KR102587604B1 - Cured film forming composition, orientation material and phase difference material - Google Patents

Abstract

(식 중, *은 고분자 화합물의 측쇄와의 결합위치를 나타내고, R¹ 및 R²는 각각 독립적으로 수소원자 또는 알킬기를 나타내고, R³은 알킬기, 알케닐기, 시클로알킬기, 방향족기를 나타내고, R¹과 R³, 또는 R²와 R³은 서로 결합하여 환을 형성할 수도 있다. X¹은 임의의 치환기로 치환되어 있을 수도 있는 페닐렌기를 나타낸다.)[Problem] To provide a cured film forming composition for providing an alignment material that has excellent photoreaction efficiency and can orient polymerizable liquid crystals with high sensitivity.
[Solutions] A cured film-forming composition characterized by containing a polymer compound having a group represented by the following formula (1) in the side chain as a photo-alignable group, a cured film obtained using the composition, an orientation material, and a retardation material.

(In the formula, * represents the bonding position with the side chain of the polymer compound, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, alkenyl group, cycloalkyl group, or aromatic group, and R ¹ and R ³ , or R ² and R ³ may be combined with each other to form a ring. X ¹ represents a phenylene group that may be substituted with an arbitrary substituent.)

Description

Cured film forming composition, orientation material and phase difference material

The present invention relates to a cured film forming composition, an orientation material, and a phase difference material.

Recently, in the field of displays such as televisions using liquid crystal panels, the development of 3D displays that can enjoy 3D images is underway in an attempt to improve performance. In a 3D display, for example, an image with a three-dimensional effect can be reproduced by causing the viewer's right eye to see the image for the right eye and the viewer's left eye to see the image for the left eye.

There are a variety of 3D display methods for displaying 3D images, and methods such as the lenticular lens method and the parallax barrier method are known as methods that do not require dedicated glasses.

Also, as one of the display methods in which an observer wears glasses to observe a 3D image, circularly polarized glasses, etc. are known (for example, see Patent Document 1).

In the case of a 3D display using circularly polarized glasses, a phase difference material is usually placed on a display element that forms an image, such as a liquid crystal panel. This phase difference material constitutes a patterned phase difference material in which a plurality of two types of phase difference regions with different phase difference characteristics are arranged regularly. Meanwhile, hereinafter, in this specification, a phase difference material patterned to arrange a plurality of phase difference regions with different phase difference characteristics is referred to as a patterned phase difference material.

A patterned phase difference material can be produced, for example, as disclosed in Patent Document 2, by optically patterning a phase difference material made of polymerizable liquid crystal. Optical patterning of a retardation material made of polymeric liquid crystal uses photo-alignment technology known for forming alignment materials for liquid crystal panels. Specifically, first, a coating film made of a photo-alignable material is prepared on a substrate, and two types of polarized light with different polarization directions are irradiated to it. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions with different liquid crystal alignment control directions are formed. A retardation material in a solution containing polymerizable liquid crystal is applied onto this photo-alignment film, and alignment of the polymerizable liquid crystal is achieved. Thereafter, the aligned polymerizable liquid crystal is cured to form a patterned phase difference material.

In the formation of an alignment material using the photo-alignment technology of the liquid crystal panel described above, acrylic resins and polyimide resins having photodimerization sites such as cinnamoyl groups and chalcone groups in the side chains are known as usable photo-alignment materials. there is. It has been reported that these resins exhibit the ability to control the orientation of liquid crystals (hereinafter also referred to as liquid crystal orientation) by irradiating polarized UV (see Patent Documents 3 to 5).

Japanese Patent Publication No. H10-232365 Japanese Patent Publication No. 2005-49865 Japanese Patent No. 3611342 Publication Japanese Patent Publication No. 2009-058584 Japanese Patent Publication No. 2001-517719

However, according to the present inventors' examination, it has been experienced that acrylic resins having photodimerization sites such as cinnamoyl groups and chalcone groups in these side chains cannot obtain sufficient orientation characteristics when applied to the formation of phase difference materials. In particular, in order to irradiate these resins with polarized UV to form an alignment material and use the alignment material to perform optical patterning of a retardation material made of polymerizable liquid crystal, a large amount of polarized UV exposure is required. The polarized UV exposure amount is significantly higher than the polarized UV exposure amount (for example, about 30 mJ/cm ² ) sufficient to orient the liquid crystals for a normal liquid crystal panel.

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

More specifically, when an alignment material is formed using an acrylic resin having a photodimerization site such as a cinnamoyl group in the side chain and the polymerizable liquid crystal is to be aligned, the acrylic resin, etc. undergoes a photodimerization reaction. After photocrosslinking is performed, resistance to the polymerizable liquid crystal solution is developed, so it is necessary to perform polarized light irradiation at a large exposure amount. In order to orient the liquid crystals of a liquid crystal panel, usually only the surface of the photo-alignable alignment material needs to be subjected to a dimerization reaction. However, if it is intended to develop solvent resistance in the alignment material using conventional materials such as the acrylic resin described above, it is necessary to proceed the reaction to the inside of the alignment material, and a larger exposure amount is required. As a result, there was a problem that the orientation sensitivity of conventional materials was very low.

Additionally, in order to develop such solvent resistance in the resin, which is the conventional material described above, a technique for adding a crosslinking agent is known. However, it has been confirmed that when a thermal curing reaction using a crosslinking agent is performed, a three-dimensional structure is formed inside the formed coating film due to the crosslinking agent, and photoreactivity is reduced. In other words, adding only a cross-linking agent to achieve solvent resistance may result in a significant decrease in orientation sensitivity, so the desired effect cannot be obtained even if only a cross-linking agent is added to a conventional material.

From the above, there is a need for a photo-alignment technology that can improve the orientation sensitivity of the alignment material and reduce the amount of polarized UV exposure, and a cured film forming composition used to form the alignment material. Additionally, there is a demand for technology that can provide patterned phase difference materials with high efficiency.

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

Another object of the present invention is to provide an alignment material formed using the cured film forming composition, which has excellent photoreaction efficiency and can orient polymerizable liquid crystals with high sensitivity, and a retardation material formed using the alignment material. It's in what it provides.

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

The first aspect of the present invention relates to a cured film forming composition characterized by containing, as component (A), a polymer compound having a group in the side chain represented by the following formula (1) as a photo-alignment group.

[Formula 1]

(In the formula, * represents the bonding position with the side chain of the polymer compound, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, alkenyl group, cycloalkyl group, or aromatic group, and R ¹ and R ³ , or R ² and R ³ may be combined with each other to form a ring. X ¹ represents a phenylene group that may be substituted with an arbitrary substituent.)

In the first aspect of the present invention, it is preferable that the polymer compound of component (A) is an acrylic copolymer.

In the first aspect of the present invention, it is preferable that the polymer compound of component (A) further has a self-crosslinkable group or at least one crosslinkable group. At this time, the crosslinkable group is a group that undergoes a thermal crosslinking reaction with a specific functional group 2 selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2).

[However, the carboxyl group resulting from dissociation of the protecting group of the photo-alignment group represented by the above formula (1) is included in specific functional group 2.]

[Formula 2]

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)

In the first aspect of the present invention, it is preferable that the polymer compound of component (A) further has at least one specific functional group 2 and at least one crosslinkable group. At this time, the specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2),

The crosslinkable group is a group that undergoes a thermal crosslinking reaction with the specific functional group 2.

[However, the carboxyl group resulting from dissociation of the protecting group of the photo-alignment group represented by the above formula (1) is included in specific functional group 2.]

[Formula 3]

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)

In the first aspect of the present invention, the polymer compound of component (A) further has at least one specific functional group 2, and the composition includes a crosslinking agent (B) that undergoes a thermal crosslinking reaction with the specific functional group 2. It is preferable to additionally contain. At this time, the specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2).

[However, the carboxyl group resulting from dissociation of the protecting group of the photo-alignment group represented by the above formula (1) is included in specific functional group 2.]

[Formula 4]

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)

In the first aspect of the present invention, it is preferable to further contain a specific polymer having at least two specific functional groups 2 as component (C). At this time, the specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the above formula (2).

In the first aspect of the present invention, it is preferable to further contain a crosslinking catalyst as component (E), wherein the crosslinking catalyst (E) is (E-1) acid or thermal acid generator, or (E -2) Either a combination of a metal chelate compound and (E-3) a silanol compound.

In the first aspect of the present invention, it is preferable to further contain as component (D) an adhesion improving component having one or more polymerizable groups, at least one specific functional group 2 or at least one crosslinkable group. At this time, the specific functional group 2 is a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2), and the crosslinkable group is a group that undergoes a thermal crosslinking reaction with the specific functional group 2. .

In the first aspect of the present invention, it is preferable that the component (F) further contains a photo-alignment group in which the heat crosslinking reactive site is bonded directly or bonded through a linking group, and a monomer having one or more polymerizable groups. .

In the first aspect of the present invention, it is preferable to contain 1 to 100 parts by mass of component (B) based on 100 parts by mass of the polymer compound that is component (A).

In the first aspect of the present invention, it is preferable to contain 10 to 200 parts by mass of component (C) based on 100 parts by mass of component (A).

In the first aspect of the present invention, based on 100 parts by mass of component (A), 0.01 to 20 parts by mass of component (E-1) is contained, or 0.1 to 30 parts by mass of (E) It is preferable to contain a combination of component -2) and 0.5 parts by mass to 70 parts by mass of component (E-3).

In the first aspect of the present invention, it is preferable to contain 1 to 80 parts by mass of component (D) based on 100 parts by mass of component (A).

In the first aspect of the present invention, it is preferable to contain 1 to 40 parts by mass of component (F) based on 100 parts by mass of component (A).

The second aspect of the present invention relates to a thermosetting film characterized by being obtained using the cured film forming composition of the first aspect of the present invention.

The third aspect of the present invention relates to an orientation material obtained using the cured film forming composition of the first aspect of the present invention.

The fourth aspect of the present invention relates to a phase difference 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 capable of forming a cured film having liquid crystal alignment ability (photo-alignment) by light irradiation in addition to high solvent resistance can be provided.

According to the second aspect of the present invention, it is possible to provide a thermosetting film that has liquid crystal alignment ability (photo-alignment) by light irradiation in addition to high solvent resistance.

According to the third aspect of the present invention, it is possible to provide an alignment material that has alignment sensitivity and pattern formation properties and can orient polymeric liquid crystals with high sensitivity.

According to the fourth aspect of the present invention, it is possible to provide a phase difference material that can be formed with high efficiency even on a resin film and is capable of optical patterning.

<Curated film forming composition>

The cured film forming composition of the present invention contains a polymer compound having a specific photo-alignment group in the side chain as component (A). Additionally, the cured film forming composition of the present invention may contain a crosslinking agent as the (B) component in addition to the (A) component. In addition, the cured film forming composition of the present invention includes (A) component and (B) component,

(C) a specific polymer having at least two specific functional groups 2 as a component,

(D) An adhesion-improving compound further having one or more polymerizable groups as a component, at least one specific functional group 2 or at least one crosslinkable group,

(E) a crosslinking catalyst as a component, and

(F) Component is a monomer having a photo-alignable group in which the heat crosslinking reactive site is directly bonded or bonded through a linking group, and one or more polymerizable groups.

It may additionally contain.

Meanwhile, the specific functional group 2 is a group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2), and the crosslinkable group is a group that undergoes a thermal crosslinking reaction with the specific functional group 2. am. [However, the carboxyl group resulting from dissociation of the protecting group of the photo-alignment group represented by the above formula (1) is included in specific functional group 2.]

[Formula 5]

(In the formula, * represents the bonding position, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)

Additionally, the cured film forming composition of the present invention may contain other additives as long as the effects of the present invention are not impaired.

Hereinafter, details of each component will be described.

<(A) Ingredient>

Component (A) contained in the cured film forming composition of the present invention is a polymer compound having a group represented by the following formula (1), which is a photo-alignment group, in its side chain.

[Formula 6]

(In the formula, * represents the bonding position with the side chain of the polymer compound, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, alkenyl group, cycloalkyl group, or aromatic group, and R ¹ and R ³ , or R ² and R ³ may be combined with each other to form a ring. X ¹ represents a phenylene group that may be substituted with an arbitrary substituent.)

The alkyl group for R ¹ and R ² includes an alkyl group having 1 to 6 carbon atoms.

The alkyl group for R ³ is an alkyl group with 1 to 6 carbon atoms, the alkenyl group is an alkenyl group with 2 to 6 carbon atoms, the cycloalkyl group is a cycloalkyl group with 3 to 8 carbon atoms, and the aromatic group is a carbon source. Aromatic groups numbered 4 to 14 can be mentioned, respectively.

The alkyl group having 1 to 6 carbon atoms may be either linear or branched, and may be methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, or t-butyl. , n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group , 2-methylpentyl group, 1,1-dimethylbutyl group, 1-ethylbutyl group, 1,1,2-trimethylpropyl group, etc.

The alkenyl group having 2 to 6 carbon atoms may be linear, branched, or cyclic, for example, ethenyl group, 1-propenyl group, 2-propenyl group, and 1-methyl-1-ethenyl group. , 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl -2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group , 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1, 2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-c-pentenyl group, 2-c-pentenyl group, 3-c-pentenyl group, 1-hexenyl group, 2-hexenyl group Senyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1- Methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pente Nyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3 -Ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl- 2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1 -methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3 -Butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3- Dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl -3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl- 3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1- Prophenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-c-pentenyl group, 1 -methyl-3-c-pentenyl group, 2-methyl-1-c-pentenyl group, 2-methyl-2-c-pentenyl group, 2-methyl-3-c-pentenyl group, 2-methyl-4-c -Pentenyl group, 2-methyl-5-c-pentenyl group, 2-methylene-c-pentyl group, 3-methyl-1-c-pentenyl group, 3-methyl-2-c-pentenyl group, 3-methyl- 3-c-pentenyl group, 3-methyl-4-c-pentenyl group, 3-methyl-5-c-pentenyl group, 3-methylene-c-pentyl group, 1-c-hexenyl group, 2-c- Hexenyl group, 3-c-hexenyl group, etc. are mentioned.

Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, and cyclooctyl group.

And the aromatic group having 4 to 14 carbon atoms may be a heterocyclic ring, for example, phenyl group, biphenylyl group, o-terphenylyl group, m-terphenylyl group, p-terphenylyl group, fluorenyl group, naphthale group. Nyl group, 1-phenylnaphthalenyl group, 2-phenylnaphthalenyl group, anthracenyl group, etc. are mentioned.

The optional substituent for the phenylene ^group of Haloalkyl groups such as trifluoromethyl group; Alkoxy groups such as methoxy group and ethoxy group; Halogen atoms such as iodine, bromine, chlorine, and fluorine; Cyano group; Nitro groups, etc. can be mentioned.

The polymer compound of component (A) is a polymer compound having an organic group in the side chain containing a group (photo-alignment group) represented by the above formula (1), specifically, a group represented by formula (1) via a spacer. A high molecular compound bonded to the main chain is preferred. On the other hand, the group represented by the above formula (1) may be bonded not only to the side chain of the polymer compound but also to the terminal of the polymer compound.

The spacer is a divalent group selected from a straight-chain alkylene group, a branched alkylene group, a cyclic alkylene group, and a phenylene group, or a group formed by combining two or more of the divalent groups. In this case, the bond between the divalent groups constituting the spacer, the bond between the spacer and the main chain, and the bond between the spacer and the group represented by the above formula (1) include a single bond, ester bond, amide bond, urea bond, or ether. Combination can be mentioned. When the above divalent groups are plural, the divalent groups may be the same or different, and when the above bonds are plural, the bonds may be the same or different.

Among these, as the component (A), an acrylic copolymer having a photo-alignment group represented by the above formula (1) is more preferable.

In the present invention, an acrylic copolymer (also referred to as acrylic resin) is a (co)polymer obtained by homopolymerization or copolymerization using at least one monomer selected from the group consisting of acrylic acid ester and methacrylic acid ester, and further these It refers to a copolymer obtained by copolymerizing other monomers with unsaturated double bonds, such as styrene, in addition to monomers. Therefore, the “acrylic copolymer” in the present invention includes acrylic polymers in addition to acrylic copolymers.

The acrylic copolymer having a photo-alignment group (hereinafter also referred to as a specific copolymer) may be an acrylic copolymer having such a structure, and there are no particular limitations on the type of main chain and side chains of the polymer constituting the acrylic copolymer.

The acrylic copolymer of component (A) preferably has a weight average molecular weight of 1,000 to 200,000, more preferably 2,000 to 150,000, and even more preferably 3,000 to 100,000. If the weight average molecular weight is excessive (exceeding 200,000), solubility in solvents may decrease and handling properties may deteriorate. If the weight average molecular weight is too low (less than 1,000), curing may be insufficient during heat curing, resulting in poor solvent resistance and Heat resistance may deteriorate. Meanwhile, the weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using polystyrene as a standard sample. Hereinafter, the same applies to this specification.

As a method for synthesizing the acrylic copolymer having a photo-alignment group as the component (A), for example, a simple method is to polymerize a monomer having a photo-alignment group represented by the above formula (1).

The monomer having a photo-alignment group represented by the above formula (1) is, for example, a carboxyl group of a monomer having a cinnamic acid group, and an ether compound represented by the formula (3-1) below or an ether represented by the formula (3-2) below. It can be obtained by reacting with a compound.

[Formula 7]

(Wherein, R ² represents a hydrogen atom or an alkyl group, R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, an alkenyl group, a cycloalkyl group, or an aromatic group, and R ² and R ³ , or R ⁵ and R ³ may be combined with each other to form a ring)

Monomers having a cinnamic acid group include monomers represented by (4) below.

[Formula 8]

(In formula ( ^{4 )} , One or more hydrogen atoms in the lene group, phenylene, or divalent carbocycle or heterocycle may be substituted with a fluorine atom or an organic group. Additionally, any methylene group (-CH ₂ -) in R ⁶ may be: It may be substituted with a phenylene group or a divalent carbocyclic ring or heterocycle, and may also be substituted with any of the following groups if they are not adjacent to each other: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ⁷ is -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO -, -NH- or -CO-, and R ⁸ is a hydrogen atom or a methyl group)

Monomers having the cinnamic acid group include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, and 4-(3-methacryloxypropyl-1). -oxy) cinnamic acid, 4-(4-(6-methacryloxyhexyl-1-oxy) benzoyloxy) cinnamic acid, etc. can be mentioned.

Compounds represented by the formula (3-1) include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, cyclohexyl vinyl ether, isobutyl vinyl ether, n-butyl vinyl ether, Vinyl ethers such as t-butyl vinyl ether and phenyl vinyl ether, and unsaturated cyclic ethers such as 2,3-dihydrofuran and 3,4-dihydro-2H-pyran.

Compounds represented by formula (3-2) include chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl n-propyl ether, chloromethyl i-propyl ether, chloromethyl cyclohexyl ether, chloromethyl isobutyl ether, and chloromethyl ether. Examples include methyl n-butyl ether, chloromethyl t-butyl ether, and chloromethyl phenyl ether.

When reacting the monomer having the cinnamic acid group and the compound represented by the formula (3-1), 0.9 mole to 1.5 mol of the compound represented by the formula (3-1) is used per mole of the monomer having the cinnamic acid group, The reaction can be carried out without a catalyst or under an acid catalyst.

The compound represented by formula (3-1) used as a starting material in the present invention can be obtained as a commercial product.

The reaction format may be either rotational (batch) or distribution.

Examples of acid catalysts used in the reaction include phosphoric acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonic acid, and methanesulfonic acid. The acid catalyst is used in an amount of 0.01 to 0.5 mol, more preferably 0.01 to 0.3 mol, per mole of the monomer having a cinnamic acid group.

Solvents used in the reaction include, for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, pentanol, isopentanol, butanol, and isobutanol, diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, Ethers such as methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether, aromatic hydrocarbons such as benzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petroleum ether, and acetonitrile. , nitriles such as propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride, formamides such as formamide, N,N-dimethylformamide, dimethyl sulfoxide, diethyl Examples include sulfoxides such as sulfoxide, sulfones such as dimethyl sulfone, diethyl sulfone, and sulfolane, or mixed solvents thereof. Preferably, aromatic hydrocarbons such as benzene, xylene, and toluene, nitriles such as acetonitrile and propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride, diethyl ether, and tetrachloride. These are ethers such as hydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether. More preferably, aromatic hydrocarbons such as benzene, xylene, and toluene, and ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether. It's Ryu.

The reaction temperature is, for example, -10 to 100°C, preferably 0 to 80°C.

The reaction time is 0.5 to 20 hours in the case of batch processing, and is preferably 1 to 15 hours.

When reacting the monomer having the cinnamic acid group and the compound represented by the formula (3-2), 0.9 mole to 1.1 mol of the compound represented by the formula (3-2) is used per mole of the monomer having the cinnamic acid group. The reaction may be carried out in a solvent in the presence of a base.

The compound represented by formula (3-2) used as a starting material in the present invention can be obtained as a commercial product.

The reaction format may be either rotational (batch) or distribution.

Bases used in the reaction include, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, triethylamine, and tributylamine. , organic bases such as diisopropylethylamine, N,N-dimethylaniline, pyridine, 4-(dimethylamino)pyridine, imidazole, 1,8-diazabicyclo[5,4,0]-7-undecene, etc. etc. can be used in an amount of 1 to 4 equivalents relative to the cinnamic acid derivative.

Solvents used in the reaction include, for example, lower alcohols such as methanol, ethanol, propanol, isopropanol, pentanol, isopentanol, butanol, and isobutanol, diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, Ethers such as methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether, aromatic hydrocarbons such as benzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petroleum ether, and acetonitrile. , nitriles such as propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride, formamides such as formamide, N,N-dimethylformamide, dimethyl sulfoxide, diethyl Examples include sulfoxides such as sulfoxide, sulfones such as dimethyl sulfone, diethyl sulfone, and sulfolane, or mixed solvents thereof. Preferably, aromatic hydrocarbons such as benzene, xylene, and toluene, nitriles such as acetonitrile and propionitrile, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and carbon tetrachloride, diethyl ether, and tetrachloride. These are ethers such as hydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether. More preferably, aromatic hydrocarbons such as benzene, xylene, and toluene, and ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, methylcyclopentyl ether, tert-butylmethyl ether, and tert-butyl ethyl ether. It's Ryu.

The reaction temperature is, for example, -10 to 100°C, preferably 0 to 80°C.

The reaction time is 0.5 to 20 hours in the case of batch processing, and is preferably 1 to 15 hours.

In this way, as an example of a monomer having a photo-alignment group represented by the above formula (1), a monomer represented by the formula (5) is obtained.

[Formula 9]

(In formula (5), R ¹ , R ² , R ³ , X ¹ , R ⁶ , R ⁷ , and R ⁸ represent the above meanings)

In addition, component (A) contained in the cured film forming composition of the present invention further has a self-crosslinking group in addition to the photo-alignment group represented by the above formula (1), or further has a specific functional group 2, or It is preferable that it is an acrylic polymer which further has a crosslinkable group. Here, the crosslinkable group refers to a group that undergoes a thermal crosslinking reaction with a specific functional group 2 selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2).

[Formula 10]

In the formula, * represents a bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group.

Meanwhile, the bonding position with another group in formula (2) refers to the bonding position at the side chain or terminal of a polymer compound (including polymers and copolymers), or the bonding position at the terminal of a monomer or compound. do.

In addition, the alkyl group and alkoxy group of R ⁹ represent an alkyl group with 1 to 6 carbon atoms and an alkoxy group with 1 to 6 carbon atoms, respectively.

In addition to the photo-alignment group represented by the formula (1), the method for synthesizing an acrylic copolymer that additionally has a self-crosslinkable group, additionally has a specific functional group 2, or has a crosslinkable group is as described above. The method of polymerizing a monomer having a photo-alignment group, a monomer having a self-crosslinking group, a monomer having a specific functional group 2, or a monomer having a crosslinking group is simple.

Examples of the self-crosslinking group include an alkoxymethylamide group, a hydroxymethylamide group, and an alkoxysilyl group. Examples of the crosslinkable group include glycidyl group, epoxycyclohexyl group, vinyl group, and block isocyanate group. That is, the monomer having a self-crosslinkable group and the monomer having a crosslinkable group refer to an unsaturated double bond involved in the formation of a copolymer and a monomer having the self-crosslinkable group or crosslinkable group.

When such a self-crosslinkable group or crosslinkable group is contained in the polymer compound of component (A), the content is preferably 0.1 to 0.9 per unit of repeating unit in the polymer compound of component (A), and the orientation of the orientation material and From the viewpoint of the balance of solvent resistance, it is more preferable that the number is 0.1 to 0.8.

Examples of monomers having a self-crosslinkable group and a crosslinkable group include N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N - (meth)acrylamide compounds substituted with a hydroxymethyl group or alkoxymethyl group such as butoxymethyl (meth)acrylamide; Monomers having a trialkoxysilyl group such as 3-trimethoxysilylpropyl acrylate, 3-triethoxysilylpropyl acrylate, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl methacrylate; Monomers having a glycidyl group or epoxycyclohexyl group such as glycidyl acrylate, glycidyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate; Monomers having a vinyl group such as 1,2-epoxy-5-hexene and 1,7-octadiene monoepoxide; Monomers having a block isocyanate group such as 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylic acid and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylic acid. I can hear it. On the other hand, (meth)acrylamide means both acrylamide and methacrylamide.

In addition, the specific functional group 2 refers to a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the above formula (2). [However, the carboxyl group resulting from dissociation of the protecting group of the photo-alignment group represented by the above formula (1) is included in specific functional group 2.]

On the other hand, in the cured film forming composition of the present invention, when using an acrylic copolymer having a photo-alignment group represented by the above formula (1) and at least one of the specific functional group 2 as the (A) component, the (B) component described later : It is desirable to use a cross-linking agent together.

Examples of the group represented by the above formula (2) include the following structures.

[Formula 11]

(In the formula, * indicates the bonding position with another group)

A method for synthesizing an acrylic copolymer that further has at least one specific functional group 2 in addition to the photo-alignable group includes a monomer having a photo-alignable group represented by the above formula (1), and at least one specific functional group 2 (hydroxy group, The method of polymerizing a monomer having a group selected from the group consisting of a carboxyl group, an amide group, an amino group, and a group represented by the above formula (2) is simple.

As a monomer having at least one specific functional group 2 (a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the above formula (2)), for example, 2-hydroxyethyl acrylic Rate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-di Hydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, Diethylene glycol monoacrylate, Diethylene glycol monomethacrylate, caprolactone 2-(acryloyloxy)ethyl ester, caprolactone 2- (methacryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, poly(ethylene glycol)ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic- Monomers having a hydroxy group such as 6-lactone and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone; Acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N -Monomers having a carboxyl group such as (carboxyphenyl)methacrylamide and N-(carboxyphenyl)acrylamide; Phenolic hydrocarbons such as hydroxystyrene, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)maleimide, and N-(hydroxyphenyl)maleimide. Monomer having a hydroxyl group; Monomers having an amide group such as acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-diethylacrylamide; Monomers having an amino group such as aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate: 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate (ethylene glycol) Monomers having a group represented by the above formula (2), such as monoacetoacetate monomethacrylate, can be mentioned.

It is preferable that component (A) contained in the cured film forming composition of the present invention is an acrylic copolymer which, in addition to the photo-alignment group represented by the formula (1), further has at least one of the specific functional groups 2 and the crosslinkable group. .

A method for synthesizing an acrylic copolymer further having a photo-alignment group represented by the formula (1), a specific functional group 2, and a crosslinkable group includes a monomer having a photo-alignment group represented by the formula (1), and the specific functional group. A monomer having 2 (a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2)), and the crosslinkable group (a group that undergoes a thermal crosslinking reaction with the specific functional group 2) There is a simple way to polymerize monomers.

On the other hand, the monomer having a photo-alignment group represented by the above formula (1), the monomer having a specific functional group 2, and the monomer having a crosslinkable group are as described above.

In addition, in the present invention, when obtaining a specific copolymer (acrylic copolymer having a photo-alignment group represented by formula (1)), a monomer having a photo-alignment group represented by the formula (1), a monomer having a self-crosslinking group Or a monomer having a crosslinkable group, and a monomer having a specific functional group 2 (a group selected from hydroxy group, carboxyl group, amide group, amino group and group represented by the formula (2) above) (hereinafter represented by the formula (1) In addition to the photo-alignment group, self-crosslinking group, crosslinking group, and specific functional group 2 (collectively referred to as specific functional group 1), monomers that do not have a specific functional group 1 that can be copolymerized with these monomers (hereinafter also referred to as other monomers) can be used together. there is.

Specific examples of such other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Hereinafter, specific examples of the above-mentioned other monomers will be given, but are not limited to these.

Examples of the acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl 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-tricyclodecyl acrylate ate, and 8-ethyl-8-tricyclodecyl acrylate.

Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthryl methyl methacrylate. Crylate, phenyl 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 methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate. there is.

Examples of the vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, and 3-ethenyl-7-oxabicyclo[4.1.0]heptane. I can hear it.

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

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

Moreover, in the present invention, when obtaining a specific copolymer, a monomer having a photo-alignment group other than the photo-alignment group represented by the above formula (1) can also be used together.

The amount of each monomer used to obtain a specific copolymer is based on the total amount of all monomers, and is 10 to 100 mol% of the monomer having a photo-alignment group represented by the above formula (1), a self-crosslinking group, a specific functional group 2, and a crosslinking group. It is preferable that the monomer having a substituent selected from the group (together, these are also referred to as specific crosslinking group 1. This includes a carboxyl group formed by dissociation of the protecting group of the photo-alignment group) is preferably 0 to 90 mol%. On the other hand, when it is intended to introduce a specific crosslinkable group 1, if the content of the monomer having the specific crosslinkable group 1 is less than 10 mol%, the effect of introducing the specific crosslinkable group 1 may not be sufficient.

In addition, when using the other monomers mentioned above when obtaining a specific copolymer, the amount used is preferably 90 mol% or less based on the total amount of all monomers.

The method for obtaining the specific copolymer used in the present invention is not particularly limited, but for example, a monomer having a specific functional group 1 and, if necessary, the other monomers and a polymerization initiator are coexisted in a solvent at a temperature of 50 to 110°C. It is obtained through a polymerization reaction under the following conditions: At this time, the solvent used is not particularly limited as long as it dissolves the monomer having a specific functional group 1, the other monomers used as necessary, and the polymerization initiator. Specific examples are described in <Solvent> described later.

The specific copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

In addition, the solution of the specific copolymer obtained by the above method is reprecipitated by adding it to diethyl ether or water under stirring, and the resulting precipitate is filtered and washed, and then dried at room temperature or heat-dried under normal or reduced pressure. It can be made from copolymer powder. Through the above operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer is obtained. If the purification is not sufficient in one operation, the obtained powder may be re-dissolved in a solvent and the above operation may be repeated.

In the present invention, the specific copolymer can be used in powder form or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

The specific copolymer of component (A) obtained in this way has excellent solubility in solvents in the state of a cured film-forming composition (for example, a coating liquid (varnish)), but after being applied to a substrate and baked, cinnamic acid group-derived The ether compound protecting the carboxyl group is liberated and solubility is reduced, thereby achieving solvent resistance. Therefore, the composition of the present invention exhibits the desired effect by containing at least the polymer compound as component (A).

Moreover, in this invention, the specific copolymer of (A) component may be a mixture of multiple types of specific copolymers.

<(B) Ingredient>

The cured film forming composition of this invention can contain a crosslinking agent as (B) component.

The cross-linking agent as component (B) is a cross-linking agent that reacts with the specific functional group 2 (a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2)) described above, that is, a specific Examples include compounds having a group that undergoes a thermal crosslinking reaction with functional group 2 to form a crosslink.

Examples of the crosslinking agent as component (B) include compounds such as epoxy compounds, methylol compounds, isocyanate compounds, phenoplast compounds, compounds having two or more trialkoxysilyl groups, and alkoxysilane compounds having an amino group; Examples include polymers of N-alkoxymethylacrylamide, polymers of compounds having an epoxy group, polymers of compounds having an alkoxysilyl group, polymers of compounds having an isocyanate group, and polymers such as melamine formaldehyde resin.

Specific examples of the above-mentioned epoxy compounds include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl. Dyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 ,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-di Glycidylaminomethyl) cyclohexane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane.

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

Specific examples of 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)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl )-4,5-dimethoxy-2-imidazolinone, etc. Commercially available products include compounds such as glycoluril compounds (brand names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Nippon Scitech Industries Co., Ltd. (formerly Mitsui Scitech Co., Ltd.), and methylated urea. Resin (brand name: UFR (registered trademark) 65), butylated urea resin (brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Co., Ltd. (Highly condensed type, brand name: Beckamine (registered trademark) J-300S, P-955, N).

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As commercial products, manufactured by Nippon Scitech Industries Co., Ltd. (Kumitsu Scitech Co., Ltd.) (Product name: Cymel (registered trademark) 1123), manufactured by Samhwa Chemical Co., Ltd. (Product name: Nikalac (registered trademark) BX -4000, BX-37, BL-60, BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. As commercial products, methoxymethyl type melamine compounds (brand name: Cymel (registered trademark) 300, 301, 303, 350) and butoxymethyl type manufactured by Nippon Scitech Industries Co., Ltd. (formerly Mitsui Scitech Co., Ltd.). Melamine compound (Product name: Mycoat (registered trademark) 506, 508), Methoxymethyl type melamine compound (Product name: Nikalac (registered trademark) MW-30, MW-22, MW-11, MS manufactured by Samhwa Chemical Co., Ltd. -001, MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compound (Product name: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. You can.

In addition, it may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds prepared from melamine compounds and benzoguanamine compounds described in U.S. Patent No. 6323310 can be mentioned. Commercially available products of the melamine compound include Brand Name: Cymel (registered trademark) 303, and commercial products of the benzoguanamine compound include Brand Name: Cymel (registered trademark) 1123 (above, Nippon Scitech Industry). Ltd. (formerly manufactured by Mitsui Saitech Co., Ltd.), etc. can be mentioned.

Specific examples of the above-mentioned isocyanate compounds include, for example, VESTANAT B1358/100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Evonik Japan (formerly Degusa Japan Co., Ltd.)) , Takenate (registered trademark) B-882N, B-7075 (above, isocyanurate type modified polyisocyanate, manufactured by Mitsui Chemicals Co., Ltd.), etc.

Specific examples of the phenoplast compounds described above include the compounds shown in [P-1] to [P-9] below, but the phenoplast compounds are not limited to the examples of the compounds below.

[Formula 12]

(In the above formula, Me represents a methyl group).

Specific examples of compounds having two or more trialkoxysilyl groups include, for example, 1,4-bis(trimethoxysilyl)benzene, 1,4-bis(triethoxysilyl)benzene, 4,4'- Bis(trimethoxysilyl)biphenyl, 4,4'-bis(triethoxysilyl)biphenyl, bis(trimethoxysilyl)ethane, bis(triethoxysilyl)ethane, bis(trimethoxysilyl) Methane, bis(triethoxysilyl)methane, bis(trimethoxysilyl)ethylene, bis(triethoxysilyl)ethylene, 1,3-bis(trimethoxysilylethyl)tetramethyldisiloxane, 1,3- Bis(triethoxysilylethyl)tetramethyldisiloxane, bis(triethoxysilylmethyl)amine, bis(trimethoxysilylmethyl)amine, bis(triethoxysilylpropyl)amine, bis(trimethoxysilylpropyl) )Amine, bis(3-trimethoxysilylpropyl)carbonate, bis(3-triethoxysilylpropyl)carbonate, bis[(3-trimethoxysilyl)propyl]disulfide, bis[(3-triethoxysilyl) )propyl]disulfide, bis[(3-trimethoxysilyl)propyl]thiourea, bis[(3-triethoxysilyl)propyl]thiourea, bis[(3-trimethoxysilyl)propyl]urea, bis [(3-triethoxysilyl)propyl]urea, 1,4-bis(trimethoxysilylmethyl)benzene, 1,4-bis(triethoxysilylmethyl)benzene, tris(trimethoxysilylpropyl)amine , Tris(triethoxysilylpropyl)amine, 1,1,2-tris(trimethoxysilyl)ethane, 1,1,2-tris(triethoxysilyl)ethane, tris(3-trimethoxysilylpropyl) ) Compounds such as isocyanurate and tris(3-triethoxysilylpropyl)isocyanurate can be mentioned.

Specific examples of alkoxysilane compounds having an amino group include, for example, N,N'-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N,N'-bis[3- (triethoxysilyl)propyl]-1,2-ethanediamine, N-[3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N-[3-(triethoxysilyl)propyl] -1,2-ethanediamine, bis-{3-(trimethoxysilyl)propyl}amine, bis-{3-(triethoxysilyl)propyl}amine, 3-aminopropyltrimethoxysilane, 3-amino Propyltriethoxysilane, trimethoxy{3-(methylamino)propyl}silane, 3-(N-allylamino)propyltrimethoxysilane, 3-(N-allylamino)propyltriethoxysilane, 3- (diethylamino)propyltrimethoxysilane, 3-(diethylamino)propyltriethoxysilane, 3-(phenylamino)propyltrimethoxysilane, and 3-(phenylamino)propyltriethoxysilane, etc. Compounds may be mentioned.

In addition, examples of the polymers of N-alkoxymethylacrylamide described above include N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, and N-ethoxymethyl(meth)acrylamide. Examples include polymers manufactured using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups such as acrylamide and N-butoxymethyl (meth)acrylamide.

Specific examples of such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, and N-hydroxymethylmethacrylamide and methyl methacrylate. Copolymers include copolymers of N-ethoxymethyl methacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl acrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. . The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

Polymers of compounds having an epoxy group include, for example, compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, and 3,4-epoxycyclohexylmethyl methacrylate. Examples include polymers manufactured using:

Specific examples of such polymers include, for example, poly(3,4-epoxycyclohexylmethyl methacrylate), poly(glycidyl methacrylate), and a mixture of glycidyl methacrylate and methyl methacrylate. Examples include polymers, copolymers of 3,4-epoxycyclohexylmethyl methacrylate and methyl methacrylate, and copolymers of glycidyl methacrylate and styrene. The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

Examples of the polymer of the compound having an alkoxysilyl group described above include a polymer manufactured using a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane.

Specific examples of such polymers include, for example, poly(3-methacryloxypropyltrimethoxysilane), copolymer of 3-methacryloxypropyltrimethoxysilane and styrene, 3-methacryloxypropyltrimeth A copolymer of oxysilane and methyl methacrylate, etc. can be mentioned. The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

Polymers of the compounds having the above-mentioned isocyanate group include, for example, 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko Co., Ltd.) and 2-isocyanatoethyl acrylic. Compounds having an isocyanate group such as RATE (Karenz AOI [registered trademark], manufactured by Showa Denko Co., Ltd.), or 2-(0-[1'-methylpropylidene amino] carboxyamino) ethyl methacrylate (Karenz MOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (KarenzMOI-BP [registered trademark], Showa Polymers manufactured using compounds having a block isocyanate group, such as those manufactured by Denko Co., Ltd., can be mentioned.

Specific examples of such polymers include, for example, poly(2-isocyanatoethyl acrylate), poly(2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate), 2 -A copolymer of isocyanatoethyl methacrylate and styrene, and a copolymer of 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and methyl methacrylate. The weight average molecular weight (polystyrene equivalent) of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

Specific examples of the melamine formaldehyde resin described above include a resin obtained by polycondensation of melamine and formaldehyde and represented by the following formula.

[Formula 13]

(In the formula, R ²¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and q is a natural number representing the number of repeating units.)

From the viewpoint of storage stability, the melamine formaldehyde resin preferably has the methylol group generated during polycondensation of melamine and formaldehyde alkylated.

The method of obtaining the melamine formaldehyde resin is not particularly limited, but is generally synthesized by mixing melamine and formaldehyde, making it slightly alkaline using sodium carbonate or ammonia, and then heating at 60°C to 100°C. The methylol group can be alkoxylated by reacting with alcohol again.

The melamine formaldehyde resin of component (B) preferably has a weight average molecular weight of 250 to 5,000, more preferably 300 to 4,000, and even more preferably 350 to 3,500. If the weight average molecular weight is excessive (exceeding 5000), the solubility in solvents may decrease and handling properties may deteriorate. If the weight average molecular weight is too low (less than 250), curing may be insufficient during heat curing, resulting in poor solvent resistance and There are cases where the effect of improving heat resistance is not sufficiently achieved.

In the cured film-forming composition of the present invention, the melamine formaldehyde resin as component (B) can be used in liquid form or in the form of a solution obtained by re-dissolving the purified liquid in a solvent described later.

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

The content when containing the crosslinking agent of component (B) in the cured film forming composition of the present invention is preferably 1 part by mass to 100 parts by mass based on 100 parts by mass of the polymer compound that is component (A). Preferably it is 5 parts by mass to 80 parts by mass. When the content of the crosslinking agent is excessive, photo-orientation and storage stability may decrease. On the other hand, when the content of the crosslinking agent is too small, there is a risk that the solvent resistance of the cured film obtained from the cured film-forming composition may decrease and the photo-alignment property may decrease.

<(C) Ingredient>

The cured film forming composition of the present invention contains, as component (C), at least two specific functional groups 2 (a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the above formula (2)). Eggplant can contain compounds. Here, (C) component is also called a specific polymer. (C) The component may be a low molecular compound or a high molecular compound.

Examples of low-molecular-weight compounds that are component (C) include pentaerythritol, dipentaerythritol, diethylene glycol, triethylene glycol, dipropylene glycol, adipic acid, adipoamide, hexamethylenediamine, and 1,4-bis. (acetoacetylaminoethyl)cyclohexane, 1-(4-(2-(4-(3-oxo-butyl)-phenoxy)-ethoxy)-phenyl)-butane-1,3-dione, and 1, 4-butanediol diacetoacetate, etc. can be mentioned.

(C) The polymer compound as component includes, for example, acrylic polymer, polyamic acid, polyimide, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, and polycapro. Polymers having a linear or branched structure such as lactone polyol, polyalkylene imine, polyallylamine, cellulose (cellulose or its derivative), phenol novolak resin, and cyclic polymer such as cyclodextrin.

Among the above, preferred polymer compounds as component (C) include acrylic polymers, cyclodextrins, celluloses, polyether polyols, polyester polyols, polycarbonate polyols, polycaprolactone polyols, and phenol novolac resins. .

Acrylic polymer, which is a preferred example of the polymer compound of component (C), is a polymer obtained by polymerizing monomers having unsaturated double bonds such as acrylic acid, methacrylic acid, styrene, and vinyl compounds, and is a monomer containing a specific functional group 2 or Any polymer obtained by polymerizing the mixture may be used, and there are no particular limitations on the type of main chain and side chains of the polymer constituting the acrylic polymer.

Monomers containing specific functional group 2 include monomers having a polyethylene glycol ester group, monomers having a hydroxyalkyl ester group of 2 to 5 carbon atoms, monomers having a phenolic hydroxy group, monomers having a carboxyl group, monomers having an amide group, and amino groups. A monomer having a and a monomer having a group represented by the above formula (2) can be mentioned.

Examples of the monomer having the polyethylene glycol ester group described above include monoacrylate or monomethacrylate of H-(OCH ₂ CH ₂ )p-OH. The value of p is 2 to 50, preferably 2 to 10.

Monomers having a hydroxyalkyl ester group having 2 to 5 carbon atoms described above include, for example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2 -Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate may be mentioned.

Examples of monomers having the above-mentioned phenolic hydroxy group include p-hydroxystyrene, m-hydroxystyrene, and o-hydroxystyrene.

Examples of the monomer having the carboxyl group described above include acrylic acid, methacrylic acid, and vinylbenzoic acid.

Examples of monomers having the above-mentioned amide group include acrylamide, methacrylamide, and the like.

Examples of monomers having the amino group described above include 2-aminoethyl acrylate, 2-aminoethyl methacrylate, aminopropyl acrylate, and aminopropyl methacrylate.

Examples of the monomer having a group represented by the formula (2) described above include 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, and the like.

In addition, in the present invention, when synthesizing an acrylic polymer, which is an example of component (C), a monomer that does not have the specific functional group 2 can be used together, as long as the effect of the present invention is not impaired.

Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Acrylic acid ester compounds include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl 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-methoxybutylacrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate , and 8-ethyl-8-tricyclodecyl acrylate.

Examples of methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, and anthryl methyl methacrylate. Latex, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxyethyl methacrylate, Toxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl -2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate.

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

Examples of styrene compounds include styrene, methylstyrene, chlorostyrene, and bromostyrene.

Examples of vinyl compounds include vinyl ether, methyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

The usage amount of the monomer having specific functional group 2 used to obtain the acrylic polymer, which is an example of component (C), is 2 mol% to 100 mol% based on the total amount of all monomers used to obtain the acrylic polymer, which is an example of component (C). desirable. When the monomer having the specific functional group 2 is too small, the liquid crystal orientation of the cured film obtained becomes insufficient.

In addition, when obtaining an acrylic polymer, when using together a monomer that does not have specific functional group 2, the amount used is preferably 98 mol% or less based on the total amount of all monomers.

The method of obtaining the acrylic polymer, which is an example of component (C), is not particularly limited, but for example, in a solvent in which a monomer having a specific functional group 2, a monomer that does not have a specific functional group 2 if necessary, a polymerization initiator, etc. coexist. , obtained by polymerization reaction at a temperature of 50°C to 110°C. At this time, the solvent used is not particularly limited as long as it dissolves the monomer having the specific functional group 2, the monomer not having the specific functional group 2 used as needed, the polymerization initiator, etc. Specific examples are described in the section <Solvent> described later.

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

In addition, the solution of acrylic polymer, which is an example of component (C), obtained by the above method is added to diethyl ether or water while stirring to cause reprecipitation, and the resulting precipitate is filtered and washed, and then dried at room temperature or under normal pressure or reduced pressure. It can be heated and dried to obtain a powder of acrylic polymer, which is an example of component (C). By the above-described operation, the polymerization initiator and unreacted monomer coexisting with the acrylic polymer, which is an example of component (C), can be removed, and as a result, the purified powder of the acrylic polymer, which is an example of component (C), is obtained. If the purification is not sufficient in one operation, the obtained powder may be re-dissolved in a solvent and the above-described operation may be repeated.

The acrylic polymer, which is a preferred example of component (C), preferably has a weight average molecular weight (polystyrene equivalent) of 3,000 to 200,000, more preferably 4,000 to 150,000, and still more preferably 5,000 to 100,000. If the weight average molecular weight is excessive (exceeding 200,000), solubility in solvents may decrease and handling properties may deteriorate. If the weight average molecular weight is too low (less than 3,000), curing may be insufficient during heat curing, resulting in poor solvent resistance and poor handling properties. Heat resistance may deteriorate.

Additionally, cyclodextrins, which are preferred examples of the polymer compound of component (C), include cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin; Methylated cyclodextrins such as methyl-α-cyclodextrin, methyl-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-hydroxypropyl-γ-cyclodextrin, 3-hydroxypropyl-α -Cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2,3-dihydroxypropyl-β -cyclodextrin and hydroxyalkyl cyclodextrin such as 2,3-dihydroxypropyl-γ-cyclodextrin, etc., for example, hydroxyalkyl cyclodextrin is preferable.

Cellulose, which is a preferred example of the polymer compound of component (C), includes hydroxyalkyl celluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylethylcellulose. and hydroxyalkyl alkyl celluloses and celluloses, and for example, hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose are preferred.

Polyether polyol, which is a preferred example of the polymer compound of component (C), includes polyethylene glycol, polypropylene glycol, propylene glycol, polyhydric alcohols such as bisphenol A, triethylene glycol, and sorbitol, propylene oxide, polyethylene glycol, polypropylene glycol, etc. can be added. Specific examples of polyether polyols include Adeka Polyether P series, G series, EDP series, BPX series, FC series, and CM series manufactured by ADEKA Co., Ltd. and Uniox (registered trademark) HC- manufactured by Nichiyu Co., Ltd. 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, etc.

Polyester polyol, which is a preferred example of the polymer compound of component (C), is:

Examples include those obtained by reacting polycarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid with diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol. Specific examples of polyester polyol include Polylite (registered trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, manufactured by DIC Corporation. 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, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, Curare Co., Ltd. Examples include F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016, etc.

Polycarbonate polyol, which is a preferred example of the polymer compound of component (C), includes a polyhydric alcohol such as trimethylolpropane or ethylene glycol reacted with diethyl carbonate, diphenyl carbonate, or ethylene carbonate. Specific examples of polycarbonate polyol include Plaxel (registered trademark) CD205, CD205PL, CD210, CD220 manufactured by Daicel Co., Ltd., and polycarbonate diol C-590, C-1050, C-2050, C-2090 manufactured by Kuraray Co., Ltd. , C-3090, etc.

Polycaprolactone polyol, which is a preferred example of the polymer compound of component (C), includes ring-opening polymerization of ε-caprolactone using a polyhydric alcohol such as trimethylolpropane or ethylene glycol as an initiator. Specific examples of polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, and OD-X-2568 manufactured by DIC Corporation, and Flaxel (registered trademark) 205 manufactured by Daicel Corporation. , L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, etc.

Examples of the phenol novolac resin, which is a preferred example of the polymer compound of component (C), include phenol-formaldehyde polycondensate.

In the cured film-forming composition of the present invention, the compound of component (C) can be used in powder form or in the form of a solution obtained by re-dissolving the purified powder in a solvent described later.

In addition, in the cured film forming composition of this invention, (C) component may be used individually by 1 type, or may be a mixture of multiple types of the compound exemplified as (C) component.

The content when containing component (C) in the cured film forming composition of the present invention is preferably 10 parts by mass to 200 parts by mass, and more preferably, based on 100 parts by mass of the polymer compound of component (A). Typically, it is 30 parts by mass to 150 parts by mass. (C) When content of component is excessive, photo-alignment property may fall. Additionally, if it is too small, the adhesion is likely to decrease.

<(D) Ingredient>

The cured film forming composition of the present invention is a compound having a polymerizable group and a group that can be thermally crosslinked with one of the components (A), (B), and (C), that is, one or more polymerizable groups, and at least one specific A compound further having 2 functional groups or at least 1 crosslinkable group can be further contained as component (D). As described above, the specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2), and the crosslinkable group undergoes a thermal crosslinking reaction with the specific functional group 2. It is a technique to do. (D) Component is a component that improves adhesion as will be described later, and is also called an adhesion improving compound.

When a cured film formed from the cured film-forming composition of the present invention containing component (D) is used as an orientation material, the compound of component (D) is used as a component of the orientation material (cured film) and the cured polymerizable liquid crystal formed thereon. It strengthens the adhesion between layers, that is, acts as an adhesion improving ingredient.

In addition, when using the cured film formed from the cured film forming composition of the present invention containing component (D) as a liquid crystal alignment film, the compound of component (D) is a liquid crystal alignment film (cured film) and a layer of polymerizable liquid crystal formed thereon. To improve adhesion, the polymerizable functional group of the polymerizable liquid crystal and the crosslinking reaction site included in the liquid crystal alignment film can be linked by a covalent bond. As a result, the phase difference material of the present invention, which is formed by laminating the cured polymeric liquid crystal on the alignment material of the present embodiment, can maintain strong adhesion even under conditions of high temperature and high humidity, and can exhibit high durability against peeling and the like.

The compound of component (D) is preferably a compound having a polymerizable group containing a C=C double bond and a hydroxy group, and a polymerizable group containing a C=C double bond and an N-alkoxymethyl group, or N- Compounds having a hydroxymethyl group can be mentioned. Polymerizable groups containing a C=C double bond include acrylic groups, methacryl groups, vinyl groups, allyl groups, and maleimide groups.

Below, preferred examples of compounds having a polymerizable group containing a C=C double bond as component (D) and a hydroxy group are given. On the other hand, the compound of component (D) is not limited to the following compound examples.

[Formula 14]

(In the formula, R ⁴¹ represents a hydrogen atom or a methyl group, and m represents an integer of 1 to 10)

In the compound having a polymerizable group containing a C=C double bond as the component (D), an N-alkoxymethyl group, or an N-hydroxymethyl group, N of the N-alkoxymethyl group or N-hydroxymethyl group, that is, nitrogen Atoms include the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, and the nitrogen atom bonded to a position adjacent to the nitrogen atom of a nitrogen-containing heterocycle. Therefore, the N-alkoxymethyl group includes the nitrogen atom of amide, the nitrogen atom of thioamide, the nitrogen atom of urea, the nitrogen atom of thiourea, the nitrogen atom of urethane, the nitrogen atom bonded to the adjacent position of the nitrogen atom of the nitrogen-containing heterocycle, etc. A structure in which an alkoxymethyl group is bonded to a nitrogen atom selected from:

The compound having a polymerizable group containing a C=C double bond in the component (D), an N-alkoxymethyl group, or an N-hydroxymethyl group may be any compound having the above-mentioned groups, and preferably has the following formula ( Compounds represented by X) can be mentioned.

[Formula 15]

(In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents a hydrogen atom or a straight-chain or branched alkyl group having 1 to 10 carbon atoms)

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and n-phene. Tyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group , 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n- Pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl -n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1, 2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, n- Heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hexyl group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-phene Tyl group, 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl- n-pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1 -Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-hep Tyl 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-phene yl 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, and n-de Examples include practical skills, etc.

Specific examples of the compound represented by the formula (X) include N-hydroxymethyl (meth)acrylamide (N-methylol (meth)acrylamide), N-methoxymethyl (meth)acrylamide, N- Acrylamide compounds substituted with a hydroxymethyl group (methylol group) or alkoxymethyl group, such as ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, and N-isobutoxymethyl (meth)acrylamide. Or a methacrylamide compound can be mentioned. Meanwhile, (meth)acrylamide refers to both methacrylamide and acrylamide.

As another embodiment of the compound having a polymerizable group containing a C=C double bond of the component (D) and an N-alkoxymethyl group, a compound represented by the following formula (X2) is preferably used, for example. .

[Formula 16]

In the formula, R ⁵¹ represents a hydrogen atom or a methyl group.

R ⁵² represents an alkyl group with 1 to 20 carbon atoms, a monovalent aliphatic ring group with 5 to 6 carbon atoms, or a monovalent aliphatic group containing an aliphatic ring with 5 to 6 carbon atoms, and may contain an ether bond in the structure. .

R ⁵³ represents a straight-chain or branched alkylene group having 2 to 20 carbon atoms, a divalent aliphatic ring group having 5 to 6 carbon atoms, or a divalent aliphatic group containing an aliphatic ring having 5 to 6 carbon atoms, and an ether bond in the structure. It may contain .

R ⁵⁴ is a linear or branched divalent aliphatic group having 1 to 20 carbon atoms, a divalent to 9 valent aliphatic ring group having 5 to 6 carbon atoms, or a divalent aliphatic ring having 5 to 6 carbon atoms. It represents an aliphatic group of 9 to 9 valence, and among these groups, one methylene group or a plurality of non-adjacent methylene groups may be substituted by an ether bond.

Z is >NCOO-, or -OCON<(where "-" indicates that the number of bonds is 1. In addition, ">" and "<" indicate that the number of bonds is 2, and one bond number contains an alkoxymethyl group ( That is, it indicates that -OR ⁵² group) is bound.

r is a natural number between 2 and 9.

Specific examples of the alkylene group having 2 to 20 carbon atoms in the definition of R ⁵³ include a divalent group obtained by removing one hydrogen atom from the alkyl group having 2 to 20 carbon atoms described later.

In addition, specific examples of the divalent to nine-valent aliphatic group having 1 to 20 carbon atoms in the definition of R ⁵⁴ include a divalent aliphatic group in which 1 to 8 hydrogen atoms are further removed from an alkyl group having 1 to 20 carbon atoms, which will be described later. to 9 valent groups may be mentioned.

The alkyl group having 1 carbon atom is a methyl group, and specific examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and s-butyl group. , t-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, n -hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 1,1,2-trimethyl- n-propyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-penta Decyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, cyclopentyl group, cyclohexyl group, one or more of these has 20 carbon atoms Examples include groups bonded within the range and groups in which one methylene group among these groups or a plurality of non-adjacent methylene groups are substituted by an ether bond.

Among these, R ⁵³ and R ⁵⁴ are preferably alkylene groups having 2 to 10 carbon atoms, and R ⁵³ is an ethylene group, and R ⁵⁴ is a hexylene group. It is particularly preferable from the viewpoint of availability of raw materials, etc.

Specific examples of an alkyl group having 1 to 20 carbon atoms in the definition of R ⁵² include specific examples of an alkyl group having 2 to 20 carbon atoms in the definition of R ⁵³ and a methyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, ethyl group, n-propyl group, or n-butyl group is particularly preferable.

r may be a natural number from 2 to 9, and among these, 2 to 6 are preferable.

Compound (X2) is obtained by the production method represented by the following reaction scheme. That is, a carbamate compound (hereinafter also referred to _as compound (X2-1)) having an acrylic or methacryl group represented by the formula ( It is prepared by reacting in a solvent to which ) (represented by n) is added to synthesize an intermediate represented by the following ^formula (

[Formula 17]

In the formula, R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , Z and r represent the above meanings, and X represents -NHCOO- or -OCONH-.

The amount of trimethylsilyl chloride and paraformaldehyde used for compound (X2-1) is not particularly limited, but in order to complete the reaction, trimethylsilyl chloride is used in an amount of 1.0 to 6.0 equivalents, paraformaldehyde, per carbamate bond in the molecule. Formaldehyde is preferably used in an amount of 1.0 to 3.0 equivalents, and it is more preferable that the equivalent amount of trimethylsilyl chloride used is greater than that of paraformaldehyde.

The reaction solvent is not particularly limited as long as it is inert to the reaction, and examples include hydrocarbons such as hexane, cyclohexane, benzene, and toluene; Halogen-based hydrocarbons such as methylene chloride, carbon tetrachloride, chloroform, and 1,2-dichloroethane; ethers such as diethyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran; Nitriles such as acetonitrile and propionitrile; Nitrogen-containing biprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone; Pyridines, such as pyridine and picoline, can be mentioned. These solvents may be used individually, or two or more types of them may be mixed and used. Preferably, it is methylene chloride and chloroform, and more preferably, it is methylene chloride.

The amount of solvent used (reaction concentration) is not particularly limited, but the reaction can be carried out without using a solvent, and when a solvent is used, 0.1 to 100 times the mass of the solvent can be used based on compound (X2-1). there is. Preferably it is 1 to 30 times by mass, and more preferably 2 to 20 times by mass.

The reaction temperature is not particularly limited, but is, for example, -90 to 200°C, preferably -20 to 100°C, and more preferably -10 to 50°C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 100 hours.

The reaction can be performed under normal or increased pressure, and can be either batch or continuous.

When reacting, a polymerization inhibitor may be added. Such polymerization inhibitors include BHT (2,6-di-tertiarybutyl-para-cresol), hydroquinone, para-methoxyphenol, etc., and are specifically limited if they inhibit the polymerization of acrylic or methacryl groups. It doesn't work.

The amount of the polymerization inhibitor added is not particularly limited, but is 0.0001 to 10 wt%, preferably 0.01 to 1 wt%, based on the total amount (mass) of compound (X2-1). In this specification, wt% means mass%.

In the step of reacting the intermediate (X2-2) with alcohol, a base may be added to suppress hydrolysis under acidic conditions. Examples of bases include pyridines such as pyridine and picoline, and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, and tributylamine. Triethylamine and diisopropylethylamine are preferable, and triethylamine is more preferable. The amount of base added is not particularly limited, but may be 0.01 to 2.0 equivalents, more preferably 0.5 to 1.0 equivalents, relative to the amount of trimethylsilyl chloride used during the reaction.

Additionally, after obtaining intermediate (X2-2) from compound (X2-1), alcohol can be added and reacted without isolating intermediate (X2-2).

The synthesis method of compound (X2-1) is not particularly limited, but can be prepared by reacting (meth)acryloyloxyalkyl isocyanate with a polyol compound or reacting a hydroxyalkyl (meth)acrylate compound with a polyisocyanate compound. You can.

Specific examples of (meth)acryloyloxyalkyl isocyanate include, for example, 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., brand name: Karen's MOI [registered trademark]), 2-acrylic Royloxyethyl isocyanate (manufactured by Showa Denko Co., Ltd., brand name: Karen's AOI [registered trademark]), etc. can be mentioned.

Specific examples of polyol compounds include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 1, Diol compounds such as 6-hexanediol and 1,4-cyclohexanedimethanol, triol compounds such as glycerin and trimethylolpropane, pentaerythritol, dipentaerythritol, diglycerol, etc. are included.

Specific examples of hydroxyalkyl (meth)acrylate compounds include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4 -Hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, poly(ethylene glycol)ethyl ether acrylate, poly(ethylene glycol)ethyl ether methacrylate Monomers having hydroxyl groups such as latex, etc. can be mentioned.

Specific examples of polyisocyanate compounds include aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and dimer acid diisocyanate, isophorone diisocyanate, and 4,4'-methylenebis(cyclohexyl). isocyanate), ω,ω'-diisocyanate, alicyclic diisocyanates such as dimethylcyclohexane, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1 and triisocyanates such as 3,6-hexamethylene triisocyanate and bicycloheptane triisocyanate.

These (meth)acryloyloxyalkyl isocyanate compounds, polyol compounds, hydroxyalkyl (meth)acrylate compounds, and polyisocyanate compounds are generally commercially available and can be synthesized by known methods.

Moreover, in the cured film forming composition of this invention, (D) component may be a mixture of multiple types of compounds of (D) component.

The content when containing component (D) in the cured film forming composition of the present invention is preferably 1 part by mass to 80 parts by mass, more preferably 100 parts by mass of the polymer compound of component (A). Typically, it is 3 parts by mass to 50 parts by mass. (D) When the content of component is more than 80 parts by mass, the photo-orientation property and solvent resistance of the cured film may decrease. Furthermore, by setting the content of component (D) to 1 part by mass or more, sufficient adhesion can be provided to the cured film formed.

<(E) Ingredient>

The composition for forming a phase difference material of the present embodiment may further contain a crosslinking catalyst as the (E) component in addition to the component (A), the component (B), the component (C), and the component (D).

(E) As a crosslinking catalyst which is a component, (E-1), an acid or a thermal acid generator is mentioned, for example. This component (E-1) is effective in accelerating the heat curing reaction of the composition when forming a cured film using the cured film forming composition of the present invention.

As specific examples of the component (E-1), the acid may include a sulfonic acid group-containing compound, hydrochloric acid, or a salt thereof. In addition, the thermal acid generator is not particularly limited as long as it is a compound that generates acid by thermal decomposition during heat treatment (pre-bake or post-bake), that is, a compound that generates acid by thermal decomposition at a temperature of 80°C to 250°C.

Specific examples of the acid include, for example, hydrochloric acid or its salt; Methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid. , 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluoro Compounds containing sulfonic acid groups such as octanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, and dodecylbenzenesulfonic acid, or hydrates or salts thereof. etc. can be mentioned.

In addition, compounds that generate acid by heat include, for example, bis(tosyloxy)ethane, bis(tosyloxy)propane, bis(tosyloxy)butane, p-nitrobenzyltosylate, o-nitrobenzyltosylate, 1,2,3-phenylene tris(methylsulfonate), p-toluenesulfonate pyridinium salt, p-toluenesulfonate morphonium salt, p-toluenesulfonate ethyl ester, p-toluenesulfonate propyl ester, p-toluene Butyl sulfonic acid, 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-hydroxybutyl-p-toluenesulfonate, N-ethyl-p-toluenesulfonamide, and further compounds represented by the following formula:

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

etc. can be mentioned.

In addition, commercially available compounds that generate acid by heat include TA100, TA120, TA160 (above, manufactured by San-Apro Co., Ltd.), K-PURE [registered trademark] TAG2689, TAG2690, CXC1614, CXC1738 (above, King Industries Inc. .), Sun Aid SI-100L, SI-180L (above, manufactured by Samshin Chemical Co., Ltd.), etc.

In addition, examples of the crosslinking catalyst of component (E) include a metal chelate compound as (E-2) and a silanol compound as (E-3). When forming a cured film using the cured film forming composition of the present invention by using the (E-2) metal chelate compound and (E-3) silanol compound in combination as a crosslinking catalyst for component (E), this composition It becomes effective in promoting the thermal curing reaction.

Examples of the (E-2) metal chelate compound include zirconium compounds, titanium compounds, aluminum compounds, and more specifically, diisopropoxy titanium bisacetylacetonate, titanium tetraacetylacetonate, Zirconium tetraacetylacetonate, diisopropoxyethylacetoacetate aluminum, diisopropoxyacetylacetonate aluminum, isopropoxybis(ethylacetoacetate)aluminum, isopropoxybis(acetylacetonate)aluminum, tris(ethylaceto) acetate) aluminum, tris(acetylacetonate) aluminum [tris(2,4-pentanedionato) aluminum(III)], monoacetylacetonate bis(ethylacetoacetate) aluminum, tetrakisisopropoxy titanium, tetrakiss normal Butoxy titanium, tetraoctyl titanate, tetrakis(normal propoxy)zirconium, tetrakis(normal butoxy)zirconium, etc. are mentioned.

Examples of the (E-3) silanol compounds include triphenylsilanol, trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1 and 4-bis(hydroxydimethylsilyl)benzene.

The content when containing component (E) in the cured film forming composition of the present invention is preferably 0.01 parts by mass with respect to 100 parts by mass of the polymer compound of component (A) in the case of (E-1). to 20 parts by mass, more preferably 0.01 to 15 parts by mass, and even more preferably 0.01 to 10 parts by mass. (E-1) By setting the content of component to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be provided. However, if it is more than 20 parts by mass, the storage stability of the composition may decrease.

When containing component (E-2) and component (E-3) in the cured film forming composition of the present invention, the content of component (E-2) is 100 mass of the polymer compound of component (A). Parts, preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.5 parts by mass to 15 parts by mass, and the content of (E-3) is based on 100 parts by mass of the polymer compound of component (A). , preferably 0.5 parts by mass to 70 parts by mass, more preferably 1 part by mass to 60 parts by mass, and even more preferably 2 parts by mass to 50 parts by mass. By setting the content of component (E-2) and component (E-3) within the above range, sufficient thermosetting properties and solvent resistance can be provided. However, if it exceeds the above range, the storage stability of the composition may decrease.

<(F) Ingredient>

The cured film-forming composition of the present invention may contain, as component (F), a monomer having a photo-alignable group formed by a thermal crosslinking reactive site bonded directly or bonded through a linking group, and one or more polymerizable groups.

The monomer of component (F) strengthens the adhesion between the cured film formed from the cured film forming composition of the present invention and the layer of the cured polymerizable liquid crystal formed thereon when used as an orientation material, that is, improves adhesion. It acts as an ingredient.

The thermal crosslinking reactive site formed by bonding to the photo-alignment group of the monomer of component (F) includes carboxyl group, amide group, N-substituted amide group, hydroxy group, amino group, alkoxysilyl group, and group represented by the above formula (2). , and groups protected by a protecting group that can dissociate by heating. Among these, a carboxyl group or an amide group is preferable.

In addition, the photo-alignment group in the monomer of component (F) refers to a functional group having a structural site that photodimerizes or photoisomerizes.

The structural site for photodimerization is a site that forms a dimer by light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, coumarin group, and anthracene group. Among these, cinnamoyl group is preferred in that it has high transparency in the visible light region and high photodimerization reactivity.

In addition, the structural site subject to photoisomerization refers to a structural site that changes into a cis-isomer and a trans-isomer upon light irradiation, and specific examples thereof include a site composed of an azobenzene structure, a stilbene structure, etc. Among these, the azobenzene structure is preferable in that it has high reactivity.

The thermal crosslinking reactive site is formed by bonding to a photo-alignment group through a direct bond or linking group, and such linking groups include a straight-chain alkylene group having 1 to 15 carbon atoms, a branched alkylene group having 3 to 20 carbon atoms, and a carbon atom number. It is a divalent group selected from 3 to 20 cyclic alkylene groups and phenylene groups, or a group formed by combining two or more of the divalent groups. In this case, the bond between the divalent groups constituting the linking group and the bond between the linking group and the heat crosslinking reactive site may include a single bond, an ester bond, an amide bond, a urea bond, or an ether bond. When the above divalent groups are plural, the divalent groups may be the same or different, and when the above bonds are plural, the bonds may be the same or different.

Examples of the linear alkylene group having 1 to 15 carbon atoms include methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, n-hexylene group, n-heptylene group, and n-octylene group. , n-nonylene group, n-decylene group, n-undecylene group, n-dodecylene group, n-tridecylene group, n-tetradecylene group, and n-pentadecylene group.

Examples of the branched alkylene group having 3 to 20 carbon atoms include i-propylene group, i-butylene group, s-butylene group, t-butylene group, 1-methyl-n-butylene group, and 2-methyl -n-butylene group, 3-methyl-n-butylene group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene group, 1- Ethyl-n-propylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n -Butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3, 3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n- In addition to propylene group, 1-ethyl-1-methyl-n-propylene group, and 1-ethyl-2-methyl-n-propylene group, alkylene groups having up to 20 carbon atoms and branching at arbitrary locations, etc. I can hear it.

Examples of the cyclic alkylene group having 3 to 20 carbon atoms include monocyclic alkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, and cyclooctylene group, and novo-alkylene group. Polycyclic alkylene groups such as nylene group, tricyclodecylene group, tetracyclododecylene group, and adamantylene group can be mentioned.

The monomer of component (F) is preferably a monomer having a photo-alignment group in which the heat crosslinking reactive site is directly bonded or bonded through a linking group, and a polymerizable group containing a C=C double bond.

As a photo-alignable group formed by the thermal crosslinking reactive site being directly bonded or bonded through a linking group, an organic group containing a structure represented by the following formula (Y) is mentioned as a preferable group.

[Formula 24]

(In the formula, * represents the bonding position with another group, and R ³¹ is a hydroxy group, an amino group, a hydroxyphenoxy group, a carboxylphenoxy group, an aminophenoxy group, an aminocarbonylphenoxy group, a phenylamino group, and a hydroxyphenylamino group. , represents a carboxylphenylamino group, aminophenylamino group, hydroxyalkylamino group or ^bis (hydroxyalkyl)amino group, The ring may be substituted with a substituent)

The above optional substituents are not particularly limited, but include, for example, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and isobutyl group; Haloalkyl groups such as trifluoromethyl group; Alkoxy groups such as methoxy group and ethoxy group; Halogen atoms such as iodine, bromine, chlorine, and fluorine; Cyano group; Nitro groups, etc. can be mentioned.

Substituents in cases where the benzene ring may be substituted with a substituent include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and isobutyl group; Haloalkyl groups such as trifluoromethyl group; Alkoxy groups such as methoxy group and ethoxy group; Halogen atoms such as iodine, bromine, chlorine, and fluorine; Cyano group; Nitro groups, etc. can be mentioned.

Among these, in formula (1), an organic group containing a structure in which R ³¹ represents a hydroxy group or an amino group and X ³ represents a phenylene group optionally substituted with an arbitrary substituent is preferable.

Additionally, polymerizable groups containing a C=C double bond include acrylic groups, methacryl groups, vinyl groups, allyl groups, and maleimide groups.

In addition, as the monomer of component (F), a monomer having a group represented by formula (1) mentioned in the component (A) can also be used. Examples of such monomers include monomers represented by formula (5) mentioned in the component (A).

As the monomer of component (F), for example, 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(3-methacryloxypropyl-1-oxy)cinnamic acid, and 4-(6) -methacryloxyhexyl-1-oxy)cinnamamide, and monomers obtained by reacting these monomers with the formula (3-1) or (3-2) mentioned in the component (A) above.

The content when containing component (F) in the cured film forming composition of the present invention is preferably 1 part by mass to 40 parts by mass, more preferably, with respect to 100 parts by mass of the polymer compound of component (A). is 5 parts by mass to 30 parts by mass. (F) When the content of component is more than 40 parts by mass, the solvent resistance of the cured film may decrease.

<Solvent>

The cured film-forming composition of the present invention is mainly used in the form of a solution (varnish) dissolved in a solvent. The solvent used at this time dissolves component (A), if necessary, component (B), component (C), component (D), component (E), component (F), and/or other additives described later. It can be done as long as it can be done, and the type and structure are not particularly limited.

Specific examples of solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, 2-methyl-1-butanol, ethylene glycol monomethyl ether, and ethylene glycol mono. Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, diethylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycol monoethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-penta. Non, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy -3-Methyl butanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxymethyl propionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate , butyl lactate, cyclopentyl methyl ether, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone.

When producing an orientation material by forming a cured film on a film using the cured film forming composition of the present invention, from the viewpoint that the film is a solvent resistant, methanol, ethanol, isopropanol, n-propanol, n-butanol, 2 -Methyl-1-butanol, 2-heptanone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol, diethylene glycol, and propylene glycol monomethyl ether acetate are preferably used.

These solvents can be used individually or in combination of two or more types.

<Other additives>

Additionally, the cured film forming composition of the present invention may contain a sensitizer, adhesion improver, silane coupling agent, surfactant, rheology modifier, pigment, dye, storage stabilizer, It may contain antifoaming agents, antioxidants, etc.

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

Sensitizers that are examples of other additives include benzophenone, anthracene, anthraquinone, thioxanthone and their derivatives, and nitrophenyl compounds. Among these, benzophenone derivatives and nitrophenyl compounds are preferred. Specific examples of preferred compounds include N,N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl, 4-nitrocinnamic acid, 4-nitrostilbene. , 4-nitrobenzophenone, and 5-nitroindole. In particular, N,N-diethylaminobenzophenone, a derivative of benzophenone, is preferred.

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

The usage ratio of the sensitizer in the cured film forming composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.2 parts by mass, based on a total of 100 parts by mass of components (A) to (F). parts by mass to 10 parts by mass. If this ratio is too small, the effect as a sensitizer may not be sufficiently obtained, and if it is too large, the transmittance may decrease and the coating film may become rough.

<Preparation of cured film forming composition>

The cured film-forming composition of the present invention contains a polymer compound as component (A) as an essential component, and also contains a crosslinking agent as component (B) and at least two specific functional groups 2 (hydroxyl group, carboxyl group, A specific polymer having a group selected from the group consisting of an amide group, an amino group, and a group represented by the above formula (2), (D) one or more polymerizable groups as component, and at least one specific functional group 2 (hydroxy group, carboxyl group) , a group selected from the group consisting of an amide group, an amino group, and a group represented by the above formula (2)) or an adhesion-improving compound having at least one crosslinkable group (a group that undergoes a thermal crosslinking reaction with the specific functional group 2), as component (E) The crosslinking catalyst and the component (F) may contain at least one component selected from the group consisting of a photo-alignment group formed by a thermal crosslinking reactive site bonded directly or bonded through a linking group, and a monomer having one or more polymerizable groups. And the cured film forming composition of this invention can contain other additives, as long as the effect of this invention is not impaired.

On the other hand, when mixing component (B), the mixing ratio of component (A) and component (B) is preferably 20:80 to 100:0 in mass ratio. (B) When the content of the component is excessive, the liquid crystal orientation tends to decrease.

Among them, preferable examples of the cured film forming composition of the present invention are as follows.

[1]: A cured film-forming composition containing component (A).

[2]: A cured film-forming composition containing 1 to 100 parts by mass of component (B) based on 100 parts by mass of the polymer compound that is component (A).

[3]: The mixing ratio of component (A) and component (B) is 20:80 to 100:0 in mass ratio, and based on 100 parts by mass of component (A), 10 to 200 parts by mass of component (C) A cured film forming composition containing.

[4]: A cured film-forming composition containing 1 to 80 parts by mass of component (D) and a solvent based on 100 parts by mass of component (A).

[5]: Based on 100 parts by mass of component (A), 10 to 200 parts by mass of component (C), 0.01 to 20 parts by mass of component (E-1), or 0.1 to 30 parts by mass ( A cured film forming composition containing a combination of component E-2) and 0.5 parts by mass to 70 parts by mass of component (E-3) and a solvent.

[6]: Based on 100 parts by mass of component (A), 10 to 200 parts by mass of component (C), 0.01 to 20 parts by mass of component (E-1), or 0.1 to 30 parts by mass ( A cured film forming composition containing a combination of component E-2) and 0.5 parts by mass to 70 parts by mass of component (E-3), 1 part by mass to 80 parts by mass of (D) component, and solvent.

[7]: Based on 100 parts by mass of component (A), 10 to 200 parts by mass of component (C), 0.01 to 20 parts by mass of component (E-1), or 0.1 to 30 parts by mass ( A combination of component E-2) and 0.5 parts by mass to 70 parts by mass of component (E-3), 1 part by mass to 80 parts by mass of component (D), 1 part by mass to 40 parts by mass of component (F), and solvent. Cured film forming composition.

The mixing ratio, preparation method, etc. when using the cured film forming composition of the present invention as a solution will be described in detail below.

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

The preparation method of the cured film forming composition of the present invention is not particularly limited. As a preparation method, for example, in a solution of component (A) dissolved in a solvent, component (B), component (C), component (D), component (E), component (F), etc. are mixed in a predetermined ratio. A method of mixing to form a uniform solution, or a method of adding and mixing other additives as necessary at an appropriate stage of this preparation method, may be used.

In preparing the cured film-forming composition of the present invention, a solution of the polymer compound (specific copolymer) of component (A) obtained by polymerization reaction in a solvent can be used as is. In this case, for example, add component (B), component (C), component (D), component (E), and component (F) to the solution of component (A) to form a uniform solution. , prepare a cured film forming composition. At this time, additional solvent may be added for the purpose of concentration adjustment. At this time, the solvent used in the production process of component (A) and the solvent used to adjust the concentration of the cured film forming composition may be the same or different.

In addition, it is preferable to use the solution of the prepared cured film-forming composition after filtering it using a filter with a pore diameter of about 0.2 μm, etc.

<Curated film, orientation material, and phase difference material>

A solution of the cured film forming composition of the present invention is applied to a substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, a quartz substrate). , ITO substrate, etc.) or films (e.g., triacetylcellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) On top of resin films such as film, acrylic film, polyethylene film, and polypropylene film (PP), etc., by barcoat, rotational application, drip application, roll application, slit application, rotational application after slit, inkjet application, printing, etc. A cured film can be formed by applying to form a coating film and then heating and drying it in a hot plate or oven, etc.

As conditions for heat drying, the crosslinking reaction using a crosslinking agent may proceed to the extent that the components of the alignment material formed from the cured film do not dissolve in the polymerizable liquid crystal solution applied thereon, for example, at a temperature of 60°C to 230°C. A heating temperature and heating time appropriately selected within the range of ℃, time 0.4 minutes to 60 minutes are adopted. The heating temperature and heating time are preferably 70°C to 230°C and 0.5 to 10 minutes.

The film thickness of the cured film (and the orientation material formed thereafter) formed using the cured film forming composition of the present invention is, for example, 0.05 μm to 5 μm, taking into account the level difference and optical and electrical properties of the substrate used. So you can choose appropriately.

The cured film formed in this way can be made to function as an orientation material, that is, a member that orients a compound having liquid crystallinity such as liquid crystal, by applying polarized UV irradiation.

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

Since the alignment material formed from the cured film-forming composition of the present invention has solvent resistance and heat resistance, the phase difference material consisting of a polymerizable liquid crystal solution is applied onto the alignment material and then heated to the phase transition temperature of the liquid crystal to change the phase difference material into a liquid crystal state. and can be oriented on an orientation material. Then, by curing the aligned phase difference material as is, a phase difference material can be formed as a layer having optical anisotropy.

As a phase difference material, for example, a liquid crystal monomer having a polymerizable group and a composition containing the same are used. And when the substrate forming the orientation material is a film, the film having the retardation material of this embodiment is useful as a retardation film. The phase difference material that forms such a phase difference material is in a liquid crystal state, and on the alignment material, there are those that take on orientation states such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment, and can be used separately according to the required phase difference. there is.

In addition, in the case of manufacturing a patterned phase difference material used in a 3D display, a cured film formed from the cured film forming composition of the present embodiment by the above-described method is applied from a predetermined standard through a mask of a line and space pattern, e.g. For example, polarized UV exposure is performed in the +45 degree direction, and then the mask is separated and then exposed to polarized UV light in the -45 degree direction to obtain an alignment material in which two types of liquid crystal alignment regions with different liquid crystal orientation control directions are formed. . After that, the retardation material made of polymerizable liquid crystal solution is applied and heated to the phase transition temperature of the liquid crystal to change the retardation material into a liquid crystal state and align it on the alignment material. Then, by curing the oriented phase difference material as is, it is possible to obtain a patterned phase difference material in which two types of phase difference regions with different phase difference characteristics are arranged in a plurality and regularly.

In addition, using two substrates formed as described above and having the alignment material of the present invention, the alignment materials on both substrates are placed to face each other with a spacer interposed therebetween, and then liquid crystal is injected between these substrates, so that the liquid crystal is aligned. It can also be used as a liquid crystal display device.

Accordingly, the cured film forming composition of the present invention can be suitably used in the manufacture of various retardation materials (retardation films), liquid crystal display elements, etc.

Example

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

[Components used in examples, etc. and their abbreviations]

Each composition used in the following examples and comparative examples is as follows.

<Component (A), component (B), component (C): raw materials>

M6CA: 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid

CN1: 4-(6-methacryloxyhexyl-1-oxy)methyl cinnamic acid

6MBe: 4-methoxyphenyl-4-((6-(methacryloxy)hexyl)oxy)benzoate

HEMA: 2-hydroxyethyl methacrylate

MAA: methacrylic acid

MMA: Methyl methacrylate

Karen's MOI-BM (registered trademark): 2-(0-(1'-methylpropylidenamino)carboxyamino)ethyl methacrylic acid (manufactured by Showa Denko Co., Ltd.)

BMAA: N-butoxymethylacrylamide

EGAMA: Ethylene glycol monoacetoacetate monomethacrylate (2-acetoacetoxyethyl methacrylate) (formula below)

[Formula 25]

GMA: glycidyl methacrylate

AIBN: α,α'-azobisisobutyronitrile

AM-1: (see Synthesis Example 1)

[Formula 26]

AM-2: (see Synthesis Example 2)

[Formula 27]

AM-3: (see Synthesis Example 3)

[Formula 28]

<Component (B): Cross-linking agent>

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

[Formula 29]

TC-401: Titanium tetraacetylacetonate (contains 35% IPA [isopropanol] as a solvent) Orgatics (registered trademark) TC-401 manufactured by Matsumoto Fine Chemical Co., Ltd.

<Component (D): Adhesion improving compound>

80MFA: Epoxy ester 80MFA (manufactured by Kyoeisha Chemical Co., Ltd.)

BMAA: N-butoxymethylacrylamide

DM-1: (see Synthesis Example 4)

[Formula 30]

DM-2: (see Synthesis Example 5)

[Formula 31]

<Ingredient (E): Crosslinking catalyst>

PTSA: p-toluenesulfonic acid

[Formula 32]

TPDA: Tris(2,4-pentanedionato)-aluminum(III)

TPS: Triphenylsilanol

TAG-2689: K-PURE [registered trademark] TAG2689 (manufactured by King Industries Inc.)

<Component (F): Monomer having a photo-alignment group and a polymerizable group>

M6CA: 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid

<Solvent>

Propylene glycol monomethyl ether: PM

Isopropanol: IPA

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example was determined as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex Co., Ltd. Measured.

Meanwhile, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene conversion values.

Column temperature: 50℃

Eluent: N,N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr·H ₂ O) is 30 mmol/L, phosphoric acid/anhydrous crystal (o-phosphoric acid) is 30 mmol/L, and tetrahydrofuran (THF) is 10mL/L)

Flow rate: 1.0mL/min

Standard samples for creating a calibration curve: TSK standard polyethylene oxide (molecular weight approximately 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weight approximately 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Measurement of ¹ H-NMR>

¹ The analysis equipment and analysis conditions used for H-NMR analysis are as follows.

Nuclear magnetic resonance device: Varian NMR System 400 NB (400 MHz)

Measurement solvent: DMSO-d ₆

Reference material: tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

<Synthesis of polymer raw materials for component (A)>

Synthesis Example 1: Synthesis of compound [AM-1]

[Formula 33]

Add 105 g of THF, 20.5 g (0.06 mol) of M6CA, 5.35 g (0.07 mol) of ethyl vinyl ether, and 0.47 g (1.90 mmol) of pyridinium paratoluenesulfonate (Py-PTS) to a 200 mL one-necked flask at room temperature. The reaction was carried out at room temperature for 14 hours while stirring with a magnetic stirrer. Purification was performed using an evaporator, liquid separation, filtration, etc. to obtain the target product [AM-1] (23.5 g, 0.058 mol, yield 94.0%). The structure of compound [AM-1] was confirmed by obtaining the following spectrum data by ¹ H-NMR analysis.

¹ H-NMR(CDCl ₃ ):δ7.62(m,3H),6.91(dd,2H),6.43(d,1H),5.96(m,2H),5.61(t,1H),4.05(t, 2H),3.95(t,2H),3.61(q,1H),3.48(q,1H),1.83(s,3H),1.64(m,4H),1.33(m,7H),1.09(t,3H) ).

Synthesis Example 2: Synthesis of compound [AM-2]

[Formula 34]

Add 106 g of THF, 19.2 g (0.06 mol) of M6CA, 6.95 g (0.07 mol) of butyl vinyl ether, and 0.44 g (1.70 mmol) of pyridinium paratoluenesulfonate (Py-PTS) to a 200 mL one-necked flask at room temperature. The reaction was carried out at room temperature for 14 hours while stirring with a magnetic stirrer. Purification was performed using an evaporator, liquid separation, filtration, etc., and the target product [AM-2] was obtained (22.5 g, 0.052 mol, yield 90.0%). The structure of compound [AM-2] was confirmed by obtaining the following spectrum data by ¹ H-NMR analysis.

¹ H-NMR(CDCl ₃ ):δ7.62(m,3H),6.96(dd,2H),6.48(d,1H),5.99(m,2H),5.66(t,1H),4.10(t, 2H),4.02(t,2H),3.60(q,1H),3.48(q,1H),1.88(s,3H),1.69(m,4H),1.34(m,11H),0.87(t,3H) ).

Synthesis Example 3: Synthesis of compound [AM-3]

[Formula 35]

Into a 200 mL one-neck flask, add 107 g of THF, 18.1 g (0.05 mol) of M6CA, 8.24 g (0.07 mol) of cyclohexyl vinyl ether, and 0.41 g (1.60 mmol) of pyridinium paratoluenesulfonate (Py-PTS) at room temperature. , reaction was performed at room temperature for 14 hours under magnetic stirrer stirring. Purification was performed using an evaporator, liquid separation, filtration, etc. to obtain the target product [AM-3] (20.4 g, 0.044 mol, yield 81.6%). The structure of compound [AM-3] was confirmed by obtaining the following spectrum data by ¹ H-NMR analysis.

¹ H-NMR(CDCl ₃ ): δ7.60(m,3H),6.96(dd,2H),6.47(d,1H),6.09(m,2H),5.67(t,1H),4.10(t, 2H),4.02(t,2H),3.52(m,1H),1.88(s,3H),1.77-1.17(br,21H).

<Synthesis of polymer of component (A)>

<Polymerization Example 1>

7.0 g of AM-2, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA1). The Mn of the obtained acrylic copolymer was 14,000 and Mw was 38,000.

<Polymerization Example 2>

5.0 g of AM-2, 5.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA2). The Mn of the obtained acrylic copolymer was 13,000 and Mw was 27,000.

<Polymerization Example 3>

3.0 g of AM-2, 7.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA3). The Mn of the obtained acrylic copolymer was 14,000 and Mw was 29,000.

<Polymerization Example 4>

7.0 g of AM-1, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA4). The Mn of the obtained acrylic copolymer was 15,000 and Mw was 32,000.

<Polymerization Example 5>

7.0 g of AM-3, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA5). The Mn of the obtained acrylic copolymer was 14,000 and Mw was 35,000.

<Polymerization Example 6>

4.3 g of AM-1, 0.5 g of 6MBe, and 0.2 g of AIBN as a polymerization catalyst were dissolved in 45.0 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 10% by mass) (PA6). The Mn of the obtained acrylic copolymer was 2,300 and Mw was 12,000.

<Polymerization Example 7>

7.0 g of AM-1, 3.0 g of Karen's MOI-BM, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to prepare an acrylic copolymer solution (solid concentration: 20% by mass) (PA7). got it The Mn of the obtained acrylic copolymer was 13,000 and Mw was 38,000.

<Polymerization Example 8>

6.0 g of AM-1, 4.0 g of EGAMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA8). The Mn of the obtained acrylic copolymer was 14,000 and Mw was 40,000.

<Polymerization Example 9>

7.0 g of AM-1, 3.0 g of GMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA9). The Mn of the obtained acrylic copolymer was 18,000 and Mw was 49,000.

<Polymerization Example 10>

7.0 g of CIN1, 3.0 g of HEMA, and 0.3 g of AIBN as a polymerization catalyst were dissolved in 41.2 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PA10). The Mn of the obtained acrylic copolymer was 13,000 and Mw was 38,000.

<Synthesis of component (B)>

<Polymerization Example 11>

100.0 g of BMAA and 4.2 g of AIBN as a polymerization catalyst were dissolved in 193.5 g of PM and reacted at 90°C for 20 hours to obtain an acrylic polymer solution (solid concentration: 35% by mass) (PB1). The Mn of the obtained acrylic copolymer was 2,700 and Mw was 3,900.

<Synthesis of component (C)>

<Polymerization Example 12>

7.0 g of MMA, 7.0 g of HEMA, 3.5 g of MAA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 53.9 g of PM and reacted at 70°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 25% by mass) (PC1). The Mn of the obtained acrylic copolymer was 10,300 and Mw was 24,600.

<Polymerization Example 13>

9.0 g of MMA, 1.0 g of HEMA, and 0.1 g of AIBN as a polymerization catalyst were dissolved in 40.4 g of PM and reacted at 80°C for 20 hours to obtain an acrylic copolymer solution (solid concentration: 20% by mass) (PC2). The Mn of the obtained acrylic copolymer was 15,900 and Mw was 29,900.

<Synthesis of (E) component>

Synthesis Example 4: Synthesis of compound [DM-1]

[Formula 36]

Under nitrogen flow, 500 g of ethyl acetate, 35.5 g (0.300 mol) of 1,6-hexanediol, and 1.80 g of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) in a 2L four-necked flask. (11.8 mmol) and 0.45 g (2.04 mmol) of 2,6-di-tertibutyl-para-cresol (BHT) were added at room temperature, and the temperature was raised to 55°C while stirring with a magnetic stirrer. 95.9 g (0.679 mol) of 2-isocyanatoethyl acrylate was added dropwise to the reaction solution, and after stirring for 2 hours, the reaction solution was analyzed by high-performance liquid chromatography. When the intermediate content became 1% or less in area percentage, The reaction was complete. After adding 328 g of hexane and cooling to room temperature, the precipitated solid was washed twice with 229 g of hexane and dried to obtain compound [A-a] (104 g, 0.260 mol, yield 86.7%).

[Formula 37]

Under a nitrogen stream, 1,330 g of dichloromethane, 100 g (0.250 mol) of compound [Aa], and 22.5 g (0.749 mol) of paraformaldehyde were added to a 2L four-neck flask, and in an ice bath, 122 g (1.12 mol) of trimethylsilyl chloride. was added dropwise. After stirring for 2 hours, a mixture of 63.2 g (0.625 mol) of triethylamine and 240 g of methanol was added dropwise. After stirring for 30 minutes, the mixture was transferred to a 5L separatory funnel, and 1500 g of water was added to perform a liquid separation operation. The obtained organic layer was dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the obtained filtrate was concentrated and dried to obtain compound [DM-1] (110 g, 0.226 mol, yield 90.3%). The structure of compound [DM-1] was confirmed by obtaining the following spectrum data by ¹ H-NMR analysis.

¹ H-NMR(CDCl ₃ ):δ6.42(d,2H J=17.2),6.17-6.08(m,2H),5.86(d,2H J=10.0),4.77(d,4H J=19.6), 4.30(m,4H),4.12(t,4H J=6.4),3.61(m,4H),3.30(d,6H J=12.8),1.67(m,4H),1.40(m,4H).

Synthesis Example 5: Synthesis of compound [DM-2]

[Formula 38]

Under nitrogen flow, 35.0 g of ethyl acetate, 87.0 g of toluene, 8.41 g (50.0 mmol) of hexamethylene diisocyanate, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) were added to a 500 mL four-necked flask. ) 0.345 g (2.27 mmol) and 70.0 mg (0.318 mmol) of 2,6-di-tertibutyl-para-cresol (BHT) were added at room temperature, and the temperature was raised to 60°C while stirring with a magnetic stirrer. A mixture of 12.8 g (111 mmol) of 2-hydroxyethyl acrylate and 26.0 g of toluene was added dropwise to the reaction solution, stirred for 1 hour, and then stirred at room temperature for 24 hours. After adding 131 g of hexane and cooling by immersing in an ice bath, the precipitated crystals were filtered and dried to obtain compound [A-b] (15.0 g, 37.4 mmol, yield 74.8%).

[Formula 39]

Under a nitrogen stream, 200 g of dichloromethane, 14.6 g (36.4 mmol) of compound [Ab], and 3.28 g (109 mmol) of paraformaldehyde were added to a 300 mL four-neck flask, and in an ice bath, 23.7 g (218 mmol) of trimethylsilyl chloride was added. Dropped. After stirring for 1 hour, 35.6 g of methanol was added dropwise and stirred for 1 hour. The organic layer was washed with 300 mL of saturated aqueous sodium bicarbonate solution, and the obtained aqueous layer was further washed with 200 g of dichloromethane. The solution in which these two organic layers were mixed was washed again with 170 g of brine, and the obtained organic layer was dried with magnesium sulfate. Magnesium sulfate was removed by filtration, and the obtained dichloromethane solution was concentrated and dried to obtain the target [DM-2] (16.2 g, 33.1 mmol, yield 91.0%). The structure of compound [DM-2] was confirmed by obtaining the following spectrum data by ¹ H-NMR analysis.

¹ H-NMR(CDCl ₃ ):δ6.33(d,2H J=17.2),6.20-6.14(m,2H),5.96(d,2H J=10.4),4.63(s,4H),4.33(m ,4H),4.27(m,4H),3.16-3.14(br,10H),1.47(m,4H),1.20(m,4H).

<Examples 1 to 20> and <Comparative Examples 1 to 2>

Each cured film forming composition of Examples 1 to 20 and Comparative Examples 1 to 2 was prepared with the composition shown in Table 1.

Meanwhile, the mixing amount of the components obtained from the (co)polymer solution in the polymerization example is the solid content conversion value, and the solvent used in Example 19 was a mixture of PM and IPA at a mixing ratio (mass conversion) of PM:IPA = 99:1. It is a solvent.

[Table 1]

Next, a cured film was produced in the following procedures using each cured film forming composition, and the orientation was evaluated for each of the obtained cured films.

[Evaluation of orientation]

Each cured film-forming composition of Examples and Comparative Examples was applied to alkali-free glass by rotating it at 2,000 rpm for 30 seconds using a spin coater, and then heated and dried on a hot plate at a temperature of 100°C for 60 seconds to form a cured film ( Drying conditions 1). This cured film was vertically irradiated with linearly polarized light of 313 nm at an exposure dose of 10 mJ/cm ² . On the exposed substrate, polymerizable liquid crystal solution RMS03-013C for horizontal alignment manufactured by Merck Co., Ltd. was applied using a spin coater, and then prebaked on a hot plate at 60°C for 60 seconds to obtain a film thickness of 1.0. A μm-thick coating film was formed. This coating film was exposed to light at 300 mJ/cm ² to produce a phase difference material.

The phase difference material on the produced substrate was sandwiched between a pair of polarizing plates, and the development of the phase difference characteristics in the phase difference material was observed. If the phase difference was expressed without defects, it was evaluated as ○, and if the phase difference was not developed, it was evaluated as ×. The obtained results are shown in the “Drying conditions 1” column in Table 2.

Regarding the evaluation result of the retardation characteristic in drying condition 1 of (Drying conditions 2), a phase difference material was prepared and evaluated in the same manner as in “Drying conditions 1”. The obtained results are shown in the column of Table 2 “Drying Conditions 2”.

[Table 2]

The cured film-forming compositions of Examples 1 to 21 were able to form a phase difference material with an exposure dose as low as 10 mJ/cm ² by drying under suitable drying conditions. On the other hand, liquid crystal orientation was not obtained in Comparative Example 1 in which the cured film-forming composition did not have thermosetting properties. On the other hand, in Comparative Example 2 using a polymer compound that has a thermosetting system but has a known ester group as a photo-alignment group, under the drying conditions (1 and 2) of Examples 1 to 21 where liquid crystal alignment was obtained, the liquid crystal alignment was not obtained.

The cured film forming composition of the present invention is very useful as an alignment material for forming a liquid crystal alignment film of a liquid crystal display device or an optically anisotropic film provided inside or outside the liquid crystal display device, and is particularly useful for forming a patterned phase difference material in a 3D display. It is suitable as a material. Furthermore, materials forming cured films such as protective films, flat films, and insulating films in various displays such as thin-film transistor (TFT) type liquid crystal displays and organic EL devices, especially interlayer insulating films of TFT type liquid crystal displays, and protective films of color filters. Alternatively, it is also suitable as a material for forming an insulating film of an organic EL device.

Claims (17)

(A) A cured film forming composition characterized by containing a polymer compound having a group represented by the following formula (1) in the side chain as a photo-alignment group.

(In the formula, * represents the bonding position with the side chain of the polymer compound, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group, R ³ represents an alkyl group, alkenyl group, cycloalkyl group, or aromatic group, and R ¹ and R ³ , or R ² and R ³ may be combined with each other to form a ring. X ¹ represents a phenylene group that may be substituted with an arbitrary substituent.)
According to paragraph 1,
A cured film forming composition wherein the polymer compound of the component (A) is an acrylic copolymer.
According to paragraph 1,
The polymer compound of component (A) further has a self-crosslinkable group, or further has at least one crosslinkable group,
The crosslinkable group is a group that undergoes a thermal crosslinking reaction with a specific functional group 2 selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2),
The self-crosslinking group is selected from the group consisting of an alkoxymethylamide group, a hydroxymethylamide group, and an alkoxysilyl group,
The crosslinkable group is selected from the group consisting of a glycidyl group, an epoxycyclohexyl group, a vinyl group, and a blocked isocyanate group.
Cured film forming composition.

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)
According to paragraph 1,
The polymer compound of component (A) further has at least one specific functional group 2 and at least one crosslinkable group,
The specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2),
The crosslinkable group is a group that undergoes a thermal crosslinking reaction with the specific functional group 2,
The crosslinkable group is selected from the group consisting of a glycidyl group, an epoxycyclohexyl group, a vinyl group, and a blocked isocyanate group.
Cured film forming composition.

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)
According to paragraph 1,
The polymer compound of component (A) further has at least one specific functional group 2,
The specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the following formula (2),
The composition further contains a cross-linking agent (B) that undergoes a thermal cross-linking reaction with the specific functional group 2,
The crosslinking agent (B) is an epoxy compound, a methylol compound, an isocyanate compound, a phenoplast compound, a compound having two or more trialkoxysilyl groups, an alkoxysilane compound having an amino group, a polymer of N-alkoxymethylacrylamide, or a compound having an epoxy group. selected from the group consisting of a polymer of a compound, a polymer of a compound having an alkoxysilyl group, a polymer of a compound having an isocyanate group, and a melamine formaldehyde resin.
Cured film forming composition.

(In the formula, * represents the bonding position with another group, and R ⁹ represents an alkyl group, an alkoxy group, or a phenyl group)
According to paragraph 1,
(C) As a component, it further contains a specific polymer having at least two specific functional groups 2, wherein the specific functional groups 2 are selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2). chosen one,
Cured film forming composition.
According to paragraph 1,
As a component (E), it further contains a crosslinking catalyst, wherein the crosslinking catalyst (E) is (E-1) an acid or a thermal acid generator, or (E-2) a metal chelate compound and (E-3) silica. Any one of the combination of nol compounds,
Cured film forming composition.
According to paragraph 1,
(D) As a component, it further contains an adhesion improving compound which further has one or more polymerizable groups, at least one specific functional group 2 or at least one crosslinkable group,
The specific functional group 2 is a group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, an amino group, and a group represented by the formula (2),
The crosslinkable group is a group that undergoes a thermal crosslinking reaction with the specific functional group 2,
The crosslinkable group is selected from the group consisting of a glycidyl group, an epoxycyclohexyl group, a vinyl group, and a blocked isocyanate group.
Cured film forming composition.
According to paragraph 1,
(F) As a component, it further contains a photo-alignment group in which the heat crosslinking reactive site is bonded directly or bonded through a linking group, and a monomer having one or more polymerizable groups,
Cured film forming composition.
According to clause 5,
A cured film forming composition containing 1 part by mass to 100 parts by mass of (B) component based on 100 parts by mass of (A) component.
According to clause 6,
A cured film forming composition containing 10 parts by mass to 200 parts by mass of (C) component based on 100 parts by mass of (A) component.
In clause 7,
Based on 100 parts by mass of component (A), it contains 0.01 to 20 parts by mass of component (E-1), or 0.1 to 30 parts by mass of component (E-2) and 0.5 to 70 parts by mass. A cured film-forming composition containing a combination of negative (E-3) components.
According to clause 8,
A cured film forming composition containing 1 to 80 parts by mass of (D) component based on 100 parts by mass of (A) component.
According to clause 9,
A cured film forming composition containing 1 part by mass to 40 parts by mass of (F) component based on 100 parts by mass of component (A).
A thermosetting film obtained using the cured film forming composition according to any one of claims 1 to 14.
An orientation material obtained using the cured film-forming composition according to any one of claims 1 to 14.
A phase difference material formed using a cured film obtained from the cured film-forming composition according to any one of claims 1 to 14.