0 ~ ^{10, L B21} is a single bond Alternatively, it represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
In the above formula (B11) ~ (B13), the definition of ^{L B} are as defined for ^{L B} in the formula (1) in ^the definition of ^{R B2} is the definition of ^{R B2} in the formula (B2) ^LB21 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
The formula (B14) in ~ ^{(B16), L B2} represents a single bond or a divalent linking ^{group, L B3} represents a divalent aliphatic hydrocarbon group having a single bond or a C 1-10, definition of R ^B2 is the same as the definition of ^{R B2} in the formula (B2).

[5] The photo-oriented polymer according to any one of [1] to [4], wherein the repeating unit having a photo-oriented group is a repeating unit represented by the following formula (A).

In the above formula (A),
^RA1 represents a hydrogen atom or a substituent.
^LA1 represents a single bond or a divalent linking group.
R ^A2 , R ^A3 , R ^A4 , R ^A5 and R ^A6 each independently represent a hydrogen atom or a substituent. Of ^RA2 , ^RA3 , ^RA4 , ^RA5 and ^RA6 , two adjacent groups may be bonded to form a ring.

[6] The photooriented polymer according to any one of [1] to [5], which further has a repeating unit having a crosslinkable group.

[7] The photooriented polymer according to [6], wherein the repeating unit having a crosslinkable group is a repeating unit represented by the following formula (C).

In the above formula (C),
^RC1 represents a hydrogen atom or a substituent.
^LC1 represents a single bond or a divalent linking group.
^LC2 represents an m + 1 valent linking group.
Z represents a crosslinkable group.
m represents an integer of 1 or more, and when it is an integer of 2 or more, the plurality of Zs may be the same or different.

[8] The photooriented polymer according to [6] or [7], wherein the crosslinkable group represents a group represented by any of the following formulas (C1) to (C4).

In the above formulas (C1) to (C4), * represents a bonding position.
In the above formula (C3), ^RC2 represents a hydrogen atom, a methyl group, or an ethyl group.
In the above formula (C4), ^RC3 represents a hydrogen atom or a methyl group.

[9] The content a of the repeating unit having a photo-oriented group, the content b of the repeating unit having a group represented by the above formula (1), and the content c of the repeating unit having a crosslinkable group are , The photooriented polymer according to any one of [6] to [8], which satisfies the following formula (D1) in terms of mass ratio.
0.03 ≤ a / (a + b + c) ≤ 0.5 ... (D1)
[10] The photooriented polymer according to any one of [1] to [9], which has a weight average molecular weight of 10,000 to 500,000.
[11] A binder composition containing the photo-oriented polymer according to any one of [1] to [10], a binder, and a photoacid generator.
[12] A binder layer formed by using the binder composition according to [11], the surface of which has an orientation control ability.
[13] The binder layer according to [12] and
An optical laminate having an optically anisotropic layer arranged on a binder layer.
[14] A step of generating an acid from a photoacid generator on a coating film obtained by using the binder composition according to [11], and then performing a photoalignment treatment to form a binder layer.
A method for producing an optical laminate, comprising a step of applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on a binder layer to form an optically anisotropic layer.
[15] An image display device having the binder layer according to [12] or the optical laminate according to [13].

According to the present invention, even when the lower layer and the upper layer are formed under a wider production condition, the photo-oriented polymer, the binder composition, the binder layer, and the optics can improve the upper layer coating property and the liquid crystal orientation. A method for manufacturing a laminate and an optical laminate and an image display device can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, the bonding direction of the divalent group (for example, -O-CO-) described in the present specification is not particularly limited, and for example, ^{L 2} is-in the bonding of ^{"L 1-} L ^2- L ^3". In the case of O-CO-, if the ^{position bonded to the L 1} side is * 1 and the position bonded to the L ³ side is * 2, L ² is * 1-O-CO- * 2. It may be * 1-CO-O- * 2.

[Photo-oriented polymer]
The photo-oriented polymer of the present invention is a photo-oriented copolymer having a repeating unit having a photo-oriented group and a repeating unit having a group represented by the formula (1) described later.

In the present invention, as described above, when a photo-oriented polymer having a repeating unit having a photo-oriented group and a repeating unit having a group represented by the formula (1) described later is blended, a lower layer is formed under a wider range of production conditions. And even when the upper layer is formed, the upper layer coating property and the liquid crystal orientation are good.
This is not clear in detail, but the present inventors speculate as follows.
The present inventors have investigated the photo-oriented polymer specifically described in Patent Document 1, and found that the cleaving group which is decomposed by the action of the acid contained in the photo-oriented polymer to form a polar group is found. It was found that it is necessary to raise the temperature in order to cleave the cleaving group because the cleaving rate decreases by passing through an intermediate that is more unstable and less likely to occur in the cleaving process. It was also found that the coatability of the upper layer was inferior due to the presence of the uncracked photo-oriented polymer that was unevenly distributed on the surface of the lower layer (the interface side with the upper layer). Furthermore, since it is a cleaving group that produces a carboxy group having strong hydrogen bonding properties (high hydrophilicity), a hydrophilic field is formed at the interface between the lower layer and the upper layer even after the cleaving, so that the lower layer and the upper layer are formed. It was found that the interaction with and was inhibited, leading to a decrease in liquid crystal orientation.
Therefore, repeated in the present invention, it comprises a cleaving group represented by the later-described formula (B1) ~ (B3), and containing a predetermined linking group L ^{B (aliphatic} hydrocarbon group) between the main chain It is considered that having the unit lowered the temperature at which the cleaving group was cleaved and suppressed the formation of the hydrophilic field even after the cleaving, so that the upper layer coating property and the liquid crystal orientation were improved.
In the following, first, the repeating unit having a group represented by the formula (1) will be described in detail.

[Repeating unit having a group represented by the formula (1)]
The photo-oriented polymer of the present invention has a repeating unit having a group represented by the following formula (1). As described above, the group represented by the following formula (1) contains a predetermined cleaving group, which is cleaved by the action of an acid to cause elimination of a group containing a fluorine atom or a silicon atom. , Produces a polar group. In the following equation (1), * represents the coupling position.

In the above formula (1), L ^B represents a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group _- some or all -CO- or - It may be replaced with O−.
The number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and 1 to 10 is preferable, 1 to 5 is more preferable, and 1 to 3 is further preferable because the liquid crystal orientation becomes better.
The aliphatic hydrocarbon group is n + 1 valent. For example, when n is 1, a divalent aliphatic hydrocarbon group (so-called alkylene group) is used, and when n is 2, a trivalent aliphatic hydrocarbon group is used. When n is 3, it represents a tetravalent aliphatic hydrocarbon group.
The aliphatic hydrocarbon group may be linear or branched. Further, the aliphatic hydrocarbon group may have a cyclic structure. Of these, linear is preferable because the liquid crystal orientation becomes better.
_{Further, "a part or all of -CH 2-} constituting the aliphatic hydrocarbon group may be substituted with -CO- or -O-" means that, for example, the aliphatic hydrocarbon group is divalent. _{When it is an aliphatic hydrocarbon group (alkylene group), a part or all of -CH 2-} constituting the alkylene group (for example, methylene group, ethylene group, propylene group, etc.) is replaced with -CO- or -O-. It means that it may be done. That is, examples of the n + 1-valent aliphatic hydrocarbon group having 1 or more carbon atoms include -CO-, -O _{-CO-O-, -CH 2} -O-, -CH _2- _{CH 2} -O-, and-. CH _2- CH _2- O-CO-, -CH ₂ _{-CH 2} -O-CO-O- and the like are also included.

X represents a cleavage group represented by any of the following formulas (B1) to (B3). These cleaving groups are cleaving groups that are decomposed by the action of an acid to produce polar groups.
In addition, * in the following formulas (B1) to (B3) represents a coupling position.

In the above formula (B1), ^RB1 independently represents a substituent, and two ^RB1s may be bonded to each other to form a ring.
Kind of substituent represented by R ^B1 is not particularly limited, it includes known substituents.
Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an aromatic heterocyclic oxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an acyloxy group. , Acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, aromatic heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphate amide Group, hydroxy group, mercapto group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydradino group, imino group, heterocyclic group (for example, heteroaryl group), silyl group, And a group that combines these. The above-mentioned substituent may be further substituted with a substituent.

In the present invention, the decomposition process of cleaving group, more stable and better degradation rate can be via a prone intermediate, because the upper layer coating property becomes better, as the substituent represented by R ^B1 Is preferably a cyclic substituent, more preferably a cyclic aliphatic (aliphatic) hydrocarbon group having 3 or more carbon atoms, or an aromatic hydrocarbon group having 6 or more carbon atoms.
Further, for the same reason, ^{it is preferable that the two RB1s} are bonded to each other to form a ring.
Here, examples of the alicyclic hydrocarbon group having 3 or more carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and an ethyl. Monocyclic saturated hydrocarbon groups such as cyclohexyl groups; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, and , Cyclodecadien group and other monocyclic unsaturated hydrocarbon groups; bicyclo [2.2.1] heptyl group, bicyclo [2.2.2] octyl group, tricyclo [5.2.1.0 ^2,6 ] Decyl group, tricyclo [3.3.1.1 ^3,7 ] decyl group, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodecyl group and polycyclic saturated hydrocarbon group such as adamantyl group;
Examples of the aromatic hydrocarbon group having 6 or more carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, a biphenyl group and the like, and an aryl group having 6 to 12 carbon atoms (particularly). Phenyl group) is preferred.

In the above formula (B2), ^RB2 each independently represents a substituent, and two ^RB2s may be bonded to each other to form a ring.
Kind of substituent represented by R ^B2 is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R ^B1.

In the present invention, because the upper layer coating property becomes better, as the substituent represented by R ^B2, the number 1 or more aliphatic hydrocarbon group having a carbon or an aromatic hydrocarbon group having 6 or more carbon atoms Is more preferable.
Here, as the aliphatic hydrocarbon group having 1 or more carbon atoms, for example, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, or an isopropyl group) is preferable. Groups, n-butyl groups, isobutyl groups, sec-butyl groups, and t-butyl groups) are more preferable, and alkyl groups having 1 to 4 carbon atoms are even more preferable.
Further, as the aromatic hydrocarbon group having 6 or more carbon atoms, the group exemplified as a preferable example of the ^{above-mentioned RB1 can be mentioned.}

In the above formula (B3), ^RB3 represents a substituent and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of ^RB3s may be the same or different.
Kind of substituent represented by R ^B3 is not particularly limited, it includes known substituents, and groups exemplified in the substituents represented by R ^B1, include fluorine atom-containing alkyl group.
Further, m is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Y represents a group containing a fluorine atom or a silicon atom.
The total number of fluorine atoms and silicon atoms contained in the group containing fluorine atoms or silicon atoms is not particularly limited, and 1 to 30 is preferable, 5 to 25 is more preferable, and 10 is preferable because the liquid crystal orientation is better. ~ 20 is more preferable.
The group containing a fluorine atom or a silicon atom is preferably a so-called organic group (a group containing a carbon atom). The number of carbon atoms contained in the group containing a fluorine atom and a silicon atom is not particularly limited, and 1 to 30 is preferable, 3 to 20 is more preferable, and 5 to 10 is further preferable, for the reason that the liquid crystal orientation becomes better.
Examples of the group containing a fluorine atom or a silicon atom include a group containing a fluorine atom-containing alkyl group described later and a group containing a polydialkylsiloxane chain.

As the group containing a fluorine atom or a silicon atom, a group represented by the formula (2) is preferable because the liquid crystal orientation becomes better.
Equation (2) * -L ^B2- Cf
^LB2 represents a single bond or a divalent linking group, and is preferably a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
Examples of the divalent linking group represented by L ^B2, for example, divalent or substituted hydrocarbon group, a divalent heterocyclic group, -O -, - S -, - N ( Q)-, -CO-, or a group combining these can be mentioned. Q represents a hydrogen atom or a substituent.
Examples of the divalent hydrocarbon group include 2 such as an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5), an alkenylene group having 1 to 10 carbon atoms, and an alkynylene group having 1 to 10 carbon atoms. Valuable aliphatic hydrocarbon groups; divalent aromatic hydrocarbon groups such as arylene groups; can be mentioned.
Examples of the divalent heterocyclic group include a divalent aromatic heterocyclic group, and specifically, a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, and thienylene (thiophene). -Diyl group), quinolylene group (quinolin-diyl group) and the like.
The group consisting of the above-mentioned divalent hydrocarbon group, divalent heterocyclic group, -O-, -S-, -N (Q)-, and -CO- as a group combining these groups. Examples thereof include a group in which at least two or more kinds selected from the above are combined. For example, -O-2-valent hydrocarbon group-,-(O-2 valent hydrocarbon group) _p- O- (p is 1 or more). (Representing an integer of), and a divalent hydrocarbon group -O-CO- and the like.
Of these divalent linking group, the divalent linking group represented by L ^B2, linear alkylene group of having 1 carbon atoms which may 10 have a substituent, a substituent Yes It may have a branched alkylene group having 3 to 10 carbon atoms, a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, and 6 carbon atoms which may have a substituent. Preferably, an arylene group of ~ 12 or -O-, -CO-, -N (Q)-, or a group in which these are combined is preferable, and a linear linear group having 1 to 10 carbon atoms which may have a substituent may be used. A branched alkylene group having 3 to 10 carbon atoms which may have an alkylene group and a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent is more preferable.
Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.
Examples of the branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
Examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.
Examples of the substituent which the divalent hydrocarbon group (alkylene group, arylene group) may have and the substituent represented by Q include a halogen atom, an alkyl group, an alkoxy group, an aryl group and an aryl. Examples thereof include an oxy group, a cyano group, a carboxy group, an alkoxycarbonyl group, and a hydroxyl group.

Cf represents a fluorine atom-containing alkyl group. The fluorine atom-containing alkyl group represents an alkyl group containing a fluorine atom, and a perfluoroalkyl group is preferable.
The number of carbon atoms of the fluorine atom-containing alkyl group is not particularly limited, and 1 to 30 is preferable, 3 to 20 is more preferable, and 5 to 10 is further preferable, because the liquid crystal orientation becomes better.
The number of fluorine atoms contained in the fluorine atom-containing alkyl group is not particularly limited, and 1 to 30 is preferable, 5 to 25 is more preferable, and 10 to 20 is further preferable, for the reason that the liquid crystal orientation becomes better.

N represents an integer of 1 or more. Among them, an integer of 1 to 10 is preferable, an integer of 1 to 5 is more preferable, and an integer of 1 to 3 is further preferable, for the reason that the liquid crystal orientation becomes better.

As the group represented by the above formula (1), a group represented by any of the following formulas (B4) to (B8) is preferable for the reason that the liquid crystal orientation becomes better.
In addition, * in the following formulas (B4) to (B8) represents a coupling position.

In the formula ^(B4), L ^B, defined and exemplified in R ^{B1, L B2} and Cf are as respectively described above.
In the above formula (B5) and ^(B6), L ^B, defined and exemplified in R ^{B2, L B2} and Cf are as respectively described above.
In the formula (B7) and ^(B8), L ^B, defined and exemplified in R B3, ^{m, L B2} and Cf are as respectively described above.

As the group represented by the above formula (1), a group represented by any of the following formulas (B9) to (B16) is preferable for the reason that the liquid crystal orientation becomes better.
In addition, * in the following formulas (B9) to (B16) represents a coupling position.

The formula (B9) in and (B10), defined and exemplified in ^{L B} and Cf are as respectively described above. Further, n represents an integer of 0 to 10, preferably an integer of 0 to 7, more preferably an integer of 0 to 5, and even more preferably an integer of 0 to 3. Further, ^LB21 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
Here, the divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by ^{LB21 may be linear or branched.} Further, the divalent aliphatic hydrocarbon group having 1 or more carbon atoms may have a cyclic structure.
Specific examples of the divalent aliphatic hydrocarbon group include a linear alkylene group, a branched alkylene group, and a cyclic alkylene group.
Examples of the linear alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a decylene group.
Examples of the branched alkylene group include a dimethylmethylene group, a methylethylene group, a 2,2-dimethylpropylene group, and a 2-ethyl-2-methylpropylene group.
Examples of the cyclic alkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, an adamantane-diyl group, a norbornane-diyl group, and an exo-. Examples include the tetrahydrodicyclopentadiene-diyl group.

The formula (B11) in ~ ^(B13), L ^{^B,} defined and exemplified in R ^{B2, L B21} and Cf are as respectively described above.

The formula (B14) in ~ ^(B16), defined and exemplified in R ^{B2, L B2} and Cf are as respectively described above. Further, ^LB3 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof are the same as those exemplified in ^LB21.

The structure of the main chain of the repeating unit having a group represented by the above formula (1) is not particularly limited, and known structures can be mentioned. For example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, and the like. A skeleton selected from the group consisting of methylpentenes, amides, and aromatic esters is preferred.
Of these, a skeleton selected from the group consisting of (meth) acrylic-based, siloxane-based, and cycloolefin-based skeletons is more preferable, and (meth) acrylic-based skeletons are even more preferable.
In addition, (meth) acrylic is a general term for acrylic and methacryl.

As the repeating unit having a group represented by the above formula (1), the repeating unit represented by the following formula (B) is preferable because the liquid crystal orientation becomes better.

In the formula (B), ^{R B} represents a hydrogen atom or a substituent, A represents, -O- or -NR ^Z - represents, ^{R Z} represents a hydrogen atom or a substituent.
Here, the kind of the substituent represented by R ^B is not particularly limited, include known substituents, include the groups exemplified in the substituents represented by R ^B1. Of these, an alkyl group is preferable.
The type of the substituents represented by R ^Z is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R ^B1. Of these, an alkyl group is preferable.
Further, ^L B, X, definitions of Y and n in the formula (B) is the same as the respective definitions of ^L B, X, Y and n in the above formula (1).

Specific examples of the repeating unit having a group represented by the above formula (1) include the following.

The content of the repeating unit having a group represented by the formula (1) in the photo-oriented polymer is not particularly limited, and for the reason that the liquid crystal orientation becomes better, the content of the repeating unit having a group represented by the formula (1) is relatively good with respect to all the repeating units of the photo-orientating polymer. 3, 3% by mass or more is preferable, 5% by mass or more is more preferable, 10% by mass or more is further preferable, 20% by mass or more is particularly preferable, 95% by mass or less is preferable, 80% by mass or less is more preferable, and 60% by mass is 60% by mass. The following is more preferable, 50% by mass or less is particularly preferable, and 30% by mass or less is most preferable.

[Repeating unit with photo-oriented group]
Photo-oriented polymers have repeating units with photo-oriented groups.
A photo-oriented group is a group having a photo-alignment function in which rearrangement or an heterogeneous chemical reaction is induced by irradiation with anisotropic light (for example, planar polarization), and the uniformity of orientation. A photo-oriented group in which at least one of dimerization and isomerization is generated by the action of light is preferable because of its excellent thermal stability and good chemical stability.

The photooriented group dimerized by the action of light includes, for example, a group having a skeleton of at least one derivative selected from the group consisting of a cinnamic acid derivative, a coumarin derivative, a chalcone derivative, a maleimide derivative, and a benzophenone derivative. Etc. are preferably mentioned.
On the other hand, as the photoorienting group that is isomerized by the action of light, at least one selected from the group consisting of, for example, an azobenzene compound, a stilbene compound, a spiropyran compound, a cinnamic acid compound, and a hydrazono-β-ketoester compound. A group having a skeleton of a compound and the like are preferably mentioned.

As the photoorienting group, a group having a skeleton of at least one derivative selected from the group consisting of a cinnamic acid derivative, a coumarin derivative, a chalcone derivative and a maleimide derivative, an azobenzene compound, a stilben compound, and a spiropyran compound is preferable. A group having a cinnamic acid derivative skeleton or a coumarin derivative skeleton is more preferable.

The structure of the main chain of the repeating unit having a photo-oriented group is not particularly limited, and known structures can be mentioned. For example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, and amide type. , And a skeleton selected from the group consisting of aromatic esters are preferred.
Of these, a skeleton selected from the group consisting of (meth) acrylic-based, siloxane-based, and cycloolefin-based skeletons is more preferable, and (meth) acrylic-based skeletons are even more preferable.

As the repeating unit having a photo-oriented group, the repeating unit represented by the following formula (A) is preferable because the liquid crystal orientation becomes better.

In the above formula (A), ^RA1 represents a hydrogen atom or a methyl group.
^LA1 represents a single bond or a divalent linking group.
Definition of the divalent linking group represented by L ^A1 is the same as the definition of the divalent linking group represented by L ^B3 described above. Among them, the divalent linking group represented by L ^A1, the liquid crystal reasons orientation becomes better, linear alkylene group of having 1 carbon atoms which may 10 have a substituent, A branched alkylene group having 3 to 10 carbon atoms which may have a substituent, a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, and a substituent may have a substituent. It may be a divalent linking group in which at least two or more groups selected from the group consisting of a good arylene group having 6 to 12 carbon atoms, -O-, -CO-, and -N (Q)-combined. preferable. Q represents a hydrogen atom or a substituent.

Substituents that the alkylene group and arylene group may have, and the substituent represented by Q include, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a cyano group, and a carboxy group. , An alkoxycarbonyl group, and a hydroxyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.
As the alkyl group, for example, a linear alkyl group having 1 to 18 carbon atoms, a branched chain chain having 3 to 18 carbon atoms or a cyclic alkyl group is preferable, and a linear alkyl group having 1 to 8 carbon atoms or a branched chain having 3 to 8 carbon atoms is preferable. Alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group) are more preferable, and the number of carbon atoms is more preferable. Linear alkyl groups 1 to 4 are more preferred, and methyl or ethyl groups are particularly preferred.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group) is more preferable. An alkoxy group having 1 to 4 carbon atoms is more preferable, and a methoxy group or an ethoxy group is particularly preferable.
Examples of the aryl group include an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group, and a phenyl group is preferable.
Examples of the aryloxy group include a phenoxy group, a naphthoxy group, an imidazolyloxy group, a benzoimidazolyloxy group, a pyridine-4-yloxy group, a pyrimidinyloxy group, a quinazolinyloxy group, a prynyloxy group, and a thiophene-3. -Iloxy group is mentioned.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

Examples of the linear alkylene group having 1 to 10 carbon atoms which may have a substituent include the linear alkylene group described in the above divalent aliphatic hydrocarbon group.
Examples of the branched alkylene group having 3 to 10 carbon atoms which may have a substituent include the branched alkylene group described in the above divalent aliphatic hydrocarbon group.
Examples of the cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent include the cyclic alkylene group described in the above divalent aliphatic hydrocarbon group.

Examples of the arylene group having 6 to 12 carbon atoms include a phenylene group, a xylylene group, a biphenylene group, a naphthylene group, and a 2,2'-methylenebisphenyl group, and a phenylene group is preferable.

Among them, the reason why the liquid crystal alignment property becomes better, as the L ^A1 in the formula (A), a straight-chain alkylene group of having 1 carbon atoms which may 10 have a substituent, a substituent A divalent linking group containing at least one of a cyclic alkylene group having 3 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms which may have a substituent is preferable. A divalent linkage containing at least a linear alkylene group having 1 to 10 carbon atoms which may have a substituent or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent. A group is more preferable, and an unsubstituted linear alkylene group having 2 to 6 carbon atoms or a divalent linking group containing an unsubstituted trans-1,4-cyclohexylene is even more preferable.
It should be noted that a divalent linking group containing at least a linear alkylene group having 1 to 10 carbon atoms which may have a substituent and a cyclic cyclic group having 3 to 10 carbon atoms which may have a substituent may be used. Comparing with a divalent linking group containing at least an alkylene group, the effect is more excellent in the case of a divalent linking group containing at least a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent.

R ^A2 , R ^A3 , R ^A4 , R ^A5 and R ^A6 each independently represent a hydrogen atom or a substituent. Type of the substituent is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R ^B2.
Of ^RA2 , ^RA3 , ^RA4 , ^RA5 and ^RA6 , two adjacent groups may be bonded to form a ring.

As ^RA2 , ^RA3 , ^RA4 , ^RA5 and ^RA6 , halogen atoms, linear alkyl groups having 1 to 20 carbon atoms, and carbon atoms are independent of each other for the reason of better liquid crystal orientation. 3 to 20 branched or cyclic alkyl groups, 1 to 20 carbon linear halogenated alkyl groups, 1 to 20 carbon alkoxy groups, 6 to 20 carbon aryl groups, 6 to 6 carbons 20 aryloxy groups, hydroxy groups, cyano groups, amino groups, or groups represented by the following formula (3) are preferable. The substituent may contain a linking group represented by − (CH ₂ ) _na − or −O − (CH ₂ ) _{na −.} na represents an integer from 1 to 10.

Here, in the above equation (3), * represents a coupling position.
^RA7 represents a monovalent organic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or a chlorine atom is preferable.

The linear alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group.
The branched-chain alkyl group having 3 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include an isopropyl group and a tert-butyl group.
The cyclic alkyl group having 3 to 20 carbon atoms is preferably an alkyl group having 3 to 6 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

As the linear alkyl halide group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms is preferable, for example, a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluoro group. A butyl group is mentioned, and a trifluoromethyl group is preferable.

As the alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 18 carbon atoms is preferable, an alkoxy group having 3 to 18 carbon atoms is more preferable, and an alkoxy group having 6 to 18 carbon atoms is further preferable. For example, methoxy group, ethoxy group, n-butoxy group, methoxyethoxy group, n-hexyloxy group, n-octyloxy group, n-decyloxy group, n-dodecyloxy group, and n-tetradecyloxy group can be mentioned. Be done.

The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group.

The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group.

Examples of the amino group include a primary amino group (-NH ₂ ); a secondary amino group such as a methylamino group; a dimethylamino group, a diethylamino group, a dibenzylamino group, and a nitrogen-containing heterocyclic compound (for example). , Pyrrolidine, piperidine, piperazine, etc.), such as a tertiary amino group having a nitrogen atom as a bond.

^{Examples of the monovalent organic group represented by RA7} in the above formula (3) include an alkyl group having 1 to 20 carbon atoms, for example, a linear group having 1 to 20 carbon atoms or a cyclic group having 3 to 20 carbon atoms. Alkyl group of.
The linear alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and an n-propyl group, and a methyl group or an ethyl group is preferable.
As the cyclic alkyl group, an alkyl group having 3 to 6 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, and a cyclohexyl group is preferable.
^{The monovalent organic group represented by RA7} in the above formula (3) may be a combination of a plurality of the above-mentioned linear alkyl group and cyclic alkyl group directly or via a single bond. good.

Photoaligning group is likely to interact with the liquid crystal compound from the viewpoint of liquid crystal alignment property becomes excellent, among the ^R ^A2, R ^A3, R ^{A4, R A5} and ^{R A6} in the formula (A), at least R ^It is preferable that A4 represents the above-mentioned substituent (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 6 to 18 carbon atoms, and particularly preferably an alkoxy group having 8 to 18 carbon atoms). ^{Furthermore, RA2} , ^RA3 , ^RA5 and ^RA6 are all hydrogen because the linearity of the obtained photo-oriented polymer is improved, it becomes easier to interact with the liquid crystal compound, and the liquid crystal orientation is improved. It is more preferable to represent an atom.

Specific examples of the repeating unit having a photo-oriented group include the following.

The content of the repeating unit having a photo-oriented group in the photo-oriented polymer is not particularly limited, and 5 to 60 mass by mass with respect to all the repeating units of the photo-oriented polymer for the reason that the liquid crystal orientation becomes better. % Is preferable, 10 to 50% by mass is more preferable, and 15 to 40% by mass is further preferable.

The photooriented polymer may have a repeating unit other than the repeating unit described above.

[Repeating unit with crosslinkable group]
The photooriented polymer may further have repeating units with crosslinkable groups.
The type of the crosslinkable group is not particularly limited, and examples thereof include known crosslinkable groups. Among them, a cationically polymerizable group or a radically polymerizable group is preferable because it has excellent adhesion to the upper layer arranged on the binder layer.

Examples of the cationically polymerizable group include an epoxy group, an epoxycyclohexyl group, and an oxetanyl group.

Examples of the radically polymerizable group include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group.

The structure of the main chain of the repeating unit having a crosslinkable group is not particularly limited, and known structures can be mentioned, for example, (meth) acrylic type, styrene type, siloxane type, cycloolefin type, methylpentene type, amide type, and the like. And a skeleton selected from the group consisting of aromatic esters is preferred.
Of these, a skeleton selected from the group consisting of (meth) acrylic-based, siloxane-based, and cycloolefin-based skeletons is more preferable, and (meth) acrylic-based skeletons are even more preferable.

As the repeating unit having a crosslinkable group, the repeating unit represented by the following formula (C) is preferable because the liquid crystal orientation becomes better.

In the above formula (C), ^RC1 represents a hydrogen atom or a substituent.
Kind of substituent represented by R ^C1 is not particularly limited, it includes known substituents, include the groups exemplified in the substituents represented by R ^C1.
Examples of the substituent represented by R ^C1, alkyl groups are preferred.

^LC1 represents a single bond or a divalent linking group.
Definition of the divalent linking group represented by L ^C1 has the same definition of the divalent linking group represented by L ^B3 described above. Among them, the divalent linking group represented by L ^C1, crystal reasons orientation becomes better, linear alkylene group of having 1 carbon atoms which may 10 have a substituent, A branched alkylene group having 3 to 10 carbon atoms which may have a substituent, a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent, and a substituent may have a substituent. It may be a divalent linking group in which at least two or more groups selected from the group consisting of a good arylene group having 6 to 12 carbon atoms, -O-, -CO-, and -N (Q)-combined. preferable. Q represents a hydrogen atom or a substituent.
Definition of each group are the same as the definition of each group described in the divalent linking group represented by L ^A1 described above.

^LC2 represents an m + 1 valent linking group.
The m + 1-valent linking group is an m + 1-valent hydrocarbon group having 1 to 24 carbon atoms which may have a substituent for the reason that the liquid crystal orientation becomes better, and constitutes a hydrocarbon group. A hydrocarbon group in which a part of the carbon atom may be substituted with a hetero atom is preferable, and an aliphatic hydrocarbon group which may contain an oxygen atom or a nitrogen atom having 1 to 10 carbon atoms is more preferable.

The number of carbon atoms contained in the m + 1 valent linking group is not particularly limited, and 1 to 24 is preferable, and 1 to 10 is more preferable, for the reason that the liquid crystal orientation becomes better.
As the m + 1 valent linking group, a divalent linking group is preferable. The definition of a divalent linking group is the same as the definition of a divalent linking group represented by ^{LB3 described above.}

Z represents a crosslinkable group. The definition of the crosslinkable group is as described above.
m represents an integer of 1 or more. Among them, an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and 1 is further preferable, for the reason that the liquid crystal orientation becomes better.

Specific examples of the repeating unit having a crosslinkable group include the following.

The content of the repeating unit having a crosslinkable group in the photo-oriented polymer is not particularly limited, and 10 to 60% by mass with respect to all the repeating units of the photo-oriented polymer for the reason that the liquid crystal orientation becomes better. Is preferable, and 20 to 50% by mass is more preferable.

In the present invention, the content a of the repeating unit having a group represented by the above-mentioned formula (1), the content b of the repeating unit having the above-mentioned photooriented group, and the above-mentioned repeating having the crosslinkable group. The unit content c preferably satisfies the following formula (D1) in terms of mass ratio because the liquid crystal orientation becomes better.
0.03 ≤ a / (a + b + c) ≤ 0.5 ... (D1)

Examples of the monomer (radical polymerizable monomer) forming other repeating units other than the above include an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, and a styrene compound. And vinyl compounds.

The method for synthesizing the photo-orientating polymer of the present invention is not particularly limited, and for example, a monomer forming a repeating unit having a group represented by the above-mentioned formula (1) and a repeating unit having the above-mentioned photoreactive group are formed. It can be synthesized by mixing a monomer to be polymerized and a monomer forming any other repeating unit and polymerizing in an organic solvent using a radical polymerization initiator.

The weight average molecular weight (Mw) of the photo-oriented polymer of the present invention is not particularly limited, and is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and even more preferably 30,000 to 150,000 because the liquid crystal orientation becomes better. ..
Here, 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 conditions shown below.
-Solvent (eluent): THF (tetrahydrofuran)
-Device name: TOSOH HLC-8320GPC
-Column: Use by connecting three TOSOH TSKgel Super HZM-H (4.6 mm x 15 cm) -Column temperature: 40 ° C
-Sample concentration: 0.1% by mass
-Flow velocity: 1.0 ml / min
-Calibration curve: TOSOH TSK standard polystyrene Mw = 2800000 to 1050 (Mw / Mn = 1.03 to 1.06) 7 samples calibration curve is used.

[Binder composition]
The binder composition of the present invention is a composition containing the photooriented polymer of the present invention, a binder, and a photoacid generator.
Here, the content of the photooriented polymer contained in the binder composition of the present invention is preferably 0.1 to 10 parts by mass, and 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder described later. More preferred.
The content of the photoacid generator contained in the binder composition of the present invention is preferably 0.5 to 50 parts by mass, more preferably 2.5 to 25 parts by mass, based on 100 parts by mass of the binder described later. preferable.

〔binder〕
The type of binder contained in the binder composition of the present invention is not particularly limited, and a resin that is simply dried and solidified so as to be composed of only a resin that does not have a polymerization reactivity (hereinafter, also referred to as "resin binder"). It may be a polymerizable compound.

<Resin binder>
Examples of the resin binder include epoxy resin, diallyl phthalate resin, silicone resin, phenol resin, unsaturated polyester resin, polyimide resin, polyurethane resin, melamine resin, urea resin, ionomer resin, ethylene ethyl acrylate resin, and acrylonitrile acrylate styrene copolymer. Resin, acrylonitrile styrene resin, acrylonitrile polyethylene chloride styrene copolymer resin, ethylene vinegar resin, ethylene vinyl alcohol copolymer resin, acrylonitrile butadiene styrene copolymer resin, vinyl chloride resin, chlorinated polyethylene resin, polyvinylidene chloride resin, cellulose acetate resin , Fluorine resin, polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyether ether ketone resin, polyether sulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene maleic acid copolymer resin, polystyrene acrylic Acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formal resin, polyvinyl alcohol, polyvinyl Examples thereof include pyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and copolymer resins thereof.

<Polymerizable compound>
Examples of the polymerizable compound include an epoxy-based monomer, a (meth) acrylic-based monomer, and an oxetanyl-based monomer, and an epoxy-based monomer or a (meth) acrylic-based monomer is preferable.
Moreover, you may use a polymerizable liquid crystal compound as a polymerizable compound.

Examples of the epoxy group-containing monomer which is an epoxy-based monomer include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, and hydroquinone type epoxy resin. Naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenylol ethane type epoxy resin, Dicyclopentadienephenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleated polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glioxal type epoxy resin, oil ring Examples thereof include a type epoxy resin and a heterocyclic epoxy resin.

As the (meth) acrylic monomer, the acrylate-based monomer and the methacrylate-based monomer, the trifunctional monomer includes trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, and trimethylolpropane EO (ethylene oxide). ) Modified triacrylate, trimethylolpropane trimethacrylate, and pentaerythritol triacrylate. Examples of the tetrafunctional or higher functional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethritol, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. ..

The polymerizable liquid crystal compound is not particularly limited, and examples thereof include compounds capable of any of homeotropic orientation, homogeneous orientation, hybrid orientation, and cholesteric orientation.
Here, in general, liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shapes. In addition, there are small molecule and high molecular types, 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). In the present invention, any liquid crystal compound can be used, but a rod-shaped liquid crystal compound or a discotic liquid crystal compound (disk-shaped liquid crystal compound) is preferable. Further, a liquid crystal compound which is a monomer or has a relatively low molecular weight having a degree of polymerization of less than 100 is preferable.
Examples of the polymerizable group contained in the polymerizable liquid crystal compound include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.
By polymerizing such a polymerizable liquid crystal compound, the orientation of the liquid crystal compound can be fixed. After the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.

As the rod-shaped liquid crystal compound, for example, those described in claim 1 of JP-A No. 11-513019 or paragraphs [0026] to [0098] of JP-A-2005-289980 are preferable, and the discotic liquid crystal compound is preferably a discotic liquid crystal compound. For example, those described in paragraphs [0020] to [0067] of JP2007-108732 or paragraphs [0013] to [0108] of JP2010-2404038 are preferable.

As the polymerizable liquid crystal compound, a liquid crystal compound having a reverse wavelength dispersibility can be used.
Here, in the present specification, the "reverse wavelength dispersibility" liquid crystal compound is a retardation film produced using the liquid crystal compound, and the in-plane retardation (Re) value at a specific wavelength (visible light range) is measured. In this case, the Re value becomes equal or higher as the measurement wavelength becomes larger.

The reverse wavelength dispersible liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersive film as described above, and is represented by, for example, the general formula (I) described in JP-A-2008-297210. (In particular, the compounds described in paragraphs [0034] to [0039]), and the compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraphs [0067] to [0073]. ], And compounds represented by the general formula (1) described in JP-A-2016-081035 (particularly, compounds described in paragraphs [0043] to [0055]).
Further, paragraphs [0027] to [0100] of JP2011-006360, paragraphs [0028] to [0125] of JP2011-006361, and paragraphs [0034] to [0034] to [0034] to JP2012-207765. 0298], paragraphs [0016] to [0345] of JP2012-077055, paragraphs [0017] to [0072] of WO12 / 141245, paragraphs [0021] to [0088] of WO12 / 147904, Examples thereof include the compounds described in paragraphs [0028] to [0115] of WO14 / 147904.

[Photoacid generator]
The binder composition of the present invention contains a photoacid generator.
The photoacid generator is not particularly limited, and a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. Further, a photoacid generator that is not directly sensitive to active light having a wavelength of 300 nm or more can be used as a sensitizer if it is a compound that is sensitive to active light having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
As the photoacid generator, a photoacid generator that generates an acid having a pKa of 4 or less is preferable, a photoacid generator that generates an acid having a pKa of 3 or less is more preferable, and a photoacid generator that generates an acid of 2 or less is more preferable. The agent is more preferred. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured by changing to a solvent suitable for measurement. Specifically, pKa described in the Chemistry Handbook and the like can be referred to. As the acid having a pKa of 3 or less, sulfonic acid or phosphonic acid is preferable, and sulfonic acid is more preferable.

Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among them, an onium salt compound, an imide sulfonate compound, or an oxime sulfonate compound is preferable, and an onium salt compound or an oxime sulfonate compound is more preferable. The photoacid generator may be used alone or in combination of two or more.

The binder composition of the present invention may contain components other than the above-mentioned photo-oriented polymer, binder, and photoacid generator.

[Polymerization initiator]
When a polymerizable compound is used as the binder, the binder composition of the present invention preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and examples thereof include a thermal polymerization initiator and a photopolymerization initiator depending on the type of the polymerization reaction.
As the polymerization initiator, a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays is preferable.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,376,661 and 236,670), acidoin ethers (described in US Pat. No. 2,448,828), and α-hydrogen-substituted fragrances. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US Pat. 3549367 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), and acyl. Examples thereof include phosphine oxide compounds (described in Japanese Patent Application Laid-Open No. 63-040799, Japanese Patent Application Laid-Open No. 5-209234, Japanese Patent Application Laid-Open No. 10-095788, and Japanese Patent Application Laid-Open No. 10-029997).

〔solvent〕
The binder composition of the present invention preferably contains a solvent from the viewpoint of workability for forming the binder layer.
Solvents include, for example, ketones (eg, acetone, 2-butanone, methylisobutylketone, cyclopentanone, and cyclohexanone), ethers (eg, dioxane, and tetrahydrofuran), aliphatic hydrocarbons (eg, eg,). (Hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, and chloro). (Toluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methylserosolves, and ethyl). Serosolves), cellosolve acetates, sulfoxides (eg, dimethylsulfoxides), amides (eg, dimethylformamides, and dimethylacetamides).
One type of solvent may be used alone, or two or more types may be used in combination.

[Binder layer]
The binder layer of the present invention is a layer formed by using the binder composition of the present invention described above, and the surface thereof has an orientation control ability. More specifically, the binder layer is a layer formed by generating an acid from a photoacid generator in a coating film of a binder composition and then performing a photoalignment treatment.
That is, in the method of forming the binder layer, after generating an acid from the photoacid generator in the coating film obtained by using the above binder composition, the coating film is subjected to a photoalignment treatment to form the binder layer. It is preferable to have a step of forming (step 1).
In addition, having an orientation control ability means having a function of orienting a liquid crystal compound arranged on a binder layer in a predetermined direction.
When the binder composition contains a polymerizable compound, in the above step 1, the coating film obtained by using the above binder composition is subjected to a curing treatment, and then an acid is applied from the photoacid generator in the coating film. It is preferable to perform a treatment for generating the binder layer (hereinafter, also simply referred to as “acid generation treatment”) and then perform a photoalignment treatment to form a binder layer.
As will be described later, the hardening treatment and the acid generation treatment may be carried out at the same time.
Hereinafter, the method of carrying out the above curing treatment will be described in detail.

The method for forming the coating film of the binder composition is not particularly limited, and examples thereof include a method of applying the binder composition on the support and performing a drying treatment as necessary.
The support will be described in detail later.
Further, an orientation layer may be arranged on the support.
The method of applying the binder composition is not particularly limited, and examples of the application method include a spin coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, and a die coating method. Can be mentioned.

Next, the coating film of the binder composition is subjected to a curing treatment and a treatment of generating an acid from the photoacid generator in the coating film (hereinafter, also referred to as “acid generation treatment”).
Examples of the curing treatment include light irradiation treatment and heat treatment.
The conditions of the curing treatment are not particularly limited, but it is preferable to use ultraviolet rays in the polymerization by light irradiation. Irradiation dose is preferably ^{10mJ / cm 2 ~ 50J / cm} 2, more preferably ^{20mJ / cm 2 ~ 5J / cm} 2, more preferably ^{30mJ / cm 2 ~ 3J / cm} 2, particularly 50 ~ 1000mJ / cm ² preferable. Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.

The treatment for generating an acid from the photoacid generator in the coating film is a treatment for generating the acid by irradiating the light that the photoacid generator contained in the binder composition is exposed to. By carrying out this treatment, cleavage at the cleavage group proceeds, and the group containing a fluorine atom or a silicon atom is eliminated.
The light irradiation treatment carried out in the above treatment may be any treatment in which the photoacid generator is exposed to light, and examples thereof include a method of irradiating ultraviolet rays. As the light source, a lamp that emits ultraviolet rays, such as a high-pressure mercury lamp and a metal halide lamp, can be used. The irradiation amount is preferably ^{10mJ / cm 2 ~ 50J / cm} 2, more preferably ^{20mJ / cm 2 ~ 5J / cm} 2, more preferably ^{30mJ / cm 2 ~ 3J / cm} 2, 50 ~ 1000mJ / cm 2 Is particularly preferable.

In the above-mentioned hardening treatment and acid generation treatment, the acid generation treatment may be carried out after the hardening treatment is carried out, or the hardening treatment and the acid generation treatment may be carried out at the same time. In particular, when the photoacid generator and the polymerization initiator in the binder composition are exposed to light of the same wavelength, it is preferable to carry out the process at the same time from the viewpoint of productivity.

The method of photoalignment treatment performed on the coating film of the binder composition formed above (including the cured film of the binder composition that has been cured) is not particularly limited, and known methods are available. Can be mentioned.
As the photoalignment treatment, for example, the coating film of the binder composition (including the cured film of the binder composition that has been cured) is irradiated with polarized light or non-polarized light from an oblique direction with respect to the surface of the coating film. There is a way to do it.

In the photo-alignment treatment, 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.
Further, the "diagonal direction" for irradiating non-polarized light is not particularly limited as long as it is tilted by a polar angle θ (0 <θ <90 °) with respect to the normal direction of the coating film surface, depending on the purpose. However, it is preferable that θ is 20 to 80 °.

The wavelength in polarized light or unpolarized light is not particularly limited as long as it is light to which the photoaligning group is sensitive, and examples thereof include ultraviolet rays, near-ultraviolet rays, and visible light, and near-ultraviolet rays having a diameter of 250 to 450 nm are preferable.
Examples of the light source for irradiating polarized or unpolarized light include a xenon lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a metal halide lamp. By using an interference filter, a color filter, or the like for ultraviolet rays or visible rays obtained from such a light source, the wavelength range to be irradiated can be limited. Further, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.

The amount of polarized or unpolarized integrated light is not particularly limited, and ^{is preferably 1 to 300 mJ / cm 2 and} more preferably 5 to 100 mJ / cm ² .
The illuminance of the polarized light or unpolarized light is not particularly limited, preferably 0.1 ~ 300mW / cm ^2, more preferably 1 ~ 100mW / cm ^2.

In the above description, an embodiment in which the curing treatment and the acid generation treatment are carried out before the photo-alignment treatment is carried out has been described, but the present invention is not limited to this embodiment, and the curing treatment is performed at the same time as the photo-alignment treatment. And acid generation treatment may be carried out.

The thickness of the binder layer is not particularly limited, and 0.1 to 10 μm is preferable, and 0.5 to 5 μm is more preferable, because the liquid crystal orientation becomes better.

[Optical laminate]
The optical laminate of the present invention has a binder layer of the present invention and an optically anisotropic layer provided on the binder layer.
As one of the preferred embodiments of the optical laminate of the present invention, an optically anisotropic layer provided on the binder layer is formed by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound, and also. An embodiment in which the binder layer and the optically anisotropic layer are laminated adjacent to each other can be mentioned.
Further, the optical laminate of the present invention preferably has a support that supports the binder layer.
Hereinafter, preferred embodiments of the optical laminate of the present invention will be described in detail.

[Support]
Examples of the support include a glass substrate and a polymer film.
Materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and polyethylene na. Polyester polymers such as phthalate; styrene polymers such as polystyrene and acrylonitrile styrene copolymers; polyolefin polymers such as polyethylene, polypropylene and ethylene / propylene copolymers; vinyl chloride polymers; nylon, aromatic polyamides, etc. Amid polymer; imide polymer; sulfone polymer; polyether sulfone polymer; polyether ether ketone polymer; polyphenylene sulfide polymer; vinylidene chloride polymer; vinyl alcohol polymer; vinyl butyral polymer; allylate polymer; Polyoxymethylene-based polymers; epoxy-based polymers; or polymers in which these polymers are mixed can be mentioned.

The thickness of the support is not particularly limited, and is preferably 5 to 200 μm, more preferably 10 to 100 μm, and even more preferably 20 to 90 μm.

[Binder layer]
The binder layer is the binder layer of the present invention described above.

[Optically anisotropic layer]
The optically anisotropic layer is preferably formed by using a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound.
Here, as the polymerizable liquid crystal composition for forming the optically anisotropic layer, for example, a composition containing the polymerizable liquid crystal compound described as an optional component in the binder composition of the present invention, a polymerization initiator, a solvent and the like. Things can be mentioned.

The thickness of the optically anisotropic layer is not particularly limited, and is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm.

[Manufacturing method of optical laminate]
The method for producing an optical laminate of the present invention is a method for producing a preferred embodiment of the optical laminate of the present invention described above, and generates acid from a photoacid generator in a coating film obtained by using the binder composition. After that, the coating film is subjected to photoalignment treatment to form a binder layer (step 1), and a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound is applied onto the binder layer to obtain optics. It has a step (step 2) of forming an anisotropic layer.

[Step 1]
Step 1 is a step of generating an acid from a photoacid generator in a coating film obtained by using the binder composition, and then performing a photoalignment treatment on the coating film to form a binder layer.
The procedure of step 1 is as described above.

[Step 2]
Step 2 is a step of applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on the binder layer to form an optically anisotropic layer.
The method for applying the polymerizable liquid crystal composition is not particularly limited, and examples thereof include the application method exemplified in step 1.

Examples of the method for forming the optically anisotropic layer include a method in which a coating film of a polymerizable liquid crystal composition is heat-treated and then cured. The polymerizable liquid crystal compound can be oriented by the above heat treatment.
In the above, the heat treatment and the hardening treatment are carried out separately, but a method of carrying out the hardening treatment under heating conditions may also be used.
In addition, when the orientation is performed without performing the heat treatment depending on the type of the polymerizable liquid crystal compound, the heat treatment may not be performed.
After heating the coating film, if necessary, the coating film may be cooled before the curing treatment described later.

The conditions of the heat treatment are not particularly limited, and may be any temperature as long as the polymerizable liquid crystal compound is oriented. The heating temperature is usually preferably 30 to 100 ° C, more preferably 50 to 80 ° C. The heating time is preferably 0.5 to 20 minutes, more preferably 1 to 5 minutes.

The method of the curing treatment is not particularly limited, and examples thereof include light irradiation treatment and heat treatment, and light irradiation treatment is preferable. Ultraviolet rays are preferable as the light in the light irradiation treatment.
The conditions for light irradiation are not particularly limited, and the irradiation amount ^{is preferably 10 mJ / cm 2} to 50 J / cm ^2, more preferably 20 mJ / cm ² to 5 J / cm ² , and 30 mJ / cm ² to 3 J / cm. ² is more preferable.
Further, in order to promote the polymerization reaction, it may be carried out under heating conditions.

[Image display device]
The image display device of the present invention is an image display device having the optically anisotropic layer of the present invention or the optical laminate of the present invention.
The display element used in the image display device of the present invention is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter abbreviated as “EL”) display panel, and a plasma display panel.
Of these, a liquid crystal cell or an organic EL display panel is preferable, and a liquid crystal cell is more preferable. That is, as the image display device of the present invention, a liquid crystal display device using a liquid crystal cell as a display element or an organic EL display device using an organic EL display panel as a display element is preferable.

[Liquid crystal display device]
The liquid crystal display device which is an example of the image display device of the present invention is a liquid crystal display device having the above-mentioned optically anisotropic layer of the present invention or the optical laminate of the present invention and a liquid crystal cell.
The liquid crystal cell used in the liquid crystal display device is a VA (Vertical Element) mode, an OCB (Optically Compensated Bend) mode, an IPS (In-Plane-Switching) mode, an FFS (Fringe-Field-Switching) mode, or a TN (Twisted) mode. The Nematic mode is preferred, but is not limited to these.

[Organic EL display device]
As the organic EL display device which is an example of the image display device of the present invention, for example, from the viewing side, the polarizer, the optically anisotropic layer of the present invention or the optical laminate of the present invention, and the organic EL display panel are used. Aspects having in order are preferably mentioned.

<Polarizer>
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.
Examples of the absorption type polarizer include an iodine-based polarizer, a dye-based polarizer using a dichroic dye, and a polyene-based polarizer. The iodine-based polarizer and the dye-based polarizer include a coating type polarizing element and a stretching type polarizing element, and both can be applied.
Further, as a method for obtaining a polarizer by stretching and dyeing a laminated film having a polyvinyl alcohol layer formed on a substrate, Japanese Patent No. 5048120, Japanese Patent No. 5143918, Japanese Patent No. 46910205, and the like. Examples thereof include the methods described in Japanese Patent No. 4751481 and Japanese Patent No. 4751486.
Examples of the reflective polarizer include a polarizer in which thin films having different birefringences are laminated, a wire grid type polarizer, and a polarizer in which a cholesteric liquid crystal having a selective reflection region and a 1/4 wave plate are combined.
Among these, a polymer containing a polyvinyl alcohol-based resin (-CH _2- CHOH- as a repeating unit. In particular, at least selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers, in that the adhesion is more excellent. A polarizer containing (1) is preferable.

The thickness of the polarizer is not particularly limited, and is preferably 3 to 60 μm, more preferably 5 to 30 μm, and even more preferably 5 to 15 μm.

<Organic EL display panel>
The organic EL display panel is a member in which a plurality of organic compound thin films including a light emitting layer or a light emitting layer are formed between a pair of electrodes of an anode and a cathode. In addition to the light emitting layer, a hole injection layer, a hole transport layer, and an electron injection It may have a layer, an electron transport layer, a protective layer, and the like, and each of these layers may have other functions. Various materials can be used to form each layer.

Hereinafter, the present invention will be described in more detail with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Synthesis of monomer mb-6]
In a 100 mL eggplant flask, 5.0 g of 1,1-dimethoxycyclohexane, 9.0 g of 2-hydroxymethacrylate, 1H, 1H, 2H, 2H-perfluorooctanol 25.0 g, pyridinium paratoluene sulfonate 0.87 g, and toluene 30 mL was weighed and stirred at 40 ° C. for 1 hour.
Then, the mixture was stirred at 40 ° C. for 4 hours under a reduced pressure of 100 mmHg.
The reaction mixture was cooled to room temperature (23 ° C.), washed separately with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. 8.0 g of the monomer mb-6 represented by the formula mB-6 as a colorless liquid was obtained (yield 40%).
The following monomer mb-6 corresponds to a monomer forming a repeating unit represented by the following formula B-6.

[Synthesis of monomer mb-72]

In a 300 mL eggplant flask, 10.0 g of 4-hydroxy-2-butanone and 20 mL of tetrahydrofuran were weighed and stirred under ice-cooling.
Then, 50 mL of phenylmagnesium bromide (3.0 M diethyl ether solution) was added dropwise using a dropping funnel over 30 minutes, and after completion of the addition, the mixture was stirred at 0 ° C. for 2 hours.
The reaction solution was separated and washed with saturated aqueous sodium hydrogen carbonate solution, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain 18.5 g of the monomer 2A represented by the above formula 2A as a yellow liquid. (Yield 99%).
Next, 10.0 g of monomer 2A, 6.7 g of pyridine, and 50 mL of dichloromethane were weighed in a 300 mL eggplant flask and stirred under ice-cooling.
Then, 8.2 g of metacloyl chloride was added dropwise using a dropping funnel over 30 minutes, and after completion of the addition, the mixture was stirred at 0 ° C. for 1 hour.
The reaction solution was separated and washed with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and silica gel column chromatography was performed to make the monomer 2B represented by the above formula 2B colorless. 7.0 g of the liquid was obtained (yield 51%).
Next, 3.0 g of monomer 2B, 2.1 g of pyridine, 78 mg of N, N-dimethyl-4-aminopyridine, and 5 mL of dichloromethane were weighed into a 100 mL eggplant flask, and the mixture was stirred at room temperature (23 ° C.).
Then, 5.5 g of 2H, 2H, 3H, 3H-perfluorononanoate chloride was added dropwise, and after completion of the addition, the mixture was stirred at 45 ° C. for 6 hours.
The reaction solution was separated and washed with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. 3.0 g of −72 as a yellow liquid was obtained (yield 39%). The monomer mM-72 corresponds to a monomer forming a repeating unit represented by the following formula B-72.

[Synthesis of monomer mb-99]

In a 100 mL eggplant flask, 6.0 g of 3,4-dihydro-2H-pyran-2-methanol, 5.9 g of triethylamine, and 24 mL of N, N-dimethylacetamide were weighed and stirred under ice-cooling.
Then, 5.8 g of metacloyl chloride was added dropwise using a dropping funnel over 30 minutes, and after completion of the addition, the mixture was stirred at 0 ° C. for 1 hour.
The reaction solution was separated and washed with saturated aqueous sodium hydrogen carbonate solution, and the obtained organic layer was dried over anhydrous magnesium sulfate and concentrated to obtain 9.4 g of the monomer 3A represented by the above formula 3A as a colorless liquid. (Yield 98%).
Then, in a 100 mL eggplant flask, 3.0 g of monomer 3A, 2H, 2H, 3H, 3H-perfluorononanonic acid 6.5 g, toluene 25 mL, dibutylhydroxytoluene 10 mg, and (+) -10-camphorsulfonic acid 1.1 mg. Was weighed and stirred at room temperature (23 ° C.) for 3 hours.
The reaction solution was separated and washed with saturated aqueous sodium hydrogen carbonate solution, the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated, and subjected to silica gel column chromatography. 7.8 g of −99 as a colorless liquid was obtained (yield 80%). The monomer mM-99 corresponds to a monomer forming a repeating unit represented by the following formula B-99.

Monomers other than the above were synthesized with reference to the above-mentioned synthetic methods and known methods (for example, the method described in International Publication No. 2018/216812).

[Example 1 (Synthesis of photo-oriented polymer P-1)]
In a flask equipped with a cooling tube, a thermometer and a stirrer, 5.5 parts by mass of monomer mA-125 represented by the following formula mA-125 and 10 parts by mass of 2-butanone as a solvent were charged, and nitrogen was added to the flask. The mixture was refluxed by heating in a water bath while flowing 5 mL / min. Here, 3.0 parts by mass of the monomer mb-6, 1.5 parts by mass of the monomer mC-4 represented by the following formula mC-4, and 2,2'-azobis (isobutyronitrile) as a polymerization initiator. Was mixed with 0.062 parts by mass and 13 parts by mass of 2-butanone as a solvent, and the solution was added dropwise over 3 hours, and the mixture was further stirred for 3 hours while maintaining the reflux state. After completion of the reaction, the mixture was allowed to cool to room temperature and diluted by adding 10 parts by mass of 2-butanone to obtain a polymer solution of about 20% by mass. The obtained polymer solution was poured into a large excess of methanol to precipitate the polymer, the recovered precipitate was filtered off, washed with a large amount of methanol, and then air-dried at 50 ° C. for 12 hours. A photo-oriented polymer P-1 represented by the following formula P-1 was obtained.

[Example 2 (Synthesis of photo-oriented polymer P-2)]
The photo-oriented polymer P-2 was synthesized in the same manner as the photo-oriented polymer P-1 synthesized in Example 1 except that the monomer mb-72 was used instead of the monomer mb-6.

[Example 3 (Synthesis of photo-oriented polymer P-3)]
The photo-oriented polymer P-3 was synthesized in the same manner as the photo-oriented polymer P-1 synthesized in Example 1 except that the monomer mb-99 was used instead of the monomer mb-6.

[Comparative Example 1 (Synthesis of Photo-Oriented Polymer H-1)]
The light synthesized in Example 1 except that the monomer mH-1 represented by the following formula mH-1 was used instead of the monomer mB-6 to form a repeating unit represented by the following formula H-1. The photo-oriented polymer H-1 was synthesized in the same manner as the oriented polymer P-1.

[Comparative Example 2 (Synthesis of Photo-Oriented Polymer H-1)]
The light synthesized in Example 1 except that the monomer mH-2 represented by the following formula mH-2 was used instead of the monomer mB-6 to form the repeating unit represented by the following formula H-2. The photo-oriented polymer H-2 was synthesized in the same manner as the oriented polymer P-1.

The weight average molecular weight of the synthesized photooriented polymer was measured by the method described above. The results are shown in Table 1 below.

[Example 1 (Manufacturing of optical laminate)]
[Preparation of support]
A cellulose acylate film (TD40UL, manufactured by FUJIFILM Corporation) is passed through a dielectric heating roll having a temperature of 60 ° C. to raise the film surface temperature to 40 ° C., and then an alkaline solution having the following composition is applied to one side of the film. , The film was applied at a coating amount of 14 ml / m ² using a bar coater, and heated to 110 ° C.
Next, the obtained film was conveyed under a steam-type far-infrared heater manufactured by Noritake Company Limited for 10 seconds.
^{Next, 3 ml / m 2 of} pure water was applied to the obtained film using the same bar coater.
Next, the obtained film was washed with water by a fountain coater and drained with an air knife three times, and then transported to a drying zone at 70 ° C. for 10 seconds to be dried to prepare an alkali saponified cellulose acylate film. Was used as a support.

[Formation of alignment layer]
An alignment layer coating solution having the following composition was continuously applied to a long cellulose acetate film saponified as described above with a wire bar of # 14. After coating, the obtained film was dried with warm air at 60 ° C. for 60 seconds, and further dried with warm air at 100 ° C. for 120 seconds. In the composition below, "polymerization initiator (IN1)" represents a photopolymerization initiator (IRGACURE2959, manufactured by BASF).
Next, the dried coating film was continuously subjected to a rubbing treatment to form an oriented layer. At this time, the longitudinal direction of the long film and the conveying direction were parallel, and the rotation axis of the rubbing roller with respect to the longitudinal direction of the film was set to a direction of 45 ° clockwise.

(In the structural formula below, the ratio is the molar ratio)

[Preparation of binder layer (lower layer)]
The following rod-shaped liquid crystal compound A (80 parts by mass), the following rod-shaped liquid crystal compound B (20 parts by mass), a photopolymerization initiator (IRGACURE819, manufactured by BASF) (3 parts by mass), the following photoacid generator (B-1-1). ) (5.0 parts by mass), the following vertical alignment agent A (1 part by mass), the following vertical alignment agent B (0.5 parts by mass), and the photoalignable polymer P-1 (3.0 parts by mass). A binder composition was prepared by dissolving in 215 parts by mass of methyl ethyl ketone. The prepared binder composition was applied onto the alignment layer with a # 3.0 wire bar. The obtained coating film is heated at the temperature shown in Table 1 below (first lower layer annealing temperature) for 2 minutes, cooled to 40 ° C., and then purged with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less. While using a 365 nm UV-LED, ultraviolet rays having ^{an irradiation volume of 500 mJ / cm 2 were irradiated.} Then, the obtained film was annealed at the temperature shown in Table 1 below (second lower layer annealing temperature) for 1 minute to prepare a cured layer.
The film thickness was about 1 μm.

[Irradiation process (giving orientation function)]
The obtained cured layer is irradiated with UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) through a wire grid polarizer at room temperature at 25 mJ / cm ² (wavelength: 313 nm) to impart an orientation function to the cured layer. Then, a binder layer was formed.

[Preparation of optically anisotropic layer (upper layer)]
The following liquid crystal compound L-1 (39 parts by mass), the following liquid crystal compound L-2 (39 parts by mass), the following liquid crystal compound L-3 (17 parts by mass), the following liquid crystal compound L-4 (5 parts by mass), photopolymerization Initiator (Irgacure 907, manufactured by BASF) (3 parts by mass), sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) (1 part by mass), and the following horizontal alignment agent (0.3 parts by mass) Was dissolved in methyl ethyl ketone (193 parts by mass) to prepare a solution for forming an optically anisotropic layer. The above-mentioned solution for forming an optically anisotropic layer was applied with a wire bar coater # 2.2 on the binder layer to which the above-mentioned orientation function was imparted. The obtained coating film was heated at the temperature shown in Table 1 below (upper layer annealing temperature) for 2 minutes, and while maintaining that temperature, 160 W was purged with nitrogen so that the oxygen concentration became an atmosphere of 1.0% by volume or less. An optically anisotropic layer was formed by irradiating ultraviolet rays with ^{an irradiation volume of 300 mJ / cm 2} using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) of / cm to prepare an optical laminate.

Liquid crystal compound L-1

Liquid crystal compound L-2

Liquid crystal compound L-3

Liquid crystal compound L-4

[Examples 2 to 3 and Comparative Examples 1 to 2 (preparation of an optical laminate)]
An optical laminate was prepared in the same manner as in Example 1 except that the photo-oriented polymers P-2 to P-3 and H-1 to H-2 were used instead of the photo-oriented polymers P-1. ..

[evaluation]
[Liquid crystal orientation]
Two polarizing plates were placed on the cross Nicol, and the obtained optical laminate was placed between them, and the degree of light leakage and the planar shape were observed with a polarizing microscope. The results are shown in Table 1 below. For the observation, an optical laminate prepared at the annealing temperature shown in Table 1 below was used.
AA: The liquid crystal director is uniformly arranged and oriented, and the display performance is excellent.
A: The liquid crystal director is not disturbed and the surface shape is stable.
B: The liquid crystal director is partially disturbed and the surface shape is stable.
C: The liquid crystal director is significantly disturbed and the surface shape is not stable, and the display performance is very poor.
Here, the stable planar shape is intended to be a state in which there are no defects such as unevenness and poor orientation when an optical laminate is placed between two polarizing plates arranged with cross Nicols and observed.
Further, the liquid crystal director is intended as a vector in the direction in which the long axis of the liquid crystal molecule is oriented (orientation main axis).

[Upper layer coatability]
The surface energy of the produced binder layer (lower layer) was measured by the method shown below, and the coatability of the upper layer was evaluated according to the following criteria. The results are shown in Table 1 below. For the measurement, a binder layer (lower layer) prepared at the annealing temperature shown in Table 1 below was used.
<Measurement method of surface energy>
The surface energy of the binder layer forming composition and the surface energy of the binder layer after heating after irradiation with UV-LED at 365 nm (measured at 110 ° C./120 ° C./135 ° C., respectively) were measured. As the surface energy, a contact angle meter [“CA-X” type contact angle meter, manufactured by Kyowa Interface Science Co., Ltd.] was used. The specific measurement method is as follows.
The object to be measured was spin-coated on a quartz substrate. When a solvent was contained, the film was dried to prepare a film. Subsequently, using a contact angle meter, a droplet having a diameter of 1.0 mm was formed on the needle tip using pure water as a liquid in a dry state (20 ° C./65% RH), and this was formed on the spin coat film described above. Droplets were formed on the film by contacting the surface. The angle between the tangent line to the liquid surface and the film surface at the point where the film and the liquid contact each other was measured with the angle on the side containing the liquid as the contact angle. In addition, the contact angle was measured using methylene iodide instead of water, and the surface free energy defined below was determined.
Here, the surface free energy (γs ^v : unit, mN / m) is defined as D.I. K. Owns: J.M. Apple. Polym. Sci. , 13, 1741 (1969), and the following simultaneous equations a from the contact angles _{θ H2} _O and θ _{CH 2} I ₂ _{of pure water H 2} O and methylene iodide CH 2 I 2 experimentally obtained on the antireflection film. was defined as a value represented by the sum of the gamma] s ^d and gamma] s ^h determined from the ^{^{b γs v (= γs d +}} γs h).
a. 1 + _{cosθ H2O} = 2√γs ^d (√γ _H2O ^d / γ _H2O ^v ) + 2√γs ^h (√γ _H2O ^h / γ _H2O ^v )
b. 1 + _{cosθ CH2I2} = 2√γs ^d (√γ _CH2I2 ^d / γ _CH2I2 ^v ) + 2√γs ^h (√γ _CH2I2 ^h / γ _CH2I2 ^v )
γ _H2O ^d = 21.8, γ _H2O ^h = 51.0, γ _H2O ^v = 72.8
γ _CH2I2 ^d = 49.5, γ _CH2I2 ^h = 1.3, γ _CH2I2 ^v = 50.8
<Evaluation criteria>
A: Difference in surface energy is 20 mN / m or more B: Difference in surface energy is 10 N / m or more and less than 20 mN / m C: Difference in surface energy is less than 10 N / m

From the results shown in Table 1 above, when a photo-oriented polymer having a repeating unit containing a cleaving group that does not correspond to any of the above formulas (B1) to (B3) is used, it depends on the production conditions of the lower layer and the upper layer. , It was found that the upper layer coating property and the liquid crystal orientation were inferior (Comparative Examples 1 and 2).
On the other hand, when a photo-oriented polymer having a repeating unit containing a cleaving group corresponding to any of the above formulas (B1) to (B3) is used, the upper layer is coated regardless of the preparation conditions of the lower layer and the upper layer. It was found that the properties and the liquid crystal orientation were good (Examples 1 to 3).

Claims

Repeating units with photo-oriented groups and
A photo-oriented polymer having a repeating unit having a group represented by the following formula (1).

In the above formula (1),
L B represents a n + 1 valent number 1 or more aliphatic hydrocarbon group having a carbon, -CH 2 constituting the aliphatic hydrocarbon group - of not partially or completely substituted with -CO- or -O- You may.
X represents a cleavage group represented by any of the following formulas (B1) to (B3).
Y represents a group containing a fluorine atom or a silicon atom.
n represents an integer of 1 or more.
* Represents the bond position.

In the formulas (B1) to (B3), * represents a bonding position.
In the above formula (B1), RB1 independently represents a substituent, and two RB1s may be bonded to each other to form a ring.
In the above formula (B2), RB2 each independently represents a substituent, and two RB2s may be bonded to each other to form a ring.
In the above formula (B3), RB3 represents a substituent and m represents an integer of 0 to 3. When m is 2 or 3, the plurality of RB3s may be the same or different.
The photooriented polymer according to claim 1, wherein the repeating unit having a group represented by the formula (1) is a repeating unit represented by the following formula (B).

In the formula (B), R B represents a hydrogen atom or a substituent, A represents, -O- or -NR Z - represents, R Z represents a hydrogen atom or a substituent.
L B, X, definitions of Y and n in the formula (B) is, L B in the formula (1), X, is the same as the respective definitions of Y and n.
The photooriented polymer according to claim 1 or 2, wherein the group represented by the formula (1) represents a group represented by any of the following formulas (B4) to (B8).

In the formula (B4) ~ (B8), * represents a bonding position, the definition of L B are as defined for L B in the formula (1), L B2 represents a single bond or a divalent Cf represents a fluorine atom-containing alkyl group.
In the formula (B4), the definition of R B1 is the same as the definition of R B1 in the formula (B1).
In the formula (B5) and (B6), the definition of R B2 is the same as the definition of R B2 in the formula (B2) in.
In the formula (B7) and (B8), the definition of R B3 and m are the same as defined in the definition of R B3 and m in the formula (B3).
The photooriented polymer according to claim 1 or 2, wherein the group represented by the formula (1) represents a group represented by any of the following formulas (B9) to (B16).

In the formulas (B9) to (B16), * represents a bond position and Cf represents a fluorine atom-containing alkyl group.
In the formula (B9) and (B10), the definition of L B, are as defined for L B in the formula (1), n represents an integer of 0 ~ 10, L B21 is a single bond Alternatively, it represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
In the formula (B11) ~ (B13), the definition of L B are as defined for L B in the formula (1), the definition of R B2 is the definition of R B2 in the formula (B2) LB21 represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms.
Formula (B14) in ~ (B16), L B2 represents a single bond or a divalent linking group, L B3 represents a divalent aliphatic hydrocarbon group having a single bond or a C 1-10, definition of R B2 is the same as the definition of R B2 in the formula (B2).
The photo-oriented polymer according to any one of claims 1 to 4, wherein the repeating unit having a photo-oriented group is a repeating unit represented by the following formula (A).

In the formula (A),
RA1 represents a hydrogen atom or a substituent.
LA1 represents a single bond or a divalent linking group.
R A2 , R A3 , R A4 , R A5 and R A6 each independently represent a hydrogen atom or a substituent. Of RA2 , RA3 , RA4 , RA5 and RA6 , two adjacent groups may be bonded to form a ring.
The photooriented polymer according to any one of claims 1 to 5, further having a repeating unit having a crosslinkable group.
The photooriented polymer according to claim 6, wherein the repeating unit having a crosslinkable group is a repeating unit represented by the following formula (C).

In the formula (C),
RC1 represents a hydrogen atom or a substituent.
LC1 represents a single bond or a divalent linking group.
LC2 represents an m + 1 valent linking group.
Z represents a crosslinkable group.
m represents an integer of 1 or more, and when it is an integer of 2 or more, the plurality of Zs may be the same or different.
The photooriented polymer according to claim 6 or 7, wherein the crosslinkable group represents a group represented by any of the following formulas (C1) to (C4).

In the formulas (C1) to (C4), * represents a bonding position.
In the formula (C3), RC2 represents a hydrogen atom, a methyl group, or an ethyl group.
In the formula (C4), RC3 represents a hydrogen atom or a methyl group.
The content a of the repeating unit having a photo-oriented group, the content b of the repeating unit having a group represented by the formula (1), and the content c of the repeating unit having a crosslinkable group are The photooriented polymer according to any one of claims 6 to 8, which satisfies the following formula (D1) in terms of mass ratio.
0.03 ≤ a / (a + b + c) ≤ 0.5 ... (D1)
The photooriented polymer according to any one of claims 1 to 9, which has a weight average molecular weight of 10,000 to 500,000.
A binder composition containing the photo-oriented polymer, binder, and photoacid generator according to any one of claims 1 to 10.
A binder layer formed by using the binder composition according to claim 11, wherein the surface thereof has an orientation control ability.
The binder layer according to claim 12 and
An optical laminate having an optically anisotropic layer arranged on the binder layer.
A step of generating an acid from the photoacid generator and then performing a photoalignment treatment on the coating film obtained by using the binder composition according to claim 11 to form a binder layer.
A method for producing an optical laminate, comprising a step of applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on the binder layer to form an optically anisotropic layer.
An image display device having the binder layer according to claim 12 or the optical laminate according to claim 13.