KR20150079744A - Cured-film-forming composition, alignment material, and phase-difference material - Google Patents

Abstract

[PROBLEMS] To provide a cured film-forming composition suitable for forming a cured film having excellent liquid crystal alignability and close durability, to provide an alignment material, and to provide a retardation using the alignment material.
The cured film-forming composition comprises (A) a compound having one photo-oriented group and one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group, (B) at least one of a hydroxyl group and a carboxyl group (C) a compound having a hydroxyl group and a (meth) acryl group other than the component (A). The cured film-forming composition is used to form a cured film, and an alignment material is formed by using a photo-alignment technique. A polymerizable liquid crystal is applied on the alignment material and cured to obtain a retardation.

Description

CURED-FILM-FORMING COMPOSITION, ALIGNMENT MATERIAL, AND PHASE-DIFFERENCE MATERIAL,

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

2. Description of the Related Art In recent years, in the field of displays such as televisions using liquid crystal panels, development of a 3D display capable of enjoying 3D images has been proceeding in an attempt to achieve high performance. In the 3D display, for example, an image with a three-dimensional effect can be displayed by viewing an image for the right eye on the right eye of the observer and viewing an image for the left eye on the left eye of the observer.

There are a variety of 3D display methods for displaying 3D images, and a lenticular lens method and a parallax barrier method are known as methods which do not require dedicated glasses.

One of display methods in which an observer wears glasses to observe a 3D image is known as a circularly polarized glasses method or the like (see, for example, Patent Document 1).

In the case of a 3D display using a circular polarizing glasses system, a phase difference is usually arranged on a display element forming an image such as a liquid crystal panel. This phase difference material has a plurality of two kinds of retardation regions with different retardation characteristics and is arranged regularly to constitute a patterned retardation material. In the following description, the patterned retardation material is referred to as a patterned retardation material in order to arrange a plurality of retardation regions having different retardation characteristics.

The patterned retardation material can be produced, for example, by optical patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 2. Optical patterning of a retardation material made of a polymerizable liquid crystal uses an optical alignment technique known in the alignment material formation of a liquid crystal panel. That is, a coating film made of a photo-orientable material is provided on a substrate, and two kinds of polarized light beams having different polarization directions are irradiated thereto. Then, a photo alignment film is obtained as an alignment material having two types of liquid crystal alignment regions in which alignment control directions of liquid crystals are different. A solution phase phase difference material containing a polymerizable liquid crystal is coated on the photo alignment layer to realize alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

In the alignment reformation using the optical alignment technique of the liquid crystal panel, acrylic resin, polyimide resin, or the like having photo dimerization sites such as a neomoyl group and a knocker on the side chain is known as a usable photo-orientable material. These resins have been reported to exhibit the performance (hereinafter also referred to as liquid crystal orientation) of controlling the orientation of liquid crystals by polarized UV irradiation (see Patent Documents 3 to 5).

Japanese Patent Application Laid-Open No. H10-232365 Japanese Patent Application Laid-Open No. 2005-49865 Japanese Patent No. 3611342 Specification Japanese Patent Application Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719

As described above, the patterned retardation material is formed by laminating layers of cured polymerizable liquid crystals on a photo alignment layer which is an alignment material. The patterned phase difference material having such a laminated structure can be used in the construction of the 3D display as it is in the laminated state.

The 3D display is often used as a home television, and high reliability, particularly long-term durability, is required. Accordingly, durability is also required for the constituent members of the 3D display. Therefore, long-term durability is essential for the patterned retardation material as well as optical patterning with high precision, high optical transmittance, and the like.

However, the conventional patterned retardation material has a problem in adhesion between the photo alignment layer and the layer of the polymerizable liquid crystal. For example, between the photo alignment layer and the layer of the polymerizable liquid crystal, there is a tendency that peeling is likely to occur from the beginning of the formation, but at the initial stage of formation there is adhesion, but with the lapse of time, the adhesion deteriorates and the peeling tends to occur easily.

Among them, peeling between the photo alignment film and the layer of the polymerizable liquid crystal, which occurs with the lapse of time, becomes a defect in the 3D display actually used, which causes the display quality of the 3D display to deteriorate. Thus, there is a demand for a patterned retardation material which is capable of high-precision optical patterning, has excellent light transmission characteristics, and is excellent in durability. Particularly, there is a demand for a patterned retardation material having excellent durability (hereinafter referred to as " close contact durability " in the present specification) while maintaining excellent adhesion between the photo alignment layer and the polymerizable liquid crystal layer in the initial stage of formation .

The present invention is based on the above findings and the results of the examination. That is, an object of the present invention is to provide a cured film-forming composition having excellent liquid crystal alignability and light transmittance characteristics and being suitable for forming a cured film having excellent adhesion durability. Particularly, when a layer of a polymerizable liquid crystal is disposed thereon, it is used as an alignment material and exhibits excellent liquid crystal alignability and light transmittance. In addition, it has excellent adhesion durability, which can maintain adhesion between layers of the polymerizable liquid crystal for a long time Film-forming composition for forming a film.

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

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

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

According to a first aspect of the present invention,

(A) a compound having one photo-oriented group and one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group,

(B) a polymer having at least one of a hydroxyl group and a carboxyl group, and

(C) a compound having a hydroxyl group and a (meth) acryl group other than the component (A)

And a curing-film-forming composition.

In the first aspect of the present invention, the compound (A) is preferably a compound having a photo-orientable group and a hydroxy group.

In the first aspect of the present invention, the compound of component (C) preferably has at least one hydroxyl group and one (meth) acryl group.

In the first aspect of the present invention, it is preferable that (D) a crosslinking agent is contained.

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

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

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

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

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

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

As described above, in order to produce a patterned retardation material having excellent durability, there is a demand for an alignment material excellent in close contact durability, particularly an alignment material excellent in adhesion durability between layers of a cured polymerizable liquid crystal. There is also a demand for a cured film forming composition favorable for the formation of an alignment material having such a performance.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to meet the above-mentioned demand. As a result, they have found that a cured film obtained from a cured film-forming composition having a specific composition is excellent in light transmittance and has a liquid crystal aligning property for regulating liquid crystal alignment And found that it can be used as an alignment material. In addition, the inventors of the present invention have found that the cured film obtained from the cured film-forming composition having the specific composition exhibits excellent adhesion durability between layers of the polymerized liquid crystal polymerized and cured thereon. That is, the cured film obtained from the cured film forming composition having the specific composition of the present invention can constitute a photo alignment film having excellent adhesion durability between the layers of the polymerizable liquid crystal.

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

≪ Cured film forming composition >

The cured film-forming composition of the present embodiment of the present invention comprises (A) a low-molecular orientation component which is a compound having a photo-orientable group and one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group, (B) A polymer having at least one of a hydroxyl group and a carboxyl group, and (C) a compound having a hydroxyl group and (meth) acryl group other than the component (A). Further, the cured film-forming composition of the present embodiment may contain a crosslinking agent as the component (D) in addition to the component (A), the component (B) and the component (C). In addition to the component (A), the component (B), the component (C) and the component (D), a crosslinking catalyst may be contained as the component (E). In addition, other additives may be added as long as the effect of the present invention is not impaired. Further, it may contain a solvent.

Hereinafter, the details of each component will be described.

[Component (A)] [

The component (A) of the cured film-forming composition of the present embodiment is a low molecular weight component. The component (A) is a component which imparts photo-alignment property to the cured film of the present embodiment obtained from the cured film-forming composition of the present embodiment, and is a photo-orientable component of low molecular weight as compared with the polymer of the component (B) .

In the cured film-forming composition of the present embodiment, the low-molecular-orientation component (A) is a compound having a photo-aligning group and a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group .

On the other hand, in the present invention, the photo-orientable group means a functional group at a structural site where the photo-dimerization or photo-isomerization occurs.

The structural moiety in which the compound of the component (A) has a light-quantifiable light quantifiable as the photo-orientable group is a moiety that forms a dimer by light irradiation. Specific examples of the moiety include a cinnamoyl group, Anthracene group and the like. Of these, a neomyl group is preferable in view of high transparency in the visible light region and high optical dimerization reactivity.

The photo-isomerizing structural moiety that the compound of component (A) may have as a photo-orientable group refers to a structural moiety that changes into a cis structure and a trans-isomer by light irradiation. Specific examples thereof include azobenzene structure, As shown in Fig. Among them, the azobenzene structure is preferable in view of high reactivity.

The compound having any one of a photo-orientable group of the component (A) and a substituent selected from a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group is, for example, a compound represented by the following formula.

[Chemical Formula 1]

Wherein A ¹ and A ² each independently represent a hydrogen atom or a methyl group and X ¹¹ represents a single bond selected from the group consisting of a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, Or a structure in which 1 to 3 substituents selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof are bonded through two or more kinds of linkages. X ¹² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. The alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to neighboring groups through a covalent bond, an ether bond, an ester bond, an amide bond or an urea bond.

X ¹³ represents 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. X ¹⁴ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, an aromatic ring group or an aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or straight-chain. X ¹⁵ represents a hydroxyl group, a carboxyl group, an amino group or an alkoxysilyl group. X represents a single bond, an oxygen atom or a sulfur atom. On the other hand, when the substituent includes a benzene ring, the benzene ring may be the same or different 1 selected from 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 may be substituted by a plurality of substituents.

Wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms A halogen atom, a trifluoromethyl group or a cyano group.

Specific examples of the compound having a photo-orientable group and a hydroxy group, which are the component (A), include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) Methyl ester, 4- (3-hydroxypropyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- , 4-hydroxymethyloxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4- 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- Cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxy cinnamic acid Esters, phenyl ester of 4- (8-hydroxyoctyloxy) cinnamate, phenyl ester of 4- (6-hydroxyhexyloxy) cinnamate, phenyl ester of 4- (4-hydroxybutyloxy) cinnamate, 4- Hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxy cinnamic acid phenyl ester, 4- (8-hydroxyoctyloxy) ) Biphenyl ester of cinnamic acid, biphenyl ester of cinnamic acid, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid biphenyl Ester, biphenyl ester of 4- (2-hydroxyethyloxy) cinnamic acid, biphenyl ester of 4-hydroxymethyloxy cinnamate, biphenyl ester of 4-hydroxycinnamic acid, 8-hydroxyoctyl ester of cinnamic acid, 6- Hexyl ester, 4-hydroxybutyl cinnamate (6-hydroxyhexyloxy) chalcone, 4 (8-hydroxyoctyloxy) chalcone, 4-ethylhexanoic acid, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxycalone, 4-hydroxycalcone, 4 4 '- (4-hydroxybutyloxy) chalcone, 4' - (3-hydroxypropyloxy) (2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxycalcone, 4'-hydroxycalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- 7- (3-hydroxypropyloxy) coumarin, 7- (2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxy coumarin, 6-hydroxy 6- (3-hydroxypropyloxy) coumarin, 6- (2-hydroxyethyloxy) coumarin, 6-hydroxybutyloxy coumarin, 6- Hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid methyl ester , 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3- hydroxypropyloxy) benzoyl] cinnamic acid methyl ester, Benzoyl] cinnamic acid methyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid methyl ester, 4- [4-hydroxybenzoyl] cinnamic acid methyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl ] Ethyl cinnamate, ethyl 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- Benzoyl] cinnamic acid ethyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester, Ethyl ester, 4- [4- hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tert- butyl ester, 4- [4- (6-hydroxyhexyloxy ) Benzoyl] cinnamic acid tert-butyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4- (3- hydroxypropyloxy) benzoyl] cinnamic acid tert- butyl ester , 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tert- Benzoyl] cinnamic acid phenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) Benzoyl] cinnamic acid phenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxy Benzoyl] cinnamic acid phenyl ester, 4- [4- hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- Benzoyl] cinnamic acid biphenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (3- hydroxypropyloxy) A biphenyl ester of 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid, a biphenyl ester of cinnamic acid 4- [4- hydroxymethyloxybenzoyl] 4-benzoyl cinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester, 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic acid hydroxymethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4- [4 4- [4- (3-hydroxypropyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] 4- (4-hydroxymethylbenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone, 4 '- [4- (8- Benzoyl] chalcone, 4 '- [4- (4-hydroxybutyloxy) benzoyl] (4-hydroxymethyloxybenzoyl) chalcone, 4 '- [4- (2-hydroxyethyloxy) benzoyl] Hydroxybenzoyl) chalcone, and the like.

Specific examples of the compound having a photo-aligning group and a carboxyl group, which are components (A), include cinnamic acid, ferulic acid, 4-nitro cinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin- , 4- (N, N-dimethylamino) cinnamic acid, and the like.

Specific examples of the compound having a photo-aligning group and an amino group as the component (A) include 4-amino cinnamic acid methyl ester, 4-amino cinnamic acid ethyl ester, 3-amino cinnamic acid methyl ester and 3-amino cinnamic acid ethyl ester. .

Specific examples of the compound having a photo-orientable group and an alkoxysilyl group as the component (A) include methyl 4- (3-trimethoxysilylpropyloxy) cinnamate, methyl 4- (3-triethoxysilylpropyloxy) Ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid methyl ester , Ethyl 4- (3-triethoxysilylhexyloxy) cinnamate, ethyl 4- (3-trimethoxysilylhexyloxy) cinnamate and 4- (3-triethoxysilylhexyloxy) cinnamate Esters and the like.

Examples of the low-molecular-orientation component as the component (A) include, but are not limited to, the specific examples described above.

The low-molecular orientation component (A) is particularly preferably a compound having a photo-orientable group and a hydroxy group. The compound having a photo-aligning group and a hydroxy group is preferably used for imparting photo-alignment properties to the cured film obtained from the cured film-forming composition of the present embodiment and improving the adhesiveness with the layer of the polymerizable liquid crystal when used as an alignment material So that it becomes particularly effective.

When the low-molecular-orientation component (A) is a compound having a photo-orientable group and a hydroxy group, the compound (A) is preferably a compound having two or more photo-orientable groups and / or two or more hydroxy groups in the molecule It is possible to use. Specifically, it is preferable to use, as the component (A), a compound having two or more photo-orientable groups in addition to one hydroxy group in the molecule, a compound having two or more hydroxy groups in addition to one photo- It is possible to use a compound having two or more tie and hydroxy groups. For example, for compounds having two or more photo-orientable groups and hydroxy groups in the molecule, the compounds represented by the following formulas can be exemplified.

(2)

By appropriately selecting such a compound, it becomes possible to control the molecular weight of the low-molecular-orientation component (A) to a value within a desired range. In order to form the cured film of the present embodiment from the cured film forming composition of the present embodiment, heat curing is required. When the heating is performed, the molecular weight of the low molecular weight component is controlled by controlling the sublimation of the low molecular weight component .

On the other hand, as the compound of the component (A) in the cured film-forming composition of the present embodiment, a compound of a plurality of compounds having one of a photo-orientable group, a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group It is possible.

[Component (B)] [

The component (B) contained in the cured film-forming composition of the present embodiment is a hydrophilic polymer.

In the composition for forming a cured film of the present embodiment, the polymer as the component (B) is preferably a polymer having a hydrophilic group such as a hydroxyl group or a carboxyl group or an amino group. Specifically, at least one of a hydroxyl group and a carboxyl group (Hereinafter also referred to as a specific polymer).

Examples of the polymer as the component (B) include polymers such as acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, A cyclic polymer such as a polymer having a straight chain structure or a branched structure such as a polyol, a polyalkyleneimine, a polyallylamine, a cellulose (a cellulose or a derivative thereof), a phenol novolac resin or a melamine formaldehyde resin and a cyclodextrin, .

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

The specific polymer as the component (B) is preferably at least one selected from the group consisting of hydroxyalkylcyclodextrins, celluloses, polyethylene glycol ester groups and hydroxyalkyl ester groups having 2 to 5 carbon atoms, a carboxyl group and a phenolic hydroxyl group An acrylic polymer having an aminoalkyl group in the side chain, a polyether polyol, a polyester polyol, a polycarbonate polyol and a polycaprolactone polyol.

An acrylic polymer having at least one of a carboxyl group and a phenolic hydroxyl group and at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, which is a preferred example of the specific polymer of component (B) Structure, and is not particularly limited as to the skeleton of the main chain of the polymer constituting the acrylic polymer, the kind of the side chain, and the like.

As the structural unit having at least one of the polyethylene glycol ester group and the hydroxyalkyl ester group having 2 to 5 carbon atoms, the preferred structural unit is represented by the following formula [B1].

As the structural unit having at least one of the above-described carboxyl group and phenolic hydroxyl group, a preferable structural unit is represented by the following formula [B2].

(3)

X ³ and X ⁴ each independently represent a hydrogen atom or a methyl group, and Y ¹ represents an H- (OCH ₂ CH ₂ ) n- group (wherein the value of n is 2 To 50, preferably 2 to 10) or a hydroxyalkyl group having 2 to 5 carbon atoms, and Y ² represents a carboxyl group or a phenolic hydroxy group.

The acrylic polymer which is an example of the component (B) has a weight average molecular weight of preferably from 3,000 to 200,000, more preferably from 4,000 to 150,000, and still more preferably from 5,000 to 100,000. If the weight average molecular weight is more than 200,000 and the molecular weight is too large, the solubility in a solvent may deteriorate and handling properties may deteriorate. If the weight average molecular weight is too small, the curing becomes insufficient at the time of thermosetting, May be lowered. On the other hand, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard data. Hereinafter, the same shall apply to the present specification.

Examples of the method for synthesizing the acrylic polymer which is an example of the component (B) include a method of reacting a monomer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms (hereinafter also referred to as a b1 monomer) A method of copolymerizing a monomer having at least one of hydroxyl groups (hereinafter also referred to as b2 monomer) is simple.

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

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

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

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

In the present embodiment, in the synthesis of the acrylic polymer which is an example of the component (B), monomers other than the b1 monomer and the b2 monomer, specifically, a hydroxyl group and a carboxyl group, Monomers that do not have all can be used in combination.

Examples of the monomer include acrylic ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl methacrylate, butyl acrylate, isobutyl acrylate and t-butyl acrylate Methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, isobutyl methacrylate and t-butyl methacrylate, maleimide, N-methyl maleimide Maleimide compounds such as N-phenylmaleimide and N-cyclohexylmaleimide, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

The amount of the b1 monomer and the b2 monomer used for obtaining the acrylic polymer which is an example of the component (B) is preferably from 2 mol% to 95 mol% based on the total amount of all the monomers used for obtaining the acrylic polymer as the component (B) , and the b2 monomer is 5 mol% to 98 mol%.

When a monomer having only a carboxyl group as the b2 monomer is used, the amount of the b1 monomer is 60 to 95 mol%, the amount of the b2 monomer is 5 to 40 mol% based on the total amount of all the monomers used to obtain the acrylic polymer as the component (B) %.

On the other hand, when a monomer having only a phenolic hydroxy group is used as the b2 monomer, it is preferable that the b1 monomer is 2 mol% to 80 mol% and the b2 monomer is 20 mol% to 98 mol%. When the b2 monomer is too small, the liquid crystal alignability of the resulting cured film tends to become insufficient. When the b2 monomer is too large, the compatibility with the low molecular weight component (A) tends to be lowered.

The method of obtaining the acrylic polymer which is an example of the polymer of the component (B) is not particularly limited. For example, in a solvent in which b1 and b2 monomers and, if necessary, monomers other than b1 and b2 monomers and a polymerization initiator are coexisted , And a polymerization reaction at a temperature of 50 캜 to 110 캜. Here, the solvent to be used is not particularly limited as long as it dissolves the b1 monomer and the b2 monomer, the b1 monomer and b2 monomer, if necessary, and the polymerization initiator. Specific examples are described in the section [solvent] described later.

The acrylic polymer having the aminoalkyl group on the side chain, which is a preferred example of the specific polymer of component (B), is a polymer of aminoalkyl such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl methacrylate and aminopropyl methacrylate A polymer obtained by polymerizing an ester monomer, or a copolymer of an aminoalkyl ester monomer and one or more kinds of monomers selected from the above acrylic monomers.

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

Further, a solution of an acrylic polymer, which is an example of a polymer of the component (B) obtained by the above-described method, is re-precipitated by being added to diethyl ether or water under stirring, and the resultant precipitate is filtered and washed. Thereafter, Dried or heated and dried to obtain a powder of an acrylic polymer which is an example of the component (B). By the above-described operation, the polymerization initiator coexisting with the acrylic polymer which is an example of the component (B) and the unreacted monomer can be removed. As a result, a powder of the acrylic polymer which is an example of the purified component (B) is obtained. When the powder can not be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above-described operation may be repeated.

Examples of the polyether polyol which is a preferred example of the specific polymer of component (B) include polyether polyols such as polyethylene glycol, polypropylene glycol, propylene glycol, polyhydric alcohols such as bisphenol A, triethylene glycol and sorbitol, propylene oxide, polyethylene glycol and poly Propylene glycol, and the like. Specific examples of the polyether polyol include ADEKA POLYETHER P series, G series, EDP series, BPX series, FC series, CM series manufactured by ADEKA Cororation, UNIOX (registered trademark) HC-40, HC-60, ST-30E , ST-40E, G-450, G-750, UNIOL (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA- NONION (registered trademark) LT-221, ST-221 and OT-221.

Examples of the polyester polyol which is a preferable example of the specific polymer of component (B) include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, polyethylene glycol and poly And a diol such as propylene glycol. Specific examples of the polyester polyol include POLYLITE (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD- OD-X-2024, OD-X-2024, OD-X-2024, OD-X-2024, OD-X- OD-X-2555, OD-X-2560, POLYOL P-510, P-1010, P-2010, P-3010, P-4010, P- 510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010 and PNNA-2016.

Examples of the polycaprolactone polyol which is a preferred example of the specific polymer of component (B) include those obtained by ring-opening polymerization of? -Caprolactone using polyhydric alcohols such as trimethylolpropane and ethylene glycol as initiators. Specific examples of the polycaprolactone polyol include POLYLITE (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Corporation, PLACCEL (registered trademark) 205 manufactured by Daicel Chemical Industries, Ltd., L205AL , 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, and the like.

Examples of polycarbonate polyols which are preferred examples of the specific polymer of component (B) include those obtained by reacting polyhydric alcohols such as trimethylolpropane and ethylene glycol with diethyl carbonate, diphenyl carbonate and ethylene carbonate. Specific examples of the polycarbonate polyol include PLACCEL (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, Ltd., C-590, C-1050, C- 2090, C-3090, and the like.

Examples of cellulose as a preferred polymer of the component (B) include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylethylcellulose and the like Hydroxyalkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl celluloses, hydroxyalkyl celluloses and hydroxypropylcelluloses.

(B) are cyclodextrins such as? -Cyclodextrin,? -Cyclodextrin and? -Cyclodextrin, methyl-? -Cyclodextrin, methyl-beta-cyclodextrin and methyl- methylated cyclodextrin such as? -cyclodextrin, and hydroxymethyl-? -cyclodextrin, hydroxymethyl-? -cyclodextrin, hydroxymethyl-? -cyclodextrin, 2-hydroxyethyl-a-cyclodextrin, 2 Hydroxypropyl-? -Cyclodextrin, 2-hydroxyethyl-? -Cyclodextrin, 2-hydroxypropyl-? -Cyclodextrin, 2-hydroxypropyl-? Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 2,3-dihydroxypropyl-? As dextrin and the like, 2,3-hydroxypropyl -β- cyclodextrin and 2,3-di-hydroxypropyl -γ- cycloalkyl hydroxyalkyl cyclodextrin, such as cyclodextrin.

Examples of the melamine formaldehyde resin which is a preferred example of the specific polymer of the component (B) include a resin represented by the following formula such as a resin obtained by polycondensation of melamine and formaldehyde.

[Chemical Formula 4]

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

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

The method for obtaining the melamine formaldehyde resin as the component (B) is not particularly limited. Generally, melamine and formaldehyde are mixed and made weakly alkaline by using sodium carbonate, ammonia or the like, and then heated at 60 ° C to 100 ° C, do. The methylol group can be alkoxylated by reacting the obtained resin with an alcohol.

The melamine formaldehyde resin as the component (B) preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and still more preferably 350 to 3500. If the weight-average molecular weight is more than 5000, the solubility in the solvent is lowered and the handling property is lowered. On the other hand, if the weight-average molecular weight is less than 250, the curing becomes insufficient at the time of thermosetting, There is a case that the improvement effect of the above-mentioned problem is not sufficiently exhibited.

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

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

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

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

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

As described above, the cured film forming composition of the present embodiment of the present invention comprises (A) a compound having a photo-aligning group and a hydroxyl group, and (B) a polymer having at least one of a hydroxyl group and a carboxyl group. In the compound as the component (A), the photo-aligning group constitutes a photoreactive portion having a hydrophobic property, and the hydroxy group constitutes a thermally reactive portion having a hydrophilic property. The polymer of the component (B) has at least one of a hydroxyl group and a carboxyl group as described above.

Therefore, the cured film formed from the cured film-forming composition of the present embodiment is formed so that the inside thereof becomes hydrophilic due to the nature of the component (B) so that the film structure is stabilized. The compound of component (A) in the cured film is localized near the surface of the cured film. More specifically, the compound of component (A) is localized in the vicinity of the surface of the cured film while taking the structure in which the hydrophilic thermoreaction part faces the inside of the cured film and the hydrophobic light reaction part faces the surface side. As a result, the cured film of the present embodiment realizes a structure in which the ratio of the photoreactive group of the component (A) present near the surface is increased. When the cured film of the present embodiment is used as an alignment material, it is possible to improve the efficiency of light reaction for photo alignment and have excellent alignment sensitivity. Further, the cured film-forming composition of the present embodiment becomes an alignment material favorable for the formation of the patterned retardation material, and the patterned retardation material produced by using the cured film-forming composition can have excellent pattern forming property.

Further, as described above, the cured film forming composition of the present embodiment may contain a crosslinking agent as the component (D). Thus, in the cured film obtained from the cured film-forming composition of the present embodiment, the crosslinking reaction by the thermal reaction using (D) the crosslinking agent can be performed before the light reaction by the photo-orientable group of the compound of the component (A). As a result, when the cured film is used as an alignment material, the resistance to the polymerizable liquid crystal applied on the alignment material and the solvent thereof can be improved.

The cured film-forming composition of the present embodiment of the present invention may further contain, as the component (C), a component having a hydroxyl group and a (meth) acrylic group other than the component (A) ≪ / RTI > The compound (C) functions to enhance the adhesion between the layers of the cured polymerizable liquid crystal formed thereon when the cured film obtained from the cured film forming composition of the present embodiment is used as an alignment material. Next, the component (C) contained in the cured film forming composition of the present embodiment will be described.

[Component (C)] [

The component (C) contained in the cured film-forming composition of the present embodiment is a compound having a hydroxyl group and a (meth) acryl group other than the component (A).

The compound of component (C) preferably has at least one hydroxyl group and at least one (meth) acryl group.

When the cured film formed from the cured film-forming composition of the present embodiment containing the component (C) is used as an alignment material, the polymerizable functional group of the polymerizable liquid crystal and the alignment material Linking reaction sites can be linked by covalent bonds. As a result, the retarder of the present embodiment, which is formed by laminating the cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under high temperature and high humidity conditions and exhibit high durability against peeling and the like .

The content of the component (C) in the cured film-forming composition of the embodiment of the present invention is preferably from 0.1 part by mass to 40 parts by mass based on 100 parts by mass of the total amount of the compound (A) Mass part, and more preferably 5 mass parts to 35 mass parts. When the content of the component (C) is 0.1 parts by mass or more, sufficient adhesion can be imparted to the cured film to be formed. However, if it is more than 40 parts by mass, the storage stability of the cured film-forming composition may be deteriorated.

In the cured film forming composition of the present embodiment, the component (C) may be a mixture of a plurality of compounds of the component (C).

Preferable examples of the compound of component (C) are given below. On the other hand, the compound of component (C) is not limited to the following compound examples.

[Chemical Formula 5]

(Wherein R ¹¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10.)

[Component (D)] [

The cured film forming composition of the present embodiment may contain a crosslinking agent as the component (D).

More specifically, the component (D) reacts with the above-described compound of the component (A), the polymer of the component (B) and the compound of the component (C) Lt; / RTI > The cross-linking agent of the component (D) can be obtained by reacting a hydroxyl group of the compound (A), a hydroxyl group and / or a carboxyl group contained in the polymer (B) C). ≪ / RTI > As a result, when the compound of component (A), the polymer of component (B) and the compound of component (C) are thermally reacted with the crosslinking agent as component (D), the compound of component (A) Can be suppressed. The cured film forming composition of the present embodiment can form an oriented material having a high photoreaction efficiency as described above as a cured film.

In the cured film forming composition of the present embodiment, it is preferable that the crosslinking agent of the component (D) is hydrophilic. (D) is preferably dispersed in the film when the cured film is formed using the cured film forming composition of the present embodiment.

Examples of the crosslinking agent as the component (D) include compounds such as epoxy compounds, methylol compounds and isocyanate compounds, preferably methylol compounds.

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

Specific examples of the above-mentioned alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) Tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3- Methoxymethyl) -4,5-dimethoxy-2-imidazolinone, and the like. As a commercial product, a compound such as a glycoluril compound (trade name: CYMEL (registered trademark) 1170, POWDERLINK (registered trademark) 1174) manufactured by Mitsui Cytec Ltd., a methylation urea resin (trade name: UFR (registered trademark) 65) (Trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation urea / formaldehyde resin (high condensation type, trade name: BECKMINE (registered trademark) P-955, N), and the like.

Specific examples of the above-mentioned alkoxymethylated benzoguanamine include, for example, tetramethoxymethylbenzoguanamine. CYMEL (registered trademark) 1123 manufactured by Mitsui Cytec Ltd., NIKALAC (registered trademark) BX-4000, BX-37 manufactured by Sanwa Chemical Co., Ltd., BL- BX-55H).

Specific examples of the alkoxymethylated melamine described above include, for example, hexamethoxymethylmelamine and the like. As a commercial product, a methoxymethyl type melamine compound (trade name: CYMEL (registered trademark) 300, copper 301, copper 303, copper 350) manufactured by Mitsui Cytec Ltd., a butoxymethyl type melamine compound (trade name: MYCOAT 506, 508), a methoxymethyl type melamine compound (trade name: NIKALAC (registered trademark) MW-30, copper MW-22, copper MW-11, copper MS-001, copper MX- (Trade name: NIKALAC (registered trademark) MX-45, MX-410, MX-302) and the like can be given as examples of the MX-730, MX-750 and MX-035.

A compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in U.S. Patent 6,323,310 can be mentioned. CYMEL (registered trademark) 303 (manufactured by Mitsui Cytec Ltd.) and the like can be used as a commercially available product of the above-mentioned melamine compound. Commercially available products of the above benzoguanamine compound include CYMEL (registered trademark) 1123 Ltd.).

Further, as the component (D), a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide and N-butoxymethylmethacrylamide, or an alkoxymethyl group Or a polymer prepared by using a methacrylamide compound may also be used.

Examples of the polymer include poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate, A copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide and benzylmethacrylate and 2-hydroxypropylmethacrylate. The weight average molecular weight of such a polymer is 1000 to 500000, preferably 2000 to 200000, more preferably 3000 to 150000, and still more preferably 3000 to 50000.

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

The content of the crosslinking agent in the component (D) in the cured film-forming composition of the present embodiment is preferably 10 parts by mass to 100 parts by mass based on 100 parts by mass of the total amount of the compound (A) More preferably 15 parts by mass to 80 parts by mass. When the content of the crosslinking agent is less than 10 parts by mass, the solvent resistance and heat resistance of the cured film obtained from the cured film-forming composition are lowered, and the orientation sensitivity at the time of light decentration is lowered. On the other hand, when the content is more than 100 parts by mass, the photoalignment property and storage stability may be deteriorated.

[Component (E)] [

The cured film-forming composition of the present embodiment may contain the above-mentioned component (D) in addition to the components (A), (B) and (C) And may contain a crosslinking catalyst as a component.

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

When an acid or a thermal acid generator is used as the component (E), the component (E) is a compound which is thermally decomposed at a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, prebake or postbake to generate an acid, It is not particularly limited as long as it is a compound which pyrolyzes at 250 DEG C to generate an acid.

Such compounds include, for example, inorganic acids such as hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, P-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, p-toluenesulfonic acid, But are not limited to, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane- Or a hydrate thereof or a salt thereof.

Examples of the compound capable of generating an acid upon exposure to heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, P-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid ethyl ester, Toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenetyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-tosylate, N-ethyl-4-toluenesulfonamide and compounds represented by the following formulas [PAG-1] to [PAG-41] .

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

[Chemical Formula 12]

The content of the crosslinking catalyst of the component (E) in the cured film-forming composition of the embodiment of the present invention is preferably 0.01 mass% or more based on 100 parts by mass of the total amount of the compound (A) To 10 parts by mass, more preferably 0.05 parts by mass to 8 parts by mass, still more preferably 0.1 parts by mass to 6 parts by mass. When the content of the component (E) is 0.01 part by mass or more, sufficient curability of the cured film of the embodiment of the present invention can be imparted with sufficient thermosetting property and solvent resistance, and high sensitivity to exposure light can be obtained. When the content of the component (E) is 10 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[Other additives]

The cured film forming composition of the embodiment of the present invention may contain other additives as long as the effect of the present invention is not impaired.

Other additives may include, for example, sensitizers. The sensitizer is effective in promoting the photoreaction when the cured film of the embodiment of the present invention is formed from the cured film forming composition of the present embodiment.

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

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

In the embodiment of the present invention, the use ratio of the sensitizer is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass 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. When the ratio is too large, the transmittance of the cured film to be formed may be lowered or the coating film may be roughened.

The cured film-forming composition of the embodiment of the present invention may contain, as other additives, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, And the like.

[solvent]

The cured film-forming composition of the embodiment of the present invention is often used in the form of a solution dissolved in a solvent. The solvent used herein is one which dissolves the component (A), the component (B) and the component (C), and optionally the component (D), the component (E) and / or other additives. If it is a solvent, its type and structure are not particularly limited.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl- Hydroxypropionate, ethyl 2-hydroxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-2-hydroxypropionate, Methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, There may be mentioned ethyl acetate, butyl acetate, ethyl lactate, lactic acid butyl, N, N- dimethylformamide, N, N- dimethylacetamide and N- methylpyrrolidone.

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

≪ Preparation of cured film forming composition >

The cured film-forming composition of the embodiment of the present invention is a thermosetting cured film-forming composition having photo-alignment property. As described above, the cured film-forming composition of the present embodiment comprises a polymer having at least one of a low-molecular-orientation component (A), a hydroxyl group and a carboxyl group as the component (B) (A), a compound having a hydroxyl group and a (meth) acryl group. Furthermore, a crosslinking agent may be contained as the component (D), and a crosslinking catalyst may be contained as the component (E). As long as the effect of the present invention is not impaired, other additives may be contained, and further, a solvent may be contained.

The blending ratio of the component (A) and the component (B) is preferably from 5:95 to 60:40 by mass ratio. When the content of the component (B) is too large, the liquid crystal alignability tends to deteriorate. When the content of the component (B) is too small, the solvent resistance tends to decrease.

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

(1): 0.1 part by mass to 40 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B), in a mass ratio of 5:95 to 60:40, By mass of the component (C).

(1): 0.1 part by mass to 40 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B), in a mass ratio of 5:95 to 60:40, A component (C) in a mass part, and a solvent.

(1): 0.1 part by mass to 40 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B), in a mass ratio of 5:95 to 60:40, (C), 10 parts by mass to 100 parts by mass of component (D), and a solvent.

(1): 0.1 part by mass to 40 parts by mass, based on 100 parts by mass of the total amount of the component (A) and the component (B), in a mass ratio of 5:95 to 60:40, (C), 10 to 100 parts by mass of component (D), 0.01 to 10 parts by mass of component (E), and a solvent.

The mixing ratio, preparation method and the like when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.

The proportion of the solid content in the cured film-forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in a solvent, but it is preferably 1% by mass to 80% by mass, and more preferably 3% Mass%, and more preferably 5 mass% to 40 mass%. Here, the solid content refers to the solvent excluding the entire components of the cured film forming composition.

The method of preparing the cured film forming composition of the present embodiment is not particularly limited. As the preparation method, for example, the component (A) and the component (C), further the components (D) and (E) are mixed at a predetermined ratio into a solution obtained by dissolving the component (B) , A method of making a homogeneous solution, or a method in which other additives are added and mixed at an appropriate stage of the preparation method, if necessary.

In the preparation of the cured film-forming composition of the present embodiment, the solution of the specific copolymer obtained by the polymerization reaction in a solvent can be used as it is. In this case, for example, at least one of a monomer having a carboxyl group and a monomer having a phenolic hydroxy group is copolymerized with at least one of a monomer having a polyethylene glycol ester group and a monomer having a hydroxyalkyl ester group having 2 to 5 carbon atoms To the obtained solution of the component (B), a component (A) and a component (C), and further the component (D) and the component (E) are added in the same manner as described above to obtain a homogeneous solution. At this time, additional solvent may be added for the purpose of concentration adjustment. At this time, the solvent used in the production of the component (B) may be the same as or different from the solvent used for adjusting the concentration of the cured film forming composition.

The solution of the prepared cured film-forming composition is preferably filtered after using a filter having a pore diameter of about 0.2 탆 or the like.

<Cured film, alignment material and retardation material>

The solution of the cured film-forming composition of the present embodiment may be applied to a substrate (e.g., a substrate coated with a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, chromium, A spin coating, a spin coating, a spin coating, a spin coating, a spin coating, a spin coating, a spin coating, or a spin coating) on a film (e.g., a quartz substrate, an ITO substrate, etc.) The cured film can be formed by applying a coating solution, a roll coating, a slit coating, a rotary coating followed by a slit, an inkjet coating, printing or the like to form a coating film and then heating and drying in a hot plate or oven.

As the conditions of the heating and drying, the curing reaction proceeds so that the component of the alignment material formed from the cured film does not dissolve in the polymerizable liquid crystal solution applied thereon. For example, the curing reaction may be performed at a temperature of 60 to 200 deg. The heating temperature and heating time appropriately selected within the range of from 60 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70 to 160 DEG C for 0.5 to 10 minutes.

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

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

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

Since the alignment material formed from the curable film composition of the present embodiment has solvent resistance and heat resistance, the retardation material made of the polymerizable liquid crystal solution is coated on the alignment material, and then heated to the phase transition temperature of the liquid crystal, The liquid crystal state is obtained and aligned on the alignment material. Then, the retardation material having the optically anisotropic layer can be formed by directly curing the retardation material in the desired alignment state.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the liquid crystal monomer are used. When the substrate on which the alignment material is formed is a film, the film having the retardation film 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 has an alignment state such as a horizontal alignment, a cholesteric alignment, a vertical alignment and a hybrid alignment on the alignment material. It can be used in accordance with the phase difference characteristic.

In the case of producing a patterned retardation material for use in a 3D display, a cured film formed by the above-described method from the cured film composition of the present embodiment is subjected to a patterning process using a line- Polarized UV exposure is performed in the direction of +45 degrees and then the mask is separated and then the polarized UV is exposed in the direction of -45 degrees to form an alignment material having two kinds of liquid crystal alignment regions in which alignment control directions of liquid crystals are different . Thereafter, the retardation material made of the polymerizable liquid crystal solution is coated, and then heated to the phase transition temperature of the liquid crystal to bring the retardation material into a liquid crystal state. The polymerizable liquid crystal in a liquid crystal state is oriented on an alignment material having two kinds of liquid crystal alignment regions, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material realizing this alignment state is intact, and the above-described alignment state is fixed, whereby a patterned retardation material in which a plurality of two kinds of retardation regions having different retardation characteristics are arranged in a regular manner can be obtained .

The alignment material formed from the cured film composition of the present embodiment can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, two substrates having the alignment material of the present embodiment formed as described above may be used. After aligning these substrates with the alignment members on both substrates facing each other with the spacer interposed therebetween, Whereby a liquid crystal display element in which liquid crystals are aligned can be manufactured.

Accordingly, the cured film-forming composition of the present embodiment can be suitably used for the production of various retardation films (phase difference films) and liquid crystal display elements.

Example

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

[Composition components used in Examples and the like]

The composition components used in the following examples and comparative examples are as follows.

&Lt; Compound having photo-orientable group and hydroxy group >

CIN1: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

[Chemical Formula 13]

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

[Chemical Formula 14]

<Polymers Having Hydroxyl Group and Carboxyl Group>

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

[Chemical Formula 15]

(Wherein R represents alkylene).

<Cross-linking agent>

HMM: melamine crosslinking agent represented by the following structural formula

[Chemical Formula 16]

PBMAA: poly (N-butoxymethyl acrylamide)

&Lt; Crosslinking catalyst &

PTSA: Paratoluenesulfonic acid

[Chemical Formula 17]

<Compounds Having Hydroxy Group and (meth) Acryl Group>

Compound C-1 having a hydroxyl group and (meth) acryl group:

[Chemical Formula 18]

Compound C-2 having a hydroxyl group and (meth) acrylic group:

[Chemical Formula 19]

Compound C-3 having a hydroxyl group and (meth) acrylic group:

[Chemical Formula 20]

<Solvent>

Each of the cured film forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM-P) and ethyl acetate (AcEt) were used as the solvent.

&Lt; Examples and Comparative Examples &

(Synthesis Example 1) Synthesis of CIN11

(Synthesis Example 1-1) Synthesis of precursor CIN11-1 of CIN11

[Chemical Formula 21]

In a 1 L four-necked flask, 80.0 g of 4-bromo-4'-hydroxybenzophenone, 500 mL of N, N-dimethylacetamide, 55.4 g of tert-butyl acrylate, 160.2 g of tributylamine, , And 3.50 g of tri (o-tolyl) phosphine were added and stirred while heating to 100 캜. After completion of the reaction, the reaction system was poured into 2 L of ethyl acetate, and extraction was carried out using a 1N aqueous hydrochloric acid solution and a saturated saline solution. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off using a rotary evaporator to obtain 109.4 g of the target CIN11-1 (reddish brownish brown). The obtained CIN11-1 was used for the next reaction without purification.

(Synthesis Example 1-2) Synthesis of CIN11

[Chemical Formula 22]

In a 2 L four-necked flask, 93.4 g of CIN11-1, 1 L of N, N-dimethylformamide, 39.3 g of 6-chloro-1-hexanol, 119.4 g of potassium carbonate and 4.8 g of potassium iodide were added, And the mixture was stirred while heating to 100 캜. After completion of the reaction, a reaction system was poured into 5 L of water, neutralized with a 1N aqueous hydrochloric acid solution, and extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The residue was recrystallized using isopropanol / hexane = 1/10 to obtain 113.8 g of CIN11 (ocher-colored solid). The results obtained by ¹ H-NMR, which is a target, are shown below. From this result, it was confirmed that the obtained solid was the target CIN11.

(23)

Polymer Synthesis Example 1

7.0 g of MAA, 7.0 g of HEMA and 0.5 g of AIBN (azobisisobutyronitrile) as a polymerization initiator were dissolved in 53.9 g of PM-P and reacted at 75 DEG C for 20 hours to obtain an acrylic copolymer solution (solids concentration 25 Mass%) was obtained (P-1). The obtained acrylic copolymer had Mn of 10,300 and Mw of 24,600.

&Lt; Examples and Comparative Examples &

Each of the cured film forming compositions of Examples 1 to 6 and Comparative Examples 1 and 2 was prepared with the composition shown in Table 1. Next, each of the cured film forming compositions was used to form a cured film, and each of the obtained cured films was evaluated for adhesion, orientation sensitivity, pattern forming property, and transmittance.

[Table 1]

[Evaluation of adhesion]

Each of the cured film forming compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was applied on a TAC film using a bar coater and then heated and dried at 110 ° C for 120 seconds in a thermocycling oven To form a cured film. This linearly polarized light of 313nm was irradiated perpendicularly to 20mJ / cm ² to 40mJ / cm ² in each hardened layer. On the cured film on the substrate after exposure, a polymerizable liquid crystal solution for horizontal orientation RMS03-013C made by Merck Ltd. was applied using a spin coater and then prebaked on a hot plate at 60 캜 for 60 seconds to form a film thickness Thereby forming a coating film having a thickness of 1.0 mu m. This film was exposed at 1000 mJ / cm ² , and the polymerizable liquid crystal was polymerized to prepare a retardation film. A cross cut (1 mm x 1 mm x 100 squares) was put into the obtained retardation film on the substrate using a cutter knife, and then a cellophane tape was attached. Subsequently, when the cellophane tape was peeled off, the number of squares remaining in the phase difference material on the substrate without peeling the polymerized liquid crystal film on the cured film in the lower layer was counted. The evaluation results are summarized in the initial column of Table 2 in the form of (number of chambers remaining without peeling the film) / 100. It was judged that the film had a good adhesion when 90 or more of the remaining cells remained without being peeled off, that is, 90/100 to 100/100.

[Evaluation of Durability of Adhesion]

The retardation material was placed in an oven set at a temperature of 80 DEG C and a humidity of 90% on the TAC film in the same manner as in the evaluation of the above-described adhesion, and the film was allowed to stand for 24 hours or longer. Thereafter, the retardation material was taken out, and the adhesion property was evaluated in the same manner as the above-described evaluation of the adhesion. The evaluation results are summarized in Table 2 as adhesion durability.

[Evaluation of alignment sensitivity (Examples 1 to 5)] [

Each of the cured film forming compositions of Examples 1 to 5 and Comparative Examples 1 and 2 was spin-coated on alkali glass at 2000 rpm for 30 seconds using a spin coater, Followed by heating and drying in an oven to form a cured film. The linearly polarized light of 313 nm was vertically irradiated to each of the cured films to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal orientation RMS03-013C made by Merck Ltd. was applied using a spin coater and then prebaked on a hot plate at 60 DEG C for 60 seconds to form a film having a thickness of 1.0 mu m Was formed. The coating film on the substrate was exposed at 1000 mJ / cm ² to prepare a retardation film. The produced retardation on the substrate was sandwiched by a pair of polarizing plates and the state of occurrence of the retardation characteristic in the retardation was observed to determine the alignment sensitivity as the exposure amount of the polarized UV required for the orientation material to exhibit liquid crystal alignability. The evaluation results are summarized in Table 2 below. The alignment material formed using each of the cured film forming compositions of Examples 1 to 5 and Comparative Examples 1 and ² had a low exposure dose of polarized UV required to exhibit liquid crystal alignment properties of 20 mJ / cm ² to 40 mJ / cm ² Value, indicating good orientation sensitivity.

[Evaluation of alignment sensitivity (Examples 6 and 7)] [

Each of the cured film forming compositions of Example 6 and Example 7 was applied to a TAC film using a bar coater and then heated and dried in a thermocycling oven at a temperature of 110 ° C for 120 seconds to form a cured film. The linearly polarized light of 313 nm was vertically irradiated to each of the cured films to form an alignment material. The polymerizable liquid crystal solution for horizontal orientation was coated on the alignment material on the substrate using a bar coater and then prebaked on a hot plate at 70 캜 for 60 seconds to form a coating film having a thickness of 1.0 탆. The coating film on the substrate was exposed at 300 mJ / cm ² to prepare a retardation film. The produced retardation on the substrate was sandwiched by a pair of polarizing plates and the state of occurrence of the retardation characteristic in the retardation was observed to determine the alignment sensitivity as the exposure amount of the polarized UV required for the orientation material to exhibit liquid crystal alignability. The evaluation results are summarized in Table 2 below.

[Evaluation of pattern formation property]

Each of the cured film forming compositions of Examples and Comparative Examples was applied to a TAC film using a bar coater and then heated and dried in a thermocycling oven at a temperature of 110 DEG C for 120 seconds to form a cured film. This cured film was vertically irradiated with linearly polarized light of 313 nm at 40 mJ / cm ^{2 through} a line-and-space mask of 350 m. Next, the mask was separated, the substrate was rotated by 90 degrees, linearly polarized light of 313 nm was vertically irradiated at 20 mJ / cm ² , and an alignment material having two types of liquid crystal alignment regions in which alignment control directions of liquid crystals were different by 90 degrees was formed . On this alignment material on the substrate, a polymerizable liquid crystal solution for horizontal orientation RMS03-013C made by Merck Ltd. was applied using a spin coater and then prebaked on a hot plate at 60 캜 for 60 seconds to obtain a film thickness of 1.0 mu m. The coating film on the substrate was exposed at 1000 mJ / cm ² to prepare a patterned retardation material in which two kinds of regions having different retardation characteristics were regularly arranged. The patterned phase difference material on the produced substrate was observed using a polarizing microscope to find that a phase difference pattern was formed without an alignment defect, and that having an alignment defect was evaluated as x. The evaluation results are summarized in Table 2 below.

[Evaluation of light transmittance (transparency)] [

Each of the cured film forming compositions of Examples and Comparative Examples was spin coated on a quartz substrate at 2000 rpm for 30 seconds using a spin coater and then heated and dried on a hot plate at a temperature of 110 캜 for 120 seconds to form a cured film having a thickness of 300 nm Respectively. The film thickness was measured using F20 manufactured by Filmetrics, Inc. The cured film was measured for transmittance with respect to light having a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADZU UV-2550 model manufactured by Shimadzu Corporation).

[Evaluation results]

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

[Table 2]

The cured films obtained by using the cured film forming compositions of Examples 1 to 5 maintained high adhesiveness even at high temperature and high humidity treatment and exhibited excellent adhesion durability.

On the contrary, the cured films obtained by using the cured film-forming compositions of Comparative Examples 1 and 2 were difficult to maintain initial adhesion after high temperature and high humidity treatment.

The alignment material obtained by using the cured film forming compositions of Examples 1 to 5 had an exposure amount of polarized UV required to exhibit liquid crystal alignment properties of 20 mJ / cm ² was to low value of 40mJ / cm ^2, it showed a good alignment sensitivity.

The alignment material obtained by using the cured film forming compositions of Examples 6 and 7 was higher in polarized UV exposure amount required to exhibit liquid crystal alignability than the alignment material obtained by using the cured film forming composition of Comparative Example 1 and Comparative Example 2 Were all low at 10 mJ / cm &lt; ² &gt; and exhibited good alignment sensitivity.

The alignment materials obtained by using the cured film forming compositions of Examples 1 to 7 exhibited good pattern forming properties as in the alignment materials obtained by using the cured film forming compositions of Comparative Examples 1 and 2.

The cured films obtained by using the cured film forming compositions of Examples 1 to 7 were 100% or more close to the light having a wavelength of 400 nm, like the cured films obtained by using the cured film forming compositions of Comparative Examples 1 and 2 Transmittance, and exhibited good light transmission characteristics.

Industrial availability

The cured film obtained from the cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside the liquid crystal display element, As a material for forming a patterned retardation material. Furthermore, a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, particularly, a material for forming an interlayer insulating film of a TFT type liquid crystal element, Or as a material for forming an insulating film of an organic EL element or the like.

Claims (7)

(A) a compound having one photo-oriented group and one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group and an alkoxysilyl group,
(B) a polymer having at least one of a hydroxyl group and a carboxyl group, and
(C) a compound having a hydroxyl group and a (meth) acryl group other than the component (A)
Wherein the cured film-forming composition is a cured film-forming composition.
The method according to claim 1,
Wherein the compound of the component (A) is a compound having a photo-orientable group and a hydroxy group.
3. The method according to claim 1 or 2,
Wherein the compound of component (C) has at least one hydroxyl group and one (meth) acryl group.
4. The method according to any one of claims 1 to 3,
(D) a cross-linking agent.
5. The method according to any one of claims 1 to 4,
(E) a cross-linking catalyst.
An alignment material obtained by using the cured film forming composition according to any one of claims 1 to 5.
A retardation film having a cured film obtained from the cured film-forming composition according to any one of claims 1 to 5.