WO2020241642A1 - Cured film formation composition, alignment member, and retardation member - Google Patents

Abstract

[Problem] To provide: an alignment member that has excellent alignment sensitivity and alignment uniformity, is resistant to a solvent in a liquid crystal solution even when the alignment member is a thin film, and can function as a protection layer for protecting a film substrate; and a cured film formation composition for obtaining the alignment member. [Solution] This cured film formation composition contains (A) a compound having a photoalignable group and a substituent selected from the group consisting of a hydroxy group, a carboxyl group, and an amino group, (B) a polymer obtained by polymerization of monomers including at least an N-alkoxymethyl (meth)acrylamide compound, and (C) a polymer obtained by polymerization of monomers including at least an N-hydroxyalkyl (meth)acrylamide compound, and optionally further contains a crosslinking catalyst as a component (D) and an adhesion-improving component as a component (E). This cured film formation composition is used to form a cured film, and a photoalignment technique is utilized to form an alignment member. A polymerizable liquid crystal is applied to the alignment member and then cured to obtain a retardation member.

Description

Hardened film forming composition, alignment material and retardation material

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

In the case of a circularly polarized glasses type 3D display, a retardation material is usually arranged on a display element such as a liquid crystal panel that forms an image. In this retardation material, a plurality of two types of retardation regions having different retardation characteristics are regularly arranged to form a patterned retardation material. Hereinafter, in the present specification, a retardation material patterned so as to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in Patent Document 1. The optical patterning of a retardation material composed of a polymerizable liquid crystal utilizes a photoalignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-oriented material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photoalignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different orientation control directions of the liquid crystal are formed. A solution-like retardation material containing a polymerizable liquid crystal is applied onto the photoalignment film to realize the orientation of the polymerizable liquid crystal. Then, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

The antireflection film of the organic EL display is composed of a linear polarizing plate and a 1/4 wavelength retardation plate, and the external light directed to the panel surface of the image display panel is converted into linear polarized light by the linear polarizing plate, followed by 1/4 wavelength. It is converted to circularly polarized light by the retardation plate. Here, the external light due to this circular polarization is reflected by the surface of the image display panel or the like, but the rotation direction of the polarizing surface is reversed during this reflection. As a result, this reflected light is converted from the 1/4 wavelength retardation plate to linearly polarized light in the direction shaded by the linear polarizing plate, and then shielded by the subsequent linear polarizing plate, contrary to the time of arrival. As a result, the emission to the outside is remarkably suppressed.

Regarding this 1/4 wavelength retardation plate, Patent Document 2 describes that the optical film has inverse dispersion characteristics by forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate. The method of constructing by is proposed. In the case of this method, in a wide wavelength band used for displaying a color image, a liquid crystal material having a positive dispersion characteristic can be used to form an optical film having a reverse dispersion characteristic.

Further, in recent years, as a liquid crystal material applicable to this retardation layer, a material having a reverse dispersion characteristic has been proposed (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate to form a 1/4 wavelength retardation plate by two retardation layers, a retardation layer is used. Can be configured with a single layer to ensure inverse dispersion characteristics, whereby an optical film capable of securing a desired phase difference in a wide wavelength band can be realized with a simple configuration.

An alignment layer is used to orient the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method and a photo-alignment method are known. The photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can quantitatively control the alignment process. Is useful in.

In the formation of an alignment material using the photo-alignment method, acrylic resin, polyimide resin, etc., which have photodimerization sites such as a cinnamoyl group and a chalcone group in the side chain, are known as usable photo-orientation materials. It has been reported that these resins exhibit the ability to control the orientation of liquid crystals (hereinafter, also referred to as liquid crystal orientation) by irradiating with polarized UV (see Patent Documents 5 to 7).

In addition, the alignment layer is required to have solvent resistance as well as liquid crystal alignment ability. 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, the liquid crystal alignment ability may be significantly reduced.

Therefore, for example, in Patent Document 8, in order to obtain a stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of a cross-linking reaction by light and a structure cross-linked by heat, and light are used. A liquid crystal alignment agent containing a polymer component having a structure capable of a cross-linking reaction and a compound having a structure cross-linked by heat has been proposed.

Japanese Unexamined Patent Publication No. 2005-49965 Japanese Unexamined Patent Publication No. 10-68816 U.S. Pat. No. 8119026 JP-A-2009-179563 Japanese Patent No. 361342 JP-A-2009-058584 Special Table 2001-517719 Japanese Patent No. 4207430

As described above, the retardation material is formed by laminating a layer of a cured polymerizable liquid crystal on a photoalignment film which is an alignment material. Therefore, it is necessary to develop an alignment material capable of achieving both excellent liquid crystal orientation and solvent resistance.

However, according to the study by the present inventor, it has been found that an acrylic resin having a photodimerization site such as a cinnamoyl group or a chalcone group in the side chain does not have sufficient characteristics when applied to the formation of a retardation material. ing. In particular, in order to irradiate these resins with polarized UV to form an alignment material and to produce a retardation material made of a polymerizable liquid crystal using the alignment material, a large amount of polarized UV exposure is required. The polarized UV exposure amount is much larger than the polarized UV exposure amount (for example, about 30 mJ / cm ² ) sufficient to orient the liquid crystal for a normal liquid crystal panel.

The reason why the amount of polarized UV exposure increases is that in the case of retardation material formation, unlike the liquid crystal for liquid crystal panels, the polymerizable liquid crystal is used in a solution state and is applied on the alignment material. There is.

When an alignment material is formed using an acrylic resin or the like having a photodimerization site such as a cinnamoyl group in the side chain to orient a polymerizable liquid crystal, the acrylic resin or the like is photocrosslinked by a photodimerization reaction. .. Then, it is necessary to perform polarized irradiation with a large exposure amount until resistance to the polymerizable liquid crystal solution is developed. In order to orient the liquid crystal of the liquid crystal panel, it is usually sufficient to carry out the dimerization reaction only on the surface of the photo-oriented aligning material. However, in order to develop solvent resistance in the alignment material using the above-mentioned conventional material such as acrylic resin, it is necessary to react even inside the alignment material, and a larger amount of exposure is required. As a result, there is a problem that the orientation sensitivity of the conventional material becomes very small.

Further, a technique of adding a cross-linking agent is known in order to develop such solvent resistance in the resin which is the above-mentioned conventional material. However, it is known that after the thermosetting reaction with a cross-linking agent, a three-dimensional structure is formed inside the coating film to be formed, and the photoreactivity is lowered. That is, the orientation sensitivity is greatly reduced, and even if a cross-linking agent is added to the conventional material and used, the desired effect is not obtained.

Further, although various organic solvents are used for the liquid crystal ink, a film having low resistance to the organic solvent may be used as the substrate, and for the purpose of protecting the film, an alignment film having high solvent resistance is used. It has been demanded.

From the above, a photo-alignment technique capable of improving the orientation sensitivity of the alignment material and reducing the amount of polarized UV exposure, and a cured film forming composition that can be used as a liquid crystal alignment agent for photo-alignment used for forming the alignment material are required. Has been done. Then, there is a demand for a technique capable of providing a retardation material with high efficiency.

The object of the present invention has been made based on the above findings and examination results. That is, an object of the present invention is to have excellent orientation sensitivity, excellent orientation uniformity, resistance to a solvent in a liquid crystal solution even if it is a thin film, and also as a protective layer for protecting a film substrate. The purpose of the present invention is to provide a cured film forming composition that can be used as a liquid crystal alignment agent for photoalignment to provide a functional alignment material.

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

The first aspect of the present invention is
(A) A compound having a photo-oriented group and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group.
(B) Containing a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound, and (C) containing a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound. The present invention relates to a cured film-forming composition.

In the first aspect of the present invention, it is preferable that the photooriented group of the component (A) is a functional group having a structure of photodimerification or photoisomerization. In the first aspect of the present invention, the light of the component (A) The orientation group is preferably a cinnamoyl group.
In the first aspect of the present invention, it is preferable that the photooriented group of the component (A) is a group having an azobenzene structure.
In the first aspect of the present invention, it is preferable to further contain a cross-linking catalyst as the component (D).
In the first aspect of the present invention, it is preferable that the component (E) further contains an adhesion improving component.
In the first aspect of the present invention, the total amount of the component (B) and the component (C) is preferably 100 to 3000 parts by mass based on 100 parts by mass of the component (A).
In the first aspect of the present invention, the mass ratio of the component (B) to the component (C) is preferably 1:99 to 99: 1.
In the first aspect of the present invention, it is preferable to contain 0.01 parts by mass to 10 parts by mass of the component (D) based on 100 parts by mass of the total amount of the component (B) and the component (C).

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

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

According to the first aspect of the present invention, it has excellent orientation sensitivity, excellent orientation uniformity, resistance to a solvent in a liquid crystal solution even if it is a thin film, and protection for protecting a film substrate. A cured film-forming composition for providing an alignment material that can also function as a layer can be provided.

According to the second aspect of the present invention, it has excellent orientation sensitivity, excellent orientation uniformity, resistance to a solvent in a liquid crystal solution even if it is a thin film, and protection for protecting a film substrate. An alignment material that can also function as a layer can be provided.

According to the third aspect of the present invention, it is possible to provide a retardation material which can be formed on a film substrate with high efficiency and can be optically patterned.

<Cured film forming composition>
The cured film-forming composition of the present invention is a compound having a photo-oriented group which is a component (A) and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group (hereinafter, "low molecular weight"). It is also described as "photo-alignment component"), a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound which is a component (B), and at least N-hydroxyalkyl which is a component (C) (C). Meta) Contains a polymer obtained by polymerizing a monomer containing an acrylamide compound. In addition to the components (A), (B), and (C), the cured film-forming composition of the present invention further improves the adhesion of the cured film as a component (D), a cross-linking catalyst, and a component (E). It can also contain a component that causes it. Then, other additives can be contained as long as the effects of the present invention are not impaired.

The details of each component will be described below.
<Ingredient (A)>
The component (A) contained in the cured film-forming composition of the present invention is the above-mentioned low-molecular-weight photoalignment component.

The low-molecular-weight photo-oriented component (A) is a compound having a photo-oriented group and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group. In a compound having a photo-oriented group and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group, as described above, the photo-oriented group reacts with light to make hydrophobic light. An oriented portion is formed, and a hydroxy group or the like constitutes a hydrophilic thermal reaction portion.
In the present invention, the photo-oriented group refers to a functional group having a structural site that undergoes photodimerization or photoisomerization.

The photodimerizable structural site is a site that forms a dimer by light irradiation, and specific examples thereof include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group having high transparency and photodimerization reactivity in the visible light region is preferable. Further, the structural site that photoisomerizes refers to a structural site that changes into a cis form and a trans form by light irradiation, and specific examples thereof include a site having an azobenzene structure, a stilbene structure, and the like. Of these, the azobenzene structure is preferable because of its high reactivity. A compound having a photo-oriented group and a hydroxy group is represented by, for example, the following formula.

In the formula [A1] or the formula [A5], respectively ^{A 1} and ^{A 2} independently represent a hydrogen atom or a methyl group, ^{X 1} is a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, amino bond Alternatively, an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or 1 to 3 groups selected from a combination thereof are bonded via one or more bonds selected from a combination thereof. Represents a divalent group. X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. At that time, the alkyl group, phenyl group, biphenyl group and cyclohexyl group having 1 to 18 carbon atoms may be bonded to the benzene ring via a covalent bond, an ether bond, an ester bond, an amide bond or a urea bond. X ⁵ represents a hydroxy group, a carboxyl group, an amino group or an alkoxysilyl group. X represents a single bond, an oxygen atom or a sulfur atom. X ⁶ 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 phenyl group, a phenoxy group or a biphenoxy group. X ⁷ is a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent group obtained by removing two hydrogen atoms from an aromatic ring, or a divalent group obtained by removing two hydrogen atoms from an aliphatic ring. Represent. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

In these substituents, the phenylene group, the phenyl group, the biphenylene group, the biphenyl group, the phenoxy group and the biphenoxy group are alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, halogen atoms, and the like. It may be substituted with the same or different substituents selected from the trifluoromethyl group and the cyano group.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, and 1 carbon atom, respectively. Represents 4 to 4 alkoxy groups, halogen atoms, trifluoromethyl groups or cyano groups.

Examples of the alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl. Group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -N-Butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group Group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl Group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n- Hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n -Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n -Pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n- Examples thereof include decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.
Examples of the alkylene group having 1 to 18 carbon atoms include a divalent group obtained by removing one hydrogen atom from the above-mentioned alkyl group.
Examples of the alkyl group having 1 to 4 carbon atoms include the group having the corresponding carbon atom number among the groups listed above.
The alkoxy group having 1 to 10 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the alkylthio group having 1 to 10 carbon atoms include the above-mentioned alkyl group oxylated or thiolated. The group having the corresponding number of carbon atoms can be mentioned.
The alkylene group having 1 to 20 carbon atoms includes the alkyl group and a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms such as an n-nonadesyl group and an n-eicosyl group. Can be mentioned.

Specific examples of the compound having a photoorientating group and a hydroxy group, which are the components (A), include 4- (8-hydroxyoctyloxy) silicic acid methyl ester and 4- (6-hydroxyhexyloxy) kei. Methyl Ester, 4- (4-Hydroxybutyloxy) Methyl Ceramic Acid, 4- (3-Hydroxypropyloxy) Methyl Ceramic Acid, 4- (2-Hydroxyethyloxy) Methyl Ceramic Acid, 4-Hydroxymethyloxy silicate methyl ester, 4-hydroxysilicic acid methyl ester, 4- (8-hydroxyoctyloxy) silicate ethyl ester, 4- (6-hydroxyhexyloxy) silicate ethyl ester, 4- (4-Hydroxybutyloxy) silicic acid ethyl ester, 4- (3-hydroxypropyloxy) silicic acid ethyl ester, 4- (2-hydroxyethyloxy) silicic acid ethyl ester, 4-hydroxymethyloxy Ethyl silicate ester, 4-hydroxy silicate ethyl ester, 4- (8-hydroxyoctyloxy) phenyl ester silicate, 4- (6-hydroxyhexyloxy) phenyl silicate ester, 4- (4- (4-) Hydroxybutyloxy) silicate phenyl ester, 4- (3-hydroxypropyloxy) phenyl ester silicate, 4- (2-hydroxyethyloxy) phenyl ester silicate, 4-hydroxymethyloxy phenyl ester silicate , 4-Hydroxysilicic acid phenyl ester, 4- (8-Hydroxyoctyloxy) citrus acid biphenyl ester, 4- (6-hydroxyhexyloxy) silicate biphenyl ester, 4- (4-hydroxybutyloxy) kei Biphenyl Ester, 4- (3-Hydroxypropyloxy) Biphenyl Esterate, 4- (2-Hydroxyethyloxy) Biphenyl Esterate, 4-Hydroxymethyloxy Biphenyl Esterate, 4-Hydroxy Biphenyl ester of dermal acid, 8-hydrochioctyl ester of silicate, 6-hydroxyhexyl ester of silicate, 4-hydroxybutyl ester of cinnamic acid, 3-hydroxypropyl ester of silicate, 2-hydroxyethyl ester of silicate, Hydroxymethyl ester of silicate, 4- (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4- (4-) Hydroxybutyloxy) azobenzene, 4- (3-hydroxypropyloxy) azobenzene, 4- (2-hydroxyethyloxy) azobenzene, 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-hydroxymethyloxy Calcon, 4-hydroxycalcon, 4'-(8-hydroxyoctyloxy) calcon, 4'-(6-hydroxyhexyloxy) calcon, 4'-(4-hydroxybutyloxy) calcon, 4'-(3-hydroxy) Propyloxy) chalcone, 4'-(2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) ) Kumarin, 7- (4-Hydroxybutyloxy) Kumarin, 7- (3-Hydroxypropyloxy) Kumarin, 7- (2-Hydroxyethyloxy) Kumarin, 7-Hydroxymethyloxy Kumarin, 7-Hydroxykumarin, 6- Hydroxyoctyloxykumarin, 6-hydroxyhexyloxykumarin, 6- (4-hydroxybutyloxy) coumarin, 6- (3-hydroxypropyloxy) coumarin, 6- (2-hydroxyethyloxy) coumarin, 6-hydroxymethyloxy Examples include coumarin and 6-hydroxycoumarin.

Specific examples of the compound having a photoorientation group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, 3,4-dimethoxycinnamic acid, and coumarin-3. -Carboxylic acid, 4- (dimethylamino) cinnamic acid and the like can be mentioned.
Specific examples of the compound having a photo-oriented group and an amino group include methyl 4-aminosilicate, ethyl 4-aminosilicate, methyl 3-aminosilicate, ethyl 3-aminosilicate and the like. Can be mentioned.
The low-molecular-weight photoalignment component (A) can be given the above specific examples, but is not limited thereto.

When the low-molecular-weight photo-oriented component (A) is a compound having a photo-oriented group and a hydroxy group, two or more photo-oriented groups and two or more photo-oriented groups are contained in the molecule as the component (A). / Or a compound having two or more hydroxy groups can be used. Specifically, as the component (A), a compound having two or more photo-oriented groups with one hydroxy group in the molecule, or two or more hydroxy groups with one photo-oriented group in the molecule. It is possible to use a compound having two or more photo-oriented groups and two or more hydroxy groups in the molecule. For example, for a compound having two or more photo-oriented groups and two or more hydroxy groups in the molecule, a compound represented by the following formula can be shown as an example.

By appropriately selecting such a compound, it is possible to control the increase in the molecular weight of the low molecular weight photoalignment component which is the component (A). As a result, as will be described later, when the low molecular weight photoalignment component which is the component (A) and the polymer which is the component (B) and the polymer which is the component (C) undergo a thermal reaction, the component (A) is used. It is possible to suppress the sublimation of low molecular weight photoalignment components. Then, the cured film forming composition of the present invention can form an alignment material having high photoreaction efficiency as a cured film.

Further, as the compound of the component (A) in the cured film forming composition of the present invention, there are a plurality of types having a photoorienting group and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group. It may be a mixture of the compounds of.

<Ingredient (B)>
The component (B) contained in the cured film-forming composition of the present invention is a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound. In addition, N-alkoxymethyl (meth) acrylamide means both N-alkoxymethylacrylamide and N-alkoxymethylmethacrylamide.

Examples of such a polymer include a polymer obtained by copolymerizing an N-alkoxymethyl (meth) acrylamide compound alone or with a copolymerizable monomer. Examples of such a polymer include poly (N-butoxymethylacrylamide), poly (N-ethoxymethylacrylamide), poly (N-methoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, and N. -Copolymers of butoxymethylacrylamide and methylmethacrylate, copolymers of N-ethoxymethylmethacrylate and benzylmethacrylate, and copolymers of N-butoxymethylacrylamide, benzylmethacrylate and 2-hydroxypropylmethacrylate, etc. Can be mentioned.

The method for obtaining the polymer as the component (B) used in the present invention is not particularly limited, but for example, a solvent in which an N-alkoxymethyl (meth) acrylamide compound, a optionally copolymerizable monomer, a polymerization initiator and the like coexist. It is obtained by subjecting it to a polymerization reaction at a temperature of 50 to 110 ° C. At that time, the solvent used is not particularly limited as long as it dissolves an N-alkoxymethyl (meth) acrylamide compound, a optionally copolymerizable monomer, a polymerization initiator and the like. Specific examples will be described in <Solvent> described later.
The polymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

Further, the polymer solution obtained by the above method is poured into diethyl ether or water under stirring to precipitate, and the resulting precipitate is filtered and washed, and then dried or heated at room temperature under normal pressure or reduced pressure. It can be dried to a polymer powder. By the above operation, the polymerization initiator and the unreacted monomer coexisting with the polymer can be removed, and as a result, a purified polymer powder is obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the present invention, the polymer as the component (B) may be used in the form of a powder, or in the form of a solution in which the purified powder is redissolved in a solvent described later.

Further, in the present invention, the polymer as the component (B) may be a mixture of a plurality of types of polymers.

In the present invention, when the above-mentioned copolymerizable monomer is used when producing the polymer which is the component (B), the amount of the copolymerizable monomer used is used to produce the polymer of the component (B). Based on the total number of moles of the monomers used, it is preferably 1 mol% to 200 mol%, more preferably 10% to 100 mol%.

The weight average molecular weight of the polymer as the component (B) is 1,000 to 500,000, preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. Yes, more preferably 3,000 to 50,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

The polymers of the component (B) can be used alone or in combination of two or more.

<Component (C)>
The component (C) is a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound. In addition, N-hydroxyalkyl (meth) acrylamide means both N-hydroxyalkylacrylamide and N-hydroxyalkylmethacrylamide.

When the composition of the present invention is used as a coating film and heat-cured, the N-alkoxymethyl group of the component (B) reacts with the hydroxy group of the component (C) to form a bond. As a result, the coating film becomes strong and solvent resistance is acquired.

Examples of the N-hydroxyalkyl (meth) acrylamide compound include N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxypropyl) acrylamide, and N- (2-hydroxypropyl). ) Methacrylate, N- (4-hydroxybutyl) acrylamide, N- (4-hydroxybutyl) methacrylamide, N- (2,3-dihydroxypropyl) acrylamide, N- (2,3-dihydroxypropyl) methacrylamide, etc. Can be mentioned.

In the present invention, when producing the polymer of the component (C), a monomer other than the above N-hydroxyalkyl (meth) acrylamide compound (hereinafter, also referred to as “other monomer”) may be copolymerized.
In the present invention, when other monomers are used in producing the polymer of the component (C), the amount of the other monomers used is the number of moles of the monomers used in producing the polymer of the component (C). Based on the total, it is preferably 30 mol% to 90 mol%, more preferably 30% to 70 mol%.

Examples of other monomers include industrially available monomers capable of radical polymerization.

Specific examples of other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, amide group-containing monomers, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and the like.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, and tert-. Butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2 -Propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, diethylene glycol monoacrylate, caprolactone 2- (Acryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, acryloylethyl isocyanate, and 8-ethyl-8-tri Cyclodecyl acrylate, glycidyl acrylate and the like can be mentioned.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate and tert-. Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ -Buchirolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, Diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, methacryloylethyl isocyanate, and 8- Examples thereof include ethyl-8-tricyclodecyl methacrylate and glycidyl methacrylate.

Examples of the amide group-containing monomer include N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-butyl. (Meta) acrylamide, N-isobutyl (meth) acrylamide, N-hexyl (meth) acrylamide, N-octyl (meth) acrylamide, N- (methoxymethyl) (meth) acrylamide, N- (methoxybutyl) (meth) acrylamide , N- (ethoxymethyl) (meth) acrylamide, N- (butoxymethyl) (meth) acrylamide, N- (isobutoxymethyl) (meth) acrylamide, N- (isobutoxyethyl) (meth) acrylamide, N-vinyl Examples thereof include phthalimide and N-vinylsuccinate imide.

Examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinyl anthracene, vinyl biphenyl, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, propyl vinyl ether and the like.

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

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

Examples of the acrylonitrile compound include acrylonitrile.

The method for obtaining the polymer as the component (C) used in the present invention is not particularly limited, but in the method for producing the polymer as the component (B), N-hydroxyalkyl (instead of the N-alkoxymethyl (meth) acrylamide compound) ( A meta) acrylamide compound may be used.

The weight average molecular weight of the polymer as the component (C) is 1,000 to 500,000, preferably 2,000 to 200,000, and more preferably 3,000 to 150,000. Yes, more preferably 3,000 to 100,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample.

The polymers of the component (C) can be used alone or in combination of two or more.

The content of the polymer which is the component (B) and the polymer which is the component (C) in the cured film forming composition of the present invention is based on 100 parts by mass of the component (A), and the component (B) and the component (C). The total amount with the components is preferably 100 to 3000 parts by mass, more preferably 200 to 2500 parts by mass, and particularly preferably 300 to 2000 parts by mass.

The mass ratio of the component (B) to the component (C) is preferably 1:99 to 99: 1, more preferably 5:95 to 95: 5, and 10:90 to 90: 5. It is particularly preferable to be 10.

<Ingredient (D)>
The cured film-forming composition of the present invention can further contain a cross-linking catalyst as a component (D) in addition to the components (A), (B) and (C).
As the cross-linking catalyst as the component (D), for example, an acid or a thermoacid generator can be used. This component (D) is effective in accelerating the thermosetting reaction of the cured film-forming composition of the present invention.

Examples of the acid include sulfonic acid group-containing compounds, hydrochloric acid or salts thereof. The thermal acid generator is particularly limited as long as it is a compound that thermally decomposes during prebaking or postbaking to generate an acid, that is, a compound that thermally decomposes at a temperature of 80 ° C to 250 ° C to generate an acid. is not.
Examples of the acid include hydrochloric acid or a salt thereof; methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphasulfonic acid, trifluo. Lomethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mecitylene sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene sulfonic acid, 1H, 1H, 2H, 2H-Perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, sulfonic acid such as dodecylbenzene sulfonic acid or hydrates and salts thereof, etc. Can be mentioned.
Examples of compounds that generate acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-. Fenilentris (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-toluene Ssulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, Examples thereof include N-ethyl-p-toluenesulfoneamide and compounds represented by the following formulas.

The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 parts by mass or more based on 100 parts by mass of the total amount of the polymer of the component (B) and the polymer of the component (C). It is 10 parts by mass, more preferably 0.1 part by mass to 6 parts by mass, and further preferably 0.5 part by mass to 5 parts by mass. By setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted, and further, high sensitivity to light irradiation can be imparted. However, if it is more than 10 parts by mass, the storage stability of the composition may decrease.

<Ingredient (E)>
The cured film forming composition of the present invention may also contain, as the component (E), a component that improves the adhesion of the formed cured film (hereinafter, also referred to as an adhesion improving component).

The adhesion improving component (E) is a polymerizable functional group and an alignment material of the polymerizable liquid crystal so as to improve the adhesion between the alignment material obtained from the cured film forming composition of the present invention and the layer of the polymerizable liquid crystal. The cross-linking reaction sites of the above can be linked by covalent bonds. As a result, the retardation material of the present embodiment, which is formed by laminating a cured polymerizable liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under high temperature and high quality conditions, and can be peeled off or the like. Can show high durability against.

As the component (E), a monomer and a polymer having a group selected from a hydroxy group and an N-alkoxymethyl group and a polymerizable group are preferable.
Such (E) components include a compound having a hydroxy group and a (meth) acrylic group, a compound having an N-alkoxymethyl group and a (meth) acrylic group, and an N-alkoxymethyl group and a (meth) acrylic group. Examples thereof include polymers having. Specific examples are shown below.

As an example of the component (E), a hydroxy group-containing polyfunctional acrylate (hereinafter, also referred to as a hydroxy group-containing polyfunctional acrylate) can be mentioned.
Examples of the hydroxy group-containing polyfunctional acrylate that is an example of the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

An example of the component (E) is a compound having one (meth) acrylic group and one or more hydroxy groups.

Further, examples of the compound of the component (E) include a compound having at least one polymerizable group containing a C = C double bond in one molecule and at least one N-alkoxymethyl group.

Examples of the polymerizable group containing a C = C double bond include an acrylic group, a methacryl group, a vinyl group, an allyl group, and a maleimide group.

As a compound having at least one polymerizable group containing a C = C double bond and at least one N-alkoxymethyl group in one molecule, for example, a compound represented by the following formula (X1) is preferable. Can be mentioned.

(In the formula, R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms).

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl. Group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-Dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -N-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group Group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl Group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n- Hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n -Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl- n-Pentyl group, 2-methyl-2-ethyl-n-Pentyl group, 2-methyl-3-ethyl-n-Pentyl group, 3-Methyl-3-ethyl-n-Pentyl group, n-nonyl group, n -Examples include a decyl group.

Specific examples of the compound represented by the above formula (X1) include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth). Examples thereof include an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group such as acrylamide or an alkoxymethyl group. Note that (meth) acrylamide means both methacrylamide and acrylamide.

Another embodiment of the compound having a polymerizable group containing a C = C double bond and an N-alkoxymethyl group of the component (E) is preferably, for example, the following compound.

The content of the component (E) in the cured film forming composition of the present invention is preferably 1 part by mass to 100 parts by mass based on 100 parts by mass of the low molecular weight photoalignment component which is the component (A). More preferably, it is 5 parts by mass to 70 parts by mass.

<Solvent>
The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at that time may be sufficient as long as it can dissolve the component (A), the component (B) and the component (C), and if necessary, the component (D), the component (E) and / or other additives described later. The type and structure are not particularly limited.

Specific examples of the solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. , Propropylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, Ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, Examples thereof include methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like. .. These solvents can be used alone or in combination of two or more.

<Other additives>
Further, the cured film-forming composition of the present invention is, if necessary, a sensitizer, a silane coupling agent, a surfactant, a rheology adjuster, a pigment, a dye, and storage stability as long as the effects of the present invention are not impaired. It can contain agents, antifoaming agents, antioxidants and the like.

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

Examples of the sensitizer, which is an example of other additives, include benzophenone, anthracene, anthraquinone, thioxanthone and its derivatives, derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of preferred compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone. , 5-Nitroindole and the like. In particular, N, N-diethylaminobenzophenone, which is a derivative of benzophenone, is preferable.

These sensitizers are not limited to the above. In addition, the sensitizer can be used alone or in combination of two or more compounds.

The ratio of the sensitizer used in the cured film forming composition of the present invention is preferably 0.1 part by mass to 20 parts by mass based on 100 parts by mass of the low molecular weight photoalignment component of the component (A). , More preferably 0.2 parts by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance may be lowered and the coating film may be roughened.

<Preparation of cured film forming composition>
The cured film-forming composition of the present embodiment is formed by polymerizing a monomer containing a low-molecular-weight photoalignment component which is a component (A) and at least an N-alkoxymethyl (meth) acrylamide compound which is a component (B). It contains a polymer and a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound which is a component (C). Then, if necessary, a cross-linking catalyst as a component (D), an adhesion improving component as a component (E), and / or other additives can be contained.

The blending ratio, preparation method, etc. when the cured film-forming composition of the present invention is used as a solution will be described in detail below.
The proportion of the solid content in the cured film-forming composition of the present 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 3. It is from mass% to 60% by mass, more preferably 5% by mass to 40% by mass. Here, the solid content refers to a composition obtained by removing the solvent 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. As a preparation method, for example, the component (A), the component (C) and, if necessary, the component (D) and the component (E) are mixed in a solution of the component (B) dissolved in a solvent at a predetermined ratio and uniformly. A method of preparing a solution, or a method of further adding and mixing other additives as needed at an appropriate stage of this preparation method can be mentioned.

In the preparation of the cured film-forming composition of the present invention, the polymer solution obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (A), the component (B) and, if necessary, the components (D) and (E) are added to the solution of the component (C) to make a uniform solution. At this time, an additional solvent may be added for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the component (C) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

Further, it is preferable that the prepared solution of the cured film-forming composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.

<Hardened film, alignment material and retardation material>
The solution of the cured film forming composition of the present invention is applied to a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, ITO. Bar coat, rotary coating, sink coating, roll coating, slit on a substrate, etc.) or film (for example, resin film such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film). A cured film can be formed by applying by coating, rotary coating following a slit, inkjet coating, printing, or the like to form a coating film, and then heating and drying in a hot plate or an oven.

As a condition of heat drying, it is sufficient that the cross-linking reaction by the cross-linking agent proceeds to the extent that the component of the alignment material formed from the cured film does not elute into the polymerizable liquid crystal solution applied thereto. For example, the temperature is 60. A heating temperature and heating time appropriately selected from the range of ° C. to 200 ° C. and a time of 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70 ° C. to 160 ° C., 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 is appropriately selected in consideration of the step of the substrate to be used and the optical and electrical properties. Can be done.

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

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

Since the alignment material formed 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 onto the alignment material, and then the liquid crystal is used. By heating to the phase transition temperature, the retardation material is put into a liquid crystal state and oriented on the alignment material. Then, by curing the alignment material in the oriented state as it is, the retardation material can be formed 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 are used. When the substrate forming the alignment material is a film, the film having the retardation material of the present invention is useful as the retardation film. Some retardation materials that form such retardation materials are in a liquid crystal state and take orientation states such as horizontal orientation, cholesteric orientation, vertical orientation, and hybrid orientation on the alignment material, and are required for each. It can be used properly according to the phase difference.

Further, in the case of producing a patterned retardation material used for a 3D display, a predetermined cured film formed from the cured film forming composition of the present invention is formed on a cured film formed by the above method via a line-and-space pattern mask. From the reference, for example, polarized UV exposure is performed in the direction of +45 degrees, then polarized UV is exposed in the direction of -45 degrees after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal orientation control directions are formed. Obtain the alignment material. Then, after applying a retardation material composed of a polymerizable liquid crystal solution, the retardation material is brought into a liquid crystal state by heating to the phase transition temperature of the liquid crystal, and is oriented on the alignment material. Then, the retarded material in the oriented state is cured as it is, and a patterned retardation material in which a plurality of two types of retardation regions having different retardation characteristics are regularly arranged can be obtained.

Further, using two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are laminated so as to face each other via a spacer, and then between the substrates. It is also possible to inject a liquid crystal into a liquid crystal display element in which the liquid crystal is oriented.
As described above, the cured film forming composition of the present invention can be suitably used for producing various retardation materials (phase difference films), liquid crystal display elements, and the like.

Hereinafter, the present invention will be specifically described with reference to examples of the present invention, but the present invention is not construed as being limited to these.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Raw materials>
BMAA: N-butoxymethylacrylamide AIBN: α, α'-azobisisobutyronitrile MMA: Methyl methacrylate HEAA: N- (2-hydroxyethyl) Acrylamide MAIB: Dimethyl 2,2-azobisisobuty

<Component A>
MCA: 4-Methoxycinnamic acid

<B component>
PB-1: It is represented by the following structural formula.

<C component>
PC-1: It is represented by the following structural formula.

PC-2: It is represented by the following structural formula.

<D component>
PTSA: p-toluenesulfonic acid monohydrate

<E component>
E-1: Compound having N-alkoxymethyl group and acrylic group represented by the following structural formula

<Solvent>
Each of the resin compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM) and butyl acetate (BA) were used as the solvent.

<Measurement of molecular weight of polymer>
For the molecular weight of the acrylic copolymer in the polymerization example, a gel permeation chromatography (GPC) apparatus (HLC-8320) manufactured by Toso Co., Ltd. and a column manufactured by Toso Co., Ltd. (TSKgel ALPHA4000, TSKgel ALPHA3000) were used. It was measured as follows.
The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.
Column temperature: 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / Standard sample for preparing a calibration curve: Standard polystyrene manufactured by Tosoh Corporation (molecular weight 427,000, 190,000, 37,900, 18,100, 5,970,2) 420, 1,010)

<Synthesis of component B>
<Polymerization Example-1>
An acrylic polymer solution was obtained by dissolving 100.0 g of BMAA and 1.0 g of AIBN as a polymerization catalyst in 193.5 g of PM and reacting at 80 ° C. for 20 hours. The obtained acrylic polymer had Mn of 10,000 and Mw of 23,000. The acrylic polymer solution was gradually added dropwise to 2000.0 g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain a polymer (PB-1).

<Synthesis of C component>
<Polymerization example-2>
7.0 g of MMA, 5.8 g of HEAA, and 0.23 g of MAIB as a polymerization catalyst were dissolved in 13.0 g of PM. An acrylic polymer solution was obtained by adding 6.50 g of PM to a four-necked flask in advance, dropping the dissolved solution into a dropping tank heated to 85 ° C. over 3 hours, and reacting under reflux for 3 hours. The obtained acrylic polymer had Mn of 12,600 and Mw of 43,100. A 40% PM solution of the target polymer (PC-1) was obtained.

<Synthesis of C component>
<Polymerization example-3>
47.10 g of BMAA, 34.5 g of HEAA, and 0.829 g of MAIB as a polymerization catalyst were dissolved in 82.50 g of PM. An acrylic polymer solution was obtained by adding 41.25 g of PM to a four-necked flask in advance, dropping the dissolved solution into a dropping tank heated to 85 ° C. over 3 hours, and reacting for 5 hours after the dropping. The obtained acrylic polymer had Mn of 6,500 and Mw of 17,000. A 40% PM solution of the target polymer (PC-2) was obtained.

<Preparation of liquid crystal alignment agent (cured film forming composition)>
<Preparation Example 1>
0.079 g of MCA as the component (A), 0.66 g of PB-1 obtained in Polymerization Example-1 as the component (B), and 40 of the polymer (PC-1) obtained in Polymerization Example-2 as the component (C). 0.26 g of% PM solution, 0.056 g of E-1 as component (E) (94.6% BA solution manufactured by Genuine Chemical Co., Ltd.), and 0.021 g of PTSA as component (D) were mixed and mixed with this. 6.65 g of PM and 1.62 g of BA as a solvent were added and stirred for 1 hour, and it was visually confirmed that the solution was obtained to obtain a solution. Then, the obtained solution was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal alignment agent (A-1).

<Preparation Examples 2 to 6>
The same procedure as in Preparation Example 1 was carried out except that each component of the type and blending amount shown in Table 1 below was used, and the liquid crystal alignment agents (A-2) to (A-4), (B-1), ( B-2) was prepared.

APEPO-1: RFK-505 (manufactured by Kawasaki Kasei Chemicals Co., Ltd.)
PEPO-1: Polylite 8651 (manufactured by DIC Corporation)

<Preparation of polymerizable liquid crystal solution for horizontal orientation>
<Production example 1>
LC-242 1.57 g (manufactured by BASF), which is a polymerizable liquid crystal for horizontal orientation, 0.047 g (manufactured by BASF), which is a photoradical initiator, and 0.008 g of BYK-361N, which is a leveling material, are added. 6.55 g of N-methylpyrrolidone (NMP) and 9.83 g of cyclopentanone were added as a solvent, and the mixture was stirred for 2 hours and visually confirmed to be dissolved to obtain a 9% by mass polymerizable liquid crystal solution LC-1. It was.

<Formation of liquid crystal alignment film and fabrication of retardation film>
<Example 1>
The liquid crystal alignment agent (A-1) prepared in Preparation Example 1 was applied onto a triacetyl cellulol (TAC) film as a substrate using a bar coater at a Wet film thickness of 6 μm. A cured film was formed on the film by heating and drying at 130 ° C. for 2 minutes in a heat-circulating oven. Next, the surface of the cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure amount of 10 mJ / cm ² to form a liquid crystal alignment film. A polymerizable liquid crystal solution LC-1 for horizontal alignment was applied onto the liquid crystal alignment film using a bar coater with a Wet film thickness of 34 μm. Next, after heat-drying at 120 ° C. for 2 minutes in an oven, the polymerizable liquid crystal was cured by vertically irradiating it with unpolarized light at 365 nm under nitrogen at an exposure amount of 300 mJ / cm ² , and the phase difference was obtained. A film was made.

<Examples 2 to 4>
Using (A-2) to (A-4) as the liquid crystal alignment agents, a retardation film was prepared by the same operation as in Example 1.

<Comparative example 1>
The liquid crystal alignment agent (B-1) prepared in Preparation Example 1 was applied onto a TAC film as a substrate with a Wet film thickness of 4 μm using a bar coater. A cured film was formed on the film by heating and drying at 130 ° C. for 2 minutes in a heat-circulating oven. Next, the surface of the cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure amount of 10 mJ / cm ² to form a liquid crystal alignment film. A polymerizable liquid crystal solution LC-1 for horizontal alignment was applied onto the liquid crystal alignment film using a bar coater with a Wet film thickness of 34 μm. Next, after heat-drying at 120 ° C. for 2 minutes in an oven, the polymerizable liquid crystal was cured by vertically irradiating it with unpolarized light at 365 nm under nitrogen at an exposure amount of 300 mJ / cm ² , and the phase difference was obtained. A film was made.

<Comparative example 2>
Using (B-1) as the liquid crystal alignment agent, the same operation as in Comparative Example 1 was carried out to prepare a retardation film.

Each retardation film produced above was evaluated by the following method. The evaluation results are shown in Table 2.

<Evaluation of orientation>
The retardation film on the prepared substrate was sandwiched between a pair of polarizing plates, and the appearance of the retardation characteristics under cross Nicol was visually observed. Those in which the phase difference is expressed without defects are marked with ◯, and those in which the phase difference is not expressed are marked with x, and are described in the “Orientation” column.

<TAC protection>
The non-curled retardation film including the prepared TAC film was marked with 〇, and the curled film was marked with x in the “Protectiveness” column.

From the results in Table 2, by using a polymer obtained by polymerizing a monomer containing an N-hydroxyalkyl (meth) acrylamide compound as the component (C), orientation with respect to a liquid crystal solution containing NMP can be obtained, and by NMP. It is clear that damage to the TAC film can also be protected.

The cured film forming composition according to the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display element or an optically anisotropic film provided inside or outside the liquid crystal display element, and in particular, It is suitable as a material for forming a patterned retardation material for a 3D display. Further, materials for forming a cured film such as a protective film, a flattening film and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, particularly an interlayer insulating film and a color filter of a TFT type liquid crystal element. It is suitable as a material for forming a protective film or an insulating film for an organic EL element.

Claims (11)

1. (A) A compound having a photo-oriented group and one substituent selected from the group consisting of a hydroxy group, a carboxyl group and an amino group.
   (B) Containing a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound, and (C) containing a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound. A cured film-forming composition comprising.
2. The cured film-forming composition according to claim 1, wherein the photo-oriented group of the component (A) is a functional group having a structure of photodimerization or photoisomerization.
3. The cured film-forming composition according to claim 1 or 2, wherein the photooriented group of the component (A) is a cinnamoyl group.
4. The cured film-forming composition according to claim 1 or 2, wherein the photo-oriented group of the component (A) is a group having an azobenzene structure.
5. The cured film-forming composition according to any one of claims 1 to 4, which further contains a cross-linking catalyst as the component (D).
6. The cured film-forming composition according to any one of claims 1 to 5, which further contains an adhesion improving component as the component (E).
7. Any one of claims 1 to 6, characterized in that the total amount of the component (B) and the component (C) is 100 to 3000 parts by mass based on 100 parts by mass of the component (A). The cured film forming composition according to the item.
8. The cured film-forming composition according to any one of claims 1 to 7, wherein the mass ratio of the component (B) to the component (C) is 1:99 to 99: 1.
9. Any one of claims 5 to 8, which contains 0.01 parts by mass to 10 parts by mass of the component (D) based on 100 parts by mass of the total amount of the component (B) and the component (C). The cured film forming composition according to.
10. An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 9.
11. A retardation material, which is formed by using a cured film obtained from the cured film forming composition according to any one of claims 1 to 9.