阅读说明：本技术 固化膜形成用组合物、取向构件和相位差构件 (Composition for forming cured film, alignment member, and phase difference member ) 是由 西村直也 伊藤润 于 2020-05-26 设计创作，主要内容包括：本发明的目的在于提供一种取向构件和用于得到该取向构件的固化膜形成用组合物,所述取向构件不仅具有优异的取向灵敏度,且取向均匀性也为优异,并且即使为薄膜,仍对液晶溶液中的溶剂具有耐性,且也能作为将膜基板予以保护的保护层发挥作用。本发明的固化膜形成用组合物,其特征为含有：(A)具有光取向性基与选自羟基、羧基及氨基中的1种取代基的化合物、(B)使至少包含N-烷氧基甲基(甲基)丙烯酰胺化合物的单体聚合而成的聚合物,以及(C)使至少包含N-羟基烷基(甲基)丙烯酰胺化合物的单体聚合而成的聚合物,并且根据需要还可以含有作为(D)成分的交联催化剂和作为(E)成分的密合性提高成分。可通过使用该固化膜形成用组合物形成固化膜,利用光取向技术形成取向构件。通过在该取向构件上涂布聚合性液晶使其固化,能够得到相位差构件。(The invention aims to provide an alignment member which has excellent alignment sensitivity and excellent alignment uniformity, is resistant to a solvent in a liquid crystal solution even in the case of a thin film, and can also function as a protective layer for protecting a film substrate, and a composition for forming a cured film for obtaining the alignment member. The composition for forming a cured film of the present invention comprises: (A) a compound having a photo-alignment group and 1 substituent selected from a hydroxyl group, a carboxyl group and an amino group, (B) a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound, and (C) a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound, and may further contain a crosslinking catalyst as the component (D) and an adhesion improving component as the component (E) as necessary. The alignment member can be formed by forming a cured film using the composition for forming a cured film and using a photo-alignment technique. The alignment member is coated with polymerizable liquid crystal and cured to obtain a retardation member.)

1. A composition for forming a cured film, which comprises a component (A), a component (B) and a component (C),

(A) component (B) is a compound having a photo-alignment group and 1 substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group,

(B) component (B) is a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound,

(C) the component (B) is a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound.

2. The cured film-forming composition according to claim 1, wherein the photo-alignment group of component (A) is a functional group having a structure which undergoes photodimerization or photoisomerization.

3. The cured film-forming composition according to claim 1 or 2, wherein the photo-alignment group of the component (A) is a cinnamoyl group.

4. The cured film-forming composition according to claim 1 or 2, wherein the photo-alignment 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, further comprising a crosslinking catalyst as the component (D).

6. The cured film forming composition according to any one of claims 1 to 5, further comprising an adhesion improving component as the component (E).

7. The cured film-forming composition according to any one of claims 1 to 6, wherein the total amount of the component (B) and the component (C) is 100 to 3000 parts by mass relative to 100 parts by mass of the component (A).

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. The composition for forming a cured film according to any one of claims 5 to 8, which comprises 0.01 to 10 parts by mass of the component (D) per 100 parts by mass of the total amount of the components (B) and (C).

10. An alignment member obtained by using the cured film-forming composition according to any one of claims 1 to 9.

11. A retardation member formed using a cured film obtained from the composition for forming a cured film according to any one of claims 1 to 9.

Technical Field

The present invention relates to a composition for forming a cured film, an alignment member, and a phase difference member.

Background

In the case of a circularly polarized glasses type 3D display, a phase difference member is generally disposed in a display unit for forming an image, such as a liquid crystal panel. The phase difference member is a patterned phase difference member in which a plurality of 2 phase difference regions having different phase difference characteristics are regularly arranged. In the present specification, a retardation member patterned to have a plurality of retardation regions having different retardation characteristics is hereinafter referred to as a patterned retardation member.

The patterned retardation member can be produced by optically patterning a retardation material containing polymerizable liquid crystal, as disclosed in patent document 1, for example. Optical patterning of a phase difference material containing a polymerizable liquid crystal utilizes a known photo-alignment technique for forming an alignment member of a liquid crystal panel. That is, a coating film containing a photo-alignment material is provided on a substrate, and 2 kinds of polarized light having different polarization directions are irradiated thereto. Subsequently, a photo alignment film was obtained as an alignment member in which 2 liquid crystal alignment regions having different liquid crystal alignment control directions were formed. The photo alignment film is coated with a solution-like retardation material containing a polymerizable liquid crystal to align the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation member.

The antireflection film of the organic EL display is composed of a linearly polarized light plate and an 1/4 wavelength phase difference plate, and converts the light coming from outside toward the panel surface of the image display panel into linearly polarized light by the linearly polarized light plate and then into circularly polarized light by the 1/4 wavelength phase difference plate. Here, although the external light composed of the circularly polarized light is reflected on the surface of the image display panel or the like, the rotation direction of the plane of polarization is reversed at the time of the reflection. As a result, the reflected light is converted into linearly polarized light in a direction shielded by the linearly polarizing plate by the 1/4 wavelength phase difference plate, and is subsequently shielded by the linearly polarizing plate, and as a result, the light emitted to the outside is significantly suppressed.

Regarding the 1/4 wavelength retardation plate, patent document 2 proposes a method of forming a 1/4 wavelength retardation plate by combining a 1/2 wavelength plate and a 1/4 wavelength plate, and forming the optical film by using a reverse dispersion characteristic. In this method, the optical film can be formed by using a liquid crystal material utilizing a forward dispersion characteristic in a wide wavelength region to be provided for color image display, and by using a reverse dispersion characteristic.

In recent years, liquid crystal materials having a reverse dispersion property have been proposed as liquid crystal materials that can be applied to the retardation layer (patent documents 3 and 4). According to the liquid crystal material having such anti-dispersion characteristics, instead of constituting the 1/4 wavelength retardation plate by 2 retardation layers in combination of the 1/2 wavelength plate and the 1/4 wavelength plate, the anti-dispersion characteristics can be secured by constituting the retardation layers by a single layer, and thus an optical film capable of securing a desired retardation in a wide wavelength region can be realized by a simple structure.

An alignment layer is used to align the liquid crystal. As a method for forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is useful in that it is possible to control a quantitative alignment treatment without causing a problem of the rubbing method, that is, without generating static electricity or dust.

In the formation of an alignment member by a photo-alignment method, an acrylic resin, a polyimide resin, or the like having a photo-dimerization site such as a cinnamoyl group or a chalcone group in a side chain is known as a material having photo-alignment properties that can be utilized. These resins have been reported to exhibit a property of controlling the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment) by polarized UV irradiation (see patent documents 5 to 7).

In addition to the liquid crystal alignment ability, the alignment layer also requires solvent resistance. For example, the alignment layer may be exposed to heat or a solvent during the manufacturing process of the retardation member. When the alignment layer is exposed to a solvent, the liquid crystal alignment ability may be significantly reduced.

Therefore, for example, patent document 8 proposes a liquid crystal aligning agent containing: a polymer component having a structure capable of undergoing a crosslinking reaction by light and a structure capable of undergoing crosslinking by heat; also proposed is a liquid crystal aligning agent containing: a polymer component having a structure capable of undergoing a crosslinking reaction by light and a compound having a structure capable of undergoing crosslinking by heat.

[ Prior art documents ]

[ patent document ]

[ patent document 1] Japanese patent laid-open No. 2005-49865

[ patent document 2] Japanese patent application laid-open No. 10-68816

[ patent document 3] specification of U.S. Pat. No. 8119026

[ patent document 4] Japanese patent laid-open No. 2009-179563

[ patent document 5] Japanese patent No. 3611342

[ patent document 6] Japanese patent laid-open No. 2009-058584

[ patent document 7] Japanese Kokai publication Hei-2001-517719

[ patent document 8] Japanese patent No. 4207430

Disclosure of Invention

[ problems to be solved by the invention ]

As described above, the retardation member is configured by laminating a layer of cured polymerizable liquid crystal on the photo-alignment film as the alignment member. Therefore, it is considered necessary to develop an alignment member that can achieve both excellent liquid crystal alignment properties and solvent resistance.

However, according to the present inventionThe inventors have found that an acrylic resin having a photodimerization site such as a cinnamoyl group or a chalcone group in a side chain does not have sufficient characteristics when applied to the formation of a retardation member. In particular, when an alignment member is formed by irradiating these resins with polarized UV light and a retardation member including polymerizable liquid crystal is manufactured using the alignment member, a large amount of polarized UV light exposure is required. The polarized UV exposure amount is larger than a polarized UV exposure amount (for example, 30 mJ/cm) sufficient for aligning liquid crystal for a general liquid crystal panel²Degree of the disease. ) And additionally becomes more.

The reason why the amount of polarized UV exposure is increased is that, when a retardation member is formed, unlike liquid crystals for liquid crystal panels, polymerizable liquid crystals are used in a solution state and applied to an alignment member.

When an alignment member is formed using an acrylic resin or the like having a photo-dimerization site such as a cinnamoyl group in a side chain and a polymerizable liquid crystal is aligned, photo-crosslinking is performed by a photo-dimerization reaction in the acrylic resin or the like. And it is necessary to irradiate polarized light with a large exposure amount until the resistance to the polymerizable liquid crystal solution is exhibited. In order to align the liquid crystal of the liquid crystal panel, generally, only the surface of the photo-alignment member is subjected to dimerization reaction. However, when attempting to make the alignment member exhibit solvent resistance using conventional materials such as the above-mentioned acrylic resins, it is necessary to make the reaction proceed to the inside of the alignment member, and a larger amount of exposure is required. As a result, the alignment sensitivity of the conventional material is extremely low.

In order to make the resin of the conventional material exhibit such solvent resistance, a technique of adding a crosslinking agent is known. However, it is known that, after the thermal curing reaction with the crosslinking agent, a 3-dimensional structure is formed in the formed coating film, and the photoreactivity is decreased. That is, the alignment sensitivity is greatly lowered, and the desired effect cannot be obtained even when a crosslinking agent is added to a conventional material.

In addition, since various organic solvents are used for liquid crystal inks and films having low resistance to organic solvents are used for substrates, alignment films having high solvent resistance are required for the reason of protecting the films.

In view of the above, a photo-alignment technique capable of improving the alignment sensitivity of an alignment member and reducing the polarized UV exposure amount, and a composition for forming a cured film which can be used as a liquid crystal alignment agent for forming the alignment member are required. And a technique for efficiently providing a phase difference member is required.

The object of the present invention is achieved based on the knowledge findings and the research results. That is, an object of the present invention is to provide a composition for forming a cured film, which can be used as a liquid crystal aligning agent for photo-alignment, which is used to provide an alignment member having excellent alignment sensitivity and alignment uniformity, and which is resistant to a solvent in a liquid crystal solution even in a thin film, and which can also function as a protective layer for protecting a film substrate.

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

[ means for solving the problems ]

The invention of claim 1 relates to a cured film-forming composition comprising:

(A) a compound having a photo-alignment group and 1 substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group,

(B) A polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound, and

(C) a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound.

In the 1 st aspect of the present invention, the photo-alignment group of the component (a) is preferably a functional group having a structure which undergoes photodimerization or photoisomerization.

In the 1 st aspect of the present invention, the photo-alignment group of the component (a) is preferably a cinnamoyl group.

In the 1 st aspect of the present invention, the photo-alignment group of the component (a) is preferably a group having an azobenzene structure.

In the 1 st aspect of the present invention, it is preferable that a crosslinking catalyst is further contained as the component (D).

In the 1 st aspect of the present invention, it is preferable that the adhesive property improving component is further contained as the (E) component.

In embodiment 1 of the present invention, the total amount of the component (B) and the component (C) is preferably 100 to 3000 parts by mass relative to 100 parts by mass of the component (a).

In embodiment 1 of the present invention, the mass ratio of the component (B) to the component (C) is preferably 1:99 to 99: 1.

In embodiment 1 of the present invention, it is preferable that the component (D) is contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total amount of the components (B) and (C).

The invention of claim 2 relates to an alignment member, which is obtained by using the composition for forming a cured film of claim 1.

The 3 rd aspect of the present invention relates to a phase difference member, which is characterized by being formed using a cured film obtained from the cured film-forming composition according to the 1 st aspect of the present invention.

[ Effect of the invention ]

According to the first aspect of the present invention, there is provided a composition for forming a cured film, which is capable of providing an alignment member that has excellent alignment sensitivity and excellent alignment uniformity, is resistant to a solvent in a liquid crystal solution even when it is a thin film, and is also capable of functioning as a protective layer for protecting a film substrate.

According to the 2 nd aspect of the present invention, there is provided an alignment member which has excellent alignment sensitivity and excellent alignment uniformity, is resistant to a solvent in a liquid crystal solution even when it is a thin film, and can function as a protective layer for protecting a film substrate.

According to the 3 rd aspect of the present invention, there can be provided a retardation member which can be formed on a film substrate with high efficiency and can be optically patterned.

Detailed Description

< composition for Forming cured film >

The composition for forming a cured film of the present invention comprises: the composition contains a component (A) which is a compound having a photo-alignment group and 1 substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group (hereinafter also referred to as "low-molecular photo-alignment component"), (B) which is a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound, and (C) which is a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound. The composition for forming a cured film of the present invention may contain, in addition to the component (a), the component (B), and the component (C), a crosslinking catalyst as the component (D), and a component for improving the adhesion of a cured film as the component (E). And may contain other additives as long as the effects of the present invention are not impaired.

The details of each component are described below.

< component (A) >

The component (a) contained in the cured film-forming composition of the present invention is a low-molecular photo-alignment component as described above.

The low-molecular photo-alignment component (a) is a compound having a photo-alignment group and 1 substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group. In the compound having the photo-alignment group and 1 substituent selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group, the photo-alignment gene is photo-reacted to form the hydrophobic photo-alignment moiety, and the hydroxyl group and the like form the hydrophilic thermal reaction moiety, as described above.

In the present invention, the photo-alignment group refers to a functional group of a structural site which undergoes photodimerization or photoisomerization.

The structural site for photodimerization means a site capable of forming a dimer by light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, coumarin group, anthracene group and the like. Among these, cinnamoyl group having high transparency in the visible light range and photodimerization reactivity is preferable. The structural site which is photoisomerized means a structural site which can be converted into a cis isomer and a trans isomer by irradiation with light, and specific examples thereof include sites including an azobenzene structure, a stilbene structure and the like. Among these, the azobenzene structure is preferable from the viewpoint of high reactivity. The compound having a photo-alignment group and a hydroxyl group is represented by the following formula, for example.

The aforementioned formula [ A1]To the formula [ A5]Middle and A¹And A²Each independently represents a hydrogen atom or a methyl group, X¹Represents a 2-valent group bonded to 1 to 3 groups selected from an alkylene group having 1 to 18 carbon atoms, a phenylene group, a biphenylene group, or a combination thereof via 1 or 2 or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, an amino bond, or a combination thereof. X²Represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group or a cyclohexyl group. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded to the benzene ring via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond. X⁵Represents a hydroxyl group, a carboxyl group, an amino group or an alkoxysilyl group. X represents a single bond, an oxygen atom or a sulfur atom. X⁶Represents 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 phenyl group, a phenoxy group or a biphenyloxy group. X⁷Represents a single bond, an alkylene group having 1 to 20 carbon atoms, a 2-valent group obtained by removing 2 hydrogen atoms from an aromatic ring, or a 2-valent group obtained by removing 2 hydrogen atoms from an aliphatic ring. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

Of these substituents, the phenylene group, the phenyl group, the biphenylene group, the biphenyl group, the phenoxy group, and the biphenyloxy group may be substituted with 1 or more substituents which may be the same or different, selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group.

In the above formula, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each 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.

Examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a1, 1-dimethyl-n-propyl group, a1, 2-dimethyl-n-propyl group, a 2, 2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a1, 1-dimethyl-n-butyl group, a1, 2-dimethyl-n-butyl group, a1, 3-dimethyl-n-butyl group, a tert-butyl group, a pentyl group, a 2-butyl group, a pentyl group, a 2-methyl group, a pentyl group, a 2-pentyl group, a, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1-dimethyl-n-pentyl, 1, 2-dimethyl-n-pentyl, 1, 3-dimethyl-n-pentyl, 2, 2-dimethyl-n-pentyl, 2-methyl-n-butyl, 1-ethyl-2-ethyl-n-butyl, 1-methyl-n-propyl, 1-methyl-n-hexyl, 1-methyl-hexyl, 1-methyl-n-pentyl, 1-methyl-pentyl, 1-pentyl, 2, 2-pentyl, or a, 2, 3-dimethyl-n-pentyl, 3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-dimethyl-n-hexyl, 2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentyl, or a-pentyl group, N-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and the like.

Examples of the alkylene group having 1 to 18 carbon atoms include a 2-valent group obtained by removing 1 hydrogen atom from the above-mentioned alkyl group.

Examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding number of carbon atoms among the above-mentioned groups.

Examples of the above alkoxy group having 1 to 10 carbon atoms, alkoxy group having 1 to 4 carbon atoms and alkylthio group having 1 to 10 carbon atoms include groups having a corresponding carbon atom number among groups obtained by alkoxylating or thiolating (thioating) the above-mentioned alkyl group.

Examples of the alkylene group having 1 to 20 carbon atoms include a 2-valent group obtained by removing 1 hydrogen atom from the alkyl group and an alkyl group having 1 to 20 carbon atoms such as an n-nonadecyl group, an n-eicosyl group, and the like.

Specific examples of the compound having a photo-alignment group and a hydroxyl group as the component (A) include methyl 4- (8-hydroxyoctyloxy) cinnamate, methyl 4- (6-hydroxyhexyloxy) cinnamate, methyl 4- (4-hydroxybutoxy) cinnamate, methyl 4- (3-hydroxypropoxy) cinnamate, methyl 4- (2-hydroxyethoxy) cinnamate, methyl 4-hydroxymethoxycinnamate, methyl 4-hydroxycinnamate, ethyl 4- (8-hydroxyoctyloxy) cinnamate, ethyl 4- (6-hydroxyhexyloxy) cinnamate, ethyl 4- (4-hydroxybutoxy) cinnamate, ethyl 4- (3-hydroxypropoxy) cinnamate, ethyl 4-hydroxybutoxy) cinnamate, methyl 4- (2-hydroxyethoxy) cinnamate, and the like, Ethyl 4- (2-hydroxyethoxy) cinnamate, ethyl 4-hydroxymethoxycinnamate, ethyl 4-hydroxycinnamate, phenyl 4- (8-hydroxyoctyloxy) cinnamate, phenyl 4- (6-hydroxyhexyloxy) cinnamate, phenyl 4- (4-hydroxybutoxy) cinnamate, phenyl 4- (3-hydroxypropoxy) cinnamate, phenyl 4- (2-hydroxyethoxy) cinnamate, phenyl 4-hydroxymethoxycinnamate, phenyl 4-hydroxycinnamate, biphenyl 4- (8-hydroxyoctyloxy) cinnamate, biphenyl 4- (6-hydroxyhexyloxy) cinnamate, biphenyl 4- (4-hydroxybutoxy) cinnamate, biphenyl, Biphenyl 4- (3-hydroxypropoxy) cinnamate, biphenyl 4- (2-hydroxyethoxy) cinnamate, biphenyl 4-hydroxymethoxycinnamate, biphenyl 4-hydroxycinnamate, 8-hydroxyoctyl cinnamate, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, 4- (8-hydroxyoctyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 4- (4-hydroxybutoxy) azobenzene, 4- (3-hydroxypropoxy) azobenzene, 4- (2-hydroxyethoxy) azobenzene, 4-hydroxymethoxyazobenzene, phenol, and the like, 4-hydroxyazobenzene, 4- (8-hydroxyoctyloxy) chalcone, 4- (6-hydroxyhexyloxy) chalcone, 4- (4-hydroxybutoxy) chalcone, 4- (3-hydroxypropoxy) chalcone, 4- (2-hydroxyethoxy) chalcone, 4-hydroxymethoxychalcone, 4-hydroxychalcone, 4 ' - (8-hydroxyoctyloxy) chalcone, 4 ' - (6-hydroxyhexyloxy) chalcone, 4 ' - (4-hydroxybutoxy) chalcone, 4 ' - (3-hydroxypropoxy) chalcone, 4 ' - (2-hydroxyethoxy) chalcone, 4 ' -hydroxymethoxychalcone, 4 ' -hydroxychalcone, 7- (8-hydroxyoctyloxy) coumarin, and mixtures thereof, 7- (6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutoxy) coumarin, 7- (3-hydroxypropoxy) coumarin, 7- (2-hydroxyethoxy) coumarin, 7-hydroxymethoxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutoxy) coumarin, 6- (3-hydroxypropoxy) coumarin, 6- (2-hydroxyethoxy) coumarin, 6-hydroxymethoxycoumarin, 6-hydroxycoumarin.

Specific examples of the compound having a photo-alignment group and a carboxyl group include cinnamic acid, ferulic acid, 4-nitrocinnamic acid, 4-methoxycinnamic acid, 3, 4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4- (dimethylamino) cinnamic acid, and the like.

Specific examples of the compound having a photo-alignment group and an amino group include methyl 4-aminocinnamate, ethyl 4-aminocinnamate, methyl 3-aminocinnamate, ethyl 3-aminocinnamate and the like.

The low-molecular photo-alignment component of the component (A) includes the above specific examples, but is not limited thereto.

In addition, when the low-molecular photo-alignment component as the component (a) is a compound having a photo-alignment group and a hydroxyl group, a compound having 2 or more photo-alignment groups and/or 2 or more hydroxyl groups in the molecule may be used as the component (a). Specifically, as the component (a), a compound having 1 hydroxyl group and 2 or more photo-alignment groups in the molecule, a compound having 1 photo-alignment group and 2 or more hydroxyl groups in the molecule, or a compound having 2 or more photo-alignment groups and hydroxyl groups in the molecule, respectively, can be used. For example, a compound having 2 or more photo-alignment groups and hydroxyl groups in the molecule may be exemplified by a compound represented by the following formula.

By appropriately selecting such a compound, it becomes possible to control and increase the molecular weight of the photo-alignment component having a low molecular weight as the component (A). As a result, as will be described later, sublimation of the photo-alignment component having a low molecular weight of the component (A) can be suppressed when the photo-alignment component having a low molecular weight of the component (A) and the polymer of the component (B) are thermally reacted with the polymer of the component (C). The cured film-forming composition of the present invention can form an alignment member having high photoreaction efficiency as a cured film.

The component (a) in the composition for forming a cured film of the present invention may be a mixture of a plurality of compounds having a photo-alignment group and 1 substituent selected from a hydroxyl group, a carboxyl group and an amino group.

< 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. Note that N-alkoxymethyl (meth) acrylamide means both N-alkoxymethyl-acrylamide and N-alkoxymethyl-methacrylamide.

Examples of such a polymer include a polymer obtained by polymerizing an N-alkoxymethyl (meth) acrylamide compound alone or a polymer obtained by copolymerizing a monomer copolymerizable therewith. Examples of such polymers include poly (N-butoxymethyl-acrylamide), poly (N-ethoxymethyl-acrylamide), poly (N-methoxymethyl-acrylamide), copolymers of N-butoxymethyl-acrylamide with styrene, copolymers of N-butoxymethyl-acrylamide with methyl methacrylate, copolymers of N-ethoxymethyl-methacrylamide with benzyl methacrylate, and copolymers of N-butoxymethyl-acrylamide with benzyl methacrylate and 2-hydroxypropyl methacrylate.

The method for obtaining the polymer of the component (B) used in the present invention is not particularly limited, and for example, the polymer can be obtained by polymerizing an N-alkoxymethyl (meth) acrylamide compound and a copolymerizable monomer and a polymerization initiator, which are added as desired, in a solvent in which they coexist at a temperature of 50 to 110 ℃. In this case, the solvent used is not particularly limited as long as it can dissolve the N-alkoxymethyl (meth) acrylamide compound, the copolymerizable monomer and the polymerization initiator which are added as desired, and the like. As a specific example, the following description is given in the section of "solvent".

The polymer obtained by the aforementioned method is usually in the state of a solution dissolved in a solvent.

The polymer solution obtained in the above-described manner is put into diethyl ether or water under stirring to precipitate the polymer, and the precipitate thus formed is filtered and washed, and then dried at normal temperature or under reduced pressure or dried by heating to obtain a polymer powder. By the above-mentioned operation, the polymerization initiator and the unreacted monomer which coexist with the polymer can be removed, and as a result, a purified polymer powder can be obtained. In the case where the purification cannot be sufficiently performed by one operation, the obtained powder may be dissolved in the solvent again, and the above operation may be repeated.

In the present invention, the polymer of component (B) may be used in the form of a powder, or may be used in the form of a solution prepared by redissolving a purified powder in a solvent to be described later.

In the present invention, the component (B) polymer may be a mixture of a plurality of polymers.

In the present invention, when the above-mentioned copolymerizable monomer is used in the production of the polymer as the component (B), the amount of the copolymerizable monomer to be used is preferably 1 to 200 mol%, more preferably 10 to 100 mol%, based on the total mole number of the monomers used in the production of the polymer as the component (B).

The weight average molecular weight of such a component (B) polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and further 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.

These (B) component polymers may be used alone, or 2 or more of them may be used in combination.

< ingredient (C) >

(C) The component (B) is a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound. The term "N-hydroxyalkyl (meth) acrylamide" means both N-hydroxyalkyl acrylamide and N-hydroxyalkyl methacrylamide.

When the composition of the present invention is formed into a coating film and thermally cured, the N-alkoxymethyl group of the component (B) and the hydroxyl group of the component (C) react to form a bond. By this, the coating film becomes strong and firm, and solvent resistance becomes available.

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

In the present invention, a monomer other than the above-mentioned N-hydroxyalkyl (meth) acrylamide compound (hereinafter, also referred to as "other monomer") may be copolymerized in the production of the polymer as the component (C).

In the present invention, when another monomer is used in the production of the polymer component (C), the amount of the other monomer to be used is preferably 30 to 90 mol%, more preferably 30 to 70 mol%, based on the total number of moles of the monomers used in the production of the polymer component (C).

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

Specific examples of the other monomer include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, amide group-containing monomers, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

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

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, phenyl acrylate, 2,2, 2-trifluoroethyl acrylate, t-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, benzyl acrylate, naphthyl acrylate, anthryl acrylate, benzyl acrylate, methyl acrylate, benzyl acrylate, methyl 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 acid-6-lactone, acryloylethyl isocyanate, and 8-ethyl-8-tricyclodecyl acrylate, epoxypropyl acrylate, and the like.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, phenyl methacrylate, 2,2, 2-trifluoroethyl methacrylate, t-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 -butyrolactone methacrylate, methyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, benzyl methacrylate, 2-ethoxyethyl methacrylate, 2-methyltetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, and the like, 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 acid-6-lactone, methacryloylethylisocyanate, and 8-ethyl-8-tricyclodecyl methacrylate, epoxypropyl methacrylate, and the like.

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, N-butyl (meth) 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-vinylacetamide, N-methylacetamide, N-methylacrylamide, and mixtures thereof, N- (isobutoxyethyl) (meth) acrylamide, N-vinylphthalimide, N-vinylsuccinimide, and the like.

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

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 and the like.

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

The weight average molecular weight of such a polymer of the component (C) is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and further 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.

These (C) component polymers may be used alone or 2 or more kinds may be used in combination.

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

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, particularly preferably 10:90 to 90: 10.

< ingredient (D) >

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

As the crosslinking catalyst of the component (D), for example, an acid or a thermal acid generator can be used. The component (D) is effective for promoting the heat curing reaction of the cured film-forming composition of the present invention.

Examples of the acid include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof. The thermal acid generator is not particularly limited as long as it is a compound that generates an acid by thermally decomposing at the time of pre-baking or post-baking, that is, a compound that generates an acid by thermally decomposing at a temperature of 80 ℃ to 250 ℃.

Examples of the acid include hydrochloric acid or a salt thereof; sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-hydroxybenzenesulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, and hydrates or salts thereof.

Examples of the compound generating an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methylsulfonate), and p-toluenesulfonate pyridineSalt, morpholine p-toluenesulfonateSalts, ethyl p-toluenesulfonate, propyl p-toluenesulfonate, butyl p-toluenesulfonate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2, 2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyl p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and compounds represented by the following formulae, and the like.

The content of the component (D) in the cured film-forming composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, and still more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total amount of the component (B) polymer and the component (C) polymer. By setting the content of the component (D) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be provided, and high sensitivity to light irradiation can also be provided. However, when the amount is more than 10 parts by mass, the storage stability of the composition may be lowered.

< ingredient (E) >

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

The adhesion improving component as the component (E) can covalently bond the polymerizable functional group of the polymerizable liquid crystal and the crosslinking reaction site of the alignment member, thereby improving the adhesion between the alignment member obtained from the composition for forming a cured film of the present invention and the layer of the polymerizable liquid crystal. As a result, the retardation member of the present embodiment obtained by laminating the cured polymerizable liquid crystal on the alignment member of the present embodiment can maintain strong adhesion even under high temperature and high humidity conditions, and can exhibit high durability against peeling and the like.

The component (E) is preferably a monomer or a polymer having a group selected from a hydroxyl group and an N-alkoxymethyl group and a polymerizable group.

Examples of the component (E) include a compound having a hydroxyl group and a (meth) acryloyl group, a compound having an N-alkoxymethyl group and a (meth) acryloyl group, and a polymer having an N-alkoxymethyl group and a (meth) acryloyl group. Specific examples are shown below.

An example of the component (E) is a hydroxyl group-containing polyfunctional acrylate (hereinafter, also referred to as hydroxyl group-containing polyfunctional acrylate).

Examples of the hydroxyl group-containing polyfunctional acrylate as the component (E) include pentaerythritol triacrylate and dipentaerythritol pentaacrylate.

An example of the component (E) is a compound having 1 (meth) acryloyl group and 1 or more hydroxyl groups.

Further, as the compound of the component (E), a compound having 1 molecule thereof at least 1 polymerizable group containing a C ═ C double bond and at least 1N-alkoxymethyl group is exemplified.

Examples of the polymerizable group containing a C ═ C double bond include an acryloyl group, a methacryloyl group, a vinyl group, an allyl group, and a maleimide group.

As the compound having at least 1 polymerizable group containing a C ═ C double bond and at least 1N-alkoxymethyl group in 1 molecule, for example, a compound represented by the following formula (X1) is preferable.

(in the formula, R³¹Represents a hydrogen atom or a methyl group, R³²Represents 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 a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a1, 1-dimethyl-n-propyl group, a1, 2-dimethyl-n-propyl group, a 2, 2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 3-methyl-n-pentyl group, a 4-methyl-n-pentyl group, a1, 1-dimethyl-n-butyl group, a1, 2-dimethyl-n-butyl group, a1, 3-dimethyl-n-butyl group, a tert-butyl group, a pentyl group, a 2-butyl group, a pentyl group, a 2-methyl group, a pentyl group, a 2-pentyl group, a, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, n-heptyl, 1-methyl-n-hexyl, 2-methyl-n-hexyl, 3-methyl-n-hexyl, 1-dimethyl-n-pentyl, 1, 2-dimethyl-n-pentyl, 1, 3-dimethyl-n-pentyl, 2, 2-dimethyl-n-pentyl, 2-methyl-n-butyl, 1-ethyl-2-ethyl-n-butyl, 1-methyl-n-propyl, 1-methyl-n-hexyl, 1-methyl-hexyl, 1-methyl-n-pentyl, 1-methyl-pentyl, 1-pentyl, 2, 2-pentyl, or a, 2, 3-dimethyl-n-pentyl, 3-dimethyl-n-pentyl, 1-ethyl-n-pentyl, 2-ethyl-n-pentyl, 3-ethyl-n-pentyl, 1-methyl-1-ethyl-n-butyl, 1-methyl-2-ethyl-n-butyl, 1-ethyl-2-methyl-n-butyl, 2-methyl-2-ethyl-n-butyl, 2-ethyl-3-methyl-n-butyl, n-octyl, 1-methyl-n-heptyl, 2-methyl-n-heptyl, 3-methyl-n-heptyl, 1-dimethyl-n-hexyl, 1, 2-dimethyl-n-hexyl, 1, 3-dimethyl-n-hexyl, 2-dimethyl-n-hexyl, 2, 3-dimethyl-n-hexyl, 3-dimethyl-n-hexyl, 1-ethyl-n-hexyl, 2-ethyl-n-hexyl, 3-ethyl-n-hexyl, 1-methyl-1-ethyl-n-pentyl, 1-methyl-2-ethyl-n-pentyl, 1-methyl-3-ethyl-n-pentyl, 2-methyl-2-ethyl-n-pentyl, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl, and the like.

Specific examples of the compound represented by the formula (X1) include acrylamide compounds or methacrylamide compounds substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. The term (meth) acrylamide refers to both methacrylamide and acrylamide.

As another embodiment of the compound having a polymerizable group containing a C ═ C double bond and an N-alkoxymethyl group in the component (E), the following compounds are more preferable.

The content of the component (E) in the cured film-forming composition of the present invention is preferably 1 to 100 parts by mass, and more preferably 5 to 70 parts by mass, based on 100 parts by mass of the low-molecular photo-alignment component as the component (a).

< solvent >

The composition for forming a cured film of the present invention is used mainly in the form of a solution dissolved in a solvent. The solvent used in this case is not particularly limited as long as it can dissolve the component (a), the component (B), and the component (C), and the component (D), the component (E), and/or other additives described later, which are added as necessary.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-heptanone, γ -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether, 2-heptanone, gamma-butyrolactone, ethyl 2-hydroxy-2-methylpropionate, ethyl 3-methoxy propionate, methyl propionate, ethyl 3-methoxy propionate, ethyl acetate, methyl propionate, ethyl acetate, ethyl propionate, and the like, Methyl 3-ethoxypropionate, methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and the like. These solvents may be used alone in 1 kind, or a combination of 2 or more kinds may be used.

< other additives >

The composition for forming a cured film of the present invention may contain a sensitizer, a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoaming agent, an antioxidant, and the like as necessary, as long as the effects of the present invention are not impaired.

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

Examples of the sensitizer as another additive include benzophenone, anthracene, anthraquinone, thioxanthone, and derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of more preferable compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene, 4-nitrobenzophenone, and 5-nitroindole. In particular, N-diethylaminobenzophenone, which is a benzophenone derivative, is preferable.

These sensitizers are not limited to the above. In addition, the sensitizer may be used alone or 2 or more compounds may be used in combination.

The sensitizer in the composition for forming a cured film of the present invention is preferably used in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the low-molecular photo-alignment component as the component (a). If the ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if too large, the transmittance and the roughness of the coating film may occur.

< preparation of composition for Forming cured film >

The cured film-forming composition of the present embodiment contains: a low-molecular photo-alignment component as component (A), a polymer obtained by polymerizing a monomer containing at least an N-alkoxymethyl (meth) acrylamide compound as component (B), and a polymer obtained by polymerizing a monomer containing at least an N-hydroxyalkyl (meth) acrylamide compound as component (C). If necessary, a crosslinking catalyst as the component (D), an adhesion improving component as the component (E), and/or other additives may be contained.

The blending ratio, preparation method and the like 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 component 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, and is 1 to 80% by mass, preferably 3 to 60% by mass, and more preferably 5 to 40% by mass. Here, the solid component refers to a component 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. Examples of the preparation method include a method of mixing the component (A), the component (C), and, if necessary, the component (D) and the component (E) in a solution of the component (B) dissolved in a solvent at a predetermined ratio to form a homogeneous solution, and a method of mixing the components in an appropriate stage of the preparation method by further adding, if necessary, other additives.

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

The solution of the cured film-forming composition prepared is preferably filtered using a filter having a pore size of about 0.2 μm and then used.

< cured film, alignment member and retardation member >

The cured film-forming composition of the present invention can be applied to a substrate (for example, a silicon/silica-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate, an ITO substrate, etc.) or a film (for example, a resin film such as a triacetyl cellulose (TAC) film, a cycloolefin polymer film, a polyethylene terephthalate film, an acrylic film, etc.) or the like from a solution, and then applied by a bar coating method, a spin coating method, a cast coating method, a roll coating method, a slit coating method, a spin coating method followed by a slit coating method, an inkjet coating method, a printing method, etc. to form a coating film, and thereafter dried by heating using a hot plate, an oven, or the like to form a cured film.

The conditions for the heat drying may be such that the components of the alignment member formed of the cured film do not precipitate to the extent of the polymerizable liquid crystal solution applied thereon and the crosslinking reaction by the crosslinking agent proceeds, and for example, a heating temperature and a heating time appropriately selected from the range of 60 ℃ to 200 ℃ and the time of 0.4 to 60 minutes may be used. The heating temperature and the heating time are preferably 70 ℃ to 160 ℃ and 0.5 minutes to 10 minutes.

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

The cured film thus formed can function as an alignment member, i.e., a member for aligning a liquid crystal compound such as a liquid crystal, by being irradiated with polarized UV light.

As a method of irradiating polarized light UV, irradiation with linear polarized light from ultraviolet light to visible light having a wavelength of 150nm to 450nm is generally performed at room temperature or in a heated state from a vertical direction or an oblique direction.

Since the alignment member formed from the composition for forming a cured film of the present invention has solvent resistance and heat resistance, a retardation material containing a polymerizable liquid crystal solution is applied to the alignment member, and then the alignment member is heated to the phase transition temperature of the liquid crystal to form the retardation material into a liquid crystal state and align the retardation material on the alignment member. Further, by directly curing the retardation material in the aligned state, the retardation member can be formed as a layer having optical anisotropy.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, and the like can be used. In addition, in the case where the substrate on which the alignment member is formed is a film, the film having the retardation member of the present invention can be used as a retardation film. The retardation material forming such a retardation member is in a liquid crystal state, and the alignment member has an alignment state such as horizontal alignment, cholesterol alignment, vertical alignment, hybrid alignment, and the like, and can be used in a different manner depending on a desired retardation.

In addition, in the case of manufacturing a patterned retardation member used for a 3D display, on a cured film formed by the above method from the cured film-forming composition of the present invention, the polarized light UV is exposed in a direction of, for example, +45 degrees on the basis of a predetermined standard through a mask of a line width and line pitch pattern, then the mask is removed, and then the polarized light UV is exposed in a direction of-45 degrees, to obtain an alignment member in which 2 liquid crystal alignment regions having different alignment control directions of liquid crystals are formed. Thereafter, a retardation material containing a polymerizable liquid crystal solution is applied, and then the retardation material is heated to a phase transition temperature of the liquid crystal to be brought into a liquid crystal state, and is aligned on the alignment member. Further, the phase difference material in the oriented state is directly cured, and a plurality of patterned phase difference members in which 2 phase difference regions having different phase difference characteristics are regularly arranged can be obtained.

Further, a liquid crystal display module in which liquid crystal is aligned can be formed by using 2 substrates having alignment members of the present invention formed through the above-described operation, bonding the alignment members on the two substrates to face each other with a spacer interposed therebetween, and then injecting liquid crystal between the substrates.

Therefore, the composition for forming a cured film of the present invention can be suitably used for producing various retardation members (retardation films), liquid crystal display devices, and the like.

Examples

The present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples.

[ omission symbols used in examples ]

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

< raw materials >

BMAA: n-butoxymethyl-acrylamide

AIBN: alpha, alpha' -azobisisobutyronitrile

MMA: methacrylic acid methyl ester

HEAA: n- (2-hydroxyethyl) acrylamide

MAIB: dimethyl 2, 2-azobisisobutyrate

< ingredient A >

MCA: 4-methoxy cinnamic acid

< ingredient B >

PB-1: the structural formula is shown in the specification.

< ingredient C >

PC-1: the structural formula is shown in the specification.

PC-2: the structural formula is shown in the specification.

< ingredient D >

PTSA: p-toluenesulfonic acid monohydrate

< ingredient E >

E-1: a compound having N-alkoxymethyl group and acryloyl group represented by the following structural formula

< solvent >

Each of the resin compositions of examples and comparative examples contains a solvent, and propylene glycol monomethyl ether (PM) and Butyl Acetate (BA) are used as the solvent.

< measurement of molecular weight of Polymer >

The molecular weight of the acrylic copolymer in the polymerization example was measured by using a Gel Permeation Chromatography (GPC) apparatus (HLC-8320) manufactured by DONG ソー, Inc., and a column (TSKgel ALPHA4000, TSKgel ALPHA3000) manufactured by カラム, manufactured by DONG ソー, Inc., and by the following procedure.

The number average molecular weight (hereinafter referred to as Mn) and the weight average molecular weight (hereinafter referred to as Mw) described below are expressed in terms of polystyrene.

Temperature of the pipe column: 40 deg.C

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Standard wire preparation standard samples: standard polystyrene (molecular weight: 427,000, 190,000, 37,900, 18,100, 5,970, 2,420, 1,010) manufactured by DONG ソー (Strain)

< Synthesis of component B >

< polymerization example-1 >

An acrylic polymer solution was obtained by dissolving 100.0g of BMAA and 1.0g of AIBN, a polymerization catalyst, in 193.5g of PM and reacting at 80 ℃ for 20 hours. The obtained acrylic polymer had Mn of 10,000 and Mw of 23,000. The acrylic polymer solution was slowly dropped into 2000.0g of hexane to precipitate a solid, which was then filtered and dried under reduced pressure to obtain polymer (PB-1).

Synthesis of < C component >

< polymerization example-2 >

MMA 7.0g, HEAA 5.8g, and polymerization catalyst MAIB 0.23g were dissolved in PM 13.0 g. 6.50g of PM was added to a four-necked flask in advance, and the dissolved solution was added dropwise over 3 hours to a dropping tank heated to 85 ℃ in advance, and the mixture was reacted under reflux for 3 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had Mn of 12,600 and Mw of 43,100. A40% PM solution of the target polymer (PC-1) was obtained.

Synthesis of < C component >

< polymerization example-3 >

47.10g of BMAA, 34.5g of HEAA and 0.829g of MAIB as a polymerization catalyst were dissolved in 82.50g of PM. A four-necked flask was charged with 41.25g of PM in advance, and the dissolved solution was added dropwise over 3 hours to a dropping tank heated to 85 ℃ in advance, and then reacted for 5 hours to obtain an acrylic polymer solution. The obtained acrylic polymer had Mn of 6,500 and Mw of 17,000. A40% PM solution of the target polymer (PC-2) was obtained.

< preparation of liquid Crystal alignment agent (composition for Forming cured film) >

< preparation example 1 >

0.079g of MCA as the component (A), 10.66 g of PB-1 as the component (B) obtained in polymerization example-1, 0.26g of a 40% PM solution of the polymer (PC-1) as the component (C) obtained in polymerization example-2, 0.8978 g of E-10.056 (94.6% BA solution manufactured by pure chemical Co., Ltd.), and 0.021g of PTSA as the component (D) were mixed, and then 6.65g of PM and 1.62g of BA as solvents were added thereto and stirred for 1 hour, and it was visually confirmed that the components dissolved, thereby obtaining a solution. Then, the obtained solution was filtered through a filter having a pore size of 0.2 μm to prepare a liquid crystal aligning agent (A-1).

< preparation examples 2 to 6 >

Liquid crystal alignment agents (A-2) to (A-4), (B-1) and (B-2) were prepared in the same manner as in preparation example 1, except that the components were used in the kinds and blending amounts shown in Table 1 below.

APEPO-1: RFK-505 (Kawasaki chemical industry Co., Ltd.)

PEPO-1: polylite 8651 (available from DIC corporation)

< preparation of polymerizable liquid Crystal solution for horizontal alignment >

< production example 1 >

To the resulting mixture were added LC-2421.57 g of a polymerizable liquid crystal for horizontal alignment (manufactured by BASF), Irgacure 9070.047 g of a photo radical initiator (manufactured by BASF), and 0.008g of a leveling agent BYK-361N, and 6.55g of N-methylpyrrolidone (NMP) and 9.83g of cyclopentanone as solvents, and the mixture was stirred for 2 hours to visually confirm the dissolution thereof, thereby obtaining a 9 mass% polymerizable liquid crystal solution LC-1.

< formation of liquid Crystal alignment film and production of retardation film >

< example 1 >

The liquid crystal aligning agent (A-1) prepared in preparation example 1 was coated on a triacetyl cellulose (TAC) film as a substrate to a wet thickness of 6 μm using a bar coater. The film was dried by heating at 130 ℃ for 2 minutes in a thermal cycle oven, to form a cured film on the film. Next, at 10mJ/cm²The exposure amount of (2) was adjusted so that a 313nm linear polarized light was perpendicularly irradiated to the surface of the cured film to form a liquid crystal alignment film. On the liquid crystal alignment film, bar coating was usedThe resulting solution LC-1 was coated to a wet film thickness of 34 μm. Next, after drying by heating at 120 ℃ for 2 minutes in an oven, the mixture was passed through a filter at 300mJ/cm under nitrogen²The exposure amount was adjusted so that 365nm unpolarized light was irradiated perpendicularly to cure the polymerizable liquid crystal, thereby producing a retardation film.

< examples 2 to 4 >

Retardation films were produced in the same manner as in example 1, using (A-2) to (A-4) as the liquid crystal aligning agents.

< comparative example 1 >

The liquid crystal aligning agent (B-1) prepared in preparation example 1 was coated on a TAC film as a substrate to a wet film thickness of 4 μm using a bar coater. The film was dried by heating at 130 ℃ for 2 minutes in a thermal cycle oven to form a cured film on the film. Next, at 10mJ/cm²The surface of the cured film was irradiated perpendicularly with 313nm of linearly polarized light to form a liquid crystal alignment film. On the liquid crystal alignment film, a polymerizable liquid crystal solution LC-1 for horizontal alignment was applied to a wet film thickness of 34 μm using a bar coater. Next, after drying by heating at 120 ℃ for 2 minutes in an oven, the mixture was passed through a filter at 300mJ/cm under nitrogen²The exposure amount was adjusted to 365nm of unpolarized light perpendicularly irradiated thereto to cure the polymerizable liquid crystal, thereby producing a retardation film.

< comparative example 2 >

A retardation film was produced in the same manner as in comparative example 1 using (B-1) as a liquid crystal aligning agent.

Each of the retardation films 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 retardation characteristics under crossed nicols was visually observed. The one exhibiting no retardation was rated as "O", and the one exhibiting no retardation was rated as "X", and the column of "orientation" shows.

< TAC protection >

The retardation film including the TAC film was evaluated as "good" in terms of no curling and as "good" in terms of curling, and is described in the column of "protective property".

TABLE 2

As is clear from the results in table 2, by using a polymer obtained by polymerizing a monomer including an N-hydroxyalkyl (meth) acrylamide compound as the component (C), it is possible to obtain alignment properties with respect to a liquid crystal solution including NMP and also prevent damage to a TAC film by NMP.

Industrial applicability

The composition for forming a cured film of the present invention is useful as a liquid crystal alignment film for a liquid crystal display module or an alignment member for forming an optically anisotropic film provided inside or outside a liquid crystal display module, and is particularly suitable as a material for forming a patterned retardation member for a 3D display. The cured film is suitable as a material for forming a protective film, a planarizing film, an insulating film, and the like in various displays such as a Thin Film Transistor (TFT) type liquid crystal display device and an organic EL device, and particularly suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal device, a protective film of a color filter, an insulating film of an organic EL device, and the like.