CN112020663A

CN112020663A - Composition for forming cured film, alignment material, and phase difference material

Info

Publication number: CN112020663A
Application number: CN201980027829.1A
Authority: CN
Inventors: 伊藤润; 西村直也
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2018-03-27
Filing date: 2019-03-26
Publication date: 2020-12-01
Also published as: WO2019189193A1; KR20200135968A; JPWO2019189193A1; TW201946941A

Abstract

The invention provides a composition for forming a cured film, which is useful for forming a cured film having excellent liquid crystal alignment properties and adhesion, and an alignment material and a phase difference material which are produced by using the cured film obtained from the composition for forming a cured film. The solution is a composition for forming a cured film, a cured film obtained from the composition for forming a cured film, and an alignment material and a phase difference material produced by using the cured film, wherein the composition for forming a cured film comprises: (A) a low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinking group; (B) a crosslinking agent; (C) a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond; and (D) a crosslinking catalyst.

Description

Composition for forming cured film, alignment material, and phase difference material

Technical Field

The present invention relates to a composition for forming a cured film, an optical film, an alignment material, and a retardation material, which form a cured film in which liquid crystal molecules are aligned. In particular, the present invention relates to a patterned retardation material used for a circularly polarized light glasses type 3D display, a retardation material used for a circularly polarized light plate used as an antireflection film of an organic EL display, and a composition for forming a cured film, an optical film, an alignment material, and a retardation material useful for producing the retardation material.

Background

In the case of a circularly polarized glasses type 3D display, a phase difference material is generally disposed on a display element such as a liquid crystal panel on which an image is formed. In this phase difference material, a plurality of 2 phase difference regions having different phase difference characteristics are regularly arranged, and a patterned phase difference material is configured. In the present specification, the retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is hereinafter referred to as a patterned retardation material.

The patterned retardation material can be produced by optically patterning a retardation material formed of polymerizable liquid crystal, as disclosed in patent document 1, for example. Optical patterning of a phase difference material formed of polymerizable liquid crystal utilizes a photo-alignment technique known in the formation of alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignment material is provided on a substrate, and 2 kinds of polarized light having different polarization directions are irradiated thereto. Then, a photo alignment film was obtained as an alignment material in which 2 liquid crystal alignment regions having different liquid crystal alignment control directions were formed. A phase difference material in a solution state containing a polymerizable liquid crystal is applied to the photo-alignment film to align the polymerizable liquid crystal. Then, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linear polarizer and an 1/4 wavelength phase difference plate, and converts external light directed to the panel surface of the image display panel into linearly polarized light by the linear polarizer and then into circularly polarized light by the 1/4 wavelength phase difference plate. Here, although the external light formed of the circularly polarized light is reflected on the surface of the image display panel, the rotation direction of the polarizing surface is reversed at the time of the reflection. As a result, the reflected light is converted into linearly polarized light in a direction in which the light is blocked by the linearly polarizing plate by the 1/4 wavelength phase difference plate, and then blocked by the linearly polarizing plate, contrary to the arrival time.

Regarding the 1/4 wavelength retardation plate, patent document 2 proposes a method of forming the optical film by inverse dispersion characteristics by forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. In the case of this method, an optical film can be formed by reverse dispersion characteristics using a liquid crystal material employing a forward dispersion characteristic in a wide wavelength band for color image display.

In recent years, liquid crystal materials having an inverse dispersion property have been proposed as liquid crystal materials that can be applied to the retardation layer (patent documents 3 and 4). According to such a liquid crystal material having an inverse dispersion characteristic, instead of constituting a 1/4 wavelength retardation plate by a 2-layer retardation layer by combining an 1/2 wavelength plate and a 1/4 wavelength plate, an optical film capable of securing a desired retardation over a wide wavelength band can be realized by a simple configuration by constituting a retardation layer by a single layer to secure an inverse dispersion characteristic.

In order to align the liquid crystal, an alignment layer is used. As a method for forming an alignment layer, for example, a rubbing method and a photo alignment method are known, and the photo alignment method is useful in that static electricity and dust, which are problems of the rubbing method, are not generated and quantitative alignment treatment can be controlled.

As a material having photo-alignment properties that can be used for formation of an alignment material using a photo-alignment method, an acrylic resin, a polyimide resin, or the like having a photo-dimerization site such as a cinnamoyl group or a chalcone group in a side chain is known. These resins have been reported to exhibit a property of controlling the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment properties) by polarized UV irradiation (see patent documents 5 to 7).

In addition, the alignment layer is required to have solvent resistance in addition to liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent during the production of the retardation material. If the alignment layer is exposed to a solvent, it is likely that the liquid crystal alignment ability is significantly reduced.

Therefore, for example, patent document 8 proposes a liquid crystal aligning agent containing a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing crosslinking by heat, and a liquid crystal aligning agent containing a compound having a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing crosslinking by heat, in order to obtain a stable liquid crystal aligning capability.

Further, the alignment layer is also required to have adhesion to the liquid crystal layer. When the adhesion force between the alignment layer and the liquid crystal layer formed thereon is insufficient, the liquid crystal layer may be peeled off in a winding step or the like in the production of the retardation film, for example.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2005-49865

Patent document 2: japanese laid-open patent publication No. 10-68816

Patent document 3: specification of U.S. Pat. No. 8119026

Patent document 4: japanese patent laid-open publication No. 2009-179563

Patent document 5: japanese patent No. 3611342

Patent document 6: japanese laid-open patent publication No. 2009-058584

Patent document 7: japanese Kohyo publication No. 2001-517719

Patent document 8: japanese patent No. 4207430

Disclosure of Invention

Problems to be solved by the invention

The present invention has been made based on the above findings and research results. That is, an object of the present invention is to provide a composition for forming a cured film used for forming an alignment material which has excellent solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and has excellent adhesion to a liquid crystal layer.

Further, an object of the present invention is to provide an optical film having the cured film, and an alignment material and a retardation material produced using the cured film or the optical film.

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

Means for solving the problems

The 1 st aspect of the present invention relates to a cured film-forming composition containing:

(A) the components: a low molecular weight compound having a photo-alignment group and a thermal-crosslinking group or a polymer having a photo-alignment group and a thermal-crosslinking group;

(B) the components: a crosslinking agent;

(C) the components: a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond; and

(D) the components: a crosslinking catalyst.

In the 1 st aspect of the present invention, the photo-alignment group of the component (a) is preferably a functional group having a structure capable of photodimerization or photoisomerization.

In the invention according to claim 1, the photo-alignment group of the component (a) is preferably a cinnamoyl group or a group having an azobenzene structure.

In the 1 st aspect of the present invention, it is preferable that the composition further contains (E): a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.

In the 1 st aspect of the present invention, the polymer as the component (C) preferably contains a structural unit having a hydroxyl group and a structural unit having a polymerizable group containing a C ═ C double bond, the proportion of the structural unit having a hydroxyl group is 20 mol% or more based on 100 mol% of all the structural units of the polymer, and the proportion of the structural unit having a polymerizable group containing a C ═ C double bond is 20 mol% or more based on 100% of all the structural units of the polymer.

In the invention of claim 1, the content ratio of the low-molecular-weight compound as the component (A) to the polymer as the component (C) is preferably 5:95 to 60:40 in terms of mass ratio.

In the invention of claim 1, the content ratio of the polymer as the component (A) to the polymer as the component (C) is preferably 5:95 to 90:10 in terms of mass ratio.

In the 1 st aspect of the present invention, it is preferable that the composition for forming a cured film contains 5 to 500 parts by mass of the component (B) based on 100 parts by mass of the total amount of the components (a) and (C).

The 2 nd aspect of the present invention relates to a cured film obtained from the cured film-forming composition of the 1 st aspect of the present invention.

The 3 rd aspect of the present invention relates to an optical film having the cured film of the 2 nd aspect of the present invention.

The 4 th aspect of the present invention relates to an alignment material produced by using the cured film of the 2 nd aspect of the present invention.

The 5 th aspect of the present invention relates to a phase difference material produced by using the cured film according to the 2 nd aspect of the present invention.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a cured film having excellent solvent resistance, capable of aligning polymerizable liquid crystals with high sensitivity, and excellent adhesion to a liquid crystal layer, and a composition for forming a cured film suitable for the formation thereof can be provided.

Further, according to the present invention, an optical film having the cured film, and an alignment material and a phase difference material produced using the cured film or the optical film can be provided.

Detailed Description

As described above, a cured film (alignment material) having excellent solvent resistance, capable of aligning a polymerizable liquid crystal with high sensitivity, and excellent adhesion to a liquid crystal layer is required. Further, a cured film-forming composition suitable for forming a cured film (alignment material) having such performance is required.

The present inventors have conducted intensive studies in response to the above-mentioned demands, and as a result, have found that a cured film obtained from a composition for forming a cured film having a specific composition has excellent solvent resistance, can align a polymerizable liquid crystal with high sensitivity, and can be used as an alignment material having excellent adhesion to a liquid crystal layer.

The composition for forming a cured film of the present invention will be described in detail below with reference to specific examples of components and the like. Further, the cured film and the alignment material of the present invention using the composition for forming a cured film of the present invention, and a retardation material and a liquid crystal display element produced using the alignment material will be described.

< composition for Forming cured film >

The composition for forming a cured film of the present invention comprises: a low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinking group as the component (A); a crosslinking agent as component (B); a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as the component (C); and a crosslinking catalyst as component (D). Further, a polymer having at least one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group may be contained as the component (E). Further, other additives may be contained as long as the effects of the present invention are not impaired. Further, a solvent may be contained.

The details of each component are described below.

[ (A) component ]

The component (a) in the cured film-forming composition of the present invention is a low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinking group. That is, the component (a) is a component that imparts photo-alignment properties to a cured film obtained from the cured film-forming composition of the present invention, and in the present specification, the component (a) is also referred to as a photo-alignment component.

< Low molecular weight Compound having photo-alignment group and thermal crosslinking group >

The low-molecular-weight compound as the component (a) is a photo-alignment component having a lower molecular weight than a polymer as the component (C) described later as a base.

In the composition for forming a cured film of the present invention, the low-molecular compound as the component (a) may be a compound having a photo-alignment group and further having one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.

In the present invention, the photo-alignment group generally refers to a functional group exhibiting a property of being aligned by light irradiation, and typically refers to a functional group of a structural site which undergoes photodimerization or photoisomerization. Examples of the other photo-alignment group include a functional group which causes a photo-Fries rearrangement reaction (exemplified by a compound such as a benzoate compound), a group which causes a photo-decomposition reaction (exemplified by a compound such as a cyclobutane ring), and the like.

The structure site that can be included as a photo-alignment group in the low-molecular-weight compound of the component (a) and undergoes photo-dimerization means a site that forms a dimer upon light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, coumarinyl group, anthracenyl group, and the like. Among them, cinnamoyl group is preferable because of high transparency in the visible light region and high photodimerization reactivity.

The structural site capable of photoisomerization which the low-molecular-weight compound as the component (a) may have as a photo-alignment group is a structural site which becomes a cis-isomer or a trans-isomer by light irradiation, and specific examples thereof include sites formed of an azobenzene structure, a stilbene structure, and the like. Among them, azobenzene structure is preferable in view of high reactivity.

The low-molecular-weight compound having a photo-alignment group and one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group is, for example, a compound represented by the following formula.

In the above formula, A¹And A²Each independently represents a hydrogen atom or a methyl group.

X¹¹Is selected from alkylene with 1-18 carbon atoms, phenylene, biphenylene or the combination thereofThe structure in which 1 to 3 substituents are bonded via 1 or 2 or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or a combination thereof may be a structure in which a plurality of the substituents are connected via the bonds.

X¹²Represents 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 to 2 or more groups via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

X¹³Represents a hydroxyl 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.

X¹⁴Represents a single bond, an alkylene group having 1 to 20 carbon atoms, a 2-valent aromatic ring group, or a 2-valent aliphatic ring group. The alkylene group having 1 to 20 carbon atoms may be branched or linear.

X¹⁵Represents a hydroxyl group, a carboxyl group, an amide group, an amino group or an alkoxysilyl group. However, in X¹⁴When it is a single bond, X¹⁵Is hydroxyl or amino.

X represents a single bond, an oxygen atom or a sulfur atom. However, in X¹⁴When it is a single bond, X is also a single bond.

In addition, in the case of containing benzene ring in these substituents, the benzene ring can be selected from the carbon atom number of 1 ~ 4 alkyl, carbon atom number of 1 ~ 4 alkoxy, halogen atoms, three methyl fluoride and cyano in the same or different 1 or more substituents.

In the above formula, R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷And R¹⁸Each independently represents 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.

Specific examples of the low-molecular-weight compound having a photo-alignment group and a hydroxyl group as the component (A) include, for example, compounds represented by the above formulas [ A11] to [ A15] and compounds other than the formulas, such as methyl 4- (8-hydroxyoctyloxy) cinnamate, methyl 4- (6-hydroxyhexyloxy) cinnamate, methyl 4- (4-hydroxybutyloxy) cinnamate, methyl 4- (3-hydroxypropyloxy) cinnamate, methyl 4- (2-hydroxyethyloxy) cinnamate, methyl 4-hydroxymethyloxy cinnamate, methyl 4-hydroxycinnamate, ethyl 4- (8-hydroxyoctyloxy) cinnamate, ethyl 4- (6-hydroxyhexyloxy) cinnamate, ethyl 4- (4-hydroxybutyloxy) cinnamate, ethyl 4- (6-hydroxyhexyloxy) cinnamate, ethyl 4-hydroxybutyloxy) cinnamate, ethyl, Ethyl 4- (3-hydroxypropyloxy) cinnamate, ethyl 4- (2-hydroxyethyloxy) cinnamate, ethyl 4-hydroxymethyloxy cinnamate, ethyl 4-hydroxycinnamate, phenyl 4- (8-hydroxyoctyloxy) cinnamate, phenyl 4- (6-hydroxyhexyloxy) cinnamate, phenyl 4- (4-hydroxybutyloxy) cinnamate, phenyl 4- (3-hydroxypropyloxy) cinnamate, phenyl 4- (2-hydroxyethyloxy) cinnamate, phenyl 4-hydroxymethyloxy cinnamate, phenyl 4-hydroxycinnamate, biphenyl 4- (8-hydroxyoctyloxy) cinnamate, biphenyl 4- (6-hydroxyhexyloxy) cinnamate, biphenyl 4- (4-hydroxybutyloxy) cinnamate, biphenyl 4- (2-hydroxyoctyloxy) cinnamate, and the like, Biphenyl 4- (3-hydroxypropyloxy) cinnamate, biphenyl 4- (2-hydroxyethyloxy) cinnamate, biphenyl 4-hydroxymethyloxy cinnamate, biphenyl 4-hydroxycinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 4- (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxymethyloxy azobenzene, biphenyl 4-hydroxyethyloxy, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxy chalcone, 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, 7- (2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxy coumarin, 6-hydroxyhexyloxy coumarin, 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, methyl 4- [4- (6-hydroxyhexyloxy) benzoyl ] cinnamate, methyl 4- [4- (4-hydroxybutyloxy) benzoyl ] cinnamate, methyl 4- [4- (3-hydroxypropyloxy) benzoyl ] cinnamate, methyl 4- [4- (2-hydroxyethyloxy) benzoyl ] cinnamate, methyl 4- [ 4-hydroxymethyloxybenzoyl ] cinnamate, methyl 4- [ 4-hydroxybenzoyl ] cinnamate, ethyl 4- [4- (8-hydroxyoctyloxy) benzoyl ] cinnamate, ethyl 4- [4- (6-hydroxyhexyloxy) benzoyl ] cinnamate, ethyl 4- [4- (4-hydroxybutyloxy) benzoyl ] cinnamate, benzoic acid, Ethyl 4- [4- (3-hydroxypropyloxy) benzoyl ] cinnamate, ethyl 4- [4- (2-hydroxyethyloxy) benzoyl ] cinnamate, ethyl 4- [ 4-hydroxymethyloxybenzoyl ] cinnamate, ethyl 4- [ 4-hydroxybenzoyl ] cinnamate, tert-butyl 4- [4- (8-hydroxyoctyloxy) benzoyl ] cinnamate, tert-butyl 4- [4- (6-hydroxyhexyloxy) benzoyl ] cinnamate, tert-butyl 4- [4- (4-hydroxybutyloxy) benzoyl ] cinnamate, tert-butyl 4- [4- (3-hydroxypropyloxy) benzoyl ] cinnamate, tert-butyl 4- [4- (2-hydroxyethyloxy) benzoyl ] cinnamate, Tert-butyl 4- [ 4-hydroxymethyloxybenzoyl ] cinnamate, phenyl 4- [4- (8-hydroxyoctyloxy) benzoyl ] cinnamate, phenyl 4- [4- (6-hydroxyhexyloxy) benzoyl ] cinnamate, phenyl 4- [4- (4-hydroxybutyloxy) benzoyl ] cinnamate, phenyl 4- [4- (3-hydroxypropyloxy) benzoyl ] cinnamate, phenyl 4- [4- (2-hydroxyethyloxy) benzoyl ] cinnamate, phenyl 4- [ 4-hydroxymethyloxybenzoyl ] cinnamate, phenyl 4- [ 4-hydroxybenzoyl ] cinnamate, biphenyl 4- [4- (8-hydroxyoctyloxy) benzoyl ] cinnamate, biphenyl, 4- [4- (6-hydroxyhexyloxy) benzoyl ] cinnamic acid biphenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl ] cinnamic acid biphenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl ] cinnamic acid biphenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl ] cinnamic acid biphenyl ester, 4- [ 4-hydroxymethyloxybenzoyl ] cinnamic acid biphenyl ester, 4- [ 4-hydroxybenzoyl ] cinnamic acid biphenyl ester, 4-benzoylcinnamic acid 8-hydroxyoctyl ester, 4-benzoylcinnamic acid 6-hydroxyhexyl ester, 4-benzoylcinnamic acid 4-hydroxybutyl ester, 4-benzoylcinnamic acid 3-hydroxypropyl ester, 4-benzoylcinnamic acid 2-hydroxyethyl ester, 4-benzoylcinnamic acid, biphenyl, Hydroxymethyl 4-benzoylcinnamate, 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-hydroxyethyloxy) benzoyl ] chalcone, 4 ' - (4-hydroxymethyloxybenzoyl) chalcone, 4 ' - (4-hydroxybenzoyl) chalcone, and the like.

Specific examples of the low-molecular-weight compound having a photo-alignment group and a carboxyl group as the component (a) include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 4-propoxycinnamic acid, 3, 4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid, and the like.

Specific examples of the low-molecular-weight compound having a photo-alignment group and an amide group as the component (a) include cinnamamide, 4-methyl cinnamamide, 4-ethyl cinnamamide, 4-methoxy cinnamamide, 4-ethoxy cinnamamide, and the like.

Specific examples of the low-molecular-weight compound having a photo-alignment group and an amino group as the component (A) include methyl 4-aminocinnamate, ethyl 4-aminocinnamate, methyl 3-aminocinnamate, ethyl 3-aminocinnamate and the like.

Specific examples of the low-molecular-weight compound having a photo-alignment group and an alkoxysilyl group as the component (A), examples thereof include methyl 4- (3-trimethoxysilylpropyloxy) cinnamate, methyl 4- (3-triethoxysilylpropyloxy) cinnamate, ethyl 4- (3-trimethoxysilylpropyloxy) cinnamate, ethyl 4- (3-triethoxysilylpropyloxy) cinnamate, methyl 4- (3-trimethoxysilylhexyloxy) cinnamate, methyl 4- (3-triethoxysilylhexyloxy) cinnamate, ethyl 4- (3-trimethoxysilylhexyloxy) cinnamate and ethyl 4- (3-triethoxysilylhexyloxy) cinnamate.

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

(in the formula, R¹⁰¹Represents a hydroxyl group, an amino group, a hydroxyphenoxy group, a carboxyphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, a hydroxyphenylamino group, a carboxyphenylamino group, an aminophenylamino group, a hydroxyalkylamino group or a bis (hydroxyalkyl) amino group, X¹⁰¹Represents a phenylene group which may be substituted with an optional substituent, and the benzene ring in the definition of these substituents may be substituted with a substituent. )

Examples of the substituent in the case where the benzene ring may be substituted with a substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an isobutyl group; halogenated alkyl groups such as trifluoromethyl; alkoxy groups such as methoxy and ethoxy; halogen atoms such as iodine atom, bromine atom, chlorine atom, fluorine atom, etc.; a cyano group; nitro, and the like.

In the above-mentioned R¹⁰¹Among them, preferred are a hydroxyl group and an amino group, and particularly preferred is a hydroxyl group.

The spacer is a divalent group selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group and a phenylene group, or a group in which a plurality of the divalent groups are bonded. 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 (1), and the bond between the spacer and the polymerizable group include a single bond, an ester bond, an amide bond, a urea bond, and an ether bond. When the number of the divalent groups is plural, the divalent groups may be the same as or different from each other, and when the number of the bonds is plural, the bonds may be the same as or different from each other.

Specific examples of the low-molecular weight compound having a polymerizable group bonded to a group in which a photo-alignment site and a thermal-reactive site are bonded as component (A) include 4- (6-methacryloyloxyhexyl-1-oxy) cinnamic acid, 4- (6-acryloyloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloyloxypropyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloyloxypropyl-1-oxy) acryloyloxy) benzoic acid, 4- (4- (6-methacryloyloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, 4- (6-methacryloyloxyhexyl-1-oxy) cinnamamide, and mixtures thereof, 4- (6-methacryloyloxyhexyl-1-oxy) -N- (4-cyanophenyl) cinnamamide, 4- (6-methacryloyloxyhexyl-1-oxy) -N-bishydroxyethylcinnamamide, and the like.

The low molecular weight photo-alignment component of the component (a) includes the above specific examples, but is not limited thereto.

As described above, in the present invention, a low molecular weight compound can be used as the component (a). The component (A) may be a mixture of 1 or more low-molecular-weight compounds.

< Polymer having photo-alignment group and thermal crosslinking group >

In the cured film-forming composition of the present invention, the polymer of component (a) is a polymer having a photo-alignment group, that is, a polymer having, as a photo-alignment group, a functional group having a structure portion which undergoes photo-dimerization or photo-isomerization, and particularly preferably an acrylic copolymer having at least a photo-dimerization portion. An acrylic copolymer having one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group (hereinafter, these groups are also referred to as a thermal crosslinking site) in addition to a photodimerization site is desirable.

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

The acrylic copolymer having a photodimerized moiety and a thermally crosslinked moiety (hereinafter also referred to as a specific copolymer) as component (a) may be any acrylic copolymer having such a structure, and the types of the backbone and side chains of the main chain of the polymer constituting the acrylic copolymer are not particularly limited.

Examples of the photodimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Among them, cinnamoyl group is preferable because of high transparency in the visible light region and high photodimerization reactivity. More preferred examples of the cinnamoyl group and the substituent having a cinnamoyl structure include those represented by the following formula [1] or formula [2 ]. In the present specification, the benzene ring in cinnamoyl group is a naphthalene ring, and "cinnamoyl group" and "substituent including a cinnamoyl structure" are also included.

In the above formula [1]In, X¹Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may be substituted with any of a halogen atom and a cyano group.

In the above formula [2]In, X²Represents 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 bonded to a plurality of groups via 1 or 2 or more bonds selected from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, and a combination thereof.

In the above formulae [1] and [2], a represents any one of the formulae [ a1], [ a2], [ A3], [ a4], [ a5] and [ a6 ].

In the above formula [ A1]A and B type[A2]Formula [ A3]Formula [ A4]Formula [ A5]And the formula [ A6]In, R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、R³⁷And R³⁸Each independently represents 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 to be bonded to the crosslinking agent as the component (B) by heating, and specific examples thereof include a hydroxyl group, a carboxyl group, an amide group, an amino group, an alkoxysilyl group and the like.

The acrylic copolymer as the component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is too large exceeding 200,000, the solubility in a solvent may be lowered to deteriorate the handling property, while if the weight average molecular weight is too small being less than 3,000, the curing may be insufficient during the heat curing to deteriorate the solvent resistance or the heat resistance.

The method for synthesizing the acrylic copolymer having a photodimerized moiety and a thermally crosslinked moiety as component (a) is simple and convenient, and the method is a method of copolymerizing a monomer having a photodimerized moiety and a monomer having a thermally crosslinked moiety.

Examples of the monomer having a photodimerized moiety include monomers having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among them, monomers having a cinnamoyl group are particularly preferable in view of high transparency in the visible light region and high photodimerization reactivity.

Among them, a cinnamoyl group having a structure represented by the above formula [1] or formula [2] and a monomer containing a substituent having a cinnamoyl structure are more preferable. Specific examples of such monomers include those represented by the following formula [3] or formula [4 ].

In the above formula [3]In, X¹Represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In this case, the phenyl group and the biphenyl group may beSubstituted by any of a halogen atom and a cyano group.

L¹And L²Each independently represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

In the above formula [4]In, X²Represents 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 bonded to a plurality of groups via 1 or 2 or more bonds selected from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, and a combination thereof.

In the above formula [3]And formula [4]In, X³And X⁵Each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a 2-valent aromatic ring, or a 2-valent aliphatic ring. The alkylene group having 1 to 20 carbon atoms may be branched or linear.

In the above formula [3]And formula [4]In, X⁴Represents a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, an acrylamide group, and a methacrylamide group.

In the above formulae [3] and [4], a represents any one of the formulae [ a1], [ a2], [ A3], [ a4], [ a5] and [ a6] as described above.

Examples of the monomer having a thermally 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-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone A monomer having a hydroxyl group such as 6-lactone; monomers having a carboxyl group such as acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, and N- (carboxyphenyl) acrylamide; phenolic hydroxyl group-containing monomers such as hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) maleimide and N- (hydroxyphenyl) maleimide; amide group-containing monomers such as acrylamide and methacrylamide; alkoxysilyl group-containing monomers such as methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, acryloxypropyltrimethoxysilane and acryloxypropyltriethoxysilane; and amino group-containing monomers such as dimethylaminoethyl methacrylate, diethylamino methacrylate, and t-butylaminoethyl methacrylate.

The amount of the monomer having a photodimerized site and the monomer having a thermal crosslinking site used to obtain the specific copolymer is preferably 40 to 95 mass% and 5 to 60 mass% based on the total amount of all the monomers used to obtain the specific copolymer. By setting the monomer content having a photodimerization site to 40 mass% or more, high sensitivity and good liquid crystal alignment properties can be imparted. On the other hand, when the content is 95% by mass or less, sufficient thermosetting properties can be imparted, and high sensitivity and good liquid crystal alignment properties can be maintained.

In addition, in the composition for forming a cured film of the present invention, when the specific copolymer is obtained, a monomer copolymerizable with a monomer having a photodimerized site and a thermally crosslinked site (hereinafter, these may also be referred to as a specific functional group) (hereinafter, also may be referred to as a monomer having a non-reactive functional group) may be used in combination.

Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

Specific examples of the above-mentioned monomer are given below, but the present invention is not limited thereto.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl 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-tricyclodecyl acrylate, and mixtures thereof, And 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl 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, and mixtures thereof, Gamma-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, and the like.

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

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

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

The method for obtaining the specific copolymer used in the composition for forming a cured film of the present invention is not particularly limited, and examples thereof include a method in which a polymerization reaction is carried out in a solvent in which a monomer having a specific functional group (a monomer having a photodimerized moiety and a monomer having a thermally crosslinked moiety), a monomer having a non-reactive functional group as required, and a polymerization initiator are coexistent, at a temperature of 50 to 110 ℃. In this case, the solvent to be used is not particularly limited as long as it can dissolve the monomer having the specific functional group, the monomer having the non-reactive functional group and the polymerization initiator, which are used as necessary. Specific examples thereof include those described below.

The specific copolymer obtained in this way is usually in the state of a solution dissolved in a solvent, and can be used as it is as a polymer solution of the component (a) in the present invention.

Further, the solution of the specific copolymer obtained as described above may be put into a reactor under stirring with ether, water or the like to reprecipitate, and the precipitate formed may be filtered and washed, and then dried at normal temperature or under reduced pressure or by heating to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the composition for forming a cured film of the present invention, the powder of the specific copolymer may be used as it is as the polymer of the component (a), or the powder may be redissolved in a solvent to be described later and used in a solution state.

As the polymer of the component (a), a polymer obtained by reacting a cinnamic acid derivative with a polymer having an epoxy group in a side chain may be used.

The polymer having an epoxy group in a side chain may be, for example, a polymer of a polymerizable unsaturated compound having an epoxy group or a copolymer of a polymerizable unsaturated compound having an epoxy group and another polymerizable unsaturated compound.

Specific examples of the polymerizable unsaturated compound having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α -ethacrylate, glycidyl α -n-propylacrylate, glycidyl α -n-butylacrylate, 3, 4-epoxybutyl acrylate, 3, 4-epoxybutyl methacrylate, 6, 7-epoxyheptyl acrylate, 6, 7-epoxyheptyl methacrylate, 6, 7-epoxyheptyl α -ethacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

Examples of the other polymerizable unsaturated compounds include alkyl (meth) acrylates, cyclic alkyl (meth) acrylates, aryl methacrylates, aryl acrylates, unsaturated dicarboxylic acid diesters, bicyclic unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic anhydrides, and polymerizable unsaturated compounds other than these compounds.

Specific examples thereof include alkyl methacrylate such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, 2, 3-dihydroxypropyl methacrylate, 2-methacryloyloxyethyl glycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and methacrylic acidN-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; examples of the alkyl acrylate include methyl acrylate, isopropyl acrylate, and the like; examples of the cyclic alkyl methacrylate include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, and tricyclo [5.2.1.0 ]^2,6]Decan-8-yl methacrylate, tricyclo [5.2.1.0^2,6]Decane-8-yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; examples of the cyclic alkyl acrylate include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, and tricyclo [5.2.1.0 ]^2,6]Decane-8-yl acrylate, tricyclo [5.2.1.0^2,6]Decane-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, etc.; examples of the aryl methacrylate include phenyl methacrylate, benzyl methacrylate and the like; examples of the aryl acrylate include phenyl acrylate, benzyl acrylate and the like; examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, and diethyl itaconate;

examples of the bicyclic unsaturated compounds include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, and the like; examples of the maleimide compounds include phenylmaleimide, cyclohexylmaleimide, benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like; examples of the unsaturated aromatic compound include styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrenes, etc.; examples of the conjugated diene compound include 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, and the like; examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like; examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; examples of the unsaturated dicarboxylic acid anhydride include the respective anhydrides of the above unsaturated dicarboxylic acids; examples of the polymerizable unsaturated compounds other than those mentioned above include acrylonitrile, methacrylonitrile, vinyl chloride, 1-dichloroethylene, acrylamide, methacrylamide, vinyl acetate, and the like.

The copolymerization ratio of the polymerizable unsaturated compound having an epoxy group in the polymer having an epoxy group in a side chain is preferably 30% by mass or more, and more preferably 50% by mass or more.

The synthesis of the polymer having an epoxy group in a side chain can be carried out by a known radical polymerization method preferably in a solvent in the presence of an appropriate polymerization initiator.

As the polymer having an epoxy group in a side chain, a commercially available product can be used. Examples of such commercially available products include EHPE3150, EHPE3150CE (manufactured by ダイセル, Inc.), UG-4010, UG-4035, UG-4040, UG-4070 (manufactured by ARUFON series, manufactured by Toyo Seisaku Co., Ltd.), ECN-1299 (manufactured by Asahi Kasei corporation, Inc.), DEN431, DEN438 (manufactured by ダウケミカル, Inc.), JeR-152 (manufactured by Mitsubishi ケミカル, Inc.), エピクロン N-660, N-665, N-670, N-673, N-695, N-740, N-770, N-775 (manufactured by DIC , old Japan インキ), EOCN-1020, and EOCN-102S, EOCN-104S (manufactured by Nippon Chemicals, Inc.), and the like.

The cinnamic acid derivative includes a cinnamic acid derivative having a carboxyl group, and examples thereof include compounds represented by any one of the following formulas (1-1) to (1-5).

(in the formula, R₁Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or the like. )

In addition, as the carboxyl group-containing cinnamic acid derivatives, also suitable for use in the above formula [3]]In the monomer shown, X¹A compound which is a hydrogen atom.

The compounds represented by the above formulae (1-1) to (1-5) can be synthesized by appropriately combining conventional methods in organic chemistry.

The reaction product of the polymer having an epoxy group in a side chain and the cinnamic acid derivative can be synthesized by reacting the polymer having an epoxy group and the cinnamic acid derivative, preferably in a suitable organic solvent, preferably in the presence of a catalyst, as described above.

The ratio of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 mol, more preferably 0.05 to 1.3 mol, and even more preferably 0.1 to 1.1 mol, based on 1 mol of the epoxy group contained in the epoxy group-containing polymer.

As the catalyst that can be used here, an organic base or a compound known as a so-called curing accelerator that accelerates the reaction of an epoxy compound and an acid anhydride can be used.

Examples of the organic base include primary to secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole; tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide, and the like. Among these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and 4-dimethylaminopyridine are preferable; quaternary organic amines such as tetramethylammonium hydroxide.

Examples of the curing accelerator include benzyldimethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, cyclohexyldimethylamine, and triethylenemelamineTertiary amines such as alcohol amines; such as 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4, 5-bis (hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-phenyl-4, 5-bis [ (2' -cyanoethoxy) methyl ] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazole

Trimellitic acid salt, 1- (2-cyanoethyl) -2-phenylimidazole

Trimellitic acid salt, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole

Imidazole compounds such as trimellitic acid salt, 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine, 2, 4-diamino-6- (2 '-n-undecylimidazolyl) ethyl-s-triazine, 2, 4-diamino-6- [ 2' -ethyl-4 '-methylimidazolyl- (1') ] -ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, isocyanuric acid adduct of 2, 4-diamino-6- [2 '-methylimidazolyl- (1') ] -ethyl-s-triazine; organic phosphorus compounds such as diphenylphosphine, triphenylphosphine and triphenyl phosphite;

such as benzyltriphenylphosphonium chloride

Tetra-n-butylbromide

Methyl triphenyl phosphonium bromide

Ethyltriphenylphosphonium bromide

N-butyl triphenyl phosphonium bromide

Tetraphenyl bromides

Ethyl triphenyl iodide

Ethyl triphenyl acetic acid

Tetra-n-butyl

O, O-diethyldithiophosphate tetra-n-butyl

Benzotriazole salts tetra-n-butyl

Tetrafluoroborate, tetra-n-butyl

Tetraphenylborate, tetraphenyl

Quaternary phosphonium salts such as tetraphenylborate

Salt; 1, 8-diazabicyclo [5.4.0 ]]Diazabicycloalkenes such as undecene-7 and organic acid salts thereof; organic metal compounds such as zinc octoate, tin octoate, and aluminum acetylacetonate complex; such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chlorideQuaternary ammonium salts such as ammonium; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin chloride; high-melting-point dispersible latent curing accelerators such as amine addition accelerators including dicyandiamide and adducts of amines and epoxy resins; mixing the imidazole compound, organic phosphorus compound and quaternary phosphonium compound

A microcapsule-type latent curing accelerator in which the surface of a curing accelerator such as a salt is coated with a polymer; an amine salt type latent curing agent accelerator; and latent curing accelerators such as high-temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

Among them, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

The catalyst is used in a proportion of preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer having an epoxy group.

Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Among them, ether compounds, ester compounds, ketone compounds and alcohol compounds are preferable from the viewpoint of solubility of raw materials and products and easiness of purification of products. The solvent is used in an amount such that the solid content concentration (the ratio of the mass of the components other than the solvent in the reaction solution to the total mass of the solution) is preferably 0.1 mass% or more, more preferably 5 to 50 mass%.

The reaction temperature is preferably 0 to 200 ℃, and more preferably 50 to 150 ℃. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

Thus, a solution containing a reaction product of the polymer having an epoxy group and the cinnamic acid derivative was obtained. The solution may be directly used for preparation of the composition for forming a cured film, or the solution may be used for preparation of the composition for forming a cured film after separating the polymer contained in the solution, or the separated polymer may be purified and used for preparation of the composition for forming a cured film.

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

As described above, in the present invention, a specific copolymer having a high molecular weight can be used as the component (A). The component (A) may be a mixture of 1 or more specific copolymers.

[ (B) component ]

The composition for forming a cured film of the present invention contains a crosslinking agent as the component (B). More specifically, the component (B) is a crosslinking agent which reacts with the components (A) and (C). (B) The component (C) is bonded to the thermally crosslinkable group of the compound or polymer as the component (A) and the hydroxyl group contained in the component (C). Further, the composition for forming a cured film of the present invention can form a cured film and form an alignment material having high photoreaction efficiency.

The crosslinking agent as the component (B) includes compounds such as epoxy compounds, methylol compounds and isocyanate compounds, and preferably methylol compounds. Among them, the crosslinking agent as the component (B) is preferably a compound having 2 or more groups capable of forming a crosslink with the functional group capable of thermally crosslinking the component (a), and is preferably a crosslinking agent having 2 or more methylol groups or alkoxymethyl groups, for example. Examples of the compound having such a group include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the methylol compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetrakis (alkoxymethyl) bisphenol, and tetrakis (hydroxymethyl) bisphenol.

Specific examples of alkoxymethylated glycolurils include 1,3,4, 6-tetrakis (methoxymethyl) glycoluril, 1,3,4, 6-tetrakis (butoxymethyl) glycoluril, 1,3,4, 6-tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1,3, 3-tetrakis (butoxymethyl) urea, 1,3, 3-tetrakis (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone, and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone. Commercially available products include glycoluril compounds (trade names: サイメル (registered trademark) 1170 and パウダーリンク (registered trademark) 1174) manufactured by Mitsui サイテック, methylated urea resins (trade name: UFR (registered trademark) 65), and urea/formaldehyde resins (highly condensed resins, trade names: ベッカミン (registered trademark) J-300S, ベッカミン P-955 and ベッカミン N) manufactured by butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R and U-VAN11HV) and DIC (chemical industry , old Japan インキ), respectively.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzguanamine and the like. Commercially available products include those manufactured by Mitsui サイテック (trade name: サイメル (registered trademark) 1123), and those manufactured by Mitsui ケミカル (trade name: ニカラック (registered trademark) BX-4000, ニカラック BX-37, ニカラック BL-60, ニカラック BX-55H).

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Examples of commercially available products include methoxymethyl-type melamine compounds (trade names: サイメル (registered trademark) 300, サイメル 301, サイメル 303, サイメル 350) manufactured by Mitsui サイテック K.K.), butoxymethyl-type melamine compounds (trade names: マイコート (registered trademark) 506, マイコート 508), (methoxymethyl-type melamine compounds (trade names: ニカラック (registered trademark) MW-30, ニカラック MW-22, ニカラック MW-11, ニカラック MW-100LM, ニカラック MS-001, ニカラック MX-002, ニカラック MX-730, ニカラック MX-750, ニカラック MX-035), butoxymethyl-type melamine compounds (trade names: ニカラック (registered trademark) MX-45, MX-83, and ケミカル), ニカラック MX-410, ニカラック MX-302), and the like.

Examples of the tetrakis (alkoxymethyl) bisphenol and tetrakis (hydroxymethyl) bisphenol include tetrakis (alkoxymethyl) bisphenol a and tetrakis (hydroxymethyl) bisphenol a.

The crosslinking agent as the component (B) may be a melamine compound, a urea compound, a glycoluril compound, or a benzoguanamine compound obtained by condensing a methylol group or an alkoxymethyl group substituted for the hydrogen atom of the amino group. Examples thereof include high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in U.S. Pat. No. 6323310. Examples of commercially available products of the melamine compound include trade names: サイメル (registered trademark) 303 (manufactured by mitsui サイテック) and the like, and commercially available products of the benzoguanamine compound include trade names: サイメル (registered trademark) 1123 (manufactured by Mitsui サイテック (incorporated by reference).

Further, as the crosslinking agent of the component (B), there can be used: and polymers produced using acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group (i.e., a hydroxymethyl group) or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, and N-butoxymethylmethacrylamide.

Examples of such polymers include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, a copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate.

As such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C ═ C double bond can be used.

Examples of the polymerizable group having a C ═ C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.

The method for obtaining the polymer as described above is not particularly limited. For example, an acrylic polymer having the specific functional group 2 is produced in advance by a polymerization method such as radical polymerization. Next, by reacting the specific functional group 2 with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound), a polymerizable group containing a C ═ C double bond can be introduced into the polymer as the component (B).

Here, the specific functional group 2 means a functional group such as a carboxyl group, a glycidyl group, a hydroxyl group, an amino group having an active hydrogen, a phenolic hydroxyl group, or an isocyanate group, or a plurality of functional groups selected from these. By polymerizing the monomer having these groups, an acrylic polymer having a specific functional group 2 can be obtained.

In the above reaction, the specific functional group 2 and a group which reacts with a functional group of the specific compound and is involved in the reaction are preferably a carboxyl group and an epoxy group, a hydroxyl group and an isocyanate group, a phenolic hydroxyl group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, a hydroxyl group and an acid chloride, or the like. Further, a more preferable combination is a carboxyl group and an epoxy group in glycidyl methacrylate, or a hydroxyl group and an isocyanate group in isocyanatoethyl methacrylate.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, and N- (carboxyphenyl) acrylamide.

Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, and 1, 7-octadiene monoepoxide.

Examples of the monomer having a hydroxyl group 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-acryloyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic acid- 6-lactones, and the like.

Examples of the monomer having an amino group include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleimide.

Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.

The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

These crosslinking agents may be used alone or in combination of 2 or more.

The content of the crosslinking agent as the component (B) in the composition for forming a cured film of the present invention is preferably 5 to 500 parts by mass, more preferably 10 to 400 parts by mass, based on 100 parts by mass of the total amount of the components (a) and (C). When the content of the crosslinking agent is too small, the solvent resistance of a cured film obtained from the composition for forming a cured film is lowered, and the liquid crystal alignment property is lowered. On the other hand, when the content of the crosslinking agent is too large, the liquid crystal alignment property and the storage stability may be deteriorated.

[ (C) ingredient ]

The component (C) contained in the cured film-forming composition of the present invention is a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as a unit structure (hereinafter, also referred to as a specific copolymer 2).

As a method for obtaining the polymer as the component (C), the method described in the above-mentioned component (B) for obtaining a polymer having a polymerizable group containing a C ═ C double bond can be used. Namely, there can be mentioned: a method in which a polymer having a carboxyl group is produced and then reacted with a monomer having a polymerizable group containing a C ═ C double bond and an epoxy group; and a method in which a polymer having an epoxy group as exemplified in the section of the component (a) is produced and then reacted with a monomer having a polymerizable group containing a C ═ C double bond and a carboxyl group.

Examples of the method for obtaining a polymer having a carboxyl group include a method in which a polymerization reaction is carried out in a solvent in which a monomer having a carboxyl group and, if necessary, other monomers and a polymerization initiator coexist, at a temperature of 50 to 110 ℃. In this case, the solvent used is not particularly limited as long as it can dissolve the monomer having a carboxyl group, and the other monomers and the polymerization initiator used as necessary. Specific examples thereof are described in the section of [ solvent ] mentioned below.

Examples of the method for obtaining the polymer having an epoxy group include a method in which a polymerization reaction is carried out in a solvent in which a monomer having an epoxy group and, if necessary, other monomers and a polymerization initiator coexist, at a temperature of 50 to 110 ℃. In this case, the solvent used is not particularly limited as long as it can dissolve the monomer having an epoxy group and, if necessary, the other monomers and the polymerization initiator. Specific examples thereof are described in the section of [ solvent ] mentioned below.

Examples of the monomer having a polymerizable group containing a C ═ C double bond and a carboxyl group include, for example, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, mono- (2- (acryloyloxy) ethyl) hexahydrophthalate, mono- (2- (methacryloyloxy) ethyl) hexahydrophthalate, mono- (2- (acryloyloxy) ethyl) succinate, mono- (2- (methacryloyloxy) ethyl) succinate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and omega-carboxy-polycaprolactone mono (meth) acrylate. As these monomers, for example, those commercially available as "ライトエステル HO-MS", "ライトアクリレート HOA-MS (N)", "ライトアクリレート HOA-HH (N)", and "ライトアクリレート HOA-MPL (N)" (trade name, manufactured by Kyoeisha chemical Co., Ltd., or the like), アロニックス M-5300, and アロニックス M-5400 (trade name, manufactured by Toyo Synthesis Co., Ltd., the like) can be used.

Examples of the monomer having a polymerizable group containing a C ═ C double bond and an epoxy group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allyl glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinyl-7-oxabicyclo [4.1.0] heptane, 1, 2-epoxy-5-hexene, 1, 7-octadiene monoepoxide, and the like.

In the production of the polymer as the component (C), it is preferable to select a monomer having a spacer between a polymerizable group and a group selected from the group consisting of an epoxy group and a carboxyl group as at least one of the monomers having an epoxy group and a carboxyl group to be raw materials. By selecting such a raw material, the cured film of the present invention obtained has better adhesion to the liquid crystal layer.

A preferred structure of the monomer having a spacer and a carboxyl group is any of the following (SC-1) and (SC-2).

In the formula, X⁴The polymerizable group is represented by the formula, and specific examples of the polymerizable group include acryloyl, methacryloyl and styrylMaleimide, acrylamide, methacrylamide, and the like. L is¹Represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond. Q¹And Q³Each independently represents an alkylene group having 2 to 10 carbon atoms, Q²Represents a divalent group having a structure derived from a dicarboxylic anhydride. n represents a natural number of 1 to 10.

As such a monomer having a spacer and a carboxyl group, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, mono- (2- (acryloyloxy) ethyl) hexahydrophthalate, mono- (2- (methacryloyloxy) ethyl) hexahydrophthalate, mono- (2- (acryloyloxy) ethyl) succinate, mono- (2- (methacryloyloxy) ethyl) succinate and ω -carboxy-polycaprolactone mono (meth) acrylate are preferable. Further, a multifunctional acrylate having a carboxyl group is also preferable. Examples of the commercially available substances include those commercially available as "ライトエステル HO-MS", "ライトアクリレート HOA-MS (N)", "ライトアクリレート HOA-HH (N)", and "ライトアクリレート HOA-MPL (N)" (trade name, manufactured by Kyodo chemical Co., Ltd.), アロニックス M-5300, and アロニックス M-5400 (trade name, manufactured by Toyo Seiya Kabushiki Kaisha).

A preferred structure of the monomer having a spacer and an epoxy group is represented by (SE-1) below.

In the formula, X⁴Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, an acrylamide group, and a methacrylamide group. L is¹Represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond. Q¹Represents an alkylene group having 2 to 10 carbon atoms.

Examples of such a monomer having a spacer and an epoxy group include 4-hydroxybutyl methacrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

The monomer having a carboxyl group and a polymerizable group having a C ═ C double bond for grafting to an epoxy group of the polymer is also preferably a multifunctional acrylate having a carboxyl group, which is represented by (SC-3) below.

In the formula, X⁴Examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styryl group, a maleimide group, an acrylamide group, and a methacrylamide group. L is¹Represents a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond. Q⁴Represents an (m +1) -valent organic group, and m represents a natural number of 2 to 10.

As such a compound, アロニックス M-510 and M-520 (trade name, manufactured by Toyo Synthesis Co., Ltd.) are commercially available.

The polymer obtained by the above method is a polymer having a hydroxyl group as a result, but when it is desired to introduce a hydroxyl group into the polymer, the monomer having a hydroxyl group may be copolymerized in the production of a polymer having a carboxyl group or a polymer having an epoxy group.

In the present invention, when the polymer as the component (C) is obtained, other monomers may be used in combination.

Specific examples of such other monomers include the acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like exemplified in the section of the component (a).

In the polymer of the component (C), the proportion of the structural unit having a hydroxyl group is preferably 20 mol% or more, and more preferably 40 mol% or more, based on 100 mol% of the total structural units of the polymer. If the total amount is less than 20 mol%, curing may be insufficient, which may adversely affect the orientation.

Here, when the polymer of component (C) contains a structural unit having 2 or more hydroxyl groups, the proportion of the structural unit having a hydroxyl group means 100 mol% (the number of moles of the structural unit having a hydroxyl group) × (the number of hydroxyl groups contained in the structural unit) relative to the total structural units of the polymer.

In the polymer of the component (C), the proportion of the structural unit having a polymerizable group containing a C ═ C double bond is preferably 20 mol% or more, and more preferably 40 mol% or more, based on 100 mol% of the total structural units of the polymer. When the total amount is less than 20 mol%, adhesion to the liquid crystal layer may be insufficient.

Here, when the polymer of the component (C) contains a structural unit having 2 or more polymerizable groups containing a C ═ C double bond, the ratio of the structural unit having a polymerizable group containing a C ═ C double bond means (the number of moles of the structural unit having a polymerizable group containing a C ═ C double bond) × (the number of polymerizable groups containing a C ═ C double bond contained in the structural unit) per 100 mol% of the total structural units of the polymer.

The acrylic polymer as an example of the component (C) obtained by the above method is usually in a state of a solution dissolved in a solvent, and can be used as it is as a solution of the component (C) in the present invention.

The polymer powder of component (C) can be prepared by putting the polymer solution of component (C) obtained by the above method into diethyl ether, water or the like under stirring to reprecipitate, filtering/washing the resultant precipitate, and then drying the precipitate at normal temperature or under reduced pressure or by heating. By the above-mentioned operation, the polymerization initiator and the unreacted monomer which coexist with the polymer as the component (C) can be removed, and as a result, a polymer powder as an example of the purified component (C) can be obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the composition for forming a cured film on the surface of the optical film of the present invention, the polymer as the component (C) may be used in the form of a powder or a solution prepared by redissolving a purified powder in a solvent to be described later.

In the cured film-forming composition for forming a cured film on the surface of the optical film of the present invention, the component (C) may be a mixture of a plurality of polymers shown as examples of the component (C).

The weight average molecular weight of the polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

The content of the component (C) in the cured film-forming composition of the present invention is preferably 5:95 to 60:40 in terms of a mass ratio of the low-molecular-weight compound as the component (a) to the polymer as the component (C). When the content of the polymer as the component (C) is too small, the solvent resistance and heat resistance of the cured film obtained from the composition for forming a cured film may be lowered, and the orientation sensitivity at the time of photo-orientation may be lowered. On the other hand, when the content of the polymer as the component (C) is too large, the photo-alignment property and the storage stability may be lowered.

In addition, the content of the component (C) in the cured film-forming composition of the present invention is preferably 5:95 to 90:10 in terms of a mass ratio of the polymer as the component (a) to the polymer as the component (C). When the content of the polymer as the component (C) is too small, adhesion to the liquid crystal layer may be reduced. On the other hand, when the content of the polymer as the component (C) is too large, the photo-alignment property may be degraded.

[ (D) component ]

The composition for forming a cured film on the surface of the optical film of the present invention further contains a crosslinking catalyst as the component (D) in addition to the components (a), (B) and (C).

Examples of the crosslinking catalyst as the component (D) include acids and thermal acid generators. The component (D) is effective for accelerating the thermosetting reaction in forming a cured film using the cured film-forming composition for forming a cured film on the surface of the optical film of the present invention.

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

Examples of such compounds include sulfonic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, hydrates, and salts thereof.

Examples of the compound which 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 (methylsulfonate), and pyridine p-toluenesulfonate

Salt, morpholine p-toluenesulfonate

Salts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluenesulfonamide, and the formula [ TAG-1]-formula [ TAG-41]Shown inCompounds, and the like.

The content of the component (D) in the cured film-forming composition of the present invention is 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and still more preferably 0.1 to 6 parts by mass, based on 100 parts by mass of the total amount of the low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinking group as the component (a) and the polymer as the component (C). By setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be provided, and high sensitivity to exposure can also be provided. Further, by setting the amount to 20 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[ (E) ingredient ]

The composition of the present invention may further contain a polymer having at least one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group as the (E) component.

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

Among these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, styrene, or the like can be used. As a method for synthesizing the same, a method of (co) polymerizing a monomer having at least one group selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an amide group, a monomer having an amino group and a monomer having an alkoxysilyl group exemplified in the above sections of the component (a), the component (B) and the component (C) with a monomer other than the above monomers as required by the method described in the above sections of the component (a), the component (B) and the component (C) is simple.

The weight average molecular weight of the acrylic polymer as an example of the component (E) is preferably 3,000 to 200,000, more preferably 4,000 to 150,000, and further preferably 5,000 to 100,000.

As a preferable example of the polyether polyol as the component (E), there can be mentioned a polyether polyol obtained by adding propylene oxide, polyethylene glycol, polypropylene glycol or the like to a polyol such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol a, triethylene glycol, sorbitol or the like. Specific examples of the polyether polyol include アデカポリエーテル P series, G series, EDP series, BPX series, FC series, CM series, ユニオックス (registered trademark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, ユニオール (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオン (registered trademark) LT-221, ST-221, OT-221 and the like manufactured by ADEKA.

As a preferable example of the polyester polyol as the component (E), there can be mentioned a polyester polyol obtained by reacting a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol or polypropylene glycol with a polycarboxylic acid such as adipic acid, sebacic acid or isophthalic acid. Specific examples of the polyester polyol include ポリライト (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, (strain) クラレポリオール P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, and the like, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, and the like.

As a preferred example of the polycaprolactone polyol as the component (E), there can be mentioned a polycaprolactone polyol obtained by ring-opening polymerization of caprolactone using a polyol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyols include ポリライト (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, manufactured by DIC (trade name) and プラクセル (registered trademark) 205, manufactured by ダイセル, L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, and 320.

Examples of the polycarbonate polyol as a preferable example of the component (E) include polycarbonate polyols 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 プラクセル (registered trademark) CD205, CD205PL, CD210, CD220 (manufactured by LTD ダイセル), C-590, C-1050, C-2050, C-2090, and C-3090 (manufactured by LTD クラレ).

Preferable examples of the cellulose as the component (E) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyalkyl celluloses such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose, and preferable examples thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.

Preferred examples of the cyclodextrin as the component (E) include cyclodextrins such as α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin, methylated cyclodextrins such as methyl- α -cyclodextrin, methyl- β -cyclodextrin and methyl- γ -cyclodextrin, hydroxymethyl- α -cyclodextrin, hydroxymethyl- β -cyclodextrin, hydroxymethyl- γ -cyclodextrin, 2-hydroxyethyl- α -cyclodextrin, 2-hydroxyethyl- β -cyclodextrin, 2-hydroxyethyl- γ -cyclodextrin, 2-hydroxypropyl- α -cyclodextrin, 2-hydroxypropyl- β -cyclodextrin, 2-hydroxypropyl- γ -cyclodextrin, 3-hydroxypropyl- α -cyclodextrin, gamma, Hydroxyalkyl cyclodextrins such as 3-hydroxypropyl- β -cyclodextrin, 3-hydroxypropyl- γ -cyclodextrin, 2, 3-dihydroxypropyl- α -cyclodextrin, 2, 3-dihydroxypropyl- β -cyclodextrin, and 2, 3-dihydroxypropyl- γ -cyclodextrin, and the like.

As a preferred example of the urethane-modified acrylic polymer as the component (E), commercially available products such as アクリット (registered trademark) 8UA-017, 8UA-239H, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366 and the like available from Daihei ファインケミカル (trademark) are exemplified.

As a preferred example of the phenol novolac resin as the component (E), for example, a phenol-formaldehyde condensation polymer and the like can be given.

In the composition of the present invention, the polymer as the component (E) may be used in the form of a powder or a solution prepared by redissolving a purified powder in a solvent to be described later.

In the composition of the present invention, the component (E) may be a mixture of a plurality of polymers exemplified as the component (E).

The content of the component (E) in the cured film-forming composition of the present invention is 5 to 500 parts by mass based on 100 parts by mass of the total amount of the components (a) and (C).

[ (F) ingredient ]

When the composition of the present invention uses a polymer as the component (a), it may further contain a low molecular photo-alignment component as the component (F). The inclusion of the low-molecular photo-alignment component increases the amount of photo-alignment groups present in the surface layer of the alignment film, thereby exhibiting the effect of improving the alignment sensitivity.

The low molecular photo-alignment component includes the formula [3] exemplified in the section of component (A) in the present specification]A monomer represented by the formula [4]]A monomer represented by the formula [3]]Radical X of the monomers shown⁴A compound substituted with a hydrogen atom, formula [4]]Radical X of the monomers shown⁴A compound substituted with a hydrogen atom, a cinnamic acid derivative having a carboxyl group represented by any one of the above formulas (1-1) to (1-5).

In the composition of the present invention, the component (F) may be a mixture of a plurality of compounds exemplified as the component (F).

When the composition for forming a cured film of the present invention contains the component (F), the content is 5 to 500 parts by mass based on 100 parts by mass of the total amount of the polymer as the component (a) and the polymer as the component (C).

[ other additives ]

The cured film-forming composition of the present invention may contain other additives as long as the effects of the present invention are not impaired.

As the other additive, for example, a sensitizer may be contained. The sensitizer is effective in promoting the photoreaction thereof when forming a cured film of the surface in the optical film of the present invention.

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

These sensitizers are not particularly limited to the above sensitizers. They can be used alone or in combination of 2 or more compounds.

In the embodiment of the present invention, the sensitizer is used in a proportion of preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the component (a). When the ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and when it is too large, the transmittance of the formed cured film may be lowered or the coating film may be rough.

The cured film-forming composition of the present invention may contain, as other additives, silane coupling agents, surfactants, rheology control agents, pigments, dyes, storage stabilizers, antifoaming agents, antioxidants, and the like, as long as the effects of the present invention are not impaired.

[ solvent ]

The cured film-forming composition of the present invention is often used in the form of a solution dissolved in a solvent. The solvent used in this case is a solvent capable of dissolving the component (a), the component (B), the component (C) and the component (D), and if necessary, the component (E), the component (F) and/or other additives, and the kind, structure and the like thereof are not particularly limited as long as they have such dissolving ability.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, methyl acetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-propyl acetate, isopropyl alcohol, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.

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

< preparation of composition for Forming cured film >

The cured film-forming composition of the present invention is a thermosetting cured film-forming composition having photo-alignment properties. The cured film-forming composition of the present invention contains, as described above: a low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinking group as the component (A); a crosslinking agent as component (B); a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as the component (C); and a crosslinking catalyst as component (D). According to the needs, contains: a polymer having at least one group selected from a hydroxyl group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group as the component (E); and/or a low-molecular photo-alignment component as the (F) component. Further, other additives may be contained as long as the effects of the present invention are not impaired, and further, a solvent may be contained.

Preferred examples of the composition for forming a cured film of the present invention are as follows.

[1]: a composition for forming a cured film, the composition comprising, in a mass ratio of 5:95 to 60:40, the content ratio of a low-molecular-weight compound having a photo-alignment group and a thermal-crosslinkable group as a component (A) to a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as a component (C), the composition comprising: a crosslinking agent as component (B) in an amount of 1 to 500 parts by mass, preferably 5 to 500 parts by mass, based on 100 parts by mass of the total amount of the low-molecular compound as component (A) and the polymer as component (C); and 0.01 to 20 parts by mass of a crosslinking catalyst as the component (D) per 100 parts by mass of the total amount of the low-molecular compound as the component (A) and the polymer as the component (C).

[2]: a composition for forming a cured film, the composition comprising, in a mass ratio of 5:95 to 60:40, the content ratio of a low-molecular-weight compound having a photo-alignment group and a thermal-crosslinkable group as a component (A) to a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as a component (C), the composition comprising: a crosslinking agent as component (B) in an amount of 1 to 500 parts by mass, preferably 5 to 500 parts by mass, based on 100 parts by mass of the total amount of the low-molecular compound as component (A) and the polymer as component (C); and 0.01 to 20 parts by mass of a crosslinking catalyst as component (D) per 100 parts by mass of the total amount of the low-molecular compound as component (A) and the polymer as component (C); and a solvent, further comprising: 5 to 500 parts by mass of a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group as the component (E) based on 100 parts by mass of the total amount of the low-molecular compound as the component (A) and the polymer as the component (C).

[3]: a composition for forming a cured film, the content ratio of a polymer having a photo-alignment group and a thermal-crosslinking group as a component (A) to a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as a component (C) being 5:95 to 90:10 by mass, the composition comprising: a crosslinking agent as component (B) in an amount of 1 to 500 parts by mass, preferably 5 to 500 parts by mass, based on 100 parts by mass of the total amount of the polymer as component (A) and the polymer as component (C); and 0.01 to 20 parts by mass of a crosslinking catalyst as the component (D) per 100 parts by mass of the total amount of the polymer as the component (A) and the polymer as the component (C).

[4]: a composition for forming a cured film, the content ratio of a polymer having a photo-alignment group and a thermal-crosslinking group as a component (A) to a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as a component (C) being 5:95 to 90:10 by mass, the composition comprising: a crosslinking agent as component (B) in an amount of 1 to 500 parts by mass, preferably 5 to 500 parts by mass, based on 100 parts by mass of the total amount of the polymer as component (A) and the polymer as component (C); and 0.01 to 20 parts by mass of a crosslinking catalyst as component (D) per 100 parts by mass of the total amount of the polymer as component (A) and the polymer as component (C); and a solvent, further comprising: 5 to 500 parts by mass of a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group as the component (E) based on 100 parts by mass of the total amount of the polymer as the component (A) and the polymer as the component (C).

The mixing ratio, the preparation method, and the like in the case of using the cured film-forming composition of the present invention in the form of a solution will be described in detail below.

The proportion of the solid component in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 to 80% by mass, preferably 2 to 60% by mass, and more preferably 3 to 40% by mass. The solid component is a component obtained by removing a solvent from all the components of the composition for forming a cured film.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method of mixing the component (a) and the component (B), the component (D), and if necessary, the component (E) and/or the component (F) in a solution of the component (C) dissolved in a solvent at a predetermined ratio to prepare a uniform solution, and a method of further adding other additives if necessary at an appropriate stage of the preparation method to mix them.

In the preparation of the composition for forming a cured film of the present invention, the specific copolymer obtained by the polymerization reaction in the solvent and/or the solution of the specific copolymer 2 may be used as it is. In this case, for example, the component (a), the component (B), the component (D), if necessary, the component (E), the component (F) and/or other additives are added to a solution prepared by preparing the acrylic polymer as the component (C) to prepare a uniform solution. In this case, a solvent may be further added for the purpose of concentration adjustment. In this case, the solvent used in the preparation of the component (C) may be the same as or different from the solvent used for the concentration adjustment of the cured film-forming composition.

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

As described above, the composition for forming a cured film of the present invention is configured to contain a low-molecular compound or polymer having a photo-alignment group and a thermal-crosslinkable group as the component (a), a crosslinking agent as the component (B), a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond as the component (C), and a crosslinking catalyst as the component (D).

Therefore, the cured film formed from the composition for forming a cured film of the present invention is formed so that the interior thereof becomes hydrophilic due to the properties of the component (C) when the component (a) is a low molecular weight compound, and further due to the properties of the components (a), (B) and (C) when the component (a) is a polymer, and the film structure is stabilized. In addition, most of the photo-alignment groups of the low-molecular compound or the polymer as the component (a) in the cured film are present in the vicinity of the surface of the cured film. More specifically, the low-molecular-weight compound or the polymer as the component (a) has a structure in which the hydrophilic thermal reaction part is oriented toward the inside of the cured film and the hydrophobic photoreactive part is oriented toward the surface side, and most of them are present in the vicinity of the surface of the cured film. As a result, the cured film of the present invention realizes a structure in which the proportion of the photoreactive group of the component (a) present in the vicinity of the surface is increased. Furthermore, when the cured film of the present invention is used as an alignment material, the efficiency of photoreaction for photo-alignment can be improved, and excellent alignment sensitivity can be obtained. Further, the alignment material can be suitably used for forming the patterned retardation material, and the patterned retardation material produced using the alignment material has excellent pattern formability.

The cured film-forming composition of the present invention contains, as the component (C), a polymer having a hydroxyl group and a polymerizable group containing a C ═ C double bond, as described above. Therefore, the cured film obtained from the composition for forming a cured film of the present invention can be internally subjected to a crosslinking reaction with the component (C) due to a thermal reaction before the photoreaction with the photo-alignment group of the low-molecular compound or polymer as the component (a). As a result, when used as an alignment material, the resistance to the polymerizable liquid crystal and the solvent applied thereto can be improved.

The polymer as the component (C) functions to enhance adhesion to a layer of a cured polymerizable liquid crystal formed thereon when a cured film obtained from the composition for forming a cured film of the present invention is used as an alignment material.

< cured film, alignment material and retardation material >

The cured film can be formed by applying a solution of the composition for forming a cured film of the present invention to a substrate (for example, a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, or the like, a glass substrate, a quartz substrate, an ITO substrate, or the like), a film (for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, an acrylic film, or the like), or the like by bar coating, spin coating, flow coating, roll coating, slit coating, post-slit spin coating, inkjet coating, printing, or the like to form a coating film, and then drying the coating film by heating with an electric heating plate, an oven, or the like.

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

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

The cured film formed in this way can be used as an alignment material, that is, a member for aligning a liquid crystal compound such as a polymerizable liquid crystal, by polarized UV irradiation.

The polarized UV irradiation method is generally performed by irradiating linearly polarized light vertically or obliquely at room temperature or in a heated state using ultraviolet light to visible light having a wavelength of 150nm to 450 nm.

Since the alignment material formed using the cured film obtained from the composition for forming a cured film of the present invention has solvent resistance and heat resistance, a phase difference material formed from a polymerizable liquid crystal solution is applied to the alignment material, and then the alignment material is heated to a phase transition temperature of the liquid crystal to bring the phase difference material into a liquid crystal state, thereby aligning the alignment material. Further, the retardation material in the desired alignment state can be directly cured to form a retardation material with a layer having optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the liquid crystal monomer, or the like can be used. Further, when the substrate on which the alignment material is formed is a film, the film having the retardation material of the present embodiment is useful as a retardation film. The retardation material forming such a retardation material is in a liquid crystal state, and there are retardation materials in which an alignment state such as a horizontal alignment, a cholesteric alignment, a vertical alignment, or a hybrid alignment is formed on an alignment material, and they can be used separately according to the required retardation characteristics.

In the case of producing a patterned retardation material used for a 3D display, a cured film formed from the cured film-forming composition of the present invention by the above-described method is subjected to polarized UV exposure from a predetermined standard, for example, in a direction of +45 degrees via a mask of a line-and-space pattern, and then the mask is removed and then the polarized UV exposure is carried out in a direction of-45 degrees, thereby forming an alignment material in which 2 liquid crystal alignment regions having different alignment control directions of liquid crystals are formed. Then, after a phase difference material formed of a polymerizable liquid crystal solution is applied, heating is performed until the phase transition temperature of the liquid crystal is reached, thereby bringing the phase difference material into a liquid crystal state. The polymerizable liquid crystal in the liquid crystal state is aligned on the alignment material in which the 2 liquid crystal alignment regions are formed, and alignment states corresponding to the respective liquid crystal alignment regions are formed. Further, by directly curing the retardation material having achieved such an alignment state and fixing the alignment state, a patterned retardation material in which a plurality of 2 retardation regions having different retardation characteristics are regularly arranged can be obtained.

Furthermore, an alignment material produced using a cured film obtained from the composition for forming a cured film of the present invention can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, a liquid crystal display element in which liquid crystal is aligned can be manufactured by using 2 substrates each having the alignment material of the present invention formed as described above, bonding the alignment materials on the two substrates to face each other with a spacer interposed therebetween, and then injecting liquid crystal between the substrates.

Therefore, the composition for forming a cured film of the present invention can be suitably used for producing various retardation materials (retardation films), liquid crystal display elements, and the like.

Examples

The present invention will be described specifically below with reference to examples of the present invention, but the present invention is not limited to these examples.

[ shorthand notation used in the examples ]

The meanings of the shorthand symbols used in the following examples are as follows.

< raw materials >

GMA: glycidyl methacrylate

AIBN: alpha, alpha' -azobisisobutyronitrile

BMAA: n-butoxymethylacrylamide

HEMA: 2-Hydroxyethyl methacrylate

< ingredient A >

CIN1：

CIN2：

CIN3：

CIN4：

CIN5：

CIN6：

EHPE3150 (manufactured by KOKAI ダイセル, epoxy equivalent 180 g/eq):

< ingredient B >

HMM: a melamine crosslinking agent represented by the following structural formula [ サイメル (CYMEL) (registered trademark) 303 (manufactured by Mitsui サイテック Co., Ltd.) ]

TM: 5, 5' - (1-methylethylidene) bis (2-hydroxy-1, 3-benzenedimethanol) (trade name: TM-BIP-A, manufactured by Asahi organic Material industries, Ltd.)

< ingredient D >

PTSA: p-toluenesulfonic acid monohydrate

< ingredient E >

PEPO: polyester polyol Polymer (adipic acid/diethylene glycol copolymer having the following structural units. molecular weight 4,800.)

(in the formula, R represents an alkylene group.)

< solvent >

PM: propylene glycol monomethyl ether

BA: acetic acid butyl ester

EA: ethyl acetate

MEK: methyl ethyl ketone

CH: cyclohexanone

< determination of the molecular weight of the Polymer >

The molecular weight of the acrylic (co) polymer in the polymerization example was measured by the following procedure using a Gel Permeation Chromatography (GPC) apparatus (GPC-101) manufactured by Shodex, Ltd., (column (KD-803, KD-805) manufactured by Shodex, Ltd.).

The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) shown below are expressed in terms of polystyrene.

Column temperature: 40 deg.C

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Standard sample for standard curve preparation: standard polystyrene (molecular weight: about 197,000, 55,100, 12,800, 3,950, 1,260, 580, manufactured by Showa Denko K.K.).

< Synthesis of component A >

< Synthesis example 1 >

GMA (15.0 g) and AIBN (0.8 g) as a polymerization catalyst were dissolved in tetrahydrofuran (63.0 g), and the mixture was reacted under heating and reflux for 20 hours to obtain an acrylic polymer solution. The acrylic polymer solution was gradually added dropwise to 500.0g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain acrylic polymer (P-1). The obtained acrylic polymer had Mn of 6,500 and Mw of 11,000.

< Synthesis example 2>

10.0g of the epoxy group-containing acrylic polymer (P-1) obtained in Synthesis example 1, 0.4g of CIN 111.3 g and benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 50.8g and reacted at 120 ℃ for 20 hours. The solution was slowly dropped into 500g of ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

< Synthesis example 3 >

10.0g of the epoxy group-containing acrylic polymer (P-1) obtained in Synthesis example 1, CINN16.3g, CINN55.4g, and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM 50.6g, and reacted at 120 ℃ for 20 hours. The solution was slowly dropped into 500g of ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

< Synthesis example 4 >

CINN615.0 g, 1.4g of HEMA, and 0.4g of AIBN as a polymerization catalyst were dissolved in 121.6g of PM and 30.4 g of CH, and reacted under heating and refluxing for 20 hours to obtain a solution containing 10 mass% of an acrylic copolymer (PA-3). The resulting acrylic copolymer had Mn of 9,000 and Mw of 22,000.

< Synthesis example 5 >

10.0g of epoxy group-containing polymer EHPE3150 (manufactured by ダイセル, Ltd.), 19.9 g of CIN and 0.4g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 47.2g of PM, and the mixture was reacted at 120 ℃ for 20 hours. The solution was slowly dropped into 500g of ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-4). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

< Synthesis example 6>

5.2g of the epoxy group-containing acrylic polymer (P-1) obtained in Synthesis example 1, 212.0 g of CIN, and Ethyl triphenyl phosphonium bromide as a reaction catalyst

0.1g of dibutylhydroxytoluene as a polymerization inhibitor was dissolved in 70.0g of PM, and reacted at 100 ℃ for 20 hours. The solution was slowly dropped into 1000g of diethyl ether to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group had disappeared.

< Synthesis of component B >

< Synthesis example 7 >

100.0g of BMAA and 4.2g of AIBN as a polymerization catalyst were dissolved in 193.5g of PM, and reacted at 90 ℃ for 20 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had Mn of 2,700 and Mw of 3,900. The acrylic polymer solution was gradually added dropwise to 2000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PB-1).

< Synthesis example 8 >

32.0g of BMAA, 8.0g of GMA and 0.8g of AIBN as a polymerization catalyst were dissolved in 204.0g of tetrahydrofuran and reacted at 60 ℃ for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic copolymer (P-2). The resulting acrylic copolymer had Mn of 7,000 and Mw of 18,000.

< synthetic example 9>

10.0g of the acrylic copolymer (P-2) obtained in Synthesis example 8, 2.2g of acrylic acid, 0.2g of dibutylhydroxytoluene, and 10mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in PM60g, and reacted at 90 ℃ for 20 hours. This solution was slowly dropped into 500g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PB-2) having an acryloyl group. To carry out¹H-NMR analysis confirmed that the polymer (PB-2) had an acryloyl group.

Synthesis of < C component >

< synthetic example 10 >

5.0g of the acrylic polymer (P-1) obtained in Synthesis example 1, 9.2g of an acryloyl group-containing carboxylic acid (trade name "アロニックス M-5300", manufactured by Toyo Kabushiki Kaisha, omega-carboxypolycaprolactone acrylate (polymerization degree n. about.2)), 0.2g of dibutylhydroxytoluene, and ethyl triphenyl brominated polycaprolactone (polymerization degree n. about.2) as a reaction catalyst were reacted with each other

0.1g was dissolved in PM 34g, and the reaction was carried out at 80 ℃ for 20 hours to obtain a solution containing 30% by mass of a polymer having an acryloyl group (PC-1). To carry out¹H-NMR analysis confirmed that the polymer (PC-1) had an acryloyl group. Epoxy value was measured, and it was confirmed that the epoxy group of the polymer disappeared.

< Synthesis example 11 >

The propylene obtained in Synthesis example 1 was reacted with5.0g of acid-based polymer (P-1), 2.2g of acrylic acid, 0.2g of dibutylhydroxytoluene, and ethyltriphenylphosphonium bromide as a reaction catalyst

0.1g was dissolved in PM 17g, and the reaction was carried out at 80 ℃ for 20 hours to obtain a solution containing 30% by mass of a polymer having an acryloyl group (PC-2). To carry out¹H-NMR analysis confirmed that the polymer (PC-2) had an acryloyl group. Epoxy value was measured, and it was confirmed that the epoxy group of the polymer disappeared.

< Synthesis example 12>

5.0g of the acrylic polymer (P-1) obtained in Synthesis example 1, 5.3g of an acryloyl group-containing carboxylic acid (Toyo Kabushiki Kaisha, trade name: アロニックス M-5300, acrylic acid ω -carboxypolycaprolactone (polymerization degree n. about.2)), 0.7g of acetic acid, 0.2g of dibutylhydroxytoluene, and ethyl triphenyl brominated polycaprolactone (polymerization degree n. about.2) as a reaction catalyst

0.1g was dissolved in PM 26g, and the reaction was carried out at 80 ℃ for 20 hours to obtain a solution containing 30% by mass of a polymer having an acryloyl group (PC-3). To carry out¹H-NMR analysis confirmed that the polymer (PC-3) had an acryloyl group. Epoxy value was measured, and it was confirmed that the epoxy group of the polymer disappeared.

< Synthesis of E component >

< synthetic example 13 >

5.0g of the acrylic polymer (P-1) obtained in Synthesis example 1, 2.2g of propionic acid, 0.2g of dibutylhydroxytoluene, and ethyltriphenylphosphonium bromide as a reaction catalyst

0.1g of the polymer (PE-1) was dissolved in 34g of PM and reacted at 80 ℃ for 20 hours to obtain a 30 mass% solution containing a polymer having no acryloyl group (PE-1). Epoxy value was measured, and it was confirmed that the epoxy group of the polymer disappeared.

< preparation of polymerizable liquid Crystal solution >

29.0g of polymerizable liquid crystal LC242 (manufactured by BASF), 0.9g of イルガキュア 907 (manufactured by BASF) as a polymerization initiator, 0.2g of BYK-361N (manufactured by BYK) as a leveling agent, and methyl isobutyl ketone as a solvent were added to obtain a polymerizable liquid crystal solution (RM-1) having a solid content concentration of 30 mass%.

< example 1 >

120 parts by mass of CIN as a component (A), 80 parts by mass of the acrylic polymer (PB-1) as a component (B) obtained in Synthesis example 7, an amount of a solution containing 30% by mass of the acrylic polymer (PC-1) as a component (C) obtained in Synthesis example 10, which solution corresponds to 100 parts by mass of the acrylic polymer (PC-3) in terms of the amount of the acrylic polymer (PC-3), and 3 parts by mass of PTSA as a component (D) were mixed, and PM, BA and EA were added thereto to prepare a solvent composition PM: BA: EA is 30: 70: 30 (mass ratio), and a solid content concentration of 5.0 mass% was used as the composition (A-1) for forming a cured film (alignment material).

< examples 2 to 12 and comparative examples 1 to 3 >

Compositions a-2 to a-15 for forming cured films (alignment materials) were prepared in the same manner as in example 1, except that the kinds and amounts of the respective components were changed as shown in table 1.

[ Table 1]

< examples 13 to 25 and comparative examples 4 to 6>

[ evaluation of orientation ]

Each of the compositions for forming cured films (alignment materials) of examples 1 to 12 and comparative examples 1 to 3 was coated on a TAC film or a COP film subjected to ozone treatment with a wet film thickness of 4 μm using a bar coater. The films were heated and dried in a thermal cycle oven at a temperature of 110 ℃ for 60 seconds, respectively, to form cured films on the films, respectively. For each cured film, 313nm linearly polarized light was applied at a dose of 20mJ/cm²The alignment material is formed by vertical irradiation with the exposure amount of (2). The polymerizable liquid crystal solution (RM-1) was applied to the alignment material on the film by a bar coater to a wet film thickness of 6 μm. Subjecting the coating film to temperatureDrying at 90 deg.C for 60 s on electric heating plate, and drying at 300mJ/cm²Exposure is performed to produce a retardation material. The retardation material on the produced film was sandwiched between a pair of polarizing plates, the appearance of retardation characteristics in the retardation material was observed, the case where the retardation appeared without defects was defined as o, and the case where the retardation did not appear was defined as x, and the column of "orientation" is described. The evaluation results are shown in table 2 below.

[ evaluation of adhesion ]

Each of the compositions for forming cured films (alignment materials) of examples 1 to 12 and comparative examples 1 to 3 was coated on a TAC film or a COP film subjected to ozone treatment with a wet film thickness of 4 μm using a bar coater. The films were heated and dried in a thermal cycle oven at a temperature of 110 ℃ for 60 seconds, respectively, to form cured films on the films, respectively. For each cured film, 313nm linearly polarized light was applied at a dose of 20mJ/cm²The alignment material is formed by vertical irradiation with the exposure amount of (2). The polymerizable liquid crystal solution (RM-1) was applied to the alignment material on the film by a bar coater to a wet film thickness of 6 μm. The coating was dried on a hot plate at 90 ℃ for 60 seconds and then dried at 300mJ/cm²Exposure is performed to produce a retardation material. The phase difference material was cut into 10 × 10 blocks at intervals of 1mm in length and width by a cutter. A cellophane tape peeling test was performed on the cut using a scotch tape. The evaluation result was "adhesiveness", and the case where all of the 100 pieces remained without peeling was "o", and the case where even 1 piece peeled off was "x". The evaluation results are summarized in table 2 below.

[ Table 2]

TABLE 2

	Composition for forming cured film	Base material	Orientation property	Adhesion Property
					Example 13	A-1	TAC	○	○
Example 14	A-2	TAC	○	○
					Example 15	A-3	TAC	○	○
Example 16	A-4	TAC	○	○
					Example 17	A-5	TAC	○	○
Example 18	A-6	TAC	○	○
					Example 19	A-7	TAC	○	○
Example 20	A-8	TAC	○	○
					Example 21	A-9	TAC	○	○
Example 22	A-10	TAC	○	○
					Example 23	A-11	TAC	○	○
Example 24	A-12	TAC	○	○
					Example 25	A-2	COP	○	○
Comparative example 4	A-13	TAC	○	×
					Comparative example 5	A-14	TAC	○	×
Comparative example 6	A-15	TAC	○	×

As shown in Table 2, the phase difference materials obtained in examples 13 to 25 exhibited good orientation and adhesion.

On the other hand, the retardation materials obtained in comparative examples 4 to 6 exhibited good orientation, but did not exhibit sufficient adhesion.

< example 26>

An amount of 80 parts by mass of the acrylic polymer (PA-1) obtained in synthesis example 2 as component (a), 30 parts by mass of HMM as component (B), and a solution containing 30% by mass of the acrylic polymer (PC-1) obtained in synthesis example 10 as component (C) in an amount equivalent to 20 parts by mass of the acrylic polymer (PC-3) in terms of the amount of the acrylic polymer (PC-3), and PTSA 3 as component (D) were mixed, and PM, BA and EA were added thereto to prepare a composition (B-1) for forming a cured film (alignment material) having a solvent composition of PM: BA: EA of 30: 70: 30 (mass ratio) and a solid content concentration of 5.0% by mass.

< examples 27 to 37 and comparative examples 7 to 9>

Compositions B-2 to B-15 for forming a cured film (alignment material) were prepared in the same manner as in example 26, except that the kinds and amounts of the respective components were changed as shown in Table 3.

[ Table 3]

< examples 38 to 50 and comparative examples 10 to 12>

The compositions for forming cured films (alignment materials) of examples 26 to 37 and comparative examples 7 to 9 were subjected to [ evaluation of alignment properties ] and [ evaluation of adhesion ] in the same manner as in the compositions for forming cured films (alignment materials) of examples 13 to 25 and comparative examples 4 to 6. The evaluation results are shown in table 4.

[ Table 4]

TABLE 4

	Composition for forming cured film	Base material	Orientation property	Adhesion Property
					Example 38	B-1	TAC	○	○
Example 39	B-2	TAC	○	○
					Example 40	B-3	TAC	○	○
EXAMPLE 41	B-4	TAC	○	○
					Example 42	B-5	TAC	○	○
Example 43	B-6	TAC	○	○
					Example 44	B-7	TAC	○	○
Example 45	B-8	TAC	○	○
					Example 46	B-9	TAC	○	○
Example 47	B-10	TAC	○	○
					Example 48	B-11	TAC	○	○
Example 49	B-12	TAC	○	○
					Example 50	B-1	COP	○	○
Comparative example 1O	B-13	TAC	○	×
					Comparative example 11	B-14	TAC	○	×
Comparative example 12	B-15	TAC	○	×

As shown in Table 4, the phase difference materials obtained in examples 38 to 50 exhibited good orientation and adhesion.

On the other hand, the retardation materials obtained in comparative examples 10 to 12 exhibited good orientation, but did not exhibit sufficient adhesion.

Industrial applicability

The cured film formed from the composition for forming a cured film of the present invention is very useful as an alignment material for a liquid crystal alignment film used for forming a liquid crystal display device and an optically anisotropic film provided inside or outside the liquid crystal display device. In particular, the composition for forming a cured film of the present invention is suitable as a material for forming a cured film used for a patterned retardation material of a 3D display. Further, the composition for forming a cured film of the present invention is suitable as a material for forming a cured film such as a protective film, a planarization 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, and particularly, a material for forming an interlayer insulating film of a TFT type liquid crystal display element, a protective film of a color filter, an insulating film of an organic EL element, and the like.

Claims

1. A cured film-forming composition comprising:

(B) the components: a crosslinking agent;

(D) the components: a crosslinking catalyst.

2. The cured film-forming composition according to claim 1, wherein the photo-alignment group of component (A) is a functional group having a structure capable of photodimerization or photoisomerization.

3. The cured film-forming composition according to claim 1 or 2, wherein the photo-alignment group of component (A) is a cinnamoyl group.

4. The cured film-forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is a group having an azobenzene structure.

5. The cured film-forming composition according to any one of claims 1 to 4, further comprising (E) a component: a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.

6. The cured film-forming composition according to any one of claims 1 to 5, wherein the polymer as the component (C) contains a structural unit having a hydroxyl group and a structural unit having a polymerizable group containing a C ═ C double bond, the proportion of the structural unit having a hydroxyl group is 20 mol% or more based on 100 mol% of all the structural units of the polymer, and the proportion of the structural unit having a polymerizable group containing a C ═ C double bond is 20 mol% or more based on 100% of all the structural units of the polymer.

7. The cured film-forming composition according to any one of claims 1 to 6, wherein the content ratio of the low-molecular compound as the component (A) to the polymer as the component (C) is 5:95 to 60:40 in terms of mass ratio.

8. The cured film-forming composition according to any one of claims 1 to 6, wherein the content ratio of the polymer as the component (A) to the polymer as the component (C) is 5:95 to 90:10 in terms of mass ratio.

9. The cured film-forming composition according to any one of claims 1 to 8, comprising 5 to 500 parts by mass of the component (B) based on 100 parts by mass of the total amount of the components (A) and (C).

10. A cured film obtained from the cured film-forming composition as defined in any one of claims 1 to 9.

11. An optical film having the cured film of claim 10.

12. An alignment material produced using the cured film according to claim 10.

13. A phase difference material produced by using the cured film according to claim 10.