TWI610976B - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

An object of the present invention is to provide a cured film-forming composition for forming a cured film having excellent photoreaction efficiency and solvent resistance, an alignment material for photo-alignment, and a retardation material formed using the alignment material.

The solution is: the hardened film forming composition of the present invention contains (A) and (B) compounds, where (A) is a photo-alignment group and is selected from the group consisting of a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group. (B) A compound having at least one kind of substituent, which is a compound having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking. A hardened film is formed using this hardened film forming composition, and an alignment material is formed using a photo-alignment technique. A polymerizable liquid crystal is coated on this alignment material and hardened to obtain a retardation material.

Description

Hardened film forming composition, alignment material and retardation material

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

In recent years, in the field of display such as a television using a liquid crystal panel, as a combination that is trending toward higher performance, 3D displays capable of enjoying 3D images have been developed. The so-called 3D display refers to, for example, an image for a right eye is viewed by a right eye of an observer, and an image for a left eye is viewed by a left eye of an observer, and an image having a three-dimensional impression can be displayed.

There are many 3D display methods for representing a 3D image. As special glasses are unnecessary methods, lenticular lens methods and parallax barrier methods are known.

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

In the case of circularly polarized glasses for 3D display, usually A phase difference material is disposed on a display element that forms an image, such as a liquid crystal panel. This phase difference material is a patterned phase difference material in which two types of phase difference regions having different phase difference characteristics are arranged in plural and regularly. In the following description, a patterned phase difference material in which such a plurality of phase difference regions having different phase difference characteristics are arranged is referred to as a patterned phase difference material.

The patterned retardation material is shown in Patent Document 2, and can be produced by optically patterning a retardation material made of a polymerizable liquid crystal. Optical patterning of a retardation material made of a polymerizable liquid crystal is based on a photo-alignment technique known for forming alignment materials for liquid crystal panels. That is, a coating film made of a photo-alignment material is provided on a substrate, and two kinds of polarized lights with different polarization directions are irradiated there. Then, a light alignment film formed as an alignment material formed by two liquid crystal alignment regions with different liquid crystal alignment control directions is obtained. A solution-like retardation material containing a polymerizable liquid crystal is coated on this photo-alignment film to realize the alignment of the polymerizable liquid crystal. Then, the aligned polymerizable liquid crystal is hardened to form a patterned retardation material.

In the formation of alignment materials using the photo-alignment technology of liquid crystal panels, as photo-alignment materials that can be used, acrylic resins and polyimines containing photodimerization sites such as cinnamyl and chalcone groups in the side chain can be used. Resins and the like are known. The report indicates that these resins exhibit properties capable of controlling liquid crystal alignment by UV polarized light irradiation (hereinafter also referred to as liquid crystal alignment). (Refer to Patent Documents 3 to 5)

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-232365

[Patent Document 2] Japanese Patent Laid-Open No. 2005-49865

[Patent Document 3] Japanese Patent No. 3611342

[Patent Document 4] Japanese Patent Laid-Open No. 2009-058584

[Patent Document 5] Japanese Patent Publication No. 2001-517719

However, according to the results of the inventors' review, it is understood that acrylic resins having photodimerization sites such as cinnamyl and chalcone groups in the side chain are suitable for the formation of retardation materials, such as liquid crystal alignment and Sufficient characteristics such as solvent resistance cannot be obtained. In particular, in order to irradiate these resins with polarized UV light to form an alignment material, and to form an optical pattern of a retardation material made of a polymerizable liquid crystal using such an alignment material, a large amount of polarized UV exposure is necessary. The amount of polarized UV exposure is much higher than a sufficient amount of polarized UV exposure (for example, about 50 mJ / cm ² ) to orient a liquid crystal for a general liquid crystal panel surface.

The reason for the increase in the amount of polarized UV exposure mentioned above is that, in the case where a retardation material is formed, unlike the liquid crystal used for the liquid crystal panel surface, a polymerizable liquid crystal is used in a solution state and applied to an alignment Material.

Specifically, the alignment material is formed by using an acrylic resin or the like containing a photodimerization site such as cassia hydrazone in the side chain. In the case of liquid crystal alignment, this acrylic resin or the like is first subjected to photocrosslinking by a photodimerization reaction. Next, it is necessary to perform polarized light irradiation for developing resistance (solvent resistance) to the polymerizable liquid crystal solution.

In general, in order to align the liquid crystal of a liquid crystal panel, it is sufficient to perform a dimerization reaction on the surface of the photo-alignable alignment material. However, in the case where an alignment material is formed using an existing material such as the above-mentioned acrylic resin, the solvent is intended to appear. In terms of resistance, it is necessary to advance the reaction to the inside of the alignment material. For this reason, more polarized light exposure is necessary, that is, there is a problem that the alignment sensitivity of an alignment material using an existing material becomes very small.

In addition, in order to make such a resin of the existing materials exhibit such a solvent resistance, a technique of adding a crosslinking agent is known. However, it is known that a three-dimensional cross-linked structure is formed in the inside of the formed coating film after the thermosetting reaction caused by the cross-linking agent is performed, and it is known that the photoreactivity (photoreaction efficiency) of the substituent is reduced. This means that the alignment sensitivity is greatly reduced, and even if a cross-linking agent is added to such an existing material, the desired photo-alignment effect cannot be obtained.

Based on the above, a photo-alignment technology that improves the alignment sensitivity of the alignment material and can reduce the amount of polarized UV exposure, and a hardened film-forming composition that can be used to form the alignment material. In addition, a technology capable of efficiently providing patterned retardation materials is being pursued.

The present invention is based on the above findings and review results. That is, an object of the present invention is to provide a cured film-forming composition for providing an alignment material that has both excellent photoreaction efficiency and solvent resistance and can align polymerizable liquid crystals with high sensitivity.

Next, another object of the present invention is to provide an alignment material obtained from such a cured film-forming composition, having excellent photoreaction efficiency and solvent resistance, and capable of orienting a polymerizable liquid crystal with high sensitivity, and using such an alignment Material is a phase difference material.

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

According to a first aspect of the present invention, a hardened film-forming composition includes: (A) one having a photo-alignment group and one selected from a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group; A compound having at least one substituent, and (B) a polymer having a substituent capable of thermally reacting with the component (A) and being self-crosslinkable.

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

In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a cinnamidine group.

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

In the first aspect of the present invention, it is preferable to further contain (C) a crosslinking catalyst in addition to the component (A) and the component (B).

In the first aspect of the present invention, the weight average molecular weight of the polymer of the component (B) is preferably 1,000 to 100,000.

A second aspect of the present invention relates to an alignment material obtained by using the heat-curable film-forming composition of the first aspect of the present invention.

A third aspect of the present invention relates to a retardation material formed of a cured film obtained by using the cured film-forming composition of the first aspect of the present invention.

According to the first aspect of the present invention, a cured film-forming composition can be provided to provide an alignment material having excellent photoreaction efficiency and solvent resistance and capable of orienting a polymerizable liquid crystal with high sensitivity.

According to the second aspect of the present invention, an alignment material having excellent photoreaction efficiency and solvent resistance and capable of orienting a polymerizable liquid crystal with high sensitivity can be provided.

According to the third aspect of the present invention, a retardation material capable of efficiently forming an optical pattern can be provided.

<Hardened film forming composition>

The cured film-forming composition of the present invention contains (A) a compound having a photo-alignment group and at least one substituent selected from any one of a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group, and (B) having A polymer which can react thermally with the component (A) and which is self-crosslinking. The hardened film-forming composition of the present invention may contain (A) component and (B) component, and may further contain It is a crosslinking catalyst of (C) component. Further, as long as the effect of the present invention is not impaired, other additives may be contained.

The details of each component are described below.

<(A) component>

In the cured film-forming composition of the present invention, the component (A) may be a compound having a photo-alignment group and at least one kind selected from any one of a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group (hereinafter (A) component is called "(low molecular) photo-alignment component").

The photo-alignment group in the present invention generally refers to a functional group that exerts its alignment property by light irradiation, and is typically a functional group of a photodimerization or photoisomerization structure site. Examples of other photo-alignment groups include a functional group (exemplified compound: benzoate compound, etc.) that causes a photo-Fries rearrangement reaction, and a group (exemplified compound: cyclobutane ring, etc.) that causes a photodecomposition reaction. Wait.

The compound of the (A) component has a photodimerization structure site | part which can be used as a photo-alignment group, and means the site | part which forms a dimmer body by light irradiation. Specific examples include cinnamyl, chalcone, coumarin, and anthracenyl. Among these, from the viewpoint of the degree of transparency in the visible light region and the strength of the photo-dimerization reactivity, cassia hydrazone is preferred.

In addition, the compound of the component (A) has a photo-isomerization structural site that can serve as a photo-alignment group, and refers to a structural site that changes cis-isomer and trans-isomer by light irradiation. As a specific example, there may be Nitrobenzene structure, stilbene structure, etc. Among these, azobenzene structure is preferable from the viewpoint of the strength of reactivity.

A compound having a photo-alignment group and at least one substituent selected from any one of a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group is, for example, the following structural formulas [A-11] to [A-15] The indicated compound.

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

X ¹¹ is one or two or more kinds of bonds selected from a single bond, an ether bond, an ester bond, a amine bond, a urethane bond, an amine group, or a combination thereof, or a combination of 1 One or two or more kinds of this bond, and a structure in which one to three kinds of substituents are selected from among 1 to 18 carbon atoms, alkylene, phenylene, or biphenyl, and combinations thereof The aforementioned substituents may have a structure in which a plurality of the substituents are individually connected by the aforementioned bonding.

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. At this time, an alkyl group, a phenyl group, a biphenyl group, or a cyclohexyl group having 1 to 18 carbon atoms may be bonded by a covalent bond, an ether bond, an ester bond, a amide bond, or a urea bond. base.

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

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

X ¹⁵ represents a hydroxyl group, a carboxyl group, an amino group, or an alkoxysilyl group.

X ¹⁶ represents a single bond, an oxygen atom, or a sulfur atom.

In addition, in the case where a benzene ring is included in these substituents, the benzene ring may also be 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 The cyano group is substituted by one or more substituents which are the same or different.

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

(A) Component containing photo-alignment group and hydroxyl group Specific examples of the compound include, for example, the compounds represented by the above structural formulae [A11] to [A15] and compounds other than the formulae, for example, methyl 4- (8-hydroxyoctyloxy) cinnamate , Methyl 4- (6-hydroxyhexyloxy) cinnamate, methyl 3-methoxy-4- (6-hydroxyhexyloxy) cinnamate, 4- (4-hydroxybutyloxy) cinnamic acid Methyl ester, methyl 4- (3-hydroxypropyloxy) cinnamate, methyl 4- (2-hydroxyethyloxy) cinnamate, methyl 4-hydroxymethyloxy cinnamate, 4-hydroxy Methyl cinnamate, ethyl 4- (8-hydroxyoctyloxy) cinnamate, ethyl 4- (6-hydroxyhexyloxy) cinnamate, ethyl 4- (4-hydroxybutyloxy) cinnamate Ester, 4- (3-hydroxypropyloxy) cinnamate, ethyl 4- (2-hydroxyethyloxy) cinnamate, 4-hydroxymethyloxy cinnamate, 4-hydroxy cinnamate Ethyl ester, 4- (8-hydroxyoctyloxy) phenyl cinnamate, 4- (6-hydroxyhexyloxy) phenyl cinnamate, 4- (4-hydroxybutyloxy) phenyl cinnamate , 4- (3-hydroxypropyloxy) phenyl cinnamate, 4- (2-hydroxyethyloxy) phenyl cinnamate, 4-hydroxymethyloxy phenyl cinnamate, 4-hydroxycinnamic acid Phenyl ester, 4- (8-hydroxyoctyloxy) biphenyl cinnamate, 4- (6-hydroxy Hexyloxy) biphenyl cinnamate, 4- (4-hydroxybutyloxy) biphenyl cinnamate, 4- (3-hydroxypropyloxy) biphenyl cinnamate, 4- (2-hydroxy (Ethyloxy) biphenyl cinnamate, biphenyl 4-hydroxymethyloxy cinnamate, biphenyl 4-hydroxycinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, cinnamon 4-hydroxybutyl acid, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 4- (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxy Hexyloxy) azobenzene, 4- (4-hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azo Azobenzene, 4-hydroxymethyloxazobenzene, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy Base) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutyloxy) chalcone, 4- (3-hydroxypropyloxy) chalcone, 4- (2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 '-(8-hydroxyoctyloxy) chalcone, 4 '-(6-hydroxyhexyloxy) chalcone, 4'-(4-hydroxybutyloxy) chalcone, 4 '-(3-hydroxypropyloxy) chalcone, 4'-( 2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- ( 6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutyloxy) coumarin, 7- (3-hydroxypropyloxy) coumarin, 7- (2-hydroxyethyloxy) Based) 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) benzylidene] methyl cinnamate, 4- [4- (6-hydroxyhexyloxy) benzylidene] Methyl cinnamate, 4- [4- (4-hydroxybutyloxy) benzylidene] Methyl Derivate, 4- [4- (3-hydroxypropyloxy) benzylidene] methyl cinnamate, 4- [4- (2-hydroxyethyloxy) benzylidene] cinnamic acid Methyl ester, methyl 4- [4-hydroxymethyloxybenzyl] cinnamate, methyl 4- [4-hydroxybenzyl] cinnamate, 4- [4- (8-hydroxyoctyl (Oxy) benzylidene] ethyl cinnamate, 4- [4- (6-hydroxyhexyloxy) benzylidene] ethyl cinnamate, 4- [4- (4-hydroxybutyloxy) Benzamyl] ethyl cinnamate, 4- [4- (3-hydroxypropyloxy) benzamyl] ethyl cinnamate, 4- [4- (2-hydroxyethyloxy) benzyl Fluorenyl] ethyl cinnamate, 4- [4-hydroxymethyloxybenzyl] ethyl cinnamate, 4- [4-hydroxybenzyl] ethyl cinnamate, 4- [4- ( 8-hydroxyl Octyloxy) benzamyl] tert-butyl cinnamate, 4- [4- (6-hydroxyhexyloxy) benzamyl] tert-butyl cinnamate, 4- [4- (4- Hydroxybutyloxy) benzamyl] tert-butyl cinnamate, 4- [4- (3-hydroxypropyloxy) benzamyl] tributyl cinnamate, 4- [4- ( 2-hydroxyethyloxy) benzamyl] tert-butyl cinnamate, 4- [4-hydroxymethyloxy benzamyl] tert-butyl cinnamate, 4- [4- (8- Hydroxyoctyloxy) benzamyl] phenyl cinnamate, 4- [4- (6-hydroxyhexyloxy) benzamyl] phenyl cinnamate, 4- [4- (4-hydroxybutyl Oxy) benzamyl] phenyl cinnamate, 4- [4- (3-hydroxypropyloxy) benzyl] phenyl cinnamate, 4- [4- (2-hydroxyethyloxy ) Benzamyl] phenyl cinnamate, 4- [4-hydroxymethyloxybenzyl] phenyl cinnamate, 4- [4-hydroxybenzyl] phenyl cinnamate, 4- [ 4- (8-hydroxyoctyloxy) benzylidene] diphenyl cinnamate, 4- [4- (6-hydroxyhexyloxy) benzylidene] bisphenyl cinnamate, 4- [4 -(4-hydroxybutyloxy) benzylidene] diphenyl cinnamate, 4- [4- (3-hydroxypropyloxy) benzylidene] biphenyl cinnamate, 4- [4 -(2-hydroxyethyloxy) benzylidene] cinnamate Phenyl ester, 4- [4-Hydroxymethyloxybenzyl] biphenyl cinnamate, 4- [4-hydroxybenzyl] phenyl cinnamate, 4-benzyl cinnamate 8 -Hydroxyoctyl ester, 4-benzylidene cinnamate 6-hydroxyhexyl ester, 4-benzylidene cinnamate 4-hydroxybutyl ester, 4-benzylidene cinnamate 3-hydroxypropyl ester, 4-benzene 2-methyl ethyl cinnamate, 4-methyl benzoyl cinnamate, 4- [4- (8-hydroxyoctyloxy) benzamyl] chalcone, 4- [4 -(6-hydroxyhexyloxy) benzylidene] chalcone, 4- [4- (4-hydroxybutyloxy) benzylidene] chalcone, 4- [4- (3-hydroxy Propyloxy) benzyl] chalcone, 4- [4- (2-hydroxyethyloxy) benzyl] chalcone, 4- (4-hydroxymethyloxybenzyl Base) chalcone, 4- (4-hydroxybenzyl) chalcone, 4 '-[4- (8-hydroxyoctyloxy) benzyl] chalcone, 4'-[4- (6-hydroxyhexyl (Oxy) benzyl] chalcone, 4 '-[4- (4-hydroxybutyloxy) benzyl] chalcone, 4'-[4- (3-hydroxypropyloxy ) Benzamyl] chalcone, 4 '-[4- (2-hydroxyethyloxy) benzyl] chalcone, 4'-(4-hydroxymethyloxybenzyl) Chalcone, 4 '-(4-hydroxybenzyl) chalcone, etc.

Specific examples of the compound having a photo-alignment group and a carboxyl group as the component (A) include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 3,4-dimethoxycinnamic acid, and aromatic compounds. Beans-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like.

Specific examples of the compound having a photo-alignment group and an amine group as the component (A) include 4-aminomethyl cinnamate, 4-amino cinnamate, and 3-amino cinnamate , Ethyl 3-aminocinnamate and the like.

Specific examples of the compound having a photo-alignment group and an alkoxysilyl group as the component (A) include methyl 4- (3-trimethoxysilylpropyloxy) cinnamate and 4- ( 3-Triethoxysilylpropyloxy) methyl cinnamate, 4- (3-trimethoxysilylpropyloxy) ethyl cinnamate, 4- (3-triethoxysilylpropyl Ethoxy) ethyl cinnamate, 4- (3-trimethoxysilylhexyloxy) methyl cinnamate, 4- (3-triethoxysilylhexyloxy) cinnamate, 4- (3-Trimethoxysilylhexyloxy) ethyl cinnamate and ethyl 4- (3-triethoxysilylhexyloxy) cinnamate.

(A) The low molecular weight photo-alignment component can be exemplified by the above specific examples, but is not limited thereto.

Among them, the low molecular photo-alignment component of the (A) component has Particularly preferred are compounds having a photo-alignment group and a hydroxyl group. The compound having a photo-alignment group and a hydroxyl group provides photo-alignment to a cured film using the cured film-forming composition of the present invention, and when used as an alignment material, adheres to a polymerizable liquid crystal layer. Sexual improvement is particularly effective.

In addition, when the low-molecular photo-alignment component of the component (A) is a compound having a photo-alignment group and a hydroxyl group, the component (A) may have two or more photo-alignment groups and / or two in the molecule. Compounds of the above hydroxy groups. Specifically, as the component (A), a compound having one hydroxyl group and two or more photo-alignment groups in the molecule and a compound having one photo-alignment group and two or more hydroxyl groups in the molecule can be used, or A compound having at least two photo-alignment groups and two hydroxyl groups in the molecule at the same time. For example, for a compound having two or more photo-alignment groups and a hydroxyl group in the molecule, a compound represented by the following formula is exemplified.

By appropriately selecting these compounds, the molecular weight of the low-molecular photo-alignment component of the component (A) can be controlled to a value within a desired range. That is, in order to form the cured film of the present invention using the cured film-forming composition of the present invention, heat curing is necessary, but when the heating is performed, In this case, it is possible to suppress the sublimation of the low-molecular photo-alignment component of the component (A).

Furthermore, the compound as the component (A) in the cured film-forming composition of the present invention has a photo-alignment group and at least one kind of substituent selected from any one of a hydroxyl group, a carboxyl group, an amino group, and an alkoxysilyl group. It may be a mixture of a plurality of compounds.

<(B) component>

In the cured film forming composition of the present invention, the component (B) is a polymer (hereinafter referred to as a specific (co) polymer) having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking.

Specifically, the component (B) has a specific crosslinkable substituent, and more specifically, it is capable of causing a self-crosslinking reaction, and can heat the component (A) at a lower temperature than the sublimation temperature of the component (A) A polymer of crosslinkable substituents for reaction. By using this polymer as the (B) component, the (B) component can react with the (A) component (thermal reaction) at a lower temperature than the sublimation temperature of the (A) component while causing a self-crosslinking reaction, and Inhibit sublimation of (A) component. Therefore, when the cured film-forming composition of the present invention is used as a cured film, as described above, an alignment material having a substituent having a high photoreaction efficiency can be formed.

Examples of preferable specific crosslinkable substituents contained in the polymer of the component (B) include (C _1-10 alkoxy) -CH ₂ -NH-C (= O)-groups and the like. Methyl formamidine, hydroxy formamidine, (C _1-5 alkoxy) ₃ Si-X- groups (here, X represents a spacer such as C _1-10 alkylene or phenylene), etc. Trialkoxysilyl and so on. The content of the specific crosslinkable substituent is preferably 0.2 to 1 per unit of the repeatability unit of the (B) component, and from the viewpoint of the solvent resistance of the alignment material, it is 0.4 to 1 Better.

Regarding the introduction of a specific crosslinkable substituent into the polymer of the component (B), it is only necessary to polymerize the aforementioned monomer having a specific crosslinkable substituent (co). Examples of such a monomer having a specific crosslinkable substituent include N-alkoxymethyl (meth) acrylamidonium and (C _1-5 alkoxy) ₃ Si- X-ester (X here means the same as X mentioned above). As the polymer obtained by using N-alkoxymethyl (meth) acrylamide, for example, N-methylol (meth) acrylamide and N-methoxymethyl (meth) acryl can be used. Hydroxymethyl or alkoxymethyl substituted acrylamide compounds such as amidine, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, or As the methacrylamide compound, if necessary, a polymer produced by using a monomer (see later) copolymerizable with the monomer may be used. The (meth) acrylamide refers to both methacrylamide and acrylamide.

Examples of such polymers include poly (N-butoxymethacrylamide), a copolymer of N-butoxymethacrylamide and styrene, and N-methylolmethacryl Copolymers of amidine and methmethacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and the like.

In addition, as the polymer of the component (B), a compound having a trialkoxysilyl group, such as 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth) acryloxy (C _1-5 alkoxy) ₃ Si-X-esters of (meth) acrylic acid such as propyltriethoxysilane (where X and X have the same meaning as above) have specific crosslinkability A polymer produced by using a monomer having a substituent and then using a monomer copolymerizable with the monomer (see later) as desired.

Examples of such polymers include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane, and styrene, Poly (3-propenyloxypropyltrimethoxysilane), a copolymer of 3-propenyloxypropyltrimethoxysilane and a methacrylate, and the like.

As described above, the polymer (specific (co) polymer) of the component (B) used in the cured film-forming composition of the present invention is a monomer that can be copolymerized with a monomer having a specific crosslinkable substituent (hereinafter also referred to as It is called a monomer having a non-crosslinkable substituent).

Specific examples of the monomer having a non-crosslinkable substituent include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, a methacrylamide compound, and propylene. Nitriles, styrene compounds and vinyl compounds.

Although specific examples of the monomers are given below, the present invention is not limited to these.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and benzene. Acrylate, epoxy acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isofluorenyl acrylate, 2-methoxyethyl acrylate Esters, methoxytriethylene glycol, propylene Acid ester, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, γ-butyrolactone acrylate , 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and the like.

Examples of the methacrylate compound include methacrylate, ethylmethacrylate, isopropylmethacrylate, benzylmethacrylate, naphthylmethacrylate, and anthracenemethyl. Acrylate, anthryl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate , Cyclohexyl methacrylate, isofluorenyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate Ester, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl 2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, and 3-vinyl-7-oxabicyclo [4.1.0] heptane. Wait.

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

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

Examples of the acrylamide compound include acrylamide, N-methacrylamide, N-ethylacrylamide, N-benzylacrylamide, N-phenylacrylamide, and N, N -Dimethacrylamide and the like.

Examples of the methacrylamide compound include methacrylamide, N-methacrylamide, N-ethylmethacrylamide, N-benzylmethacrylamine, N -Phenylmethacrylamide and N, N-dimethylmethacrylamine.

In addition, although a monomer having a substituent selected from a hydroxyl group, a carboxyl group, and an amine group can be used in combination with the monomer copolymerizable with the component (B) without impairing the effects of the present invention, it is effectively From the viewpoint of thermal reaction of the component (A), it is preferred that the component (B) does not contain repeating units derived from such monomers; even if it is contained, it is polymerized per unit of the component (B). Of the repeatable units of the substance, less than 0.1 units are preferred.

A method for obtaining a polymer of the component (B) used in the cured film-forming composition of the present invention: a specific (co) polymer is not particularly limited, but, for example, the aforementioned compounds having a specific crosslinkable substituent, It is obtained by subjecting a monomer such as a monomer having a non-crosslinkable substituent and a polymerization initiator to a polymerization reaction at a temperature of 50 ° C to 110 ° C. In this case, the solvent used is not particularly limited as long as it is capable of dissolving a monomer having a specific crosslinkable substituent, a monomer having a non-crosslinkable substituent to be used as desired, a polymerization initiator, and the like. Specific examples include solvents described in solvents described later.

Specific (co) polymerization of the (B) component polymer obtained in this way The substance is usually in the state of a solution which has been dissolved in a solvent, and can be used as the solution of the component (B) in the present invention.

In addition, the specific (co) polymer solution of the component polymer (B) obtained by the above-mentioned method is reprecipitated by adding diethyl ether, water, and the like with stirring. After filtering and washing the formed precipitate, it can be dried under normal pressure or reduced pressure at normal temperature or under heating to form a powder of a specific (co) polymer. By this operation, the polymerization initiator and unreacted monomer that coexist with the specific (co) polymer can be removed, and as a result, a powder of the purified (co) polymer can be obtained. In the case where sufficient purification cannot be performed in one operation, the obtained powder may be redissolved in a solvent, and the above operations may be repeated.

In the cured film forming composition of the present invention, the powder of the specific (co) polymer of the component (B) polymer may be used as it is, or the powder may be re-dissolved in, for example, a solvent described later, and the solution may be It can also be used in its state.

The polymer of the component (B) in the present invention can be used alone or in combination of two or more kinds, that is, it can be used as a mixture of a plurality of specific (co) polymers.

The weight average molecular weight of the polymer of the component (B) is 1,000 to 500,000, preferably 1,000 to 200,000, more preferably 1,000 to 100,000, and even more preferably 2,000 to 50,000.

<C component>

The cured film-forming composition of the present invention is the component (A) described above, and The component (B) is added, and a crosslinking catalyst as a component (C) may be contained as desired.

Examples of the (C) component of the crosslinking catalyst include an acid or a thermal acid generator. The cross-linking catalyst of the component (C) is effective in promoting a thermosetting reaction during the formation of a cured film using the cured film-forming composition of the present invention.

In the case of using an acid or a hot acid generator as the component (C), the component (C) may be a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, and a compound that generates an acid through thermal decomposition during pre-baking or post-baking. That is, as long as the compound can be thermally decomposed at a temperature of 80 ° C to 250 ° C to generate an acid, it is not particularly limited.

Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and Fmethanesulfonic 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 Acids such as sulfonic acids or hydrates or salts thereof.

Examples of the compound that generates an acid due to heat include bis (tosylsulfonyloxy) ethane, bis (tosylsulfonyloxy) propane, bis (tosylsulfonyloxy) butane, and p-nitro. Benzyl p-toluenesulfonate, o-nitrobenzyl p-toluenesulfonate, 1,2,3-phenylene ginseng (methylsulfonate), p-toluenesulfonic acid pyridine salt, p-toluenesulfonate Acid morpholine, ethyl p-toluenesulfonate, p-propyltoluenesulfonate, p-butyltoluenesulfonate, p-toluenesulfonic acid Isobutyl ester, p-toluenesulfonate, p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2 -Hydroxybutyl p-toluenesulfonate, N-ethyl-4-toluenesulfonamide, and compounds represented by the following structural formulas [PAG-1] to [PAG-41], and the like.

The content of the component (C) in the cured film-forming composition of the present invention is preferably 100 parts by mass based on 100 parts by mass of the total amount of the compound having a photo-alignment group, a hydroxyl group, etc. of the component (A) and the polymer of the component (B). for 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.1 to 6 parts by mass. When the content of the cross-linking catalyst of the component (C) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Moreover, when it is set to 10 parts by mass or less, the storage stability of the cured film-forming composition is improved.

<Solvent>

The cured film-forming composition of the present invention can be used mainly in a solution state dissolved in a solvent. The solvent used at this time is only required to be capable of dissolving the component (A) and the component (B), other required (C) components, and other additives described later, and the type, structure, and the like are not particularly limited.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cyperidine acetate, ethyl cyperidine acetate, and diethylene glycol monoethyl ether. Methyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclic Pentane, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, 2-hydroxy- Ethyl 2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone.

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

<Other additives>

Furthermore, the hardened film-forming composition of the present invention may contain a sensitizer, a silane coupling agent, a surfactant, a rheological agent, a pigment, a dye, a storage stabilizer, and the like, without impairing the effects of the present invention. Defoamer, antioxidant, etc.

For example, a sensitizer is effective for promoting a photoreaction after forming a thermosetting film using the cured film-forming composition of the present invention.

Examples of the sensitizers of other additives include benzophenone, anthracene, anthraquinone, thioxanthone, and their derivatives, and nitrophenyl compounds. Among these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of suitable compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitrofluorene, and 4-nitrobiphenyl , 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, 5-nitroindole and the like. Particularly preferred is a benzophenone derivative -N, N-diethylaminobenzophenone.

These sensitizers are not limited to the above. Moreover, a sensitizer can be used individually by 1 type or in combination of 2 or more types.

The use ratio of the sensitizer in the cured film-forming composition of the present invention is relative to the total amount of the specific (co) polymer of the compound having a photo-alignment group, a hydroxyl group, etc. of the component (A) and the polymer of the component (B). For 100 parts by mass, 0.1 to 20 parts by mass is preferred, and the more preferred It is 0.2 to 10 parts by mass. In the case where the ratio is too small, the effect as a sensitizer may not be sufficiently obtained; in the case where it is too large, the light transmittance may be reduced and wrinkles of the coating film may be generated.

<Preparation of hardened film forming composition>

The hardened film-forming composition of the present invention dissolves a low-molecular photo-alignment component of the component (A) and a polymer having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking in the component (B) Solvent. Further, the cured film-forming composition of the present invention may contain a crosslinking catalyst as a component (C). Further, to the extent that the effects of the present invention are not impaired, other additives may be contained.

The blending ratio (content ratio) of the component (A) and the component (B) is preferably a mass ratio of 5:95 to 60:40. (B) When the content of the component is too high, the alignment of the liquid crystal is likely to decrease. When the content is too low, the alignment resistance is liable to decrease due to the decrease in the solvent resistance.

Preferred examples of the hardened film-forming composition of the present invention are as follows:

[1]: The blending ratio of (A) component and (B) component is a cured film-forming composition containing a solvent other than (A) component and (B) component at a mass ratio of 5:95 to 60:40.

[2]: The blending ratio of (A) component and (B) component is based on a mass ratio of 5:95 to 60:40, based on 100 parts by mass of the total amount of (A) component and (B) component, and contains 0.01 mass Part to 10 parts by mass of the component (C) and the cured film forming composition of the solvent Thing.

The compounding ratio and method of the cured film-forming composition of the present invention when used as a solution are described in detail below.

Although the proportion of the solid component in the hardened film forming composition of the present invention is not particularly limited as long as each component can be uniformly dissolved in a solvent, 1% to 80% by mass, preferably 3% to 60% by mass, More preferred is 5 to 40% by mass. The solid content as used herein refers to a solvent that is removed from all the components of the cured film-forming composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. Examples of the preparation method include a method in which the component (B) is dissolved in a solvent, the component (A) is mixed at a predetermined ratio, and the component (C) is desired to obtain a uniform solution. In the appropriate stage of this preparation method, it is necessary to add other additives after mixing as necessary.

In the preparation of the cured film-forming composition of the present invention, as described above, a solution of a specific (co) polymer ((B) component) obtained by a polymerization reaction in a solvent can be directly used. In this case, for example, the component (B) obtained by polymerizing N-butoxymethacrylamide is added with the same components (A) and (C) as described above to obtain a uniform solution. In this case, an additional solvent can be added for the purpose of concentration adjustment. At this time, the solvent used in the manufacturing process of the component (B) and the solvent used in the concentration adjustment of the cured film-forming composition may be the same or different.

The prepared cured film-forming composition solution is preferably used after filtration using a filter having a pore size of about 0.2 μm or the like.

<Hardened film, alignment material, and retardation material>

The hardened film forming composition of the present invention is such a solution on a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a coated substrate such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc. ) And films (for example, cellulose triacetate (TAC) films, cycloolefin polymer films, resin films such as polyethylene terephthalate films, acrylic films), etc., by bar coating, spin coating, Flow coating, roll coating, slit coating, continuous slit spin coating, spray coating, printing, and other coatings are used to form a coating film, and then a heating plate or an oven is used to heat and dry to form a hardened film.

As a condition for heating and drying, when a cured film is used as the liquid crystal alignment material, the components of the cured film (alignment material) are capable of self-dissolving to such an extent that they do not melt out from the polymerizable liquid crystal solution applied thereon. A cross-linking reaction such as cross-linking may be used. For example, a heating temperature and a heating time appropriately selected from a range of a temperature of 60 ° C. to 200 ° C. and a time of 0.4 minutes to 60 minutes are used. 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 using the cured film-forming composition of the present invention, for example, 0.05 μm to 5 μm, can be appropriately selected in consideration of the level difference, optical, and electrical properties of the substrate used.

The hardened film produced in this way can be used as an alignment material by performing polarized UV irradiation, and can also function as a member for alignment of liquid crystal compounds such as polymerizable liquid crystals.

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

Because the alignment material formed from the hardened film composition of the present invention has solvent resistance and heat resistance, a phase difference material made of a polymerizable liquid crystal solution is applied to this alignment material, and then the phase transition temperature of the liquid crystal is heated by this. Until now, the retardation material is changed to a liquid crystal state, and aligned on the alignment material. Then, the retardation material that has been in the aligned state is directly cured to form a retardation material as a layer having optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same can be used. When the substrate forming the alignment material is a thin film, the thin film having the retardation material of the present invention is useful as a retardation film. The phase difference material forming such a phase difference material is in a liquid crystal state, and those who adopt an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, and mixed alignment on the alignment material can be individually used according to their necessary retardation characteristics. .

In addition, in the case of manufacturing a patterned retardation material for 3D display, the hardened film from the hardened film composition of the present invention and formed by the above-mentioned method intervenes with a mask of a line and a space pattern to define a As a reference, for example, the polarized UV is exposed in the +45 degree direction, and then the polarized UV is exposed in the -45 degree direction after removing the mask, to obtain an alignment material that forms two types of liquid crystal alignment regions with different liquid crystal alignment control directions. After that, after applying a retardation material made of a polymerizable liquid crystal solution, the retardation material is changed to a liquid crystal state by heating to a phase transition temperature of the liquid crystal. Will become liquid crystal The polymerizable liquid crystal in the state is aligned on the alignment material forming the two types of liquid crystal alignment regions, and is formed in the corresponding alignment state in each liquid crystal alignment region. Next, the phase difference material that has achieved such an alignment state is directly hardened, and the above-mentioned alignment state is fixed to obtain a patterned phase in which the two types of phase difference regions having different phase difference characteristics are each plurally and regularly arranged. Poor material.

In addition, two substrates having the alignment material of the present invention formed as described above are used, and the alignment materials on the two substrates are bonded to each other face to face through a spacer, and then liquid crystal is injected between these substrates to form a liquid crystal substrate. Aligned liquid crystal display element.

Therefore, the cured film-forming composition of the present invention can be suitably used in various manufacturing processes such as a retardation material (a retardation film) or a liquid crystal display element.

[Example]

Although the present invention will be described in more detail with examples below, the present invention is not limited to these examples.

Code [Code used in the examples]

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

<Compound with photo-alignment group and hydroxyl group>

CIN1: 4- (6-hydroxyhexyloxy) methyl cinnamate

CIN2: 3-methoxy-4- (6-hydroxyhexyloxy) methyl cinnamate

CIN11: 4- [4- (6-hydroxyhexyloxy) benzamidine] tert-butyl cinnamate

<Specific (co) polymer (acrylic (co) polymer) raw material>

BMAA: N-butoxymethacrylamide

MPTS: 3-methacryloxypropyltrimethoxysilane

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AAM: Acrylamide

CIN: methyl 4- (6-methacryloxyhexyl-1-oxy) cinnamate

AIBN: α, α’-azobisisobutyronitrile

<Crosslinking Catalyst>

PTSA: p-toluenesulfonic acid monohydrate

<Crosslinking agent>

HMM: hexamethoxymethyl melamine

<Solvent>

PM: Propylene glycol monomethyl ether

PMA: propylene glycol monomethyl ether acetate

CHN: cyclohexanone

The number average molecular weight and the weight average molecular weight of the acrylic copolymer obtained following the following synthesis examples were obtained using a GPC device (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation, and the solvent was tetrahydrofuran at 1 mL / min The flow rate was measured under the condition that the column was passed (column temperature 40 ° C) to dissolve. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis example 1>

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 copolymer solution (solid content concentration: 35% by mass) (P1). The obtained acrylic copolymer had Mn of 2,672 and Mw of 3,895.

<Synthesis example 2>

100.0 g of BMAA and 2.1 g of AIBN as a polymerization catalyst were dissolved in 408.4 g of PM and reacted at 90 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20% by mass) (P2). The obtained acrylic copolymer had Mn of 10,311 and Mw of 25,245.

<Synthesis example 3>

100.0 g of MPTS and 3.0 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 copolymer solution (solid content concentration: 20% by mass) (P3). Acrylic acid obtained The Mn of the polymer was 4,061 and the Mw was 5,721.

<Synthesis example 4>

42.0 g of CIN, 18.0 g of HEMA, and 1.3 g of AIBN as a polymerization catalyst were dissolved in 166.8 g of CHN and reacted at 80 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 27% by mass) (P4). Mn of the obtained acrylic copolymer was 8,500 and Mw was 16,500.

<Synthesis example 5>

3.5 g of MAA, 7.0 g of MMA, 7.0 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 53.9 g of PM and reacted at 70 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) (P5). The obtained acrylic copolymer had Mn of 10,300 and Mw of 24,600.

<Synthesis example 6>

60.0 g of BMAA, 40.0 g of AAM, and 4.8 g of AIBN as a polymerization catalyst were dissolved in 313.9 g of PM and reacted at 85 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) (P6). The obtained acrylic copolymer had Mn of 3,560 and Mw of 4,820.

<Synthesis Example 7> Synthesis of CIN11 (Synthesis example 7-1) Synthesis of CIN11 precursor CIN11-1

In a 1L four-neck flask, 80.0 g of 4-bromo-4'-hydroxybenzophenone, 500 mL of N, N-dimethylacetamide, 55.4 g of tert-butyl acrylate, 160.2 g of tributylamine, and acetic acid 1.29 g of palladium and 3.50 g of tris (o-tolyl) phosphine were stirred while heating at 100 ° C. After the reaction was completed, the reaction system was poured into 2 L of ethyl acetate, and extracted with a 1N-hydrochloric acid aqueous solution and saturated brine. Anhydrous magnesium sulfate was added to the extracted organic layer for dehydration and drying, and the anhydrous magnesium sulfate was filtered off. The solvent was distilled off from the obtained filtrate using a rotary evaporator, and 109.4 g of a target product CIN11-1 (reddish brown slime) was obtained. The obtained CIN11-1 was used in the next reaction without purification.

(Synthesis example 7-2) Synthesis of CIN11

In a 2L four-necked flask, 93.4 g of CIN11-1, 1L of N, N-dimethylformamide, 39.3 g of 6-chloro-1-hexanol, 119.4 g of potassium carbonate, and 4.8 g of potassium iodide were added, and heated at 100 ° C. While stirring. After the reaction, the reaction system was poured into 5 L of water, neutralized with a 1N-hydrochloric acid aqueous solution, and extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the extracted organic layer for dehydration and drying, and the anhydrous magnesium sulfate was filtered off. The solvent was distilled off from the obtained filtrate using a rotary evaporator. The residue was recrystallized using isopropanol / hexane = 1/10 to obtain 113.8 g of CIN11 (yellow solid). The results of ¹ H-NMR measurement of the target are shown below. From this result, the obtained solid was confirmed as the target CIN11.

¹ H NMR (400MHz, [D ₆ ] -DMSO): δ7.86-7.88 (d, 2H), 7.73-7.75 (d, 2H), 7.69-7.71 (d, 2H), 7.62-7.66 (d, 1H ), 7.08-7.10 (d, 2H), 6.65-6.69 (d, 1H), 4.35-4.37 (t, 1H), 4.06-4.09 (t, 2H), 3.37-3.42 (q, 2H), 1.73-1.77 (m, 2H), 1.50 (s, 9H), 1.37-1.46 (m, 6H)

<Examples 1 to 7>

Each of the cured film-forming compositions of Examples 1 to 7 was prepared with the composition shown in Table 1, and the alignment sensitivity, pattern formation, and transmittance were evaluated according to each.

<Comparative Examples 1 to 3>

Using acrylic copolymer P4, P5, or HMM instead of polymer (B) as a component that has a substituent capable of thermally reacting with component (A) and capable of self-crosslinking reaction, Comparative Example 1 ~ was prepared with the composition shown in Table 2 Each cured film-forming composition of 3 was evaluated for alignment sensitivity, pattern formability, and transmittance on a case-by-case basis.

[Evaluation of alignment sensitivity]

Each of the cured film-forming compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was spin-coated on an alkali-free glass using a spin coater at 2000 rpm for 30 seconds, and then heated and dried on a hot plate at a temperature of 140 ° C. 120 seconds, a hardened film was formed. To this cured film, linearly polarized light of 313 nm was irradiated vertically. On the exposed substrate, a polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, followed by pre-baking at 60 ° C on a hot plate for 60 seconds to form a film thickness of 1.0. μm coating film. This film was exposed at 300 mJ / cm ^{2 to} produce a retardation material.

The produced retardation material was sandwiched by a pair of polarizing plates, and the performance of the retardation characteristics in the retardation material was observed. In order to display the alignment property of the alignment material, the necessary polarized UV exposure amount (mJ / cm ² ) was evaluated as the alignment sensitivity (maximum polarized UV exposure amount: performed at 50 mJ / cm ² ).

[Evaluation of pattern formation]

Each of the cured film-forming compositions of Examples 1 to 7 and Comparative Examples 1 to 3 was spin-coated on an alkali-free glass using a spin coater at 2000 rpm for 30 seconds, and then heated and dried on a hot plate at a temperature of 140 ° C. 120 seconds, a hardened film was formed. A linearly polarized light beam of 313 nm was irradiated vertically at 40 mJ / cm ² through a 100 μm line and a space mask through the cured film. After removing the mask and rotating the substrate by 90 degrees, linearly polarized light of 313 nm was irradiated at 20 mJ / cm ² vertically to obtain alignment materials having two types of liquid crystal alignment regions with liquid crystal alignment control directions different from each other by 90 degrees.

On the alignment material on this substrate, a polymer liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, followed by pre-baking at 60 ° C on a hot plate for 60 seconds to form a film. 1.0 μm thick coating film. The coating film on the substrate was exposed at 300 mJ / cm ^{2 to} produce a patterned retardation material.

The patterned retardation material on the produced substrate was observed with a polarizing microscope, and it was evaluated as ○ when the phase difference pattern was formed without alignment defects, and × when the alignment defects were found.

[Evaluation of light transmittance (transparency)]

Each of the cured film-forming compositions of Examples 1 to 7 was spin-coated on a quartz substrate using a spin coater at 2000 rpm for 30 seconds, and then heated and dried on a hot plate at a temperature of 180 ° C for 120 seconds to form a film. 300nm thick hardened film. The film thickness was measured using F20 by FILMETRICS. This hardened film uses an ultraviolet-visible light photometer (made by Shimadzu) (Made by SHIMADZU UV-2550 model), and measured light transmittance for light with a wavelength of 400 nm.

[evaluation result]

The results of the above evaluations are shown in Table 3.

Any of Examples 1 to 7 shows the alignment of the liquid crystal with a small exposure of 10 to 20 mJ / cm ² , that is, it has high alignment sensitivity and can be used for optical patterning. Furthermore, it exhibited high transparency.

On the other hand, Comparative Examples 1, 2 in which a compound having a specific crosslinkable substituent was not used, and Comparative Example 3, which is a low-molecular compound although having a specific crosslinkable substituent, were both at an exposure of 50 mJ / cm ² still cannot display liquid crystal alignment, that is, its alignment sensitivity is very low, and it is very difficult to perform optical pattern molding.

[Industrial possibilities]

The cured film-forming composition of the present invention is very useful as an alignment material for forming a liquid crystal alignment film for a liquid crystal display element or an optical anisotropic film provided inside or outside the liquid crystal display element, and is particularly suitable for use as a 3D display. Patterning material for forming a retardation material. Furthermore, it is a material suitable for forming protective films, flattening films, and insulating films on various displays such as thin-film transistor (TFT) liquid crystal display elements and organic EL elements, and is particularly suitable for forming TFT-type liquid crystal elements. Materials such as an interlayer insulating film, a protective film of a color filter, or an insulating film of an organic EL element.

Claims (5)

A hardened film-forming composition, comprising: (A) the following formula [A] having a photo-alignment group and at least one substituent selected from any one of a hydroxyl group, a carboxyl group, an amine group, and an alkoxysilyl group; -11] ~ [A-15] The compound represented by any one of [A-15], and (B) has a compound selected from the group consisting of an alkoxyformamido group, a hydroxyformamido group, and a trialkoxysilyl group ( A) Polymers that are thermally reactive and self-crosslinking;

In the foregoing formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and X ¹¹ is a single bond, an ether bond, an ester bond, a amide bond, a urethane bond, an amine bond, or the like One or two or more kinds of bonds selected from the combination, or one or two or more kinds of such bonds, from alkylene, phenylene, and biphenylene having 1 to 18 carbon atoms Or a combination of 1 to 3 kinds of substituents selected from these combinations, and the aforementioned substituents may also have a structure in which a plurality of each are connected by the aforementioned bonds, and 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, and at this time, an alkyl group, a phenyl group, a biphenyl group, and a cyclohexyl group having 1 to 18 carbon atoms, Two or more kinds of groups may be bonded by covalent bond, ether bond, ester bond, amido bond, or urea bond. X ¹³ represents a hydroxyl group, a mercapto group, an alkoxy group having 1 to 10 carbon atoms, and a carbon atom. Alkylthio, phenoxy, biphenyloxy or phenyl having a number of 1 to 10, and X ¹⁴ represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent Cycloaliphatic radical, here Atoms of 1 to 20 alkylene may also be branched, straight chain, X ¹⁵ represents a hydroxyl group-based, a carboxyl group, alkoxy group or silicon based, X ¹⁶ represents a single bond lines, an oxygen atom or a sulfur atom Moreover, in the case that these substituents contain a benzene ring, the benzene ring may also be selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, and trifluoromethyl Selected from the same or different substituents selected from the group consisting of cyano and cyano. In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each substituted. Independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group or a cyano group. The cured film-forming composition according to claim 1, further comprising (C) a crosslinking catalyst. The cured film-forming composition according to claim 1, wherein the weight average molecular weight of the polymer of the component (B) is 1,000 to 100,000. An alignment material, which is obtained by using a cured film-forming composition according to any one of claim 1 to claim 3. A retardation material formed by using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 3.