WO2015056741A1

WO2015056741A1 - Composition for forming cured film, alignment material, and retardation material

Info

Publication number: WO2015056741A1
Application number: PCT/JP2014/077546
Authority: WO
Inventors: 伊藤　潤; 昇志郎湯川; 耕平後藤; 真畑中
Original assignee: 日産化学工業株式会社
Priority date: 2013-10-17
Filing date: 2014-10-16
Publication date: 2015-04-23
Also published as: TW201529669A; JP6429030B2; KR102333902B1; KR20160075515A; KR20210049950A; JPWO2015056741A1; TWI650356B; CN105659120A

Abstract

[Problem] To provide a composition for forming a cured film that is suitable for forming a cured film that has excellent liquid crystal alignment properties and adhesion durability, to provide an alignment material, and to use the alignment material to provide a retardation material. [Solution] A composition for forming a cured film that contains: (A) at least one substance selected from among low molecular weight compounds that comprise a photoalignable group and at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group, and the group that is represented by formula (2) (chemical formula (1)) and polymers that comprise a photoalignable group and a substituent that is selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the group that is represented by formula (2); (B) a polymer that comprises at least one substituent selected from among a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group, and the group that is represented by formula (2); (C) a crosslinking agent; and (D) a low molecular weight compound that comprises at least one polymerizable group having a C=C double bond per molecule thereof and at least one N-alkoxymethyl group. The composition for forming a cured film is used to form a cured film, and photoalignment technology is used to form the alignment material. A polymerizable liquid crystal is applied on the alignment material and cured in order to obtain the retardation material.

Description

Cured film forming composition, alignment material and retardation material

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

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

There are various 3D display methods for displaying 3D images, and lenticular lens methods, parallax barrier methods, and the like are known as methods that do not require dedicated glasses.
And as one of the display systems in which an observer wears glasses and observes a 3D image, a circularly polarized glasses system or the like is known (see, for example, Patent Document 1).

In the case of a circularly polarized glasses type 3D display, a retardation material is usually disposed on a display element such as a liquid crystal panel. In this retardation material, a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged, and a patterned retardation material is formed. Hereinafter, in the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics 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. Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-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-like retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

In the formation of alignment materials using the photo-alignment technology of liquid crystal panels, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials. . These resins have been reported to exhibit the ability to control the alignment of liquid crystals (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV (see Patent Documents 3 to 5).

Japanese Patent Laid-Open No. 10-232365 JP 2005-49865 A Japanese Patent No. 3611342 JP 2009-058584 A JP-T-2001-517719

As described above, the patterned retardation material is configured by laminating a cured polymerizable liquid crystal layer on a photo-alignment film that is an alignment material. And the patterned phase difference material which has such a laminated structure can be used for the structure of 3D display with the laminated state.

The 3D display is sometimes used as a home television, and is required to have high reliability, particularly durability over a long period of time. For this reason, durability is also required for components of 3D displays. Accordingly, the patterned phase difference agent also has long-term durability as well as being subjected to optical patterning with high accuracy and having high light transmission characteristics.

However, the conventional patterned retardation material has a problem in the adhesion between the photo-alignment film and the polymerizable liquid crystal layer. For example, between the photo-alignment film and the polymerizable liquid crystal layer, it is easy to peel off from the initial stage of formation, or it is excellent in adhesiveness at the initial stage of formation, but the adhesiveness is likely to deteriorate with the passage of time and easily peel off. There was something to be.

In particular, peeling between the photo-alignment film and the polymerizable liquid crystal layer, which occurs with the passage of time, becomes a defect in a 3D display that is actually used and causes the display quality of the 3D display to deteriorate. Accordingly, there is a need for a patterned phase difference material that is capable of high-precision optical patterning, has excellent light transmission characteristics, and has excellent durability. In particular, the adhesion between the photo-alignment film at the initial stage of formation and the polymerizable liquid crystal layer is excellent, and the durability for maintaining the excellent adhesion for a long period of time (hereinafter referred to as adhesion durability in the present specification). There is a need for a patterned retardation material comprising:

The present invention has been made based on the above knowledge 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 orientation and light transmission characteristics and excellent adhesion durability. In particular, when it is used as an alignment material and a polymerizable liquid crystal layer is disposed thereon, it exhibits excellent liquid crystal alignment and light transmission properties, and has a long adhesion with the polymerizable liquid crystal layer. It is to provide a cured film forming composition that can be maintained for a period and forms a cured film having excellent adhesion durability.

An object of the present invention is to provide an alignment material that is excellent in liquid crystal alignment and light transmission characteristics and excellent in adhesion durability.

An object of the present invention is to provide a retardation material capable of high-precision optical patterning and having excellent durability.

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

The first aspect of the present invention is:
(A) a low orientation having a photo-alignment group and at least one substituent 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) Polymer having molecular compound and photo-alignment group, and at least one substituent 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) At least one selected from

(Wherein R ⁶² represents an alkyl group, an alkoxy group or a phenyl group.)
(B) a polymer having at least one substituent 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);
(C) a crosslinking agent, and (D) a low molecular compound having at least one polymerizable group containing a C═C double bond and at least one N-alkoxymethyl group in one molecule. It relates to the cured film formation composition characterized by these.

In the first embodiment of the present invention, the component (A) is a low molecular compound having a photoalignment group and a hydroxy group and / or a carboxyl group, and a polymer having a photoalignment group and a hydroxy group and / or a carboxyl group. It is preferable that it is 1 type chosen from.

1st aspect of this invention WHEREIN: It is preferable that the compound of (D) component is a compound which has a structure represented by following formula (1).

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms),

1st aspect of this invention WHEREIN: It is preferable that the compound of (D) component is a compound which has a structure represented by following formula (X2).

[Wherein, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵³ is independently a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. It represents a divalent aliphatic group containing, and an ether bond may be included in the structure of these groups. R ⁵⁴ is a divalent to nonvalent radical having a structure in which 1 to 8 hydrogen atoms are further removed from a linear or branched alkyl group having 2 to 20 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent to a non-valent radical having a structure in which 1 to 8 hydrogen atoms are further removed from the group, or a divalent to a non-valent radical containing a C 5 to C 6 aliphatic ring, May contain an ether bond. R ⁵² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent aliphatic group, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond. Z is> NCOO-, or -OCON <(where "-" indicates that there is one bond, and ">" and "<" indicate that there are two bonds. N atom Any one of the bonds represents a bond with —CH ₂ OR ⁵² ). r is a natural number of 2 or more and 9 or less. ]

In the first aspect of the present invention, it is preferable to contain (E) a crosslinking catalyst.

The second aspect of the present invention relates to an alignment material characterized by being obtained using the cured film forming composition of the first aspect of the present invention.

The third aspect of the present invention relates to a retardation material characterized by having a cured film obtained from the cured film forming composition of the first aspect of the present invention.

According to the first aspect of the present invention, it is possible to provide a cured film forming composition suitable for forming a cured film having excellent liquid crystal orientation and light transmittance and excellent adhesion durability.

According to the second aspect of the present invention, it is possible to provide an alignment material that is excellent in liquid crystal alignment and light transmittance and excellent in adhesion durability.

According to the third aspect of the present invention, it is possible to provide a retardation material that is capable of high-precision optical patterning and excellent in durability.

As described above, an alignment material excellent in adhesion durability, in particular, an alignment excellent in adhesion durability with a cured polymerizable liquid crystal layer, in order to produce a patterned retardation material having excellent durability. There is a need for materials. And the cured film formation composition suitable for formation of the orientation material of such a performance is calculated | required.

As a result of intensive studies in order to meet the above requirements, the present inventor has found that a cured film obtained from a cured film-forming composition having a specific composition is excellent in light transmittance, and has a liquid crystal orientation by polarization exposure. It has been found that it can be used as an alignment material by showing liquid crystal alignment to be regulated. In addition, the present inventor shows excellent adhesion durability between the cured film obtained from the cured film-forming composition having the specific composition and the polymerizable liquid crystal layer polymerized and cured thereon. I found out. That is, the cured film obtained from the cured film-forming composition having a specific composition of the present invention can constitute a photo-alignment film having excellent adhesion durability with the polymerizable liquid crystal layer.

Hereinafter, the cured film forming composition of the present invention will be described in detail with specific examples of components and the like. The cured film and alignment material of the present invention using the cured film forming composition of the present invention, the retardation material formed using the alignment material, the liquid crystal display element, and the like will be described.

<Curing film forming composition>
The cured film forming composition of this embodiment of the present invention comprises (A) a photo-alignment group, 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 low molecular weight compound having at least one substituent selected from the group consisting of: a photoalignment group, a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the above formula (2) At least one selected from polymers having at least one substituent selected from the group consisting of: (B) a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the above formula (2) Polymer having at least one selected substituent, (C) crosslinker as component, and (D) polymerizability containing C═C double bond in one molecule The at least one of a and N- alkoxymethyl group having at least one low-molecular compound curable film-forming composition of the thermosetting containing. Furthermore, in addition to the component (A), the component (B), the component (C) and the component (D), a crosslinking catalyst can be contained as the component (E). Furthermore, other additives can be contained as long as the effects of the present invention are not impaired. Furthermore, a solvent can be contained.
Hereinafter, details of each component will be described.

[(A) component]
(A) component of the cured film formation composition of this embodiment is at least 1 type chosen from a low molecular photo-alignment component and a polymer photo-alignment component. First, the case where the component (A) is a low molecular photo-alignment component will be described below. The low molecular photo-alignment component that is the component (A) is a component that imparts photo-alignment to the cured film of the present embodiment obtained from the cured film-forming composition of the present embodiment. It becomes a low molecular photo-alignment component compared with the component polymer.

In the cured film forming composition of the present embodiment, the low molecular photoalignment component as the component (A) includes a photoalignment group, a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula ( A low molecular compound having at least one substituent selected from the group consisting of groups represented by 2) can be obtained.
In the present invention, the photo-alignment group means a functional group at a structural site that undergoes photodimerization or photoisomerization.

The structural part to be photodimerized that the low molecular compound of the component (A) can have as a photoalignment group is a part that forms a dimer by light irradiation. Specific examples thereof include a cinnamoyl group and a chalcone group. , A coumarin group, an anthracene group and the like. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity.

In addition, the photoisomerizable structural moiety that the low molecular compound of component (A) can have as a photoalignable group refers to a structural moiety that changes into a cis isomer and a trans isomer by light irradiation. Examples include an azobenzene structure, a stilbene structure, and the like. Of these, an azobenzene structure is preferred because of its high reactivity.
Furthermore, as the alkoxysilyl group in the present embodiment, a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a methoxydimethylsilyl group, An ethoxydimethylsilyl group etc. are mentioned.

A low molecular compound having a photo-alignment group and any one of a substituent selected from a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and a group represented by the above formula (2) is, for example, It is a compound represented by the following formula.

In the above formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and X ¹¹ is a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, an carbonyl, or their A structure in which one to three substituents selected from an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a combination thereof are bonded through one or two or more bonds selected from a combination Represents. X ¹² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded through a covalent bond, an ether bond, an ester bond, an amide bond, a urethane bond, a carbonyl, or a urea bond. .

In the above formula, X ¹³ represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group, or a phenyl group. X ¹⁴ each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear. X ¹⁵ represents a hydroxy group, a carboxyl group, an amino group, an alkoxysilyl group or a group represented by the above formula (2). However, when X ¹⁴ is a single bond, X ¹⁵ is a hydroxy group or an amino group. X ⁰ represents a single bond, an oxygen atom or a sulfur atom. However, when X ¹⁴ is a single bond, X ⁰ is also a single bond.
In addition, when these substituents include a benzene ring, the benzene ring includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group. It may be substituted with one or a plurality of substituents which are the same or different.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. Represents an alkoxy group, a halogen atom, a trifluoromethyl group, or a cyano group.
Examples of the alkyl group having 1 to 18 carbon atoms defined above include, for example, 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 2,3-dimethyl-n-butyl group, 3,3-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, 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, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group 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, 1-methyl Ru-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl 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 Can be mentioned. Similarly, examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding number of carbon atoms among the groups listed above.
In addition, examples of the alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkylthio group having 1 to 10 carbon atoms include groups obtained by oxidizing or thiolating the alkyl groups listed above. Among them, groups having the corresponding number of carbon atoms are mentioned.
Further, the alkylene group having 1 to 20 carbon atoms is a divalent group obtained by removing one hydrogen atom from the above alkyl group or an alkyl group having 19 to 20 carbon atoms such as n-nonadecyl group and n-eicosyl group. Is mentioned.

In the above formula (2), examples of the alkyl group for R ⁶² include an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Group having the corresponding number of carbon atoms. Examples of the alkoxy group for R ⁶² include an alkoxy group having 1 to 10 carbon atoms. For example, the alkyl groups exemplified above such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group are oxidized. Group having the corresponding number of carbon atoms.
Examples of the group represented by the above formula (2) include the following structures.

Specific examples of the low molecular weight compound having a photo-alignable group and a hydroxy group as the component (A) include 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyl), and the like. Oxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3-hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid Methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid Ethyl ester, 4- (4-hydroxybutyloxy) cinnamic acid ethyl ester, 4- (3- Roxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4- (8- Hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid phenyl ester, 4- (3-hydroxypropyloxy) silicic acid Cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxycinnamic acid phenyl ester, 4- (8-hydroxyoctyloxy) silicic acid Cinnamic acid biphenyl ester, 4- (6- Droxyhexyloxy) cinnamic acid biphenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4- (2-hydroxyethyloxy) Cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxy Butyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4- Hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 '-(8-hydroxyoctyloxy) Chalcone, 4 ′-(6-hydroxyhexyloxy) chalcone, 4 ′-(4-hydroxybutyloxy) chalcone, 4 ′-(3-hydroxypropyloxy) chalcone, 4 ′-(2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutyloxy) coumarin, 7- ( 3-hydroxypropyloxy) coumarin, -(2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutyloxy) coumarin, 6- ( 3-hydroxypropyloxy) coumarin, 6- (2-hydroxyethyloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid methyl ester 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3-hydroxy Propyloxy) benzoyl] cinnamon Methyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid methyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid methyl ester, 4- [4-hydroxybenzoyl] cinnamic acid Methyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (4 -Hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid Ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester 4- [4-hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (6-hydroxyhexyloxy) Benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tarsha L-butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tertiary butyl ester, 4- [4- ( 8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, -[4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3-hydroxypropyloxy) ) Benzoyl] cinnamic acid phenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [4- Hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4 -[4- (4-hydroxybutyloxy) benzoyl] cinnamon Biphenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxymethyl Oxybenzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid biphenyl ester, 4-benzoyl cinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester, 4-benzoyl Cinnamic acid 4-hydroxybutyl ester, 4-benzoylcinnamic acid 3-hydroxypropyl ester, 4-benzoyl cinnamic acid 2-hydroxyethyl ester, 4-benzoyl cinnamic acid hydroxymethyl ester, 4- [4- (8 -Hydroxyoctyloxy ) Benzoyl] chalcone, 4- [4- (6-hydroxyhexyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4- [4- (3-hydroxypropyloxy) benzoyl ] Chalcone, 4- [4- (2-hydroxyethyloxy) benzoyl] chalcone, 4- (4-hydroxymethyloxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone, 4 '-[4- (8- Hydroxyoctyloxy) benzoyl] chalcone, 4 ′-[4- (6-hydroxyhexyloxy) benzoyl] chalcone, 4 ′-[4- (4-hydroxybutyloxy) benzoyl] chalcone, 4 ′-[4- (3 -Hydroxypropyloxy) benzoyl] chalcone, 4 '-[4- (2-hydroxyethyl) Oxy) benzoyl] chalcone, 4 '- (4-hydroxymethyl-oxybenzoyl) chalcone, 4' - (4-hydroxybenzoyl) chalcone and the like.

Specific examples of the low molecular weight compound having a photo-alignable group and a carboxyl group as component (A) include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, 3,4- Dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid, 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloxy) (Hexyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloxypropyl-1-oxy) acryloxy) benzoic acid, 4 And-(4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid.

Specific examples of the low molecular weight compound having a photo-alignable group and an amide group as component (A) include cinnamic acid amide, 4-methyl cinnamic acid amide, 4-ethyl cinnamic acid amide, 4-methoxy cinnamic acid. Cinnamamide, 4-ethoxycinnamic acid amide 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N- (4-cyanophenyl) cinnamamide, 4- (6-Methacryloxyhexyl-1-oxy) -N-bishydroxyethylcinnamamide and the like.

Specific examples of the low molecular weight compound having a photo-alignable group and an amino group as component (A) include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, and 3-aminocinnamic acid methyl ester. Examples include esters and 3-aminocinnamic acid ethyl ester.

Specific examples of the low molecular weight compound having a photo-alignable group and an alkoxysilyl group as the component (A) include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-tri Ethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3- Trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3 -Triethoxysilylhexyloxy) cinnamic acid ethyl ester and the like.

Specific examples of the low molecular weight compound having the photoalignable group and the group represented by the above formula (2), which are the component (A), include compounds represented by the following formula (wherein, Me Represents a methyl group).

The component (A) is preferably a low-molecular compound in which a polymerizable group is bonded to a group in which a photo-alignment site and a thermally reactive site represented by the following formula (1a) are bonded via a spacer.

(In the formula, R ¹⁰¹ represents a hydroxy group, an amino group, a hydroxyphenoxy group, a carboxylphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxylphenylamino group, an aminophenylamino group, a hydroxy group, Represents an alkylamino group or a bis (hydroxyalkyl) amino group, X ¹⁰¹ represents a phenylene group which may be substituted with any substituent, and the benzene ring in the definition of these substituents is substituted with a substituent; May be.)

When the benzene ring may be substituted with a substituent, examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; a haloalkyl group such as a trifluoromethyl group; a methoxy group, Examples thereof include alkoxy groups such as ethoxy group; halogen atoms such as iodine, bromine, chlorine and fluorine; cyano group; nitro group and the like.

Among R ¹⁰¹ described above, a hydroxy group and an amino group are preferable, and a hydroxy group is particularly preferable.

The spacer is a divalent group selected from linear alkylene, branched alkylene, cyclic alkylene and phenylene, or a group formed by bonding a plurality of such divalent groups. In this case, the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by the above formula (1a), and the bond between the spacer and the polymerizable group include a single bond, an ester bond, and an amide bond. , Urea bond, urethane bond, carbonyl or ether bond. When there are a plurality of the divalent groups, the divalent groups may be the same or different, and when there are a plurality of the bonds, the bonds may be the same or different.

Specific examples of the monomer in which a polymerizable group is bonded to a group in which a photo-alignment site and a heat-reactive site are combined as the component (A) include 4- (6-methacryloxyhexyl-1-oxy). Cinnamic acid, 4- (6-acryloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloxypropyl- 1-oxy) acryloxy) benzoic acid, 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N- (4-cyanophenyl) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N-bishydro Such as phenoxyethyl cinnamaldehyde amides.

Specific examples of the low molecular weight photo-alignment component as component (A) can include the above-mentioned specific examples, but are not limited thereto.

Next, details when the component (A) is a polymer, that is, a high molecular weight polymer will be described below.

When the component (A) contained in the cured film forming composition of the present invention is a polymer having a high molecular weight, the component (A) is a polymer having a photoalignment group, that is, as a photoalignment group. A polymer having a functional group at a structural site to be quantified or photoisomerized, particularly an acrylic copolymer having at least a photodimerization site is preferable. Furthermore, in addition to the photodimerization site, at least one substituent 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) (hereinafter referred to as these An acrylic copolymer having a group including a group) is also desirable.

In the present invention, the acrylic copolymer refers to a copolymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylic ester, a methacrylic ester or styrene.

The acrylic copolymer having a photodimerization site and a thermal crosslinking site (A) as the component (hereinafter also referred to as a specific copolymer) may be an acrylic copolymer having such a structure. There are no particular restrictions on the main chain skeleton and side chain type of the polymer.

Examples of the photodimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred examples of the cinnamoyl group and the substituent containing a cinnamoyl structure include structures represented by the following formula [1] or [2]. In the present specification, a group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the “cinnamoyl group” and the “substituent containing a cinnamoyl structure”.

In the above formula [1], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In that case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.

In the above formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be formed from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl, or a combination thereof. Plural types may be bonded through one or two or more selected bonds.

In the above formula [1] and formula [2], A represents one of formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6].

In the above formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6], R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, or a cyano group.

The thermal crosslinking site is a site that is bonded to the component (B) by heating. Specific examples thereof include a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and a group represented by the formula (2). Can be mentioned.

The component (A) acrylic copolymer preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. On the other hand, the weight average molecular weight is less than 3,000 and is too small. In some cases, the heat resistance may cause insufficient curing, resulting in a decrease in solvent resistance or a decrease in heat resistance.

(A) The method for synthesizing the acrylic copolymer having a photodimerization site and a thermal crosslinking site as the component (A) is a simple method of copolymerizing a monomer having a photodimerization site and a monomer having a thermal crosslinking site.

Examples of the monomer having a photodimerization site include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among these, a monomer having a cinnamoyl group is particularly preferable because of its high transparency in the visible light region and high photodimerization reactivity.

Among these, a cinnamoyl group having a structure represented by the above formula [1] or [2] and a monomer having a substituent containing a cinnamoyl structure are more preferable. When the specific example of such a monomer is given, it is a monomer represented by the following formula [3] or formula [4].

In the above formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In that case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.
L ¹ and L ² each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

In the above formula [4], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At that time, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

In the above formulas [3] and [4], X ³ and X ⁵ are each independently a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Show. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

In the above formula [3] and formula [4], X ⁴ and X ⁶ represent a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

In the above formula [3] and formula [4], A is the same as formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] as in formula [1] and formula [2]. ] And formula [A6].
Examples of the alkyl group and alkylene group are given as the alkyl group having 1 to 18 carbon atoms and the alkylene group having 1 to 20 carbon atoms in the definitions of the groups in the formulas [1] to [4]. Can do.

Examples of the monomer having a thermal crosslinking site include 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- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl Monomers having a hydroxy group such as cis-6-hydroxynorbornene-2-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone; acrylic acid, methacrylic acid, crotonic acid , Mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) Monomers having a carboxyl group such as acrylamide; hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) maleimide, N- (hydroxyphenyl) Monomers having phenolic hydroxy groups such as maleimide; monomers having amide groups such as acrylamide and methacrylamide; methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane Monomers having an alkoxysilyl group such as: Monomers having an amino group such as dimethylaminoethyl methacrylate, diethylamino methacrylate, tert-butylaminoethyl methacrylate; Formula (2) such as 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate And a monomer having a group represented by the formula:

The amount of the monomer having a photodimerization site and the monomer having a thermal crosslinking site used for obtaining the specific copolymer is determined based on the total amount of all monomers used for obtaining the specific copolymer. It is preferable that the monomer having 40 mass% to 95 mass% and the monomer having a thermal crosslinking site is 5 mass% to 60 mass%. By setting the content of the monomer having a photodimerization site to 40% by mass or more, high sensitivity and good liquid crystal orientation can be imparted. On the other hand, by setting it to 95% by mass or less, sufficient thermosetting property can be imparted, and high liquid crystal orientation can be maintained with high sensitivity.

In the cured film-forming composition of the present invention, a monomer copolymerizable with a monomer having a photodimerization site and a thermal crosslinking site (hereinafter also referred to as a specific functional group) when obtaining a specific copolymer ( (Hereinafter also referred to as a monomer having a non-reactive functional group) can be used in combination.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, this invention is not limited to these.

Examples of the acrylic ester compound described above include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl. Acrylate, tert-butyl 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 Tricyclodecylacrylate, and, like 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compounds described above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl. Methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2- Adamantyl methacrylate, γ-butyrolactone Methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

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, and 1,2-epoxy-5. Examples include hexene and 1,7-octadiene monoepoxide.

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

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

The method for obtaining the specific copolymer used in the cured film-forming composition of the present invention is not particularly limited. For example, a monomer having a specific functional group (a monomer having a photodimerization site and a monomer having a thermal cross-linking site), or non-specific if desired. 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 a reactive functional group and a polymerization initiator coexist. In that case, the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which has a non-reactive functional group used depending on necessity, a polymerization initiator, etc. Specific examples include solvents described in Solvents described below.

The specific copolymer thus obtained is usually in the form of a solution dissolved in a solvent and can be used as it is as the solution of component (A) in the present invention.

In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved 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 invention, the powder of the specific copolymer may be used as it is as the component (A), or the powder is re-dissolved in, for example, a solvent described later to form a solution. It may be used.

In the present embodiment, the acrylic copolymer as the component (A) may be a mixture of a plurality of types of specific copolymers.

As described above, in the present invention, a low molecular weight compound or a high molecular weight specific copolymer can be used as the component (A). The component (A) may be a mixture of one or more low molecular weight compounds and a high molecular weight specific copolymer.

[Component (B)]
The component (B) contained in the cured film forming composition of this embodiment is at least one selected from 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 polymer having two substituents (hereinafter also referred to as specific functional groups). As the alkoxysilyl group in the component (B), a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, a methoxydimethylsilyl group, An ethoxydimethylsilyl group etc. are mentioned.

Examples of the polymer as the component (B) include acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, poly Examples include allylamine, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resin and melamine formaldehyde resin, and cyclic polymers such as cyclodextrins.

Preferred examples of the specific polymer (B) include acrylic polymers, hydroxyalkylcyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone polyols.

The acrylic polymer which is a preferred example of the specific polymer of the component (B) is a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid, methacrylic acid, styrene, and a vinyl compound. Any polymer may be used as long as it is a polymer obtained by polymerizing a monomer containing a monomer having a specific functional group or a mixture thereof, and the type of the main chain skeleton and side chain of the polymer constituting the acrylic polymer is not particularly limited. .

The monomer having a specific functional group includes a monomer having a polyethylene glycol ester group, a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms, a monomer having a phenolic hydroxy group, a monomer having a carboxyl group, and an amide group. Monomers, monomers having an amino group, alkoxysilyl groups, and monomers having a group represented by the above formula (2).

Examples of the monomer having a polyethylene glycol ester group described above include monoacrylate or monomethacrylate of H— (OCH ₂ CH ₂ ) n—OH. The value of n is 2 to 50, preferably 2 to 10.

Examples of the monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, and 4-hydroxybutyl acrylate. 4-hydroxybutyl methacrylate.

Examples of the above-mentioned monomer having a phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

Examples of the above-mentioned monomer having a carboxyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid.

Examples of the monomer having an amino group in the side chain described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

Examples of the monomer having an alkoxysilyl group in the side chain include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxy. Examples thereof include silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.

Examples of the monomer having a group represented by the above formula (2) in the side chain include 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, and the like.

Moreover, in this embodiment, when synthesizing an acrylic polymer which is an example of the component (B), a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, A monomer that does not have any of the groups represented by formula (2) 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.

Examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl. 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, Beauty, etc. 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl. Methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2- Propyl-2-adamantyl methacrylate, 8-me Le -8- tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

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

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

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

(B) The usage-amount of the monomer which has a specific functional group used in order to obtain the acrylic polymer which is an example of a component is based on the total amount of all the monomers used in order to obtain the acrylic polymer which is (B) component, It is preferably 2 mol% to 98 mol%. When the monomer having the specific functional group is too small, the liquid crystal orientation of the resulting cured film tends to be insufficient, and when it is too large, the compatibility with the component (A) tends to decrease.

(B) Although the method to obtain the acrylic polymer which is an example of a component is not specifically limited, For example, the monomer containing the monomer which has a specific functional group, the monomer which does not have a specific functional group depending on necessity, a polymerization initiator, etc. Is obtained by a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent coexisting with. In that case, the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which does not have the specific functional group used depending on necessity, a polymerization initiator, etc. Specific examples are described in the section of [Solvent] described later.

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

In addition, the acrylic polymer solution, which is an example of the component (B) obtained by the above method, is poured into diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate is filtered and washed. Under normal pressure or reduced pressure, it can be dried at room temperature or dried to obtain an acrylic polymer powder as an example of the component (B). By the above operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer which is an example of the component (B) can be removed, and as a result, the acrylic polymer which is an example of the purified component (B) Of powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

The acrylic polymer which is a preferred example of the component (B) has a weight average molecular weight of preferably 3000 to 200000, more preferably 4000 to 150,000, and still more preferably 5000 to 100,000. If the weight average molecular weight exceeds 200,000, the solvent solubility may decrease and handling may decrease. If the weight average molecular weight is less than 3,000, the curing may be insufficient during thermal curing. The solvent resistance and heat resistance may be reduced. The weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC). Hereinafter, the same applies to this specification.

Next, as a polyether polyol which is a preferable example of the specific polymer of the component (B), polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol and other polyhydric alcohols, propylene oxide and polyethylene glycol , And polypropylene glycol added. Specific examples of polyether polyols include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF UNIOX (registered trademark) 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.

(B) As a polyester polyol which is a preferable example of the specific polymer of component, diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol and polypropylene glycol are added to polyvalent carboxylic acids such as adipic acid, sebacic acid and isophthalic acid. Can be mentioned. Specific examples of the polyester polyol include DIC polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, 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, Kuraray polyols P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

Examples of the polycaprolactone polyol which is a preferred example of the specific polymer of the component (B) include those obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of the polycaprolactone polyol include DIC's Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Plaxel (registered trademark) 205, L205AL, 205U, 208, 210 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

Examples of the polycarbonate polyol which is a preferable example of the specific polymer of the component (B) include those obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate, or the like. Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, and C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.

Examples of cellulose that is a preferred example of the specific polymer of component (B) include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose and hydroxyethylethylcellulose, and cellulose. For example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Examples of the cyclodextrin which is a preferable example of the specific polymer of the component (B) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γcyclodextrin, 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-hydroxy Ethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl Lopyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 , 3-dihydroxypropyl-β-cyclodextrin, 2,3-dihydroxypropyl-γ-cyclodextrin, and the like.

The melamine formaldehyde resin which is a preferable example of the specific polymer of the component (B) is a resin obtained by polycondensation of melamine and formaldehyde, and is represented by the following formula.

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units. Examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding number of carbon atoms among the alkyl groups exemplified above or below.

In the melamine formaldehyde resin as the component (B), it is preferable that the methylol group generated during the polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.

The method for obtaining the melamine formaldehyde resin as the component (B) is not particularly limited, but in general, melamine and formaldehyde are mixed, made weakly alkaline using sodium carbonate, ammonia, etc., and then heated at 60 ° C. to 100 ° C. Is synthesized. Further, the methylol group can be alkoxylated by reacting with alcohol.

The (B) component melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight exceeds 5,000, the solubility in the solvent may decrease and handling may decrease. If the weight average molecular weight is less than 250, the curing may be insufficient during thermal curing. Therefore, the effect of improving solvent resistance and heat resistance may not be sufficiently exhibited.

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

In the embodiment of the present invention, the melamine formaldehyde resin as the component (B) may be a mixture of plural types of melamine formaldehyde resins as the component (B).

Examples of the phenol novolak resin which is a preferred example of the specific polymer of the component (B) include phenol-formaldehyde polycondensate.

In the cured film forming composition of the present embodiment, the polymer of the component (B) may be used in a powder form or in a solution form in which a purified powder is redissolved in a solvent described later.

Further, in the cured film forming composition of the present embodiment, the component (B) may be a mixture of a plurality of types of polymers exemplified as the component (B).

[Component (C)]
The cured film forming composition of this embodiment contains a crosslinking agent as (C) component. More specifically, the component (C) reacts with the component (A), the component (B) and the component (D) described later, and the component (A) is a low molecular photo-alignment component. A) A crosslinking agent that reacts at a temperature lower than the sublimation temperature of the component. The component (C) is at a temperature lower than the sublimation temperature of the component (A), and the hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and the above formula (A) Substituents selected from the groups represented by 2), hydroxy groups, carboxyl groups, amide groups, amino groups, alkoxysilyl groups contained in the component (B) and substitutions selected from the groups represented by the above formula (2) Bonds to the group (D) component compound. As a result, as will be described later, when the (A) component, the (B) component, the (D) component, and the crosslinking agent as the (C) component are thermally reacted, the (A) component is prevented from sublimating. can do. And the cured film formation composition of this Embodiment can form alignment material with high photoreaction efficiency as a cured film.

Examples of the crosslinking agent (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, for example, 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) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Beccamine (registered trademark) J-300S, P-955, N) and the like.

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

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

Further, it may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.). Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).

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, N-butoxymethylmethacrylamide, or the like Polymers produced using methacrylamide compounds can also 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 a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1000 to 500000, preferably 2000 to 200000, more preferably 3000 to 150,000, and still more preferably 3000 to 50000.

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

The content of the crosslinking agent of component (C) in the cured film forming composition of the present embodiment is the total amount of at least one selected from the low molecular compound and polymer as component (A) and the polymer of component (B). It is preferably 10 to 100 parts by mass, more preferably 15 to 80 parts by mass based on 100 parts by mass. When content of a crosslinking agent is too small, the solvent tolerance and heat resistance of the cured film obtained from a cured film formation composition will fall, and the orientation sensitivity at the time of photo-alignment will fall. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be lowered.

[(D) component]
The component (D) contained in the cured film forming composition of this embodiment has at least one polymerizable group containing a C═C double bond in one molecule and at least one N-alkoxymethyl group. Low molecular weight compound.

When the cured film formed from the cured film-forming composition of this embodiment containing the component (D) is used as an alignment material, the polymerizable liquid crystal of the polymerizable liquid crystal is improved so that the adhesion between the alignment material and the polymerizable liquid crystal layer is improved. The polymerizable functional group and the crosslinking reaction site of the alignment material can be linked by a covalent bond. As a result, the retardation material of this embodiment formed by laminating a cured polymerizable liquid crystal on the alignment material of this embodiment can maintain strong adhesion even under high temperature and high quality conditions, such as peeling. High durability can be exhibited.

Examples of the polymerizable group containing a C═C double bond include an acryl group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

N of N-alkoxymethyl group, that is, nitrogen atom is adjacent to amide nitrogen atom, thioamide nitrogen atom, urea nitrogen atom, thiourea nitrogen atom, urethane nitrogen atom, nitrogen atom of nitrogen-containing heterocycle And a nitrogen atom bonded to. Therefore, the N-alkoxymethyl group includes an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring. Examples include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

As the component (D), any compound having the above-mentioned group may be used, and preferably, for example, a compound represented by the following formula (1) is exemplified.

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² 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, and 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, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl 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- A pentyl group, a 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, 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. .

Specific examples of the compound represented by the above formula (1) include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-methylolacrylamide and the like. .

As another embodiment of the compound having a polymerizable group containing a C═C double bond and an N-alkoxymethyl group as component (D), for example, a compound represented by the following formula (X2) is preferable. .

[Wherein, R ⁵¹ represents a hydrogen atom or a methyl group. R ⁵³ is a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent group composed of an aliphatic ring having 5 to 6 carbon atoms, or a divalent group containing an aliphatic ring having 5 to 6 carbon atoms. Represents a valent aliphatic group and may contain an ether bond in the structure. R ⁵⁴ is a divalent to nonvalent group having a structure in which 1 to 8 hydrogen atoms are removed from a linear or branched alkyl group having 2 to 20 carbon atoms, or an aliphatic cyclic group having 5 to 6 carbon atoms. Represents a divalent to nine-valent group having a structure in which 1 to 8 hydrogen atoms are further removed from the divalent to divalent to nine-valent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, An ether bond may be included. R ⁵² represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent aliphatic group, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond. Z is> NCOO-, or -OCON <(where "-" indicates that there is one bond, and ">" and "<" indicate that there are two bonds. N atom Any one of the bonds represents a bond with —CH ₂ OR ⁵² ). r is a natural number of 2 or more and 9 or less. ]

A divalent structure having a structure in which 1 to 8 hydrogen atoms are removed from an alkylene group having 2 to 20 carbon atoms in the definition of R ^{53 and} a linear or branched alkyl group having 2 to 20 carbon atoms in the definition of R ⁵⁴ Specific examples of the thruvalent group include divalent to ninevalent groups in which 1 to 8 hydrogen atoms are further removed from the alkyl group having 2 to 20 carbon atoms shown below.
Specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 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, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, n- Heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n- Heptadecyl group, n-octadecyl group, n- A nadecyl group, an n-eicosyl group, a group in which one or more of these groups are bonded within a range of up to 20 carbon atoms, and one methylene group or a plurality of methylene groups not adjacent to each other is an ether. An example is a group replaced with a bond.

Among 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, 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 an alkyl group having 2 to 20 carbon atoms and a methyl group in the description of the definitions of R ⁵³ and R ⁵⁴ above. 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 the aliphatic ring group having 5 to 6 carbon atoms in the definition of R ⁵² , R ⁵³ and R ⁵⁴ include a group based on a cyclopentyl group and a cyclohexyl group, and a monovalent group such as a cyclopentyl group and a cyclohexyl group. In addition, a divalent to a nonvalent group having a structure in which 1 to 8 hydrogen atoms are further removed from the aliphatic ring group having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms, And a group in which one or a plurality of monovalent or divalent to nine-valent aliphatic groups are bonded in the range of up to 20 carbon atoms, and one methylene of these groups or a plurality of methylenes not adjacent to each other And a group in which the group is replaced with an ether bond.

R may be a natural number of 2 or more and 9 or less, preferably 2 to 6.

Compound (X2) is obtained by the production method represented by the following reaction scheme. That is, a carbamate compound having an acryl or methacryl group represented by the following formula (X2-1) (hereinafter also referred to as compound (X2-1)) is reacted in a solvent to which trimethylsilyl chloride and paraformaldehyde are added. It is produced by synthesizing an intermediate represented by the following formula (X2-2), and adding and reacting an alcohol represented by R ⁵² —OH to the reaction solution.

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

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

The reaction solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, cyclohexane, benzene and toluene; methylene chloride, carbon tetrachloride, chloroform, 1,2-dichloroethane and the like 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 these may be mixed and used. Preferred are methylene chloride and chloroform, and more preferred is methylene chloride.

The amount of solvent used (reaction concentration) is not particularly limited, but the reaction may be carried out without using a solvent. When a solvent is used, 0.1 to 100 mass relative to compound (X2-1) is used. Double the solvent may be used. Preferably it is 1 thru | or 30 times mass, More preferably, it is 2 thru | or 20 times 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 at normal pressure or under pressure, and can be batch or continuous.

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, etc. can be used, which inhibits polymerization of acrylic groups and methacrylic groups. If there is no particular limitation.

The addition amount in the case of adding a 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 compound (X2-1). is there. In the present specification, wt% means mass%.

In the step of reacting alcohol with the intermediate (X2-2), a base may be added 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. Triethylamine and diisopropylethylamine are preferable, and triethylamine is more preferable. The addition amount in the case of adding a base is not particularly limited, but it may be used 0.01 to 2.0 equivalents, more preferably 0.5 to 1 with respect to the addition amount of trimethylsilyl chloride used in the reaction. 0.0 equivalents.

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

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

Specific examples of (meth) acryloyloxyalkyl isocyanate include, for example, 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz MOI [registered trademark]), 2-acryloyloxyethyl isocyanate (Showa). Denko Co., Ltd., trade name: Karenz AOI [registered trademark]) and the like.

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 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 hydroxyalkyl (meth) acrylate compounds 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, poly (ethylene glycol) ethyl ether methacrylate, and the like.

Specific examples of the polyisocyanate compound include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and dimer diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as' -diisocyanate dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, And triisocyanates 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.

The content of the component (D) in the cured film-forming composition of the embodiment of the present invention is at least one selected from the low molecular compound and polymer as the component (A), the polymer as the component (B), and the component (C). Preferably it is 0.1 mass part thru | or 40 mass parts with respect to 100 mass parts of the total amount of a crosslinking agent, More preferably, it is 5 mass parts thru | or 35 mass parts. When the content of the component (D) is 0.1 parts by mass or more, sufficient adhesion can be imparted to the formed cured film. However, when it is more than 40 parts by mass, the storage stability of the cured film forming composition may be lowered.

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

[(E) component]
The cured film forming composition of the present embodiment may contain a crosslinking catalyst as the component (E) in addition to the component (A), the component (B), the component (C) and the component (D) described above. it can.

(E) As a crosslinking catalyst which is a component, it can be set as an acid or a thermal acid generator, for example. This component (E) is effective in promoting a thermosetting reaction in the formation of a cured film using the cured film forming composition of the present embodiment.

When an acid or a thermal acid generator is used as the component (E), the component (E) is a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, a compound that generates an acid by thermal decomposition 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 capable of generating an acid by thermal decomposition at from 250C to 250C.

Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro. L-methanesulfonic 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, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid such as dodecylbenzenesulfonic acid, or a hydrate or salt thereof Is mentioned.

Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 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-toluenesulfonic 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-H Rokishibuchiru p- tosylate, 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 cured film forming composition according to the embodiment of the present invention is at least one selected from the low molecular compound and polymer as the component (A), the polymer as the component (B), and the component (C). Preferably it is 0.01 mass part thru | or 10 mass parts with respect to 100 mass parts of the total amount of a crosslinking agent and the low molecular compound of (D) component, More preferably, 0.05 mass part thru | or 8 mass parts, More preferably 0.1 parts by mass to 6 parts by mass. By setting the content of the component (E) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Moreover, the storage stability of a cured film forming composition can be made favorable by setting it as 10 mass parts or less.

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

Examples of the sensitizer include benzophenone, anthracene, anthraquinone and thioxanthone derivatives and nitrophenyl compounds. Of these, N, N-diethylaminobenzophenone which is a derivative of benzophenone and 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, which are nitrophenyl compounds, 4- Nitrostilbene, 4-nitrobenzophenone and 5-nitroindole are particularly preferred.
These sensitizers are not particularly limited to those described 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 0.1 parts by mass to 100 parts by mass of the total amount of the component (A), the component (B), the component (C), and the component (D). It is preferably 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained. If it is too large, the transmittance of the formed cured film may be reduced or the coating film may be roughened. There are things to do.

In addition, the cured film forming composition according to the embodiment of the present invention includes, as other additives, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stability, as long as the effects of the present invention are not impaired. Agents, antifoaming agents, antioxidants, and the like.

[solvent]
The cured film forming composition of the embodiment of the present invention is often used in a solution state dissolved in a solvent. The solvent used in that case is one that dissolves the component (A), the component (B), the component (C) and the component (D), and if necessary, the component (E) and / or other additives. There are no particular limitations on the type and structure of the solvent as long as it has such solubility.

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 acetate, cyclopentyl methyl ether, isopropyl alcohol, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , Ethyl 2-hydroxypropionate, 2- Ethyl droxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3- Examples thereof include methyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

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-methoxypropion Ethyl acid, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferred because of their good film formability and high safety.

<Preparation of cured film forming composition>
The cured film forming composition of the embodiment of the present invention is a thermosetting cured film forming composition having photo-alignment properties. As described above, the cured film forming composition of the present embodiment is at least one selected from the low molecular compound and polymer as the component (A), and the hydroxy group, carboxyl group, amide group, amino group as the component (B). , A polymer having at least one substituent selected from an alkoxysilyl group and a group represented by the above formula (2), (C) a crosslinking agent as component, and (D) component, It contains a low molecular compound having at least one polymerizable group containing a C double bond and having at least one N-alkoxymethyl group. Moreover, a crosslinking catalyst can be contained as (E) component. And as long as the effect of this invention is not impaired, another additive can be contained and a solvent can be contained further.

The mixing ratio of the component (A) and the component (B) is preferably 5:95 to 80:20 by mass ratio. When the content of the component (B) is excessive, the liquid crystal orientation is liable to be lowered, and when it is too small, the solvent resistance is lowered and the orientation is liable to be lowered.

Preferred examples of the cured film forming composition of the present embodiment are as follows.

[1]: At least one selected from the group consisting of a photoalignable group as component (A), 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 low molecular compound having two substituents (low molecular photoalignment component) and (B) component hydroxy group, carboxyl group, amide group, amino group, alkoxysilyl group and the group represented by the above formula (2) The blending ratio with the polymer having at least one substituent selected is 5:95 to 80:20 by mass ratio, and the low molecular weight compound as the component (A) and at least one selected from the polymer and the component (B) Based on 100 parts by mass of the total amount with the polymer, 10 to 100 parts by mass of the (C) component crosslinking agent, and the (A) component low molecular compound and polymer In 100 molecules of the total amount of at least one kind selected from the polymer of the component (B) and the crosslinking agent of the component (C), 0.1 part by weight to 40 parts by weight of the component (D) in one molecule A cured film forming composition comprising a low molecular compound having at least one polymerizable group containing a C = C double bond and having at least one N-alkoxymethyl group.

[2]: The blending ratio of the component (A) and the component (B) is 5:95 to 80:20 by mass ratio, and the component (A) is at least one selected from low molecular compounds and polymers, and (B) 10 parts by mass to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of the components with the polymer, and at least one selected from low molecular compounds and polymers as component (A), component (B) The cured film forming composition containing 0.1 mass part thru | or 40 mass parts (D) component and a solvent with respect to 100 mass parts of the total amount of the polymer of (C), and the crosslinking agent of (C) component.

[3] The blending ratio of the component (A) and the component (B) is 5:95 to 80:20 by mass ratio, and the component (A) is at least one selected from low molecular compounds and polymers, and (B) 10 parts by weight to 100 parts by weight of component (C) based on 100 parts by weight of the total amount of the component polymer, component (A), low molecular weight compound, and polymer selected from polymer (B) And 100 parts by mass of the total amount of the crosslinking agent of component (C), selected from 0.1 part by mass to 40 parts by mass of component (D), and (A) component low molecular weight compound and polymer. 0.01 parts by mass to 10 parts by mass of the component (E) with respect to 100 parts by mass of the total amount of at least one kind of the polymer of the component (B), the crosslinking agent of the component (C) and the compound of the component (D), Cured film forming set containing solvent Thing.

The blending ratio, preparation method, and the like when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.
The ratio of the solid content in the cured film forming composition of the present embodiment 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 It is 3% by mass to 60% by mass, and more preferably 5% by mass to 40% by mass. Here, solid content means what remove | excluded the solvent from all the components of the cured film formation composition.

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

In the preparation of the cured film forming composition of this embodiment, a solution of a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, the (A) component, the (C) component, the (D) component, and the (E) component are added to the solution prepared from the (B) component acrylic polymer to obtain a uniform solution. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the preparation 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 cured film-forming composition solution is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

As described above, the cured film forming composition of this embodiment of the present invention is represented by (A) a photo-alignment group and a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula (2). A low molecular compound having at least one substituent selected from the group to be selected and at least one selected from polymers, (B) a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above formula (2) And a polymer having at least one substituent selected from the above groups. In at least one selected from the low molecular weight compound and polymer as the component (A), the photoalignment group constitutes a hydrophobic photoreactive portion, and includes a hydroxy group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group, and the above At least one substituent selected from the group represented by the formula (2) constitutes a hydrophilic thermal reaction part. The hydroxyl group, carboxyl group, amide group, amino group, alkoxysilyl group and at least one substituent selected from the group represented by the above formula (2) are also hydrophilic.

Therefore, the cured film formed from the cured film forming composition of the present embodiment is formed with hydrophilic inside due to the nature of the component (B) so that the film structure is stabilized. . And at least 1 type chosen from the low molecular compound and polymer of (A) component in a cured film comes to be unevenly distributed in the surface vicinity of a cured film. More specifically, at least one selected from the low molecular compound and polymer of the component (A) has a structure in which the hydrophilic thermal reaction part faces the inner side of the cured film and the hydrophobic photoreaction part faces the surface side. While being removed, it is unevenly distributed near the surface of the cured film. As a result, the cured film of the present embodiment realizes a structure in which the ratio of the photoreactive group of the component (A) existing near the surface is increased. And when the cured film of this embodiment is used as an alignment material, the efficiency of the photoreaction for photo-alignment can be improved and it can have the outstanding orientation sensitivity. Furthermore, it becomes an orientation material suitable for formation of a patterned phase difference material, and the patterned phase difference material manufactured using this can have the outstanding pattern formation property.

Moreover, the cured film forming composition of this embodiment contains a crosslinking agent as (C) component as mentioned above. Therefore, in the cured film obtained from the cured film-forming composition of the present embodiment, before the photoreaction with at least one photoalignable group selected from the low molecular compound and polymer of the component (A) (C ) A crosslinking reaction by a thermal reaction with a crosslinking agent can be performed. As a result, when used as an alignment material, it is possible to improve the resistance to the polymerizable liquid crystal applied thereon and its solvent.

And the cured film formation composition of this embodiment of this invention contains a C = C double bond in 1 molecule as (D) component with (A) component, (B) component, and (C) component. It contains a low molecular compound having at least one polymerizable group and at least one N-alkoxymethyl group. When the cured film obtained from the cured film-forming composition of the present embodiment is used as an alignment material, the compound as component (D) is between the cured polymerizable liquid crystal layer formed thereon. It functions to reinforce the adhesion.

<Hardened film, alignment material and retardation material>
A solution of the cured film forming composition according to the present embodiment is applied to a substrate (for example, 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, or a quartz substrate. , ITO substrate, etc.) and films (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coating, spin coating, flow coating, roll coating A cured film can be formed by coating by slit coating, spin coating following the slit, inkjet coating, printing, or the like to form a coating film, followed by heat drying with a hot plate or oven.

The heating and drying conditions may be such that the curing reaction proceeds to such an extent that the alignment material component formed from the cured film does 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 appropriately selected from the range of time 0.4 minutes to 60 minutes are employed. The heating temperature and heating time are preferably 70 ° C. to 160 ° C., 0.5 minutes to 10 minutes.

The film thickness of the cured film formed using the curable composition of the present embodiment is, for example, 0.05 μm to 5 μm, and is appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties. be able to.

The cured film thus formed can function as an alignment material, that is, a member for aligning a liquid crystalline compound including a polymerizable liquid crystal by performing polarized UV irradiation.

As an irradiation method of polarized UV, ultraviolet light or visible light having a wavelength of 150 nm to 450 nm is usually used, and irradiation 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 cured film composition of the present embodiment has solvent resistance and heat resistance, after applying a retardation material comprising a polymerizable liquid crystal solution on the alignment material, the liquid crystal The phase difference material is brought into a liquid crystal state by heating up to the phase transition temperature, and aligned on the alignment material. Then, the retardation material in a desired orientation state is cured as it is, and a retardation material having a layer having optical anisotropy can be formed.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the board | substrate with which an orientation material is formed is a film, the film which has the phase difference material of this Embodiment becomes useful as a phase difference film. The phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference characteristic.

Moreover, when manufacturing the patterned phase difference material used for 3D display, it is predetermined | prescribed via the mask of a line and space pattern to the cured film formed by the above-mentioned method from the cured film composition of this embodiment. For example, polarized UV exposure is performed in the +45 degree direction from the reference, and then the polarized UV light is exposed in the -45 degree direction after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. Forming an alignment material. Thereafter, 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 a phase transition temperature of the liquid crystal. The polymerizable liquid crystal in a liquid crystal state is aligned on an alignment material on which two types of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material in which such an orientation state is realized is cured as it is, the above-described orientation state is fixed, and a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged. A phase difference material can be obtained.

Moreover, the alignment material formed from the cured film composition of this embodiment can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, after using the two substrates having the alignment material of the present embodiment formed as described above, the alignment materials on both the substrates are bonded to each other via a spacer, and then between the substrates. A liquid crystal display element in which liquid crystal is aligned can be manufactured by injecting liquid crystal into the liquid crystal.
Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Compositional components used in Examples and their abbreviations]
Each composition component used in the following examples and comparative examples is as follows. In the following formulae, Me represents a methyl group, and t-Bu represents a tert-butyl group.

<Component (A): Low molecular photo-alignment component>
CIN1: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

CIN2: 3-methoxy-4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

CIN3: 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid tertiary butyl ester

CIN 4: 4- (6-Methacryloxyhexyl-1-oxy) cinnamic acid

CIN5: 4-propyloxycinnamic acid

<Specific polymer raw material>
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CIN 4: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid AIBN: α, α′-azobisisobutyronitrile

<Component (B)>
PEPO: Polyester polyol polymer (Adipic acid / diethylene glycol copolymer having the following structural units. Molecular weight 4,800)

(In the above formula, R represents alkylene.)

<Component (C): Crosslinking agent>
HMM: Hexamethoxymethylmelamine

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

<Component (D): Low molecular weight compound having an N-alkoxymethyl group and a polymerizable group>
D-1: N-methoxymethyl methacrylamide

D-2: N-methoxymethylacrylamide

D-3: Nn-butoxymethylacrylamide (BMAA)

D-4: N-isobutoxymethylacrylamide

D-5:

D-6:

<Other reagents>
BHT: 2,6-di-tert-butyl-para-cresol DBU: 1,8-diazabicyclo [5.4.0] -7-undecene

<Solvent>
Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), and methyl ethyl ketone (MEK) were used as the solvent.

<Measurement of molecular weight of polymer>
The molecular weight of the polyimide, polyamic acid, or acrylic polymer in the synthesis example was measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and columns (KD-803, KD-805) manufactured by Shodex. Measurement was performed as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 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 preparing 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 Laboratories) Molecular weight about 12,000, 4,000, 1,000).

<Examples and Comparative Examples>
<Polymerization Example 1>
3.5 g of MAA, 7.0 g of MMA, 7.0 g of HEMA, 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% by mass) (P1) was obtained. Mn of the obtained acrylic copolymer was 10,300 and Mw was 24,600.

<Polymerization example 2>
MMA 100.0 g, HEMA 11.1 g, and AIBN 5.6 g as a polymerization catalyst are dissolved in 450.0 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration 20 mass%) (P2) Got. Mn of the obtained acrylic copolymer was 4,200 and Mw was 7,600.

<Polymerization Example 3>
100.0 g of Nn-butoxymethylacrylamide (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 react an acrylic polymer solution (solid content concentration: 35 mass). %) (P3). Mn of the obtained acrylic copolymer was 2,700 and Mw was 3,900.

<Polymerization example 4>
CIN4 4.0g, Styrene 4.0g, HEMA 2.0g, AIBN 0.1g as a polymerization catalyst was dissolved in PM 90.9g and reacted at 80 ° C for 20 hours to give an acrylic polymer solution (solid content concentration 10 mass) %) (CIN6). Mn of the obtained acrylic copolymer was 20,000 and Mw was 55,000.

Synthesis of Compound [D-5]

Under a nitrogen stream, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) were added to a 2 L four-necked flask. 1.80 g (11.8 mmol) and 2,5-ditertiarybutyl-para-cresol (BHT) 0.45 g (2.04 mmol) were charged at room temperature, and the temperature was raised to 55 ° C. while stirring with a magnetic stirrer. Warm up. To the reaction solution, 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was added dropwise, and after stirring for 2 hours, the reaction solution was analyzed by high performance liquid chromatography. The intermediate was 1% or less in terms of area percentage. The reaction was complete as soon as possible. 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 [Aa] (104 g, 0.260 mol, yield 86.7%). .

Under a nitrogen stream, 13L of dichloromethane, 100 g (0.250 mol) of compound [Aa] and 22.5 g (0.749 mol) of paraformaldehyde were charged in a 2 L four-necked flask, and 122 g (1) of trimethylsilyl chloride in an ice bath. .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 separatory funnel, and 1500 g of water was added to carry out a separation operation. The obtained organic layer was dried over magnesium sulfate, and the filtrate obtained by removing magnesium sulfate by filtration was concentrated and dried to obtain compound [D-5] (110 g, 0.226 mol, yield 90.). 3%). The structure of the compound [D-5] was confirmed by obtaining the following spectral data by ¹ H-NMR analysis.
¹ H-NMR (CDCl ₃ ): δ 6.42 (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 of Compound [D-6]

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

Under a nitrogen stream, a 300 mL four-necked flask was charged with 200 g of dichloromethane, 14.6 g (36.4 mmol) of the compound [Ab] and 3.28 g (0.109 mmol) of paraformaldehyde, and trimethylsilyl chloride 23 in an ice bath. 0.7 g (0.218 mmol) was added dropwise. After stirring for 1 hour, 35.6 g of methanol was added dropwise and stirred for 1 hour. The organic layer was washed with 300 mL of a saturated aqueous sodium hydrogen carbonate solution, and the resulting aqueous layer was further washed with 200 g of dichloromethane. The mixed solution of 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 resulting dichloromethane solution was concentrated and dried to obtain the desired [D-6] (16.2 g, 33.1 mmol, yield 91.0%).
The structure of the compound [D-6] 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).

<Creation of base film>
The acrylic film used as the substrate can be prepared, for example, by the following method. That is, raw material pellets made of a copolymer containing methyl methacrylate as a main component are melted by an extruder at 250 ° C., passed through a T-die, and an acrylic film having a thickness of 40 μm is formed through a casting roll and a drying roll. can do. A TAC film can be similarly produced.

<Examples 1 to 18 and Comparative Examples 1 and 2>
Each cured film formation composition of an Example and a comparative example was prepared with the composition shown in Table 1, and orientation, pattern formation property, and adhesiveness were evaluated about each.

[Evaluation of orientation]
Each of the cured film forming compositions of Examples and Comparative Examples was applied onto a film using a bar coater, and then heated and dried in a heat circulation oven at a temperature of 110 ° C. for 2 minutes to form a cured film. Each cured film was irradiated vertically with 313 nm linearly polarized light at an exposure amount of 10 mJ / cm ² to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked on a hot plate at 70 ° C. for 60 seconds to form a coating film having a thickness of 1.0 μm. did. The coating film on this substrate was exposed at 300 mJ / cm ² to produce a retardation material. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, the state of the phase difference characteristic in the phase difference material is observed, ○ if the phase difference is expressed without defects, and no phase difference is expressed This was described as x in the column of “Orientation” in Table 2.

[Evaluation of pattern formability]
After each cured film forming composition of Examples and Comparative Examples was applied on an acrylic film or TAC film using a bar coater, the cured film was formed by heating and drying in a thermal circulation oven at a temperature of 110 ° C. for 2 minutes. did. This cured film was irradiated with 20 mJ / cm ² perpendicularly with 313 nm linearly polarized light through a 350 μm line and space mask. Next, after removing the mask and rotating the substrate by 90 degrees, 313 nm linearly polarized light was irradiated vertically by 10 mJ / cm ² , and the alignment in which two kinds of liquid crystal alignment regions differing in the liquid crystal alignment control direction by 90 degrees was formed. I got the material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked on a hot plate at 70 ° C. for 60 seconds to form a coating film having a thickness of 1.0 μm. did. The coating film on this substrate was exposed at 300 mJ / cm ² to prepare a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged. The patterned retardation material on the produced substrate was observed using a polarizing microscope. “Pattern formation” in Table 2 was defined as “O” in which a phase difference pattern was formed without alignment defects and “X” in which alignment defects were observed. "In the column.

[Evaluation of adhesion]
After each cured film forming composition of Examples and Comparative Examples was applied on an acrylic film or TAC film using a bar coater, the cured film was formed by heating and drying in a thermal circulation oven at a temperature of 110 ° C. for 2 minutes. did. This cured film was irradiated with 20 mJ / cm ² perpendicularly with 313 nm linearly polarized light through a 350 μm line and space mask. Next, after removing the mask and rotating the substrate by 90 degrees, 313 nm linearly polarized light was irradiated vertically by 10 mJ / cm ² , and the alignment in which two kinds of liquid crystal alignment regions differing in the liquid crystal alignment control direction by 90 degrees was formed. I got the material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked on a hot plate at 70 ° C. for 60 seconds to form a coating film having a thickness of 1.0 μm. did. The coating film on this substrate was exposed at 300 mJ / cm ² to prepare a patterned retardation material in which two types of regions having different retardation characteristics were regularly arranged.
This patterned phase difference material was cut with a cutter knife so as to be 5 × 5 squares at 1 mm vertical and horizontal intervals. A cellophane tape peeling test was performed on the cut using a scotch tape. The evaluation result was “initial”, and the case where all the 25 squares were not peeled off was marked with ○, and the case where even one square was peeled was marked with ×. The evaluation results are summarized in Table 2 later.

[Evaluation of durability adhesion]
The retardation material on the acrylic film or TAC film produced by the method in the same manner as in the evaluation of adhesion described above was placed in an oven set at a temperature of 80 ° C. and a humidity of 90% and allowed to stand for 72 hours or more. Thereafter, the phase difference material was taken out, and the adhesion was evaluated by the same method as the above-described evaluation of adhesion. The evaluation results are collectively shown in Table 2 as “endurance”.

[Evaluation results]
The results of the above evaluation are shown in Table 2 as described above.

The alignment material obtained by using the cured film forming compositions of Examples 1 to 18 showed good alignment properties, similar to the alignment material obtained by using the cured film forming composition of the comparative example.
In addition, the alignment material obtained using the cured film forming compositions of Examples 1 to 18 showed good pattern formability similarly to the alignment material obtained using the cured film forming composition of the comparative example. It was.
Furthermore, the cured films obtained using the cured film forming compositions of Examples 1 to 18 maintained high adhesion even after high temperature and high humidity treatment, and exhibited excellent adhesion durability.
On the other hand, it was difficult for the cured film obtained using the cured film forming composition of the comparative example to maintain the initial adhesion after the high temperature and high humidity treatment.

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

Claims

(A) a low orientation having a photo-alignment group and at least one substituent 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) Polymer having molecular compound and photo-alignment group, and at least one substituent 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) At least one selected from

(Wherein R 62 represents an alkyl group, an alkoxy group or a phenyl group.)
(B) a polymer having at least one substituent 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);
(C) a crosslinking agent, and
(D) Formation of a cured film characterized by containing a low molecular compound having at least one polymerizable group containing a C═C double bond in one molecule and having at least one N-alkoxymethyl group Composition.
The component (A) is a kind selected from a low molecular compound having a photo-alignable group and a hydroxy group and / or carboxyl group and a polymer having a photo-alignable group and a hydroxy group and / or carboxyl group. 2. The cured film forming composition according to claim 1, wherein
The cured film forming composition according to claim 1 or 2, wherein the component (D) is a compound having a structure represented by the following formula (1).

(In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.)
The cured film forming composition according to claim 1 or 2, wherein the component (D) is a compound having a structure represented by the following formula (X2).

[Wherein, R 51 represents a hydrogen atom or a methyl group. R 53 is independently a linear or branched alkylene group having 2 to 20 carbon atoms, a divalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. It represents a divalent aliphatic group containing, and an ether bond may be included in the structure of these groups. R 54 is a divalent to nonvalent radical having a structure in which 1 to 8 hydrogen atoms are further removed from a linear or branched alkyl group having 2 to 20 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent to a non-valent radical having a structure in which 1 to 8 hydrogen atoms are further removed from the group, or a divalent to a non-valent radical containing a C 5 to C 6 aliphatic ring, May contain an ether bond. R 52 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a monovalent group consisting of an aliphatic ring having 5 to 6 carbon atoms, or an aliphatic ring having 5 to 6 carbon atoms. Represents a divalent aliphatic group, and one methylene group or a plurality of non-adjacent methylene groups in these groups may be replaced by an ether bond. Z is> NCOO-, or -OCON <(where "-" indicates that there is one bond, and ">" and "<" indicate that there are two bonds. N atom Any one of the bonds represents a bond with —CH 2 OR 52 ). r is a natural number of 2 or more and 9 or less. ]
(E) The cured film forming composition according to claim 1, further comprising a crosslinking catalyst.
An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 5.
A retardation material comprising a cured film obtained from the cured film-forming composition according to any one of claims 1 to 5.