JP6683958B2 - Cured film forming composition, alignment material and retardation material - Google Patents

Description

  The present invention relates to a cured film forming composition, an alignment material and a retardation material.

  2. Description of the Related Art In recent years, in the field of displays such as televisions using liquid crystal panels, development of 3D displays that allow users to enjoy 3D images has been promoted as an effort to improve performance. In the 3D display, for example, the image for the right eye is visually recognized by the observer's right eye, and the image for the left eye is visually recognized by the observer's left eye, whereby an image having a stereoscopic effect can be displayed.

There are various 3D display systems for displaying 3D images, and lenticular lens systems and parallax barrier systems are known as systems that do not require special glasses.
Then, as one of the display systems in which an observer wears glasses to observe a 3D image, a circular polarization glasses system and the like are known (for example, refer to Patent Document 1).

  In the case of a circularly polarized glasses type 3D display, it is usual that a retardation material is arranged on a display element that forms an image, such as a liquid crystal panel. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged, respectively, to form a patterned retardation material. Hereinafter, in this specification, a retardation material patterned such that a plurality of retardation regions having different retardation characteristics are arranged is referred to as a patterned retardation material.

  The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2. The optical patterning of the retardation material composed of the polymerizable liquid crystal utilizes the optical alignment technique known for forming the alignment material of the liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two kinds of polarized light having different polarization directions are irradiated on the coating film. Then, an optical alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. A solution type retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

  Acrylic resins and polyimide resins having a photodimerization site such as a cinnamoyl group and a chalcone group in the side chain are known as usable photo-alignment materials for forming alignment materials using photo-alignment technology for liquid crystal panels. . It has been reported that these resins exhibit a property of controlling the alignment of liquid crystal (hereinafter, also referred to as liquid crystal aligning property) by irradiation with polarized UV (see Patent Documents 3 to 5).

JP, 10-232365, A JP, 2005-49865, A Japanese Patent No. 3611342 JP, 2009-058584, A Special table 2001-517719 gazette

As described above, the patterned retardation material is configured by laminating the layer of cured polymerizable liquid crystal on the photo-alignment film which is the alignment material. Then, the patterned retardation material having such a laminated structure can be used for the constitution of the 3D display in the laminated state.
Therefore, there is a need to develop a cured film that can be used as an alignment material that has both excellent liquid crystal alignment properties and light transmission properties, and a cured film forming composition for forming the cured film.

  The object of the present invention has been made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film forming composition suitable for forming a cured film having excellent liquid crystal alignment and light transmission properties. In particular, an object of the present invention is to provide a cured film-forming composition which can be used as an alignment material and can form a cured film exhibiting excellent liquid crystal alignment and light transmittance when a layer of a polymerizable liquid crystal is arranged thereon. It is to provide things.

  An object of the present invention is to provide an alignment material having excellent liquid crystal alignment properties and light transmission properties.

  An object of the present invention is to provide a retardation material capable of highly precise optical patterning.

  Other objects and advantages of the present invention will be apparent from the following description.

（式中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はアルキル基を表し、Ｒ^３はアルキル基、アルケニル基、シクロアルキル基、芳香族基を表し、Ｒ^１とＲ^３、又はＲ^２とＲ^３は互いに結合して環を形成しても良い。Ｘ^１は任意の置換基で置換されていても良いフェニレン基を表す。）
（Ｂ）下記（Ｂ−１）乃至（Ｂ−３）からなる群から選ばれる少なくとも一種のポリマー、
（Ｂ−１）：ヒドロキシ基、カルボキシル基、アミド基、アミノ基、アルコキシシリル基および下記式（２）で表される基からなる群から選ばれる少なくとも一つの基を少なくとも２つ有するポリマー、

（式中、Ｒ^６２はアルキル基、アルコキシ基又はフェニル基を表す。）
（Ｂ−２）：ヒドロキシ基、カルボキシル基、アミド基、アミノ基、アルコキシシリル基および上記式（２）で表される基からなる群から選ばれる少なくとも一つの基と熱反応可能であり且つ自己架橋可能なポリマー、及び
（Ｂ−３）：メラミンホルムアルデヒド樹脂、
並びに
（Ｃ）架橋剤（但し、（Ｂ）成分が上記（Ｂ−２）であるときは、（Ｂ−２）成分と同じであってもよい。）を含有する硬化膜形成組成物に関する。
本発明の第１態様のうち、好ましい態様の１つとして、
（Ａ）下記式（１）で表される基を有するけい皮酸エステルの一種または複数種、

（式中、Ｒ ^１ 及びＲ ^２ はそれぞれ独立に水素原子又はアルキル基を表し、Ｒ ^３ はアルキル基、アルケニル基、シクロアルキル基、芳香族基を表し、Ｒ ^１ とＲ ^３ 、又はＲ ^２ とＲ ^３ は互いに結合して環を形成しても良い。Ｘ ^１ は任意の置換基で置換されていても良いフェニレン基を表す。）
（Ｂ）下記（Ｂ−１）乃至（Ｂ−３）からなる群から選ばれる少なくとも一種のポリマー、
（Ｂ−１）：ヒドロキシ基、カルボキシル基、アミド基、アミノ基、アルコキシシリル基および下記式（２）で表される基からなる群から選ばれる少なくとも一つの基を少なくとも２つ有するポリマー、

（式中、Ｒ ^６２ はアルキル基、アルコキシ基又はフェニル基を表す。）
（Ｂ−２）：ヒドロキシ基、カルボキシル基、アミド基、アミノ基、アルコキシシリル基および上記式（２）で表される基からなる群から選ばれる少なくとも一つの基と熱反応可能であり且つ自己架橋可能なポリマー、及び
（Ｂ−３）：メラミンホルムアルデヒド樹脂、
並びに
（Ｃ）アルコキシメチル化メラミン、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、ヒドロキシメチル基又はアルコキシメチル基で置換されたアクリルアミド化合物を使用して製造されたポリマーおよびヒドロキシメチル基又はアルコキシメチル基で置換されたメタクリルアミド化合物を使用して製造されたポリマーからなる群から選ばれる少なくとも１種の架橋剤（但し、（Ｂ−１）成分を除く。また（Ｂ）成分が上記（Ｂ−２）を含むときは、（Ｂ−２）成分と同じであってもよい。）を含有する硬化膜形成組成物が挙げられる。 The first aspect of the present invention is
(A) one or more kinds of cinnamic acid ester having a group represented by the following formula (1),

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aromatic group, R ¹ and R ³ , or R ² and R ³ may combine with each other to form a ring, and X ¹ represents a phenylene group which may be substituted with any substituent.)
(B) at least one polymer selected from the group consisting of the following (B-1) to (B-3),
(B-1): a polymer having at least two groups selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2),

(In the formula, R ⁶² represents an alkyl group, an alkoxy group or a phenyl group.)
(B-2): capable of thermal reaction with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2), and self. Crosslinkable polymer, and (B-3): melamine formaldehyde resin,
And a cured film forming composition containing (C) a cross-linking agent (however, when the component (B) is the component (B-2), it may be the same as the component (B-2)).
Among the first aspect of the present invention, as one of the preferable aspects,
(A) one or more kinds of cinnamic acid ester having a group represented by the following formula (1),

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aromatic group, R ¹ and R ³ , or R ² and R ³ may combine with each other to form a ring, and X ¹ represents a phenylene group which may be substituted with any substituent.)
(B) at least one polymer selected from the group consisting of the following (B-1) to (B-3),
(B-1): a polymer having at least two groups selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2),

(In the formula, R ⁶² represents an alkyl group, an alkoxy group or a phenyl group.)
(B-2): capable of thermal reaction with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2), and self. Crosslinkable polymer, and
(B-3): Melamine formaldehyde resin,
And
(C) Alkoxymethylated melamine, alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, polymer produced using an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, and substituted with a hydroxymethyl group or an alkoxymethyl group At least one cross-linking agent selected from the group consisting of polymers produced by using the methacrylamide compound (provided that the component (B-1) is excluded. When it is included, it may be the same as the component (B-2).

In the first aspect of the present invention, it is preferable to contain (E) a crosslinking catalyst.
In the first aspect of the present invention, one or more polymerizable groups as the component (D), a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2) It is preferable to contain a compound having at least one group A selected from the group consisting of or at least one group reactive with the group A.

In the first aspect of the present invention, the mixing ratio of the component (A) and the component (B) is preferably 5:95 to 60:40 in terms of mass ratio.
In the first aspect of the present invention, it is preferable to contain 10 to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the components (A) and (B).
In the first aspect of the present invention, 0.01 to 10 parts by mass of (E) is used with respect to 100 parts by mass of the total amount of the cinnamic acid ester as the component (A) and the polymer as the component (B). ) Component is preferably contained.
In the first aspect of the present invention, 0.01 parts by mass or more and 100 parts by mass or less are based on 100 parts by mass of the total amount of the components (A), (B), (C) and (E). It is preferable to contain the component (D).

  A second aspect of the present invention relates to a cured film formed using the cured film forming composition of the first aspect of the present invention.

  A third aspect of the present invention relates to an alignment material formed by using the cured film forming composition of the first aspect of the present invention.

  A fourth aspect of the present invention relates to a retardation material having a cured film obtained from the cured film forming composition of the first aspect of the present invention.

（式中、Ｒ¹及びＲ²はそれぞれ独立に水素原子又はアルキル基を表し、Ｒ³はアルキル基、アルケニル基、シクロアルキル基、芳香族基を表し、Ｒ¹とＲ³、又はＲ²とＲ³は互いに結合して環を形成しても良い。Ｘ¹は任意の置換基で置換されていても良いフェニレン基を表す。）A fifth aspect of the present invention relates to a cinnamic acid ester having a group represented by the following formula (1).

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aromatic group, R ¹ and R ³ , or R ² and R ³ may combine with each other to form a ring, and X ¹ represents a phenylene group which may be substituted with any substituent.)

  According to the first aspect of the present invention, there is provided a cured film forming composition capable of forming a cured film having liquid crystal alignment ability (photoalignment) by light irradiation in addition to high transparency, high solvent resistance and high heat resistance. Can be provided.

  According to the second aspect of the present invention, it is possible to provide a cured film having high transparency, high solvent resistance, high heat resistance, and liquid crystal alignment ability (photoalignment) by light irradiation.

  According to the third aspect of the present invention, it is possible to provide an alignment material having excellent adhesion, alignment sensitivity, pattern formability and adhesion durability, and capable of aligning a polymerizable liquid crystal with high sensitivity.

  According to the fourth aspect of the present invention, it is possible to provide a retardation material that can be formed on a resin film with high efficiency and can be optically patterned.

  According to the fifth aspect of the present invention, a novel cinnamic acid ester useful as a low molecular weight photo-alignment component can be provided.

  Hereinafter, the cured film forming composition of the present invention (hereinafter, also referred to as the present invention composition) will be described in detail with reference to specific examples of components and the like. Then, the cured film and the aligning material of the present invention using the cured film forming composition of the present invention, and the retardation material and the liquid crystal display element formed by using the aligning material will be described.

（式中、Ｒ¹及びＲ²はそれぞれ独立に水素原子又はアルキル基を表し、Ｒ³はアルキル基、アルケニル基、シクロアルキル基、芳香族基を表し、Ｒ¹とＲ³、又はＲ²とＲ³は互いに結合して環を形成しても良い。Ｘ¹は任意の置換基で置換されていても良いフェニレン基を表す。）[(A) component]
The component (A) of the composition of the present invention is a cinnamic acid ester having a group represented by the following formula (1) as a photoalignment site.

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aromatic group, R ¹ and R ³ , or R ² and R ³ may combine with each other to form a ring, and X ¹ represents a phenylene group which may be substituted with any substituent.)

Examples of the alkyl group for R ¹ and R ² include an alkyl group having 1 to 6 carbon atoms.
The alkyl group in R ³ is an alkyl group having 1 to 6 carbon atoms, the alkenyl group is an alkenyl group having 2 to 6 carbon atoms, and the cycloalkyl group is a cycloalkyl group having 3 to 8 carbon atoms. Examples of the aromatic group include aromatic groups having 4 to 14 carbon atoms.
The alkyl group having 1 to 6 carbon atoms may be linear or branched, and may be methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s- Butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1 -Methylpentyl group, 2-methylpentyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group and the like can be mentioned.
The alkenyl group having 2 to 6 carbon atoms may be linear, branched or cyclic, and includes, for example, ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl -2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2- Butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3- Methyl 1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1 -Propenyl group, 1,2-dimethyl-2-propenyl group, 1-c-pentenyl group, 2-c-pentenyl group, 3-c-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group , 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n -Butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1 -Pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3- Butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1 -S-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2- Dimethyl-3-butenyl group , 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl -1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl- 2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group Group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group Group, 1-i-propyl-2- Lopenyl group, 1-methyl-2-c-pentenyl group, 1-methyl-3-c-pentenyl group, 2-methyl-1-c-pentenyl group, 2-methyl-2-c-pentenyl group, 2-methyl -3-c-pentenyl group, 2-methyl-4-c-pentenyl group, 2-methyl-5-c-pentenyl group, 2-methylene-c-pentyl group, 3-methyl-1-c-pentenyl group, 3-methyl-2-c-pentenyl group, 3-methyl-3-c-pentenyl group, 3-methyl-4-c-pentenyl group, 3-methyl-5-c-pentenyl group, 3-methylene-c- Examples thereof include a pentyl group, a 1-c-hexenyl group, a 2-c-hexenyl group and a 3-c-hexenyl group.
Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
The aromatic group having 4 to 14 carbon atoms may be a heterocycle, for example, a phenyl group, a biphenylyl group, an o-terphenylyl group, a m-terphenylyl group, a p-terphenylyl group, a fluorenyl group, a naphthalenyl group. , 1-phenylnaphthalenyl group, 2-phenylnaphthalenyl group, anthracenyl group and the like.
The optional substituent of X ¹ is not particularly limited, but examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and isobutyl group; haloalkyl groups such as trifluoromethyl group; methoxy group, ethoxy group and the like. Alkoxy groups; halogen atoms such as iodine atom, bromine atom, chlorine atom, and fluorine atom; cyano group; nitro group.

  As the component (A), a compound in which a polymerizable group is bonded to the group represented by the above formula (1) via a spacer is also preferable. The spacer is a divalent group selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group and a phenylene group, or a group formed by bonding a plurality of the divalent groups. In this case, a bond between the divalent groups constituting the spacer, a bond between the spacer and the group represented by the above formula (1), and a bond between the spacer and the polymerizable group include a single bond, an ester bond and an amide bond. , A urea bond or an ether bond. When the divalent group is plural, the divalent groups may be the same or different, and when the bond is plural, the bonds may be the same or different.

（式中、Ｒ²は水素原子又はアルキル基を表し、Ｒ⁴及びＲ⁵はそれぞれ独立に水素原子またはアルキル基を表し、Ｒ³はアルキル基、アルケニル基、シクロアルキル基又は芳香族基を表し、Ｒ²とＲ³、又はＲ⁵とＲ³は互いに結合して環を形成しても良い。）The cinnamic acid ester, which is the component (A), is a carboxyl group of cinnamic acid or a derivative thereof and an ether compound represented by the following formula (3-1) or an ether compound represented by the following formula (3-2). It is obtained by reacting with.

(In the formula, R ² represents a hydrogen atom or an alkyl group, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, and R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group or an aromatic group. , R ² and R ³ , or R ⁵ and R ³ may combine with each other to form a ring.)

［式中、Ｘ¹は前記の意味を表し、Ｊ¹は水素原子、ハロゲン原子、炭素数１乃至６のアルキル基、炭素数１乃至６のハロアルキル基、炭素数１乃至６のアルコキシ基、炭素数１乃至６のハロアルコキシ基、シアノ基、及びニトロ基から選ばれる置換基を表すか、又は下記式（４−２）で表される基である。

（式中、Ｒ⁶は炭素数１〜３０のアルキレン基、フェニレン基または二価の炭素環若しくは複素環であり、このアルキレン基、フェニレン基または二価の炭素環若しくは複素環中の１つ若しくは複数の水素原子は、フッ素原子又は有機基で置き換えられていてもよい。また、Ｒ⁶中の−ＣＨ₂−は、フェニレン基または二価の炭素環若しくは複素環に置き換えられていてもよく、さらに、次に挙げるいずれかの基が互いに隣り合わない場合において、これらの基に置き換えられていてもよい；−Ｏ−、−ＮＨＣＯ−、−ＣＯＮＨ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−、−ＮＨＣＯＮＨ−、−ＣＯ−。Ｒ⁷は−ＣＨ₂−、−Ｏ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨ−又は−ＣＯ−である。Ｒ⁸は水素原子又はメチル基である。）］Examples of the cinnamic acid or its derivative include a compound represented by the following formula (4-1).

[Wherein, X ¹ represents the above-mentioned meaning, J ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, carbon It represents a substituent selected from a haloalkoxy group, a cyano group, and a nitro group of the formulas 1 to 6, or a group represented by the following formula (4-2).

(In the formula, R ⁶ is an alkylene group having 1 to 30 carbon atoms, a phenylene group, a divalent carbon ring or a heterocycle, and one of the alkylene group, the phenylene group, the divalent carbocycle or the heterocycle, or A plurality of hydrogen atoms may be replaced by a fluorine atom or an organic group, and —CH ₂ — in R ⁶ may be replaced by a phenylene group or a divalent carbon ring or a heterocycle. Further, when any of the following groups are not adjacent to each other, they may be substituted with these groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH. -, - NHCONH -, - CO -.R 7 is _{-CH 2 -, - O -,} - CONH -, - NHCO -, - COO -, - OCO -, - NH- or -CO- is .R ⁸ Is a hydrogen atom or methyl A group.)]

J ¹ is preferably bonded to the 4-position of the benzene ring X ¹ of cinnamic acid.

  Examples of the cinnamic acid represented by the formula (4-1) and its derivatives include cinnamic acid, 4-methoxycinnamic acid, 4-ethoxycinnamic acid, 4-propoxycinnamic acid, and 4-fluoro. Cinnamic acid derivatives such as cinnamic acid; 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxyhexyl-1-oxy) cinnamic acid, 4- (3- Examples thereof include monomers having a cinnamic acid group such as methacryloxypropyl-1-oxy) cinnamic acid and 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.

  Examples of the compound represented by the formula (3-1) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, cyclohexyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether and phenyl vinyl ether. Examples of unsaturated cyclic ethers include vinyl ether, 2,3-dihydrofuran, and 3,4-dihydro-2H-pyran.

  Examples of the compound represented by the formula (3-2) include chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl n-propyl ether, chloromethyl i-propyl ether, chloromethyl cyclohexyl ether, chloromethyl isobutyl ether, chloromethyl. Examples thereof include n-butyl ether, chloromethyl t-butyl ether, chloromethyl phenyl ether and the like.

  When the cinnamic acid derivative is reacted with the compound represented by the formula (3-1), 0.9 mol to 1.5 mol of the formula (3- The compound represented by 1) may be reacted without a catalyst or under an acid catalyst.

The compound represented by the formula (3-1) used as a starting material in the present invention can be obtained as a commercial product.
The reaction system may be a rotary system (batch system) or a flow system.

  Examples of the acid catalyst used in the reaction include phosphoric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and methanesulfonic acid. The acid catalyst is used in an amount of 0.01 mol to 0.5 mol, more preferably 0.01 mol to 0.3 mol, based on 1 mol of the cinnamic acid derivative.

  The solvent used in the reaction is, for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, pentanol, isopentanol, butanol, isobutanol, diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl. Ethers such as methyl ether and tert-butyl ethyl ether, aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, nitriles such as acetonitrile and propionitrile. , Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride, formamides such as formamide and N, N-dimethylformamide, dimethyi Sulfoxides, sulfoxides such as diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, sulfones such as sulfolane, or a mixed solvent thereof. Preferably, aromatic hydrocarbons such as benzene, xylene and toluene, nitriles such as acetonitrile and propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride, diethyl ether and tetrahydrofuran. , Dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl methyl ether, tert-butyl ethyl ether and the like. More preferred are aromatic hydrocarbons such as benzene, xylene and toluene, and ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl methyl ether and tert-butyl ethyl ether.

The reaction temperature is, for example, -10 to 100 ° C, preferably 0 to 80 ° C.
The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours in the case of batch processing.

  When the cinnamic acid derivative and the compound represented by the formula (3-2) are reacted with each other, 0.9 mol to 1.1 mol of the formula (3- The compound represented by 2) may be reacted in a solvent in the presence of a base.

The compound represented by the formula (3-2) used as a starting material in the present invention can be obtained as a commercial product.
The reaction system may be a rotary system (batch system) or a flow system.

  Examples of the base used in the reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, and triethylamine. , Tributylamine, diisopropylethylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, and other organic bases. .

  The solvent used in the reaction is, for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, pentanol, isopentanol, butanol, isobutanol, diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl. Ethers such as methyl ether and tert-butyl ethyl ether, aromatic hydrocarbons such as benzene, xylene and toluene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, nitriles such as acetonitrile and propionitrile. , Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride, formamides such as formamide and N, N-dimethylformamide, dimethyi Sulfoxides, sulfoxides such as diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, sulfones such as sulfolane, or a mixed solvent thereof. Preferably, aromatic hydrocarbons such as benzene, xylene and toluene, nitriles such as acetonitrile and propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride, diethyl ether and tetrahydrofuran. , Dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl methyl ether, tert-butyl ethyl ether and the like. More preferred are aromatic hydrocarbons such as benzene, xylene and toluene, and ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butyl methyl ether and tert-butyl ethyl ether.

The reaction temperature is, for example, -10 to 100 ° C, preferably 0 to 80 ° C.
The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours in the case of batch processing.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｘ¹及びＪ¹は前記の意味を表す。）Examples of the compound (A) thus obtained include compounds represented by the formula (1-1).

(In the formula, R ¹ , R ² , R ³ , X ¹ and J ¹ have the above-mentioned meanings.)

  Examples of the low molecular weight photo-alignment component which is the component (A) include the above specific examples, but the invention is not limited thereto.

  In addition, as the cinnamic acid ester of the component (A) in the composition forming the cured film on the surface of the optical film of the present invention, plural kinds of cinnamic acid ester having a photoalignable group represented by the above formula (1) are used. It may be a mixture of cinnamic acid esters.

[(B) component]
The component (B) contained in the composition of the present invention is at least one polymer selected from the following (B-1) to (B-3).
(B-1): a polymer having at least two groups selected from the group consisting of a hydroxy group, a carboxyl group, an amido group, an amino group, an alkoxysilyl group and a group represented by the formula (2),
(B-2): capable of thermal reaction with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2), and self. Crosslinkable polymer, and (B-3): melamine formaldehyde resin,
Hereinafter, each component will be described in detail.

[Component (B-1)]
The component (B-1) has at least two at least one group selected from the group consisting of (hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and group represented by the formula (2). It is a polymer (hereinafter, also referred to as a specific (co) polymer 1).
In the above formula (2), examples of the alkyl group for R ⁶² include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group.
^Examples of the alkoxy group for R ⁶² include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group.

  Examples of the polymer as the component (B-1) include acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactones. Examples thereof include polymers having a linear or branched structure such as polyols, polyalkyleneimines, polyallylamine, celluloses (cellulose or derivatives thereof) and phenol novolac resins, and cyclic polymers such as cyclodextrins.

  Among these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, or styrene can be applied.

  As the acrylic polymer which is a preferred example of the specific (co) polymer 1 of the component (B-1), a (co) polymer of an acrylic acid ester compound and / or a methacrylic acid ester compound, and styrene in addition to these ester compounds A copolymer obtained by polymerizing a monomer having an unsaturated double bond such as can be applied.

  The method for synthesizing the acrylic polymer as an example of the component (B-1) is selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2). As the monomer having at least one group (hereinafter also referred to as (B-1) substituent) to be used, an acrylic acid ester compound or a methacrylic acid ester compound having these (B-1) substituents is used, and a monomer other than that is used if desired. A method of (co) polymerizing these using and is simple.

  When the monomer having a (B-1) substituent is a monomer that does not correspond to an acrylic acid ester compound or a methacrylic acid ester compound, in addition to the monomer having a (B-1) substituent, an acrylic acid ester compound or a methacrylic acid compound is used. The acrylic polymer can be obtained by a method of (co) polymerizing an acid ester compound (the ester compound may further have a (B-1) substituent) and, if desired, a monomer other than that. it can.

  As a monomer having the (B-1) substituent (at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the formula (2)) Is, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2, 3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyl ester) Si) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxy Monomers having a hydroxy group such as norbornene-2-carboxylic-6-lactone, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl. ) Monomers having a carboxyl group such as phthalate, vinylbenzoic acid, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, etc. And a monomer having a phenolic hydroxy group such as p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide and N- (hydroxyphenyl) maleimide. , Acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and other amide group-containing monomers, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate. Group-containing monomers, trimethoxysilylpropyl acrylate, trimethoxysilylpropyl methacrylate, triethoxysilylpropyl acrylate and Examples thereof include monomers having an alkoxysilyl group such as triethoxysilylpropyl methacrylate, and monomers having a group represented by the above formula (2) such as 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

  In addition, in the present invention, when the acrylic polymer which is an example of the component (B-1) is obtained, the substituent (B-1) (hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and In addition to a monomer (including an acrylic acid ester compound / methacrylic acid ester compound having the substituent) having at least one group selected from the group consisting of the groups represented by the formula (2), A monomer that is polymerizable and does not have the (B-1) substituent can be used in combination.

  Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Hereinafter, specific examples of the monomer will be given, but the monomer is not limited thereto.
Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate. , Glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl Acrylate, 2-methyl-2-adamantyl acrylate, 2- Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate. , Glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl Methacrylate, 2 Methyl-2-adamantyl methacrylate, .gamma.-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

  Examples of the styrene compound include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene. , And 1,7-octadiene monoepoxide and the like.

  In order to obtain the acrylic polymer which is an example of the component (B-1), the (B-1) substituent (hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and the above formula (2) The amount of the monomer (including the acrylic acid ester compound / methacrylic acid ester compound having the substituent) having at least one group selected from the group consisting of the groups represented by the amount of the polymer of the component (B-1) is It is preferably from 5 mol% to 100 mol% based on the total amount of all monomers used to obtain.

  The method for obtaining the acrylic polymer, which is an example of the component (B-1), is not particularly limited. For example, the substituent (B-1) (hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and A monomer (including an acrylic acid ester compound / methacrylic acid ester compound having the substituent) having at least one group selected from the group consisting of groups represented by formula (2), and optionally (B-1) ) It is obtained by carrying out a polymerization reaction at a temperature of 50 ° C to 110 ° C in a solvent in which a monomer having no substituent and a polymerization initiator and the like coexist. In that case, the solvent used is particularly preferably one that dissolves the monomer having the (B-1) substituent, and optionally the monomer not having the (B-1) substituent, a polymerization initiator and the like. Not limited. Specific examples are described in the section [solvent] described later.

  The acrylic polymer which is an example of the component (B-1) obtained by the above method is usually in the state of a solution dissolved in a solvent.

  Further, the solution of the acrylic polymer, which is an example of the component (B-1) obtained by the above method, was poured into diethyl ether, water or the like with stirring to cause reprecipitation, and the generated precipitate was filtered and washed. After that, it can be dried at room temperature or heated under normal pressure or reduced pressure to obtain an acrylic polymer powder as an example of the component (B-1). By the above-mentioned operation, the polymerization initiator and the unreacted monomer that coexist with the acrylic polymer which is an example of the component (B-1) can be removed. As a result, in the example of the purified component (B-1) A powder of an acrylic polymer is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  The weight average molecular weight of the acrylic polymer, which is an example of the component (B-1), is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and even more preferably 5,000 to 100,000. If the weight average molecular weight exceeds 200,000 and is too large, the solubility in a solvent may decrease and the handling property may decrease. If the weight average molecular weight is less than 3,000 and is too small, insufficient curing may occur during heat curing. And the solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. The same applies hereinafter in this specification.

  Next, as the polyether polyol which is a preferred example of the specific (co) polymer 1 as the component (B-1), there are polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol and sorbitol. Examples thereof include those to which propylene oxide, polyethylene glycol, polypropylene glycol and the like have been added. Specific examples of commercially available polyether polyols include ADEKA CORPORATION ADEKA POLYETHER P series, G series, EDP series, BPX series, FC series, CM series, and NOIOX (registered trademark) manufactured by NOF CORPORATION. HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA. -400, DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221 and the like can be mentioned.

  As the polyester polyol which is a preferred example of the specific (co) polymer 1 as the component (B-1), polyhydric carboxylic acids such as adipic acid, sebacic acid, isophthalic acid, etc. may be used ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol. , Those obtained by reacting diols such as polypropylene glycol. Specific examples of commercially available polyester polyols include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, and OD-X-240 manufactured by DIC Corporation. , OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD. -X-2523, OD-X-2555, OD-X-2560, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010 manufactured by Kuraray Co., Ltd. , F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like. .

  The polycaprolactone polyol, which is a preferred example of the specific (co) polymer 1 of the component (B-1), is obtained by ring-opening polymerization of ε-caprolactone with a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Is mentioned. Specific examples of commercially available polycaprolactone polyols include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Corporation, and Praxel (registered trademark) manufactured by Daicel Corporation. 205, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

  As the polycarbonate polyol which is a preferred example of the specific (co) polymer 1 of the component (B-1), a polyhydric alcohol such as trimethylolpropane or ethylene glycol is reacted with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Is mentioned. Specific examples of commercially available products of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Co., Ltd., C-590, C-1050, C-2050, and C-2090 manufactured by Kuraray Co., Ltd. , C-3090 and the like.

  Cellulose, which is a preferred example of the specific (co) polymer 1 of the component (B-1), includes hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose. Examples thereof include hydroxyalkylalkylcelluloses and cellulose, and for example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferable.

  The cyclodextrin which is a preferred example of the specific (co) polymer 1 of the component (B-1) includes cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin, and methyl-α-cyclodextrin. , Methyl-β-cyclodextrin and methylated cyclodextrins such as methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl- α-cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2 -Hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin And hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

  As a urethane-modified acrylic polymer which is a preferred example of the specific (co) polymer 1 of the component (B-1), as a commercial item, Acrit (registered trademark) 8UA-017, 8UA-239, 8UA manufactured by Taisei Fine Chemical Co., Ltd. -239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366 etc. are mentioned.

  Examples of the phenol novolac resin, which is a preferred example of the specific (co) polymer 1 as the component (B-1), include phenol-formaldehyde polycondensates.

  The polyether polyols, polyester polyols, polycaprolactone polyols, polycarbonate polyols, celluloses, cyclodextrins, urethane-modified acrylic polymers, and phenol novolac resins that have been mentioned as preferred examples of the specific (co) polymer 1 of the component (B-1). It is preferable that the weight average molecular weight Mw of the above is, for example, about 100 to 200,000.

  In the composition of the present invention, the polymer as the component (B-1) may be used in the form of powder or in the form of a solution in which purified powder is redissolved in a solvent described later.

  Further, in the composition of the present invention, the component (B-1) may be a mixture of plural kinds of polymers exemplified as the component (B-1).

[Component (B-2)]
In the cured film forming composition of the present embodiment, the component (B-2) is selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2). It is a polymer capable of thermal reaction with at least one group (hereinafter, also referred to as a specific (co) polymer 2).

  The specific (co) polymer 2 is more specifically at least one selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2). A group, for example, a group which causes a thermal reaction and a self-crosslinking reaction with a carboxyl group formed by the protective group being separated from the cinnamic acid ester of the component (A) and which reacts at a temperature lower than the sublimation temperature of the component (A). It is a polymer having a self-crosslinkable group (crosslinkable substituent). Here, examples of preferable crosslinkable substituents include a hydroxymethylamide group, an alkoxymethylamide group, and an alkoxysilyl group.

  The cinnamic acid derivative derived from the component (A) is sublimated by thermal reaction between the carboxyl group generated by the separation of the protective group from the cinnamic acid ester of the component (A) and the crosslinkable substituent of the component (B-2). Can be suppressed. Then, the cured film forming composition of the present embodiment can form, as a cured film, an alignment material having high photoreaction efficiency, as described above.

  In the following, the crosslinkable substituent, the hydroxy group, the carboxyl group, the amide group, the amino group, the alkoxysilyl group and the group represented by the formula (2) will be collectively referred to as a “specific functional group”.

  In the polymer of the component (B-2), the content of the crosslinkable substituent is preferably 0.5 to 1 per 1 unit of the repeating unit of the component (B-2), and the solvent resistance of the aligning material. From the viewpoint of sex, the number is more preferably 0.8 to 1.

The polymer as the component (B-2) is, for example, substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide and the like. Polymers produced using acrylamide compounds or methacrylamide compounds can be used.
Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.

Further, as the component (B-2), a polymer produced by using a compound having an alkoxysilyl group can also be used.
Examples of such a polymer include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, poly (3-acryloxypropyltrimethoxysilane), 3 Examples thereof include a copolymer of acryloxypropyltrimethoxysilane and methyl methacrylate.

Further, in the specific (co) polymer 2 used in the cured film forming composition of the present embodiment, a monomer having a specific functional group (the above-mentioned crosslinkable substituent, hydroxy group, carboxyl group, amide group, amino group, alkoxy group) is used. A monomer copolymerizable with a silyl group and a monomer having at least one of the groups represented by the above formula (2) (that is, a monomer having no specific functional group, hereinafter, a monomer having a non-reactive functional group) (Also referred to as)) can be used in combination.
Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Specific examples of the above-mentioned monomer are as described in the illustration of specific examples of the component (B-1).

The method for obtaining the specific (co) polymer 2 used in the cured film-forming composition of the present embodiment is not particularly limited, but for example, a monomer having a specific functional group (that is, the crosslinkable substituent, the hydroxy group, the carboxyl group, In a solvent in which an amide group, an amino group, an alkoxysilyl group, and a monomer having at least one of the groups represented by the above formula (2)), a monomer having a non-reactive functional group, a polymerization initiator, and the like coexist. In, a polymerization reaction is performed at a temperature of 50 ° C to 110 ° C. At that time, the solvent to be used is not particularly limited as long as it dissolves the monomer having a specific functional group, the monomer having a non-reactive functional group optionally used, a polymerization initiator and the like. Specific examples thereof include the solvents described below for the solvent.
The specific (co) polymer 2 thus obtained is usually in the state of a solution dissolved in a solvent.

  In addition, the solution of the specific (co) polymer 2 obtained as described above is re-precipitated by throwing it under stirring with diethyl ether, water or the like, and the formed precipitate is filtered and washed, and then at normal pressure. Alternatively, the powder of the specific (co) polymer 2 can be obtained by drying at room temperature or by heating under reduced pressure. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific (co) polymer 2 can be removed, and as a result, a purified powder of the specific (co) polymer 2 is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  In the cured film-forming composition of the present embodiment, the powder of the specific (co) polymer 2 may be used as it is, or the powder may be redissolved in, for example, a solvent described below to form a solution. You may use.

  Further, in the present embodiment, the polymer as the component (B-2) may be a mixture of a plurality of types of the specific (co) polymer 2.

The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 1,000 to 200,000, more preferably 1,000 to 100,000, and further preferably 2,000 to 50,000.
These polymers may be used alone or in combination of two or more.

（式中、Ｒ²¹は水素原子または炭素原子数１乃至４のアルキル基を表し、ｎ１は繰り返し単位の数を表す自然数である。）[(B-3) component]
The melamine-formaldehyde resin as the component (B-3) is a resin obtained by polycondensing melamine and formaldehyde and is represented by the following formula.

(In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n 1 is a natural number representing the number of repeating units.)

In the melamine-formaldehyde resin as the component (B-3), the methylol group (—CH ₂ —OH) produced during polycondensation of melamine and formaldehyde is O-alkylated from the viewpoint of storage stability (—CH _2- O-alkyl groups) are preferred.

  The method for obtaining the melamine-formaldehyde resin as the component (B-3) is not particularly limited, but generally, melamine and formaldehyde are mixed and made weakly alkaline with sodium carbonate, ammonia or the like, and then at 60 ° C to 100 ° C. It is synthesized by heating. Further, the methylol group can be alkoxylated by reacting with alcohol.

  The melamine formaldehyde resin as the component (B-3) has a weight average molecular weight of preferably 250 to 5,000, more preferably 300 to 4,000, and further preferably 350 to 3,500. If the weight average molecular weight is more than 5000 and is too large, the solubility in a solvent may be lowered and the handling property may be lowered. If the weight average molecular weight is less than 250 and is too small, insufficient curing may occur during heat curing. In some cases, the effect of improving solvent resistance and heat resistance may not be fully exhibited.

  In the embodiment of the present invention, the melamine formaldehyde resin as the component (B-3) may be used in a liquid form or in a solution form in which a purified liquid is redissolved in a solvent described later.

  Further, in the embodiment of the present invention, the component (B) may be a mixture of plural kinds of polymers selected from (B-1), (B-2) and (B-3).

[(C) component]
The composition of the present invention contains a crosslinking agent as the component (C).

  More specifically, the cross-linking agent of the component (C) is a compound that reacts with the above-mentioned component (A) or component (B), or both of them, and that reacts at a temperature lower than the sublimation temperature of the component (A). Further, when the cured film forming composition of the present embodiment contains an adhesion component as the component (E) described later, the component (C) can react with the component (E).

  The component (C) is separated from the cinnamic acid ester of the component (A) at a temperature lower than the sublimation temperature of the cinnamic acid derivative formed by the separation of the protective group from the cinnamic acid ester of the component (A). Produced carboxyl group, component (B): at least one selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group in the polymer (B-1) and a group represented by the above formula (2). One group, (B-2) a crosslinkable substituent in the polymer, (B-3) a (O-alkylated) methylol group in the polymer, and (B) in the compound of the component (D) described later. -1) Substituent (at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amido group, an amino group, an alkoxysilyl group and a group represented by the formula (2)) or the (B-1) Replacement Binds to at least one group that reacts with.

  Examples of the cross-linking agent that is the component (C) include compounds such as epoxy compounds, methylol compounds, and isocyanate compounds, with methylol compounds being preferred.

  Specific examples of the methylol compound described above include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

  Specific examples of the alkoxymethylated glycoluril include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4. , 6-Tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone and the like can be mentioned. As commercially available products, compounds such as glycoluril compound (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN (registered trademark) 10S60, U-VAN (registered trademark) 10R, U-VAN (registered trademark) 11HV), manufactured by DIC Corporation. Examples include urea / formaldehyde resin (highly condensed type, trade name: Beckamine (registered trademark) J-300S, P-955, N).

  Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine and the like. As commercially available products, manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicalac (registered trademark) BX-4000, BX-37, BL-37) 60, the same BX-55H) and the like.

  Specific examples of the alkoxymethylated melamine include hexamethoxymethylmelamine and the like. As commercially available products, Mitsui Cytec Co., Ltd. methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade name: Nicalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-). 002, the same MX-730, the same MX-750, the same MX-035), butoxymethyl type melamine compound (trade name: Nicalac (registered trademark) MX-45, the same MX-410, the same MX-302) and the like. .

  Further, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 may be mentioned. Examples of commercial products of the melamine compound include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.) and the like, and examples of commercial products of the benzoguanamine compound include commercial name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd., etc. may be mentioned.

Further, as the component (C), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide or N-butoxymethylmethacrylamide, or Polymers produced using methacrylamide compounds can also be used. In this case, when the component (B) is the component (B-2), the component (C) may be the same as the component (B-2).
Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include copolymers of methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and further preferably 3,000 to 50,000.

  These cross-linking agents can be used alone or in combination of two or more kinds.

  The content of the crosslinking agent as the component (C) in the composition of the present invention is 10 parts by mass to 400 parts by mass based on 100 parts by mass of the total amount of the cinnamic acid ester as the component (A) and the polymer as the component (B). The amount is preferably parts by mass, more preferably 15 parts by mass to 200 parts by mass. When the component (B) is the component (B-2) and the components (C) and (B-2) are the same (the same compound), the blending amount of the component (C) is (B). It is assumed as the blending amount of the components (in this case, the blending amount of the component (C) is 0).

  When the content of the cross-linking agent is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film-forming composition decrease, and the alignment sensitivity during photo-alignment decreases. On the other hand, if the content is too large, the photo-alignment property and storage stability may decrease.

[(D) component]
The cured film-forming composition of the present invention is a compound having a thermally crosslinkable group and a polymerizable group with any of the components (A), (B), and (C), that is, one or more polymerizable compounds. Group and the (B-1) substituent (at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amido group, an amino group, an alkoxysilyl group and a group represented by the formula (2)) or A compound having at least one group that reacts with the (B-1) substituent can be contained as the component (D).
When a cured film formed from the cured film-forming composition of the present invention containing the component (D) is used as an alignment material, the compound of the component (D) is a cured polymerizable resin formed on the cured film. It enhances the adhesiveness between the liquid crystal layer and the layer, that is, acts as an adhesiveness improving component.

  The compound as the component (D) is preferably a compound having a polymerizable group containing a C = C double bond and a hydroxy group, and a compound having a polymerizable group containing a C = C double bond and an N-alkoxymethyl group. It is a compound. Examples of the polymerizable group containing a C = C double bond include an acrylic group, a methacrylic group, a vinyl group, an allyl group, and a maleimide group.

  Preferred examples of the compound having a C = C double bond-containing polymerizable group and a hydroxy group of the component (D) are shown below. The compound of the component (D) is not limited to the following compound examples.

（式中、Ｒ⁴¹は水素原子又はメチル基を表し、ｍは１乃至１０の整数を表す。）

(In the formula, R ⁴¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.)

  In the compound having a C = C double bond-containing polymerizable group and an N-alkoxymethyl group of the component (D), N of the N-alkoxymethyl group, that is, a nitrogen atom, is an amide nitrogen atom or a thioamide nitrogen atom. , A urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen atom bonded to a nitrogen-containing heterocycle. Therefore, the N-alkoxymethyl group is selected from amide nitrogen atom, thioamide nitrogen atom, urea nitrogen atom, thiourea nitrogen atom, urethane nitrogen atom, and nitrogen atom bonded to a nitrogen-containing heterocycle. Examples include a structure in which an alkoxymethyl group is bonded to a nitrogen atom.

  The compound having a C = C double bond-containing polymerizable group and an N-alkoxymethyl group of the component (D) may be one having the above groups, but is preferably, for example, the following formula (X): The compound represented by

（式中、Ｒ¹¹は水素原子又はメチル基を表し、Ｒ¹²は水素原子、若しくは直鎖又は分岐の炭素原子数１乃至１０のアルキル基を表す）

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.)

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methyl-n. -Butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl- n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl- n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2 , 3-dimethyl-n-butyl group, 3, -Dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group Group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group , 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n -Pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n- Pentyl group, 1-methyl-1-ethyl-n-butyl group, -Methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group , N-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl- n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1 -Ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group Group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl Examples include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, and n-decyl group. To be

  Specific examples of the compound represented by the above formula (X) include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide and the like. .

  As another aspect of the compound having a C = C double bond-containing polymerizable group and an N-alkoxymethyl group of the component (D), preferably, for example, a compound represented by the following formula (X2) can be mentioned. .

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group.
R ⁵² represents an alkyl group having 1 to 20 carbon atoms, a monovalent aliphatic ring group having 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, The structure may contain an ether bond.
R ⁵³ is a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic cyclic group having 5 to 6 carbon atoms, or a divalent group containing an aliphatic ring having 5 to 6 carbon atoms. Represents an aliphatic group and may have an ether bond in the structure.
R ⁵⁴ is a linear or branched divalent to 9-valent aliphatic group having 1 to 20 carbon atoms, a divalent to 9-valent aliphatic cyclic group having 5 to 6 carbon atoms, or 5 carbon atoms. It represents a divalent to 9-valent aliphatic group containing an aliphatic ring of 6 to 6, and one methylene group or a plurality of non-adjacent methylene groups of these groups may be replaced with an ether bond.
Z is> NCOO-, or -OCON <(where "-" indicates that there is one bond. Also, ">" and "<" indicate that there are two bonds, and It represents that an alkoxymethyl group (that is, -OR ⁵² group) is bonded to either one of the bonds.
r is a natural number of 2 or more and 9 or less.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ include a divalent group obtained by removing one hydrogen atom from an alkyl group having 2 to 20 carbon atoms.
Further, as a specific example of the divalent to 9-valent aliphatic group having 1 to 20 carbon atoms in the definition of R ⁵⁴ , 1 to 8 hydrogen atoms are further removed from the alkyl group having 1 to 20 carbon atoms. A divalent to 9-valent group is mentioned.

  The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group and i-butyl. Group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl- n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1, 1,2-trimethyl-n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group , N-pentadecyl group, n-hexadecyl group, n Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, a group in which one or more of them are bonded in a range of up to 20 carbon atoms, and one of these groups An example is a methylene group or a group in which a plurality of methylene groups that are not adjacent to each other are replaced with ether bonds.

Of these, an alkylene group having 2 to 10 carbon atoms is preferable, R ⁵³ is an ethylene group, and R ⁵⁴ is a hexylene group is particularly preferable from the viewpoint of availability of raw materials.

Specific examples of the alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include a specific example of the alkyl group having 2 to 20 carbon atoms in the definition of R ⁵³ and a methyl group. Of these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group or an n-butyl group is particularly preferable.

  Examples of r include natural numbers of 2 or more and 9 or less, and among them, 2 to 6 are preferable.

Compound (X2) can be obtained by the production method represented by the following reaction scheme. That is, a carbamate compound having an acrylic group or a methacryl group represented by the following formula (X2-1) (hereinafter, also referred to as compound (X2-1)) is reacted in a solvent containing trimethylsilyl chloride and paraformaldehyde. Then, an intermediate represented by the following formula (X2-2) is synthesized, and an alcohol represented by R ⁵² —OH is added to the reaction solution to cause a reaction to be produced.

（式中、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³、Ｒ⁵⁴、Ｚ及びｒは前記の意味を表し、Ｘは−ＮＨＣＯＯ−または−ＯＣＯＮＨ−を表す。）

(In the formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , Z and r represent the above meanings, and X represents —NHCOO— or —OCONH—.)

  The amounts of trimethylsilyl chloride and paraformaldehyde used with respect to compound (X2-1) are not particularly limited, but in order to complete the reaction, trimethylsilyl chloride is 1.0 to 6.0 equivalent times with respect to one carbamate bond in the molecule, Paraformaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and the equivalent of trimethylsilyl chloride used is more preferably greater than the equivalent of paraformaldehyde used.

  The reaction solvent is not particularly limited as long as it is inert to the reaction, for example, hydrocarbons such as hexane, cyclohexane, benzene, toluene; methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane, etc. Halogenated hydrocarbons; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane and tetrahydrofuran; nitriles such as acetonitrile and propionitrile; N, N-dimethylformamide, N, N-dimethylacetamide, N -Nitrogen-containing aprotic polar solvents such as -methyl-2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; pyridines such as pyridine and picoline. These solvents may be used alone or two or more of them may be mixed and used. Preferred are methylene chloride and chloroform, and more preferred is methylene chloride.

  The amount of the solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent, and when a solvent is used, it is 0.1 to 100 mass relative to the compound (X2-1). Double solvent may be used. The amount is preferably 1 to 30 times by mass, more preferably 2 to 20 times by mass.

  The reaction temperature is not particularly limited, but is, for example, −90 to 200 ° C., preferably −20 to 100 ° C., and more preferably −10 to 50 ° C.

  The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

  The reaction can be carried out under normal pressure or under pressure, and may be a batch system or a continuous system.

  A polymerization inhibitor may be added during the reaction. As such a polymerization inhibitor, BHT (2,6-di-tert-butyl-para-cresol), hydroquinone, para-methoxyphenol or the like can be used, and it inhibits the polymerization of acrylic group and methacrylic group. If there is no particular limitation.

  The addition amount of the polymerization inhibitor is not particularly limited, but is 0.0001 to 10 wt%, preferably 0.01 to 1 wt% with respect to the total amount (mass) of the compound (X2-1). is there. In this specification, wt% means mass%.

  In the step of reacting the intermediate (X2-2) with alcohol, a base may be added in order to suppress hydrolysis under acidic conditions. Examples of the base include pyridines such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and tributylamine. Preferred are triethylamine and diisopropylethylamine, and more preferred is triethylamine. The addition amount of the base is not particularly limited, but may be 0.01 to 2.0 equivalent times, more preferably 0.5 to 1 equivalent to the addition amount of trimethylsilyl chloride used in the reaction. 0.0 equivalent.

  Moreover, after obtaining the intermediate (X2-2) from the compound (X2-1), alcohol may be added and reacted without isolating the intermediate (X2-2).

  The synthesis method of the compound (X2-1) is not particularly limited, but it is produced by reacting a (meth) acryloyloxyalkyl isocyanate with a polyol compound or by reacting a hydroxyalkyl (meth) acrylate compound with a polyisocyanate compound. You can do it.

  Specific examples of the (meth) acryloyloxyalkyl isocyanate include 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz MOI [registered trademark]), 2-acryloyloxyethyl isocyanate (Showa Denko). A product name: Karens AOI [registered trademark] manufactured by Denko Co., Ltd., etc. may be mentioned.

  Specific examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, Examples thereof include diol compounds such as 1,6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, and diglycerin.

  Specific examples of the hydroxyalkyl (meth) acrylate compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate and diethylene glycol. Examples thereof include monomers having a hydroxy group such as monoacrylate, diethylene glycol monomethacrylate, poly (ethylene glycol) ethyl ether acrylate, and poly (ethylene glycol) ethyl ether methacrylate.

  Specific examples of the polyisocyanate compound include hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), ω, ω. Alicyclic diisocyanate such as'-diisocyanate dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanate such as bicycloheptane triisocyanate.

  These (meth) acryloyloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth) acrylate compounds and polyisocyanate compounds are generally commercially available and can be synthesized by known methods.

  Further, in the cured film-forming composition of the present invention, the component (D) may be a mixture of a plurality of types of compounds of the component (D).

  When a cured film formed from the cured film-forming composition of the present invention containing the component (D) is used as a liquid crystal alignment film, the compound of the component (D) is formed on the liquid crystal alignment film (cured film) and the liquid crystal alignment film (cured film). The polymerizable functional group of the polymerizable liquid crystal and the cross-linking reaction site contained in the liquid crystal alignment film can be linked by a covalent bond so as to improve the adhesion to the layer of the polymerizable liquid crystal. As a result, the retardation material of the present embodiment, which is obtained by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under the condition of high temperature and high quality, such as peeling. It can exhibit high durability against.

  The content of the component (D) in the cured film-forming composition of the present invention is as follows: the cinnamic acid ester as the component (A), the polymer as the component (B), the crosslinking agent as the component (C), and the component (E). It is preferably 0.01 parts by mass or more and 100 parts by mass or less, and more preferably 50 parts by mass or less with respect to 100 parts by mass in total of the crosslinking catalyst. When the content of the component (D) is more than 100 parts by mass, the photo-alignment property and solvent resistance of the cured film may deteriorate.

[(E) component]
The composition of the present invention can further contain a crosslinking catalyst as the component (E) in addition to the components (A), (B) and (C) described above.

  The crosslinking catalyst that is the component (E) can be, for example, an acid or a thermal acid generator. The component (E) is effective in promoting a thermosetting reaction in the formation of a cured film using the composition of the present invention.

  When an acid or thermal acid generator is used as the component (E), the component (E) is a compound containing a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that thermally decomposes to generate an acid during pre-baking or post-baking, that is, a temperature of 80. The compound is not particularly limited as long as it is a compound that thermally decomposes to generate an acid at ℃ to 250 ℃.

  Examples of such a compound include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluorosulfonic acid. Rmethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, Sulfonic acids such as 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, hydrates or salts thereof, etc. Is mentioned.

  Examples of the compound that generates an acid by heat include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl p-toluenesulfonate, o-nitrobenzyl p-toluenesulfonate, 1,2,3-Phenylene tris (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluene sulfone Acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p Toluenesulfonate, 2-hydroxybutyl p- toluenesulfonate, N- ethyl-4-toluenesulfonamide, and the following formula [TAG-1] to may be mentioned a compound represented by such formula [TAG-41].

  The content of the component (E) in the composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the total amount of the cinnamic acid ester as the component (A) and the polymer as the component (B). Parts to 10 parts by mass, more preferably 0.05 parts to 8 parts by mass, and further preferably 0.1 parts to 6 parts by mass. When the content of the component (E) is 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Further, when the amount is 10 parts by mass or less, the storage stability of the cured film forming composition can be improved.

[Other additives]
The composition of the present invention may contain other additives as long as the effects of the present invention are not impaired.
As the other additive, for example, a sensitizer can be contained. The sensitizer is effective in promoting the photoreaction when forming the cured film of the embodiment of the present invention from the composition of the present invention.

  Examples of the sensitizer include derivatives such as benzophenone, anthracene, anthraquinone and thioxanthone, and nitrophenyl compounds. Among these, N, N-diethylaminobenzophenone which is a derivative of benzophenone and 2-nitrofluorene which is a nitrophenyl compound, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4- Nitrostilbene, 4-nitrobenzophenone, 5-nitroindole are particularly preferred.

  These sensitizers are not particularly limited to those mentioned above. These can be used alone or in combination of two or more compounds.

  In the embodiment of the present invention, the use ratio of the sensitizer is preferably 0.1 parts by mass to 20 parts by mass, and more preferably 0.2 parts by mass to 100 parts by mass of the component (A). 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance of the formed cured film may decrease or the coating film may become rough. I have something to do.

  Further, the composition of the present invention, as long as it does not impair the effects of the present invention, as other additives, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, Antioxidants and the like can be contained.

[solvent]
The composition of the present invention is often used in the form of a solution dissolved in a solvent. The solvent used at that time is a solvent that dissolves the component (A), the component (B) and the component (C), and if necessary, the component (D), the component (E), and / or other additives. There is no particular limitation on the type and structure of the solvent as long as it has such a dissolving ability.

  Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether. Acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2 -Ethyl hydroxypropionate, 2-hydroxy-2- Ethyl chloropropionate, Ethyl ethoxyacetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Methyl 3-ethoxypropionate , Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone.

  These solvents can be used alone or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, 3-methoxypropione. Ethyl acid, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate are more preferable because they have good film-forming properties and high safety.

<Preparation of cured film forming composition>
The composition of the present invention is a thermosetting cured film forming composition having photoalignment. As described above, the composition of the present invention comprises the cinnamic acid ester as the component (A), the polymer as the component (B) [(B-1): hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group. A polymer having at least two groups selected from the group consisting of groups and groups represented by the above formula (2), (B-2): hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group. And at least one polymer selected from the group consisting of the group represented by the formula (2), which is capable of thermally reacting with at least one group and self-crosslinking, or (B-3): melamine formaldehyde resin. Of the polymer] and a cross-linking agent which is the component (C). Further, as the component (D), at least one selected from the group consisting of one or more polymerizable groups, a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2). A compound having one group A or at least one group reactive with the group A can be contained. Further, a crosslinking catalyst can be contained as the component (E). And, as long as the effects of the present invention are not impaired, other additives may be contained, and further, a solvent may be contained.

  The mixing ratio of the components (A) and (B) is preferably 5:95 to 60:40 in terms of mass ratio. If the content of the component (B) is too large, the liquid crystal alignment is likely to decrease, and if it is too small, the solvent resistance is reduced and the alignment is likely to be decreased.

  Preferred examples of the composition of the present invention are as follows.

  [1]: based on 100 parts by mass of the total amount of the components (A) and (B), the compounding ratio of the components (A) and (B) is 5:95 to 60:40 by mass ratio. A cured film-forming composition containing 10 parts by mass to 400 parts by mass of component (C).

  [2]: The blending ratio of the component (A) and the component (B) is 5:95 to 60:40 by mass, and based on 100 parts by mass of the total amount of the component (A) and the component (B). A cured film-forming composition containing 10 parts by mass to 400 parts by mass of component (C) and a solvent.

  [3]: based on 100 parts by mass of the total amount of the components (A) and (B), the compounding ratio of the components (A) and (B) is 5:95 to 60:40. A cured film-forming composition containing 10 parts by mass to 400 parts by mass of the component (C), 0.01 parts by mass to 10 parts by mass of the component (E), and a solvent.

  [4]: The mixing ratio of the components (A) and (B) is 5:95 to 60:40 in terms of mass ratio, and based on 100 parts by mass of the total amount of the components (A) and (B). 10 parts by mass to 400 parts by mass of the component (C), 0.01 parts by mass to 10 parts by mass of the component (E), and the components (A), (B), (C) and (E). The cured film forming composition contains 0.01 part by mass or more and 100 parts by mass or less of the component (D) and a solvent based on 100 parts by mass of the total amount.

The compounding ratio, the preparation method and the like when the composition of the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 80% by mass, preferably 3% by mass to The content is 60% by mass, and more preferably 5% by mass to 40% by mass. Here, the solid content refers to all components of the cured film-forming composition excluding the solvent.

  The method for preparing the composition of the present invention is not particularly limited. As a preparation method, for example, a solution of the component (B) dissolved in a solvent is mixed with the components (A) and (C), and further the components (D) and (E) at a predetermined ratio to obtain a uniform solution. Or a method in which other additives are further added and mixed, if necessary, at an appropriate stage of this preparation method.

  In the preparation of the composition of the present invention, the solution of the specific (co) polymer 1 and / or the specific (co) polymer 2 obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, the component (A) and the component (C) as well as the component (D), the component (E), etc. are added to the solution of the component (B) to form a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (B) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.

  The prepared solution of the cured film-forming composition is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Cured film, alignment material and retardation material>
A solution of the composition of the present invention is applied to a substrate (eg, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, a quartz substrate, an ITO substrate, etc.). Or film (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc. on a bar coat, spin coat, flow coat, roll coat, slit coat, slit coat Then, spin coating, inkjet coating, printing, etc. are applied to form a coating film, and then the coating film is heated and dried with a hot plate, an oven or the like to form a cured film.

  The heating and drying conditions may be such that the curing reaction proceeds to such an extent that the components of the alignment material formed from the cured film do not elute into the polymerizable liquid crystal solution applied thereon, for example, a temperature of 60 ° C. to 200 ° C. The heating temperature and the heating time are appropriately selected from the range of 0.4 minutes to 60 minutes. The heating temperature and the heating time are preferably 70 ° C. to 160 ° C. and 0.5 minutes to 10 minutes.

  The film thickness of the cured film formed by using the composition of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected in consideration of the steps of the substrate to be used and optical and electrical properties.

  The cured film thus formed can be made to function as a member for orienting an aligning material, that is, a compound having a liquid crystallinity including a polymerizable liquid crystal by irradiating polarized UV.

  As a method of irradiating polarized UV, ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used, and is performed by irradiating linearly polarized light from a vertical or oblique direction at room temperature or in a heated state.

  Since the alignment material formed from the composition of the present invention has solvent resistance and heat resistance, after applying a retardation material composed of a polymerizable liquid crystal solution onto this alignment material, the phase transition of the liquid crystal The retardation material is brought into a liquid crystal state by heating to the temperature and is aligned on the alignment material. Then, the retardation material in the desired alignment state can be cured as it is to form a retardation material having a layer having optical anisotropy.

  As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. When the substrate on which the alignment material is formed is a film, the film having the retardation material of the present embodiment is useful as a retardation film. There is a phase difference material forming such a phase difference material which is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment or hybrid alignment on the alignment material. It can be used properly according to the phase difference characteristics.

  Further, in the case of producing a patterned retardation material used for a 3D display, a cured film formed from the composition of the present invention by the above-mentioned method is subjected to a predetermined standard via a line-and-space pattern mask, For example, an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed by exposing polarized UV to a direction of +45 degrees and then exposing the polarized UV to a direction of -45 degrees after removing the mask. To form. Then, after applying a retardation material composed of a polymerizable liquid crystal solution, the retardation material is brought into a liquid crystal state by heating to the phase transition temperature of the liquid crystal. The polymerizable liquid crystal in the liquid crystal state is aligned on the alignment material in which two types of liquid crystal alignment regions are formed, and forms alignment states corresponding to the respective liquid crystal alignment regions. Then, the phase difference material in which such an alignment state is realized is cured as it is, the above alignment state is fixed, and a plurality of two types of phase difference regions having different phase difference characteristics are regularly arranged. It is possible to obtain a chemical retardation material.

Moreover, the alignment material formed from the composition of the present invention can be used as a liquid crystal alignment film of a liquid crystal display device. For example, using two substrates having the alignment material of the present embodiment formed as described above, the alignment materials on both substrates are bonded to each other via a spacer, and By injecting liquid crystal into the liquid crystal, a liquid crystal display device in which the liquid crystal is aligned can be manufactured.
Therefore, the composition of the present invention can be suitably used for manufacturing various retardation materials (retardation films), liquid crystal display elements and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The abbreviations of the components are as follows.

<Component (A), component (B), component (C): raw material>
M6CA: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid 4MeOCA: 4-methoxycinnamic acid CN1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid methyl CN2: 4-methoxy Methyl cinnamate HEMA: 2-hydroxyethyl methacrylate MAA: Methacrylic acid MMA: Methyl methacrylate BMAA: N-Butoxymethylacrylamide AIBN: α, α′-azobisisobutyronitrile

HMM: Melamine cross-linking agent represented by the following structural formula [CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.]]

（上記式中、Ｒは、アルキレン基を表す。）PEPO: Polyester polyol polymer (adipic acid / diethylene glycol copolymer having the following structural unit. Molecular weight 4,800)

(In the above formula, R represents an alkylene group.)

PUA: Polyurethane graft acrylic polymer [Acryt (registered trademark) 8UA-301 (manufactured by Taisei Fine Chemical Co., Ltd.)]
PCDO: Polycarbonate diol [C-590 (manufactured by Kuraray Co., Ltd.)]
HPC: Hydroxypropyl cellulose [NISSO HPC SSL (manufactured by Nippon Soda Co., Ltd.), molecular weight 40,000]

<Component (D): Crosslinking catalyst component>
PTSA: p-toluenesulfonic acid

ＤＭ−２：<Component (E): adhesion component>
80MFA: Epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.)
BMAA: N-butoxymethylacrylamide DM-1:

DM-2:

<Solvent>
Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), methyl ethyl ketone (MEK), 2-propanol (IPA) and ethyl lactate (EL) were used as the solvent. .

<Measurement of molecular weight of polymer>
The molecular weight of the acrylic copolymer in the polymerization example is as follows using a Shodex Co. room temperature gel permeation chromatography (GPC) device (GPC-101) and a Shodex column (KD-803, KD-805). Was measured.
The number average molecular weight (hereinafter, referred to as Mn) and the weight average molecular weight (hereinafter, referred to as Mw) described below were expressed in terms of polystyrene.
Column temperature: 50 ° C
Eluent: N, N-a-dimethylformamide (additive, lithium bromide - hydrate (LiBr-H ₂ O) is 30 mmol / L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF is 10 mL / L)
Flow rate: 1.0 mL / min Standard sample for creating a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (manufactured by Polymer Laboratory Co., Ltd.) Molecular weight is about 12,000, 4,000, 1,000).

< ¹ H-NMR measurement>
^The analyzer and analysis conditions used for ¹ H-NMR analysis are as follows.
Nuclear magnetic resonance apparatus: Varian NMR System 400 NB (400 MHz)
Measurement solvent: DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm for ¹ H)

<Polymerization example 1>
7.0 g of MMA, 7.0 g of HEMA, 3.5 g of MAA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 53.9 g of PM and reacted at 70 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration). 25 mass%) (PB1) was obtained. The obtained acrylic copolymer had Mn of 10,300 and Mw of 24,600.

<Polymerization example 2>
MMA 9.0 g, HEMA 1.0 g, and AIBN 0.1 g as a polymerization catalyst were dissolved in PM 40.4 g and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20% by mass) ( PB2) was obtained. The obtained acrylic copolymer had Mn of 15,900 and Mw of 29,900.

<Polymerization example 3>
100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration 35% by mass) (PC1). The obtained acrylic copolymer had Mn of 2,700 and Mw of 3,900.

<Synthesis of component (A)>
Synthesis Example 1: Synthesis of compound [AM-1]

Tetrahydrofuran (THF) 105 g, M6CA 20.5 g (0.06 mol), ethyl vinyl ether 5.35 g (0.07 mol), and pyridinium paratoluenesulfonate (Py-PTS) 0.47 g (1.90 mmol) in a 200 mL one-necked flask. Was charged at room temperature, and the mixture was reacted for 14 hours at room temperature (RT) with magnetic stirring. Purification operation was performed using an evaporator, liquid separation, filtration and the like to obtain the target product [AM-1] (23.5 g, 0.058 mol, yield 94.0%). The structure of the compound [AM-1] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ7.62 (m, 3H), 6.91 (dd, 2H), 6.43 (d, 1H), 5.96 (m, 2H), 5.61 (t. , 1H), 4.05 (t, 2H), 3.95 (t, 2H), 3.61 (q, 1H), 3.48 (q, 1H), 1.83 (s, 3H), 1 64 (m, 4H), 1.33 (m, 7H), 1.09 (t, 3H).

Synthesis Example 2: Synthesis of compound [AM-2]

In a 200 mL one-necked flask, 106 g of THF, 19.2 g (0.06 mol) of M6CA, 6.95 g (0.07 mol) of butyl vinyl ether, and 0.44 g (1.70 mmol) of pyridinium paratoluenesulfonate (Py-PTS) at room temperature. After charging, the mixture was reacted at room temperature under magnetic stirring for 14 hours. Purification operation was performed using an evaporator, liquid separation, filtration and the like to obtain the target product [AM-2] (22.5 g, 0.052 mol, yield 90.0%). The structure of the compound [AM-2] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ7.62 (m, 3H), 6.96 (dd, 2H), 6.48 (d, 1H), 5.99 (m, 2H), 5.66 (t. , 1H), 4.10 (t, 2H), 4.02 (t, 2H), 3.60 (q, 1H), 3.48 (q, 1H), 1.88 (s, 3H), 1 .69 (m, 4H), 1.34 (m, 11H), 0.87 (t, 3H).

Synthesis Example 3: Synthesis of compound [AM-3]

In a 200 mL one-necked flask, 107 g of THF, 18.1 g (0.05 mol) of M6CA, 8.24 g (0.07 mol) of cyclohexyl vinyl ether, and 0.41 g (1.60 mmol) of pyridinium paratoluenesulfonate (Py-PTS) at room temperature. After charging, the mixture was reacted at room temperature under magnetic stirring for 14 hours. Purification operation was performed using an evaporator, liquid separation, filtration and the like to obtain the target product [AM-3] (20.4 g, 0.044 mol, yield 81.6%). The structure of the compound [AM-3] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 7.60 (m, 3H), 6.96 (dd, 2H), 6.47 (d, 1H), 6.09 (m, 2H), 5.67 (t. , 1H), 4.10 (t, 2H), 4.02 (t, 2H), 3.52 (m, 1H), 1.88 (s, 3H), 1.77-1.17 (br, 21H).

Synthesis Example 4: Synthesis of compound [AM-4]

In a 200 mL one-neck flask, THF 110 g, 4MeOCA 12.8 g (0.07 mol), butyl vinyl ether 8.63 g (0.08 mol), and pyridinium paratoluenesulfonate (Py-PTS) 0.54 g (2.20 mmol) at room temperature. After charging, the mixture was reacted at room temperature under magnetic stirring for 14 hours. Purification operation was performed using an evaporator, liquid separation, filtration and the like to obtain the target product [AM-4] (20.4 g, 0.044 mol, yield 81.6%). The structure of the compound [AM-4] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 7.69 (m, 3H), 6.98 (dd, 2H), 6.497 (d, 1H), 5.98 (q, 1H), 3.80 (s. , 3H), 3.49 (m, 2H), 1.48 (quint, 2H), 1.37 (d, 3H), 1.31 (quint, 2H), 0.87 (t, 3H).

<Synthesis of component (E)>
Synthesis Example 5: Synthesis of compound [DM-1]

  Under a nitrogen stream, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, and 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) were placed in a 2 L four-necked flask. 1.80 g (11.8 mmol) and 2,6-di-tert-butyl-para-cresol (BHT) 0.45 g (2.04 mmol) were charged at room temperature, and the temperature was raised to 55 ° C. under magnetic stirring. Warmed. To the reaction solution, 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was dropped, and after stirring for 2 hours, the reaction solution was analyzed by high performance liquid chromatography, and the intermediate was 1% or less in area percentage. The reaction was completed in the open. After adding 328 g of hexane and cooling to room temperature, the precipitated solid was washed twice with 229 g of hexane and dried to obtain compound [A-a] (104 g, 0.260 mol, yield 86.7%). .

In a nitrogen stream, 1330 g of dichloromethane (CH ₂ Cl ₂ ), 100 g (0.250 mol) of compound [A-a] and 22.5 g (0.749 mol) of paraformaldehyde were charged into a ₂ L four-necked flask and placed in an ice bath. , Trimethylsilyl chloride (122 g, 1.12 mol) was added dropwise. After stirring for 2 hours, a mixed solution of 63.2 g (0.625 mol) of triethylamine and 240 g of methanol was added dropwise. After stirring for 30 minutes, the mixture was transferred to a 5 L separating funnel, and 1500 g of water was added to carry out a separating operation. The obtained organic layer was dried over magnesium sulfate, the magnesium sulfate was removed by filtration, and the obtained filtrate was concentrated and dried to obtain compound [DM-1] (110 g, 0.226 mol, yield 90. 3%). The structure of the compound [DM-1] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ6.42 (d, 2H J = 17.2), 6.17-6.08 (m, 2H), 5.86 (d, 2H J = 10.0), 4.77 (d, 4H J = 19.6), 4.30 (m, 4H), 4.12 (t, 4H J = 6.4), 3.61 (m, 4H), 3.30 ( d, 6H J = 12.8), 1.67 (m, 4H), 1.40 (m, 4H).

Synthesis Example 6: Synthesis of compound [DM-2]

  In a 500 mL four-necked flask under a nitrogen stream, ethyl acetate 35.0 g, toluene 87.0 g, hexamethylene diisocyanate 8.41 g (50.0 mmol), 1,8-diazabicyclo [5.4.0] -7- Undecene (DBU) 0.345 g (2.27 mmol) and 2,6-di-tert-butyl-para-cresol (BHT) 70.0 mg (0.318 mmol) were charged at room temperature, and the mixture was stirred with a magnetic stirrer. The temperature was raised to 60 ° C. A mixed solution of 12.8 g (111 mmol) of 2-hydroxyethyl acrylate and 26.0 g of toluene was added dropwise to the reaction solution, and the mixture was stirred for 1 hour and then at room temperature for 24 hours. 131 g of hexane was added and the mixture was immersed in an ice bath and cooled, and then the precipitated crystals were filtered and dried to obtain compound [Ab] (15.0 g, 37.4 mmol, yield 74.8%).

In a nitrogen stream, 200 g of dichloromethane (CH ₂ Cl ₂ ), 14.6 g (36.4 mmol) of compound [Ab] and 3.28 g (109 mmol) of paraformaldehyde were charged into a 300 mL four-necked flask, and the mixture was placed in an ice bath. Then, 23.7 g (218 mmol) of trimethylsilyl chloride was added dropwise. After stirring for 1 hour, 35.6 g of methanol was added dropwise and the mixture was stirred for 1 hour. The organic layer was washed with 300 mL of saturated aqueous sodium hydrogen carbonate solution, and the obtained aqueous layer was further washed with 200 g of dichloromethane. The solution obtained by mixing the two organic layers was further washed with 170 g of brine, and the obtained organic layer was dried over magnesium sulfate. Magnesium sulfate was removed by filtration, and the obtained dichloromethane solution was concentrated and dried to obtain the desired [DM-2] (16.2 g, 33.1 mmol, yield 91.0%). The structure of the compound [DM-2] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.

¹ H-NMR (CDCl ₃ ): δ 6.33 (d, 2H J = 17.2), 6.20-6.14 (m, 2H), 5.96 (d, 2H J = 10.4), 4.63 (s, 4H), 4.33 (m, 4H), 4.27 (m, 4H), 3.16-3.14 (br, 10H), 1.47 (m, 4H), 1 .20 (m, 4H).

<Examples 1 to 15> and <Comparative examples 1 to 2>
The compositions shown in Table 1 were used to prepare the cured film forming compositions of Examples 1 to 15 and Comparative Examples 1 and 2. Next, a cured film was formed using each cured film forming composition, and the orientation of each of the obtained cured films was evaluated.

[Evaluation of orientation]
The cured film forming compositions of Examples and Comparative Examples were spin-coated on a non-alkali glass at 2000 rpm for 30 seconds using a spin coater, and then heat-dried at a temperature of 100 ° C. for 60 seconds on a hot plate to form a cured film. Formed. This cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure dose of 10 mJ / cm ² to form an alignment material. A horizontal alignment polymerizable liquid crystal solution RMS03-013C manufactured by Merck Ltd. was applied onto this alignment material using a spin coater, and then prebaked at 60 ° C. for 60 seconds on a hot plate to give a film thickness of 1.0 μm. Was formed. This coating film was exposed at 300 mJ / cm ² to prepare a retardation material. The retardation material on the manufactured substrate is sandwiched between a pair of polarizing plates, and the appearance of the retardation characteristics in the retardation material is observed. When the retardation is expressed without any defect, ○, the retardation is not expressed The thing was described as x.

[Evaluation result]
The results of the above evaluations are shown in Table 2.

In Examples 1 to 15, the retardation material could be formed with a low exposure amount of 10 mJ / cm ² . On the other hand, in Comparative Examples 1 and 2, liquid crystal alignment was not obtained.

  The cured film forming composition of the present invention is very useful as a liquid crystal alignment film for a liquid crystal display device and as an alignment material for forming an optically anisotropic film provided inside or outside the liquid crystal display device, and particularly 3D. It is suitable as a material for forming a patterned retardation material for a display. Furthermore, materials for forming a protective film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, a cured film such as a flat film and an insulating film, particularly an interlayer insulating film of a TFT type liquid crystal display element and a color filter It is also suitable as a material for forming a protective film or an insulating film of an organic EL element.

Claims (10)

(A) one or more kinds of cinnamic acid ester having a group represented by the following formula (1),

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, an aromatic group, R ¹ and R ³ , or R ² and R ³ may combine with each other to form a ring, and X ¹ represents a phenylene group which may be substituted with any substituent.)
(B) at least one polymer selected from the group consisting of the following (B-1) to (B-3),
(B-1): a polymer having at least two groups selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the following formula (2),

(In the formula, R ⁶² represents an alkyl group, an alkoxy group or a phenyl group.)
(B-2): capable of thermal reaction with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2), and self. Crosslinkable polymer, and (B-3): melamine formaldehyde resin,
And (C) a polymer prepared using an alkoxymethylated melamine, an alkoxymethylated glycoluril, an alkoxymethylated benzoguanamine, an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, and a hydroxymethyl group or an alkoxymethyl group. At least one cross-linking agent selected from the group consisting of polymers produced by using a substituted methacrylamide compound (provided that the component (B-1) is excluded. When it contains, it may be the same as the component (B-2).   The composition according to claim 1, further comprising (E) a crosslinking catalyst.   As component (D), at least one polymerizable group and at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2). The composition according to claim 1 or 2, further comprising a compound having A or at least one group reactive with the group A.   4. The composition according to claim 1, wherein the compounding ratio of the component (A) and the component (B) is 5:95 to 60:40 in mass ratio.   5. The composition according to claim 1, further comprising 10 parts by mass to 400 parts by mass of the component (C) based on 100 parts by mass of the total amount of the components (A) and (B). The composition according to the item.   It is characterized by containing 0.01 to 10 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of the cinnamic acid ester which is the component (A) and the polymer of the component (B). The composition according to any one of claims 2 to 5.   Based on 100 parts by mass of the total amount of the components (A), (B), (C) and (E), 0.01 to 100 parts by mass of the component (D) is contained. 7. A composition according to any one of claims 3 to 6 characterized.   A cured film formed using the cured film-forming composition according to claim 1.   An alignment material formed by using the cured film-forming composition according to any one of claims 1 to 7.   A retardation material comprising a cured film obtained from the cured film-forming composition according to claim 1.