KR20200135968A - Cured film forming composition, alignment material, and retardation material - Google Patents

Abstract

[Problem] A cured film forming composition useful for forming a cured film having excellent liquid crystal orientation and adhesion, an alignment material and a retardation material formed using a cured film obtained from the cured film forming composition are provided.
[Solution] (A) a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group, (B) a crosslinking agent, (C) a polymer having a polymerizable group including a hydroxyl group and a C=C double bond, and (D ) A cured film-forming composition containing a cross-linking catalyst, a cured film obtained from the cured film-forming composition, and an alignment material and a retardation material formed using the cured film.

Description

Cured film forming composition, alignment material, and retardation material

The present invention relates to a cured film forming composition, a cured film, an optical film, an alignment material, and a retardation material to form a cured film for aligning liquid crystal molecules. In particular, the present invention is a patterned retardation material used in a 3D display of a circular polarizing glasses method, a retardation material used in a circularly polarizing plate used as an antireflection film of an organic EL display, and a cured film forming composition useful for producing the retardation material , A cured film, an optical film, an alignment material and a retardation material.

In the case of a 3D display of the circular polarization glasses system, a retardation material is usually disposed on a display device that forms an image such as a liquid crystal panel. In this phase difference material, a plurality of two types of phase difference regions having different phase difference characteristics are regularly arranged, respectively, and constitutes a patterned phase difference material. In the following, in the present specification, a phase difference material patterned so as to arrange a plurality of phase difference regions having different phase difference characteristics is referred to as a patterned phase difference material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal as disclosed in Patent Document 1. Optical patterning of a retardation material made of a polymerizable liquid crystal uses an optical alignment technique known as forming an alignment material for a liquid crystal panel. That is, a coating film made of a material having a photo-alignment property is provided on the substrate, and two types of polarized light having different polarization directions are irradiated thereto. Then, a photo-alignment film is obtained as an alignment material in which two kinds of liquid crystal alignment regions having different alignment control directions of the liquid crystal are formed. A solution phase difference material containing a polymerizable liquid crystal is applied on the photo-alignment film to achieve alignment of the polymerizable liquid crystal. After that, the aligned polymeric liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linearly polarizing plate and a quarter-wavelength retardation plate, and converts the extraneous light directed to the panel surface of the image display panel into linearly polarized light by the linearly polarizing plate, followed by a quarter-wavelength retardation plate. It is converted into circularly polarized light by Here, the extraneous light caused by this circularly polarized light is reflected from the surface of the image display panel or the like, but at the time of this reflection, the rotational direction of the polarization plane is reversed. As a result, this reflected light is converted to linearly polarized light in the direction to be blocked by the linearly polarizing plate from the quarter-wavelength retardation plate, contrary to the arrival, and then is shielded by the subsequent linearly polarizing plate. The emission is significantly suppressed.

Regarding this quarter-wavelength retardation plate, Patent Document 2 discloses that a quarter-wavelength retardation plate is formed by combining a half-wavelength plate and a quarter-wavelength plate, so that this optical film is constituted by inverse dispersion characteristics. A method is proposed. In this method, in a wide wavelength band provided for display of a color image, a liquid crystal material having a positive dispersion characteristic can be used, and an optical film can be formed by inverse dispersion characteristic.

Further, recently, as a liquid crystal material applicable to this phase difference layer, it has been proposed to have an inverse dispersion characteristic (Patent Documents 3 and 4). According to the liquid crystal material having such an inverse dispersion characteristic, instead of forming a quarter-wavelength retardation plate with two retardation layers by combining a half-wave plate and a quarter-wave plate, the retardation layer is composed of a single layer. Thus, inverse dispersion characteristics can be secured, and thus an optical film capable of securing a desired retardation in a wide wavelength band can be realized by a simple configuration.

In order to align the liquid crystal, an alignment layer is used. As a method of forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is useful in that it does not generate static electricity or dust, which is a problem of the rubbing method, and allows quantitative control of alignment treatment. Do.

In forming an alignment material using a photo-alignment method, as a photo-alignment material that can be used, an acrylic resin or polyimide resin having a photo-dimerization site such as a cinnamoyl group and a chalcone group in the side chain is known. It is reported that these resins exhibit the ability to control the alignment of a liquid crystal (hereinafter, also referred to as liquid crystal alignment property) by irradiating with polarized UV light (refer to Patent Documents 5 to 7).

In addition, in addition to liquid crystal alignment ability, solvent resistance is required for the alignment layer. For example, the alignment layer may be exposed to heat or a solvent during the manufacturing process of the retardation material. When the alignment layer is exposed to a solvent, there is a concern that the liquid crystal alignment ability is remarkably reduced.

Thus, for example, in Patent Document 8, in order to obtain a stable liquid crystal alignment ability, a liquid crystal alignment agent containing a polymer component having a structure capable of crosslinking by light and a structure crosslinking by heat, and a crosslinking reaction by light A liquid crystal aligning agent containing a polymer component having this possible structure and a compound having a structure crosslinked by heat has been proposed.

In addition, adhesion to the liquid crystal layer is required for the alignment layer. When the adhesion between the alignment layer and the liquid crystal layer formed thereon is not sufficient, for example, the liquid crystal layer may be peeled off in a winding process during manufacturing a retardation film.

Japanese Patent Laid-Open No. 2005-49865 Japanese Patent Laid-Open No. H10-68816 US Patent No. 8119026 Specification Japanese Patent Publication No. 2009-179563 Japanese Patent No. 3611342 Japanese Patent Publication No. 2009-058584 Japanese Patent Publication No. 2001-517719 Japanese Patent No. 4207430

The present invention has been made based on the above findings and examination results. That is, it is an object of the present invention to provide a cured film forming composition for forming a cured film used for formation of an alignment material having excellent solvent resistance and high sensitivity, and is capable of aligning a polymerizable liquid crystal with excellent adhesion to a liquid crystal layer. will be.

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

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

The first aspect of the present invention,

(A) a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group,

(B) crosslinking agent,

(C) a polymer having a hydroxy group and a polymerizable group containing a C=C double bond, and

(D) It relates to a cured film-forming composition containing a crosslinking catalyst.

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

In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a group having a cinnamoyl group or an azobenzene structure.

In the first aspect of the present invention, it is preferable to further contain a polymer having at least one group selected from the group consisting of (E) a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group.

In the first aspect of the present invention, the polymer of component (C) includes a structural unit having a hydroxy group and a structural unit having a polymerizable group including a C=C double bond, and the structural unit having a hydroxy group The ratio is 20 mol% or more with respect to 100 mol% of the total structural units of this polymer, and the proportion of the structural units having a polymerizable group containing this C=C double bond is 20 mol to 100% of the total structural units of this polymer. It is preferably at least %.

In the first aspect of the present invention, the content ratio of the low molecular weight compound of the component (A) and the polymer of the component (C) is preferably 5:95 to 60:40 in terms of mass ratio.

In the first aspect of the present invention, it is preferable that the content ratio of the polymer of the component (A) and the polymer of the component (C) is 5:95 to 90:10 in terms of mass ratio.

In the first aspect of the present invention, the cured film forming composition contains 5 parts by mass to 500 parts by mass of (B) component based on 100 parts by mass of the total amount of the component (A) and the component (C). desirable.

The second aspect of the present invention relates to a cured film obtained from the cured film forming composition of the first aspect of the present invention.

A third aspect of the present invention relates to an optical film having a cured film of the second aspect of the present invention.

The fourth aspect of the present invention relates to an alignment material formed using the cured film of the second aspect of the present invention.

The fifth aspect of the present invention relates to a retardation material formed using the cured film of the second aspect of the present invention.

ADVANTAGE OF THE INVENTION According to this invention, it has excellent solvent resistance, can align a polymeric liquid crystal with high sensitivity, and can provide a cured film excellent in adhesiveness with a liquid crystal layer, and a cured film forming composition suitable for its formation.

In addition, according to the present invention, it is possible to provide an optical film having the cured film, and an alignment material and a retardation material formed using the cured film or the optical film.

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

The inventors of the present invention conducted a thorough review in order to meet the above-described requirements, and as a result, the cured film obtained from the cured film-forming composition having a specific composition has excellent solvent resistance and can align a polymerizable liquid crystal with high sensitivity, It has been discovered that it can be used as an orientation material having excellent adhesion to the layer.

Hereinafter, the cured film-forming composition of the present invention will be described in detail with reference to specific examples such as components. Then, the cured film and alignment material of the present invention using the cured film forming composition of the present invention, and the retardation material and liquid crystal display device formed by using the alignment material will be described.

<Cured film forming composition>

The cured film forming composition of the present invention comprises a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group as component (A), a crosslinking agent as component (B), a hydroxyl group as a component (C), and a C=C double bond. It contains the polymer which has a polymerizable group to contain, and the crosslinking catalyst which is (D) component. Further, it is possible to contain a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group, which are the component (E). Furthermore, other additives may be contained as long as the effect of the present invention is not impaired. Moreover, it may contain a solvent.

Hereinafter, the details of each component will be described.

[(A) component]

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

<Low molecular weight compound having photo-alignment group and thermal crosslinkable group>

The low molecular weight compound of the component (A) becomes a photo-alignment component having a low molecular weight compared to the polymer of the component (C) described later as a base.

In the cured film forming composition of the present invention, the low molecular weight compound of the component (A) is a compound having a photo-alignment group, and further has one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. It can be done with a compound.

On the other hand, in the present invention, the photo-alignment group generally refers to a functional group that exhibits the property of being oriented by light irradiation, and typically refers to a functional group of a structural portion that is photo-dimerized or photo-isomerized. As other photo-alignment groups, for example, a functional group that causes a photofreeze potential reaction (example compound: a benzoic acid ester compound, etc.), a group that causes a photodecomposition reaction (example compound: a cyclobutane ring, etc.) may be mentioned.

The light-dimerizing structural portion that the low molecular weight compound of the component (A) may have as a photo-alignment group is a portion that forms a dimer by light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, and coumarin group. And anthracene group. Among these, a cinnamoyl group is preferable from the height of transparency in the visible region and the height of photodimerization reactivity.

In addition, the structural moiety for photoisomerization that the low-molecular compound of component (A) may have as a photo-alignment group refers to a structural moiety that is converted into a cis body and a trans form by light irradiation, and specific examples thereof include an azobenzene structure and a stilbene structure. And the like. Among these, the azobenzene structure is preferable from the high level of reactivity.

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

[Formula 1]

In the above formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group.

X ¹¹ is a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl bond, or one or two or more bonds selected from a combination thereof and having 1 to 18 carbon atoms. As a structure in which 1 to 3 substituents selected from an alkylene group, a phenylene group, a biphenylene group, or a combination thereof are bonded, the substituent may be a structure in which a plurality of substituents are connected through the bond.

X ¹² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. In this case, the alkyl group, phenyl group, biphenyl group and cyclohexyl group having 1 to 18 carbon atoms may be bonded to two or more groups via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

X ¹³ represents a hydroxy group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a phenoxy group, a biphenyloxy group, or a phenyl group.

X ¹⁴ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic cyclic group, or a divalent aliphatic cyclic group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

X ¹⁵ represents a hydroxy group, a carboxyl group, an amide group, an amino group or an alkoxysilyl group. However, when X ¹⁴ is a single bond, X ¹⁵ is a hydroxy group or an amino group.

X represents a single bond, an oxygen atom or a sulfur atom. However, when X ¹⁴ is a single bond, X is also a single bond.

On the other hand, when a benzene ring is included in these substituents, the benzene ring is 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, and a cyano group. Or it may be substituted by a plurality of substituents.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy having 1 to 4 carbon atoms Group, a halogen atom, a trifluoromethyl group, or a cyano group.

(A) As a specific example of a low-molecular compound having a photo-alignment group and a hydroxyl group as a component, for example, as a compound represented by the above formulas [A11] to [A15] and compounds other than this formula, for example, 4 -(8-hydroxyoctyloxy) cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid methyl ester, 4-(4-hydroxybutyloxy) cinnamic acid methyl ester, 4-(3-hydroxypropyl Oxy) cinnamic acid methyl ester, 4-(2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic acid methyl ester, 4-hydroxy cinnamic acid methyl ester, 4-(8-hydroxyoctyloxy) ethyl cinnamate Ester, 4-(6-hydroxyhexyloxy) ethyl cinnamic ester, 4-(4-hydroxybutyloxy) ethyl cinnamic ester, 4-(3-hydroxypropyloxy) ethyl cinnamic acid, 4-(2- Hydroxyethyloxy) Cinnamic acid ethyl ester, 4-hydroxymethyloxy Cinnamic acid ethyl ester, 4-hydroxy cinnamic acid ethyl ester, 4-(8-hydroxyoctyloxy) Cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy) Si) Cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy) cinnamic acid phenyl ester, 4-(3-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) cinnamic acid biphenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4-( 4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4-(2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxy cinnamic acid ratio Phenyl ester, 4-hydroxy cinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl Ester, cinnamic acid hydroxymethyl ester, 4-(8-hydroxyoctyloxy)azobenzene, 4-(6-hydroxyhexyloxy)azobenzene, 4-(4-hydroxybutyloxy)azobenzene, 4-(3- Hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azo Benzene, 4-hydroxymethyloxyazobenzene, 4-hydroxyazobenzene, 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxyhexyloxy)chalcone, 4-(4-hydroxybutyloxy )Chalcone, 4-(3-hydroxypropyloxy)chalcone, 4-(2-hydroxyethyloxy)chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyl) Oxy)chalcone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-(3-hydroxypropyloxy)chalcone, 4'-(2- Hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy)coumarin, 7-(6-hydroxyhexyloxy)coumarin, 7- (4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7-(2-hydroxyethyloxy)coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6- Hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy)coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4-[4-(8-hydroxyoctyloxy)benzoyl] cinnamic acid methyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl] cinnamic acid Methyl ester, 4-[4-(4-hydroxybutyloxy)benzoyl] cinnamic acid methyl ester, 4-[4-(3-hydroxypropyloxy) benzoyl] cinnamic acid methyl ester, 4-[4-(2-hydroxyl) Roxyethyloxy)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 cinnamic ester, 4-[4-(6-hydroxyhexyloxy)benzoyl]ethyl cinnamic ester, 4-[4-(4-hydroxybutyloxy)benzoyl]ethyl cinnamic ester, 4-[4 -(3-hydroxypropyloxy)benzoyl] ethyl cinnamic ester, 4-[4-(2-hydroxyethyloxy) benzoyl] ethyl cinnamic ester, 4-[4-hydroxymethyloxybenzoyl] ethyl cinnamic acid, 4 -[4-hydroxybenzoyl]ethyl cinnamic acid, 4-[4-(8-hydroxyoctyloxy)benzoyl] cinnamic acid Tertiary butyl ester, 4-[4-(6-hydroxyhexyloxy)benzoyl] cinnamic acid tertiary butyl ester, 4-[4-(4-hydroxybutyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4-(3-hydroxypropyloxy)benzoyl] cinnamic acid tertiary butyl ester, 4-[4-(2-hydroxyethyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4-[4-hydroxymethyloxybenzoyl ]Cinnamic acid tertiary butyl ester, 4-[4-(8-hydroxyoctyloxy)benzoyl] cinnamic acid phenyl ester, 4-[4-(6-hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4-[4 -(4-hydroxybutyloxy)benzoyl] phenyl cinnamic acid, 4-[4-(3-hydroxypropyloxy) benzoyl] phenyl cinnamic acid, 4-[4-(2-hydroxyethyloxy) benzoyl] cinnamic acid Phenyl ester, 4-[4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4-[4-hydroxybenzoyl] cinnamic acid phenyl ester, 4-[4-(8-hydroxyoctyloxy) benzoyl] cinnamic acid biphenyl ester , 4-[4-(6-hydroxyhexyloxy)benzoyl] cinnamic acid biphenyl ester, 4-[4-(4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4-[4-(3- Hydroxypropyloxy)benzoyl] cinnamic acid biphenyl ester, 4-[4-(2-hydroxyethyloxy)benzoyl] cinnamic acid biphenyl ester, 4-[4-hydroxymethyloxybenzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid biphenyl ester, 4-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-(8-hydroxyoctyloxy)benzoyl]chalcone, 4-[4-(6 -Hydroxyhexyloxy)benzoyl]chalcone, 4-[4-(4-hydroxybutyloxy)benzoyl]chalcone, 4-[4-(3-hydroxypropyloxy)benzoyl]chalcone, 4-[4- (2-hydroxyethyloxy)benzoyl]chalcone, 4-(4-hydroxymethyloxybenzoyl)chalcone, 4-(4-hydroxybenzoyl)chalcone, 4'-[4-(8-hydroxyoctyloxy) Benzoyl]chalcone, 4'-[4-(6-hydroxyhexyloxy)benzoyl]chalcone, 4'- [4-(4-hydroxybutyloxy)benzoyl]chalcone, 4'-[4-(3-hydroxypropyloxy)benzoyl]chalcone, 4'-[4-(2-hydroxyethyloxy)benzoyl]chalcone , 4'-(4-hydroxymethyloxybenzoyl)chalcone, 4'-(4-hydroxybenzoyl)chalcone, and the like.

(A) As a specific example of the low molecular weight compound which has a photo-alignment group and a carboxyl group which is a component, cinnamic acid, ferulic acid, 4-methoxy cinnamic acid, 4-propoxycic acid, 3,4-dimethoxy cinnamic acid, coumarin-3- Carboxylic acid, 4-(N,N-dimethylamino)cinnamic acid, etc. are mentioned.

(A) As a specific example of the low molecular weight compound which has a photo-alignment group and an amide group which is a component, cinnamic acid amide, 4-methyl cinnamic acid amide, 4-ethyl cinnamic acid amide, 4-methoxy cinnamic acid amide, 4-ethoxy cinnamic acid amide, etc. Can be mentioned.

Specific examples of the low-molecular compound having a photo-alignment group and an amino group as a 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. Can be lifted.

(A) As a specific example of the low molecular weight compound which has a photo-alignment group and an alkoxysilyl group which is a component, 4-(3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4-(3-triethoxysilylpropyloxy) cinnamic acid Methyl ester, 4-(3-trimethoxysilylpropyloxy) ethyl cinnamic ester, 4-(3-triethoxysilylpropyloxy) ethyl cinnamic acid ester, 4-(3-trimethoxysilylhexyloxy) methyl cinnamate Ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3-triethoxysilylhexyloxy) cinnamic acid Ethyl ester, etc. are mentioned.

As the low molecular weight compound of the component (A), a compound in which a polymerizable group is bonded via a spacer to a group in which a photo-alignment moiety and a thermally reactive moiety represented by the following formula (1) are bonded is preferable.

[Formula 2]

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

Examples of the substituent in the case where the benzene ring may be substituted with a substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group; Haloalkyl groups such as trifluoromethyl groups; Alkoxy groups such as methoxy group and ethoxy group; Halogen atoms such as iodine atom, bromine atom, chlorine atom, and fluorine atom; Cyano group; And nitro group.

In R ¹⁰¹ , a hydroxy group and an amino group are preferable, and a hydroxy group is particularly preferable.

The spacer represents a divalent group selected from a linear alkylene group, a branched alkylene group, a cyclic alkylene group, and a phenylene group, or a group formed by a plurality of the divalent groups. In this case, the bond between the divalent groups constituting the spacer, the bond between the spacer and the group represented by the above formula (1), and the bond between the spacer and the polymerizable group include a single bond, an ester bond, an amide bond, a urea bond, or Ether bonds. When the said divalent group is plural, the divalent groups may be the same or different, and when the said bond is plural, the bonds may be the same or different.

Specific examples of the low-molecular compound in which the polymerizable group is bonded to the group in which the photo-alignment site and the thermally reactive site, which are the component (A), are bonded, include 4-(6-methacryloxyhexyl-1-oxy)cinic acid, 4-(6-acrylic Oxyhexyl-1-oxy) cinnamic acid, 4-(3-methacryloxypropyl-1-oxy) cinnamic acid, 4-(4-(3-methacryloxypropyl-1-oxy)acryloxy)benzoic acid, 4-( 4-(6-methacryloxyhexyl-1-oxy)benzoyloxy)cinnamic acid, 4-(6-methacryloxyhexyl-1-oxy)cinnamamide, 4-(6-methacryloxyhexyl-1-oxy) -N-(4-cyanophenyl)cinnamamide, 4-(6-methacryloxyhexyl-1-oxy)-N-bishydroxyethylcinnamamide, etc. are mentioned.

Although the low molecular weight photo-alignment component which is the component (A) includes the above specific examples, it is not limited thereto.

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

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

In the cured film forming composition of the present invention, the polymer of component (A) is a polymer having a photo-alignment group, i.e., a polymer having a functional group of a structural moiety to be photo-dimerized or photo-isomerized as a photo-alignment group, particularly at least a photo-dimerization site It is preferably an acrylic copolymer having. In addition, in addition to the photodimerization site, an acrylic copolymer having one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group (hereinafter, also referred to as a thermal crosslinking site including these groups) is desirable.

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

The acrylic copolymer (hereinafter, also referred to as a specific copolymer) having a photo-dimerization site and a thermal crosslinking site of the component (A) may be an acrylic copolymer having such a structure, and the main chain of the polymer constituting the acrylic copolymer is There is no particular limitation on the kind of skeleton and side chain.

Examples of the photodimerization site include cinnamoyl group, chalcone group, coumarin group, and anthracene group. Among these, a cinnamoyl group is preferable from the height of transparency in the visible region and the height of photodimerization reactivity. As a more preferable substituent containing a cinnamoyl group and a cinnamoyl structure, the structure represented by the following formula [1] or formula [2] is mentioned. On the other hand, in the present specification, the group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the "cinnamoyl group" and the "substituent group including the cinnamoyl structure".

[Formula 3]

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

In the above formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms are selected from covalent bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amino bonds, carbonyl bonds, or combinations thereof. Multiple types may be combined via one or two or more combinations.

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

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

The thermal crosslinking site is a site bonded to the crosslinking agent (B) component by heating, and specific examples thereof include a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.

It is preferable that the acrylic copolymer of (A) component has a weight average molecular weight of 3,000-200,000. If the weight average molecular weight exceeds 200,000 and is excessive, the solubility in the solvent may decrease and the handling property may decrease. On the other hand, if the weight average molecular weight is insufficient, such as less than 3,000, the solvent is insufficient due to insufficient curing during thermal curing. Resistance may decrease or heat resistance may decrease.

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

As a monomer having a photodimerization site, a monomer having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, or the like can be exemplified. Among these, a monomer having a cinnamoyl group is particularly preferable from the height of transparency in the visible region and the height of photodimerization reactivity.

Among them, a monomer having a cinnamoyl group having a structure represented by the above formula [1] or [2] and a substituent including a cinnamoyl structure is more preferable. A specific example of such a monomer is a monomer represented by the following formula [3] or [4].

[Formula 4]

In the above formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group.

L ¹ and L ² each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, or a urethane bond.

In the above formula [4], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group, phenyl group, biphenyl group, and cyclohexyl group having 1 to 18 carbon atoms are selected from covalent bonds, ether bonds, ester bonds, amide bonds, urea bonds, urethane bonds, amino bonds, carbonyl bonds, or combinations thereof. Multiple types may be combined via one or two or more combinations.

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

In the above formulas [3] and [4], X ⁴ represents a polymerizable group. As a specific example of this polymerizable group, an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, a methacrylamide group, etc. are mentioned, for example.

In the above formulas [3] and [4], A is any one of formulas [A1], [A2], [A3], [A4], [A5] and [A6] as above. Represents.

As a monomer having a thermal crosslinking site, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Roxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacryl Rate, caprolactone 2-(acryloyloxy) ethyl ester, caprolactone 2-(methacryloyloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, etc. A monomer having a hydroxy group; Acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N Monomers having a carboxyl group such as -(carboxyphenyl)methacrylamide and N-(carboxyphenyl)acrylamide; Phenolic hydroxy, such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide A monomer having a group; Monomers having an amide group such as acrylamide and methacrylamide; Monomers having an alkoxysilyl group such as methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxysilane; And monomers having an amino group such as dimethylaminoethyl methacrylate, diethylaminomethacrylate, and tert-butylaminoethylmethacrylate.

The amount of monomer having a photodimerization site and a monomer having a thermal crosslinking site used to obtain a specific copolymer is based on the total amount of all monomers used to obtain a specific copolymer, and the amount of the monomer having a photodimerization site is 40 It is preferable that mass%-95 mass% and the monomer which has a thermal crosslinking site are 5 mass%-60 %. When the content of the monomer having a photodimerization site is 40% by mass or more, it is possible to impart high sensitivity and good liquid crystal orientation. On the other hand, by setting it as 95 mass% or less, sufficient thermosetting property can be provided, and it can maintain high sensitivity and favorable liquid crystal orientation.

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

Specific examples of such a monomer include an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, a styrene compound, and a vinyl compound.

Hereinafter, specific examples of the monomer will be given, but the present invention is not limited thereto.

As the acrylic acid ester compound described above, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, benzyl acrylate, naphthyl acrylic Rate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylic Rate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl Acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate.

As the methacrylic acid ester compound described above, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , Benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate , tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofur Furyl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8 -Methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. are mentioned.

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

As the above-described styrene compound, styrene, methylstyrene, chlorostyrene, and bromostyrene are mentioned, for example.

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

A method of obtaining a specific copolymer used in the cured film forming composition of the present invention is not particularly limited, but, for example, a monomer having a specific functional group (a monomer having a photodimerization site and a monomer having a thermal crosslinking site), if necessary In a solvent in which a monomer having a non-reactive functional group, a polymerization initiator, and the like are coexisted, a method obtained by performing a polymerization reaction at a temperature of 50°C to 110°C is mentioned. In this case, the solvent to be used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having a non-reactive functional group, and a polymerization initiator used as necessary. As a specific example, the solvent described in the solvent mentioned later is mentioned.

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

In addition, the solution of the specific copolymer obtained as described above is added under stirring such as diethyl ether or water to reprecipitate, and the resulting precipitate is filtered and washed, followed by drying at room temperature or heat under normal pressure or reduced pressure, It can be made into powder of a specific copolymer. By such an operation, the polymerization initiator and unreacted monomer that coexist with the specific copolymer can be removed, and as a result, the purified specific copolymer powder is obtained. When it is not possible to sufficiently purify in a single operation, the obtained powder may be re-dissolved in a solvent, and the above operation may be repeated.

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

In addition, as the polymer of the component (A), a polymer obtained by reacting a cinnamic acid derivative with a polymer having an epoxy group in the side chain can also be used.

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

As specific examples of the polymerizable unsaturated compound having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α-n- Glycidyl butylacrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid -6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

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

As a specific example of these, as an alkyl methacrylate ester, For example, hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate , Diethylene glycol monomethacrylate, 2,3-dihydroxypropyl methacrylate, 2-methacryloxyethylglycoside, 4-hydroxyphenyl methacrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, sec-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like; As an acrylic acid alkyl ester, For example, methyl acrylate, isopropyl acrylate, etc.; As methacrylic acid cyclic alkyl ester, for example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate, tricyclo[5.2. 1.0 ^2,6 ]decane-8- ^yloxyethyl methacrylate, isobornyl methacrylate, cholestanyl methacrylate, etc.; As the acrylic acid cyclic alkyl ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-ylacrylate, tricyclo[5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, isobornyl acrylate, cholestanyl acrylate, and the like; As aryl methacrylate ester, phenyl methacrylate, benzyl methacrylate, etc.; As an acrylic acid aryl ester, For example, phenyl acrylate, benzyl acrylate, etc.; Examples of unsaturated dicarboxylic acid diesters include diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like;

As bicyclo unsaturated compounds, for example, bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept -2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'- Hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2 .1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, etc.; As maleimide compounds, for example, phenylmaleimide, cyclohexylmaleimide, benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succin Imidyl-6-maleimidecaproate, N-succinimidyl-3-maleimide propionate, N-(9-acridinyl)maleimide, etc.; As the unsaturated aromatic compound, For example, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, and the like; As a conjugated diene compound, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.; As the unsaturated monocarboxylic acid, for example, acrylic acid, methacrylic acid, crotonic acid, etc.; Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like; As an unsaturated dicarboxylic acid anhydride, each anhydride of the unsaturated dicarboxylic acid; As polymerizable unsaturated compounds other than the above, for example, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, and the like, respectively.

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

Synthesis of a polymer having an epoxy group in the side chain can be performed by a known radical polymerization method, preferably in a solvent in the presence of an appropriate polymerization initiator.

As a polymer having an epoxy group in the side chain, a commercial item can also be used. Examples of such commercial products include EHPE3150, EHPE3150CE (above, manufactured by Daicel Corporation), UG-4010, UG-4035, UG-4040, UG-4070 (above, ARUFON series manufactured by Dong-A Synthetic Corporation), ECN -1299 (manufactured by Asahi Chemical Corporation), DEN431, DEN438 (above, manufactured by Dow Chemical), jER-152 (manufactured by Mitsubishi Chemical), Epiclon N-660, N-665, N-670, N- 673, N-695, N-740, N-770, N-775 (above, DIC Co., Ltd. (formerly manufactured by Dai Nippon Ink Co., Ltd.)), EOCN-1020, EOCN-102S, EOCN-104S ( As mentioned above, Japan Explosives Co., Ltd. product) etc. are mentioned.

Examples of the cinnamic acid derivative include a cinnamic acid derivative having a carboxyl group, and for example, the following formulas (1-1) to (1-5)

[Formula 5]

(In the formula, R ¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and the like.) A compound represented by any one of them may be mentioned.

Further, as a cinnamic acid derivative having a carboxyl group, in the monomer represented by the above formula [3], a compound in which X ¹ is a hydrogen atom is also preferably used.

Compounds represented by the above formulas (1-1) to (1-5) can be synthesized by appropriately combining the normal methods of organic chemistry.

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

The proportion of the cinnamic acid derivative used in the reaction is preferably 0.01 to 1.5 moles, more preferably 0.05 to 1.3 moles, further preferably 0.1 to 1 mole of the epoxy group contained in the polymer having an epoxy group. It is 1.1 moles.

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

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

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2- Methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methyl Midazole, 1-(2-cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)- 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-di(hydroxymethyl)imidazole, 1-(2- Cyanoethyl)-2-phenyl-4,5-di[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimelli Tate, 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitate, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-(2'-n-undecylimidazolyl)ethyl-s -Triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')] ethyl-s-triazine, isocyanuric acid addition of 2-methylimidazole Water, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')] ethyl-s-triazine isocyanuric acid adduct Imidazole compounds such as; Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite;

Benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium Nium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o,o-diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetra Quaternary phosphonium salts such as fluoroborate, tetra-n-butylphosphonium tetraphenylborate, and tetraphenylphosphonium tetraphenylborate; Diazabicycloalkenes such as 1,8-diazabicyclo[5.4.0]undecene-7 or organic acid salts thereof; Organometallic compounds such as zinc octylate, tin octylate, and aluminum acetylacetone complex; Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride; Boron compounds such as boron trifluoride and triphenyl borate; Metal halogen compounds such as zinc chloride and tin chloride; High melting point dispersion type latent curing accelerators such as dicyandiamide and amine addition type accelerators such as adducts of amines and epoxy resins; A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as the imidazole compound, organophosphorus compound or quaternary phosphonium salt is coated with a polymer; Amine salt type latent hardening accelerator; Latent hardening accelerators, such as a high-temperature dissolution type thermocationic polymerization type latent hardening accelerator, such as a Lewis acid salt and a Bronsted acid salt, etc. are mentioned.

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

As the ratio of use of the catalyst, it is preferably 100 parts by mass or less, more preferably 0.01 to 100 parts by mass, and still more preferably 0.1 to 20 parts by mass, based on 100 parts by mass of the polymer having an epoxy group.

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

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

In this way, a solution containing the reaction product of the polymer having an epoxy group and the cinnamic acid derivative is obtained. This solution may be provided as it is to prepare a cured film forming composition, or after isolating the polymer contained in the solution, it may be provided to prepare a cured film forming composition, or after purifying the isolated polymer, It can also be provided for preparation.

In addition, in this embodiment, the acrylic copolymer of (A) component may be a mixture of several types of specific copolymers.

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

[(B) component]

The cured film formation composition of this invention contains a crosslinking agent as (B) component. More specifically, (B) component is a crosslinking agent which reacts with the (A) component and (C) component mentioned above. The (B) component binds to the thermal crosslinkable group of the compound or polymer which is the component (A) and the hydroxyl group contained in the component (C). In addition, the cured film forming composition of the present invention can form an alignment material having high photoreaction efficiency as a cured film.

Although compounds such as an epoxy compound, a methylol compound, and an isocyanate compound are mentioned as a crosslinking agent which is a component (B), Preferably it is a methylol compound. Among them, as the crosslinking agent that is the component (B), a compound having two or more groups forming a crosslinking group with a thermally crosslinkable functional group of the component (A) is preferable, for example, a compound having two or more methylol groups or alkoxymethyl groups. It is preferably a crosslinking agent. Examples of the compound having these groups include methylol compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

Specific examples of the above-described methylol compound include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, tetra(alkoxymethyl)bisphenol, and tetra(hydroxymethyl)bisphenol. I can.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 ,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl) )-4,5-dimethoxy-2-imidazolinone, etc. are mentioned. As commercial products, compounds such as Mitsui Cytec Co., Ltd. glycoluril compounds (trade name: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65), butyl Urea/formaldehyde resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (formerly Dai Nippon Inki Chemical Industry Co., Ltd.) urea/formaldehyde resin (high Condensation type, brand name: Beccamin (registered trademark) J-300S, P-955, N), etc. are mentioned.

As a specific example of alkoxymethylated benzoguanamine, tetramethoxymethylbenzoguanamine etc. are mentioned, for example. As a commercial item, Mitsui Cytec Co., Ltd. (brand name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (brand name: Nikarak (registered trademark) BX-4000, BX-37, BL-60, BX-55H), etc. are mentioned.

As a specific example of an alkoxymethylated melamine, hexamethoxymethylmelamine etc. are mentioned, for example. As a commercial item, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, copper 301, copper 303, copper 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compound (trade name: Mycoat (registered trademark) ) 506, copper 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nikarak (registered trademark) MW-30, copper MW-22, copper MW-11, copper MW-100LM, copper MS- 001, copper MX-002, copper MX-730, copper MX-750, copper MX-035), butoxymethyl type melamine compound (trade name: Nikarak (registered trademark) MX-45, copper MX-410, copper MX- 302) and the like.

Examples of tetra(alkoxymethyl)bisphenol and tetra(hydroxymethyl)bisphenol include tetra(alkoxymethyl)bisphenol A and tetra(hydroxymethyl)bisphenol A.

Further, the crosslinking agent of the component (B) may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of such an amino group is substituted with a methylol group or an alkoxymethyl group. For example, a high molecular weight compound prepared from a melamine compound and a benzoguanamine compound described in US Patent No. 6323310 may be mentioned. Commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and as commercially available products of the benzoguanamine compound, trade name: Cymel (registered trademark) 1123 (Mitsui Saitech Co., Ltd. product) etc. are mentioned.

Furthermore, as the crosslinking agent of component (B), hydroxymethyl groups such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide (ie A polymer prepared using an acrylamide compound or a methacrylamide compound substituted with a methylol group) or an alkoxymethyl group may also be used.

Such polymers include, for example, poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, and copolymers of N-hydroxymethylmethacrylamide and methylmethacrylate. Coalescence, a copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide and benzyl methacrylate and 2-hydroxypropyl methacrylate. have.

In addition, as such a polymer, a polymer having an N-alkoxymethyl group and a polymerizable group containing a C=C double bond may be used.

As a polymerizable group containing a C=C double bond, an acrylic group, a methacrylic group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned.

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

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

In the above-described reaction, a preferred combination of a specific functional group 2 and a group involved in the reaction as a functional group of a specific compound is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, a phenolic hydroxy group and an epoxy group, a carboxyl group and an isocyanate group, They are an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Further, a more preferable combination is an epoxy group in a carboxyl group and glycidyl methacrylate, or an isocyanate group in a hydroxy group and isocyanate ethyl methacrylate.

As a monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate , N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

As a monomer having a glycidyl group, for example, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1 , 2-epoxy-5-hexene and 1,7-octane diene monoepoxide, and the like.

As a monomer having a hydroxy group, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxy Butyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate , Caprolactone 2-(acryloyloxy) ethyl ester, caprolactone 2-(methacryloyloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5 -Acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, etc. I can.

As a monomer having an amino group, 2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned, for example.

As a monomer having a phenolic hydroxy group, for example, hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl)maleimide, etc. Can be lifted.

As a monomer having an isocyanate group, acryloyl ethyl isocyanate, methacryloyl ethyl isocyanate, m-tetramethyl xylene isocyanate, etc. are mentioned, for example.

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

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

In the cured film forming composition of the present invention, the content of the crosslinking agent of the component (B) is preferably 5 parts by mass to 500 parts by mass, more preferably based on 100 parts by mass of the total amount of the component (A) and the component (C). It is 10 parts by mass to 400 parts by mass. When the content of the crosslinking agent is insufficient, the solvent resistance of the cured film obtained from the cured film forming composition decreases, and the liquid crystal orientation decreases. On the other hand, when the content of the crosslinking agent is excessive, liquid crystal orientation and storage stability may decrease.

[(C) ingredient]

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

As a polymerizable group containing a C=C double bond, an acrylic group, a methacrylic group, a vinyl group, an allyl group, a maleimide group, etc. are mentioned.

As a method of obtaining the polymer which is the component (C), the method of obtaining the polymer having a polymerizable group containing a C=C double bond described in the component (B) can be used. That is, after preparing a polymer having a carboxyl group, a method of reacting a monomer having an epoxy group with a polymerizable group containing a C=C double bond, and a polymer having an epoxy group exemplified in the chapter (A) Subsequently, a method of reacting a polymerizable group containing a C=C double bond and a monomer having a carboxyl group is mentioned.

As a method of obtaining a polymer having a carboxyl group, for example, in a solvent in which a monomer having a carboxyl group and a monomer and a polymerization initiator other than that are coexisted, if necessary, by polymerization at a temperature of 50°C to 110°C, A method of obtaining a polymer having a carboxyl group is mentioned. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer having a carboxyl group, other monomers and polymerization initiators used as necessary. As a specific example, it describes in the section of [solvent] mentioned later.

As a method of obtaining a polymer having an epoxy group, for example, in a solvent in which a monomer having an epoxy group and a monomer other than that and a polymerization initiator are coexisted, if necessary, by polymerization at a temperature of 50°C to 110°C, A method of obtaining a polymer having an epoxy group is mentioned. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer having the above epoxy group, the other monomers and polymerization initiators used as necessary. As a specific example, it describes in the section of [solvent] mentioned later.

As a monomer having a polymerizable group containing a C=C double bond and a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2 -(Methacryloyloxy)ethyl)phthalate, mono-(2-(acryloyloxy)ethyl)hexahydrophthalate, mono-(2-(methacryloyloxy)ethyl)hexahydrophthalate, mono-( 2-(acryloyloxy)ethyl)succinate, mono-(2-(methacryloyloxy)ethyl)succinate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N -(Carboxyphenyl)acrylamide and ω-carboxy-polycaprolactone mono(meth)acrylate. Examples of these monomers include "light ester HO-MS", "light acrylate HOA-MS(N)", "light acrylate HOA-HH(N)", and "light acrylate HOA-MPL(N )'' (above, Kyoeisa Chemical Co., Ltd. make, brand name), Aaronix M-5300, Aaronix M-5400 (above, Dong-A Synthetic Co., Ltd. product, brand name) commercially available ones can be used.

As a monomer having a polymerizable group containing a C=C double bond and an epoxy group, for example, glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl methacrylate glycidyl ether, allylgly Cidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1, 2-epoxy-5-hexene and 1,7-octadiene monoepoxide, and the like.

Here, in the production of the polymer as component (C), at least one of the monomer having an epoxy group and the monomer having a carboxyl group as raw materials is selected to have a spacer between a polymerizable group and a group selected from an epoxy group and a carboxyl group. It is desirable. By selecting such a raw material, the obtained cured film of the present invention has more favorable adhesion to the liquid crystal layer.

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

[Formula 6]

In the formula, X ⁴ represents a polymerizable group, and specific examples of this polymerizable group include, for example, acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, methacrylamide group, etc. Can be lifted. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ¹ and Q ³ each independently represent an alkylene group having 2 to 10 carbon atoms, and Q ² represents a divalent group having a structure derived from a dicarboxylic acid anhydride. n represents a natural number from 1 to 10.

Mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, mono-(2-(acryloyloxy)ethyl)phthalate, and mono-(2-(acryloyloxy)ethyl)phthalate as such a spacer and a monomer having a carboxyl group Si) ethyl) hexahydrophthalate, mono-(2-(methacryloyloxy)ethyl)hexahydrophthalate, mono-(2-(acryloyloxy)ethyl)succinate, mono-(2-(methacrylic) Royloxy)ethyl)succinate and ω-carboxy-polycaprolactone mono(meth)acrylate are preferred. Further, a polyfunctional acrylate having a carboxyl group is also preferable. As commercially available ones, for example, "light ester HO-MS", "light acrylate HOA-MS(N)", "light acrylate HOA-HH(N)" and "lite acrylate HOA-MPL ( N)" (above, Kyoeisa Chemical Co., Ltd. make, brand name), Aaronix M-5300, Aaronix M-5400 (above, Dong-A Synthetic Co., Ltd. make, brand name) commercially available ones can be used.

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

[Formula 7]

In the formula, X ⁴ represents a polymerizable group, and specific examples of this polymerizable group include, for example, acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, methacrylamide group, etc. Can be lifted. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ¹ represents an alkylene group having 2 to 10 carbon atoms.

As a monomer having such a spacer and an epoxy group, for example, 4-hydroxybutyl methacrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzylgly Cidyl ether, etc. are mentioned.

As a monomer having a polymerizable group and a carboxyl group containing a C=C double bond for grafting to an epoxy group of the polymer, a polyfunctional acrylate having a carboxyl group represented by the following (SC-3) is also preferable.

[Formula 8]

In the formula, X ⁴ represents a polymerizable group, and specific examples of this polymerizable group include, for example, acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, methacrylamide group, etc. Can be lifted. L ¹ represents a covalent bond, ether bond, ester bond, amide bond, urea bond or urethane bond. Q ⁴ represents a (m+1) valent organic group, and m represents a natural number of 2 to 10.

As such compounds, commercially available compounds as Aaronix M-510 and M-520 (above, manufactured by Dong-A Synthetic Co., Ltd., brand name) can be used.

As a result, the polymer obtained by the above method has a hydroxyl group. However, when preparing a polymer having a carboxyl group or a polymer having an epoxy group, in the case of further introducing a hydroxyl group into this polymer, A monomer having a group can also be copolymerized.

Moreover, in this invention, when obtaining the polymer of (C) component, other monomers can be used together.

Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydrides, styrene compounds and vinyl compounds exemplified in the chapter of component (A). And the like.

In the polymer of component (C), the proportion of the structural unit having a hydroxy group is preferably 20 mol% or more, and more preferably 40 mol% or more with respect to 100 mol% of the total structural units of the polymer. When the total is less than 20 mol%, curing may be insufficient and the orientation may be adversely affected.

Here, when the polymer of component (C) contains a structural unit having two or more hydroxy groups, the ratio of the structural unit having a hydroxy group means (Structural unit having a hydroxy group) based on 100 mol% of the total structural units of the polymer. Represents the number of moles) × (the number of hydroxyl groups contained in this structural unit).

In the polymer of component (C), the proportion of the structural unit having a polymerizable group including a C=C double bond is preferably 20 mol% or more, and 40 mol% or more with respect to 100 mol% of the total structural units of this polymer. More preferable. When the total is less than 20 mol%, the adhesiveness with the liquid crystal layer may become insufficient.

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

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

In addition, the polymer solution of component (C) obtained by the above method was added to diethyl ether or water under stirring to reprecipitate, and the resulting precipitate was filtered and washed, followed by drying at room temperature or heating under normal pressure or reduced pressure. , (C) can be used as the polymer powder of the component. By the above-described operation, the polymerization initiator and unreacted monomer coexisting with the polymer of the component (C) can be removed, and as a result, a polymer powder which is an example of the purified component (C) is obtained. When it is not possible to sufficiently purify in a single operation, the obtained powder may be redissolved in a solvent, and the above-described operation may be repeated.

In the cured film-forming composition for forming the cured film on the surface of the optical film of the present invention, the polymer of component (C) 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. have.

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

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

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

In addition, as for the content of the component (C) in the cured film forming composition of the present invention, the content ratio of the polymer of the component (A) and the polymer of the component (C) is preferably 5:95 to 90:10 by mass ratio. . When the content of the polymer in the component (C) is insufficient, there is a fear that the adhesiveness with the liquid crystal layer may decrease. On the other hand, when the content of the polymer of the component (C) is excessive, the photo-alignment property may decrease.

[(D) ingredient]

The cured film forming composition for forming the cured film on the surface of the optical film of the present invention, in addition to the above-described (A) component, (B) component, and (C) component, further comprises a crosslinking catalyst as a component (D). Contains.

(D) As a crosslinking catalyst which is a component, an acid or a thermal acid generator is mentioned, for example. This component (D) is effective for accelerating a thermosetting reaction in the formation of a cured film using a cured film forming composition for forming a cured film on the surface of the optical film of the present invention.

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

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

In addition, as a compound that generates an acid by heat, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate , 1,2,3-phenylene tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p- Toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethylp-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], and the like. .

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

The content of the component (D) in the cured film forming composition of the present invention is 100 mass of the total amount of the low-molecular compound or polymer having a photo-alignment group and a thermal crosslinkable group as the component (A), and the polymer as the component (C) With respect to parts, it is 0.01 mass part-20 mass part, Preferably it is 0.01 mass part-10 mass part, More preferably, it is 0.05 mass part-8 mass part, More preferably, it is 0.1 mass part-6 mass part. When the content of the component (D) is 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be provided, and high sensitivity to exposure can also be provided. Moreover, by setting it as 20 mass parts or less, the storage stability of a cured film-forming composition can be made favorable.

[(E) component]

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

(E) As the polymer which is a component, for example, acrylic polymer, urethane-modified acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate Polymers having a linear or branched structure such as polyol, polycaprolactone polyol, polyalkyleneimine, polyallylamine, cellulose (cellulose or derivatives thereof), phenol novolak resin, cyclic polymers such as cyclodextrins, etc. I can.

Among them, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic acid ester, methacrylic acid ester, and styrene may be applied. The synthesis method includes a monomer having a hydroxy group, a monomer having a carboxyl group, a monomer having an amide group, a monomer having an amino group, and an alkoxysilyl as exemplified in the chapters of the component (A), the component (B) and the component (C). Monomers having at least one group selected from the group consisting of group-containing monomers and monomers other than those selected from the group consisting of group-containing monomers, if necessary, are prepared by the method described in the (A) component, the (B) component and (C) component chapters ( Co) polymerization method is simple.

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

(E) As a polyether polyol which is a preferable example of the component, propylene oxide, polyethylene glycol, polypropylene glycol, etc. are added to polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol or bisphenol A, triethylene glycol, and sorbitol. Can be mentioned. Specific examples of polyether polyols include ADEKA Co., Ltd. Adeca polyether P series, G series, EDP series, BPX series, FC series, CM series, Nichiyu Corporation Uniox (registered trademark) HC-40 , HC-60, ST-30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400 , DA-700, DB-400, Nonion (registered trademark) LT-221, ST-221, OT-221, and the like.

(E) As a polyester polyol which is a preferred example of the component, a diol such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol is reacted with polyvalent carboxylic acids such as adipic acid, sebacic acid, and isophthalic acid. What was ordered is mentioned. As a specific example of the polyester polyol, DIC Corporation's Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD -X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X -2523, OD-X-2555, OD-X-2560, Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc. are mentioned.

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

As a polycarbonate polyol which is a preferable example of (E) component, what made polyhydric alcohol, such as trimethylolpropane and ethylene glycol, react with diethyl carbonate, diphenyl carbonate, ethylene carbonate, etc. are mentioned. Specific examples of polycarbonate polyols include Fraxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel, C-590, C-1050, C-2050, C-2090, C manufactured by Kuraray, Inc. -3090 etc. are mentioned.

As a cellulose which is a preferable example of (E) component, hydroxyalkyl celluloses, such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, etc. And alkylalkyl celluloses and celluloses, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

Cyclodextrins that are preferred examples of the component (E) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γ cyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin, and methyl-γ-cyclo Methylated cyclodextrins such as dextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxyethyl -β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3 -Hydroxyalkylcyclodextrins such as dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin, and the like.

(E) As a urethane-modified acrylic polymer that is a preferred example of the component, as a commercial item, AcriT (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, 8UA- manufactured by Taisei Fine Chemicals Co., Ltd. 146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366, and the like.

As a phenol novolak resin which is a preferable example of (E) component, a phenol-formaldehyde polycondensate etc. are mentioned, for example.

In the composition of the present invention, the polymer of component (E) may be used in the form of a powder or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

In addition, in the composition of the present invention, the component (E) may be a mixture of plural types of polymers exemplified as the component (E).

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

[(F) ingredient]

When a polymer is used as the (A) component, the composition of the present invention may further contain a low molecular weight photo-alignment component as the (F) component. By containing the low-molecular photo-alignment component, the amount of the photo-alignment group in the surface layer of the alignment layer increases, and the orientation sensitivity is improved.

As such a low molecular weight photo-alignment component, the group X ⁴ of a monomer represented by formula [3], a monomer represented by formula [4], and a monomer represented by formula [3] exemplified in the section of component (A) of the present specification. Is a compound substituted with a hydrogen atom, a compound in which X ⁴ is substituted with a hydrogen atom, and a cinnamic acid derivative having a carboxyl group represented by one of the formulas (1-1) to (1-5). I can.

In addition, in the composition of the present invention, the component (F) may be a mixture of plural types of compounds exemplified as the component (F).

The content in the case where the component (F) is included in the cured film forming composition of the present invention is 5 parts by mass to 500 parts by mass based on 100 parts by mass of the total amount of the polymer of the component (A) and the polymer of the component (C). .

[Other additives]

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

Other additives may contain, for example, a sensitizer. The sensitizer is effective in promoting the photoreaction when forming a cured film on the surface of the optical film of the present invention.

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

These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more kinds of 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 based on 100 parts by mass of the component (A). When this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and when it is excessive, the transmittance of the formed cured film may decrease or the coating film may become rough.

In addition, the cured film forming composition of the present invention, as other additives, as long as the effects of the present invention are not impaired, a silan coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant, etc. It may contain.

[solvent]

The cured film forming composition of the present invention is often used in a solution state dissolved in a solvent. The solvent used at this time is one that dissolves (A) component, (B) component, (C) component and (D) component, if necessary, (E) component, (F) component and/or other additives, As long as it is a solvent having such a solubility, its kind and structure are not particularly limited.

Specific examples of the solvent, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene Glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2- Butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxyethylpropionate, 2-hydroxy-2-methylpropionate ethyl, ethoxyethyl acetate , Ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, pyruvate Ethyl, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrroly Such as money.

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

<Preparation of cured film forming composition>

The cured film forming composition of the present invention is a thermosetting cured film forming composition having photo-alignment. The cured film forming composition of the present invention, as described above, is a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group as a component (A), a crosslinking agent as a component (B), and a hydroxyl group as a component (C), It contains a polymer having a polymerizable group containing a C=C double bond and a crosslinking catalyst as a component (D). If necessary, a polymer having at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group as the component (E), or a low-molecular photo-alignment component as the component (F) is contained. And, as long as the effect of the present invention is not impaired, other additives may be contained, and further, a solvent may be contained.

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

[1]: The content ratio of the low-molecular compound having a photo-alignment group and a thermal crosslinkable group as component (A) and a hydroxy group as component (C) and a polymer having a polymerizable group including a C=C double bond is 5 in terms of mass ratio :95 to 60:40, based on 100 parts by mass of the total amount of the low-molecular compound (A) component and the polymer (C) component, based on 100 parts by mass, preferably 5 to 500 parts by mass Containing a crosslinking catalyst as a component (D) of 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the total amount of the crosslinking agent as a component (B) and the low molecular compound as a component (A) and the polymer as a component (C) Cured film forming composition.

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

[3]: The content ratio of the polymer having a photo-alignment group and a thermal crosslinkable group as component (A), a hydroxy group as component (C), and a polymer having a polymerizable group including a C=C double bond is 5 in terms of mass ratio :95 to 90:10, based on 100 parts by mass of the total amount of the polymer as the component (A) and the polymer as the component (C), based on 100 parts by mass, preferably 5 to 500 parts by mass ( A cured film containing 0.01 parts by mass to 20 parts by mass of a crosslinking catalyst as a component (D) based on 100 parts by mass of the total amount of the B) component crosslinking agent and the (A) component polymer and the (C) component polymer Forming composition.

[4]: The content ratio of the polymer having a photo-alignment group and a thermal crosslinkable group as component (A) and a hydroxy group as component (C) and a polymer having a polymerizable group including a C=C double bond is 5 in terms of mass ratio :95 to 90:10, based on 100 parts by mass of the total amount of the polymer as the component (A) and the polymer as the component (C), based on 100 parts by mass, preferably 5 to 500 parts by mass ( B) contains a crosslinking agent as a component, and 0.01 parts by mass to 20 parts by mass of a crosslinking catalyst as a component (D) and a solvent based on 100 parts by mass of the total amount of the polymer as the component (A) and the polymer as the component (C). In addition, based on 100 mass parts of the total amount of the polymer as the component (A) and the polymer of the component (C), 5 parts by mass to 500 parts by mass of the (E) component hydroxy group, carboxyl group, amide group, amino group and A cured film-forming composition containing a polymer having at least one group selected from the group consisting of alkoxysilyl groups.

In the case of using the cured film forming composition of the present invention as a solution, the mixing ratio, preparation method, etc. will be described in detail below.

The ratio of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1% by mass to 80% by mass, preferably 2% by mass to 60% by mass %, and more preferably 3% by mass to 40%. Here, the solid content refers to the thing excluding the solvent from all components of the cured film-forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. In the preparation method, for example, (A) component and (B) component, (D) component, if necessary, (E) component, and/or (F) component are added to a solution of component (C) dissolved in a solvent. A method of mixing in a predetermined ratio and obtaining a homogeneous solution, or a method of adding and mixing other additives as necessary in an appropriate step of this preparation method may be mentioned.

In the preparation of the cured film forming composition of the present invention, a solution of a specific copolymer and/or a specific copolymer 2 obtained by polymerization reaction in a solvent can be used as it is. In this case, for example, (A) component, (B) component, (D) component, if necessary, (E) component, (F) component and/or others in a solution prepared by preparing the acrylic polymer as component (C). Add additives to make a homogeneous solution. At this time, it is also possible to add a solvent for the purpose of concentration adjustment. At this time, the solvent used in the preparation process of the component (C) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or may be different.

In addition, it is preferable to use the solution of the prepared cured film-forming composition after filtering with a filter or the like having a pore diameter of about 0.2 μm.

As described above, the cured film forming composition of the present invention has a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group as a component (A), a crosslinking agent as a component (B), a hydroxyl group as a component (C), and C= It is constituted by containing a polymer having a polymerizable group containing a C double bond, and a crosslinking catalyst as a component (D).

Therefore, in the cured film formed from the cured film forming composition of the present invention, so that the film structure is stabilized, in the case where the component (A) is a low molecular weight compound, due to the properties of the component (C), the component (A) is a polymer. In the case, due to the properties of the (A) component, (B) component and (C) component, the interior thereof is formed to be hydrophilic. And the photo-alignment group of the low molecular compound or polymer of the component (A) in the cured film is unevenly distributed in the vicinity of the surface of the cured film. More specifically, the low molecular weight compound or polymer of the component (A) is unevenly distributed in the vicinity of the surface of the cured film while taking a structure in which the hydrophilic thermal reaction portion faces the inner side of the cured film and the hydrophobic photoreactive portion faces the surface side. As a result, the cured film of the present invention realizes a structure in which the ratio of the photoreactive groups of the component (A) present in the vicinity of the surface is increased. In addition, when the cured film of the present invention is used as an alignment material, it is possible to improve the efficiency of photoreaction for photo-alignment, and thus can have excellent alignment sensitivity. Furthermore, it becomes an orientation material suitable for formation of a patterned retardation material, and the patterned retardation material manufactured using this can have excellent pattern formation.

Moreover, as mentioned above, the cured film formation composition of this invention contains a hydroxy group and a polymer which has a polymerizable group containing a C=C double bond as a component (C). Therefore, in the interior of the cured film obtained from the cured film-forming composition of the present invention, a crosslinking reaction by thermal reaction with the component (C) can be performed before the photoreaction with the low molecular weight compound of component (A) or the photo-alignment group of the polymer. . As a result, when used as an alignment material, resistance to a polymerizable liquid crystal applied thereon and a solvent thereof can be improved.

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

<Cured film, alignment material and retardation material>

The solution of the cured film forming composition of the present invention is applied to a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, chromium, etc. coated substrate, a glass substrate, a quartz substrate) , ITO substrate, etc.) or films (e.g., triacetylcellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coat, rotation coating, spill coating, A cured film can be formed by applying roll coating, slit coating, rotational coating following the slit, ink jet coating, printing or the like to form a coating film, and then drying by heating in a hot plate or an oven.

As conditions for heat drying, the curing reaction may proceed to such an extent that the component of the alignment material formed from the cured film does not elute in the polymerizable liquid crystal solution applied thereon. For example, a temperature of 60°C to 200°C, a time of 0.4 A heating temperature and heating time appropriately selected from the range of minutes to 60 minutes are employed. The heating temperature and heating time are preferably 70° C. to 160° C., and 0.5 minutes to 10 minutes.

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

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

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

Since the alignment material formed using the cured film obtained from the cured film-forming composition of the present invention has solvent resistance and heat resistance, a retardation material composed of a polymerizable liquid crystal solution is applied on the alignment material and then heated to the phase transition temperature of the liquid crystal. By doing so, the retardation material is made into a liquid crystal state and is aligned on the alignment material. Then, a retardation material having a layer having optical anisotropy can be formed by curing the retardation material in a desired orientation as it is.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the substrate on which the alignment material is formed is a film, the film having the retardation material of the present embodiment becomes useful as a retardation film. The retardation material forming such a retardation material is in a liquid crystal state, and on the alignment material, there are some that take an orientation state such as horizontal orientation, cholesteric orientation, vertical orientation, and hybrid orientation, and are classified according to the required retardation characteristics. Can be used.

In addition, in the case of manufacturing a patterned retardation material used for a 3D display, the cured film formed by the above method from the cured film forming composition of the present invention, through a line-and-space pattern mask, from a predetermined standard, for example. For example, polarized UV exposure is performed in the direction of +45 degrees, and then the polarized UV is exposed in the direction of -45 degrees after removing the mask to form an alignment material in which two kinds of liquid crystal alignment regions having different orientation control directions of the liquid crystal are formed. . Thereafter, a retardation material comprising a polymerizable liquid crystal solution is applied, and then the retardation material is brought into a liquid crystal state by heating to a phase transition temperature of the liquid crystal. The polymerizable liquid crystal in a liquid crystal state is aligned on an alignment material in which two kinds of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material in which such an orientation state is realized is hardened as it is, and the above-described orientation state is fixed to obtain a patterned retardation material in which a plurality of two types of retardation regions having different retardation characteristics are arranged regularly. .

In addition, the alignment material formed using the cured film obtained from the cured film forming composition of the present invention can also be used as a liquid crystal alignment film of a liquid crystal display device. For example, using two substrates having the alignment material of the present invention formed as described above, bonding the alignment materials on both substrates to face each other through a spacer, and then injecting a liquid crystal between the substrates , It is possible to manufacture a liquid crystal display device in which the liquid crystal is aligned.

Therefore, the cured film forming composition of the present invention can be suitably used for manufacturing various retardation materials (phase difference films) and liquid crystal display devices.

Example

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

[Abbreviation symbols used in the examples]

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

<raw material>

GMA: glycidyl methacrylate

AIBN: α,α'-azobisisobutyronitrile

BMAA: N-butoxymethylacrylamide

HEMA: 2-hydroxyethyl methacrylate

<A component>

CIN1:

[Formula 16]

CIN2:

[Formula 17]

CIN3:

[Formula 18]

CIN4:

[Formula 19]

CIN5:

[Formula 20]

CIN6:

[Formula 21]

EHPE3150 (manufactured by Daicel Co., Ltd., epoxy equivalent 180g/eq):

[Formula 22]

<Component B>

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

[Formula 23]

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

[Formula 24]

<D component>

PTSA: p-toluenesulfonic acid monohydrate

<E component>

PEPO: Polyester polyol polymer (adipic acid/diethylene glycol copolymer having the following structural units. Molecular weight 4,800.)

[Formula 25]

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

<solvent>

PM: propylene glycol monomethyl ether

BA: butyl acetate

EA: ethyl acetate

MEK: methyl ethyl ketone

CH: cyclohexanone

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic (co)polymer in the polymerization example is a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. It was measured as follows using.

In addition, the following number average molecular weight (hereinafter, referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

Column temperature: 40℃

Eluent: Tetrahydrofuran

Flow rate: 1.0 mL/min

Standard sample for calibration curve preparation: Showa Electric Co., Ltd. standard polystyrene (molecular weight approx. 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Synthesis of component A>

<Synthesis Example 1>

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

<Synthesis Example 2>

10.0 g of the acrylic polymer (P-1) having an epoxy group obtained in Synthesis Example 1, 11.3 g of CIN1, and 0.4 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50.8 g of PM, and reacted at 120° C. for 20 hours. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-1). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 3>

10.0 g of acrylic polymer (P-1) having an epoxy group obtained in Synthesis Example 1, 6.3 g of CIN1, 5.4 g of CIN5, 0.4 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 50.6 g of PM, and reacted at 120° C. for 20 hours. Made it. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-2). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 4>

15.0 g of CIN6, 1.4 g of HEMA, 0.4 g of AIBN as a polymerization catalyst were dissolved in 121.6 g of PM and 30.4 of CH, and reacted for 20 hours under heating and reflux to obtain a solution containing 10% by mass of an acrylic copolymer (PA-3). . Mn of the obtained acrylic copolymer was 9,000 and Mw was 22,000.

<Synthesis Example 5>

Polymer EHPE3150 having an epoxy group (manufactured by Daicel Co., Ltd.) 10.0 g, CIN1 9.9 g, and 0.4 g of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 47.2 g of PM, and reacted at 120° C. for 20 hours. This solution was gradually added dropwise to 500 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-4). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis Example 6>

5.2 g of the acrylic polymer (P-1) having an epoxy group obtained in Synthesis Example 1, 12.0 g of CIN2, 0.1 g of ethyl triphenylphosphonium bromide as a reaction catalyst, 0.2 g of dibutylhydroxytoluene as a polymerization inhibitor were added to 70.0 g of PM. It was dissolved and reacted at 100°C for 20 hours. This solution was gradually added dropwise to 1000 g of diethyl ether to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PA-5). The epoxy value of the obtained polymer was measured, and it was confirmed that the epoxy group disappeared.

<Synthesis of component B>

<Synthesis Example 7>

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

<Synthesis Example 8>

32.0 g of BMAA, 8.0 g of GMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain an acrylic copolymer (P-2). Mn of the obtained acrylic copolymer was 7,000 and Mw was 18,000.

<Synthesis Example 9>

10.0 g of the acrylic copolymer (P-2) obtained in Synthesis Example 8, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM, and reacted at 90°C for 20 hours. Made it. This solution was gradually dropped into 500 g of hexane to precipitate a solid, followed by filtration and drying under reduced pressure to obtain a polymer (PB-2) having an acryloyl group. ¹ H-NMR analysis was performed, and it was confirmed that the polymer (PB-2) had an acryloyl group.

<Synthesis of C component>

<Synthesis Example 10>

5.0 g of acrylic polymer (P-1) obtained in Synthesis Example 1, 9.2 g of acrylic group-containing carboxylic acid (Dong-A Synthetic Co., Ltd., brand name "Aronix M-5300", acrylic acid ω-carboxypolycaprolactone (polymerization degree n ≒ 2)) , 0.2 g of dibutylhydroxytoluene, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst were dissolved in 34 g of PM, and reacted at 80° C. for 20 hours to obtain 30% by mass of a polymer (PC-1) having an acryloyl group. A containing solution was obtained. ¹ H-NMR analysis was performed, and it was confirmed that the polymer (PC-1) had an acryloyl group. The epoxy value was measured and it was confirmed that the epoxy group of the polymer was lost.

<Synthesis Example 11>

5.0 g of acrylic polymer (P-1) obtained in Synthesis Example 1, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst were dissolved in 17 g of PM, and at 80°C for 20 hours It was made to react, and a solution containing 30 mass% of the polymer (PC-2) which has an acryloyl group was obtained. ¹ H-NMR analysis was performed, and it was confirmed that the polymer (PC-2) had an acryloyl group. The epoxy value was measured, and it was confirmed that the epoxy group of the polymer was lost.

<Synthesis Example 12>

5.3 g of acrylic polymer (P-1) obtained in Synthesis Example 1, 5.0 g of acrylic group-containing carboxylic acid (Dong-A Synthetic Co., Ltd., brand name "Aronix M-5300", acrylic acid ω-carboxypolycaprolactone (polymerization degree n ≒ 2)) , 0.7 g of acetic acid, 0.2 g of dibutylhydroxytoluene, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst were dissolved in 26 g of PM, and reacted at 80° C. for 20 hours, a polymer having an acryloyl group (PC-3) A solution containing 30% by mass was obtained. ¹ H-NMR analysis was performed, and it was confirmed that the polymer (PC-3) had an acryloyl group. The epoxy value was measured, and it was confirmed that the epoxy group of the polymer was lost.

<Synthesis of E component>

<Synthesis Example 13>

5.0 g of acrylic polymer (P-1) obtained in Synthesis Example 1, 2.2 g of propionic acid, 0.2 g of dibutylhydroxytoluene, 0.1 g of ethyltriphenylphosphonium bromide as a reaction catalyst were dissolved in 34 g of PM, and at 80°C for 20 hours It was made to react, and the solution containing 30 mass% of the polymer (PE-1) which does not have an acryloyl group was obtained. The epoxy value was measured, and it was confirmed that the epoxy group of the polymer was lost.

<Preparation of polymerizable liquid crystal solution>

Polymerizable liquid crystal LC242 (manufactured by BASF) 29.0g, Irgacure 907 (manufactured by BASF) 0.9g as a polymerization initiator, BYK-361N (manufactured by BYK) 0.2g as a leveling agent, methylisobutyl ketone was added as a solvent to achieve a solid content concentration A 30 mass% polymerizable liquid crystal solution (RM-1) was obtained.

<Example 1>

(A) 20 parts by mass of CIN1 as a component, (B) 80 parts by mass of the acrylic polymer (PB-1) obtained in Synthesis Example 7 as a component, and (C) the acrylic polymer (PC-) obtained in Synthesis Example 10 as a component 1) in an amount equivalent to 100 parts by mass in terms of acrylic polymer (PC-3) in a solution containing 30% by mass, (D) 3 parts by mass of PTSA as component are mixed, and PM, BA and EA are added thereto, A cured film (alignment material) forming composition (A-1) having a solvent composition of PM:BA:EA=30:70:30 (mass ratio) and a solid content concentration of 5.0% by mass was prepared.

<Examples 2 to 12 and Comparative Examples 1 to 3>

Except having the kind and amount of each component as described in Table 1, respectively, it carried out similarly to Example 1, and cured film (alignment material) forming compositions A-2 to A-15 were prepared, respectively.

[Table 1]

<Examples 13-25 and Comparative Examples 4-6>

[Evaluation of orientation]

Each cured film (each orientation material) forming composition of Examples 1 to 12 and Comparative Examples 1 to 3 was applied on a TAC film or on a COP film subjected to ozone treatment with a wet film thickness of 4 μm using a bar coater. Each of them was heated and dried at a temperature of 110° C. for 60 seconds in a heat-circulating oven to form a cured film on the film. Each cured film was irradiated with 313 nm linearly polarized light vertically at an exposure dose of 20 mJ/cm 2 to form an alignment material. On the alignment material on the film, a polymerizable liquid crystal solution (RM-1) was applied with a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90° C. for 60 seconds and then exposed at 300 mJ/cm 2 to prepare a retardation material. The retardation material on the produced film was sandwiched between a pair of polarizing plates, and the state of the retardation characteristic in the retardation material was observed. It is described in the column of. The evaluation results are put together in Table 2 and shown later.

[Evaluation of adhesion]

Each cured film (each alignment material) forming composition of Examples 1 to 12 and Comparative Examples 1 to 3 was applied on a TAC film or on a COP film subjected to ozone treatment with a wet film thickness of 4 μm using a bar coater. Each of them was heated and dried at a temperature of 110° C. for 60 seconds in a heat-circulating oven to form a cured film on the film. Each cured film was irradiated with 313 nm linearly polarized light vertically at an exposure dose of 20 mJ/cm 2 to form an alignment material. On the alignment material on the film, a polymerizable liquid crystal solution (RM-1) was applied with a wet film thickness of 6 μm using a bar coater. This coating film was dried on a hot plate at a temperature of 90° C. for 60 seconds and then exposed at 300 mJ/cm 2 to prepare a retardation material. Incisions were made in the phase difference material with a cutter knife so as to be 10 x 10 spaces at 1 mm horizontally and vertically. A cellophane tape peeling test was performed on this incision using a scotch tape. The evaluation result was taken as "adhesiveness", and the thing which remained without peeling off all 100 cells was set as ○, and the thing which peeled even one cell was set as x. The evaluation results are put together in Table 2 and shown later.

[Table 2]

As shown in Table 2, the retardation materials obtained in Examples 13 to 25 showed good orientation and adhesion.

On the other hand, the retardation material obtained in Comparative Examples 4 to 6 showed good orientation, but sufficient adhesiveness was not obtained.

<Example 26>

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

<Examples 27 to 37 and Comparative Examples 7 to 9>

Except having the kind and amount of each component as described in Table 3, respectively, it carried out similarly to Example 26, and cured film (alignment material) forming compositions B-2 to B-15 were each prepared.

[Table 3]

<Examples 38-50 and Comparative Examples 10-12>

About the cured film (each oriented material) forming composition of Examples 26 to 37 and Comparative Examples 7 to 9, the [orientation property] related to the cured film (each oriented material) forming composition of Examples 13 to 25 and Comparative Examples 4 to 6 [Evaluation of orientation] and [evaluation of adhesion] were performed by the same means as for [evaluation of] and [evaluation of adhesion]. Table 4 shows these evaluation results.

[Table 4]

As shown in Table 4, the retardation material obtained in Examples 38-50 showed good orientation and adhesiveness.

On the other hand, the retardation material obtained in Comparative Examples 10 to 12 showed good orientation, but sufficient adhesion was not obtained.

Industrial availability

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

Claims (13)

(A) a low molecular weight compound or polymer having a photo-alignment group and a thermal crosslinkable group,
(B) crosslinking agent,
(C) a polymer having a hydroxy group and a polymerizable group containing a C=C double bond, and
(D) Cured film formation composition containing a crosslinking catalyst. The method of claim 1,
(A) The photo-alignment group of a component is a functional group which has a structure which photodimerizes or photoisomerizes, Cured film formation composition. The method according to claim 1 or 2,
(A) The photo-alignment group of a component is cinnamoyl group, Cured film formation composition. The method according to claim 1 or 2,
The photo-alignment group of the component (A) is a group having an azobenzene structure, and a cured film forming composition. The method according to any one of claims 1 to 4,
(E) A cured film forming composition further containing a polymer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. The method according to any one of claims 1 to 5,
The polymer of component (C) contains a structural unit having a hydroxy group and a structural unit having a polymerizable group including a C=C double bond, and the proportion of the structural unit having this hydroxy group is 100 moles of the total structural units of this polymer. The composition for forming a cured film, wherein the ratio of the structural unit having a polymerizable group including the C=C double bond is 20 mol% or more with respect to 100% of the total structural units of the polymer. The method according to any one of claims 1 to 6,
The cured film-forming composition in which the content ratio of the low molecular weight compound of the component (A) and the polymer of the component (C) is 5:95 to 60:40 by mass ratio. The method according to any one of claims 1 to 6,
The cured film-forming composition in which the content ratio of the polymer of the component (A) and the polymer of the component (C) is 5:95 to 90:10 by mass. The method according to any one of claims 1 to 8,
A cured film forming composition containing 5 parts by mass to 500 parts by mass of (B) component based on 100 parts by mass of the total amount of the component (A) and the component (C). A cured film obtained from the cured film forming composition according to any one of claims 1 to 9. An optical film having the cured film according to claim 10. An orientation material formed using the cured film according to claim 10. A retardation material formed using the cured film according to claim 10.