JP2020019964A - Polymer containing repeating unit having n-alkoxymethyl group and repeating unit having side chain containing polymerizable c=c double bond - Google Patents

Abstract

To provide a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C=C double bond.SOLUTION: The present invention discloses: a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C=C double bond; a polymer to be used as a component for producing an optical film, which contains a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C=C double bond; a polymer to be used as a component for producing a liquid crystal aligning material, which contains a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C=C double bond; and a polymer to be used as a component for producing a retardation material, which contains a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C=C double bond.SELECTED DRAWING: None

Description

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

  2. Description of the Related Art In recent years, in the field of displays such as televisions using liquid crystal panels, the development of 3D displays capable of enjoying 3D images has been promoted as an effort for higher performance. In the 3D display, for example, an image with a three-dimensional effect can be displayed by causing the observer to visually recognize the right-eye image and the left eye to visually recognize the left-eye image.

There are various types of 3D display systems for displaying 3D images, and lenticular lens systems and parallax barrier systems are known as systems that do not require special glasses.
As one of display systems in which an observer wears glasses and observes a 3D image, a circularly polarized glasses system or the like is known (for example, see Patent Literature 1).

  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 on which an image is formed. In this phase difference material, a plurality of two types of phase difference regions having different phase difference characteristics are regularly arranged, respectively, to form a patterned phase difference material. Hereinafter, in the present specification, a retardation material patterned to arrange a plurality of retardation regions having different retardation characteristics is referred to as a patterned retardation material.

  As disclosed in Patent Document 2, for example, a patterned retardation material can be produced by optically patterning a retardation material made of a polymerizable liquid crystal. Optical patterning of a retardation material composed of a polymerizable liquid crystal utilizes an optical alignment technique known for forming an alignment material of a liquid crystal panel. That is, a coating film made of a photo-alignable material is provided on a substrate, and two types of polarized lights having different polarization directions are irradiated on the coating film. Then, an optical alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. A solution type retardation material containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

  In the formation of an alignment material using the optical alignment technology of a liquid crystal panel, an acrylic resin or a polyimide resin having a photodimerization site such as a cinnamoyl group and a chalcone group in a side chain is known as a usable optical alignment material. . It has been reported that these resins exhibit the ability to control the orientation of liquid crystal (hereinafter, also referred to as liquid crystal orientation) by irradiation with polarized UV (see Patent Documents 3 to 5).

JP-A-10-232365 JP 2005-49865 A Patent No. 3611342 JP 2009-058584 A JP 2001-517719 A

  As described above, the patterned retardation material is formed by laminating a cured polymerizable liquid crystal layer on the photo-alignment film as the alignment material. Then, the patterned retardation material having such a laminated structure can be used for a configuration of a 3D display in its laminated state.

  The 3D display is sometimes used as a home television, and is required to have high reliability, especially durability over a long period of time. Therefore, durability is also required for the constituent members of the 3D display. Therefore, the patterned retarder must have high-precision optical patterning, have high light transmission characteristics, and have long-term durability.

  However, the conventional patterned retardation material has a problem in the adhesion between the photo-alignment film and the polymerizable liquid crystal layer. For example, between the photo-alignment film and the polymerizable liquid crystal layer, those that easily peel off from the initial stage of formation, and those that have excellent adhesion in the early stage of formation, are likely to peel off due to a decrease in adhesion over time. There was something.

  Above all, peeling between the photo-alignment film and the polymerizable liquid crystal layer, which occurs with the passage of time, becomes a defect of the 3D display actually used, and causes the display quality of the 3D display to deteriorate. Therefore, there is a need for a patterned retardation material that can perform optical patterning with high precision, has excellent light transmission characteristics, and has excellent durability. In particular, the adhesion between the photo-alignment film and the polymerizable liquid crystal layer in the initial stage of formation is excellent, and the durability for maintaining the excellent adhesion for a long period of time (hereinafter, in this specification, the adhesion durability ) Is demanded.

  The present invention has been made based on the above findings and examination results. That is, an object of the present invention is to provide a cured film forming composition which has excellent liquid crystal alignment properties and light transmission properties and is suitable for forming a cured film having excellent adhesion durability. In particular, when used as an alignment material and a layer of polymerizable liquid crystal is disposed thereon, it exhibits excellent liquid crystal alignment and light transmittance, and also has a long adhesiveness with the layer of polymerizable liquid crystal. An object of the present invention is to provide a cured film forming composition which forms a cured film having excellent adhesion durability which can be maintained for a period.

  An object of the present invention is to provide an alignment material which is excellent in liquid crystal alignment and light transmission properties and has excellent adhesion durability.

  An object of the present invention is to provide a retardation material that can perform optical patterning with high precision and has excellent durability.

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

A first aspect of the present invention provides:
(A) at least one compound having a photo-alignable group and a thermally crosslinkable group; and (B) a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C = C double bond. And a cured film-forming composition containing a polymer.
In the first embodiment of the present invention, the photo-alignable group of the component (A) is preferably a functional group having a structure that undergoes photodimerization or photoisomerization.
In the first aspect of the present invention, the photo-alignment group of the component (A) is preferably a cinnamoyl group or a group having an azobenzene structure.
In the first aspect of the present invention, (C) (C-1): a polymer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group; (C-2): A self-crosslinkable polymer having a substituent capable of thermally reacting with the component (A), and at least one polymer selected from the group consisting of (C-3): melamine formaldehyde resin. Is preferred.
In the first aspect of the present invention, it is preferable to further include (D) a crosslinking catalyst.
In the first aspect of the present invention, it is preferable that the composition further contains (E) a crosslinking agent.
In the first embodiment of the present invention, the proportion of the repeating unit having an N-alkoxymethyl group in the polymer as the component (B) is from 40 mol% to 90 mol% per 100 mol of all repeating units of the polymer. The proportion of the repeating unit having a side chain containing a polymerizable C ＝ C double bond is preferably from 10 mol% to 60 mol% per 100 mol of all repeating units of the polymer.
In the first embodiment of the present invention, the content ratio of the component (A) to the component (B) is preferably from 5:95 to 60:40 by mass ratio.
In the first aspect of the present invention, the composition for forming a cured film contains 5 to 500 parts by mass of the component (C) based on 100 parts by mass of the total of the components (A) and (B). Is preferred.

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

A third aspect of the present invention relates to a retardation material formed using a cured film obtained from the cured film forming composition of the first aspect of the present invention.
According to a fourth aspect of the present invention, there is provided a cured film forming composition according to the first aspect of the present invention, wherein a side chain containing a repeating unit having an N-alkoxymethyl group and a polymerizable C ＝ C double bond is used. A polymer comprising a repeating unit having the same. Furthermore, the present invention relates to a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C ＝ C double bond for use as a component for producing an optical film. Further, the present invention relates to a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C ＝ C double bond for use as a component for producing a liquid crystal alignment material. Further, the present invention relates to a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C ＝ C double bond for use as a component for producing a retardation material.

  According to the first aspect of the present invention, a cured film forming composition for providing an alignment material having excellent photoreaction efficiency and solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity even on a resin film. Things can be provided.

  According to the second aspect of the present invention, it is possible to provide an alignment material having excellent photoreaction efficiency and solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity even on a resin film.

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

  As described above, in order to produce a patterned retardation material having excellent durability, an alignment material having excellent adhesion durability, particularly, an alignment having excellent adhesion durability between a layer of a cured polymerizable liquid crystal. Materials are required. There is a need for a cured film forming composition suitable for forming an alignment material having such performance.

  The present inventor has conducted intensive studies in order to meet the above-described requirements, and as a result, a cured film obtained from a cured film forming composition having a specific composition has excellent light transmittance, and has a liquid crystal alignment by polarized light exposure. It has been found that it can be used as an alignment material by exhibiting a regulated liquid crystal alignment property. In addition, the present inventors have found that a cured film obtained from a cured film-forming composition having the specific composition exhibits excellent adhesion durability with a polymerizable liquid crystal layer polymerized and cured thereon. I found that. That is, the cured film obtained from the cured film forming composition having the specific composition of the present invention can constitute a photo-alignment film having excellent adhesion durability with the polymerizable liquid crystal layer.

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

<Curing film forming composition>
The cured film-forming composition of the present invention comprises (A) at least one compound having a photo-alignable group and a thermally crosslinkable group, (B) a repeating unit having an N-alkoxymethyl group, and a polymerizable C ＝ C double A polymer containing a repeating unit having a side chain containing a bond, (C-1) which is a component (C): at least one substitution selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. A polymer having a group, (C-2): a polymer having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking, and (C-3): a melamine formaldehyde resin. It may contain a kind of polymer and a crosslinking catalyst as the component (D). Further, a crosslinking agent can be contained as the component (E). Further, other additives can be contained as long as the effects of the present invention are not impaired. Further, a solvent can be contained.
Hereinafter, details of each component will be described.

[(A) component]
The component (A) in the cured film forming composition of the present invention is at least one compound having a photo-alignable group and a thermally crosslinkable group. As the component (A), a polymer can be used, but a compound other than the polymer can also be used. Here, the compound other than the polymer specifically means a compound having no repeating unit in the molecule, and is usually a low molecular compound. Therefore, the component (A) is at least one kind of a polymer having a photo-alignable group and a thermo-crosslinkable group, at least one kind of a compound other than the polymer having a photo-alignable group and a heat cross-linkable group, or It may be a mixture of a polymer having a thermocrosslinkable group and a compound other than the polymer having a photoalignable group and a thermocrosslinkable group.
The component (A) is a component that imparts photo-alignment to a cured film obtained from the cured film-forming composition of the present invention. In this specification, the component (A) is also referred to as a photo-alignment component.

The details when the component (A) is a compound other than a polymer will be described below.
When the component (A) is a compound other than the polymer, the component is usually a photo-alignment component having a lower molecular weight than the base polymer (B) described below.

In the cured film forming composition of the present invention, when the component (A) is a compound other than a polymer, the component (A) is a compound having a photo-alignable group, and further has a hydroxy group, a carboxyl group, an amide group, and an amino group. It can be a compound having one group selected from the group consisting of a group and an alkoxysilyl group.
In the present invention, the photo-alignable group generally refers to a functional group exhibiting the property of being oriented by light irradiation, and typically refers to a functional group having a photodimerizing or photoisomerizing structural site. Examples of the other photo-alignment group include a functional group (example compound: benzoic acid ester compound or the like) that causes a photo-Fries rearrangement reaction, a group (example compound; a cyclobutane ring or the like) that causes a photolysis reaction, and the like.

  The photodimerized structural site that the compound other than the polymer as the component (A) can have as a photoalignable group is a site that forms a dimer upon irradiation with light, and specific examples thereof include a cinnamoyl group and a chalcone. Groups, coumarin groups, anthracene groups and the like. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity.

  In addition, the photoisomerizable structural moiety that the compound other than the polymer as the component (A) can have as a photoalignable group refers to a structural moiety that is converted into a cis-form and a trans-form by light irradiation. Is a site having an azobenzene structure, a stilbene structure or the like. Of these, the azobenzene structure is preferred because of its high reactivity.

  The compound other than the polymer having a photo-alignment group and one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group is, for example, a compound represented by the following formula.

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

X ¹¹ is one or more bonds selected from a single bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl or a combination thereof, or one or more of the one or more bonds A structure in which 1 to 3 substituents selected from alkylene having 1 to 18 carbon atoms, phenylene, biphenylene or a combination thereof are bonded via a bond, wherein the substituents are respectively bonded via the bond A structure formed by connecting a plurality of pieces may be used.

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

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

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

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

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

  When a benzene ring is included in these substituents, the benzene ring is formed from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and a cyano group. It may be substituted by one or more selected same or different substituents.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon atom having 1 carbon atom. To 4 alkoxy groups, halogen atoms, trifluoromethyl groups or cyano groups.
Examples of the alkyl group having 1 to 18 carbon atoms defined above include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert group. -Butyl group, 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 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, 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 , 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-
A methyl-3-ethyl-n-pentyl group, a 2-methyl-2-ethyl-n-pentyl group, a 2-methyl-3-ethyl-n-pentyl group, a 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, etc. Is mentioned. Similarly, examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding carbon atoms among the groups listed above. Examples of 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 groups obtained by oxidizing or thiolating the above-mentioned alkyl groups. Among them, a group having a corresponding number of carbon atoms can be mentioned. Further, as the alkylene group having 1 to 20 carbon atoms, the above-mentioned alkyl group and a divalent group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms such as n-nonadecyl group and n-eicosyl group. Is mentioned.

Specific examples of the compound other than the polymer having a photo-alignable group and a hydroxy group as the component (A) include, for example, the compounds represented by the above formulas [A11] to [A15] and the compound other than the above formula. 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3- (Hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxycinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4- (8- Hydroxyoctyloxy) cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid Ester, ethyl 4- (4-hydroxybutyloxy) cinnamate, ethyl 4- (3-hydroxypropyloxy) cinnamate, ethyl 4- (2-hydroxyethyloxy) cinnamate, 4-hydroxy Methyloxycinnamic acid ethyl ester, 4-hydroxycinnamic acid ethyl ester, 4- (8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4- ( 4-hydroxybutyloxy) cinnamic acid phenyl ester, 4- (3-hydroxypropyloxy) cinnamic acid phenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxycinnamic acid Phenyl ester, phenyl 4-hydroxycinnamate Stele, 4- (8-hydroxyoctyloxy) cinnamic acid biphenyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4- (4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4- ( 3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4- (2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxycinnamic acid biphenyl ester, 4-hydroxycinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, 6-hydroxyhexyl cinnamate, 4-hydroxybutyl cinnamate, 3-hydroxypropyl cinnamate, 2-hydroxyethyl cinnamate, hydroxymethyl cinnamate, -(8-hydroxy (Octyloxy) azobenzene, 4- (6-hydroxyhexyloxy) azobenzene, 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-hydroxymethyloxychalcone, 4-hydroxychalcone, 4 ′-(8-hydroxyoctyloxy) chalcone, 4 ′-(6-hydroxyhexyloxy ) Lucone, 4 '-(4-hydroxybutyloxy) chalcone, 4'-(3-hydroxypropyloxy) chalcone, 4 '-(2-hydroxyethyloxy) chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxy Chalcone, 7- (8-hydroxyoctyloxy) coumarin, 7- (6-hydroxyhexyloxy) coumarin, 7- (4-hydroxybutyloxy) coumarin, 7- (3-hydroxypropyloxy) coumarin, 7- (2 -Hydroxyethyloxy) coumarin, 7-hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6- (4-hydroxybutyloxy) coumarin, 6- (3-hydroxy Propyloxy) coumarin, 6- (2 (Hydroxyethyloxy) coumarin, 6-hydroxymethyloxycoumarin, 6-hydroxycoumarin, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (6-hydroxyhexyloxy) Benzoyl] cinnamic acid methyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid methyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid methyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid methyl ester, 4- [4-hydroxybenzoyl] cinnamic acid methyl ester, 4- [4- (8-Hydroxyoctyloxy) benzoyl] cinskin Ethyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (3 -Hydroxypropyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid ethyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid ethyl ester, -[4-hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] silicon Tertiary butyl cinnamate, 4- [4- (4-hydroxybutyloxy) ) Benzoyl] cinnamic acid tert-butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tert-butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid Tertiary butyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tertiary butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (6 -Hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid Phenyl ester, 4- [4- (2-hydroxyethyloxy) Benzoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyloxy) Benzoyl] cinnamic acid biphenyl ester, 4- [4- (6-hydroxyhexyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic acid biphenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic Acid biphenyl ester, 4- [4-hydroxy Zoyl] cinnamic acid biphenyl ester, 4-benzoylcinnamic acid 8-hydroxyoctyl ester, 4-benzoylcinnamic acid 6-hydroxyhexyl ester, 4-benzoylcinnamic acid 4-hydroxybutyl ester, 4-benzoylcinnamic acid 3-hydroxypropyl ester, 4-benzoylcinnamic acid 2-hydroxyethyl ester, 4-benzoylcinnamic acid hydroxymethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4- [4- ( 6-hydroxyhexyloxy) benzoyl] chalcone, 4- [4- (4-hydroxybutyloxy) benzoyl] chalcone, 4- [4- (3-hydroxypropyloxy) benzoyl] chalcone, 4- [4- (2- Hydroxyethyloxy) benzoyl] chalcone, 4 -(4-hydroxymethyloxybenzoyl) chalcone, 4- (4-hydroxybenzoyl) chalcone, 4 ′-[4- (8-hydroxyoctyloxy) benzoyl] chalcone, 4 ′-[4- (6-hydroxyhexyloxy) ) Benzoyl] chalcone, 4 ′-[4- (4-hydroxybutyloxy) benzoyl] chalcone, 4 ′-[4- (3-hydroxypropyloxy) benzoyl] chalcone, 4′-
[4- (2-hydroxyethyloxy) benzoyl] chalcone, 4 ′-(4-hydroxymethyloxybenzoyl) chalcone, 4 ′-(4-hydroxybenzoyl) chalcone and the like.

  Specific examples of the compound other than the polymer having a photo-alignable group and a carboxyl group as the component (A) include cinnamic acid, ferulic acid, 4-methoxycinnamic acid, 4-ethoxycinnamic acid, 4-n -Propyloxycinnamic acid, 3,4-dimethoxycinnamic acid, coumarin-3-carboxylic acid, 4- (N, N-dimethylamino) cinnamic acid and the like.

  Specific examples of the compound other than the polymer having a photo-alignable group and an amide group as the component (A) include cinnamamide, 4-methylcinnamic amide, 4-ethylcinnamic amide, and 4-methoxy Cinnamic acid amide, 4-ethoxycinnamic acid amide and the like can be mentioned.

  Specific examples of the compound other than the polymer having a photo-alignable group and an amino group as the component (A) include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, and 3-aminocinnamic acid Methyl ester, 3-aminocinnamic acid ethyl ester and the like can be mentioned.

  Specific examples of the compound other than the polymer having a photo-alignable group and an alkoxysilyl group as the component (A) include methyl 4- (3-trimethoxysilylpropyloxy) cinnamate and 4- (3- Methyl triethoxysilylpropyloxy) cinnamate, ethyl 4- (3-trimethoxysilylpropyloxy) cinnamate, ethyl 4- (3-triethoxysilylpropyloxy) cinnamate, 4- (3 -Trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester 3-triethoxysilylhexyloxy) cinnamic acid ethyl ester and the like.

  As the component (A), a compound other than a polymer in which a polymerizable group is bonded via a spacer to a group in which a photo-orientable site represented by the following formula (1) is bonded to a heat-reactive site is preferable.

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

  When the benzene ring may be substituted with a substituent, examples of the substituent include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and an isobutyl group; a haloalkyl group such as a trifluoromethyl group; Alkoxy groups such as ethoxy groups; halogen atoms such as iodine, bromine, chlorine and fluorine; cyano groups; nitro groups.

Among the above R ^101, hydroxy group and amino group are preferred, a hydroxy group are particularly preferred.

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

  As a specific example of such a monomer in which a polymerizable group is bonded to a group in which a photo-alignment site and a heat-reactive site are bonded as the component (A), 4- (6-methacryloxyhexyl-1-oxy) Cinnamic acid, 4- (6-acryloxyhexyl-1-oxy) cinnamic acid, 4- (3-methacryloxypropyl-1-oxy) cinnamic acid, 4- (4- (3-methacryloxypropyl-) 1-oxy) acryloxy) benzoic acid, 4- (4- (6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, 4- (6-methacryloxyhexyl-1-oxy) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N- (4-cyanophenyl) cinnamamide, 4- (6-methacryloxyhexyl-1-oxy) -N-bishydro Such as phenoxyethyl cinnamaldehyde amides.

  Examples of the photo-alignment component of the compound other than the polymer as the component (A) include the above specific examples, but are not limited thereto.

  Next, details when the component (A) is a polymer, that is, a polymer having a high molecular weight, will be described below.

  When the component (A) contained in the cured film forming composition of the present invention is a polymer having a high molecular weight, the component (A) is a polymer having a photo-alignment group, that is, a photo-alignable group. It is preferable to use a polymer having a functional group of a structural part that undergoes quantification or photoisomerization, particularly an acrylic copolymer having at least a photodimerization part. Furthermore, an acrylic having one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group (hereinafter, also referred to as a thermal crosslinking site including these groups) in addition to the photodimerization site. Desirably, it is a copolymer.

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

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

  Examples of the photodimerization site include a cinnamoyl group, a chalcone group, a coumarin group, and an anthracene group. Of these, a cinnamoyl group is preferred because of its high transparency in the visible light region and high photodimerization reactivity. More preferred examples of the cinnamoyl group and the substituent having a cinnamoyl structure include a structure represented by the following formula [1] or [2]. In this specification, a group in which a benzene ring in a cinnamoyl group is a naphthalene ring is also included in the “cinnamoyl group” and the “substituent having a cinnamoyl structure”.

In the above formula [1], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At that time, the phenyl group and the biphenyl group may be substituted by any of a halogen atom and a cyano group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as the groups exemplified above as the alkyl group having 1 to 18 carbon atoms.

In the formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as the groups exemplified above as the alkyl group having 1 to 18 carbon atoms. At this time, the alkyl group having 1 to 18 carbon atoms, phenyl group, biphenyl group and cyclohexyl group are formed from a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond, a urethane bond, an amino bond, a carbonyl or a combination thereof. A plurality of types may be bonded via one or more selected types of bonds.

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

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

  The thermal cross-linking site is a site that bonds to the component (B) by heating, and specific examples thereof include a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxysilyl group.

  The acrylic copolymer as the component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight-average molecular weight is more than 200,000, the solubility in a solvent may be reduced and the handling property may be reduced. On the other hand, if the weight-average molecular weight is less than 3,000, it may be too small. In some cases, insufficient curing occurs during thermal curing, resulting in reduced solvent resistance or reduced heat resistance.

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

  Examples of the monomer having a photodimerization site include a monomer having a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, and the like. Among these, a monomer having a cinnamoyl group is particularly preferable because of its high transparency in the visible light region and high photodimerization reactivity.

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

In the above formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. At that time, the phenyl group and the biphenyl group may be substituted by any of a halogen atom and a cyano group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as the groups exemplified above as the alkyl group having 1 to 18 carbon atoms.
L ¹ and L ² each independently represent a covalent bond, an ether bond, an ester bond, an amide bond, a urea bond or a urethane bond.

In the above formula [4], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as the groups exemplified above as the alkyl group having 1 to 18 carbon atoms. At this time, the alkyl group having 1 to 18 carbon atoms, phenyl group, biphenyl group, and cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

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

In the above formulas [3] and [4], X ⁴ and X ⁶ represent a polymerizable group. Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, a styrene group, a maleimide group, an acrylamide group, and a methacrylamide group.

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

  Examples of the monomer having a thermal crosslinking site include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, and 2,3. -Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, Poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyl oxy Monomers having a hydroxy group such as -6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone; acrylic acid, methacrylic acid, crotonic acid, Mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide Monomers having a carboxyl group such as hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) maleimide, N- (hydroxyphenyl) Monomers having a phenolic hydroxy group such as reimide; monomers having an amide group such as acrylamide and methacrylamide; methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltriethoxysilane, acryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane And other monomers having an alkoxysilyl group.

  The amount of the monomer having a photodimerization site used to obtain the specific copolymer and the amount of the monomer having a thermal crosslinking site used is determined based on the total amount of all monomers used to obtain the specific copolymer. It is preferable that the amount of the monomer having 40% by mass to 95% by mass and the amount of the monomer having the thermal crosslinking site be 5% by mass to 60% by mass. By setting the content of the monomer having a photodimerization site to 40% by mass or more, high sensitivity and good liquid crystal alignment can be provided. On the other hand, when the content is 95% by mass or less, sufficient thermosetting can be imparted, and high sensitivity and good liquid crystal alignment can be maintained.

  In the cured film-forming composition of the present invention, when a specific copolymer is obtained, a monomer copolymerizable with a monomer having a photodimerization site and a thermal crosslinking site (hereinafter, also referred to as a specific functional group) ( Hereinafter, also referred to as a monomer having a non-reactive functional group).

Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.
Hereinafter, specific examples of the above monomer will be given, but the present invention is not limited to these.

  Examples of the above-mentioned acrylate compound include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl Acrylate, 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- Li cycloalkyl decyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylate compound described above include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl Methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2- Adamantyl methacrylate, γ-butyrolactone Acrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and, 8-ethyl-8-tricyclodecyl methacrylate.

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

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

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

  The method for obtaining the specific copolymer used in the cured film forming composition of the present invention is not particularly limited. For example, a monomer having a specific functional group (a monomer having a photodimerization site and a monomer having a thermal crosslinking site), and optionally a non-functional monomer It is obtained by performing a polymerization reaction at a temperature of 50 ° C to 110 ° C in a solvent in which a monomer having a reactive functional group, a polymerization initiator, and the like coexist. At this time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having a non-reactive functional group optionally used, a polymerization initiator, and the like. Specific examples include the solvents described in the solvent described below.

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

Further, the solution of the specific copolymer obtained as described above is charged under stirring with diethyl ether, water, or the like to reprecipitate, and the resulting precipitate is filtered and washed, and then subjected to normal pressure or reduced pressure. By drying at room temperature or under heating, a powder of the specific copolymer can be obtained. By such an operation, a polymerization initiator and an unreacted monomer that coexist with the specific copolymer can be removed, and as a result, a purified specific copolymer powder can be obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

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

  In the present embodiment, the acrylic copolymer of the component (A) may be a mixture of a plurality of specific copolymers.

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

[Component (B)]
The component (B) contained in the cured film forming composition of the present invention is a polymer containing a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable CＣC double bond (hereinafter, referred to as a polymer). Specific copolymer 2).

  The N of the N-alkoxymethyl group, that is, the nitrogen atom, is the nitrogen atom of an amide, the nitrogen atom of a thioamide, the nitrogen atom of a urea, the nitrogen atom of a thiourea, the nitrogen atom of a urethane, or the adjacent position of the nitrogen atom of a nitrogen-containing heterocycle. And a nitrogen atom bonded thereto. Therefore, as the N-alkoxymethyl group, a nitrogen atom of an amide, a nitrogen atom of a thioamide, a nitrogen atom of a urea, a nitrogen atom of a thiourea, a nitrogen atom of a urethane, a nitrogen atom bonded to a nitrogen atom adjacent to a nitrogen atom of a nitrogen-containing heterocycle. And a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

The monomer that provides a repeating unit having an N-alkoxymethyl group (hereinafter, also referred to as a specific monomer X1) is not particularly limited as long as it is a monomer having the above group, but is preferably, for example, represented by the following formula (b1). Compounds to be used.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.)

Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 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, -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, 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- Butyl 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, 2-methyl-3-ethyl-n-pentyl, 3-methyl-3-ethyl-n-pentyl, n-nonyl, n-decyl and the like.

  Specific examples of such a monomer include hydroxymethyl groups such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Or an acrylamide compound or a methacrylamide compound substituted with an alkoxymethyl group. In addition, (meth) acrylamide means both methacrylamide and acrylamide.

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

  The specific side chain in the repeating unit having a side chain containing a polymerizable C = C double bond of the component (B) has 3 to 16 carbon atoms and has an unsaturated bond at a terminal. Is preferable, and a specific side chain represented by the formula (b2) is particularly preferable. The specific side chain represented by the formula (b2) binds to the ester bond of the acrylic polymer as shown in the formula (b2-1).

In the formula (b2), R ⁵¹ has 1 to 14 carbon atoms and is an organic group selected from the group consisting of an aliphatic group, an aliphatic group having a cyclic structure and an aromatic group, or An organic group consisting of a combination of a plurality of organic groups selected. R ⁵¹ may include an ester bond, an ether bond, an amide bond, a urethane bond, or the like.

In the formula (b2), R ⁵² is a hydrogen atom or a methyl group, and is preferably a specific side chain in which R ⁵² is a hydrogen atom, and more preferably a specific side chain whose terminal is an acryloyl group, a methacryloyl group or a styryl group. is there.

In the formula (b2-1), R ⁵³ is a hydrogen atom or a methyl group.

  The method for obtaining the polymer having the specific side chain as described above is not particularly limited. For example, an acrylic polymer having a specific functional group is generated in advance by a polymerization method such as radical polymerization. Next, the specific functional group is reacted with a compound having an unsaturated bond at a terminal (hereinafter, referred to as a specific compound) to generate a specific side chain, whereby the polymer as the component (B) is polymerized. Side chains containing C = C double bonds can be introduced.

  Here, the specific functional group refers to a functional group such as a carboxyl group, a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group, or a plurality of types of functional groups selected from these. .

  In the above-described reaction for generating the specific side chain, a specific combination of a specific functional group and a functional group possessed by the specific compound and involved in the reaction is preferably a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, and a phenolic group. Examples include a hydroxy group and an epoxy group, a carboxyl group and an isocyanate group, an amino group and an isocyanate group, or a hydroxy group and an acid chloride. Further, a more preferred combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

  In the above-described reaction for generating a specific side chain, the polymer having a specific functional group is a monomer having a functional group (specific functional group) for reacting with a specific compound in addition to the specific monomer X1, that is, a carboxyl group. A monomer having a glycidyl group, a hydroxy group, an amino group having an active hydrogen, a phenolic hydroxy group or an isocyanate group (hereinafter also referred to as a specific monomer X2) as an essential component; It has a molecular weight of 2,000 to 25,000. Here, the monomer having a specific functional group used for the polymerization may be used alone or in combination of two or more as long as the combination does not react during the polymerization.

  Hereinafter, specific examples of the monomer necessary for obtaining the polymer having the specific functional group, that is, the specific monomer X2 will be described. However, it is not limited to these.

  Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl) ) Maleimide, N- (carboxyphenyl) methacrylamide and N- (carboxyphenyl) acrylamide.

Examples of the monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7 -Octadiene monoepoxide and the like.

  Examples of the monomer having a hydroxy group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3- Dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether acrylate, poly (Ethylene glycol) ethyl ether methacrylate, 5-acryloyl Shi-6-hydroxy-norbornene-2-carboxylic-6-lactone and 5-methacryloyloxy such acryloyloxy-6-hydroxy-norbornene-2-carboxylic-6-lactone.

  Examples of the monomer having an amino group include 2-aminoethyl acrylate and 2-aminomethyl methacrylate.

  Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleimide.

  Examples of the monomer having an isocyanate group include acryloylethyl isocyanate, methacryloylethyl isocyanate, and m-tetramethylxylene isocyanate.

In such a side chain represented by the obtained formula (b2) in the, specific examples of R ⁵¹ are, like the following formula (B-1) ~ formula (B-11).

  In addition, in the present invention, when obtaining the polymer of the component (B), in addition to the specific monomer X1 and the specific monomer X2, the specific monomer X1 does not have the substituent capable of being copolymerized with the monomer and capable of being thermally crosslinked. Monomers can be used in combination.

Specific examples of such a monomer include the specific monomer X1, and an acrylate or methacrylate compound having a structure different from that of the specific monomer X2, a maleimide compound, an acrylamide compound, an acrylonitrile, a maleic anhydride, and a styrene compound. And vinyl compounds.

Hereinafter, specific examples of the monomer will be described, but the invention is not limited thereto.
Examples of the acrylate compound having a structure different from the specific monomer X1 and the like include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, Naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl 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, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylate compound having a structure different from the specific monomer X1 or the like include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, Naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2 -Ethoxyethyl methacrylate, tetrahydrofurfuryl meth Acrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8- Tricyclodecyl methacrylate and the like.

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

  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.

  The proportion of the repeating unit having an N-alkoxymethyl group in the polymer of the component (B) is preferably from 40 mol% to 90 mol%, more preferably from 50 mol% to 85 mol%, per 100 mol of all repeating units of the polymer. Mole% is more preferred.

That is, the amount of the specific monomer X1 used to obtain the specific copolymer 2 as the component (B) is based on the total amount of all the monomers used to obtain the specific copolymer 2 as the component (B). Therefore, it is preferably from 40 mol% to 90 mol%, more preferably from 50 mol% to 85 mol%.
If the total is less than 40 mol%, the curing by thermal crosslinking with the component (A) may be insufficient, and if it is more than 90 mol%, the adhesiveness to the substrate may be adversely affected. There is.

  (B) The proportion of the repeating unit having a side chain containing a polymerizable C ＝ C double bond in the polymer of the component is 10 mol% to 60 mol% per 100 mol of all repeating units of the polymer. Is preferably, and more preferably, 15 to 50 mol%.

That is, the amount of the specific monomer X2 used to obtain the specific copolymer 2 as the component (B) is based on the total amount of all the monomers used to obtain the specific copolymer 2 as the component (B). Therefore, it is preferably from 10 mol% to 60 mol%, and more preferably from 15 mol% to 50 mol%.
When the total is less than 10 mol%, the adhesion to the liquid crystal layer may be insufficient, and when the total is more than 60 mol%, curing by thermal crosslinking with the component (A) may be insufficient. May be.

  The method for obtaining the specific copolymer 2 which is an example of the component (B) is not particularly limited. For example, a specific monomer X1, a specific monomer X2, and, if desired, other monomers and a polymerization initiator are allowed to coexist. It is obtained by a polymerization reaction at a temperature of 50 ° C to 110 ° C in a solvent. At this time, the solvent used is not particularly limited as long as it dissolves the monomer represented by the above formula X, the other monomers used as desired, the polymerization initiator, and the like. Specific examples are described in the section of [solvent] described below.

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

  Further, a solution of an acrylic polymer, which is an example of the component (B) obtained by the above method, is put into diethyl ether, water, or the like with stirring to reprecipitate, and the generated precipitate is filtered and washed. It can be dried at normal temperature or under reduced pressure at normal temperature or under heat to obtain a powder of the specific copolymer 2 of the component (B). By the above-mentioned operation, the polymerization initiator and the unreacted monomer which coexist with the specific copolymer 2 of the component (B) can be removed. As a result, the specific copolymer which is an example of the purified component (B) can be removed. 2 powder is obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  In the composition for forming a cured film on the surface of the optical film of the present invention, the specific copolymer 2 of the component (B) is used in the form of a powder or a solution in which a purified powder is redissolved in a solvent described below. You may.

  In the composition for forming a cured film on the surface of the optical film of the present invention, the component (B) may be a mixture of a plurality of types of the specific copolymer 2 shown as an example of the component (B).

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

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

The content of the component (B) in the cured film forming composition of the present invention is preferably such that the content ratio of the component (A) to the component (B) is from 5:95 to 60:40 by mass. If the content of the polymer as the component (B) is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film-forming composition are reduced, and the alignment sensitivity at the time of optical alignment is reduced. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be reduced.

[(C) component]
The component (C) contained in the composition of the present invention is (C-1): a polymer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. , (C-2): a self-crosslinkable polymer having a substituent capable of thermally reacting with the component (A), or (C-3): a melamine formaldehyde resin; is there. Hereinafter, each component will be described in detail.

[(C-1) component]
The component (C-1) is a polymer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group (hereinafter also referred to as a specific (co) polymer 1). ).

  Examples of the polymer as the component (C-1) include acrylic polymers, urethane-modified acrylic polymers, polyamic acids, polyimides, polyvinyl alcohols, polyesters, polyester polycarboxylic acids, polyether polyols, polyester polyols, polycarbonate polyols, and polycaprolactone. Examples thereof include polymers having a linear or branched structure such as polyol, polyalkyleneimine, polyallylamine, celluloses (cellulose or derivatives thereof), and phenol novolak resins, and cyclic polymers such as cyclodextrins.

  Among them, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as an acrylate, a methacrylate, or styrene can be used.

  The method for synthesizing the acrylic polymer as an example of the component (C-1) includes a monomer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group; If desired, a method of (co) polymerizing another monomer is simple.

Examples of the monomer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl Acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy ) Ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) Ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone Monomers having a hydroxy group such as acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, vinylbenzoic acid, N- ( Monomers having a carboxyl group such as carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and p-hydroxystyrene, m-hydroxys Monomers having a phenolic hydroxyl group such as len, o-hydroxystyrene, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) acrylamide and N- (hydroxyphenyl) maleimide, acrylamide, methacrylamide, N-methylacrylamide, Monomers having an amide group such as N, N-dimethylacrylamide and N, N-diethylacrylamide; monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate and aminopropyl methacrylate; trimethoxysilylpropyl acrylate; Alkoxy such as trimethoxysilylpropyl methacrylate, triethoxysilylpropyl acrylate and triethoxysilylpropyl methacrylate Examples include a monomer having a silyl group.

  Further, in the present invention, when obtaining an acrylic polymer as an example of the component (C-1), at least one substitution selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. In addition to the monomer having a group, a monomer having no substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, which can be copolymerized with the monomer, can be used in combination. .

  Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.

Hereinafter, specific examples of the monomer will be described, but the invention is not limited thereto.
Examples of the acrylate compound include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, and phenyl acrylate. Glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl Acrylate, 3-methoxybutyl acrylate, 2-methyl-2- Daman chill acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and the like 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylate compound include, for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate Glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl Methacrylate, 3- Toxibutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate And the like.

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

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

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

  The amount of the monomer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group used for obtaining an acrylic polymer as an example of the component (C-1) Is preferably 5 mol% to 100 mol% based on the total amount of all monomers used to obtain the acrylic polymer which is an example of the component (C-1).

  The method for obtaining the acrylic polymer as an example of the component (C-1) is not particularly limited. For example, at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group In a solvent in which a monomer having no, optionally a hydroxy group, a carboxyl group, an amide group, an amino group and an unsubstituted monomer selected from the group consisting of an alkoxysilyl group and a polymerization initiator, etc. It is obtained by a polymerization reaction at a temperature of from 110 to 110 ° C. At that time, the solvent used is a monomer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group, and optionally a hydroxy group, a carboxyl group, an amide group, There is no particular limitation as long as it dissolves a monomer having no substituent selected from the group consisting of an amino group and an alkoxysilyl group, a polymerization initiator, and the like. Specific examples are described in the section of [solvent] described below.

  The acrylic polymer which is an example of the component (C-1) obtained by the above method is usually in a state of a solution dissolved in a solvent.

  The solution of the acrylic polymer as an example of the component (C-1) obtained by the above method was poured into diethyl ether, water, or the like with stirring to reprecipitate, and the generated precipitate was filtered and washed. Thereafter, the resultant is dried at normal temperature or under reduced pressure at normal temperature or under heat to obtain an acrylic polymer powder as an example of the component (C-1). By the above operation, the polymerization initiator and the unreacted monomer coexisting with the acrylic polymer as an example of the component (C-1) can be removed, and as a result, the acrylic as an example of the purified component (B) can be removed. A polymer powder is obtained. When the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  The acrylic polymer as an example of the component (C-1) preferably has a weight average molecular weight of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight-average molecular weight is more than 200,000, the solubility in a solvent may be reduced and handling properties may be reduced. If the weight-average molecular weight is less than 3,000, the curing is insufficient during thermal curing. And the solvent resistance and heat resistance may decrease. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as standard data. Hereinafter, the same applies to this specification.

Next, polyether polyols, which are preferable examples of the specific (co) polymer 1 of the component (C-1), include polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, and sorbitol. To which propylene oxide, polyethylene glycol, polypropylene glycol or the like is added. Specific examples of the polyether polyols include ADEKA polyether P series, G series, EDP series, BPX series, FC series, CM series, NOOX UNIOX (registered trademark) HC-40, HC-60, and ST- made by ADEKA. 30E,
ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, Nonion (Registered trademark) LT-221, ST-221, OT-221 and the like.

  Examples of the polyester polyol which is a preferred example of the specific (co) polymer of the component (C-1) include polycarboxylic acids such as adipic acid, sebacic acid and isophthalic acid, as well as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and the like. Those obtained by reacting a diol such as polypropylene glycol can be used. Specific examples of polyester polyols include DIC Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD-X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X-2523, OD- X-2555, OD-X-2560, Kuraray polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F -2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

  The polycaprolactone polyol, which is a preferred example of the specific (co) polymer of the component (C-1), is obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. No. Specific examples of the polycaprolactone polyol include DIC-made Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, and Daicel Chemical's Praxel (registered trademark) 205, L205AL, 205U, 208, 210. , 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320 and the like.

  As a polycarbonate polyol which is a preferred example of the specific (co) polymer of the component (C-1), a polycarbonate polyol obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like is used. No. Specific examples of the polycarbonate polyol include Praxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, Ltd., and C-590, C-1050, C-2050, C-2090, and C-3090 manufactured by Kuraray.

  Examples of cellulose which is a preferred example of the specific (co) polymer 1 of the component (C-1) include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, and hydroxy such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl ethyl cellulose. Examples thereof include alkylalkyl celluloses and cellulose, and preferred examples thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose.

Examples of the cyclodextrin which is a preferred example of the specific (co) polymer 1 of the component (C-1) include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ cyclodextrin, methyl-α-cyclodextrin, methyl Methylated cyclodextrins such as -β-cyclodextrin and methyl-γ-cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α- Cyclodextrin, 2-hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-h Droxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin And 2,3-dihydroxypropyl-β-cyclodextrin, and hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-γ-cyclodextrin.

  As a urethane-modified acrylic polymer which is a preferred example of the specific (co) polymer 1 of the component (C-1), commercially available products of Acryt (registered trademark) 8UA-017, 8UA-239, 8UA-239H, manufactured by Taisei Fine Chemical, 8UA-140, 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, 8UA-366 and the like.

  Examples of the phenol novolak resin, which is a preferred example of the specific (co) polymer 1 of the component (C-1), include a phenol-formaldehyde polycondensate.

  In the composition of the present invention, the polymer of the component (C-1) may be used in the form of a powder or a solution in which a purified powder is redissolved in a solvent described below.

  In the composition of the present invention, the component (C-1) may be a mixture of a plurality of types of the polymers exemplified as the component (C-1).

[(C-2) component]
In the cured film forming composition of the present embodiment, the component (C-2) has a substituent capable of thermally reacting with the component (A), and is a self-crosslinkable polymer (hereinafter also referred to as a specific (co) polymer 2). ).

  More specifically, the specific (co) polymer 2 causes a thermal reaction and a self-crosslinking reaction with the component (A), and reacts at a temperature lower than the sublimation temperature of the component (A). A polymer having a substituent and a hydroxy group, a carboxyl group, an amino group, an amide group, and an alkoxysilyl group. Sublimation of the component (A) due to the thermal reaction between the component (A) and the component (C-2) can be suppressed. Then, the cured film forming composition of the present embodiment can form an alignment material having high photoreaction efficiency as a cured film, as described above.

  Preferred crosslinking substituents contained in the polymer (C-2) include an alkoxymethylamide group and an alkoxysilyl group. The content of such a crosslinkable substituent is preferably from 0.5 to 1 per one repeating unit of the component (C-2), and from the viewpoint of the solvent resistance of the alignment material, from 0.8 to 1 per unit. More preferably, the number is

  The polymer as the component (C-2) is, for example, substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide. A polymer produced using an acrylamide compound or a methacrylamide compound can be used.

  Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl. Examples include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.

Further, as the component (C-2), a polymer produced using a compound having an alkoxysilyl group can also be used.
Examples of such a polymer include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, poly (3-acryloxypropyltrimethoxysilane), -A copolymer of acryloxypropyltrimethoxysilane and methyl methacrylate.

  In the specific (co) polymer 2 used in the cured film forming composition of the present embodiment, a monomer copolymerizable with a monomer having a specific functional group (hereinafter also referred to as a monomer having a non-reactive functional group) is used. Can be used together.

Specific examples of such a monomer include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl compound.
Specific examples of the monomer are as described for the component (C-1).

The method for obtaining the specific (co) polymer 2 used in the cured film forming composition of the present embodiment is not particularly limited. For example, a monomer having a specific functional group, a monomer having a non-reactive functional group if desired, and polymerization initiation It is obtained by performing a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which an agent or the like coexists. At this time, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer having a non-reactive functional group optionally used, a polymerization initiator, and the like. Specific examples include the solvents described in the solvent described below.
The specific (co) polymer 2 thus obtained is usually in the form of a solution dissolved in a solvent.

  The solution of the specific (co) polymer 2 obtained as described above is charged under stirring with diethyl ether, water, or the like to cause reprecipitation, and the generated precipitate is filtered and washed, and then subjected to normal pressure. Alternatively, the powder of the specific (co) polymer 2 can be obtained by drying at room temperature or under heat under reduced pressure. By such an operation, a polymerization initiator and an unreacted monomer that coexist with the specific (co) polymer 2 can be removed, and as a result, a purified powder of the specific (co) polymer 2 is obtained. When purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  In the cured film forming composition of the present embodiment, the powder of the specific (co) polymer 2 may be used as it is, or the powder is redissolved in, for example, a solvent described below to form a solution. May be used.

    In the present embodiment, the polymer of the component (C-2) may be a mixture of a plurality of specific (co) polymers 2.

The weight average molecular weight of such a polymer is from 1,000 to 500,000, preferably from 1,000 to 200,000, more preferably from 1,000 to 100,000, and even more preferably from 2,000 to 50,000.
These polymers can be used alone or in combination of two or more.
[(C-3) component]

  The melamine formaldehyde resin of the component (C-3) is a resin obtained by polycondensing melamine and formaldehyde, and is represented by the following formula.

In the above formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n is a natural number representing the number of repeating units. Examples of the alkyl group having 1 to 4 carbon atoms include groups having the corresponding carbon atoms among the above-described alkyl groups.

  In the melamine formaldehyde resin of the component (C-3), it is preferable that a methylol group generated during polycondensation of melamine and formaldehyde is alkylated from the viewpoint of storage stability.

  The method for obtaining the melamine formaldehyde resin of the component (C-3) is not particularly limited, but generally, melamine and formaldehyde are mixed, and the mixture is made weakly alkaline with sodium carbonate, ammonia, or the like, and then heated at 60 ° C to 100 ° C. It is synthesized by heating. Further, a methylol group can be alkoxylated by reacting with an alcohol.

  The weight average molecular weight of the melamine formaldehyde resin (C-3) is preferably from 250 to 5,000, more preferably from 300 to 4,000, and even more preferably from 350 to 3,500. If the weight average molecular weight is more than 5,000 and is too large, the solubility in a solvent may be reduced and handling properties may be reduced. If the weight average molecular weight is less than 250 and too small, insufficient curing may occur during thermal curing. And the effect of improving solvent resistance and heat resistance may not be sufficiently exhibited.

  In the embodiment of the present invention, the melamine formaldehyde resin as the component (C-3) may be used in a liquid form or a solution form in which a purified liquid is redissolved in a solvent described below.

  In the embodiment of the present invention, the component (C) may be a mixture of a plurality of types of polymers selected from the group consisting of (C-1), (C-2), and (C-3). .

  The content of the component (C) in the cured film forming composition of the present invention is 5 parts by mass to 500 parts by mass based on 100 parts by mass of the total amount of the components (A) and (B). When the content of the polymer as the component (C) is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film forming composition decrease, and the alignment sensitivity at the time of photo-alignment decreases. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be reduced.

[(D) component]
The composition for forming a cured film on the surface of the optical film of the present invention can contain a crosslinking catalyst as a component (D) in addition to the components (A), (B) and (C) described above. .
Examples of the crosslinking catalyst as the component (D) include an acid or a thermal acid generator. The component (D) is effective for promoting a thermosetting reaction in forming a cured film using the composition for forming a cured surface film in the optical film of the present invention.

  When an acid or a thermal acid generator is used as the component (D), the component (D) is a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, a compound capable of generating an acid by thermal decomposition during prebaking or postbaking, that is, a temperature of 80%. The compound is not particularly limited as long as it is a compound that generates an acid by being thermally decomposed at a temperature of from 250C to 250C.

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

  Compounds that generate an acid by heat include, for example, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,2 3-phenylene squirt (methyl sulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluenesulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydrido Kishibuchiru p- tosylate, N- ethyl-4-toluenesulfonamide, and the following formula [TAG-1] to may be mentioned a compound represented by such formula [TAG-41].

  The content of the component (D) in the cured film-forming composition of the embodiment of the present invention is at least one type of a compound having a photo-alignable group and a thermally crosslinkable group as a component (A), and a polymer as a component (B). , (C) 0.01 to 20 parts by mass, preferably 0.01 to 10 parts by mass, more preferably 0.05 part by mass based on 100 parts by mass of the total amount of the polymer as the component (C). To 8 parts by mass, more preferably 0.1 to 6 parts by mass. When the content of the component (D) is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted, and high sensitivity to exposure can be imparted. When the content is 20 parts by mass or less, the storage stability of the cured film-forming composition can be improved.

[(E) component]
The cured film forming composition of the present embodiment optionally contains a crosslinking agent as the component (E). More specifically, the component (E) is a crosslinking agent that reacts with the components (A) and (C) described above. The component (E) includes a substituent selected from a hydroxy group, a carboxyl group, an amide group, an amino group and a trialkoxysilyl group of the compound as the component (A), a hydroxy group, a carboxyl group, and an amino group contained in the component (C). And a substituent selected from a group and a trialkoxysilyl group. And the cured film forming composition of the present embodiment can form an alignment material having high photoreaction efficiency as a cured film.

  Examples of the crosslinking agent as the component (E) include compounds such as an epoxy compound, a methylol compound, and an isocyanate compound, and are preferably a methylol compound.

  Specific examples of the above-mentioned methylol compound include, for example, compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.

  Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4 1,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds (trade names: Cymel (registered trademark) 1170, powder link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by Dainippon Ink and Chemicals, Inc. (high condensation type, commercial product) Name: Beckamine (registered trademark) J-300S, P-955, N).

  Specific examples of the alkoxymethylated benzoguanamine include, for example, tetramethoxymethylbenzoguanamine. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicaraq (registered trademark) BX-4000, BX-37, BL-) 60 and BX-55H).

Specific examples of the alkoxymethylated melamine include, for example, hexamethoxymethyl melamine. Commercially available products include methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) and butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark) manufactured by Mitsui Cytec Co., Ltd.) ), 506) and methoxymethyl type melamine compound manufactured by Sanwa Chemical (trade names: Nicarack (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, and MX-002). M
X-730, MX-750, and MX-035), butoxymethyl-type melamine compounds (trade names: Niclac (registered trademark) MX-45, MX-410, and MX-302).

  Further, a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group may be used. For example, high molecular weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,323,310 are mentioned. Commercial products of the melamine compound include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.) and the like. Commercial products of the benzoguanamine compound include a commercial name of Cymel (registered trademark) 1123 ( (Mitsui Cytec Co., Ltd.).

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

  In the cured film forming composition of the present embodiment, the content of the crosslinking agent of the component (E) is the total amount of the compound of the component (A), the polymer of the component (B), and the polymer of the component (C). It is preferably at most 50 parts by mass, more preferably at most 30 parts by mass, based on 100 parts by mass. If the content of the crosslinking agent is too large, the photo-alignment property and the storage stability may decrease.

[Other additives]
The cured film forming composition of the embodiment of the present invention may contain other additives as long as the effects of the present invention are not impaired.
As other additives, for example, a sensitizer can be contained. The sensitizer is effective in promoting a photoreaction when forming a cured film on the surface of the optical film of the present invention.

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

  These sensitizers are not particularly limited to those described above. These can be used alone or in combination of two or more.

  In the embodiment of the present invention, the use ratio of the sensitizer is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 100 parts by mass of the component (A). 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained.If the ratio is too large, the transmittance of a cured film to be formed may decrease or the coating film may be roughened. May be.

  In addition, the cured film-forming composition according to the embodiment of the present invention includes a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, and storage stability as long as the effects of the present invention are not impaired. Agents, defoamers, antioxidants and the like.

[solvent]
The cured film forming composition of the embodiment of the present invention is often used in a solution state dissolved in a solvent. The solvent used at that time dissolves the component (A) and the component (B), and optionally the component (C), the component (D), the component (E), and / or other additives. As long as the solvent has such a dissolving ability, its 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, propylene glycol monomethyl ether Acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, cyclopentyl methyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ -Butyrolactone, 2-hydroxypropion Ethyl, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate, isopropanol, N, N-dimethylformamide, N, N- Dimethylacetamide, N-methyl-2-pyrrolidone, and the like.

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

<Preparation of cured film forming composition>
The cured film forming composition of the embodiment of the present invention is a thermosetting cured film forming composition having photo-alignment. As described above, the cured film-forming composition of the present embodiment contains at least one compound having a photo-alignment group and a thermally crosslinkable group as the component (A) and an N-alkoxymethyl group as the component (B). Containing a repeating unit having a repeating unit having a polymerizable C 側 C double bond and a repeating unit having a side chain containing a polymerizable C 、 C double bond, if necessary, a component (C) (C-1): a hydroxy group, a carboxyl group, or an amide group , A polymer having at least one substituent selected from the group consisting of an amino group and an alkoxysilyl group, (C-2): a polymer having a substituent thermally reactable with the component (A), and capable of being self-crosslinked. (C-3): At least one polymer selected from the group consisting of melamine formaldehyde resin, and if necessary, a crosslinking catalyst as a component (D). If necessary, a crosslinking agent may be contained as the component (E). As long as the effects of the present invention are not impaired, other additives can be contained, and further, a solvent can be contained.

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

[1]: At least one compound having a photo-alignment group and a thermo-crosslinkable group as the component (A) and a repeating unit having an N-alkoxymethyl group as the component (B) and a polymerizable CＣC double The compounding ratio with the polymer containing a repeating unit having a side chain containing a bond is from 5:95 to 60:40 by mass ratio, and the total of at least one compound as the component (A) and the polymer as the component (B) (C-1) which is 5 parts by mass to 500 parts by mass based on 100 parts by mass of the component (C-1): at least selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group and an alkoxysilyl group. A group comprising a polymer having one substituent, (C-2): a polymer having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking, and (C-3): a melamine formaldehyde resin. Et least one polymer selected, the cured film-forming composition containing a solvent.

  [2]: The compounding ratio of the component (A) and the component (B) is 5:95 to 60:40 in terms of mass ratio, and the total amount of the compound (A) and the polymer of the component (B) is 100. 5 parts by mass to 500 parts by mass of component (C) and 100 parts by mass of the total amount of the component (A), the polymer of component (B) and the polymer of component (C) based on parts by mass. A cured film-forming composition containing 0.1 to 40 parts by mass of a crosslinking catalyst as a component (D) and a solvent.

  [3]: The compounding ratio of the component (A) and the component (B) is from 5:95 to 60:40 by mass ratio, and the total amount of the compound (A) and the polymer of the component (B) is 100. 5 parts by mass to 500 parts by mass based on 100 parts by mass of the component (C), the compound as the component (A), the polymer of the component (B) and the polymer of the component (C), 0.1 to 40 parts by mass of the component (D) and 100 parts by mass of the compound (A), the polymer of the component (B) and the polymer of the component (C) in an amount of 100 parts by mass. A cured film forming composition containing 0.011 parts by mass to 10 parts by mass of the component (E) and a solvent.

  The mixing ratio and the preparation method when the cured film forming composition of the present embodiment is used as a solution will be described in detail below.

  The proportion of the solid content in the cured film forming composition of the present embodiment is not particularly limited as long as each component is uniformly dissolved in the solvent, but is preferably 1% by mass to 80% by mass, and is preferably It is 2% by mass to 60% by mass, and more preferably 3% by mass to 40% by mass. Here, the solid content refers to a composition obtained by removing the solvent from all components of the cured film forming composition.

  The method for preparing the cured film forming composition of the present embodiment is not particularly limited. As a preparation method, for example, a solution of the component (B) dissolved in a solvent is mixed with the components (A), (C), (D) and (E) at a predetermined ratio to form a uniform solution. Or a method of adding and mixing other additives as necessary at an appropriate stage of the preparation method.

  In the preparation of the cured film forming composition of the present embodiment, a solution of the specific copolymer obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (A), the component (C), the component (D), and the component (E) are added to the solution prepared from the component (B) acrylic polymer to form a uniform solution. At this time, a solvent may be additionally introduced for the purpose of adjusting the concentration. At this time, the solvent used in the process of preparing the component (B) and the solvent used for adjusting the concentration of the cured film-forming composition may be the same or different.

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

As described above, the cured film-forming composition of the present embodiment of the present invention comprises at least one of the compound having a photo-alignable group and a thermally crosslinkable group as the component (A), and the N-alkoxy as the component (B). Polymer containing a repeating unit having a methyl group and a repeating unit having a side chain containing a polymerizable CＣC double bond, component (C) (C-1): hydroxy group, carboxyl group, amide group, amino A polymer having at least one substituent selected from the group consisting of a group and an alkoxysilyl group, (C-2): a polymer having a substituent capable of thermally reacting with the component (A), and a self-crosslinkable polymer; -3): at least one polymer selected from the group consisting of melamine formaldehyde resin, and a crosslinking catalyst as component (D). In the compound which is the component (A), the photo-alignable group constitutes a hydrophobic photoreactive part, and at least one substituent selected from a hydroxy group, a carboxyl group, an amino group and a trialkoxysilyl group has a hydrophilic thermo-reactive group. Configure the reaction section. At least one substituent selected from the hydroxy, carboxyl, amino and trialkoxysilyl groups of the polymer of component (C) is also hydrophilic.

  Therefore, the cured film formed from the cured film forming composition of the present embodiment is formed such that the inside thereof becomes hydrophilic due to the property of the component (C) so that the film structure is stabilized. . The compound of the component (A) in the cured film is unevenly distributed near the surface of the cured film. More specifically, the compound of the component (A) has a structure in which the hydrophilic heat-reactive portion faces the inside of the cured film and the hydrophobic photoreactive portion faces the surface, and the compound has a structure near the surface of the cured film. Unevenly distributed. As a result, the cured film of the present embodiment realizes a structure in which the proportion of the photoreactive group of the component (A) existing near the surface is increased. When the cured film of the present embodiment is used as an alignment material, the efficiency of a photoreaction for optical alignment can be improved, and excellent alignment sensitivity can be obtained. Furthermore, it becomes an orientation material suitable for forming a patterned retardation material, and a patterned retardation material manufactured using the same can have excellent pattern formability.

  Further, as described above, the cured film forming composition of the present embodiment has, as the component (B), a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable CＣC double bond. Contains a polymer containing units. Therefore, inside the cured film obtained from the cured film forming composition of the present embodiment, a crosslinking reaction due to a thermal reaction with the component (B) before the photoreaction of the compound of the component (A) by the photo-alignable group. It can be performed. As a result, when used as an alignment material, it is possible to improve the resistance to a polymerizable liquid crystal applied thereon and its solvent.

  Further, when the cured film obtained from the cured film forming composition of the present embodiment is used as an alignment material, the polymer as the component (B) is used as a cured polymerizable liquid crystal layer formed thereon. It functions to enhance the adhesion between the layers.

<Curing film, alignment material and retardation material>
A solution of the cured film forming composition of the present embodiment is applied to a substrate (eg, 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 substrate, etc.) and films (for example, resin films such as triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, acrylic film, etc.), bar coating, spin coating, flow coating, roll coating. A cured film can be formed by applying a film by slit coating, spin coating subsequent to the slit, spin coating, inkjet coating, printing, or the like, and then heating and drying with a hot plate or an oven.

  The heating and drying conditions may be such that the curing reaction proceeds to such an extent that the components of the alignment material formed from the cured film do not elute into the polymerizable liquid crystal solution applied thereon. For example, the temperature is 60 ° C. to 200 ° C. And a heating temperature and a heating time appropriately selected from the range of 0.4 to 60 minutes. The heating temperature and the heating time are preferably 70 ° C to 160 ° C, for 0.5 minute to 10 minutes.

  The thickness of the cured film formed using the curable composition of the present embodiment is, for example, 0.05 μm to 5 μm, and is appropriately selected in consideration of the step and the optical and electrical properties of the substrate used. be able to.

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

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

  Since the alignment material formed from the cured film composition of the present embodiment has solvent resistance and heat resistance, after applying a retardation material composed of a polymerizable liquid crystal solution on this alignment material, Is heated to the phase transition temperature to bring the retardation material into a liquid crystal state and is oriented on the alignment material. Then, the retardation material in a desired orientation state is cured as it is, and a retardation material having a layer having optical anisotropy can be formed.

  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 on which the alignment material is formed is a film, the film having the retardation material of the present embodiment is useful as a retardation film. A retardation material forming such a retardation material is in a liquid crystal state, and on an alignment material, there are alignment alignment states such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment, each of which is required. Can be used properly according to the phase difference characteristics.

  In the case of manufacturing a patterned retardation material used for a 3D display, a cured film formed by the method described above from the cured film composition of the present embodiment is applied to a cured film formed by a predetermined 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, after removing the mask, polarized UV is exposed in the direction of -45 degrees, thereby forming two types of liquid crystal alignment regions having different alignment control directions of the liquid crystal. An oriented material is formed. After that, a retardation material composed of a polymerizable liquid crystal solution is applied, and then heated to a liquid crystal phase transition temperature to bring the retardation material into a liquid crystal state. The polymerizable liquid crystal in the liquid crystal state is aligned on the alignment material in which two types of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the phase difference material in which such an alignment state is realized is cured as it is, and the above-described alignment state is fixed, and a plurality of two types of phase difference regions having different phase difference characteristics are respectively and regularly arranged. A retardation material can be obtained.

Further, the alignment material formed from the cured film composition of the present embodiment can also be used as a liquid crystal alignment film of a liquid crystal display device. For example, using two substrates having the alignment material of the present embodiment formed as described above, and after bonding the alignment materials on both substrates to each other via a spacer, the two substrates are placed between the substrates. A liquid crystal display device in which liquid crystal is aligned can be manufactured by injecting liquid crystal into the liquid crystal display device.
Therefore, the cured film forming composition of the present embodiment can be suitably used for manufacturing various retardation materials (retardation films), liquid crystal display elements, and the like.

  Hereinafter, the present embodiment will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

[Composition Components Used in Examples and Their Abbreviations]
The components used in the following examples and comparative examples are as follows.

<Component (A)>
CIN1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid

CIN2: 4- (3-methacryloxypropyl-1-oxy) cinnamic acid

CIN3: 4-propyloxycinnamic acid

CIN4: 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

CIN5: 3-methoxy-4- (6-hydroxyhexyloxy) cinnamic acid methyl ester

<Component (C)>
PEPO: polyester polyol polymer (adipic acid / diethylene glycol copolymer having the following structural unit; molecular weight: 4,800)

(In the above formula, R represents alkylene.)
<Component (D)>
PTSA: paratoluenesulfonic acid

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

<Polymer raw materials of components (A), (B), and (C)>
CIN1: 4- (6-methacryloxyhexyl-1-oxy) cinnamic acid HEMA: 2-hydroxyethyl methacrylate MMA: methyl methacrylate BMAA: N-butoxymethyl acrylamide AIBN: α, α′-azobisisobutyronitrile

<Solvent>
Each of the phase difference material forming compositions of Examples and Comparative Examples contained a solvent, and propylene glycol monomethyl ether (PM), butyl acetate (BA), methyl ethyl ketone (MEK), and cyclohexanone (CHN) were used as the solvent.

<Measurement of molecular weight of polymer>
The molecular weight of the polyimide, polyamic acid or acrylic polymer in the synthesis example was measured using a room temperature gel permeation chromatography (GPC) device (GPC-101) manufactured by Shodex, and columns (KD-803, KD-805) manufactured by Shodex. It was measured as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide hydrate (LiBr.H2O) 30 mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) ) Is 10 mL / L)
Flow rate: 1.0 mL / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol manufactured by Polymer Laboratory ( Molecular weight about 12,000, 4,000, 1,000).

^<1 H-NMR analysis>
^The analyzer and analysis conditions used for ¹ H-NMR analysis are as follows.
Nuclear magnetic resonance apparatus: Varian NMR System 400 NB (400 MHz)
Measurement solvent: DMSO-d ⁶
Reference substance: tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

<Polymerization Example 1>
4.0 g of M6CA, 4.0 g of styrene, 2.0 g of HEMA, and 0.1 g of AIBN as a polymerization catalyst were dissolved in 90.9 g of PM and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration). 10% by mass) (CIN6). Mn of the obtained acrylic copolymer was 20,000 and Mw was 55,000.

<Polymerization Example 2>
32.0 g of BMAA, 8.0 g of HEMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-1). Mn of the obtained acrylic copolymer was 7,000 and Mw was 20,000.

<Polymerization Example 3>
28.0 g of BMAA, 12.0 g of HEMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-2). Mn of the obtained acrylic copolymer was 8,300 and Mw was 25,000.

<Polymerization Example 4>
24.0 g of BMAA, 16.0 g of HEMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran, and reacted at 60 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-3). Mn of the obtained acrylic copolymer was 9,800 and Mw was 35,000.

<Polymerization Example 5>
32.0 g of BMAA, 8.0 g of GMA, and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-4). Mn of the obtained acrylic copolymer was 7,000 and Mw was 18,000.

<Polymerization Example 6>
40.0 g of GMA and 0.8 g of AIBN as a polymerization catalyst were dissolved in 204.0 g of tetrahydrofuran and reacted at 60 ° C. for 20 hours to obtain an acrylic polymer solution. The acrylic polymer solution was gradually dropped into 1000 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic polymer (PB-5). Mn of the obtained acrylic polymer was 8,000 and Mw was 20,000.

<Polymerization Example 7>
100.0 g of MMA, 11.1 g of HEMA, and 5.6 g of AIBN as a polymerization catalyst were dissolved in 450.0 g of PM, and reacted at 80 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 20% by mass) (PC -1) was obtained. Mn of the obtained acrylic copolymer was 4,200 and Mw was 7,600.

<Polymerization Example 8>
100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration: 35% by mass) (PC-2). . Mn of the obtained acrylic copolymer was 2,700 and Mw was 3,900.

<Synthesis example 1>
10.0 g of the acrylic copolymer (PB-1) obtained in Polymerization Example 2, 4.3 g of 2-acryloyloxyethyl isocyanate, 0.4 g of dibutylhydroxytoluene, and 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran. The reaction was performed at 60 ° C. for 5 hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer having an acroyl group (PB-6). ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PB-6) had an acroyl group.

<Synthesis Example 2>
10.0 g of the acrylic copolymer (PB-1) obtained in Polymerization Example 2, 4.3 g of 2-methacryloyloxyethyl isocyanate, 0.4 g of dibutylhydroxytoluene, and 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran. The reaction was performed at 60 ° C. for 5 hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-7) having a methacryloyl group. 1H-NMR analysis was performed to confirm that the acrylic copolymer (PB-7) had a methacryloyl group.

<Synthesis Example 3>
10.0 g of the acrylic copolymer (PB-2) obtained in Polymerization Example 3, 6.5 g of 2-acryloyloxyethyl isocyanate, 0.6 g of dibutylhydroxytoluene, and 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran. The reaction was performed at 60 ° C. for 5 hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer having an acroyl group (PB-8). ¹
H-NMR analysis was performed to confirm that the acrylic copolymer (PB-8) had an acroyl group.

<Synthesis example 4>
10.0 g of the acrylic copolymer (PB-3) obtained in Polymerization Example 4, 8.7 g of 2-acryloyloxyethyl isocyanate, 0.9 g of dibutylhydroxytoluene, and 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran. The reaction was performed at 60 ° C. for 5 hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer having an acroyl group (PB-9). ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PB-9) had an acroyl group.

<Synthesis example 5>
10.0 g of the acrylic copolymer (PB-4) obtained in Polymerization Example 5, 2.2 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM. Allowed to react for hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer having an acroyl group (PB-10). ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PB-10) had an acroyl group.

<Synthesis example 6>
10.0 g of the acrylic copolymer (PB-4) obtained in Polymerization Example 5, 2.2 g of methacrylic acid, 0.2 g of dibutylhydroxytoluene, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM. Allowed to react for hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-11) having a methacryloyl group. ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PB-11) had a methacryloyl group.

<Synthesis Example 7>
10.0 g of the acrylic copolymer (PB-5) obtained in Polymerization Example 6, 2.0 g of acrylic acid, 0.2 g of dibutylhydroxytoluene, and 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM. Allowed to react for hours. This solution was gradually dropped into 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer having an acroyl group (PB-12). ¹ H-NMR analysis was performed to confirm that the acrylic copolymer (PB-12) had an acroyl group.

<Preparation of base film>
The acrylic film used as a substrate can be prepared, for example, by the following method. That is, raw material pellets composed of a copolymer or the like containing methyl methacrylate as a main component are melted at 250 ° C. by an extruder, passed through a T-die, passed through a casting roll, a drying roll, and the like to form an acrylic film having a thickness of 40 μm. Can be created.

<Examples and comparative examples>
With the compositions shown in Table 1, cured film forming compositions of Examples and Comparative Examples were prepared. Next, a cured film was formed using each phase difference material forming composition, and the orientation and adhesion of each of the obtained cured films were evaluated.

[Evaluation of orientation]
Each of the cured film forming compositions of Examples and Comparative Examples was applied on a film using a bar coater, and then heated and dried in a heat circulating oven at a temperature of 100 ° C. for 2 minutes to form a cured film. Each cured film was vertically irradiated with 313 nm linearly polarized light at an exposure of 20 mJ / cm ² to form an alignment material. A polymerizable liquid crystal solution for horizontal alignment is applied on the alignment material on the substrate using a bar coater, and then prebaked on a hot plate at 70 ° C. for 60 seconds to form a coating film having a thickness of 1.0 μm. did. The coating film on this substrate was exposed at 300 mJ / cm 2 to produce a retardation material. The phase difference material on the prepared substrate is sandwiched between a pair of polarizing plates, and the state of the phase difference characteristics of the phase difference material is observed. The results were described as "Poor" in the column of "Orientation".

[Evaluation of adhesion]
Each of the cured film forming compositions of Examples and Comparative Examples was applied on a film using a bar coater, and then heated and dried in a heat circulating oven at a temperature of 100 ° C. for 2 minutes to form a cured film. Each cured film was vertically irradiated with 313 nm linearly polarized light at an exposure of 20 mJ / cm ² to form an alignment material. A polymerizable liquid crystal solution for horizontal alignment is applied on the alignment material on the substrate using a bar coater, and then prebaked on a hot plate at 70 ° C. for 60 seconds to form a coating film having a thickness of 1.0 μm. did. The coating film on this substrate was exposed at 300 mJ / cm ² to produce a retardation material. The phase difference material was cut with a cutter knife so as to form 10 × 10 squares at intervals of 1 mm vertically and horizontally. A cellophane tape peeling test was performed on the cut using a scotch tape. The result of the evaluation was “initial”, and all the 100 squares which remained without being peeled were evaluated as ○, and those which were peeled even in one square were evaluated as ×. The evaluation results are summarized in Table 2 later.

[Evaluation of durability adhesion]
The retardation material on the film produced in the same manner as in the evaluation of the adhesion described above was placed in an oven set at a temperature of 80 ° C. and a humidity of 90%, and allowed to stand for 72 hours or more. Thereafter, the retardation material was taken out, and the adhesion was evaluated by the same method as the evaluation of the adhesion described above. The evaluation results are collectively shown in Table 2 as “durability”.

[Result of evaluation]
Table 2 shows the results of the above evaluation, as described above.

The cured films obtained using the retardation material forming compositions of Examples 1 to 17 and Comparative Examples 1 and ² were able to form retardation materials with a low exposure dose of 20 mJ / cm ² . On the other hand, the cured film obtained by using each of the retardation material forming compositions of Comparative Example 3 did not have an orientation.

  The cured films obtained using the retardation material-forming compositions of Examples 1 to 17 maintained high adhesion even at the initial stage and at high temperature and high humidity, and exhibited excellent adhesion.

  On the other hand, the cured films obtained using the cured film forming compositions of Comparative Examples 1 to 3 were difficult to maintain adhesion both at the initial stage and after the high-temperature and high-humidity treatment.

The composition for forming a retardation material of the present invention is very useful as a liquid crystal alignment film of a liquid crystal display element, or an alignment material for forming an optically anisotropic film provided inside or outside a liquid crystal display element, Particularly, it is suitable as a material for forming a patterned retardation material of a 3D display. Further, a material for forming a cured film such as a protective film, a flat 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 of a TFT type liquid crystal display element and a color filter. It is also suitable as a material for forming a protective film or an insulating film of an organic EL element.

Claims (4)

A polymer comprising a repeating unit having an N-alkoxymethyl group and a repeating unit having a side chain containing a polymerizable C ＝ C double bond. The polymer of claim 1 for use as a component for making an optical film. The polymer according to claim 1, which is used as a component for producing a liquid crystal alignment material. The polymer according to claim 1, for use as a component for producing a retardation material.