KR20150143540A - Cured film-forming composition, alignment material, and phase difference material - Google Patents

Abstract

[PROBLEMS] To provide a cured film-forming composition for forming a cured film having excellent photoreaction efficiency, solvent resistance and high adhesion, and to provide an alignment material for optical alignment and a phase difference material formed using the alignment material.
A cured film-forming composition comprises (A) a compound having a photo-orientable group and at least one substituent selected from a hydroxyl group, a carboxyl group, a trialkoxysilyl group and an amino group, (B) a compound having a hydroxyl group, (C) a compound having at least two trialkoxysilyl groups, and (D) a cross-linking catalyst. The hydrophilic polymer is preferably a hydrophilic polymer having at least one substituent selected from the group consisting of a carboxyl group and an amino group. The cured film-forming composition is used to form a cured film, and an alignment material is formed using a photo-alignment technique. The 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 < RTI ID = 0.0 >

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

2. Description of the Related Art In recent years, in the field of displays such as televisions using liquid crystal panels, development of 3D displays capable of enjoying 3D images has been underway as 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 various types of 3D display methods for displaying 3D images, and lenticular lens method and parallax barrier method are known as methods which do not require dedicated glasses.

One of the display methods for observers to observe a 3D image by wearing glasses is a circular polarizing glasses method or the like (see, for example, Patent Document 1).

In the case of a 3D display of a circular polarizing glasses system, a phase difference material is usually arranged on a display element forming an image of a liquid crystal panel or the like. This phase difference material has a plurality of regularly arranged two kinds of retardation regions having different retardation characteristics, and thus constitutes a patterned retardation material. Hereinafter, in the present specification, the retardation patterned to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by 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 a photo-alignment technique known as 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 types of polarized light having different polarization directions are irradiated thereon. 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 applied on the photo alignment layer to realize alignment of the polymerizable liquid crystal. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned retardation material.

In the alignment reformation using the optical alignment technique of a liquid crystal panel, acrylic resin, polyimide resin, or the like having a photo-dimerization site 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 performance (hereinafter, also referred to as liquid crystal alignability) for controlling alignment 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 Japanese Patent Application Laid-Open No. 2009-058584 Japanese Patent Publication No. 2001-517719

However, according to the study of the present inventors, it has been confirmed that an acrylic resin having a light dimerization site such as a cinnamoyl group or a knicaine group in such a side chain can not obtain sufficient characteristics when applied to the formation of a retardation film. In particular, in order to form an alignment material by irradiating polarized UV to these resins, and to perform optical patterning of a retardation material made of a polymerizable liquid crystal by using the alignment material, a large polarized UV exposure amount is required. The amount of polarized UV exposure is significantly larger than the amount of polarized UV exposure (for example, about 100 mJ / cm ² ) sufficient for aligning a liquid crystal for general liquid crystal panel.

The reason why the amount of polarized UV exposure is increased is that, in the case of retardation reformation, unlike liquid crystal for liquid crystal panel, the polymerizable liquid crystal is used in a solution state and applied on an alignment material.

When an alignment material is formed by using an acrylic resin or the like having a photo-dimerization site such as a cinnamoyl group on the side chain to orient the polymerizable liquid crystal, in the acrylic resin or the like, photo-crosslinking by the photo- I do. Then, it is necessary to continue the polarizing irradiation with a large exposure dose until the resistance to the polymerizable liquid crystal solution is manifested. In order to align the liquid crystal of the liquid crystal panel, usually only the surface of the optically oriented alignment material is subjected to dimerization reaction. However, when attempting to develop solvent resistance in an alignment material by using a conventional material such as the acrylic resin described above, it is necessary to perform the reaction to the inside of the alignment material, and a larger exposure dose is required. As a result, there has been a problem that the orientation sensitivity of conventional materials becomes very small.

Further, a technique of adding a cross-linking agent to a resin, which is a conventional material described above, in order to exhibit such solvent resistance is known. However, after the thermosetting reaction with the crosslinking agent was carried out, it was found that a three-dimensional structure was formed inside the coating film to be formed, and the photoreactivity was lowered. That is, the orientation sensitivity is significantly lowered, and a desired effect can not be obtained even when a cross-linking agent is added to a conventional material.

From the above, there is a demand for a photo-alignment technique capable of improving the alignment sensitivity of the alignment material and reducing the amount of polarized UV exposure and a cured film forming composition used for forming the alignment material. Further, there is a demand for a technique capable of providing a patterned retardation material with high efficiency.

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 for providing an alignment material having excellent light reaction efficiency and solvent resistance and capable of orienting a polymerizable liquid crystal with high sensitivity.

Another object of the present invention is to provide an alignment material which is obtained from the composition for forming a cured film and which has excellent photoreaction efficiency and is excellent in solvent resistance and can orient the polymerizable liquid crystal with high sensitivity and an alignment material To provide a phase difference material.

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 a photo-orientable group and at least one substituent selected from a hydroxyl group, a carboxyl group, a trialkoxysilyl group and an amino group,

(B) a hydrophilic polymer having at least one substituent selected from a hydroxyl group, a carboxyl group and an amino group,

(C) a compound having two or more trialkoxysilyl groups, and

(D) a cross-linking catalyst.

In the first aspect of the present invention, it is preferable that the photo-orientable group of the component (A) is a functional group having a structure of photo-dimerization or photo-isomerization.

In the first aspect of the present invention, it is preferable that the photo-orientable group of the component (A) is a cinnamoyl group.

In the first aspect of the present invention, it is preferable that the photo-orientable group of the component (A) is a group of an azobenzene structure.

In the first aspect of the present invention, it is preferable that the compound of component (A) has two or more hydroxy groups.

In the first aspect of the present invention, the component (B) is preferably at least one hydrophilic polymer selected from the group consisting of a polyether polyol, a polyester polyol, a polycarbonate polyol and a polycaprolactone polyol.

In the first aspect of the present invention, the component (B) is preferably cellulose or a derivative thereof.

In the first aspect of the present invention, the component (B) is at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and an acrylic polymer having at least one of a carboxyl group and a phenolic hydroxyl group .

In the first aspect of the present invention, the component (B) is 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, a monomer having a carboxyl group and a phenolic hydroxy group Is preferably an acrylic copolymer obtained by a polymerization reaction of a monomer containing at least one of the monomers.

In the first aspect of the present invention, the component (B) is preferably a cyclodextrin or a derivative thereof.

In the first aspect of the present invention, the component (D) is preferably an acid or a thermal acid generator.

In the first aspect of the present invention, the ratio of the component (A) to the component (B) is preferably 5:95 to 65:35 in terms of mass ratio.

In the first aspect of the present invention, it is preferable to contain 10 parts by mass to 100 parts by mass of the component (C) based on 100 parts by mass of the total amount of components (A) and (B).

In the first aspect of the present invention, it is preferable to contain the component (D) in an amount of from 0.5 parts by mass to 20 parts by mass based on 100 parts by mass of the total amount of components (A) and (B).

A second aspect of the present invention relates to an alignment material characterized by being produced from the thermosetting film forming composition of the first aspect of the present invention.

A third aspect of the present invention relates to a phase difference material characterized by being formed using 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, there can be provided a cured film-forming composition for providing an alignment material having excellent light reaction efficiency and solvent resistance and capable of orienting a polymerizable liquid crystal with high sensitivity.

According to the second aspect of the present invention, it is possible to provide an alignment material having excellent light reaction efficiency and solvent resistance and capable of orienting the polymerizable liquid crystal with high sensitivity.

According to the third aspect of the present invention, it is possible to provide a phase difference material which can be formed with high efficiency and can be subjected to optical patterning.

≪ Cured film forming composition >

The cured film-forming composition of the present embodiment is a cured film-forming composition of (A) a low-molecular photo-aligning component, (B) a hydrophilic polymer, (C) a compound having two or more trialkoxysilyl groups, Lt; / RTI > The cured film forming composition of the present embodiment may contain other additives in addition to the components (A), (B), (C) and (D), so long as the effect of the present invention is not impaired.

Hereinafter, the details of each component will be described.

≪ Component (A) >

The component (A) contained in the cured film-forming composition of the present embodiment is a compound having a photo-orientable group and at least one substituent selected from a hydroxyl group, a carboxyl group, a trialkoxysilyl group and an amino group.

In the compound of the component (A), the photo-orientable group reacts with light to form a hydrophobic photo-alignment portion, while the substituent selected from a carboxyl group, a trialkoxysilyl group and an amino group constitutes a hydrophilic thermal reaction portion. That is, the component (A) is a component that imparts a photo-alignment property to the cured film, and in the present specification, the component (A) is also referred to as a photo-alignment component or a photo-alignment component of a low molecular weight.

In the present invention, the photo-orientable group refers to a functional group at a structural site where light is diminished or photo-isomerized.

The light-quantifiable structural moiety is a moiety that forms a dimer by light irradiation. Specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group having high transparency and photo-dimerization reactivity in the visible light region is preferable. In addition, the structural part to be optically isomerized refers to a structural part which is changed into a cis body and a trans-body by light irradiation, and specific examples thereof include an azobenzene structure, a stilbene structure, and the like. Among them, the azobenzene structure is preferable from the height of the reactivity. The compound having a photo-orientable group and a hydroxy group is represented by the following formula, for example. Specific examples of such compounds are shown by the following formulas [A1] to [A5].

[Chemical Formula 1]

Wherein X ¹ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, A phenyl group, a biphenyl group, or a combination thereof. X ² 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. Here, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond or an urea bond. X ³ represents a hydroxyl group, a phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or an alkoxy group. X ⁴ 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 ⁵ 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.

In these substituents, the phenyl group and the biphenyl group may be the same or different from each other 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, and a cyano group ≪ / RTI >

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ 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.

In the above formula, A ¹ represents a hydrogen atom or a methyl group. A2 represents a hydrogen atom or a methyl group.

Specific examples of the compound having a photo-orientable group and a hydroxy group as the component (A) include methyl 4- (8-hydroxyoctyloxy) cinnamate, 4- (6-hydroxyhexyloxy) methyl cinnamate Ester, methyl ester of 3-methoxy-4- (6-hydroxyhexyloxy) cinnamate, methyl ester of 4- (4-hydroxybutyloxy) cinnamate, methyl ester of 4- (3-hydroxypropyloxy) 4-hydroxymethyloxycinnamic acid methyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyethyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, Ethyl ester, ethyl 4-hydroxymethyloxy cinnamate, ethyl 4-hydroxycinnamate 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 (4-hydroxyhexyloxy) azobenzene, 4 (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- Azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 4-hydroxymethyloxyazobenzene, 4- 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) chalcone, 4- (4-hydroxybutyloxy) (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxycalcone, 4-hydroxycalcone, 4 '- (8-hydroxyoctyloxy) , 4'- (4-hydroxybutyloxy) chalcone, 4'- (3-hydroxypropyloxy) chalcone, 4'- (2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxycalone, 4 '- Hydroxycal 7- (4-hydroxybutyloxy) coumarin, 7- (3-hydroxypropyloxy) coumarin, 7- , 7- (2-hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxy coumarin, 6- Hydroxypropyloxy) coumarin, 6- (2-hydroxyethyloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4- [4- Benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- , Methyl 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxymethyloxybenzoyl) (4-hydroxybenzoyl) cinnamic acid methyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- Benzoyl] cinnamic acid ethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3- hydroxypropyloxy) Hydroxymethylbenzoyl] cinnamic acid ethyl ester, 4- [4-hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxymethylbenzoyl) cinnamic acid ethyl ester, 4- [ Benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid Tert-butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid tertiary (4-hydroxymethyloxybenzoyl) cinnamic acid tert-butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- Benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3- hydroxypropyloxy) 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [ (4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- Biphenyl ester of cinnamic acid, biphenyl ester of cinnamic acid, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (2- - [4-hydroxymethyloxybenzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid biphenyl ester, 4-benzoyl cinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester , 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic acid 3-hydroxypropyl ester, 4-benzoyl cinnamic acid 2-hydroxyethyl ester, 4-benzoyl cinnamic acid hydroxymethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] (4-hydroxymethyloxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) quinolone, 4- ) Chalcone, 4 '- [4- (4-hydroxycyclohexyloxy) benzoyl] chalcone, 4' - [4- Roxybutyloxy) benzoyl] , 4 '- (4-hydroxymethyloxybenzoyl) chalcone, 4'- [4- (2-hydroxyethyloxy) benzoyl] , 4 '- (4-hydroxybenzoyl) chalcone.

Specific examples of the compound having a photo-orientable group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitro cinnamic acid, 4-methoxy cinnamic acid, 3,4-dimethoxy cinnamic acid, coumarin- Dimethylamino) cinnamic acid and the like.

Specific examples of the compound having a photo-orientable group, a carboxyl group and an amino group include methyl-4-amino cinnamic acid, ethyl-4-amino cinnamic acid, methyl-3-amino cinnamic acid and ethyl-3-amino cinnamic acid.

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 photo-alignment group and trialkoxysilyl group as component (A) include 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylpropyloxy) Methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- Ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3-triethoxysilylhexyloxy) Ethyl ester and the like.

Examples of the photo-alignment component of the low molecular weight component (A) include, but are not limited to, the above specific examples.

When the photo-orientable component (A) is a compound having a photo-orientable group and a hydroxy group, a compound having two or more photo-orientable groups and / or two or more hydroxy groups in the molecule is used as the component (A) It is possible. 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, as a compound having two or more photo-orientable groups and two or more hydroxy groups in the molecule, a compound represented by the following formula can be shown as an example.

(2)

By appropriately selecting such a compound, it becomes possible to control the molecular weight of the photo-alignment component (A) to be increased. As a result, as described later, when the photo-alignment component (A), the polymer as the component (B) and the cross-linking agent as the component (C) are thermally reacted, sublimation of the photo- have. The cured film forming composition of the present embodiment can form an alignment material having a high photoreaction efficiency as a cured film.

The compound of component (A) in the cured film forming composition of the present embodiment may be a mixture of plural kinds of compounds each having a photo-orientable group and any substituent selected from a hydroxyl group, a carboxyl group and an amino group have.

≪ Component (B) >

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

The hydrophilic polymer as the component (B) may be a polymer having at least one substituent selected from a hydroxyl group, a carboxyl group and an amino group (hereinafter also referred to as a specific polymer).

In the cured film-forming composition of the present embodiment, the specific polymer as the component (B) is preferably a highly hydrophilic polymer having high hydrophilicity so as to be more hydrophilic than the compound of the component (A). The specific polymer is preferably a polymer having a hydrophilic group such as a hydroxy group, a carboxyl group and an amino group, and more specifically, a polymer having one or more substituents selected from a hydroxyl group, a carboxyl group and an amino group Do. That is, the term "hydrophilic" in the hydrophilic polymer of the component (B) in the present specification means that it is more hydrophilic than the compound of the component (A).

Examples of the hydrophilic polymer as the component (B) include an acrylic polymer, a polyamic acid, a polyimide, a polyvinyl alcohol, a polyester, a polyester polycarboxylic acid, a polyether polyol, a polyester polyol, a polycarbonate polyol, Cyclic polymers such as cyclodextrins and the like having a linear or branched structure such as a lactone polyol, a polyalkyleneimine, a polyallylamine, a cellulose (a cellulose or a derivative thereof), a phenol novolac resin and a melamine formaldehyde resin, .

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 a hydroxyalkylcyclodextrin, a cellulose, a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, a carboxyl group and a phenolic hydroxy 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 hydroxy 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 preferable example of the specific polymer of the 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.

A polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms, and the preferable structural unit is represented by the following formula [B1].

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

(3)

In the formula [B1] and the formula [B2], X ¹¹ and X ¹² each independently represent a hydrogen atom or a methyl group, Y ¹ represents an H- (OCH ₂ CH ₂ ) _n - group 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 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight is over 200,000 and the weight average molecular weight is excessively large, the solubility in a solvent is lowered and the handling property may be lowered. If the weight average molecular weight is less than 3,000, The heat resistance may be lowered. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. 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 synthesizing the acrylic polymer which is an example of the component (B), monomers other than the b1 monomer and the b2 monomer, specifically, a monomer having a hydroxyl group and a carboxyl group Monomers that do not have any can be used in combination.

Examples of such a 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 excessively low, the liquid crystal alignability tends to become insufficient, and when the b2 monomer is excessive, compatibility with the component (A) tends to decrease.

The method for obtaining the acrylic polymer which is an example of the component (B) is not particularly limited. For example, in a solvent in which b1 monomer, b2 monomer and, if necessary, monomers other than b1 monomer and b2 monomer and a polymerization initiator coexist, An acrylic polymer is obtained by polymerization reaction at a temperature of 占 폚 to 110 占 폚. Here, the solvent to be used is not particularly limited as long as it dissolves the b1 monomer and the b2 monomer, the monomer other than the b1 monomer and the b2 monomer which are used if necessary, and the polymerization initiator. Specific examples are described in the section " Solvent "

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

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

In addition, a solution of an acrylic polymer, which is an example of the component (B) obtained by the above-described method, is re-precipitated by putting it in diethyl ether or water under stirring, filtering and washing the resultant precipitate and then drying at room temperature or reduced pressure And dried by heating to obtain a powder of an acrylic polymer which is an example of the component (B). By the above 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 an 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 operation may be repeated.

Examples of the polyether polyol which is a preferable example of the specific polymer of the component (B) include polypropylene glycol, polypropylene glycol, propylene glycol, polyhydric alcohols such as bisphenol A, triethylene glycol and sorbitol, propylene oxide, polyethylene glycol, And the like. Specific examples of the polyether polyol include adio polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by ADEKA, UNIOX (registered trademark) HC-40, HC- DA-400, DA-700, DB-400, TG-1000, TG-3000, TG-4000, HS-1600D, ST-40E, G-450, G-750, UNIOL (registered trademark) , 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 the component (B) include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, poly And a diol such as propylene glycol. Specific examples of the polyester polyol include POLYLITE TM 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-5010, P-6010, F-510 manufactured by Kuraray Co., , 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 preferable example of the specific polymer of the component (B) include those obtained by ring-opening polymerization of? -Caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as a initiator. 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 the polycarbonate polyol which is a preferable example of the specific polymer of the component (B) include those obtained by reacting polyhydric alcohols such as trimethylolpropane and ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate and the like. 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-2050, C-2090 manufactured by Kuraray Co., , C-3090, and the like.

Examples of the cellulose which is a preferable example of the specific polymer of component (B) include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylethylcellulose and the like Hydroxyalkylcelluloses such as hydroxyethylcellulose, hydroxypropylcellulose and the like are preferable, and hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Examples of the cyclodextrin which is a preferable example of the specific polymer of the component (B) include cyclodextrins such as -cyclodextrin, -cyclodextrin and -cyclodextrin, methyl-? -Cyclodextrin, methyl? -Cyclodextrin and methyl methylated cyclodextrin such as cyclodextrin, methylated cyclodextrin such as cyclodextrin and cyclodextrin, hydroxymethyl-cyclodextrin, hydroxymethyl-beta-cyclodextrin, hydroxymethyl-gamma-cyclodextrin, 2-hydroxyethyl- Hydroxypropyl-? -Cyclodextrin, 2-hydroxyethyl-? -Cyclodextrin, 2-hydroxypropyl-? -Cyclodextrin, 2-hydroxypropyl-? Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 3-hydroxypropyl-? -Cyclodextrin, 2,3-dihydroxypropyl -? - Lin host, and the like can be mentioned 2,3-di-hydroxypropyl -β- cyclodextrin, 2,3-di-hydroxypropyl -γ- cycloalkyl hydroxyalkyl cyclodextrin, such as cyclodextrin.

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

[Chemical Formula 4]

In the formula, R 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, but it is generally synthesized by mixing melamine and formaldehyde, making the mixture weak alkaline using sodium carbonate, ammonia, etc. and then heating at 60-100 ° C. Further, the methylol group can be alkoxylated by reacting with an alcohol.

The melamine formaldehyde resin as the component (B) preferably has a weight average molecular weight of 250 to 5,000, more preferably 300 to 4,000, and still more preferably 350 to 3,500. If the weight average molecular weight exceeds 5,000 and the weight average molecular weight is excessively large, the solubility in a solvent may deteriorate and the handling property may deteriorate. If the weight average molecular weight is less than 250, The heat resistance may be lowered.

In 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 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 a preferable example of the 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) is in the form of powder, or the purified powder may be used in the form of a solution which is redissolved in a solvent to be described later.

In the cured film-forming composition of the present embodiment, the polymer of component (B) may be a mixture of a plurality of polymers of component (B).

≪ Component (C) >

The component (C) contained in the cured film-forming composition of the present embodiment is a compound having two or more trialkoxysilyl groups. Or a polymer having a trialkoxysilyl group.

Specific examples of the compound having two or more trialkoxysilyl groups include 1,4-bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene, 4,4'-bis (trimethoxy Bis (trimethoxysilyl) ethane, bis (trimethoxysilyl) methane, bis (triethoxysilyl) ethane, bis Bis (trimethoxysilyl) ethylene, 1,3-bis (trimethoxysilylethyl) tetramethyldisiloxane, 1,3-bis (triethoxysilyl) (Triethoxysilylmethyl) amine, bis (triethoxysilylpropyl) amine, bis (trimethoxysilylpropyl) amine, bis (trimethoxysilylmethyl) (3-trimethoxysilyl) propyl carbonate, bis [3-triethoxysilylpropyl] carbonate, bis (3-triethoxysilyl) Bis [(3-trimethoxysilyl) propyl] thiourea, bis [(3-triethoxysilyl) propyl] thiourea, bis [ (Trimethoxysilylmethyl) benzene, 1,4-bis (trimethoxysilylmethyl) benzene, tris (trimethoxysilylmethyl) benzene, Tris (triethoxysilylpropyl) amine, 1,1,2-tris (trimethoxysilyl) ethane, 1,1,2-tris (triethoxysilyl) ethane, tris (3-trimethoxysilylpropyl) Isocyanurate, and tris (3-triethoxysilylpropyl) isocyanurate, a homopolymer or copolymer of methacryloyloxypropyltrimethoxysilane and acryloyloxypropyltriethoxysilane, .

These compounds having two or more trialkoxysilyl groups may be used alone or in combination of two or more.

The content of the compound having two or more trialkoxysilyl groups in the component (C) in the cured film-forming composition of the present embodiment is preferably in the range of 100 parts by mass based on 100 parts by mass of the total amount of the compound (A) Preferably 10 parts by mass to 100 parts by mass, more preferably 15 parts by mass to 80 parts by mass. When the content of the compound having two or more trialkoxysilyl groups as the component (C) is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film-forming composition are lowered, and sensitivity at the time of light decoloration is lowered. On the other hand, when the content is excessive, the photoalignment property and the storage stability may be deteriorated.

≪ Component (D) >

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

The crosslinking catalyst as the component (D) may be, for example, an acid or a thermal acid generator. The component (D) 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 (D), the component (D) is preferably a compound capable of generating an acid by thermal decomposition at a sulfonic acid group-containing compound, hydrochloric acid or its salt, prebake or postbake, Is not particularly limited as far as it is a compound which generates an acid by pyrolysis at 250 ° C.

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 [TAG-1] to [TAG-41] .

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

(11)

The content of the component (D) in the cured film-forming composition of the embodiment of the present invention is preferably 0.5 part by mass to 100 parts by mass based on 100 parts by mass of the total amount of the compound (A) More preferably 0.8 parts by mass to 15 parts by mass, still more preferably 0.8 parts by mass to 6 parts by mass. When the content of the component (D) is at least 0.5 part by mass, sufficient thermosetting property and solvent resistance can be imparted, and high sensitivity to exposure can be given. When the amount is 20 parts by mass or less, the storage stability of the cured film forming composition can be improved.

<Solvent>

The cured film forming composition of the present embodiment is mainly used in a solution state dissolved in a solvent. The solvent to be used herein is not particularly limited as long as it is capable of dissolving the component (A), the component (B), the component (C) and the component (D) and / It is not.

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- Hydroxybutyl lactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, And the like can be set acid 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.

<Other additives>

Further, the cured film-forming composition of the present embodiment may contain a polymerization initiator, a sensitizer, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, Antifoaming agents, antioxidants, and the like.

For example, the sensitizer is effective in promoting the photoreaction after the thermosetting film is formed using the cured film forming composition of the present embodiment.

Examples of the sensitizer which is an example of other additives include benzophenone, anthracene, anthraquinone, thioxanthone, and derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of preferred compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroasenaphthene, 4-nitrobiphenyl, 4-nitro cinnamic acid, 4-nitrobenzophenone, 5-nitroindole, and the like. Particularly, N, N-diethylaminobenzophenone, which is a benzophenone derivative, is preferred.

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

The use ratio of the sensitizer in the cured film forming composition of the present embodiment is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the total mass of the components (A) and (B) Is from 0.2 parts by mass to 10 parts by mass. When the ratio is too small, the effect as a sensitizer may not be sufficiently obtained. In the case where the ratio is excessive, the transmittance may be lowered and the coating film may be roughened.

&Lt; Preparation of cured film forming composition >

The cured film-forming composition of the present embodiment is a cured film-forming composition comprising a photo-aligned component of low molecular weight which is a component (A), a polymer which is more hydrophilic than the photo-orientable component of the component (A), which is the component (B), and a trialkoxysilyl group, A compound having two or more groups, and (D) a crosslinking catalyst. Other additives may be added as long as the effect of the present invention is not impaired.

The blending ratio of the component (A) and the component (B) is preferably from 5:95 to 65:35 in terms of the mass ratio. When the content of the component (B) is excessive, the liquid crystal alignability tends to deteriorate. If the content of the component (B) is too low, the solvent resistance tends to decrease.

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

[1] A process for producing a polyester resin composition, which comprises mixing a component (A) and a component (B) in a mass ratio of 5:95 to 65:35 and 10 parts by mass to 100 parts by mass of the total amount of the components (A) 100 parts by mass of the component (C) and 0.5 to 20 parts by mass of the component (D).

[2] A composition according to any one of [1] to [5], wherein the mixing ratio of the component (A) to the component (B) is 5:95 to 65:35 in terms of a mass ratio and 10 parts by mass to 100 parts by mass of the total amount of the components (A) 100 parts by mass of the component (C), 0.5 to 20 parts by mass of the component (D), 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, more preferably 3% By mass to 60% by mass, and more preferably 5% by mass to 40% by 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. Examples of the preparation method include a method of mixing a component (A), a component (C) and a component (D) in a predetermined ratio to a solution of the component (B) dissolved in a solvent to obtain a homogeneous solution, In a suitable step of this preparation method, other additives may be further added and mixed as required.

In the preparation of the cured film-forming composition of the present embodiment, a solution of a specific polymer obtained by 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 (A), (C) and (D) are added to the solution of the component (B) to obtain a homogeneous solution. At this time, a solvent may be further 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, A spin coating, a flow coating, a spin coating, a spin coating, a spin coating, a spin coating, or a spin coating) on a substrate (e.g., a substrate, an ITO substrate, or the like) or a film (e.g., a triacetylcellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, , A roll coating, a slit coating, a rotary coating followed by a slit, an ink jet coating, a printing, or the like to form a coating film, and then heating and drying the coating film with a hot plate or an oven.

As the conditions of the heating and drying, a crosslinking reaction by the crosslinking agent proceeds so that the components of the alignment material formed from the cured film do not dissolve in the polymerizable liquid crystal solution applied thereon. For example, Lt; 0 &gt; C, a time of 0.4 minute to 60 minutes, and a heating time. The heating temperature and the heating time are preferably 70 to 160 DEG C for 0.5 to 10 minutes.

The film 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 of the substrate to be used and the optical and electrical properties.

The cured film thus formed can function as a member for orienting an alignment material, that is, a liquid crystalline compound such as a 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 irradiated with linearly polarized light from the vertical or tilted direction at room temperature or in a heated state.

Since the alignment material formed from the cured film composition of the present embodiment has solvent resistance and heat resistance, a phase difference material comprising a polymerizable liquid crystal solution is coated on the alignment material, and then the phase difference material is heated to the phase transition temperature of the liquid crystal, And aligned on the alignment material. Then, the retardation material in the aligned state can be cured as it is, and the retardation material can be formed as a layer having optically anisotropy.

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 a retardation 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. Can be used.

In the case of producing the patterned retardation material for use in the 3D display, the cured film formed by the above-described method from the cured film composition of the present embodiment is applied to the cured film through a line and space pattern mask from a predetermined reference, Polarized UV exposure in the direction of +45 degrees, then the mask is removed, and then the polarized UV is exposed in the direction of -45 degrees to obtain an alignment material having two types 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 make the retardation material into a liquid crystal state and align on the alignment material. Then, the phase difference material in the aligned state is intactly cured, and a patterned phase difference material in which a plurality of two kinds of retardation regions having different retardation characteristics are arranged respectively and regularly can be obtained.

Further, two substrates having the alignment material of the present embodiment formed as described above are used, the alignment materials on the two substrates face each other through the spacers, liquid crystal is injected between these substrates, The liquid crystal display element may be an aligned liquid crystal display element.

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

[Example]

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

[Abbreviation used in the examples]

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

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

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

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

&Lt; Specific polymer raw material >

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AIBN: α, α'-azobisisobutyronitrile

HPCEL: Hydroxypropylcellulose

AADEG: Polyester (adipic acid / diethylene glycol)

<Alkoxysilane compound>

TTMSI: Tris (3-trimethoxysilylpropyl) isocyanurate

BTMSE: bis (trimethoxysilyl) ethane

&Lt; Crosslinking catalyst &

PTSA: Para-toluenesulfonic acid monohydrate

PPTS: Paratoluenesulfonic acid pyridine salt

<Solvent>

PM: Propylene glycol monomethyl ether

The number-average molecular weight and the weight-average molecular weight of the acrylic copolymer obtained according to the following Synthesis Example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation and eluting solvent tetrahydrofuran at a flow rate of 1 mL / min (Column temperature: 40 占 폚) and eluted. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in polystyrene conversion values.

&Lt; Synthesis Example 1 &

2.5 g of MAA, 9.2 g of MMA, 5.0 g of HEMA and 0.2 g of AIBN as a polymerization catalyst were dissolved in 50.7 g of PM and reacted at 70 DEG C for 20 hours to obtain an acrylic copolymer solution (solid concentration 25 mass%) (P1). The obtained acrylic copolymer had 19,600 Mn and 45,200 Mw.

&Lt; Examples 1 to 5, Comparative Examples 1 and 2 >

Each of the cured film forming compositions of the examples and comparative examples was prepared with the composition shown in Table 1, and the adhesion, the orientation sensitivity, the pattern forming property, and the transmittance were evaluated.

[Evaluation of adhesion]

Each of the cured film forming compositions of the Examples and Comparative Examples was spin-coated on alkali-free glass using a spin coater at 2000 rpm for 30 seconds and then heated and dried in a thermocycling oven at a temperature of 130 캜 for 120 seconds to form a cured film . This cured film was vertically irradiated with linearly polarized light of 313 nm at 50 mJ / cm ² . The polymerizable liquid crystal solution RMS03-013C for horizontal orientation made by Merck KGaA was applied to the surface of the cured film formed on the exposed substrate using a spin coater and then prebaked on a hot plate at 60 DEG C for 60 seconds To form a coating film having a thickness of 1.0 mu m. This coating film was exposed at 1000 mJ / cm ² to prepare a phase retarder having a polymerizable liquid crystal layer on the cured film. A cross cut (1 mm x 1 mm x 100 scales) was placed on the obtained retardation surface of the substrate using a cutter knife, and then the adhesive tape was attached. Then, when the adhesive tape was peeled off, And the polymerizable liquid crystal layer) were not peeled, and the number of remaining scales was counted. It was judged that the adhesion was good when the phase difference was not peeled off and the remaining scale remained 90 or more.

[Evaluation of orientation sensitivity]

Each of the cured film forming compositions of the examples and the comparative examples was spin-coated on alkali-free glass using a spin coater at 2000 rpm for 30 seconds and then heated and dried in a thermocycling oven at a temperature of 130 캜 for 120 seconds to form a cured film Respectively. This cured film was vertically irradiated with linearly polarized light of 313 nm to form an alignment material. A polymerizable liquid crystal solution for horizontal orientation RMS03-013C made by Merck KGaA was applied to the surface of the alignment material on the substrate using a spin coater and then prebaked on a hot plate at 60 DEG C for 60 seconds to form a film thickness Thereby forming a coating film having a thickness of 1.0 mu m. This coating film was exposed at 1000 mJ / cm ² to prepare a phase difference material having a polymerizable liquid crystal layer on the alignment material. The retardation on the produced substrate was sandwiched by a pair of polarizing plates and the state of occurrence of the retardation characteristic in the retardation was observed to measure the exposure amount of the polarized UV required for the alignment material to exhibit liquid crystal alignability. An alignment material having a high alignment sensitivity can exhibit alignment in the polymerizable liquid crystal layer on the alignment material at a low exposure dose.

[Evaluation of pattern formation property]

Each of the cured film forming compositions of the Examples and Comparative Examples was spin-coated on alkali-free glass using a spin coater at 2000 rpm for 30 seconds and then heated and dried in a thermocycling oven at a temperature of 130 캜 for 120 seconds to form a cured film . This cured film was irradiated with linearly polarized light of 313 nm at a rate of 30 mJ / cm ² vertically through a 100 μm line and space mask. After the mask was separated and the substrate was rotated by 90 degrees, linearly polarized light of 313 nm was irradiated vertically at 15 mJ / cm ² to obtain an alignment material having two kinds of liquid crystal alignment regions in which alignment control directions of liquid crystals were different by 90 degrees. A polymerizable liquid crystal solution for horizontal orientation RMS03-013C of Merck KGaA made by Merck KGaA was coated on the alignment material on the substrate by using a spin coater and then subjected to prebaking on a hot plate at 60 DEG C for 60 seconds, Thereby forming a coating film having a thickness of 1.0 mu m. This coating film was exposed at 1000 mJ / cm ² and the polymerizable liquid crystal was polymerized to prepare a patterned retardation material in which two kinds of regions having different retardation characteristics were regularly arranged. The patterned retardation material on the produced substrate was observed using a polarizing microscope to find that a retardation pattern was formed without an alignment defect, and that having alignment defect was evaluated as x.

[Evaluation of light transmittance (transparency)] [

Each of the cured film forming compositions of the examples and the comparative examples was spin coated on a quartz substrate at 2000 rpm for 30 seconds using a spin coater and then subjected to heat drying and baking on a hot plate at a temperature of 130 캜 for 120 seconds to cure Film. The film thickness was measured using F20 manufactured by FILMETRICS. The cured film was measured for transmittance to light having a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADZU UV-2550 model manufactured by SHIMADZU Corporation).

[Results of evaluation]

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

It can be understood that the alignment material obtained by using the thermosetting film forming composition prepared in Examples 1 to 5 exhibits liquid crystal alignability at an exposure amount less than 100 mJ / cm ² and has high alignment sensitivity. In addition, optical patterning could be performed. Furthermore, it showed high transparency.

In Comparative Examples 1 and 2, it was difficult to align them, and optical patterning could not be performed.

[Industrial Availability]

The cured film forming composition according to the present invention is very useful as a liquid crystal alignment film of a liquid crystal display element or an alignment material for forming an optically anisotropic film provided inside or outside a liquid crystal display element, As a material for forming the ash.

Claims (15)

(A) a compound having at least one photo-oriented group and at least one substituent selected from a hydroxyl group, a carboxyl group, a trialkoxysilyl group and an amino group,
(B) a hydrophilic polymer having at least one substituent selected from a hydroxyl group, a carboxyl group and an amino group,
(C) a compound having two or more trialkoxysilyl groups, and
(D) a crosslinking catalyst
By weight based on the total weight of the composition.
The method according to claim 1,
Wherein the photo-orientable group of the component (A) is a functional group having a structure of photo-dimerization or photo-isomerization.
3. The method according to claim 1 or 2,
Wherein the photo-orientable group of the component (A) is a cinnamoyl group.
3. The method according to claim 1 or 2,
Wherein the photo-orientable group of the component (A) is a group of an azobenzene structure.
5. The method according to any one of claims 1 to 4,
Wherein the compound of the component (A) has two or more hydroxy groups.
6. The method according to any one of claims 1 to 5,
Wherein the component (B) is at least one polymer selected from the group consisting of a polyether polyol, a polyester polyol, a polycarbonate polyol and a polycaprolactone polyol.
6. The method according to any one of claims 1 to 5,
Wherein the component (B) is cellulose or a derivative thereof.
6. The method according to any one of claims 1 to 5,
Wherein the component (B) is an acrylic polymer having at least one of a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 5 carbon atoms and at least one of a carboxyl group and a phenolic hydroxyl group Composition.
6. The method according to any one of claims 1 to 5,
Wherein the component (B) is a cyclodextrin or a derivative thereof.
10. The method according to any one of claims 1 to 9,
Wherein the component (D) is an acid or a thermal acid generator.
11. The method according to any one of claims 1 to 10,
Wherein the ratio of the component (A) to the component (B) is from 5:95 to 65:35 in terms of mass ratio.
12. The method according to any one of claims 1 to 11,
(C) component based on 100 parts by mass of the total amount of the component (A) and the component (B) in an amount of 10 parts by mass to 100 parts by mass.
13. The method according to any one of claims 1 to 12,
(D) component based on 100 parts by mass of the total amount of the component (A) and the component (B).
An alignment material made from the cured film-forming composition according to any one of claims 1 to 13.
A retardation film which is formed by using a cured film obtained from the cured film forming composition according to any one of claims 1 to 13.