JP6358400B2 - Polymer for photo-alignment film, polymer solution, photo-alignment film, optical anisotropic body, and liquid crystal display element - Google Patents

Description

  The present invention relates to a polymer for a photoalignment film, a polymer solution, a photoalignment film, an optical anisotropic body, and a liquid crystal display element.

  The photo-alignment film has excellent characteristics that there is no micro-scratch due to mechanical rubbing, there is no risk of dust generation due to rubbing and the accompanying destruction of the TFT element, and high-definition patterning is possible. For this reason, the application to various liquid crystal displays is energetically advanced. In particular, there is a great demand for a photo-alignment film for horizontal alignment (planar alignment) used for an IPS / FFS display.

  As a method for producing a photo-alignment film that is not subjected to rubbing treatment, first, a solution containing a photo-alignment polymer is applied on a substrate to form a dried film, and then the liquid crystal is irradiated with polarized light. A method of imparting an alignment regulating force to the surface of the photo-alignment film is generally used (see, for example, Patent Document 1).

International Publication No. 2013/002260

  In order to obtain an excellent liquid crystal driving force in a liquid crystal display element (liquid crystal panel), the liquid crystal is required to have a high voltage holding ratio (VHR). Since the alignment regulating power of the photo-alignment film has a great influence on the VHR performance, an excellent photo-alignment film capable of obtaining a high VHR is desired.

The present invention has been made in view of the above circumstances, a polymer for a photoalignment film capable of forming a photoalignment film capable of obtaining a high VHR, a photoalignment film formed by the polymer for a photoalignment film, and the photoalignment It is an object to provide an optical anisotropic body having a film and a liquid crystal display element.

  The first aspect of the present invention is the following general formula (X):

（上記一般式（Ｘ）中、
Ｓｐ^１およびＳｐ^２はそれぞれ独立して、スペーサー基を表し、
Ｒ^１１は、２つ以上の原子によって構成される１価の置換基又はハロゲン原子を表し、前記１価の置換基において互いに結合する２つの原子の任意の組み合わせの中に、原子同士の電気陰性度の差の絶対値が０．４５以上１．７０以下である組み合わせが含まれ、
ｍは１〜５の整数であり、ｍが２以上である場合は、複数のＲ^１１は互いに同じであっても良いし異なっていても良く、
Ａ^２１、Ａ^２２およびＡ^２３は、それぞれ独立して、
（ａ）トランス−１，４−シクロへキシレン基（この基中に存在する１個のメチレン基又は隣接していない２個以上のメチレン基は−Ｏ−、−ＮＨ−又は−Ｓ−に置き換えられても良い。）、
（ｂ）１，４−フェニレン基（この基中に存在する１個又は２個以上の−ＣＨ＝は−Ｎ＝に置き換えられても良い。）、及び
（ｃ）１，４−シクロヘキセニレン基、２，５−チオフェニレン基、２，５−フラニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ナフタレン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）又は基（ｃ）はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、アルキル基又はアルコキシ基によって置換されていても良く、
ｐ、ｑおよびｒはそれぞれ独立して、０〜４の整数を表し、ｐ、ｑおよびｒが２以上である場合は、複数のＡ^２１、Ａ^２２、Ａ^２３、Ｚ^２２およびＺ^２４は互いに同じであっても良いし異なっていても良く、
Ｚ^２１、Ｚ^２２、Ｚ^２３およびＺ^２４はそれぞれ独立して、単結合、−Ｏ−、−（ＣＨ_２）_ｕ−（式中、ｕは１〜２０を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−および−Ｃ≡Ｃ−からなる群から選択される少なくとも１種の二価の連結基を表し、
Ｄ^１が−（Ｌ^１−Ａ^１）_ｋ−Ｃ（＝Ｏ）−であり、かつＤ^２が単結合である条件、または、Ｄ^２が−Ｃ（＝Ｏ）−（Ａ^１−Ｌ^１）_ｆ−であり、かつＤ^１が単結合である条件のいずれかを満たし、
Ｌ^１は、単結合、−（ＣＨ_２）_ｕ−（式中、ｕは１〜２０を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表し、Ｌ^１を構成する非隣接の−ＣＨ_２−基の一つ以上は独立して、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓｉ（ＣＨ_３）_２−Ｏ−Ｓｉ（ＣＨ_３）_２―、−ＮＲ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−ＮＲ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−又は−Ｏ−ＣＯ−Ｏ−（式中、Ｒは独立して水素又は炭素原子数１〜５のアルキル基を表す。）で置換されていても良く、ｋおよびｆは０〜３の整数であり、
Ａ^１は、
（ａ）トランス−１，４−シクロへキシレン基（この基中に存在する１個のメチレン基又は隣接していない２個以上のメチレン基は−Ｏ−、−ＮＨ−又は−Ｓ−に置き換えられても良い。）、
（ｂ）１，４−フェニレン基（この基中に存在する１個又は２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい。）、及び
（ｃ）１，４−シクロヘキセニレン基、２，５−チオフェニレン基、２，５−フラニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ナフタレン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）又は基（ｃ）はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良く、
ＸおよびＹはそれぞれ独立して、水素原子またはハロゲン原子を表し、
Ｚは、一般式（ＩＩａ）又は（ＩＩｂ）

(In the above general formula (X),
Sp ¹ and Sp ² each independently represent a spacer group,
R ¹¹ represents a monovalent substituent or a halogen atom composed of two or more atoms, and among any combination of two atoms bonded to each other in the monovalent substituent, an electronegativity between atoms Including combinations in which the absolute value of the degree difference is 0.45 or more and 1.70 or less,
m is an integer of 1 to 5, and when m is 2 or more, the plurality of R ¹¹ may be the same or different from each other,
A ²¹ , A ²² and A ²³ are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, alkyl or alkoxy groups,
p, q and r each independently represents an integer of 0 to 4, and when p, q and r are 2 or more, a plurality of A ²¹ , A ²² , A ²³ , Z ²² and Z ²⁴ are May be the same or different,
Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, From —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — and —C≡C—. Represents at least one divalent linking group selected from the group consisting of:
The condition that D ¹ is — (L ¹ -A ¹ ) _k —C (═O) — and D ² is a single bond, or D ² is —C (═O) — (A ¹ -L ¹ ) _Satisfy any of the following conditions: _f − and D ¹ is a single bond,
L ¹ is a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— represents ^one of non-adjacent —CH ₂ — groups constituting L ^1. Two or more are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, — NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—. CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), k and f are integers of 0 to 3,
A ¹ is,
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups;
X and Y each independently represent a hydrogen atom or a halogen atom,
Z represents the general formula (IIa) or (IIb)

（式中、破線はＤ^２への結合を表し、
Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は直鎖状若しくは分岐状の炭素原子数１〜５０のアルキル基を表し、Ｒ^１及びＲ^２中の１つの−ＣＨ_２−基又は２以上の非隣接−ＣＨ_２−基は、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＣＨ_３−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−及び−Ｃ≡Ｃ−からなる群から選ばれる一つ以上で置換されていても良く、Ｒ^１及びＲ^２中の１つ又は２以上の−ＣＨ_２−基はそれぞれ独立して環員数３〜８のシクロアルキル基で置換されていても良く、Ｒ^１及びＲ^２中の水素原子は炭素原子数１〜２０のアルキル基、シアノ基又はハロゲン原子で置換されていても良い。）を表し、
ａ、ｂ及びｃは、コポリマーのモル分率を表すものであって、いずれの場合にも０＜ａ≦１かつ０＜ｂ≦１かつ０≦ｃ＜１であり、
Ｍａ、Ｍｂ及びＭｄのモノマー単位の並びは式と同一であっても良いし異なっていても良く、Ｍａ、Ｍｂ及びＭｄのモノマー単位は各々独立して１種類でも２種類以上の異なる単位であっても良く、Ｍa、Ｍｂ及びＭｄの各モノマー単位は、それぞれ独立して、一般式（Ｕ−１）〜（Ｕ−１３）

(Wherein the dashed line represents a bond to the D ^2,
R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, one —CH ₂ — group in R ¹ and R ² , or two or more Non-adjacent —CH ₂ — groups are —O—, —CO—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NCH ₃ —, —CH═CH. One or more —CH ₂ — groups in R ¹ and R ² may be substituted with one or more selected from the group consisting of —, —CF═CF— and —C≡C—. It may be independently substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in R ¹ and R ² is substituted with an alkyl group having 1 to 20 carbon atoms, a cyano group, or a halogen atom. Also good. )
a, b and c represent the molar fraction of the copolymer, and in each case 0 <a ≦ 1, 0 <b ≦ 1, and 0 ≦ c <1;
The sequence of the monomer units of Ma, Mb and Md may be the same as or different from the formula, and the monomer units of Ma, Mb and Md are each independently one type or two or more types of different units. Each monomer unit of Ma, Mb and Md may be independently represented by the general formulas (U-1) to (U-13).

（上記一般式（Ｕ−１）〜（Ｕ−１３）中、
当該式がＭａ、Ｍｂを表す場合には破線はＳｐ^１、Ｓｐ^２への結合をそれぞれ表し、当該式がＭｄを表す場合には破線は水素原子又は一価の有機基への結合を表し、
Ｒ^ａは独立して水素原子、炭素原子数１〜５のアルキル基、フェニル基、ハロゲン原子を表し、上記一般式（Ｕ−１）〜（Ｕ−１３）中の任意の水素原子はフッ素原子、塩素原子、メチル基、フェニル基、又はメトキシ基によって置換されていても良く；
Ｒ^１ａは４価の環構造、Ｒ^２ａは３価の有機基、Ｒ^３ａは水素原子、水酸基、炭素原子数１〜１５のアルキル基、又は炭素原子数１〜１５のアルコキシ基を表す。）
のいずれか１種の繰り返し単位を表す。）
で表される光配向膜用ポリマーである。
本発明の第二の態様は、第一の態様の光配向膜用ポリマーと有機溶剤とを必須成分とするポリマー溶液である。
本発明の第三の態様は、第一の態様の光配向膜用ポリマーによって形成された光配向膜
である。
本発明の第四の態様は、第三の態様の光配向膜を有する光学異方体である。
本発明の第五の態様は、第三の態様の光配向膜を有する液晶表示素子である。

(In the above general formulas (U-1) to (U-13),
When the formula represents Ma and Mb, the broken lines represent bonds to Sp ¹ and Sp ² , respectively, and when the formula represents Md, the broken lines represent a bond to a hydrogen atom or a monovalent organic group,
R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom, and any hydrogen atom in the above general formulas (U-1) to (U-13) is a fluorine atom Optionally substituted by a chlorine atom, a methyl group, a phenyl group, or a methoxy group;
R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, R ^3a represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms. )
Any one kind of repeating unit is represented. )
It is a polymer for photo-alignment films | membrane represented by these.
The second aspect of the present invention is a polymer solution containing the polymer for photoalignment film of the first aspect and an organic solvent as essential components.
The third aspect of the present invention is a photo-alignment film formed by the polymer for photo-alignment films of the first aspect.
The fourth aspect of the present invention is an optical anisotropic body having the photo-alignment film of the third aspect.
The fifth aspect of the present invention is a liquid crystal display element having the photo-alignment film of the third aspect.

  According to the polymer for a photoalignment film according to the present invention, it is possible to form a photoalignment film that can induce alignment of liquid crystal with a small amount of polarized light irradiation and can obtain a high VHR. Since the photo-alignment film according to the present invention has excellent liquid crystal alignment, an excellent optical anisotropic body and liquid crystal alignment layer can be formed. According to the liquid crystal display element according to the present invention, a high VHR can be obtained.

  Hereinafter, although this invention is demonstrated based on suitable embodiment, this invention is not limited to this embodiment.

<< polymer for photo-alignment film >>
The polymer for photoalignment films according to the first embodiment of the present invention is a polymer represented by the following general formula (X).

(In the above general formula (X),
Sp ¹ and Sp ² each independently represent a spacer group,
R ¹¹ represents a monovalent substituent composed of two or more atoms or a halogen atom,
In any combination of two atoms bonded to each other in the monovalent substituent, a combination in which an absolute value of a difference in electronegativity between atoms is 0.45 or more and 1.70 or less is included,
m is an integer of 1 to 5, and when m is 2 or more, the plurality of R ¹¹ may be the same or different from each other,
A ²¹ , A ²² and A ²³ are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, alkyl or alkoxy groups,
p, q and r each independently represents an integer of 0 to 4, and when p, q and r are 2 or more, a plurality of A ²¹ , A ²² , A ²³ , Z ²² and Z ²⁴ are May be the same or different,
Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, From —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — and —C≡C—. Represents at least one divalent linking group selected from the group consisting of:

The condition that D ¹ is — (L ¹ -A ¹ ) _k —C (═O) — and D ² is a single bond, or D ² is —C (═O) — (A ¹ -L ¹ ) _Satisfy any of the following conditions: _f − and D ¹ is a single bond,
L ¹ is a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— represents ^one of non-adjacent —CH ₂ — groups constituting L ^1. Two or more are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, — NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—. CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), k and f are integers of 0 to 3,
A ¹ is,
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups;
X and Y each independently represent a hydrogen atom or a halogen atom,
Z represents the general formula (IIa) or (IIb)

（式中、破線はＤ^２への結合を表し、
Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は直鎖状若しくは分岐状の炭素原子数１〜５０のアルキル基を表し、Ｒ^１及びＲ^２中の１つの−ＣＨ_２−基又は２以上の非隣接−ＣＨ_２−基は、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＣＨ_３−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−及び−Ｃ≡Ｃ−からなる群から選ばれる一つ以上で置換されていても良く、Ｒ^１及びＲ^２中の１つ又は２以上の−ＣＨ_２−基はそれぞれ独立して環員数３〜８のシクロアルキル基で置換されていても良く、Ｒ^１及びＲ^２中の水素原子は炭素原子数１〜２０のアルキル基、シアノ基又はハロゲン原子で置換されていても良い。）を表し、
ａ、ｂ及びｃは、コポリマーのモル分率を表すものであって、いずれの場合にも０＜ａ≦１かつ０＜ｂ≦１かつ０≦ｃ＜１であり、
Ｍａ、Ｍｂ及びＭｄのモノマー単位の並びは式と同一であっても良いし異なっていても良く、Ｍａ、Ｍｂ及びＭｄのモノマー単位は各々独立して１種類でも２種類以上の異なる単位であっても良く、Ｍa、Ｍｂ及びＭｄの各モノマー単位は、それぞれ独立して、一般式（Ｕ−１）〜（Ｕ−１３）

(Wherein the dashed line represents a bond to the D ^2,
R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, one —CH ₂ — group in R ¹ and R ² , or two or more Non-adjacent —CH ₂ — groups are —O—, —CO—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NCH ₃ —, —CH═CH. One or more —CH ₂ — groups in R ¹ and R ² may be substituted with one or more selected from the group consisting of —, —CF═CF— and —C≡C—. It may be independently substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in R ¹ and R ² is substituted with an alkyl group having 1 to 20 carbon atoms, a cyano group, or a halogen atom. Also good. )
a, b and c represent the molar fraction of the copolymer, and in each case 0 <a ≦ 1, 0 <b ≦ 1, and 0 ≦ c <1;
The sequence of the monomer units of Ma, Mb and Md may be the same as or different from the formula, and the monomer units of Ma, Mb and Md are each independently one type or two or more types of different units. Each monomer unit of Ma, Mb and Md may be independently represented by the general formulas (U-1) to (U-13).

（上記一般式（Ｕ−１）〜（Ｕ−１３）中、
当該式がＭａ、Ｍｂを表す場合には破線はＳｐ^１、Ｓｐ^２への結合をそれぞれ表し、当該式がＭｄを表す場合には破線は水素原子又は一価の有機基への結合を表し、
Ｒ^ａは独立して水素原子、炭素原子数１〜５のアルキル基、フェニル基、ハロゲン原子を表し、上記一般式（Ｕ−１）〜（Ｕ−１３）中の任意の水素原子はフッ素原子、塩素原子、メチル基、フェニル基、又はメトキシ基によって置換されていても良く；
Ｒ^１ａは４価の環構造、Ｒ^２ａは３価の有機基、Ｒ^３ａは水素原子、水酸基、炭素原子数１〜１５のアルキル基、又は炭素原子数１〜１５のアルコキシ基を表す。）
のいずれか１種の繰り返し単位を表す。）

(In the above general formulas (U-1) to (U-13),
When the formula represents Ma and Mb, the broken lines represent bonds to Sp ¹ and Sp ² , respectively, and when the formula represents Md, the broken lines represent a bond to a hydrogen atom or a monovalent organic group,
R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom, and any hydrogen atom in the above general formulas (U-1) to (U-13) is a fluorine atom Optionally substituted by a chlorine atom, a methyl group, a phenyl group, or a methoxy group;
R ^1a represents a tetravalent ring structure, R ^2a represents a trivalent organic group, R ^3a represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms. )
Any one kind of repeating unit is represented. )

  The polymer represented by the general formula (X) is a copolymer having a side chain unit MA bonded to the monomer unit Ma and a side chain unit MB bonded to the monomer unit Mb.

《Side chain unit MA》

<About Sp ¹ >
In the general formula (X), the spacer group represented by Sp ¹ represents a single bond, a linear or branched alkylene group having 1 to 40 carbon atoms, or the following general formula (IVa). One or more of adjacent —CH ₂ — is independently —O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —C≡C—, —CO—, —S—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR′—, —NR′—CO— , -CO-NR'-, -NR'-CO-O-, -O-CO-NR'-, -NR'-CO-NR'-, -CH = CH-, -C≡C- or -O -CO-O- (wherein R 'independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), and One or more hydrogen atoms of —CH ₂ — in the len group may be substituted with a fluorine atom, a chlorine atom, a hydroxy group, or a cyano group. In addition, when the group connected to Sp ¹ and Sp ¹ has a hetero atom, the case where the hetero atom is connected is excluded.

When Z ²¹ is a single bond, Sp ¹ is preferably a structure represented by the alkylene group or the following general formula (IVa).
2-20 are preferable, as for the carbon atom number of the said alkylene group, 3-15 are more preferable, and 4-10 are more preferable. With these suitable spacer groups, the VHR of a liquid crystal display device provided with a liquid crystal alignment layer using the polymer for photoalignment films according to the present embodiment can be improved.

Suitable spacer groups represented by Sp ¹ include, for example, groups represented by the following general formula (IVa), among which chemical formulas (Sp-a-1) to (Sp-a-20), chemical formulas (Sp-b-1) to (Sp-b-14), chemical formula (Sp-c-1) to (Sp-c-14) and chemical formula (Sp-d-1) to (Sp-d-16) The spacer group represented is mentioned as a preferable group.

The spacer group represented by Sp ¹ in the general formula (X) may be the same as or different from the spacer group represented by Sp ² described later.

<For ^{Z 21} and ^{Z 22>}
In the general formula (X), Z ²¹ and Z ²² are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —. _{, -CH 2 O -, - COO} -, - OCO -, - CH = CH -, - CF = CF -, - CF 2 O -, - OCF 2 -, - CF 2 CF 2 - and -C≡C- Represents at least one divalent linking group selected from the group consisting of
In the general formula (X), if Z ²² is plural, Z ²² may be the same as each other or may be different.

In general formula (X), p and q each independently represent an integer of 0 to 4.
When p is 2 or more, the plurality of A ²¹ may be the same or different from each other, and the plurality of Z ²² may be the same or different from each other.
When q is 2 or more, the plurality of A ²² may be the same as or different from each other.
p is preferably 0 or 1, and q is preferably 0 or 1.

<A ²¹ OyobiA ²² Nitsuite>
In the general formula (X), A ²¹ and A ²² are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be substituted by fluorine, chlorine, cyano, alkyl or alkoxy groups.

In the general formula ^{(X), if A 21} and ^{A 22} have multiple respective plurality of ^{A 21} and ^{A 22} may be the same as each other or may be different.

<For ^{R 11>}
R ¹¹ represents a monovalent substituent composed of two or more atoms or a halogen atom. The arbitrary combination of two atoms bonded to each other in the monovalent substituent includes a combination in which the absolute value of the difference in electronegativity between atoms is 0.45 or more and 1.70 or less. m is an integer of 1 to 5, and when m is 2 or more, the plurality of R ¹¹ may be the same as or different from each other.

  The above `` electronegativity '' is described in Shriver and Atkins, Inorganic Chemistry, 5th ed., Freeman: New York, 2010 and Huheey, JE, Inorganic Chemistry, Harper & Row: New York, 1983. “Negativeness χp”. Based on this electronegativity, Table 1 shows a combination table in which one of two atoms bonded to each other is written side by side and the other atom is arranged vertically.

この組み合わせ表において、縦と横が交差する位置に記載した値が、「電気陰性度の差」の絶対値である。例えば、互いに結合する炭素原子−窒素原子（ＣＮ）の電気陰性度の差は０．４９であり、互いに結合する炭素原子−酸素原子（ＣＯ）の電気陰性度の差は０．８９であり、互いに結合する炭素原子−フッ素原子（ＣＦ）の電気陰性度の差は１．４３であり、互いに結合する酸素原子−水素原子（ＯＨ）の電気陰性度の差は１．２４である。

In this combination table, the value described at the position where the vertical and horizontal crosses is the absolute value of the “difference in electronegativity”. For example, the difference in electronegativity of carbon atom-nitrogen atom (CN) bonded to each other is 0.49, and the difference in electronegativity of carbon atom-oxygen atom (CO) bonded to each other is 0.89, The difference in electronegativity between carbon atoms and fluorine atoms (CF) bonded to each other is 1.43, and the difference in electronegativity between oxygen atoms and hydrogen atoms (OH) bonded to each other is 1.24.

When R ¹¹ has the above monovalent substituent or halogen atom, the reason why a photo-alignment film having an excellent voltage holding ratio can be formed is that the side chain unit is appropriately polarized by having R ¹¹ , It is thought that impurities contained in can be collected. Although the detailed mechanism is not yet elucidated, it is considered that when the absolute value of the difference in electronegativity is within the above range, the degree of polarization of R ¹¹ is likely to be moderate and an action of collecting impurities is likely to occur. .

In the general formula (X), R ¹¹ is a cyano group, a hydroxyl group, a carboxyl group, an amide group, a fluorine atom, a chlorine atom, a thiol group, a sulfonic acid group, a nitro group, a linear or branched carbon atom number of 1 to 20 Or an alkyl group having 1 to 20 carbon atoms, or the following general formula (QX)

（式中、破線は結合手を表し、Ｓ_aaはスペーサー基を表し、Ｖaは側鎖末端を表す。）
で表される基であることが好ましい。

(In the formula, a broken line represents a bond, S _aa represents a spacer group, and Va represents a side chain end.)
It is preferable that it is group represented by these.

One of the —CH ₂ — groups constituting the alkyl group and the alkoxy group, or two or more non-adjacent groups are independently —O—, —CO—, —CO—O—, —O—CO—, — Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, — NR—CO—NR— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), —CH═CH—, —C≡C—, —O—CO—O— , -CH = CH-CO-O-, and one or more substituents selected from a divalent ring structure.

  One or more hydrogen atoms bonded to the alkyl group, the alkoxy group and the group represented by the general formula (QX) are fluorine atom, chlorine atom, cyano group, hydroxyl group, carboxyl group, amide group, sulfonic acid group. The nitro group may be substituted.

The alkyl group constituting the alkyl group and the alkoxy group may be linear, branched or cyclic alkyl groups. A part of the methylene group of the linear alkyl group may be substituted with a cyclic alkyl group.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, from the viewpoint of improving the solubility of the polymer.

Examples of the divalent ring structure include an aromatic cyclic group, a heterocyclic group, and a cyclic alkyl group.
When the divalent ring structure substitutes the —CH ₂ — group of the alkyl group, the ring structure preferably substitutes the terminal —CH ₂ — group of the alkyl group. That is, the divalent ring structure is preferably a monovalent ring structure that replaces the terminal methyl group of the alkyl group.

Examples of the divalent ring structure and the monovalent ring structure include a divalent or monovalent ring structure in which any two or one hydrogen atoms constituting benzene, naphthalene, and anthracene are removed and two or one bond is present. It is preferably a monovalent ring structure.

m is an integer of 1 to 5, and when m is 2 or more, the plurality of R ¹¹ may be the same as or different from each other. When m is 1, the bond position value of R ¹¹ is preferably a meta position or a para position, and more preferably a para position. With these preferable bond position values, the VHR of the liquid crystal display device provided with the photo-alignment film according to the present invention can be further improved.

When R ¹¹ is a group represented by the general formula (QX), examples of S _{aa in} the formula include groups represented by the following general formula (VI).

（式中、左の破線は一般式（ＱＸ）の破線と同じ意味を表し、右の破線はＶ_ａへの結合を表し；
Ｚ^１１、Ｚ^１２及びＺ^１３は、それぞれ独立して単結合、−(ＣＨ_２)_u−（式中、uは１〜２０を表す。）、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、―ＣＯＯ−、−ＯＣＯ−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表すが、これらの置換基において非隣接の−ＣＨ_２−基の１つ以上は独立して、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−Ｓｉ（ＣＨ_３）_２−Ｏ−Ｓｉ（ＣＨ_３）_２―、−ＮＲ−、−ＮＲ−ＣＯ−、−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−Ｏ−、−Ｏ−ＣＯ−ＮＲ−、−ＮＲ−ＣＯ−ＮＲ−（式中、Ｒは独立して水素又は炭素原子数１〜５のアルキル基を表す。）、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−Ｏ−ＣＯ−Ｏ−、又は−ＣＨ＝ＣＨ−ＣＯ−Ｏ−で置換することができ、
Ａ^１１及びＡ^１２は、それぞれ独立して
（ａ） トランス−１，４−シクロへキシレン基（この基中に存在する１個のメチレン基又は隣接していない２個以上のメチレン基は−Ｏ−、−ＮＨ−又は−Ｓ−に置き換えられてもよい）、
（ｂ） １，４−フェニレン基（この基中に存在する１個又は２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい）、及び
（ｃ） １，４−シクロヘキセニレン基、２，５−チオフェニレン基、２，５−フラニレン基、１，４−ビシクロ［２．２．２］オクチレン基、ナフタレン−１，４−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）又は基（ｃ）はそれぞれ無置換であるか又は一個以上の水素原子がフッ素原子、塩素原子、シアノ基、メチル基又はメトキシ基によって置換されていても良く、
p及びqは、それぞれ独立して、０又は１を表す。）

(In the formula, the left broken line represents the same meaning as that of the general formula (QX), and the right broken line represents the bond to V _a ;
Z ¹¹ , Z ¹² and Z ¹³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, — COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, but these substituents In the formula, one or more of non-adjacent —CH ₂ — groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si ( CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR— (wherein R Independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms.), —CH═CH—, —C≡C—, —O—CO—O—, or —CH═CH—CO—O—. so Can be replaced,
A ¹¹ and A ¹² are each independently (a) a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more methylene groups not adjacent to each other is —O -, -NH- or -S-).
(B) a 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) a 1,4-cyclohexenylene group 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, deca Represents a group selected from the group consisting of a hydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, the group (a), group (b) or group (C) is each unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a chlorine atom, a cyano group, a methyl group or a methoxy group,
p and q each independently represent 0 or 1. )

Z ¹¹ , Z ¹² and Z ¹³ in the general formula (VI) are each independently a single bond or — (CH ₂ ) _u — (wherein _u represents 1 to 12, and 1 of non-adjacent CH ₂ groups Two or more are independently —O—, —CO—, —CO—O—, —O—CO—, —CH═CH—, —C≡C—, —O—CO—O—, or —CH. ═CH—CO—O— may be substituted.
A ¹¹ and A ^{12 in} formula (VI) each independently represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group, which are unsubstituted or have one or more hydrogen atoms. It is preferably substituted by a fluorine atom, a chlorine atom, a methyl group or a methoxy group.

In formula (QX), _{V a} is represented by the following general formula (VII)

( _Where the dashed line represents the bond to Saa;
Z ⁴ , Z ⁵ , Z ⁶ and Z ⁷ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O. —, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— One or more of the non-adjacent —CH ₂ — groups in the substituents of —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O —Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, — CH = CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms),
A ³ , A ⁴ , A ⁵ and A ⁶ are each independently (a) a trans-1,4-cyclohexylene group (one methylene group present in this group or two or more not adjacent to each other) The methylene group may be replaced by -O-, -NH- or -S-),
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups;
r1, s1, t1, and u1 each independently represent 0 or 1,
R ¹² represents a hydrogen atom, a halogen or a linear or branched alkyl group having 1 to 20 carbon atoms, hydrogen atoms in the alkyl group may be substituted with halogen or cyano groups, one -CH ₂ A group or two or more non-adjacent CH ₂ groups may be substituted with —O—, —CO—O—, —O—CO— and / or —CH═CH—. )
It is preferable that it is a structure represented by these.

In general formula (VII), r1, s1, t1, and u1 are preferably 0.
In the general formula (VII), R ¹² is preferably a linear alkyl group having 1 to 20 carbon atoms, and the hydrogen atom in the alkyl group is preferably substituted with a halogen or a cyano group.

《Side chain unit MB》

<About Sp ² >
In the general formula (X), the spacer group represented by Sp ² independently represents Sp ¹ described above, a single bond, a linear or branched alkylene group having 1 to 40 carbon atoms, or the following general formula (IVa): And one or more of non-adjacent —CH ₂ — in the alkylene group is independently —O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ —, —C≡C—, —CO—, —S—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR '-, -NR'-CO-, -CO-NR'-, -NR'-CO-O-, -O-CO-NR'-, -NR'-CO-NR'-, -CH = CH- , —C≡C— or —O—CO—O— (wherein R ′ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). At best, further -CH 2 in the alkylene group _- At least one hydrogen atom is a fluorine atom, chlorine atom, hydroxy group, or may be substituted with a cyano group. In addition, when the group connected to Sp ² and Sp ² has a hetero atom, the case where the hetero atom is connected is excluded.
If Z ²³ is a single bond, Sp ² is preferably the a structure represented by an alkylene group or the following general formula (IVa).

In the general formula (IVa), the left dashed line represents a bond to Mb, the right dashed line represents a bond to Z ^23,
Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, — Represents COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, wherein Z ¹ , Z ^{In 2} and Z ³ , one —CH ₂ — group or two or more non-adjacent groups are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO— Substitution with NR—, —CH═CH—, —C≡C— or —O—CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms). Can ,
A ¹ and A ² are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups;
p1 and q1 each independently represent 0 or 1. )
It is represented by

  From the viewpoint of improving the VHR of the liquid crystal display element of the present invention, each group in the general formula (IVa) is preferably the following group.

In the general formula (IVa), Z ¹ , Z ² and Z ³ are each independently a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20, and —CH ₂ — Two or more of one or non-adjacent —CH ₂ — groups are independently substituted with —O—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—. Or —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═CH—, or —C≡C—.

In the general formula (IVa), p1 is preferably 0.
In general formula (IVa), q1 is preferably 1.

In the general formula (IVa), A ¹ and A ² are each independently any group of a trans-1,4-cyclohexylene group, a 2,6-naphthylene group, or a 1,4-phenylene group. Is preferred. The hydrogen atoms of these groups may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a methyl group or a methoxy group.

As Sp ² represented by the general formula (IVa), for example, those represented by the following chemical formulas (Sp-a-1) to (Sp-ah1-8) are preferable. In these formulas, the left dashed line represents a bond to a monomer unit Mb, right dashed line represents a bond to Z ^23.
Although it can be selected as necessary, among these, chemical formulas (Sp-a-6) to (Sp-a-20), chemical formulas (Sp-b-3) to (Sp-b-10), chemical formulas ( Sp-c-3) to (Sp-c-10), chemical formula (Sp-d-3) to (Sp-d-12), chemical formula (Sp-k-4) to (Sp-k-7), chemical formula (Sp-l-13) to (Sp-l-17), chemical formula (Sp-o-3) to (Sp-o-14), chemical formula (Sp-p-2) to (Sp-p-13), Chemical formula (Sp-s-1) to (Sp-s-8), Chemical formula (Sp-t-1) to (Sp-t-8), Chemical formula (Sp-y-1) to (Sp-y-9) And those represented by chemical formulas (Sp-aa-1) to (Sp-aa-9) are more preferred.

<For ^{Z 23} and ^{Z 24>}
In General Formula (X), Z ²³ and Z ²⁴ are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —. _{, -CH 2 O -, - COO} -, - OCO -, - CH = CH -, - CF = CF -, - CF 2 O -, - OCF 2 -, - CF 2 CF 2 - and -C≡C- Represents at least one divalent linking group selected from the group consisting of
In the general formula (X), when there are a plurality of Z ²⁴ , the plurality of Z ²³ may be the same as or different from each other.

In general formula (X), r represents the integer of 0-4. r is preferably 0 or 1. When r is 2 or more, the plurality of A ²³ may be the same or different from each other, and the plurality of Z ²⁴ may be the same or different from each other.

<A ²³ Nitsuite>
In the general formula (X), A ²³ is
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be substituted by fluorine, chlorine, cyano, alkyl or alkoxy groups.

A ²³ is preferably the group (b).
One or more alkoxy groups of the hydrogen atoms of A ^23, it is preferable that preferably substituted by a methoxy group or an ethoxy group.

In the general formula (X), if A ²³ there are a plurality each of a plurality of A ²³ may be the same as each other or may be different.

<For ^{D 1} and ^{D 2>}
In General Formula (X), D ¹ and D ² are the conditions in which D ¹ is — (L ¹ -A ¹ ) _k —C (═O) — and D ² is a single bond, or D ² Is -C (= O)-(A ¹ -L ¹ ) _f- and D ¹ is a single bond.

L ¹ is a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C—, one or more of non-adjacent CH ₂ groups constituting L ¹ Are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—. CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—CO—. O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms) may be substituted.

A ¹ constituting D ¹ and D ² is each independently any group of a trans-1,4-cyclohexylene group, a 2,6-naphthylene group, or a 1,4-phenylene group. preferable. The hydrogen atoms of these groups may be unsubstituted or one or more hydrogen atoms may be substituted with a fluorine atom, a methyl group or a methoxy group.

k and f are integers of 0 to 3, and are preferably 0 or 1.
If k or f is 2 or 3, or different may be a plurality of L1 is the same as each other which constitutes the D ¹ and D ^2, a plurality of A ¹ constituting the D ¹ and D ² may be the same as each other May be different.

<About X and Y>
In general formula (X), X and Y each independently represent a hydrogen atom or a halogen atom, preferably a hydrogen atom.

<About Z>
In general formula (X), Z represents general formula (IIa) or (IIb).

（式中、破線はＤ^２への結合を表し、Ｒ^１及びＲ^２はそれぞれ独立して水素原子又は直鎖状若しくは分岐状の炭素原子数１〜５０のアルキル基を表し、Ｒ^１及びＲ^２中の１つの−ＣＨ_２−基又は２つ以上の非隣接−ＣＨ_２−基は、−Ｏ−、−ＣＯ−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＯ−ＮＨ−、−ＮＨ−ＣＯ−、−ＮＣＨ_３−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−及び−Ｃ≡Ｃ−からなる群から選ばれる一つ以上で置換されていても良く、Ｒ^１及びＲ^２中の１つ又は２以上の−ＣＨ_２−基はそれぞれ独立して環員数３〜８のシクロアルキル基で置換されていても良く、Ｒ^１及びＲ^２中の水素原子は炭素原子数１〜２０のアルキル基、シアノ基又はハロゲン原子で置換されていても良い。）

(In the formula, a broken line represents a bond to D ² , R ¹ and R ² each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, and R ¹ and R 2) 1 in ^two -CH ₂ - group or two or more non-adjacent -CH ₂ - groups, -O -, - CO -, - CO-O -, - O-CO -, - CO-NH-, R ¹ and R ² may be substituted with one or more selected from the group consisting of —NH—CO—, —NCH ₃ —, —CH═CH—, —CF═CF— and —C≡C—. One or two or more —CH ₂ — groups therein may be each independently substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in R ¹ and R ² may have 1 to 20 may be substituted with an alkyl group, a cyano group or a halogen atom.)

In the general formula (IIa) or (IIb), R ¹ is a linear or branched alkyl group having 1 to 30 carbon atoms (one —CH ₂ — group in the alkyl group or two or more non-adjacent— The CH ₂ — group may be substituted with —O—, —CO—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NCH ₃ —, One or two or more —CH ₂ — groups in the alkyl group may each independently be substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in the alkyl group has 1 to 1 carbon atoms. 20 may be substituted with an alkyl group, a cyano group or a halogen atom)
R ² is a linear or branched alkyl group having 1 to 30 carbon atoms (one or two or more —CH ₂ — groups in the alkyl group are each independently a cycloalkyl group having 3 to 8 ring members). And a hydrogen atom in the alkyl group may be unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms, a cyano group, or a halogen atom. preferable.

<Monomer unit>
In the general formula (X), the arrangement of the monomer units of Ma, Mb, and Md may be the same as or different from those of the formula, and the monomer units of Ma, Mb, and Md are each independently one type or two. More than one kind of different units may be used, and each monomer unit of Ma, Mb, and Md independently represents any one of the repeating units of the general formulas (U-1) to (U-13). .

（上記一般式（Ｕ−１）〜（Ｕ−１３）中、当該式がＭａ、Ｍｂを表す場合には破線はＳｐ^１、Ｓｐ^２への結合をそれぞれ表し、当該式がＭｄを表す場合には破線は水素原子又は一価の有機基への結合を表し、Ｒ^ａは独立して水素原子、炭素原子数１〜５のアルキル基、フェニル基、ハロゲン原子を表し、上記一般式（Ｕ−１）〜（Ｕ−１３）中の任意の水素原子はフッ素原子、塩素原子、メチル基、フェニル基、又はメトキシ基によって置換されていても良く；Ｒ^１ａは４価の環構造、Ｒ^２ａは３価の有機基、Ｒ^３ａは水素原子、水酸基、炭素原子数１〜１５のアルキル基、炭素原子数１〜１５のアルコキシ基を表す。）

(In the above general formulas (U-1) to (U-13), when the formula represents Ma and Mb, the broken lines represent the bonds to Sp ¹ and Sp ² respectively, and the formula represents Md. the dashed line represents a bond to a hydrogen atom or a monovalent organic group, R ^a are independently a hydrogen atom, an alkyl group, a phenyl group having 1 to 5 carbon atoms, a halogen atom, the general formula (U- Any hydrogen atom in 1) to (U-13) may be substituted by a fluorine atom, a chlorine atom, a methyl group, a phenyl group, or a methoxy group; R ^1a is a tetravalent ring structure, R ^2a is A trivalent organic group, R ^3a represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, or an alkoxy group having 1 to 15 carbon atoms.

Suitable monomer units of Ma, Mb, and Md are monomer units represented by the general formula (U-1).

In general formulas (U-1) to (U-13), R ^a is preferably independently a hydrogen atom or a methyl group, and one or more of the hydrogen atoms bonded to the methyl group are substituted with a fluorine atom. May be.

^Examples of the tetravalent ring structure represented by R ^1a include a cyclic group having four bonds in which four hydrogen atoms bonded to an aromatic ring, a heterocyclic ring, and an aliphatic ring are removed. Cycloalkanes such as cyclobutane, cyclopentane and cyclohexane are preferred.

^Examples of the trivalent ring structure represented by R ^2a include a cyclic group having three bonds by removing three hydrogen atoms bonded to an aromatic ring, a heterocyclic ring, and an aliphatic ring. A group in which three hydrogen atoms are removed from a benzene ring is preferred.

If the general formula (U-1) ~ (U -13) represents a monomer unit Ma, dashed line in the formula represents a bond to Sp ^1.
If the general formula (U-1) ~ (U -13) represents a monomer unit Mb, dashed line in the formula represents a bond to Sp ^2.
When the general formulas (U-1) to (U-13) represent the monomer unit Md, the broken line in the formula represents a bond to a hydrogen atom or a monovalent organic group.
As said monovalent organic group, group represented by the said general formula (QX) is mentioned, for example.

<Polymer composition>
The polymer for photoalignment films represented by the general formula (X) has a side chain unit MA bonded to the monomer unit Ma and a side chain unit MB bonded to the monomer unit Mb. The side chain unit MA is preferably photochemically isomerizable and not photochemically crosslinked. The side chain unit MB is preferably photochemically crosslinkable. The polymer for a photoalignment film may include a side chain unit MD bonded to the monomer unit Md.

  In the general formula (X), a, b and c represent the molar fraction of the copolymer, and in any case, 0 <a ≦ 1, 0 <b ≦ 1, and 0 ≦ c <1 .

In the molar fraction, the ratio represented by a / (a + b + c) × 100% is preferably 0.1 to 20%, more preferably 1 to 15%, and still more preferably 2 to 10%.
VHR can be further improved in the preferable range.

<< Synthesis of polymer for photo-alignment >>
The method for synthesizing the photoalignment polymer of the present invention is not particularly limited, and for example, the method described in Patent Document 1 can be applied. In the synthesis of the polymer for photo-alignment, a known polymerization initiator can be used in accordance with the polymerization mode of the polymerization functional group. As the polymerization initiator, for example, known polymerization initiators described in polymer synthesis and reaction (edited by the Society of Polymer Science, Kyoritsu Shuppan) and the like can be applied.
The addition amount of the said polymerization initiator can be 0.1-10 mass% with respect to the total mass of the mixture containing the monomer composition to superpose | polymerize. Moreover, the target polymer can also be synthesized by performing an addition reaction to the polymer main chain using a polysiloxane compound.

The polymer for photo-alignment of the present invention can be obtained by conducting a polymerization reaction in a reaction vessel and further purifying it. Examples of the solvent in the polymerization reaction include benzene, toluene, xylene, ethylbenzene, pentane, hexane, heptane, octane, cyclohexane, cycloheptane, methanol, ethanol, 1-propanol, 2-propanol, ethylene glycol, ethylene glycol monomethyl ether, Examples include ethylene glycol dimethyl ether, 2-butanone, acetone, tetrahydrofuran, γ-butyrolactone, N-methyl-pyrrolidone, dimethyl sulfoxide, and dimethylformamide. The solvent used for the polymerization reaction may be one type or a combination of two or more types.
The polymer for photoalignment of the present invention may also be obtained by a method in which a composition containing each monomer is applied on a substrate and the solvent is dried and removed as necessary, followed by a polymerization reaction by heating or light irradiation. it can.

  In addition, the polymer for photoalignment of the present invention is obtained by applying a polymer solution containing the photoalignment polymer and an organic solvent as essential components onto a substrate, drying and removing the organic solvent, and then performing a polymerization reaction by heating or light irradiation. It can also be obtained by the method of performing. The organic solvent that can be used here is not particularly limited. For example, N-methylpyrrolidinone, butoxyethanol, 1,1,2-trichloroethane, N-methylpyrrolidone, γ-butyrolactone, ethylene glycol, polyethylene glycol monomethyl ether, propylene glycol 2-pyrrolidone, N, N-dimethylformamide, phenoxyethanol, tetrahydrofuran, dimethyl sulfoxide, methyl isobutyl ketone, cyclohexanone and the like, and two or more organic solvents may be used in combination. Examples of the mixed solvent in which two or more kinds are used in combination include N-methylpyrrolidinone: butoxyethanol = 1: 1 (mass ratio). The polymer solution preferably has a solid content in the range of 1 to 20% by mass, particularly 0.5 to 10% by mass from the viewpoint of coating properties.

<< Formation of photo-alignment film >>
By irradiating the film made of the polymer of the present invention with polarized ultraviolet rays, a photo-alignment film having an alignment regulating force can be obtained. As a method for obtaining a film made of the polymer, for example, it can be obtained by applying a solution of the polymer to a substrate and drying it.

  The photo-alignment film (liquid crystal alignment layer) of the present invention can be applied to a horizontal alignment or vertical alignment mode liquid crystal display element.

Examples of the material for the substrate include glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, and triacetyl cellulose.
These substrates may be provided with an electrode layer such as an ITO film made of Cr, Al, In ₂ O ₃ —SnO ₂ , or a NESA film made of SnO ₂ . For patterning these electrode layers, a photo-etching method or a method using a mask when forming the electrode layers is used. Furthermore, a color filter layer or the like may be formed on the substrate.

Examples of the method for applying the polymer-containing solution on the substrate include spin coating, die coating, gravure coating, flexographic printing, and inkjet printing.
The solid concentration of the solution at the time of application is preferably 0.5 to 10% by weight. It is more preferable to select from this range in consideration of the method of applying the solution on the substrate, viscosity, volatility and the like.
After applying the polymer solution on the substrate, it is preferable to heat the coated surface to remove the solvent. As heating temperature, 50-300 degreeC is preferable, for example, and 80-200 degreeC is more preferable. As heating time in this suitable temperature range, 2-200 minutes are preferable, for example, and 2-100 minutes are more preferable.

  Side chain unit MA photoisomerization reaction and side chain unit MB are applied to the coating film formed on the substrate by irradiation with linearly polarized light from the normal direction of the coating film surface and / or irradiation with non-polarized light or linearly polarized light from the oblique direction. By causing this photocrosslinking reaction, a photo-alignment film imparted with an alignment control ability can be obtained. In order to provide a desired pretilt angle, linearly polarized light irradiation from an oblique direction is preferable. Here, the irradiation from the oblique direction refers to a case where the angle formed between the light irradiation direction and the substrate surface is not less than 1 degree and not more than 89 degrees. When used as a photo-alignment film for vertical alignment, generally, the pretilt angle is preferably 70 to 89.8 °. Further, when used as a photo-alignment film for horizontal alignment, it is generally preferable that the pretilt angle is 0 to 20 °.

For example, ultraviolet light and visible light including light having a wavelength of 150 nm to 800 nm can be used as the light applied to the coating film, and ultraviolet light of 270 nm to 450 nm is particularly preferable.
Examples of the light source include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp. Linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources. Further, the wavelength range of the ultraviolet light and visible light obtained from such a light source may be limited using an interference filter or a color filter.
The thickness of the formed photoalignment film is preferably about 10 to 250 nm, more preferably about 10 to 100 nm.

≪Liquid crystal display element manufacturing method≫
Using the photo-alignment film of the present invention, for example, a liquid crystal cell in which a liquid crystal composition is sandwiched between a pair of substrates and a liquid crystal display device using the same can be manufactured as follows.
A liquid crystal cell can be manufactured by preparing two substrates on which the photo-alignment film in the present invention is formed and disposing a liquid crystal between the two substrates. The photo-alignment film may be formed on only one of the two substrates.
As a manufacturing method of a liquid crystal cell, the following method is mentioned, for example. First, two substrates are arranged so that the respective photo-alignment films face each other, and the peripheral portion is bonded using a sealing agent while maintaining a certain gap (cell gap) between the two substrates. A liquid crystal cell can be manufactured by injecting and filling the liquid crystal composition into the cell gap defined by the substrate surface and the sealing agent, and then sealing the injection hole.

The liquid crystal cell can also be manufactured by a technique called an ODF (One Drop Fill) method. As a procedure, for example, an ultraviolet light curable sealant is applied to a predetermined place on the substrate on which the photo-alignment film is formed, and a liquid crystal composition is further dropped on the photo-alignment film, and then the photo-alignment film The other substrate is bonded so that the two face each other. Next, the liquid crystal cell can be manufactured by irradiating the entire surface of the substrate with ultraviolet light to cure the sealing agent.
The liquid crystal photo-alignment film used here is preferably heated to a temperature at which it takes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment generated at the time of injection.

The liquid crystal composition is not particularly limited, and for example, a known nematic liquid crystal composition can be used. In the case of a vertical alignment type liquid crystal cell, those having negative dielectric anisotropy are preferable. In the case of a horizontal alignment type liquid crystal cell, those having positive dielectric anisotropy are preferred.
A liquid crystal display element can be obtained by bonding a known polarizing plate to the outer surface of the liquid crystal cell.

<< Optical Anisotropic Manufacturing Method >>
The optical anisotropic body of the present invention has the photo-alignment film of the present invention. The optical anisotropic body of the present invention may have the photo-alignment film of the present invention and a film made of a polymer of a polymerizable liquid crystal composition formed on the photo-alignment film. This optical anisotropic body is useful for applications such as an optical anisotropic film used for optical compensation of a liquid crystal display element. In an optical anisotropic body, when light travels through the optical anisotropic body, optical properties such as light propagation speed, refractive index, and absorption differ depending on the traveling direction.
As a method for producing the optical anisotropic body of the present invention, for example, a photo-alignment film is formed on a substrate, a polymerizable liquid crystal composition is applied thereon, and the liquid crystal molecules aligned by the photo-alignment film are included. A method of forming a polymer film may be mentioned.

  When an optical anisotropic body is produced by applying a polymerizable liquid crystal composition on a photo-alignment film, bar coating, spin coating, roll coating, gravure coating, spray coating, die coating, cap coating, dipping method, etc. A known coating method can be applied. In order to improve coatability, a known organic solvent may be added to the polymerizable liquid crystal composition. When an organic solvent is added, after coating a polymerizable liquid crystal composition on the photo-alignment film, the organic solvent is removed by a known drying method.

  Examples of the method for polymerizing the polymerizable liquid crystal composition include a method of irradiating the polymerizable liquid crystal composition with active energy rays and a thermal polymerization method.

When the polymerizable liquid crystal composition is polymerized by irradiation with active energy rays, it is preferable that the polymerizable liquid crystal composition is applied on the photo-alignment film and polymerized in a state where the polymerizable liquid crystal molecules are aligned.
When polymerizing the polymerizable liquid crystal composition by irradiation with active energy rays, for example, a method of irradiating ultraviolet rays with an irradiation intensity of 1 W / m ^{2 to} 10 kW / m ² can be mentioned.

The temperature at which the polymerizable liquid crystal composition is polymerized by heat is preferably a temperature at which the polymerizable liquid crystal composition exhibits a liquid crystal phase or lower. As specific heating temperature, 20 to 300 degreeC is preferable, for example, 30 to 200 degreeC is more preferable, and 30 to 120 degreeC is more preferable. Moreover, when a polymeric group is a (meth) acryloyloxy group, it is preferable to carry out at the temperature lower than 90 degreeC. When the temperature is suitable, heterogeneous polymerization due to heat can be prevented.
As a polymerization method of the polymerizable liquid crystal composition, either one or both of photopolymerization and thermal polymerization can be employed.

  The optical axis of the optical anisotropic body of the present invention can be adjusted by controlling the pretilt angle with the photo-alignment film. In order to adjust the angle formed by the optical axis with respect to the substrate surface from 0 degrees to 45 degrees, the pretilt angle is preferably from 0 degrees to 45 degrees. Similarly, in order to change the angle formed by the optical axis with respect to the substrate surface from 45 degrees to 90 degrees, the pretilt angle is preferably 45 degrees to 90 degrees.

As a manufacturing process of the optical anisotropic body provided with the photo-alignment film of the present invention, for example, the following method is exemplified. As a first step, a coating film of the polymer is formed on a substrate. As a 2nd process, the light which has anisotropy is irradiated, an orientation control ability is provided to the said coating film, and a photo-alignment film is formed. As a third step, a polymerizable liquid crystal composition film is formed on the photo-alignment film. As a fourth step, the film of the polymerizable liquid crystal composition is polymerized to form an optical anisotropic body. In this fourth step, an isomerization reaction or a crosslinking reaction may proceed simultaneously in the photo-alignment film.
In the production process exemplified above, since the polymer coating film is directly irradiated with light, it is possible to obtain a photo-alignment film excellent in the alignment regulating force of liquid crystal molecules.

  Moreover, the following method is mentioned as another manufacturing method. As a first step, a coating film of the polymer is formed on the substrate. As a second step, a film of a polymerizable liquid crystal composition is formed on the coating film. As a third step, light having anisotropy is irradiated to impart a liquid crystal alignment control force to the polymer coating film to form a photo-alignment film. As a fourth step, the film of the polymerizable liquid crystal composition is polymerized to form an optical anisotropic body. Here, the third step and the fourth step may be performed simultaneously by light irradiation or the like. The number of processes can be reduced by simultaneous progress.

If necessary, a plurality of layers made of optical anisotropic bodies may be stacked. As a method of forming a laminated body of optical anisotropic bodies, a method of repeating a method of forming a single layer a plurality of times can be mentioned. For example, a first layer of an optical anisotropic body is formed on the photo-alignment film, a new photo-alignment film is formed on the first layer, and a second layer of the optical anisotropic body is formed on the photo-alignment film. And a method of directly forming the second layer of the optical anisotropic body on the first layer of the optical anisotropic body formed on the photo-alignment film.
Examples of the use of an optical anisotropic laminate having a plurality of optical anisotropic layers include simultaneous use of optical compensation of a liquid crystal layer and a polarizing plate of a liquid crystal display element, and optical compensation of a liquid crystal layer of a liquid crystal display element. And the use of simultaneously improving the brightness, the use of simultaneously improving the optical compensation of the polarizing plate of the liquid crystal display element and the brightness, and the like.

  In order to stabilize the solvent resistance and heat resistance of the obtained optical anisotropic body, the optical anisotropic body can be subjected to a heat aging treatment.

  The polymerizable liquid crystal composition used for the production of the optical anisotropic body is not particularly limited, and a known liquid crystal composition containing a polymerizable liquid crystal exhibiting liquid crystallinity alone or in a composition with another liquid crystal compound can be applied. is there.

  The optical anisotropic body obtained by the above steps may be used alone as an optical anisotropic body by peeling the optical anisotropic layer from the substrate, or without being peeled from the substrate. It can also be used as a cuboid.

<Terminology>
In this specification, the optical axis means that the refractive index is constant in a liquid crystal display element or optical anisotropic body, and birefringence does not occur even when unpolarized light is incident, and ordinary light and extraordinary light coincide. Or the direction in which the deviation is minimized.
In the present specification, the orientation is the direction when the liquid crystal molecules in the liquid crystal cell of the liquid crystal display element or the polymerizable liquid crystal molecules forming the optical anisotropic body are oriented in a certain direction, In the case of rod-like liquid crystal molecules, the direction taken by the molecular long axis is assumed, and in the case of disc-like liquid crystal molecules, the direction is normal to the disc surface.
In this specification, the pretilt angle is an angle formed between the alignment direction of liquid crystal molecules or polymerizable liquid crystal molecules and the substrate surface.
In this specification, the polymerizable liquid crystal is a compound that exhibits a liquid crystal phase and includes a polymerizable chemical structure.
In the present specification, the homogeneous alignment is an alignment having a pretilt angle of 0 degree or more and 20 degrees or less.
In this specification, the homeotropic alignment is an alignment having a pretilt angle of 70 degrees or more and 90 degrees or less. The angle formed by the optical axis with respect to the substrate surface and the pretilt angle may or may not match.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited by these examples. Hereinafter, unless otherwise specified, “part” and “%” are based on mass.

<Synthesis Example 1>
A compound represented by the following formula (1) is added to a reaction vessel equipped with a thermometer and a stirring device, suspended in an aqueous hydrochloric acid solution, reacted with sodium nitrite while cooling with ice, phenol, sodium hydroxide, By reacting, a compound represented by the following formula (2) was obtained.
A reaction vessel equipped with a thermometer, a stirrer, and a Dean-Stark device is reacted with a compound represented by the following formula (3), methacrylic acid and p-toluenesulfonic acid monohydrate and represented by the following formula (4). The compound obtained was obtained.
A compound represented by the following formula (2) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirrer, and reacted with a compound represented by the following formula (4) to be represented by the following formula (m1). A compound was obtained.

<Synthesis Example 2>
After adding a compound represented by the following formula (5) to a reaction vessel equipped with a thermometer and a stirrer and reacting with t-butyl acrylate in the presence of a palladium catalyst, a compound represented by the following formula (6) was obtained. Then, it was reacted with hydrogen in the presence of zinc and ammonium chloride to obtain a compound represented by the following formula (7).
A compound represented by the following formula (7) is suspended in a hydrochloric acid aqueous solution in a reaction vessel equipped with a thermometer and a stirring device, reacted with sodium nitrite while cooling with ice, and then reacted with phenol and sodium hydroxide. As a result, a compound represented by the following formula (8) was obtained.
In a reaction vessel equipped with a thermometer, a stirrer, and a Dean-Stark device, a compound represented by the following formula (3) is reacted with acrylic acid and p-toluenesulfonic acid monohydrate, and the following formula (9) The compound represented was obtained.

  A compound represented by the following formula (8) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirrer, and reacted with a compound represented by the following formula (9) to be represented by the following formula (10). After obtaining the compound, it was reacted with trifluoroacetic acid to obtain a compound represented by the following formula (11).

A compound represented by the following formula (12) was added to a reaction vessel equipped with a thermometer and a stirrer and reacted with t-butyl alcohol to obtain a compound represented by the following formula (13). It was made to react with the compound represented by 14), and the compound represented by following formula (15) was obtained.
A reaction vessel equipped with a thermometer and a stirrer is reacted with a compound represented by the following formula (15) in the presence of a compound represented by the following formula (11), azodicarboxylic acid and triphenylphosphine, and the following formula (16 ) Was obtained.
A compound represented by the following formula (16) was added to a reaction vessel equipped with a thermometer and a stirring device, reacted with trifluoroacetic acid, then reacted with ethylene cyanohydrin in the presence of azodicarboxylic acid and triphenylphosphine, A compound represented by the formula (m2) was obtained.

<Synthesis Example 3>
A compound represented by the following formula (5) was added to a reaction vessel equipped with a thermometer and a stirrer and reacted with t-butyl acrylate in the presence of a palladium catalyst to obtain a compound represented by the following formula (6). Thereafter, it was reacted with hydrogen in the presence of zinc and ammonium chloride to obtain a compound represented by the following formula (17).
A compound represented by the following formula (17) is suspended in an aqueous hydrochloric acid solution in a reaction vessel equipped with a thermometer and a stirring device, reacted with sodium nitrite while cooling with ice, and then reacted with phenol and sodium hydroxide. As a result, a compound represented by the following formula (18) was obtained.

After obtaining a compound represented by the following formula (18) by the same method as in Synthesis Example 2, a compound represented by the following formula (9) and potassium carbonate were added to a reaction vessel equipped with a thermometer and a stirrer. A compound represented by the following formula (19) was obtained.
The following formula (19) is reacted with trifluoroacetic acid in the same manner as in Synthesis Example 2, and then reacted with ethylene cyanohydrin in the presence of azodicarboxylic acid and triphenylphosphine to obtain a compound represented by the following formula (m3). Obtained.

<Synthesis Example 4>
A compound represented by the following formula (20) is added to a reaction vessel equipped with a thermometer and a stirrer, and reacted with ^t BuOK to obtain a compound represented by the following formula (21), and then in the presence of palladium / carbon. Then, it was reacted with hydrogen to obtain a compound represented by the following formula (22).
A compound represented by the following formula (22) is suspended in a hydrochloric acid aqueous solution in a reaction vessel equipped with a thermometer and a stirring device, reacted with sodium nitrite while cooling with ice, and then reacted with phenol and sodium hydroxide. By doing so, a compound represented by the following formula (23) was obtained.
A compound represented by the following formula (23) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirrer, and reacted with a compound represented by the following formula (9), which is represented by the following formula (24). A compound was obtained.
In a reaction vessel equipped with a thermometer and a stirrer, a compound represented by the following formula (24) is added and reacted with trifluoroacetic acid in the same manner as in Synthesis Example 2, and then in the presence of azodicarboxylic acid and triphenylphosphine. Then, it was reacted with ethylene cyanohydrin to obtain a compound represented by the following formula (m4).

<Synthesis Example 5>
A compound represented by the following formula (18) obtained by the same method as in Synthesis Example 2 and potassium carbonate were added to a reaction vessel equipped with a thermometer and a stirrer, and the following formula (4) obtained in Synthesis Example 1 was added. The compound represented by formula (25) was obtained and then reacted with trifluoroacetic acid to obtain a compound represented by formula (m5).

<Synthesis Example 6>
(M5) obtained in Synthesis Example 5 was reacted with ethylene cyanohydrin in the presence of azodicarboxylic acid and triphenylphosphine to obtain a compound represented by the following formula (m6).

<Synthesis Example 7>
After obtaining the compound represented by the formula (23) by the same method as in Synthesis Example 4, the compound represented by the following formula (4) and potassium carbonate were added to a reaction vessel equipped with a thermometer and a stirring device. A compound represented by the formula (26) was obtained.
A compound represented by the following formula (26) is added to a reaction vessel equipped with a thermometer and a stirrer and reacted with trifluoroacetic acid, and then reacted with ethylene cyanohydrin in the presence of azodicarboxylic acid and triphenylphosphine. A compound represented by the formula (m7) was obtained.

<Synthesis Example 8>
A compound represented by the formula (26) was obtained in the same manner as in Synthesis Example 7, and then reacted with trifluoroacetic acid to obtain a compound represented by the following formula (m8).

<Synthesis Example 9>
In a reaction vessel equipped with a thermometer, a stirrer, and a Dean-Stark device, the compound represented by the following formula (27) is reacted with methacrylic acid and p-toluenesulfonic acid monohydrate, and the following formula (28) The compound represented was obtained.

31.50 g of the compound represented by the following formula (29), 1.09 g of DMF, and 120 mL of CH ₂ Cl ₂ were mixed. To this, 20.83 g of oxalyl dichloride was added dropwise, and then heated under reflux for 2 hours. By concentrating the obtained solution, 37.00 g of a compound represented by the following formula (30) was obtained.
37.00 g of a compound represented by the following formula (30) and 120 mL of THF were mixed. To this, 23.44 g of tert-butoxypotassium was dissolved in 176 mL of THF and added dropwise at 5 to 10 ° C. After reacting at room temperature for 2 hours, 200 mL of water and 400 mL of toluene were added for liquid separation. The resulting solution was concentrated and purified by column chromatography (eluent: hexane / ethyl acetate mixed solvent) to obtain 43.42 g of a compound represented by the following formula (31).
40.00 g of the compound represented by the following formula (31), 4.00 g of 5 wt% palladium carbon, and 160 mL of ethanol were mixed, and the mixture was stirred at 40 ° C. for 10 hours under a hydrogen pressure of 0.5 MPa. The catalyst was removed by filtration, and the resulting solution was concentrated to obtain 34.50 g of a compound represented by the following formula (32).
15.00 g of the compound represented by the following formula (32) was suspended in 1.7 M hydrochloric acid. Here, 3.53 g of sodium nitrite was dissolved in 35 mL of water, added at 2 to 3 ° C., and further stirred at 2 to 3 ° C. for a while. It was then diluted with 300 mL MeOH. 4.81 g of phenol was dissolved in an aqueous potassium hydroxide solution, added dropwise at 0 to 2 ° C., and further stirred at 0 to 2 ° C. for a while. After adding hydrochloric acid at 2-7 ° C., the precipitate taken out by filtration is purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) to give 6.32 g of the compound represented by the following formula (33) Got.
3.00 g of the compound represented by the following formula (33), 1.77 g of potassium carbonate and 0.5 mg of methoxyphenol were mixed with 23 mL of DMF. 1.75 g of the compound represented by the following formula (28) was dissolved in 2 mL of DMF, and added dropwise at 70 to 85 ° C. The mixture was further stirred at 85 ° C. for 7.5 hours. After cooling to room temperature, water was added, extracted with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) to obtain 2.69 g of a compound represented by the following formula (34).
1.5 g of di-tert-butyl 5-((4-((1- (methacryloyloxy) octyl) oxy) phenyl) diazenyl) isophthalate and 9 mL of CH ₂ Cl ₂ were mixed. Here, 3 mL of trifluoroacetic acid was added dropwise at 0 to 2 ° C. After stirring at room temperature for 2 hours, the reaction solution was concentrated. Next, the obtained solid was dissolved in THF, hexane was added, and reprecipitation was performed to obtain 0.75 g of a compound represented by the following formula (m9).

<Synthesis Example 10>
40 g of a compound represented by the following formula (35), 1.60 g of DMF, and 160 mL of CH ₂ Cl ₂ were mixed. 30.71 g of oxalyl dichloride was added dropwise thereto, and the mixture was heated to reflux for 2 hours. By concentrating the obtained solution, 43.90 g of a compound represented by the following formula (36) was obtained.
40.00 g of a compound represented by the following formula (26) and 200 mL of THF were mixed. Here, 26.99 g of tert-butoxypotassium was dissolved in 100 mL of THF and added dropwise at 5 to 10 ° C. After reacting at room temperature for 2 hours, 200 mL of water and 600 mL of toluene were added for liquid separation. The obtained solution was concentrated and purified by column chromatography (eluent: hexane / ethyl acetate mixed solvent) to obtain 28.53 g of a compound represented by the following formula (37).
25.00 g of the compound represented by the following formula (37), 2.50 g of 5 wt% palladium carbon, and 150 mL of THF were mixed and stirred at 25 ° C. for 6 hours under a hydrogen pressure of 0.3 MPa. The catalyst was removed by filtration, and the resulting solution was concentrated to obtain 21.0 g of a compound represented by the following formula (38).
20 g of the compound represented by the following formula (38) was suspended in 88 mL of 10% hydrochloric acid. Here, 7.3 g of sodium nitrite was dissolved in 75 mL of water, added at 2 to 3 ° C., and further stirred at 2 to 3 ° C. for a while. Next, a solution in which 9.08 g of phenol, 40.9 g of sodium carbonate, and 250 mL of water were mixed was added dropwise at 0 to 2 ° C., and further stirred at 0 to 2 ° C. for a while. After adding 10% hydrochloric acid at 2 to 7 ° C., the precipitate taken out by filtration is purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) to express 24.1 g of the following formula (39). A compound was obtained.
20.00 g of the compound represented by the following formula (39), 17.70 g of potassium carbonate and 4 mg of methoxyphenol were mixed with 300 mL of DMF. 17.88 g of the compound represented by the following formula (28) was added dropwise thereto at 70 to 85 ° C. The mixture was further stirred at 85 ° C. for 7.5 hours. After cooling to room temperature, water was added to obtain a precipitate. This was filtered and purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) and recrystallization (EtOH) to obtain 25.06 g of a compound represented by the following formula (40).
10 g of a compound represented by the following formula (40) and 60 mL of CH ₂ Cl ₂ were mixed. 20 mL of trifluoroacetic acid was added dropwise thereto at 0 to 2 ° C. After stirring at room temperature for 2 hours, the reaction solution was concentrated. Next, after the obtained solid was dissolved in THF, hexane was added and reprecipitated to obtain 7.56 g of a compound represented by the following formula (m10).

<Synthesis Example 11>
20 g of the compound represented by the following formula (41) was suspended in 170 g of 10% hydrochloric acid. Here, 12.63 g of sodium nitrite was dissolved in 120 mL of water, added at 2-3 ° C., and further stirred at 2-3 ° C. for a while. Next, 17.22 g of phenol was dissolved in 220 g of 10% aqueous sodium hydroxide solution, added dropwise at 0 to 2 ° C., and further stirred at 0 to 2 ° C. for a while. Concentrated hydrochloric acid was added at 2-7 ° C. The precipitate taken out by filtration was purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) and further recrystallized from hexane / toluene mixed solvent to obtain 13.7 g of the compound represented by the following formula (42). Obtained.
10.00 g 4,4 ′-(diazene-1,2-diyl) diphenol, 6.45 g potassium carbonate and 2 mg methoxyphenol were mixed in 80 mL DMF. To this, 10.87 g of a compound represented by the following formula (28) was added dropwise at 70 to 85 ° C. The mixture was further stirred at 85 ° C. for 7.5 hours. After cooling to room temperature, water was added and extracted with ethyl acetate. The organic layer was washed with 10% hydrochloric acid and then with water and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was separated and purified by silica gel chromatography (eluent: hexane / ethyl acetate mixed solvent) to obtain 2.88 g of a compound represented by the following formula (m11).

<Synthesis Example 12>
34 g of 10-bromo-1-decanol, 22 g of methacrylic acid, 70 mg of 4-methoxyphenol, 2 g of p-toluenesulfonic acid monohydrate, 200 mL of cyclohexane and 40 mL of diisopropyl ether were mixed and heated in an oil bath. Refluxed for 8 hours. After allowing the reaction solution to cool to 30 ° C., 100 mL of water was added to the reaction solution to extract the organic layer. The organic layer was washed twice with 100 mL of 5% aqueous sodium hydrogen carbonate solution and once with 100 mL of saturated brine. The organic layer after washing was concentrated under reduced pressure to obtain 50 g of a compound represented by the following formula (a-1-1) as a colorless liquid. In a reaction vessel, 23 g of p-hydroxybenzaldehyde, 46 g of potassium carbonate, and 46 g of compound (a-1-1) were suspended in 300 mL of DMF and stirred at 90 ° C. for 6 hours to complete the reaction. After cooling the reaction solution to 10 ° C., 650 mL of water was added dropwise to the reaction solution to precipitate a solid. The solid was collected by filtration to obtain 72 g of a compound represented by the following formula (a-1-2) which is a brown granular solid. In a reaction vessel, 66 g of a compound represented by the following formula (a-1-2) is dissolved in 980 mL of methanol, and an aqueous sodium dihydrogen phosphate solution (19 g of sodium dihydrogen phosphate dihydrate is added to 250 mL of water). Dissolved solution) and 32 mL of 30% aqueous hydrogen peroxide were sequentially added. A sodium chlorite aqueous solution (a solution in which 27 g of sodium chlorite having a purity of 80% was dissolved in 220 mL of water) was added dropwise. After completion of dropping, the reaction solution was stirred at 45 ° C. for 3 hours to complete the reaction. After the reaction solution is slowly cooled to 20 ° C., water is added dropwise to the reaction solution to precipitate a solid. The solid was collected by filtration, and the solid was washed with water by shaking. The crude product of colorless scaly crystals thus obtained was dried under reduced pressure for 8 hours to obtain 47 g of compound (a-1-3) as colorless crystals.
On the other hand, 54 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.3 g of 4-dimethylaminopyridine were dissolved in 406 mL of 2-cyanoethanol. A solution prepared by dissolving 50 g of ferulic acid in 203 mL of 2-cyanoethanol was added dropwise to this solution at 10 ° C. over 1 hour, followed by stirring at room temperature for 4 hours. The reaction solution and 15 ° C. cold water were mixed, and a toluene / THF mixed solvent was added to the mixture to extract an organic layer. The organic layer was washed with 200 mL of saturated brine and then concentrated, and the resulting yellow solid was recrystallized to obtain 37 g of a compound represented by the following formula (a-1-4) as a white solid.
39 g of the compound represented by the following formula (a-1-3), 28 g of the compound represented by the following formula (a-1-4), and 0.3 g of 4-dimethylaminopyridine were suspended in 140 mL of dichloromethane, and the internal temperature 172 g of diisopropylcarbodiimide was added dropwise while keeping the temperature at 10 ° C. or lower, and the mixture was stirred at 15 to 25 ° C. for 3 hours. After confirming disappearance of the raw materials, the reaction was deactivated by adding water to the reaction solution. The resulting precipitate was separated by filtration to make a dichloromethane solution, and then purified by column chromatography. Dichloromethane was distilled off from the dichloromethane solution under reduced pressure, methanol was added, and the mixture was cooled to 0 ° C. to precipitate crystals. The crystals were separated by filtration and dried under reduced pressure to obtain 51 g of a compound represented by the following formula (a-1) which is a cinnamic acid methacrylate monomer.

<Synthesis Example 13>
A compound represented by the following formula (43) is added to a reaction vessel equipped with a thermometer and a stirring device, suspended in an aqueous hydrochloric acid solution, reacted with sodium nitrite while cooling with ice, and then phenol, sodium hydroxide. To obtain a compound represented by the following formula (44).
A compound represented by the following formula (44) and potassium carbonate are added to a reaction vessel equipped with a thermometer and a stirrer, and reacted with a compound represented by the following formula (4), and represented by the following formula (ref-m). The compound obtained was obtained.

<Polymer synthesis>
<Synthesis Example 14>
3.0 g monomer (a-1) obtained in Synthesis Example 12, 0.1 g monomer (m1) obtained in Synthesis Example 1, 115 mg V-65 (2,2′-Azobis (2.4-dimethylvaleronitrile) ) And 9 mL of THF for 15 hours at 50 ° C., the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer, the solvent was removed by decantation, and the precipitate was dissolved again in THF. This decantation operation was further carried out 7 times, followed by drying under reduced pressure to obtain 1.5 g of a copolymer (P1) represented by the following formula (P1).
When the molecular weight of the obtained copolymer was measured by gel permeation chromatography (GPC) under the conditions described later, the polystyrene standard had a weight average molecular weight (Mw) of 197,655, a dispersion ratio (Mw / Mn) of 2.96, and the residual monomer amount was 0.02%. there were.

<GPC measurement conditions>
Column: Showa Denko Co., Ltd. Shodex KF-803L, KF-804L, KF-805, KF-806
(These are connected in series.)
Eluent: THF
Sample solution concentration: 0.1 (w / v)% (solvent THF)
Sample injection volume: 200 μL
Column temperature: 40 ° C
Column flow rate: 1.0mL / min
Detector: RI
Thereafter, the GPC measurement conditions are the same.

<Synthesis Example 15>
8 hours at 55 ° C. using 3.0 g monomer (a-1) obtained in Synthesis Example 12, 0.175 g monomer (m2) obtained in Synthesis Example 2, 8.3 mg AIBN and 15 mL THF Except for stirring, 1.1 g of a copolymer (P2) represented by the following formula (P2) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, the polystyrene standard was found to have a weight average molecular weight (Mw) of 194,288, a dispersion ratio (Mw / Mn) of 3.07, and the residual monomer amount was 0.08%.

<Synthesis Example 16>
5.756 g monomer (a-1) obtained in Synthesis Example 12, 244 mg monomer (m3) obtained in Synthesis Example 3, 67.3 mg AIBN and 16.0 ml tetrahydrofuran (THF) were mixed in a flask. After stirring for 1.75 hours at 55 ° C under a nitrogen atmosphere, add 5 times the amount of monomer used (5 mL to 1 g of monomer) of hexane (30 mL in this synthesis example) and add the reaction mixture. And the supernatant was removed by decantation. The reaction mixture was redissolved in THF (18 mL in this synthesis example) 3 times the amount of monomer used (3 mL per 1 g of monomer), and 5 times the amount of monomer used (single amount) 5 mL) of hexane (30 mL in this synthesis example) was added to precipitate the reaction mixture, and the supernatant was removed by decantation. After further redissolution in THF, precipitation with hexane, and decantation, the reaction mixture obtained was dried under reduced pressure at 20 ° C. and 0.13 kPa for 24 hours under light shielding to obtain 1.46 g of the following formula A copolymer (P3) represented by (p3) was obtained.
The molecular weight of the obtained copolymer was determined by GPC measurement. The weight average molecular weight (Mw) was 233,911, the dispersion ratio (Mw / Mn) was 2.02, and the remaining amount of monomer was 0.15% based on polystyrene.

<Synthesis Example 17>
2 hours at 60 ° C. using 5.756 g monomer (a-1) obtained in Synthesis Example 12, 244 mg monomer (m4) obtained in Synthesis Example 4, 16.8 mg AIBN and 16.0 ml THF Except for stirring, 1.28 g of a copolymer (P4) represented by the following formula (p4) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, it was found that the weight average molecular weight (Mw) was 224,302, the dispersion ratio (Mw / Mn) was 1.99, and the residual monomer amount was 0.01% based on polystyrene.

<Synthesis Example 18>
Using 4.813 g monomer (a-1) obtained in Synthesis Example 12, 187 mg monomer (m5) obtained in Synthesis Example 5, 14.1 mg AIBN and 16.0 ml THF at 60 ° C. for 4 hours Except for stirring, 1.58 g of a copolymer (P5) represented by the following formula (p5) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, the polystyrene standard was found to have a weight average molecular weight (Mw) of 203,802, a dispersion ratio (Mw / Mn) of 1.97, and the residual monomer amount was 0.08%.

<Synthesis Example 19>
2 hours at 60 ° C. using 4.791 g monomer (a-1) obtained in Synthesis Example 12, 209 mg monomer (m6) obtained in Synthesis Example 6, 14.0 mg AIBN and 13.2 ml THF Except for stirring, 0.97 g of a copolymer (P6) represented by the following formula (p6) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, the weight average molecular weight (Mw) was 269,843, the dispersion ratio (Mw / Mn) was 1.76, and the remaining amount of monomer was 0.01% by polystyrene standard.

<Synthesis Example 20>
Using 3.0 g monomer (a-1) obtained in Synthesis Example 12, 0.12 g monomer (m7) obtained in Synthesis Example 7, 26.1 mg AIBN and 10 mL THF at 60 ° C. for 2 hours Except for stirring, 1.0 g of a copolymer (P7) represented by the following formula (p7) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, it was found that the polystyrene standard had a weight average molecular weight (Mw) of 157,437 and a dispersion ratio (Mw / Mn) of 1.95.

<Synthesis Example 21>
2 hours at 60 ° C. using 5.0 g monomer (a-1) obtained in Synthesis Example 12, 0.18 g monomer (m8) obtained in Synthesis Example 8, 14.6 mg AIBN and 14 mL THF Except for stirring, 1.4 g of the copolymer (P8) represented by the following formula (p8) was obtained in the same manner as in Synthesis Example 14.
When the molecular weight of the obtained copolymer was measured by GPC, it was found to have a weight average molecular weight (Mw) of 241,740 and a dispersion ratio (Mw / Mn) of 1.93 according to polystyrene standards.

<Synthesis Example 22>
2.33 g of the monomer (a-1) obtained in Synthesis Example 12 and 0.100 g of the monomer (m9) obtained in Synthesis Example 9 and 11.2 mg of AIBN were dissolved in THF, and the mixture was heated at 60 ° C. in a nitrogen atmosphere. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by decantation, and the precipitate was dissolved again in THF and precipitated with hexane. This decantation operation was further carried out 7 times and then dried under reduced pressure to obtain 0.73 g of a copolymer (P9) represented by the following formula (p9).
When the molecular weight of the obtained copolymer was measured by GPC, it was a weight average molecular weight (Mw) 208790 and a dispersion ratio (Mw / Mn) 2.13 based on polystyrene.

<Synthesis Example 23>
3.73 g of the monomer (a-1) obtained in Synthesis Example 12 and 0.150 g of the monomer (m10) obtained in Synthesis Example 10 and 15.2 mg of AIBN were dissolved in THF. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by decantation, and the precipitate was dissolved again in THF and precipitated with hexane. This decantation operation was further carried out 7 times and then dried under reduced pressure to obtain 1.23 g of a copolymer (P10) represented by the following formula (p10).
When the molecular weight of the obtained copolymer was measured by GPC, it was a weight average molecular weight (Mw) 217725 and a dispersion ratio (Mw / Mn) 2.04 based on polystyrene.

<Synthesis Example 24>
2.19 g of the monomer (a-1) obtained in Synthesis Example 12 and 0.080 g of the monomer (m11) obtained in Synthesis Example 11 and 13.2 mg of AIBN were dissolved in THF. After the reaction, the reaction mixture was cooled to room temperature and added to hexane to precipitate a polymer. The solvent was removed by decantation, and the precipitate was dissolved again in THF and precipitated with hexane. This decantation operation was further carried out 7 times and then dried under reduced pressure to obtain 0.63 g of a copolymer (P11) represented by the following formula (p11).
When the molecular weight of the obtained copolymer was measured by GPC, it was found that the polystyrene standard had a weight average molecular weight (Mw) of 253167 and a dispersion ratio (Mw / Mn) of 1.99.

<Synthesis Example 25>
20.0 g monomer (a-1) obtained in Synthesis Example 12, 0.78 g monomer (ref-m) obtained in Synthesis Example 13, 55.5 mg AIBN and 80 mL tetrahydrofuran (THF) were added to the flask. After stirring for 7 hours at 55 ° C under a nitrogen atmosphere, add 5 times the amount of monomer used (5 mL to 1 g of monomer) and add hexane (100 mL in this synthesis example) to the reaction mixture. And the supernatant was removed by decantation. The reaction mixture was redissolved in THF (60 mL in this synthesis example) of 3 times the amount of monomer used (3 mL per 1 g of monomer), and 5 times the amount of monomer used (single amount) 5 mL of hexane (100 mL in this synthesis example) was added to precipitate the reaction mixture, and the supernatant was removed by decantation. After further redissolution in THF, precipitation with hexane, and decantation, the reaction mixture obtained was dried under reduced pressure at 20 ° C. and 0.13 kPa for 24 hours under light shielding, and 9.1 g of the following formula A copolymer (Ref-p) represented by (Ref-p) was obtained.
The molecular weight of the obtained copolymer was determined by GPC measurement. The weight average molecular weight (Mw) was 235,306, the dispersion ratio (Mw / Mn) was 2.16, and the residual monomer amount was 0.24%.

[Example 1]
The copolymer (p1) is dissolved in N-methyl-2-pyrrolidone (hereinafter referred to as NMP) and then 2-butoxyethanol is added, and the weight ratio is adjusted to be NMP: 2-butoxyethanol: (P1) = 47.5: 47.5: 5 And it filtered using the MS PTFE syringe filter (5um, 1um, 0.45um) by a menbrane solution company, and obtained the polymer solution for photo-alignment films | membranes. This solution was spin-coated on a IPS3035-2up substrate made of FPD solution and a counter substrate using a spin coater IH-DX-2 manufactured by Mikasa Co., Ltd. so as to have a thickness of about 90 nm. Thereafter, it was dried at 80 ° C. for 3 minutes on a digital hot plate NINOS ND1 manufactured by AS ONE, and further dried at 150 ° C. for 5 minutes in an air atmosphere using an oven DO-600FA manufactured by AS ONE. After drying, it was gradually cooled to room temperature. Then, to prepare a dry film 7.5 seconds linearly polarized light of 313nm at an intensity of ^{20mw / cm 2, 150mJ / cm} 2 irradiated to the photo-alignment film of Example 1 using Mejiro Precision manufactured polarizing device.
Using a seal dispenser manufactured by Musashi Engineering Co., Ltd., struct bond XN-21-S manufactured by Mitsui Chemicals Co., Ltd. was applied to the IPS substrate side on the substrate on which the photo-alignment film was formed. After coating, the sealant was dried at 90 ° C. for 30 minutes, and the substrates were bonded together. After laminating the substrates, heating was performed at 150 ° C. for 90 minutes to produce a glass cell. After cooling to room temperature, liquid crystal PA0500 manufactured by DIC Corporation was injected into the prepared cell using a vacuum injection device manufactured by Mikasa Corporation. After the injection, a sealing material 3026B manufactured by 3M was applied to the cell opening, and only the vicinity of the sealing agent was irradiated with ultraviolet rays using a UV irradiation device manufactured by Fujiwara Seisakusho and sealed.
A conducting wire was attached to the obtained liquid crystal cell and heated at 92 ° C. for 2 minutes. Thereafter, the voltage holding ratio was measured at an ambient temperature of 60 ° C., a frame time of 16.6 msec, and an applied voltage of 5 V using a VHR measuring device VHRAMP01 manufactured by Toyo Technica. As a result, VHR was 96.8%.

The nematic liquid crystal mixed PA0500 manufactured by DIC Corporation is prepared by blending the liquid crystal compounds shown in Table 2 in the blending amounts shown in the same table. As a result of thermal analysis on the obtained nematic liquid crystal mixture PA0500, the nematic-isotropic liquid phase transition temperature (clearing point) was 85.6 ° C. Further, the extraordinary refractive index _{n e} at a wavelength of 589nm is 1.596, the ordinary refractive index n _o at a wavelength of 589nm was 1.491. The dielectric anisotropy was +7.0, and K ₂₂ (twist elastic modulus) was 7.4 pN.

[Examples 2 to 11]
A photo-alignment film and a liquid crystal cell using the copolymers (p2) to (p11) were prepared in the same manner as in Example 1, and VHR was measured. The results are shown in Table 2.

[Comparative Example 1]
A photo-alignment film and a liquid crystal cell using a copolymer (Ref-p) were prepared in the same manner as in Example 1, and VHR was measured. The results are shown in Table 3.

  From the above results, it was confirmed that the liquid crystal cell provided with the photo-alignment film of the example according to the present invention exhibits an excellent voltage holding ratio (VHR). From this, it was found that the photo-alignment films of the examples according to the present invention exhibited an excellent alignment regulating force. Further, in the production of the photo-alignment film, since the irradiation amount of polarized ultraviolet rays was small, it was found that the photo-alignable polymers of the examples according to the present invention have high sensitivity to polarized ultraviolet rays.

<Preparation of photo-alignment film and optical anisotropic body>
[Example 12]
5 parts of copolymer (p1) was dissolved in a mixed solvent of 47.5 parts of N-methyl-2-pyrrolidone and 47.5 parts of 2-butoxyethanol and stirred at room temperature for 10 minutes. Next, the solution was applied to each of two glass plates as a substrate using a spin coater. Here, of the two glass plates to be paired, one glass plate is formed with comb-shaped ITO electrodes having an electrode interval of 5 μm along the long side direction of the glass plate. Subsequently, the two glass plates coated with the above solution were heated at 80 ° C. for 3 minutes and further at 180 ° C. for 5 minutes to obtain a coating film of polymer (p1) having a film thickness of about 0.1 μm. The polymer (p1) was uniformly applied on the glass plate, and a smooth film was formed.
Next, ultraviolet light (313 nm, illuminance 20 mW / cm ² ) is irradiated as parallel light to the surface on which the coating film of the glass plate is formed through a wavelength cut filter, a band pass filter, and a polarizing filter from an ultra high pressure mercury lamp. Thus, a photo-alignment film (photo-alignment layer) was obtained. The irradiated ultraviolet light is linearly polarized light, and ultraviolet light from the normal direction to the glass plate surface so that the vibration direction of the electric field of the linearly polarized light is parallel to the comb pattern ITO electrode (long side direction of the glass plate). Was irradiated. The ultraviolet light irradiation energy was 100 mJ / cm ² .
A polymerizable liquid crystal composition (LC-1) in which the liquid crystal compounds shown in Table 4 were blended in the blending amounts shown in the same table was applied on the photo-alignment film obtained above with a spin coater, and then at 80 ° C. for 1 minute. After drying, ultraviolet light was irradiated at 1 J / cm ^{2 in} a nitrogen atmosphere to polymerize the polymerizable liquid crystal composition (LC-1) to obtain an optical anisotropic body.
As a result of evaluating the obtained optical anisotropic body by the following method, the orientation was A, and good orientation could be obtained with a small dose of 100 mJ / cm ² . When the orientation direction was observed, the orientation was homogeneous. Further, it has been found that the optical anisotropic body of the present invention can impart orientation and control the orientation direction with an extremely small amount of ultraviolet irradiation during production.

(Evaluation method of orientation)
By visually inspecting the appearance of the optical anisotropic body and further observing with a polarizing microscope, the optical anisotropic body was evaluated in the following five stages.
A: Uniform orientation is obtained visually, and there are no defects even when observed with a polarizing microscope.
B: Although uniform orientation is obtained visually, the orientation area in the polarizing microscope observation is 90 to 100%.
C: Although alignment as much as A and B is not obtained by visual observation, the alignment area in the polarization microscope observation is 60 to 90%.
D: Although it is close to non-orientation visually, the orientation area in polarizing microscope observation is 40 to 60%.
E: Non-orientated visually, and the orientation area by polarizing microscope observation is 40% or less.

[Examples 13 to 22]
An optical anisotropic body was obtained in the same manner as in Example 12 except that the copolymers (p2) to (P11) were used instead of the copolymer (p1). As a result of evaluating the obtained optical anisotropic body by the above method, the orientation was A, and when the orientation direction was observed, the orientation was homogeneous. Therefore, like Example 12, the optical anisotropic body which has the outstanding orientation with the small light irradiation amount of 100 mJ / cm < ² > was able to be manufactured.

[Comparative Example 2]
An optical anisotropic body was obtained in the same manner as in Example 12 except that the copolymer (Ref-p) was used instead of the copolymer (p1) and the polymerizable liquid crystal composition (LC-1) was used. As a result of evaluating the obtained optical anisotropic body, the orientation was B. When the orientation direction was observed, the orientation was homogeneous.

  The polymer for photo-alignment films according to the present invention is widely applicable in the field of liquid crystal displays.

Claims (9)

The following general formula (X):

(In the above general formula (X),
Sp ¹ and Sp ² each independently represent a spacer group,
R ¹¹ represents a monovalent substituent composed of two or more atoms or a halogen atom,
In any combination of two atoms bonded to each other in the monovalent substituent, a combination in which an absolute value of a difference in electronegativity between atoms is 0.45 or more and 1.70 or less is included,
m is an integer of 1 to 5, and when m is 2 or more, the plurality of R ¹¹ may be the same or different from each other,
A ²¹ , A ²² and A ²³ are each independently
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, alkyl or alkoxy groups,
p, q and r each independently represents an integer of 0 to 4, and when p, q and r are 2 or more, a plurality of A ²¹ , A ²² , A ²³ , Z ²² and Z ²⁴ are May be the same or different,
Z ²¹ , Z ²² , Z ²³ and Z ²⁴ are each independently a single bond, —O—, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, From —CH ₂ O—, —COO—, —OCO—, —CH═CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — and —C≡C—. Represents at least one divalent linking group selected from the group consisting of:
The condition that D ¹ is — (L ¹ -A ¹ ) _k —C (═O) — and D ² is a single bond, or D ² is —C (═O) — (A ¹ -L ¹ ) _Satisfy any of the following conditions: _f − and D ¹ is a single bond,
L ¹ is a single bond, — (CH ₂ ) _u — (wherein _u represents 1 to 20), —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CH═. CH—, —CF═CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CF ₂ — or —C≡C— represents ^one of non-adjacent —CH ₂ — groups constituting L ^1. Two or more are independently —O—, —CO—, —CO—O—, —O—CO—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, — NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, —NR—CO—NR—, —CH═CH—, —C≡C— or —O—. CO—O— (wherein R independently represents hydrogen or an alkyl group having 1 to 5 carbon atoms), k and f are integers of 0 to 3,
A ¹ is,
(A) trans-1,4-cyclohexylene group (in this group, one methylene group or two or more methylene groups which are not adjacent to each other are replaced by —O—, —NH— or —S—) May be)
(B) 1,4-phenylene group (one or more of —CH═ present in this group may be replaced by —N═), and (c) 1,4-cyclohexenylene. Group, 2,5-thiophenylene group, 2,5-furylene group, 1,4-bicyclo [2.2.2] octylene group, naphthalene-1,4-diyl group, naphthalene-2,6-diyl group, Represents a group selected from the group consisting of a decahydronaphthalene-2,6-diyl group and a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the group (a), group (b) or Each group (c) may be unsubstituted or one or more hydrogen atoms may be replaced by fluorine, chlorine, cyano, methyl or methoxy groups;
X and Y each independently represent a hydrogen atom or a halogen atom,
Z represents the general formula (IIa) or (IIb)

(Wherein the dashed line represents a bond to the D ^2,
R ¹ and R ² each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 50 carbon atoms, one —CH ₂ — group in R ¹ and R ² , or two or more Non-adjacent —CH ₂ — groups are —O—, —CO—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —NCH ₃ —, —CH═CH. One or more —CH ₂ — groups in R ¹ and R ² may be substituted with one or more selected from the group consisting of —, —CF═CF— and —C≡C—. It may be independently substituted with a cycloalkyl group having 3 to 8 ring members, and the hydrogen atom in R ¹ and R ² is substituted with an alkyl group having 1 to 20 carbon atoms, a cyano group, or a halogen atom. Also good. )
a, b and c represent the molar fraction of the copolymer, and in each case 0 <a ≦ 1, 0 <b ≦ 1, and 0 ≦ c <1;
The sequence of the monomer units of Ma, Mb and Md may be the same as or different from the formula, and the monomer units of Ma, Mb and Md are each independently one type or two or more types of different units. Each monomer unit of Ma, Mb and Md may be independently represented by the general formulas (U-1) to (U-3).

(In the above general formulas (U-1) to (U-3) ,
When the formula represents Ma and Mb, the broken lines represent bonds to Sp ¹ and Sp ² , respectively, and when the formula represents Md, the broken lines represent a bond to a hydrogen atom or a monovalent organic group,
R ^a independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom, and any hydrogen atom in the general formulas (U-1) to (U-3) is a fluorine atom. , a chlorine atom, a methyl group, a phenyl group, or but it may also be substituted by a methoxy group. Represents one type of repeating unit. )
The polymer for photo-alignment films | membrane represented by these. In the general formula (X),
R ¹¹ is a cyano group, a hydroxyl group, a carboxyl group, an amide group, fluorine, chlorine, a thiol group, a nitro group, a sulfonic acid group, a linear or branched alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atom. 20 alkoxy groups or the following general formula (QX)

(In the formula, a broken line represents a bond, S _aa represents a spacer group, and Va represents a side chain end).
One of the —CH ₂ — groups constituting the alkyl group and the alkoxy group, or two or more non-adjacent groups are independently —O—, —CO—, —CO—O—, —O—CO—, — Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ —, —NR—, —NR—CO—, —CO—NR—, —NR—CO—O—, —O—CO—NR—, — NR—CO—NR—, —CH═CH—, —C≡C—, —O—CO—O— (wherein R independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ), And may be substituted with one or more substituents selected from a divalent ring structure,
One or more hydrogen atoms bonded to the alkyl group, the alkoxy group and the group represented by the general formula (QX) are a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a carboxyl group, an amide group, fluorine, sulfone. The polymer for photo-alignment films according to claim 1, which may be substituted with an acid group or a nitro group.   The polymer for photo-alignment films according to claim 1 or 2 whose ratio expressed by a / (a + b + c) x100% in the mole fraction is 0.1 to 20%. The polymer for photo-alignment films according to any one of claims 1 to 3, wherein the Sp ¹ is a linear divalent linking group having 2 to 20 carbon atoms. A polymer solution comprising the polymer for a photoalignment film according to claim 1 and an organic solvent as essential components. Range solid concentration of 1 to 20 mass%, the polymer is an optical alignment film polymer of claim 4 wherein, the an organic solvent essential component solution.   The photo-alignment film formed with the polymer for photo-alignment films as described in any one of Claims 1-4.   An optical anisotropic body having the photo-alignment film according to claim 7.   A liquid crystal display device having the photo-alignment film according to claim 7.