JP6604483B2 - Cured film forming composition, alignment material and retardation material - Google Patents

Description

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

  In recent years, in the field of displays such as a television using a liquid crystal panel, development of a 3D display capable of enjoying 3D images has been promoted as an effort toward high performance. In the 3D display, for example, a right-eye image is visually recognized by an observer's right eye, and a left-eye image is visually recognized by an observer's left eye, whereby a stereoscopic image can be displayed.

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

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

  For example, as disclosed in Patent Document 2, the patterned retardation material can be produced by optically patterning a retardation material made of a polymerizable liquid crystal. Optical patterning of a retardation material made of a polymerizable liquid crystal utilizes a photo-alignment technique known for forming an alignment material for a liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on a substrate, and two types of polarized light having different polarization directions are irradiated on the coating film. Then, a photo-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-like 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 aligned polymerizable liquid crystal is cured to form a patterned retardation material.

  In the formation of alignment materials using the photo-alignment technology of liquid crystal panels, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chain are known as usable photo-alignment materials. . It has been reported that these resins exhibit the ability to control the alignment of liquid crystal (hereinafter also referred to as liquid crystal alignment) by irradiation with polarized UV (see Patent Documents 3 to 5).

Japanese Patent Laid-Open No. 10-232365 JP 2005-49865 A Japanese Patent No. 3611342 JP 2009-058584 A JP-T-2001-517719

  As described above, the patterned retardation material is configured by laminating a cured polymerizable liquid crystal layer on a photo-alignment film that is an alignment material. And the patterned phase difference material which has such a laminated structure can be used for the structure of 3D display with the laminated state.

  The 3D display is sometimes used as a home television, and is required to have high reliability, particularly durability over a long period of time. For this reason, durability is also required for components of 3D displays. Accordingly, the patterned phase difference agent also has long-term durability as well as being subjected to optical patterning with high accuracy and having high light transmission characteristics.

  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, it is easy to peel off from the initial stage of formation, or it is excellent in adhesiveness at the initial stage of formation, but the adhesiveness is likely to deteriorate with the passage of time and easily peel off. There was something to be.

  In particular, peeling between the photo-alignment film and the polymerizable liquid crystal layer, which occurs with the passage of time, becomes a defect in a 3D display that is actually used and causes a reduction in display quality of the 3D display. Accordingly, there is a need for a patterned phase difference material that is capable of high-precision optical patterning, has excellent light transmission characteristics, and has excellent durability. In particular, the adhesion between the photo-alignment film at the initial stage of formation and the polymerizable liquid crystal layer is excellent, and the durability for maintaining the excellent adhesion for a long period of time (hereinafter referred to as adhesion durability in the present specification). There is a need for a patterned retardation material comprising:

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

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

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

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

The first aspect of the present invention is:
(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 The present invention relates to a cured film forming composition containing a polymer comprising
In the first aspect of the present invention, the photoalignable group of the component (A) is preferably a functional group having a structure that undergoes photodimerization or photoisomerization.
In the first embodiment of the present invention, the photoalignable group of the component (A) is preferably a cinnamoyl group or an azobenzene structure group.
In the first embodiment 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): containing at least one polymer selected from the group consisting of (A) a component having a substituent capable of thermally reacting with component (A) and capable of self-crosslinking, and (C-3): melamine formaldehyde resin It is preferable to do.
In the first aspect of the present invention, it is preferable that (D) a crosslinking catalyst is further contained.
In the first aspect of the present invention, it is preferable that (E) a crosslinking agent is further contained.
In the first embodiment of the present invention, the proportion of the repeating unit having an N-alkoxymethyl group in the polymer of the component (B) is 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 10 mol% to 60 mol% per 100 mol of all repeating units of the polymer.
1st aspect of this invention WHEREIN: It is preferable that content ratio of (A) component and (B) component is 5:95 thru | or 60:40 by mass ratio.
1st aspect of this invention WHEREIN: The said cured film forming composition contains 5 mass parts thru | or 500 mass parts (C) component based on 100 mass parts of total amounts of (A) component and (B) component. It is preferable to do.

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

  According to the first aspect of the present invention, 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 that has excellent photoreaction efficiency and solvent resistance and can align 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 that can be formed on a resin film with high efficiency and can be subjected to optical patterning.

  As described above, an alignment material excellent in adhesion durability, in particular, an alignment excellent in adhesion durability with a cured polymerizable liquid crystal layer, in order to produce a patterned retardation material having excellent durability. There is a need for materials. And the cured film formation composition suitable for formation of the orientation material of such a performance is calculated | required.

  As a result of intensive studies in order to meet the above requirements, the present inventor has found that a cured film obtained from a cured film-forming composition having a specific composition is excellent in light transmittance, and has a liquid crystal orientation by polarization exposure. It has been found that it can be used as an alignment material by showing liquid crystal alignment to be regulated. In addition, the present inventor shows excellent adhesion durability between the cured film obtained from the cured film-forming composition having the specific composition and the polymerizable liquid crystal layer polymerized and cured thereon. I found out. That is, the cured film obtained from the cured film-forming composition having a specific composition of the present invention can constitute a photo-alignment film having excellent adhesion durability with the polymerizable liquid crystal layer.

  Below, the cured film forming composition of this invention is demonstrated in detail, giving specific examples, such as a component. The cured film and alignment material of the present invention using the cured film forming composition of the present invention, the retardation material formed using the alignment material, the liquid crystal display element, and the like 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. Polymer containing a repeating unit having a side chain containing a bond, (C) 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 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. A kind of polymer and a crosslinking catalyst may be contained as the component (D). Moreover, a crosslinking agent can be contained as (E) component. Furthermore, other additives can be contained as long as the effects of the present invention are not impaired. Furthermore, a solvent can be contained.
Hereinafter, details of each component will be described.

[(A) component]
(A) component in the cured film formation composition of this invention is at least 1 type of the compound which has a photo-alignment group and a heat crosslinkable group. (A) Although a polymer can be used as a component, compounds other than a 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) includes at least one kind of a polymer having a photoalignable group and a thermally crosslinkable group, at least one kind of a compound other than the polymer having a photoalignable group and a heat crosslinkable group, or a photoalignable group and It may be a mixture of a polymer having a thermally crosslinkable group and a compound other than the polymer having a photoalignable group and a thermally crosslinkable group.
(A) component is a component which provides photo-alignment property to the cured film obtained from the cured film formation composition of this invention, and (A) component is also called a photo-alignment component in this specification.

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 a polymer, it is usually a photo-alignment component having a low molecular weight as compared with the later-described polymer (B) as a base.

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-alignment group, and further a hydroxy group, carboxyl group, amide group, amino And a compound having one group selected from the group consisting of a group and an alkoxysilyl group.
In the present invention, the photo-alignment group generally refers to a functional group that exhibits the property of being aligned by light irradiation, and typically refers to a functional group at a structural site that undergoes photodimerization or photoisomerization. Examples of other photo-alignment groups include a functional group that causes a photofleece rearrangement reaction (example compound: benzoate ester compound), a group that causes a photodecomposition reaction (example compound: cyclobutane ring, etc.), and the like.

  The photo-dimerizing structural moiety that the compound other than the polymer of component (A) can have as a photo-alignment group is a moiety that forms a dimer by light irradiation. Specific examples thereof include a cinnamoyl group, a chalcone Group, coumarin group, anthracene group 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 a compound other than the polymer of component (A) can have as a photoalignable group refers to a structural moiety that changes into a cis isomer and a trans isomer by light irradiation. May be a site comprising an azobenzene structure, a stilbene structure, or the like. Of these, an azobenzene structure is preferred because of its high reactivity.

  A compound other than a 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 formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group.

X ¹¹ represents 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 two or more of them. 1 to 3 substituents selected from alkylene having 1 to 18 carbon atoms, phenylene, biphenylene, or a combination thereof are bonded via a bond, and each of the substituents is bonded via the bond. A structure in which a plurality are connected 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. At that time, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to two or more groups via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond. 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.

  In addition, when these substituents include a benzene ring, the benzene ring includes 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 with one or a plurality of substituents which are the same or different.

In the above formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom. To 4 alkoxy groups, a halogen atom, a trifluoromethyl group or a cyano group;
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 The 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, 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 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n- Butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1, 1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n- Hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n -Pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl Til-3-ethyl-n-pentyl group, 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-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 number of carbon atoms among the groups listed above. In addition, 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-described alkyl groups. Among them, groups having the corresponding number of carbon atoms are mentioned. Further, as the alkylene group having 1 to 20 carbon atoms, a divalent group in which one hydrogen atom is removed from the above alkyl group and alkyl groups having 1 to 20 carbon atoms such as n-nonadecyl group and n-eicosyl group. Is mentioned.

  As specific examples of the compound other than the polymer having a photo-alignable group and a hydroxy group as the component (A), for example, the compounds represented by the above formulas [A11] to [A15] and the compounds other than the formula include, for example, 4- (8-hydroxyoctyloxy) cinnamic acid methyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4- (3- Hydroxypropyloxy) cinnamic acid methyl ester, 4- (2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic acid methyl ester, 4-hydroxycinnamic acid methyl ester, 4- (8- Hydroxyoctyloxy) cinnamic acid ethyl ester, 4- (6-hydroxyhexyloxy) cinnamic acid Ester, 4- (4-hydroxybutyloxy) cinnamic acid ethyl ester, 4- (3-hydroxypropyloxy) cinnamic acid ethyl ester, 4- (2-hydroxyethyloxy) cinnamic acid ethyl ester, 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-hydroxymethyloxy cinnamic acid Phenyl ester, phenyl 4-hydroxycinnamate Stell, 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, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4-hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4 -(8-hydroxy Thiooctyloxy) 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) Chalcone, 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 ] Cinnamic acid 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- [4-hydroxybenzoyl] cinnamic acid ethyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (6-hydroxyhexyloxy) ) Benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (4-hydroxybutyrate) Ruoxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic acid tertiary butyl ester, 4- [4- (2-hydroxyethyloxy) benzoyl] cinnamic Acid tertiary butyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid tertiary butyl ester, 4- [4- (8-hydroxyoctyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- ( 6-hydroxyhexyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (4-hydroxybutyloxy) benzoyl] cinnamic acid phenyl ester, 4- [4- (3-hydroxypropyloxy) benzoyl] cinnamic Acid phenyl ester, 4- [4- (2-hydroxyethyl) Oxy) benzoyl] cinnamic acid phenyl ester, 4- [4-hydroxymethyloxybenzoyl] cinnamic acid phenyl ester, 4- [4-hydroxybenzoyl] cinnamic acid phenyl ester, 4- [4- (8-hydroxyoctyl) Oxy) 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-hydride] Roxybenzoyl] cinnamic acid biphenyl ester, 4-benzoyl cinnamic acid 8-hydroxyoctyl ester, 4-benzoyl cinnamic acid 6-hydroxyhexyl ester, 4-benzoyl cinnamic acid 4-hydroxybutyl ester, 4-benzoyl cinnamic Acid 3-hydroxypropyl ester, 4-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] Con, 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 (A) other than the polymer having a photo-alignable group and a carboxyl group 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 (A) other than the polymer having a photo-alignment group and an amide group include cinnamic acid amide, 4-methylcinnamic acid amide, 4-ethyl cinnamic acid amide, 4-methoxy. Cinnamic acid amide, 4-ethoxycinnamic acid amide and the like can be mentioned.

  Specific examples of the compound (A) other than the polymer having a photoalignable group and an amino group include 4-aminocinnamic acid methyl ester, 4-aminocinnamic acid ethyl ester, and 3-amino cinnamic acid. Examples include methyl ester and 3-aminocinnamic acid ethyl ester.

  Specific examples of the compound (A) other than the polymer having a photo-alignment group and an alkoxysilyl group are 4- (3-trimethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3- Triethoxysilylpropyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3-triethoxysilylpropyloxy) cinnamic acid ethyl ester, 4- (3 -Trimethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-triethoxysilylhexyloxy) cinnamic acid methyl ester, 4- (3-trimethoxysilylhexyloxy) cinnamic acid ethyl ester and 4- ( 3-triethoxysilylhexyloxy) cinnamic acid ethyl ester and the like.

  The component (A) is preferably a compound other than a polymer in which a polymerizable group is bonded via a spacer to a group in which a photo-alignment site and a thermoreactive site represented by the following formula (1) are bonded.

(In the formula, 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, a hydroxy 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; a methoxy group, Examples thereof include alkoxy groups such as ethoxy group; halogen atoms such as iodine, bromine, chlorine and fluorine; cyano group; nitro group and the like.

Among R ¹⁰¹ described above, a hydroxy group and an amino group are preferable, and a hydroxy group is particularly preferable.

  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 such 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. , Urea bonds or ether bonds. When there are a plurality of the 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 a monomer in which a polymerizable group is bonded to a group in which a photo-alignment site and a heat-reactive site which are the component (A) are bonded, 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 (A) can include the above specific examples, but are not limited thereto.

  Next, details when the component (A) is a polymer, that is, a high molecular weight polymer 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 photoalignment group, that is, as a photoalignment group. A polymer having a functional group at a structural site to be quantified or photoisomerized, particularly an acrylic copolymer having at least a photodimerization site is preferable. Further, in addition to the photodimerization site, 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). A copolymer is desirable.

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

  The acrylic copolymer having a photodimerization site and a thermal crosslinking site (A) as the component (hereinafter also referred to as a specific copolymer) may be an acrylic copolymer having such a structure. There are no particular restrictions on the main chain skeleton and side chain type of the 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 containing a cinnamoyl structure include structures represented by the following formula [1] or [2]. In the present specification, a group in which the benzene ring in the cinnamoyl group is a naphthalene ring is also included in the “cinnamoyl group” and the “substituent containing 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. In that case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as those exemplified above as the alkyl group having 1 to 18 carbon atoms.

In the above formula [2], X ² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as those exemplified above as the alkyl group having 1 to 18 carbon atoms. In this case, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be 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. Plural types may be bonded through one or two or more selected bonds.

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

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

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

  The acrylic copolymer as component (A) preferably has a weight average molecular weight of 3,000 to 200,000. If the weight average molecular weight is over 200,000, the solubility in the solvent may be lowered and the handling property may be lowered. On the other hand, the weight average molecular weight is less than 3,000 and is too small. In some cases, the heat resistance may cause insufficient curing, resulting in a decrease in solvent resistance or a decrease in 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 monomers 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 these, a cinnamoyl group having a structure represented by the above formula [1] or [2] and a monomer having a substituent containing a cinnamoyl structure are more preferable. When the specific example of such a monomer is given, it is a monomer represented by the following formula [3] or formula [4].

In the above formula [3], X ¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a biphenyl group. In that case, the phenyl group and the biphenyl group may be substituted by either a halogen atom or a cyano group. Examples of the alkyl group having 1 to 18 carbon atoms include the same groups as those 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 those exemplified above as the alkyl group having 1 to 18 carbon atoms. At that time, the alkyl group having 1 to 18 carbon atoms, the phenyl group, the biphenyl group, and the cyclohexyl group may be bonded via a covalent bond, an ether bond, an ester bond, an amide bond, or a urea bond.

In the above formulas [3] and [4], X ³ and X ⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring, 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 formula [3] and formula [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 Formula [3] and Formula [4], A is any of Formula [A1], Formula [A2], Formula [A3], Formula [A4], Formula [A5], and Formula [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, 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 Monomers having a hydroxy group such as -6-hydroxynorbornene-2-carboxyl-6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-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 phenolic hydroxy groups such as reimide; monomers having amide groups 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 and the monomer having a thermal crosslinking site used for obtaining the specific copolymer is determined based on the total amount of all monomers used for obtaining the specific copolymer. It is preferable that the monomer having 40% by mass to 95% by mass and the monomer having a thermal crosslinking site is 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 orientation can be imparted. On the other hand, by setting it to 95% by mass or less, sufficient thermosetting property can be imparted, and high liquid crystal orientation can be maintained with high sensitivity.

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

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
Hereinafter, although the specific example of the said monomer is given, this invention is not limited to these.

  Examples of the acrylic ester compound described above include 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 methacrylic ester compounds described above include 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. Examples include hexene and 1,7-octadiene monoepoxide.

  Examples of the styrene compound described above 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 cross-linking site), or non-specific if desired. It is obtained by carrying out 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. In that case, the solvent used will not be specifically limited if it dissolves the monomer which has a specific functional group, the monomer which has a non-reactive functional group used depending on necessity, a polymerization initiator, etc. Specific examples include solvents described in Solvents 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 the solution of the component (A) in the present invention.

  In addition, the solution of the specific copolymer obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved 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 re-dissolved in, for example, a solvent described later to form a solution. It may be used.

  In the present embodiment, the acrylic copolymer of component (A) may be a mixture of a plurality of types 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 C═C double bond (hereinafter, Also referred to as specific copolymer 2.

  N of the N-alkoxymethyl group, that is, the nitrogen atom includes the amide nitrogen atom, the thioamide nitrogen atom, the urea nitrogen atom, the thiourea nitrogen atom, the urethane nitrogen atom, and the adjacent nitrogen atom of the nitrogen-containing heterocycle And a nitrogen atom bonded to. Therefore, the N-alkoxymethyl group includes an amide nitrogen atom, a thioamide nitrogen atom, a urea nitrogen atom, a thiourea nitrogen atom, a urethane nitrogen atom, and a nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocyclic ring. Examples include a structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from atoms and the like.

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

(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 group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and 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- A pentyl group, a 1-methyl-1-ethyl-n-butyl group, -Methyl-2-ethyl-n-butyl group, 1-ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group N-octyl group, 1-methyl-n-heptyl group, 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl- n-hexyl group, 1,3-dimethyl-n-hexyl group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1 -Ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl Group, 1-methyl-3-ethyl-n-pentyl group, 2-methyl Examples include ru-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group and the like. .

  Specific examples of such monomers include hydroxymethyl groups such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and N-butoxymethyl (meth) acrylamide. Or the acrylamide compound or the methacrylamide compound substituted by the alkoxymethyl group is mentioned. (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 as the component (B) has 3 to 16 carbon atoms and has an unsaturated bond at the terminal. The specific side chain represented by the formula (b2) is particularly preferable. The specific side chain represented by Formula (b2) binds to the ester bond portion of the acrylic polymer as shown in Formula (b2-1).

In 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 containing a cyclic structure, and an aromatic group, or from this group An organic group comprising a combination of a plurality of organic groups selected. R ⁵¹ may contain 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 a specific side chain in which R ⁵² is a hydrogen atom is preferable, and more preferably a specific side chain in which the terminal is an acryloyl group, a methacryloyl group, or a styryl group. is there.

In formula (b2-1), R ⁵³ represents 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, by reacting this specific functional group with a compound having an unsaturated bond at the terminal (hereinafter referred to as a specific compound) to generate a specific side chain, the polymer as the component (B) is polymerizable. Side chains containing C═C double bonds can be introduced.

  Here, the specific functional group means 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 functional groups. .

  In the reaction for generating the specific side chain described above, the preferred combination of the specific functional group and the functional group of the specific compound that is involved in the reaction is a carboxyl group and an epoxy group, a hydroxy group and an isocyanate group, or a phenolic group. 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. Furthermore, a more preferable combination is a carboxyl group and glycidyl methacrylate, or a hydroxy group and isocyanate ethyl methacrylate.

  In the reaction for generating the specific side chain described above, the polymer having the specific functional group is a monomer having a functional group (specific functional group) for reacting with the specific compound in addition to the specific monomer X1, that is, a carboxyl group. , A copolymer obtained by using, as an essential component, a monomer having a glycidyl group, a hydroxy group, an amino group having active hydrogen, a phenolic hydroxy group or an isocyanate group (hereinafter also referred to as a specific monomer X2), and its number average The molecular weight is 2,000 to 25,000. Here, the monomer having the specific functional group used for the polymerization may be used alone, or a plurality of types may be used in combination as long as the combination does not react during the polymerization.

  The specific example of the monomer required in order to obtain the polymer which has a specific functional group, ie, specific monomer X2, is given to the following. 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.

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

In the side chain represented by the formula (b2) thus obtained, specific examples of R ⁵¹ include the following formulas (B-1) to (B-11).

  In addition, in the present invention, when obtaining the polymer of component (B), in addition to the specific monomer X1 and the specific monomer X2, there is no substituent which can be copolymerized with the monomer and can be thermally cross-linked. Monomers can be used in combination.

  Specific examples of such monomers include the specific monomer X1 and the acrylic acid ester compound or methacrylic acid ester compound, maleimide compound, acrylamide compound, acrylonitrile, maleic anhydride, styrene compound having a structure different from that of the specific monomer X2. And vinyl compounds.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
Examples of the acrylate compound having a structure different from that of 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 methacrylic acid ester compound having a structure different from that of the specific monomer X1 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 meta Relate, 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- And tricyclodecyl methacrylate.

  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.

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

That is, the use amount of the specific monomer X1 used for obtaining the specific copolymer 2 as the component (B) is based on the total amount of all monomers used for obtaining the specific copolymer 2 as the component (B). Thus, it is preferably 40 mol% to 90 mol%, more preferably 50 mol% to 85 mol%.
When the total is less than 40 mol%, curing by thermal crosslinking with the component (A) may be insufficient, and when it is more than 90 mol%, the adhesion to the substrate is adversely affected. There is.

  In the polymer of component (B), the ratio of the repeating units having a side chain containing a polymerizable C═C double bond is 10 mol% to 60 mol% per 100 mol of all the repeating units of the polymer. It is more preferable that it is 15 mol%-50 mol%.

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

  The method for obtaining the specific copolymer 2 which is an example of the component (B) is not particularly limited. For example, the specific monomer X1, the specific monomer X2, and, if desired, other monomers and a polymerization initiator are allowed to coexist. In a solvent, it is obtained by a polymerization reaction at a temperature of 50 to 110 ° C. In that case, the solvent used will not be specifically limited if it can melt | dissolve the monomer shown by said Formula X, the said other monomer used depending on necessity, a polymerization initiator, etc. Specific examples are described in the section of [Solvent] described later.

  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 as the solution of the component (B) in the present invention.

  In addition, the acrylic polymer solution, which is an example of the component (B) obtained by the above method, is re-precipitated by adding it to diethyl ether or water under stirring, and the generated precipitate is filtered and washed. Under normal pressure or reduced pressure, the powder can be dried at room temperature or heated to obtain a powder of the specific copolymer 2 as the component (B). By the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer 2 of the component (B) can be removed, and as a result, the specific copolymer which is an example of the purified component (B) 2 powder is obtained. When it cannot be purified sufficiently by a single 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 a powder form or in a solution form in which purified powder is redissolved in a solvent described later. May be.

  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 plural kinds of the specific copolymer 2 shown as an example of the component (B).

  The weight average molecular weight of such a polymer is 1,000 to 500,000, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and even more preferably 3 , 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) and the component (B) is 5:95 to 60:40 by mass ratio. When the content of the component (B) polymer is too small, the solvent resistance and heat resistance of the cured film obtained from the cured film forming composition are lowered, and the orientation sensitivity during photo-alignment is lowered. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be lowered.

[Component (C)]
The component (C) contained in the composition of the present invention includes (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 polymer having a substituent capable of thermally reacting with the component (A) and capable of self-crosslinking, or (C-3): at least one polymer selected from the group consisting of 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 component (C-1) include acrylic polymer, urethane-modified acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone. Examples include polyols, polyalkylenimines, polyallylamines, celluloses (cellulose or derivatives thereof), polymers having a linear or branched structure such as phenol novolac resins, and cyclic polymers such as cyclodextrins.

  Among these, as the acrylic polymer, a polymer obtained by polymerizing a monomer having an unsaturated double bond such as acrylic ester, methacrylic ester or styrene can be applied.

  As a synthesis method of an acrylic polymer which is an example of the component (C-1), 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 with other monomers is convenient.

  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 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 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-carboxyl-6-lactone, 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-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 phenolic hydroxyl groups 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, 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 thereof include a monomer having a silyl group.

  Moreover, in this invention, when obtaining the acrylic polymer which is an example of (C-1) component, at least 1 substitution chosen from the group which consists 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 monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.
Examples of the acrylic ester 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 methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, and 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 Etc.

  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.

  (C-1) Amount of 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 to obtain an acrylic polymer which is an example of the component Is preferably 5 mol% to 100 mol% based on the total amount of all monomers used to obtain an acrylic polymer which is an example of the component (C-1).

  (C-1) Although the method to obtain the acrylic polymer which is an example of a component is not specifically limited, For example, at least 1 substituent chosen from the group which consists of a hydroxy group, a carboxyl group, an amide group, an amino group, and an alkoxy silyl group. In a solvent in which 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, and a polymerization initiator, if desired, are allowed to coexist. It can be obtained by a polymerization reaction at a temperature of from 1 to 110 ° C. In that case, 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, It is not particularly limited 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 later.

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

  Moreover, the solution of the acrylic polymer which is an example of the component (C-1) obtained by the above method was added to diethyl ether or water under stirring to cause reprecipitation, and the generated precipitate was filtered and washed. Thereafter, it can be dried at normal temperature or under reduced pressure at room temperature or by heating to obtain an acrylic polymer powder as an example of the component (C-1). By the above-mentioned operation, the polymerization initiator coexisting with the acrylic polymer which is an example of the component (C-1) and unreacted monomers can be removed, and as a result, the acrylic which is an example of the purified component (B). A polymer powder is obtained. If sufficient purification cannot be achieved by a single 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 3000 to 200000, more preferably 4000 to 150,000, and still more preferably 5000 to 100,000. If the weight average molecular weight exceeds 200,000, the solvent solubility may decrease and handling may decrease. If the weight average molecular weight is less than 3,000, the curing may be insufficient during thermal curing. The solvent resistance and heat resistance may be reduced. The weight average molecular weight is a value obtained by using gel as a standard material by gel permeation chromatography (GPC). Hereinafter, the same applies to this specification.

  Next, as a polyether polyol which is a preferred example of the specific (co) polymer 1 of the component (C-1), polyhydric alcohols such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol and sorbitol And propylene oxide, polyethylene glycol, polypropylene glycol and the like. Specific examples of the polyether polyol include ADEKA Adeka Polyether P Series, G Series, EDP Series, BPX Series, FC Series, CM Series, NOF UNIOX (registered trademark) HC-40, HC-60, ST- 30E, ST-40E, G-450, G-750, Uniol (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400 Nonion (registered trademark) LT-221, ST-221, OT-221 and the like.

  As a polyester polyol which is a preferred example of the specific (co) polymer of the component (C-1), a polyvalent carboxylic acid such as adipic acid, sebacic acid, isophthalic acid, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, What reacted with diols, such as polypropylene glycol, is mentioned. Specific examples of the polyester polyol 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 polyols 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.

  As the polycaprolactone polyol which is a preferred example of the specific (co) polymer of the component (C-1), one obtained by ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator is used. Can be mentioned. Specific examples of the polycaprolactone polyol include DIC polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, Daicel Chemical's Plaxel (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 product obtained by reacting a polyhydric alcohol such as trimethylolpropane or ethylene glycol with diethyl carbonate, diphenyl carbonate, ethylene carbonate or the like. Can be mentioned. Specific examples of the polycarbonate polyol include Placel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Chemical Industries, C-590, C-1050, C-2050, C-2090, C-3090 manufactured by Kuraray, and the like.

  (C-1) Specific examples of the specific (co) polymer 1 of the cellulose include cellulose, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyethylethylcellulose and the like. Examples include alkylalkyl celluloses and celluloses, and hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferable.

  (C-1) Component Specific Cyclodextrin which is a preferred example of the (co) polymer 1 includes cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γcyclodextrin, 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-hydroxy Droxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin And hydroxyalkyl cyclodextrins such as 2,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

  As a urethane-modified acrylic polymer which is a preferable example of the specific (co) polymer 1 of the component (C-1), as a commercially available product, Arit (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 a powder form or in a solution form in which a purified powder is redissolved in a solvent described later.

  In the composition of the present invention, the component (C-1) may be a mixture of a plurality of 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 undergoes 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) (hereinafter, crosslinkable). A polymer having a substituent and a hydroxy group, a carboxyl group, an amino group, an amide group, and an alkoxysilyl group are also referred to as a specific functional group. The sublimation of the component (A) can be suppressed by the thermal reaction between the component (A) and the component (C-2). And the cured film formation composition of this Embodiment can form the orientation material with high photoreaction efficiency as above-mentioned as a cured film.

  Preferred crosslinkable substituents contained in the polymer of component (C-2) include alkoxymethylamide groups and alkoxysilyl groups. The content of the crosslinkable substituent is preferably 0.5 to 1 per repeating unit of the component (C-2). From the viewpoint of solvent resistance of the alignment material, 0.8 to 1 More preferably.

  As the polymer of component (C-2), for example, substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using acrylamide compounds or methacrylamide compounds 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 methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate.

Moreover, the polymer manufactured using the compound which has an alkoxy silyl group as (C-2) component can also be used.
Examples of such a polymer include poly (3-methacryloxypropyltrimethoxysilane), a copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, poly (3-acryloxypropyltrimethoxysilane), 3 -A copolymer of acryloxypropyltrimethoxysilane and methyl methacrylate, and the like.

  Moreover, in the specific (co) polymer 2 used for the cured film forming composition of this Embodiment, the monomer (henceforth the monomer which has a non-reactive functional group) copolymerizable with the monomer which has a specific functional group is used. Can be used together.

Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.
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 carrying out a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which an agent or the like is present. In that case, the solvent used will not be specifically limited if the monomer which has a specific functional group, the monomer which has a non-reactive functional group used depending on necessity, a polymerization initiator, etc. are dissolved. Specific examples include solvents described in Solvents described below.
The specific (co) polymer 2 thus obtained is usually in the state of a solution dissolved in a solvent.

  In addition, the solution of the specific (co) polymer 2 obtained as described above is re-precipitated by stirring with stirring such as diethyl ether or water, and the generated precipitate is filtered and washed. Or it can be set as the powder of the specific (co) polymer 2 by carrying out normal temperature or heat drying under reduced pressure. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific (co) polymer 2 can be removed, and as a result, a purified powder of the specific (co) polymer 2 is obtained. If sufficient purification cannot be achieved by a single 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 later to form a solution state. It may be used.

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

The weight average molecular weight of such a polymer is 1000 to 500000, preferably 1000 to 200000, more preferably 1000 to 100,000, and still more preferably 2000 to 50000.
These polymers can be used alone or in combination of two or more.
[(C-3) component]

  The (C-3) component melamine formaldehyde resin is a resin obtained by polycondensation of 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 number of carbon atoms among the alkyl groups listed above.

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

  The method for obtaining the melamine formaldehyde resin as the component (C-3) is not particularly limited, but in general, melamine and formaldehyde are mixed and made weakly alkaline using sodium carbonate, ammonia or the like, and then at 60 ° C to 100 ° C. Synthesized by heating. Further, the methylol group can be alkoxylated by reacting with alcohol.

  The (C-3) component melamine formaldehyde resin preferably has a weight average molecular weight of 250 to 5000, more preferably 300 to 4000, and even more preferably 350 to 3500. If the weight average molecular weight exceeds 5,000, the solubility in the solvent may decrease and handling may decrease. If the weight average molecular weight is less than 250, the curing may be insufficient during thermal curing. Therefore, 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 later.

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

  Content of (C) component in the cured film forming composition of this invention is 5 mass parts thru | or 500 mass parts based on 100 mass parts of total amounts of (A) component and (B) component. When the content of the component (C) polymer 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 during photo-alignment is decreased. On the other hand, when the content is excessive, the photo-alignment property and the storage stability may be lowered.

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

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

  Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoro. L-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 or the hydrates and salts thereof Is mentioned.

  Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2, 3-phenylene tris (methylsulfonate), 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-hydride 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].

  Content of (D) component in the cured film formation composition of embodiment of this invention is at least 1 type of the compound which has the photo-alignment group which is (A) component, and a thermal crosslinkable group, The polymer which is (B) component , With respect to 100 parts by mass of the total amount of the polymer as component (C), 0.01 parts by mass to 20 parts by mass, preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass. -8 parts by mass, more preferably 0.1-6 parts by mass. By setting the content of component (D) to 0.01 parts by mass or more, sufficient thermosetting and solvent resistance can be imparted, and high sensitivity to exposure can also be imparted. Moreover, the storage stability of a cured film forming composition can be made favorable by setting it as 20 mass parts or less.

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

  (E) As a crosslinking agent which is a component, compounds, such as an epoxy compound, a methylol compound, and an isocyanate compound, are mentioned, Preferably it is a methylol compound.

  Specific examples of the methylol compound described above include 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 , 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, Powderlink (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, commercial product) manufactured by Dainippon Ink & Chemicals, Inc. Name: Becamine (registered trademark) J-300S, P-955, N) and the like.

  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 names: Nikarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.

  Specific examples of alkoxymethylated melamine include, for example, hexamethoxymethylmelamine. As commercially available products, methoxymethyl type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade name: My Coat (registered trademark)) 506, 508), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicalac (registered trademark) MW-30, MW-22, MW-11, MS-001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade names: Nicalac (registered trademark) MX-45, MX-410, MX-302) and the like.

  Moreover, the compound obtained by condensing the melamine compound by which the hydrogen atom of such an amino group was substituted by the methylol group or the alkoxymethyl group, the urea compound, the glycoluril compound, and the benzoguanamine compound may be sufficient. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.). Examples of commercially available products of the benzoguanamine compound include product name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.).

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

  The content of the crosslinking agent of component (E) in the cured film forming composition of the present embodiment is the total amount of the compound that is component (A), the polymer that is component (B), and the polymer that is component (C). It is preferable that it is 50 mass parts or less based on 100 mass parts, More preferably, it is 30 mass parts or less. When the content of the crosslinking agent is excessive, the photo-alignment property and the storage stability may be lowered.

[Other additives]
The cured film forming composition of the embodiment of the present invention can 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 the photoreaction when forming the cured film on the surface of the optical film of the present invention.

  Examples of the sensitizer include benzophenone, anthracene, anthraquinone and thioxanthone derivatives 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, 4 -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 compounds.

  In the embodiment of the present invention, the use ratio of the sensitizer is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass with respect 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 it is too large, the transmittance of the formed cured film may be reduced or the coating film may be roughened. There are things to do.

  In addition, the cured film forming composition according to the embodiment of the present invention includes, as other additives, silane coupling agents, surfactants, rheology modifiers, pigments, dyes, storage stability, as long as the effects of the present invention are not impaired. Agents, antifoaming agents, 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 in that case is one that dissolves the component (A) and the component (B), and optionally the component (C), the component (D), the component (E), and / or other additives, The type and structure of the solvent are not particularly limited as long as the solvent has such solubility.

  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- Examples thereof include dimethylacetamide and N-methyl-2-pyrrolidone.

  These solvents can be used singly or in combination of two or more. Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl acetate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate are more preferable because of 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 properties. As described above, the cured film forming composition of the present embodiment includes at least one compound having a photo-alignable group and a thermally crosslinkable group as component (A), and an N-alkoxymethyl group as component (B). A polymer containing a repeating unit having a repeating unit having a side chain containing a polymerizable C═C double bond, and optionally (C-1) component (C-1): a hydroxy group, a carboxyl group, 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 capable of thermally reacting with the component (A) and capable of self-crosslinking, and (C-3): contains at least one polymer selected from the group consisting of melamine formaldehyde resin, and contains a crosslinking catalyst as component (D) as necessary. Moreover, a crosslinking agent can be contained as (E) component as needed. And as long as the effect of this invention is not impaired, another additive can be contained and a solvent can be contained further.

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

  [1]: At least one compound having a photo-alignable group and a thermally crosslinkable group as component (A) and a repeating unit having an N-alkoxymethyl group as component (B) and polymerizable C = C double The blending ratio with the polymer containing a repeating unit having a side chain containing a bond is 5:95 to 60:40 in terms of mass ratio, and the sum of at least one of the compounds as component (A) and the polymer as component (B) Component (C-1) which is 5 to 500 parts by weight of component (C-1) based on 100 parts by weight of the amount: at least selected from the group consisting of hydroxy group, carboxyl group, amide group, amino group and alkoxysilyl group 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 blending ratio of the component (A) and the component (B) is 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. Based on 100 parts by mass of the total amount of component (C) of 5 parts by mass to 500 parts by mass based on parts by mass, compound (A), polymer of component (B), and polymer of component (C) A cured film-forming composition containing a crosslinking catalyst and a solvent as the component (D) in an amount of 0.1 to 40 parts by mass.

  [3]: The mixing 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. Based on 100 parts by mass of the total amount of (C) component, (A) component, (B) component polymer, and (C) component polymer based on 5 parts by mass, 0.1 parts by weight to 40 parts by weight of component (D) and 100 parts by weight of the total amount of the compound (A), the polymer (B) and the polymer (C) A cured film forming composition containing 0.01 parts by mass to 10 parts by mass of component (E) and a solvent.

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

  The ratio 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 1% by mass to 80% by mass, preferably It is 2 mass%-60 mass%, More preferably, it is 3 mass%-40 mass%. Here, solid content means what remove | excluded the solvent from all the components of the cured film formation composition.

  The preparation method of the cured film forming composition of this embodiment is not specifically limited. As a preparation method, for example, the (A) component, the (C) component, the (D) component, and the (E) component are mixed in a predetermined ratio to the solution of the (B) component dissolved in the solvent to obtain a uniform solution. Or a method in which other additives are further added and mixed 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 a specific copolymer obtained by a polymerization reaction in a solvent can be used as it is. In this case, for example, the (A) component, the (C) component, the (D) component, and the (E) component are added to the solution prepared from the (B) component acrylic polymer to obtain a uniform solution. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the preparation process of the component (B) and the solvent used for adjusting the concentration of the cured film forming composition may be the same or different.

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

  As mentioned above, the cured film forming composition of this embodiment of this invention is N-alkoxy which is at least 1 type of the compound which has a photo-alignment group which is (A) component, and a thermal crosslinkable group, and (B) component. Polymer containing a repeating unit having a methyl group and a repeating unit having a side chain containing a polymerizable C═C double bond, (C) component (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 capable of self-crosslinking, and (C -3): Containing at least one polymer selected from the group consisting of melamine formaldehyde resins, and a crosslinking catalyst as component (D). In the compound which is component (A), the photo-alignment group constitutes a hydrophobic photoreactive portion, and at least one substituent selected from a hydroxy group, a carboxyl group, an amino group and a trialkoxysilyl group is a hydrophilic heat. The reaction part is configured. At least one substituent selected from a hydroxy group, a carboxyl group, an amino group, and a trialkoxysilyl group of the component (C) polymer is also hydrophilic.

  Therefore, the cured film formed from the cured film forming composition of the present embodiment is formed with hydrophilic inside due to the nature of the component (C) so that the film structure is stabilized. . And the compound of the (A) component in a cured film comes to be unevenly distributed in the surface vicinity of a cured film. More specifically, the compound of component (A) has a structure in which the hydrophilic thermal reaction part faces the inner side of the cured film and the hydrophobic photoreactive part faces the surface side, and the vicinity of the surface of the cured film. Is unevenly distributed. As a result, the cured film of the present embodiment realizes a structure in which the ratio of the photoreactive group of the component (A) existing near the surface is increased. And when the cured film of this embodiment is used as an alignment material, the efficiency of the photoreaction for photo-alignment can be improved and it can have the outstanding orientation sensitivity. Furthermore, it becomes an orientation material suitable for formation of a patterned phase difference material, and the patterned phase difference material manufactured using this can have the outstanding pattern formation property.

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

  In addition, the polymer as the component (B) includes a cured polymerizable liquid crystal layer formed thereon when a cured film obtained from the cured film forming composition of the present embodiment is used as an alignment material. Functions to reinforce the adhesion between the two.

<Hardened film, alignment material and retardation material>
A solution of the cured film forming composition according to the present embodiment is applied to a substrate (for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, or chromium, a glass substrate, or a quartz substrate. , ITO substrate, etc.) and films (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., bar coating, spin coating, flow coating, roll coating A cured film can be formed by coating by slit coating, spin coating following the slit, inkjet coating, printing, or the like to form a coating film, followed by heat drying with a hot plate or oven.

  As the conditions for the heat drying, it is sufficient 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, a temperature of 60 ° C. to 200 ° C. The heating temperature and the heating time appropriately selected from the range of 0.4 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70 to 160 ° C. and 0.5 to 10 minutes.

  The film 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 level difference of the substrate to be used and optical and electrical properties. be able to.

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

  As the irradiation method of polarized UV, ultraviolet light to visible light having a wavelength of 150 nm to 450 nm is usually used, and it is performed by irradiating linearly polarized light from a vertical or 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 comprising a polymerizable liquid crystal solution on the alignment material, the liquid crystal The phase difference material is brought into a liquid crystal state by heating up to the phase transition temperature, and aligned 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. And when the board | substrate with which an orientation material is formed is a film, the film which has the phase difference material of this Embodiment becomes useful as a phase difference film. The phase difference material that forms such a phase difference material is in a liquid crystal state and has an alignment state such as horizontal alignment, cholesteric alignment, vertical alignment, hybrid alignment, etc. on the alignment material. It can be used properly according to the phase difference characteristic.

  Moreover, when manufacturing the patterned phase difference material used for 3D display, it is predetermined | prescribed via the mask of a line and space pattern to the cured film formed by the above-mentioned method from the cured film composition of this embodiment. For example, polarized UV exposure is performed in a +45 degree direction from the reference, and then the polarized UV light is exposed in a -45 degree direction after removing the mask, and two types of liquid crystal alignment regions having different liquid crystal alignment control directions are formed. Forming an alignment material. Thereafter, after applying a retardation material composed of a polymerizable liquid crystal solution, the retardation material is brought into a liquid crystal state by heating to a phase transition temperature of the liquid crystal. The polymerizable liquid crystal in a liquid crystal state is aligned on an alignment material on which two types of liquid crystal alignment regions are formed, and forms an alignment state corresponding to each liquid crystal alignment region. Then, the retardation material in which such an orientation state is realized is cured as it is, the above-described orientation state is fixed, and a plurality of two kinds of retardation regions having different retardation characteristics are regularly arranged. A phase difference material can be obtained.

Moreover, the alignment material formed from the cured film composition of this embodiment can also be used as a liquid crystal alignment film of a liquid crystal display element. For example, after using the two substrates having the alignment material of the present embodiment formed as described above, the alignment materials on both the substrates are bonded to each other via a spacer, and then between the substrates. A liquid crystal display element in which liquid crystal is aligned can be manufactured by injecting liquid crystal into the liquid crystal.
Therefore, the cured film forming composition of this Embodiment can be used suitably for manufacture of various retardation materials (retardation film), a liquid crystal display element, etc.

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

[Compositional components used in Examples and their abbreviations]
Each composition component used in the following examples and comparative examples is as follows.

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

CIN 2: 4- (3-methacryloxypropyl-1-oxy) cinnamic acid

CIN3: 4-propyloxycinnamic acid

CIN 4: 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 units. Molecular weight 4,800)

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

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

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

<Solvent>
Each phase difference material formation composition of an Example and a comparative example 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 uses a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and columns (KD-803, KD-805) manufactured by Shodex. Measurement was performed as follows.
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) ) Is 10 mL / L)
Flow rate: 1.0 mL / minute 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 Laboratories ( Molecular weight about 12,000, 4,000, 1,000).

^<1 H-NMR analysis>
^The analysis apparatus and analysis conditions used for ¹ H-NMR analysis are as follows.
Nuclear magnetic resonance apparatus: Varian NMR System 400 NB (400 MHz)
Measuring 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) (CIN 6) was obtained. 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 added dropwise to 1000.0 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-1). The obtained acrylic copolymer had Mn of 7,000 and Mw of 20,000.

<Polymerization Example 3>
BMAA 28.0g, HEMA 12.0g, and AIBN 0.8g as a polymerization catalyst were dissolved in tetrahydrofuran 204.0g and reacted at 60 ° C for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, 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>
BMAA 24.0 g, HEMA 16.0 g, and AIBN 0.8 g as a polymerization catalyst were dissolved in tetrahydrofuran 204.0 g and reacted at 60 ° C. for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually added dropwise to 1000.0 g of hexane to precipitate a solid, 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 added dropwise to 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 added dropwise to 1000 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic polymer (PB-5). The obtained acrylic polymer had Mn of 8,000 and Mw of 20,000.

<Polymerization Example 7>
MMA 100.0 g, HEMA 11.1 g, and AIBN 5.6 g 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>
BMAA 100.0 g and AIBN 4.2 g as a polymerization catalyst were dissolved in PM 193.5 g 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, 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran, The reaction was carried out at 60 ° C. for 5 hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-6) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed 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, 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran, The reaction was carried out at 60 ° C. for 5 hours. This solution was gradually added dropwise to 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. ¹ H-NMR analysis was performed, and it was confirmed 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, 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran, The reaction was carried out at 60 ° C. for 5 hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-8) having an acryloyl group. ¹ H-NMR analysis was performed and it was confirmed 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, 10 mg of dibutyltin dilaurate as a reaction catalyst were dissolved in 60 g of tetrahydrofuran, The reaction was carried out at 60 ° C. for 5 hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-9) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed 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, 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM, and 20 ° C. at 90 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-10) having an acroyl group. 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, 10 mg of benzyltriethylammonium chloride as a reaction catalyst were dissolved in 60 g of PM, and 20 at 90 ° C. Reacted for hours. The solution was gradually added dropwise to 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 and it was confirmed 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; 10 mg of benzyltriethylammonium chloride as a reaction catalyst are dissolved in 60 g of PM, and 20 at 90 ° C. Reacted for hours. This solution was gradually added dropwise to 500 g of hexane to precipitate a solid, which was filtered and dried under reduced pressure to obtain an acrylic copolymer (PB-12) having an acroyl group. ¹ H-NMR analysis was performed and it was confirmed that the acrylic copolymer (PB-12) had an acroyl group.

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

<Examples and comparative examples>
Each cured film forming composition of an Example and a comparative example was prepared with the composition shown in Table 1. Next, a cured film was formed using each phase difference material formation composition, and orientation and adhesion nature were evaluated about each obtained cured film.

[Evaluation of orientation]
Each of the cured film forming compositions of Examples and Comparative Examples was applied onto a film using a bar coater, and then heated and dried in a heat circulation oven at a temperature of 100 ° C. for 2 minutes to form a cured film. Each cured film was irradiated vertically with 313 nm linearly polarized light at an exposure amount of 20 mJ / cm ² to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked 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, the state of the phase difference characteristic in the phase difference material is observed, ○ if the phase difference is expressed without defects, and no phase difference is expressed The thing was described in the column of "orientation" as x.

[Evaluation of adhesion]
Each of the cured film forming compositions of Examples and Comparative Examples was applied onto a film using a bar coater, and then heated and dried in a heat circulation oven at a temperature of 100 ° C. for 2 minutes to form a cured film. Each cured film was irradiated vertically with 313 nm linearly polarized light at an exposure amount of 20 mJ / cm ² to form an alignment material. On the alignment material on the substrate, a polymerizable liquid crystal solution for horizontal alignment is applied using a bar coater, and then pre-baked 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. This phase difference material was cut with a cutter knife so as to be 10 × 10 squares at intervals of 1 mm in length and width. A cellophane tape peeling test was performed on the cut using a scotch tape. The evaluation result was “initial”, and the case where all 100 squares were not peeled off was marked with ○, and the case where even one square was peeled was marked with ×. The evaluation results are summarized in Table 2 later.

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

[Evaluation results]
The results of the above evaluation are shown in Table 2 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 capable of forming a retardation material with an exposure amount as low as 20 mJ / cm ² . On the other hand, the cured film obtained using each retardation material forming composition of Comparative Example 3 did not have orientation.

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

  On the other hand, it was difficult for the cured films obtained using the cured film forming compositions of Comparative Examples 1 to 3 to maintain the 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 an alignment material for forming a liquid crystal alignment film of a liquid crystal display element and an optically anisotropic film provided inside or outside the liquid crystal display element, It is particularly suitable as a material for forming a patterned retardation material for a 3D display. Furthermore, 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, 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 (13)

(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 The cured film formation composition containing the polymer containing this. The cured film forming composition according to claim 1, wherein the photoalignable group of the component (A) is a functional group having a structure that undergoes photodimerization or photoisomerization. The cured film forming composition of Claim 1 or Claim 2 whose photo-alignment group of (A) component is a cinnamoyl group. The cured film forming composition of Claim 1 or Claim 2 whose photo-alignment group of (A) component is group of azobenzene structure.   And (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) 5. The polymer according to claim 1, comprising at least one polymer selected from the group consisting of a polymer having a substituent capable of thermally reacting with a component and capable of self-crosslinking, and (C-3): melamine formaldehyde resin. 2. A cured film forming composition according to item 1.   Furthermore, the cured film formation composition of any one of Claims 1 thru | or 5 containing the crosslinking catalyst (D).   Furthermore, the cured film forming composition of any one of Claims 1 thru | or 6 containing (E) crosslinking agent. The proportion of the repeating unit having an N-alkoxymethyl group in the polymer of component (B) is 40 to 90 mol% per 100 mol of all repeating units of the polymer, and the polymerizable C = C double The curing according to any one of claims 1 to 7, wherein the proportion of the repeating unit having a side chain containing a bond is 10 mol% to 60 mol% per 100 mol of all repeating units of the polymer. Film-forming composition. The cured film forming composition according to any one of claims 1 to 8, wherein a content ratio of the component (A) to the component (B) is 5:95 to 60:40 in terms of mass ratio. The cured film forming composition of Claim 5 which contains 5 mass parts thru | or 500 mass parts (C) component based on 100 mass parts of total amounts of (A) component and (B) component. The optical film obtained from the cured film formation composition as described in any one of Claims 1 thru | or 10. The liquid crystal aligning material formed using the optical film of Claim 11. A retardation material formed using the optical film according to claim 11.