KR20200093068A - Cured film forming composition, alignment material and retardation material - Google Patents

Abstract

[Problem] A cured film forming composition that is used as an alignment material and forms a cured film exhibiting excellent liquid crystal orientation, light transmittance and solvent resistance under conditions of relatively low temperature and short time when a layer of a polymerizable liquid crystal is disposed thereon will be.
[Solutions] As a component (A), a compound containing a Michael donor site, a component (B) containing a compound containing a Michael acceptor site, and at least one of the components (A) and (B) is a liquid crystal. A cured film-forming composition comprising an alignment group, a cured film and an alignment material obtained using the composition, and a retardation material formed using the alignment material.

Description

Cured film forming composition, alignment material and retardation material

The present invention relates to a cured film forming composition, an alignment material, and a retardation material to form a cured film for aligning liquid crystal molecules. Particularly, the present invention is a cured film forming composition, an alignment material, and a phase difference useful for producing a patterned retardation material used in a circularly polarized glasses type 3D display or a retardation material used in a circular polarizing plate used as an anti-reflection film for an organic EL display. It is about ash.

In the case of a 3D display of the circularly polarized spectacles method, it is common that a phase difference material is disposed on a display element forming an image such as a liquid crystal panel. In this phase difference material, two or more types of phase difference regions having different phase difference characteristics are arranged regularly and constitute a patterned phase difference material. Meanwhile, in the present specification, a retardation material patterned to arrange a plurality of retardation regions having different retardation characteristics will be referred to as a patterned retardation material.

The patterned retardation material can be produced, for example, by optically patterning a retardation material made of a polymerizable liquid crystal, as disclosed in Patent Document 1. The optical patterning of the retardation material made of a polymerizable liquid crystal uses a photo-alignment technique known as an alignment reformation of the liquid crystal panel. That is, a coating film made of a photo-alignment material is provided on the substrate, and two kinds of polarizations having different polarization directions are irradiated thereon. Then, a photo-alignment film is obtained as an alignment material in which two types of liquid crystal alignment regions having different alignment control directions of liquid crystals are formed. A phase difference material in a solution phase containing a polymerizable liquid crystal is applied on the photo-alignment film to realize the alignment of the polymerizable liquid crystal. Thereafter, the oriented polymerizable liquid crystal is cured to form a patterned retardation material.

The anti-reflection film of the organic EL display is composed of a linearly polarizing plate and a quarter-wave retardation plate, and converts foreign light toward the panel surface of the image display panel to linearly polarized by a linearly polarizing plate, followed by a continuous quarter-wave retardation plate. It converts into circularly polarized light. Here, by the circularly polarized light, the external light is reflected from the surface of the image display panel or the like, but upon the reflection, the rotational direction of the polarizing surface is reversed. As a result, the reflected light is converted to linearly polarized light in a direction shielded by the linearly polarized plate from the quarter-wave retardation plate, as opposed to upon arrival, and then blocked by the subsequent linearly polarized plate, and as a result, to the outside. The emission is significantly suppressed.

About this quarter-wave retardation plate, in patent document 2, a 1/2-wavelength plate and a quarter-wavelength plate are combined to form a quarter-wavelength retardation plate, thereby constituting this optical film by reverse dispersion characteristics. A method has been proposed. In the case of this method, in the wide wavelength band provided for the display of a color image, an optical film can be constructed by a reverse dispersion characteristic using a liquid crystal material having a positive dispersion characteristic.

Moreover, recently, as a liquid crystal material applicable to this retardation layer, it has been proposed to have inverse dispersion characteristics (Patent Documents 3 and 4). According to the liquid crystal material having such a reverse dispersion characteristic, instead of forming a quarter-wave retardation plate by a two-layer retardation layer by combining a half-wave plate and a quarter-wave plate, a retardation layer is composed of a single layer. By doing so, it is possible to secure the inverse dispersion characteristic, and accordingly, an optical film capable of securing a desired phase difference in a wide wavelength band can be realized by a simple configuration.

An alignment layer is used to align the liquid crystal. As a method of forming an alignment layer, for example, a rubbing method or a photo-alignment method is known, and the photo-alignment method is useful in that it does not generate static electricity or dust, which is a problem of the rubbing method, and thus can control quantitative alignment processing. .

In the alignment reformation using the photo-alignment method, as an available photo-alignment material, acrylic resins, polyimide resins, and the like having a light dimerization site such as cinnamoyl group and chalcone group on the side chain are known. It has been reported that these resins exhibit the ability to control the alignment of liquid crystals (hereinafter, also referred to as liquid crystal alignment properties) by irradiating polarized UV (see Patent Documents 5 to 7).

In addition, solvent resistance is required for the alignment layer in addition to the liquid crystal alignment ability. For example, the alignment layer may be exposed to heat or a solvent in the process of manufacturing the phase difference material. When the alignment layer with low solvent resistance is exposed to a solvent, there is a fear that the liquid crystal alignment ability is significantly lowered.

Thus, in Patent Document 8, for example, in order to obtain a stable liquid crystal alignment capability, a liquid crystal alignment agent containing a polymer component having a structure capable of crosslinking by light and a structure crosslinking by heat, and a crosslinking reaction by light A liquid crystal aligning agent containing a polymer component having this possible structure and a compound having a structure crosslinked by heat has been proposed.

On the other hand, since the thermal stress applied to the film substrate is reduced, the lowering of the manufacturing process of the phase difference material has been studied. One of the processes requiring the highest temperature in manufacturing a phase difference material is a process of forming a liquid crystal alignment film, and a reduction in the deposition process of the liquid crystal alignment film is required.

As a method of forming a liquid crystal alignment film at a low temperature, a system using an acrylic resin, an acid derived from a thermal acid generator as a catalyst, and a thermal crosslinking system that proceeds at a relatively low temperature (around 100°C) has been proposed (patent) Document 9).

Japanese Patent Publication No. 2005-49865 Japanese Patent Publication H10-68816 US Patent No. 8119026 Japanese Patent Publication 2009-179563 Japanese Patent No. 3611342 Japanese Patent Publication 2009-058584 Japanese Patent Publication No. 2001-517719 Japanese Patent No. 4207430 International Publication No. 2010/150748

The object of the present invention was achieved based on the above findings and findings. That is, an object of the present invention is to provide a liquid crystal alignment agent for photo-alignment which has excellent solvent resistance and can form an alignment film capable of aligning a polymerizable liquid crystal with high sensitivity under conditions of relatively low temperature and short time.

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

In order to achieve the above object, the present inventors, through repeated studies, selected a cured film-forming material based on a cured film-forming composition containing a component having a Michael donor site and a component having a Michael acceptor site, It has been found that a cured film having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity can be formed under relatively low temperature and short time conditions, thereby completing the present invention.

That is, the present invention is a first aspect,

(A) As a component, a compound containing a Michael donor site,

(B) As a component, the compound containing the Michael acceptor site is included,

At least one of (A) component and (B) component is related with the cured film forming composition containing a liquid crystal aligning group.

As a 2nd viewpoint, it is related with the cured film formation composition as described in 1st viewpoint which (A) component and (B) component are the same compound containing a Michael donor site, a Michael acceptor site, and a liquid crystal orientation group.

As a third aspect,

(A) At least one component selected from a compound (A2) having one Michael donor site, a low-molecular compound (A1) having a liquid crystal alignment group, and two or more Michael donor sites, and containing or containing a liquid crystal alignment group. Type 1,

(B) As a component, it is selected from the compound (B2) which has one Michael acceptor site, a low molecular compound (B1) having a liquid crystal orientation group, and two or more Michael acceptor sites and does not contain or contains a liquid crystal orientation group. It contains at least one kind,

(A2) component and (B2) component may be a low molecular compound or a high molecular compound,

It is related with the cured film forming composition described in a 1st viewpoint or a 2nd viewpoint.

As a 4th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint-3rd viewpoint which the Michael donor part of (A) component is an active methylene group or an active methine group.

As a 5th viewpoint, it is related with the cured film formation composition in any one of the 1st viewpoint-the 4th viewpoint which further contains the catalyst addition reaction catalyst (C).

As a 6th viewpoint, it is related with the cured film formation composition in any one of the 1st viewpoint-the 5th viewpoint in which a Michael acceptor part is an acrylic group.

As a 7th viewpoint, it is related with the cured film formation composition in any one of 1st viewpoint-6th viewpoint containing 1 mass part-2,000 mass parts (B) component with respect to 100 mass parts of (A) component.

As the eighth aspect, the cured film formation according to any one of the fifth aspect to the seventh aspect containing 0.01 to 20 parts by mass of the (C) component relative to 100 parts by mass of the (A) component and the (B) component in total. It relates to a composition.

As a 9th viewpoint, it is related with the cured film obtained using the cured film forming composition in any one of 1st viewpoint-8th viewpoint.

As a 10th viewpoint, it is related with the orientation material obtained using the cured film forming composition in any one of 1st viewpoint-8th viewpoint.

As an 11th viewpoint, it is related with the phase difference material formed using the orientation material described in a 10th viewpoint.

According to the present invention, there is provided a cured film having excellent solvent resistance and capable of aligning a polymerizable liquid crystal with high sensitivity, and a cured film forming composition suitable for the formation of the cured film and capable of being formed under conditions of relatively low temperature and short time. Can.

According to the present invention, it is possible to provide an alignment material excellent in liquid crystal alignment and light transmittance, and a phase difference material capable of high-precision optical patterning.

<Cure film forming composition>

The cured film-forming composition of the present invention contains a component containing one or two or more structures selected from the group consisting of a Michael donor site, a Michael acceptor site, and a liquid crystal alignment group. It is a cured film forming composition containing a structure as an essential.

Specifically, as a component (A), a compound containing a Michael donor site and a compound containing a Michael acceptor site as a component (B), and at least one of the components (A) and (B) is a liquid crystal. It is a cured film forming composition containing an alignment group. The component (A) and the component (B) may be the same compound containing a Michael donor site, a Michael acceptor site, and a liquid crystal alignment group.

The cured film-forming composition of the present invention, as the component (A), has one Michael donor site, a low-molecular compound (A1) having a liquid crystal alignment group, and two or more Michael donor sites, and contains no liquid crystal alignment group or It has at least one member selected from the compound (A2) to contain, and as the component (B), has one Michael acceptor site, a low-molecular compound (B1) having a liquid crystal orientation group, and two or more Michael acceptor sites. , At least one selected from compounds (B2) that do not contain or contain a liquid crystal alignment group, wherein the (A2) component and (B2) component may be a low molecular compound or a high molecular compound, or may be in the sun. .

In addition, other additives may be contained as long as the effects of the present invention are not impaired.

On the other hand, in the above, "low molecular compound" means compounds other than "polymer compound (polymer)", that is, compounds other than compounds having a repeating unit (by polymerization) formed in the compound.

Hereinafter, details of each component will be described.

<Michael donor site>

(A) As a Michael donor site|part according to a component, a mercapto group, an amino group, an active methylene group, and an active methine group are mentioned, for example.

The active methylene group refers to a methylene group (-CH ₂ -) having a carbonyl group at an adjacent position, and having reactivity to the nucleophilic reagent. In addition, in the present invention, the active methine group means a structure in which one hydrogen atom of the methylene group (-CH ₂ -) in the active methylene group is substituted with an alkyl group, and has reactivity to the nucleophilic reagent.

As the active methylene group and active methine group, a group represented by the following formula (a1) is more preferable.

[Formula 1]

(In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the broken line represents the number of bonds.)

In the formula (a1), examples of the alkyl group represented by R include, for example, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.

As such an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, etc. are mentioned, for example.

Especially, methyl group, ethyl group, n-propyl group, etc. are preferable.

In the formula (a1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferable.

Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group and the like. have.

Especially, a methoxy group, an ethoxy group, n-propoxy group, etc. are preferable.

As a group represented by said formula (a1), the following structures etc. are mentioned, for example. On the other hand, in the structural formula, the broken line represents the number of bonds.

[Formula 2]

<Introduction method of group (Michael donor site) represented by formula (a1)>

As a method of introducing the group represented by formula (a1) into each component, for example, a method of reacting acyl meldrum acid obtained by reacting meldrum acid and carboxylic acid chloride with a low-molecular compound or polymer having a hydroxy group is used. Can be lifted. This method is known. Here, as R, a methyl group is preferable in view of availability and orientation.

[Formula 3]

As another method, a method of reacting tert-butyl acyl acetate with a low-molecular compound or polymer having a hydroxy group is exemplified. This method is known. Here, as R, a methyl group is preferable in view of availability and orientation.

[Formula 4]

Moreover, the compound (component (A2) mentioned later) which has two or more Michael donor sites can be obtained as a polymer by copolymerizing the monomer which has a Michael donor site.

As a monomer having a Michael donor site, 2-acetoacetoxyethyl acrylate (ethylene glycol monoacetoacetate monoacrylate), 2-acetoacetoxyethyl methacrylate (ethylene glycol monoacetoacetate monomethacrylate), etc. Can be lifted.

<Michael acceptor part>

(B) Michael acceptor site according to the component, for example, (meth)acrylic group and maleimide group, that is, CH ₂ =CH-C(=O)- group, CH ₂ =C(CH ₃ ) -C(=O)- group, and maleimide group. On the other hand, in this specification, descriptions such as “(meth)acrylic group” refer to both acrylic and methacryl groups.

<Method of introducing (meth)acrylic group>

As a method of introduce|transducing a (meth)acrylic group into each component, the method of making (meth)acrylic acid react with the component which has an epoxy group by a well-known method is mentioned. Further, there may be mentioned a method in which a compound component having a (meth)acrylic group and an isocyanate group is reacted by a known method to a copolymer obtained by using a monomer having a hydroxyalkyl group such as hydroxyethyl (meth)acrylate. .

<Introduction of maleimide groups>

As a method of introducing a maleimide group into each component, a method in which N-(4-carboxyphenyl) maleimide or N-(4-hydroxyphenyl) maleimide is reacted with a component having an epoxy group by a known method Can be lifted. Moreover, the method of making N-(4-hydroxyphenyl) maleimide react with the component which has an isocyanate group by a well-known method is also mentioned.

<Liquid crystal orientation>

Examples of the liquid crystal alignment group used in the present invention contained in at least one of the component (A) and the component (B) include a vertical alignment group and an optical alignment group.

<Optical orientation system>

In the present invention, the photo-alignment group refers to a functional group (also referred to as a light dimerization site or a photoisomerization site) for photodimerization or photoisomerization.

The light dimerization site is a site that forms a dimer by light irradiation, and specific examples thereof include cinnamoyl group, chalcone group, coumarin group, and anthracene group. Of these, cinnamoyl groups having high transparency in the visible light region and light dimerization reaction are preferred.

In addition, the photoisomerization site is a site in which the cis body and the trans body are changed by light irradiation, and specific examples thereof include an azobenzene structure and a stilbene structure. Among them, azobenzene structure is preferred from the height of reactivity.

As a photodimerization site, an example of the structure of a more preferable cinnamoyl group is shown in the following formula [1] or formula [2].

[Formula 5]

In the formula [1], X ¹¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group.

In the formula [2], X ¹² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to a benzene ring via a single bond, ether bond, ester bond, amide bond, or urea bond.

<Introduction method of optical orientation device>

In order to introduce such a photo-alignment group into each component of the present invention, a Michael donor site by the method described in <Introduction Method of a Group (Michael Donor Part) Represented by Formula (a1)> in a compound having a photo-alignment group and a hydroxyl group A method for introducing, a method of using an acrylic monomer having a photo-alignment group as it is, or copolymerizing it, a method of reacting a component having an epoxy group with a cinnamic acid derivative having a carboxyl group (photo-alignment group (cinnamoyl group) and a compound having a carboxyl group) And the like.

The compound having a photo-alignment group and a hydroxy group is represented by any one of the following formulas [A1] to [A5].

[Formula 6]

In the above formula, A ¹ and A ² each independently represent a hydrogen atom or a methyl group, and X ¹ is a single bond, ether bond, ester bond, amide bond, urethane bond, amino bond, or a combination thereof. It shows the structure which combines 1 to 3 divalent groups chosen from alkylene group of 1-18 carbon atoms, a phenylene group, a biphenylene group, or a combination of these via 2 or more types of bonds.

X ² represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to a benzene ring via a covalent bond, ether bond, ester bond, amide bond or urea bond.

X ³ is a hydroxy group, a mercapto group, an amino group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, a phenoxy group, a phenylthio group, or a phenylamino group , Biphenylamino group, phenyl group or biphenyl group.

X ⁴ each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or linear.

X represents a single bond, an oxygen atom or a sulfur atom.

On the other hand, in these groups, the hydrogen atom on the phenyl group, biphenyl group, phenylene group and biphenylene group includes an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a trifluoromethyl group, and It may be substituted by the same or different 1 or a plurality of substituents selected from the cyano group.

In the above formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms Group, halogen atom, trifluoromethyl group or cyano group.

As a specific example of the compound which has a photo-alignment group and a hydroxyl group, for example, 4-(8-hydroxyoctyloxy) cinnamic acid methyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid methyl ester, 4- (4-hydroxybutyloxy) cinnamic acid methyl ester, 4-(3-hydroxypropyloxy) cinnamic acid methyl ester, 4-(2-hydroxyethyloxy) cinnamic acid methyl ester, 4-hydroxymethyloxy cinnamic acid methyl ester, 4-hydroxy-acetate methyl ester, 4-(8-hydroxyoctyloxy) ethyl acetate, 4-(6-hydroxyhexyloxy) ethyl acetate, 4-(4-hydroxybutyloxy) ethyl acetate , 4-(3-hydroxypropyloxy) cinnamic acid ethyl ester, 4-(2-hydroxyethyloxy) cinnamic acid ethyl ester, 4-hydroxymethyloxy cinnamic acid ethyl ester, 4-hydroxy cinnamic acid ethyl ester, 4-( 8-hydroxyoctyloxy) cinnamic acid phenyl ester, 4-(6-hydroxyhexyloxy) cinnamic acid phenyl ester, 4-(4-hydroxybutyloxy) cinnamic acid phenyl ester, 4-(3-hydroxypropyloxy) Cinnamic acid phenyl ester, 4-(2-hydroxyethyloxy) cinnamic acid phenyl ester, 4-hydroxymethyloxy cinnamic acid phenyl ester, 4-hydroxy cinnamic acid phenyl ester, 4-(8-hydroxyoctyloxy) cinnamic acid biphenyl ester , 4-(6-hydroxyhexyloxy) cinnamic acid biphenyl ester, 4-(4-hydroxybutyloxy) cinnamic acid biphenyl ester, 4-(3-hydroxypropyloxy) cinnamic acid biphenyl ester, 4-( 2-hydroxyethyloxy) cinnamic acid biphenyl ester, 4-hydroxymethyloxy cinnamic acid biphenyl ester, 4-hydroxy cinnamic acid biphenyl ester, cinnamic acid 8-hydroxyoctyl ester, cinnamic acid 6-hydroxyhexyl ester, cinnamic acid 4 -Hydroxybutyl ester, cinnamic acid 3-hydroxypropyl ester, cinnamic acid 2-hydroxyethyl ester, cinnamic acid hydroxymethyl ester, 4-(8-hydroxyoctyloxy) azobenzene, 4-(6-hydroxyhexyloxy Azobenzene, 4-(4-hydroxybutyloxy)azobenzene, 4-(3-hydroxypropyloxy)azobenzene, 4-(2-hydroxyethyloxy)azobenzene, 4-hydroxymethyloxyazobenzene, 4-hydroxy Loxiazobenzene, 4-(8-hydroxyoctyloxy)chalcone, 4-(6-hydroxy Cyhexyloxy) chalcone, 4-(4-hydroxybutyloxy) chalcone, 4-(3-hydroxypropyloxy) chalcone, 4-(2-hydroxyethyloxy) chalcone, 4-hydroxymethyloxy chalcone, 4-hydroxychalcone, 4'-(8-hydroxyoctyloxy)chalcone, 4'-(6-hydroxyhexyloxy)chalcone, 4'-(4-hydroxybutyloxy)chalcone, 4'-( 3-hydroxypropyloxy)chalcone, 4'-(2-hydroxyethyloxy)chalcone, 4'-hydroxymethyloxychalcone, 4'-hydroxychalcone, 7-(8-hydroxyoctyloxy)coumarin, 7-(6-hydroxyhexyloxy)coumarin, 7-(4-hydroxybutyloxy)coumarin, 7-(3-hydroxypropyloxy)coumarin, 7-(2-hydroxyethyloxy)coumarin, 7 -Hydroxymethyloxycoumarin, 7-hydroxycoumarin, 6-hydroxyoctyloxycoumarin, 6-hydroxyhexyloxycoumarin, 6-(4-hydroxybutyloxy)coumarin, 6-(3-hydroxypropyloxy )Coumarin, 6-(2-hydroxyethyloxy)coumarin, 6-hydroxymethyloxycoumarin, and 6-hydroxycoumarin.

In addition, the compound having a photo-alignment group and a carboxyl group is represented by the following formula.

[Formula 7]

In Formula (1), A ¹¹ and A ¹² each independently represent a hydrogen atom or a methyl group.

R ¹¹ is a hydrogen atom, a halogen atom, C ₁ ~C ₆ alkyl, C ₁ ~C ₆ haloalkyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₆ haloalkoxy, C ₃ ~C ₈ cycloalkyl, C ₃ ~ C ₈ halocycloalkyl, C ₂ ~C ₆ alkenyl, C ₂ ~C ₆ haloalkenyl, C ₃ ~C ₈ cycloalkenyl, C ₃ ~C ₈ halocycloalkenyl, C ₂ ~C ₆ alkynyl, C ₂ ~C ₆ haloalkynyl, C ₁ ~C ₆ alkoxy, C ₁ ~C ₆ haloalkoxy, (C ₁ ~C ₆ alkyl)carbonyl, (C ₁ ~C ₆ haloalkyl)carbonyl, (C ₁ ~C ₆ alkoxy)carbonyl, (C ₁ ~C ₆ haloalkoxy)carbonyl, (C ₁ ~C ₆ alkylamino)carbonyl, (C ₁ ~C ₆ haloalkyl)aminocarbonyl, di(C ₁ ~ C ₆ alkyl)aminocarbonyl, cyano, nitro and the following formula (c-2)

[Formula 8]

(In formula (c-2), the broken line represents the number of bonds, R ¹⁰¹ is an alkylene group having 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group may be substituted with a fluorine atom or an organic group. Further, -CH ₂ CH ₂ -in R ¹⁰¹ may be substituted with -CH=CH-, and further, when any one of the following groups is not adjacent to each other, -O-, -NHCO It may be substituted with a group selected from the group consisting of -, -CONH-, -COO-, -OCO-, -NH-, -NHCONH- and -CO-, and M ¹ is a hydrogen atom or a methyl group.) Represents the group

R ¹² is a divalent aromatic group, a divalent alicyclic group, a divalent heterocyclic group, or a divalent condensed cyclic group,

R ¹³ is Single bond, oxygen atom, -COO- or -OCO-,

R ¹⁴ to R ¹⁷ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a haloalkoxy group having 1 to 6 carbon atoms. , Cyano group, and nitro group,

n is an integer from 0 to 3.)

Preferred examples of the compound represented by the formula (1) are, for example, the following formulas (1-1) to (1-5)

[Formula 9]

(In the above formula, R ¹¹ is synonymous with R ¹¹ in the formula (1), respectively.) The compound represented by each, etc. are mentioned.

In the compound represented by the formula (1), preferred examples of the compound in which R ¹¹ is a group represented by the formula (c-2) include, for example, the following formulas M1-1 to M1-5.

[Formula 10]

(In the formula, M ¹ is a hydrogen atom or a methyl group, s1 represents the number of methylene groups, and is a natural number from 2 to 9.)

The compound represented by the formula (1) can be synthesized by appropriately combining organic chemical methods.

As a monomer which has a photodimerization site, the monomer which has cinnamoyl group, chalcone group, coumarin group, or anthracene group etc. is mentioned, for example. Of these, monomers having cinnamoyl groups having good transparency and light dimerization in the visible region are particularly preferred.

In particular, a monomer having a cinnamoyl group having a structure represented by the formula [1] or formula [2] is more preferable. The specific example of such a monomer is shown in following formula [3] or formula [4].

[Formula 11]

In the formula [3], X ¹¹ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a biphenyl group. At this time, the phenyl group and the biphenyl group may be substituted with any one of a halogen atom, an alkyl group, an alkoxy group, and a cyano group.

In the formula [4], X ¹² represents a hydrogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. At this time, the alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, and a cyclohexyl group may be bonded to a benzene ring through a single bond, ether bond, ester bond, amide bond or urea bond.

In the formula [3] or formula [4], X ¹³ and X ¹⁵ each independently represent a single bond, an alkylene group having 1 to 20 carbon atoms, a divalent aromatic ring group, or a divalent aliphatic ring group. Here, the alkylene group having 1 to 20 carbon atoms may be branched or straight chain, or substituted with a hydroxy group, and at least one bond selected from ether bonds, ester bonds, amide bonds, urea bonds, and urethane bonds It may be stopped by. X ¹⁴ and X ¹⁶ represent a polymerizable group. As a specific example of this polymerizable group, an acryloyl group, methacryloyl group, styrene group, maleimide group, acrylamide group, methacrylamide group, etc. are mentioned, for example.

On the other hand, the compound having a photo-alignment group and a hydroxy group, or a monomer having a photo-alignment group is known, Japanese Patent Publication No. S62-284350, U.S. Patent No. 4,696,990, Japanese Patent Publication H9-118717, U.S. Patent It can be manufactured according to the method described in the specifications of No. 6,107,427.

Moreover, as a monomer having a photodimerization site, a compound obtained by reacting a cinnamic acid derivative represented by the formulas (1-1) to (1-5) with a (meth)acrylic monomer having an epoxy group is also suitably used. do.

<Vertical orientation system>

The vertical alignment group is not particularly limited, but a group containing a hydrocarbon group having 6 to 20 carbon atoms is preferable, and specifically, a group represented by formula (2) is suitable.

[Formula 12]

In formula (2), Y ¹ is a single bond, or -O-, -CH ₂ O-, -COO-, -OCO-, -NHCO-, -NH-CO-O- and -NH-CO-NH Represents a bonding group selected from -, Y ² represents a single bond, an alkylene group having 1 to 15 carbon atoms or a -CH ₂ -CH(OH)-CH ₂ -group, or from a benzene ring, cyclohexane ring or heterocycle It represents the divalent cyclic group selected, and any hydrogen atom on the cyclic group may be substituted with Z, Y ³ represents a single bond or an alkylene group having 1 to 15 carbon atoms, and Y ⁴ represents a single bond or a benzene ring , A divalent cyclic group selected from a cyclohexane ring or a heterocycle, or a divalent organic group having a steroid skeleton having 17 to 30 carbon atoms, and any hydrogen atom on the cyclic group may be substituted with Z, Y ⁵ is , A bivalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, any hydrogen atom on these cyclic groups may be substituted with Z, m represents an integer from 0 to 4, and m is 2 or more , Y ⁵ may be the same as or different from each other, and Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorinated alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 1 to 1 carbon atom. 18 represents a fluorinated alkoxy group, Z represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms, an fluorinated alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. , An alkylene group, an alkyl group, an fluorinated alkyl group, an alkoxy group and an fluorinated alkoxy group may have 1 to 3 of the above bonding groups, unless the linking groups are adjacent to each other, and in Y ² to Y ⁶ , an alkylene group,- The CH ₂ -CH(OH)-CH ₂ -group, a divalent cyclic group, a divalent organic group having a steroid skeleton, an alkyl group, and an fluorinated alkyl group may be bonded via a group adjacent to them and the linking group. However, the total number of carbon atoms of the substituents represented by Y ² to Y ⁶ is 6 to 30.

Examples of the alkylene group having 1 to 15 carbon atoms include a divalent group in which one hydrogen atom is removed from an alkyl group having 1 to 15 carbon atoms among the alkyl groups having 1 to 18 carbon atoms described later, and specific examples thereof include a methylene group. , Ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, and the like.

Specific examples of the heterocyclic ring include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, tiadia Sol ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, sinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring , Oxadiazole ring, acridine ring and the like, among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, carbazole ring, pyridazine ring, pyrazoline ring, tria A true ring, a pyrazolidine ring, a triazole ring, a pyrazine ring, and a benzimidazole ring are preferable.

As the alkyl group having 1 to 18 carbon atoms, a methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1- Dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methylcyclobutyl group, 2 -Methylcyclobutyl group, 3-methylcyclobutyl group, 1,2-dimethylcyclopropyl group, 2,3-dimethylcyclopropyl group, 1-ethylcyclopropyl group, 2-ethylcyclopropyl 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, cyclohexyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 1-ethyl Cyclobutyl group, 2-ethylcyclobutyl group, 3-ethylcyclobutyl group, 1,2-dimethylcyclobutyl group, 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethyl Cyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-propylcyclopropyl group, 2-propylcyclopropyl group, 1-isopropylcyclopropyl group, 2-isopropylcyclopropyl Group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl- 1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, n-heptyl group, 1-methyl-n-hexyl group, 2-methyl-n-hex Practical group, 3-methyl-n-hexyl group, 1,1-dimethyl-n-pentyl group, 1,2-dimethyl-n-pentyl group , 1,3-dimethyl-n-pentyl group, 2,2-dimethyl-n-pentyl group, 2,3-dimethyl-n-pentyl group, 3,3-dimethyl-n-pentyl group, 1-ethyl-n -Pentyl group, 2-ethyl-n-pentyl group, 3-ethyl-n-pentyl group, 1-methyl-1-ethyl-n-butyl group, 1-methyl-2-ethyl-n-butyl group, 1- Ethyl-2-methyl-n-butyl group, 2-methyl-2-ethyl-n-butyl group, 2-ethyl-3-methyl-n-butyl group, n-octyl group, 1-methyl-n-heptyl group , 2-methyl-n-heptyl group, 3-methyl-n-heptyl group, 1,1-dimethyl-n-hexyl group, 1,2-dimethyl-n-hexyl group, 1,3-dimethyl-n-hexyl Real group, 2,2-dimethyl-n-hexyl group, 2,3-dimethyl-n-hexyl group, 3,3-dimethyl-n-hexyl group, 1-ethyl-n-hexyl group, 2-ethyl-n- Hexyl group, 3-ethyl-n-hexyl group, 1-methyl-1-ethyl-n-pentyl group, 1-methyl-2-ethyl-n-pentyl group, 1-methyl-3-ethyl-n-pentyl group , 2-methyl-2-ethyl-n-pentyl group, 2-methyl-3-ethyl-n-pentyl group, 3-methyl-3-ethyl-n-pentyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, etc. may be mentioned. .

Further, examples of the alkoxy group having 1 to 18 carbon atoms include a group in which an oxygen atom (-O-) is bonded to the alkyl group having 1 to 18 carbon atoms.

Examples of the fluorinated alkyl group having 1 to 18 carbon atoms include a group in which at least one hydrogen atom in the alkyl group having 1 to 18 carbon atoms is substituted with a fluorine atom, and specific examples thereof include fluoromethyl group and difluoro. Methyl group, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3 ,3-tetrafluoropropyl group, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl group, nonafluorobutyl group, 4,4,4-trifluorobutyl group, undecafluoro Lopentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, Tridecafluorohexyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4,4,5, 5,6,6-decafluorohexyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group, etc. are mentioned.

Specific examples of the fluorinated alkoxy group having 1 to 18 carbon atoms include a group in which an oxygen atom (-O-) is bonded to the fluorinated alkyl group having 1 to 18 carbon atoms, and specific examples thereof include a fluoromethoxy group, Difluoromethoxy group, trifluoromethoxy group, pentafluoroethoxy group, 2,2,2-trifluoroethoxy group, heptafluoropropoxy group, 2,2,3,3,3-penta Fluoropropoxy group, 2,2,3,3-tetrafluoropropoxy group, 2,2,2-trifluoro-1-(trifluoromethyl)ethoxy group, nonafluorobutoxy group, 4, 4,4-trifluorobutoxy group, undecafluoropentyloxy group, 2,2,3,3,4,4,5,5,5-nonafluoropentyloxy group, 2,2,3,3 ,4,4,5,5-octafluoropentyloxy group, tridecafluorohexyloxy group, 2,2,3,3,4,4,5,5,6,6,6-undecafluoro Hexyloxy group, 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy group, 3,3,4,4,5,5,6,6,6-nona And fluorohexyloxy groups.

On the other hand, as the alkyl group having 1 to 3 carbon atoms in Z, examples of the groups exemplified in 1 to 18 carbon atoms include those having 1 to 3 carbon atoms, and examples of the alkoxy group having 1 to 3 carbon atoms are: Of the groups exemplified by the alkoxy group having 1 to 18 carbon atoms, those having 1 to 3 carbon atoms (with oxygen atoms (-O-) bonded to those having 1 to 3 carbon atoms among the groups exemplified in 1 to 18 carbon atoms) ), and examples of the fluorinated alkyl group having 1 to 3 carbon atoms include those having 1 to 3 carbon atoms among the groups exemplified by the fluorinated alkyl group having 1 to 18 carbon atoms, and fluorinated alkoxy having 1 to 3 carbon atoms. As the group, among the groups exemplified in the fluorinated alkoxy group having 1 to 18 carbon atoms, those having 1 to 3 carbon atoms are mentioned.

The total number of carbon atoms of the substituents represented by Y ² to Y ⁶ is 6 to 30, but 6 to 20 is preferable.

In particular, in consideration of the vertical alignment property and coating properties of the resulting liquid crystal polymer, the vertical alignment group is preferably a group containing an alkyl group having 7 to 18 carbon atoms, particularly 8 to 15 carbon atoms.

As a specific vertical alignment group, a hydrocarbon group of about 6 to 20 carbon atoms is mentioned, for example. Examples of the hydrocarbon group having 6 to 20 carbon atoms include a straight-chain, branched or cyclic alkyl group having 6 to 20 carbon atoms or a hydrocarbon group having 6 to 20 carbon atoms including an aromatic group.

Accordingly, in the formula (2), Y ¹ , Y ² and Y ⁴ are a single bond, and Y ³ is a single bond or an alkylene group having 1 to 15 carbon atoms (preferably alkyl having 1 to 15 carbon atoms). Ren group), m is 0, Y ⁶ is an alkyl group having 1 to 18 carbon atoms, and the total number of carbon atoms in Y ³ and Y ⁶ is preferably an alkyl group (a-1) having 6 to 20 atoms, and the total number of carbon atoms is A 7-18 alkyl group is more preferable, and a total carbon atom number 8-15 alkyl group is more preferable.

As a specific example of such a vertical alignment group (a-1), in addition to the alkyl group having 6 to 18 carbon atoms exemplified in the above-described alkyl group having 1 to 18 carbon atoms, n-nonadecyl, n-ecocinyl group, etc. are mentioned. Can.

In addition, in addition to the vertical alignment group (a-1), for example, Y ¹ to Y ⁴ is a single bond, m is 2 or 3, Y ⁵ is a benzene ring or a cyclohexane ring, Y ⁶ , a vertical alignment group (a-2), which is an alkyl group having 1 to 18 carbon atoms, can also be suitably used.

As specific examples of the vertical alignment group (a-2), groups represented by the following (a-2-1) to (a-2-6) may be mentioned, but the present invention is not limited thereto.

[Formula 13]

(In the formula, Y ⁶ and Y ⁶ is an agreement in the formula (2).)

<Introduction Method of Vertical Orientation System>

In order to introduce the vertical alignment group described above into each component of the present invention, Michael is introduced into a compound having a vertical alignment group and a hydroxy group, as described in the above <Method of introducing a group represented by formula (a1) (Michael donor site)> And a method of introducing a donor site, an acrylic monomer having a vertical alignment group as it is, or copolymerizing it, a method of reacting a component having an epoxy group with a compound having a carboxyl group bonded to the vertical alignment group.

Examples of the monomer having a vertical alignment group include alkyl esters of (meth)acrylic acid, alkyl vinyl ethers, 2-alkylstyrenes, 3-alkylstyrenes, 4-alkylstyrenes, and N-alkylmaleimides, of the alkyl groups in these compounds. And compounds having 6 to 20 carbon atoms.

These monomers can be produced by a known method, and some are available as commercial products.

On the other hand, when a vertical alignment group is introduced into a polymer using a (meth)acrylic monomer having a vertical alignment group represented by the formula (2), the vertical alignment side chain is represented by the following equation (2').

[Formula 14]

(In the formula, Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , and m are synonymous with each group in formula (2).)

<(A1) Low molecular compound having one Michael donor site and a liquid crystal alignment group>

As one low-molecular compound (A1) having a Michael donor site and a liquid crystal orientation group, it is described in <Method of introducing a group represented by formula (a1) (Michael donor region)> into a compound having a photo-alignment group and a hydroxyl group. As a method, a compound obtained by introducing a Michael donor site, a method described in the <Introduction method for a group represented by formula (a1) (Michael donor site)> in a compound having a vertical alignment group and a hydroxy group, is a Michael donor site. And compounds obtained by introducing.

<(A2) Compound having two or more Michael donor sites (low molecular compound)>

When the compound (A2) having two or more Michael donor sites is a low-molecular compound, as the low-molecular compound (A2), a group represented by <Formula (a1) above in a low-molecular compound having two or more hydroxy groups (Michael Donor) As the method described in >Introduction method of site), a compound obtained by introducing a Michael donor site, polyfunctional thiol, diamine, and the like can be given.

<Low molecular compound having two or more hydroxy groups>

Specific examples of the dihydric alcohol having two alcoholic hydroxy groups include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butanediol , Pentanediol, hexanediol, heptanediol, nonanediol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, dioxane glycol, N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine , N-tert-butyldiethanolamine, N-lauryldiethanolamine, stearyldiethanolamine, N-phenyldiethanolamine, m-tolyldiethanolamine, p-tolyldiethanolamine and the like.

Specific examples of the trihydric alcohol having three alcoholic hydroxy groups include trimethylolethane, trimethylolpropane, glycerin, tris(2-hydroxyethyl)isocyanurate, hexanetriol, octanetriol, and decantriol , Triethanolamine, triisopropanolamine, and the like.

Specific examples of the tetrahydric alcohol having four alcoholic hydroxy groups include ditrimethylolethane, ditrimethylolpropane, diglycerin, and pentaerythritol.

In the present invention, these polyhydric alcohols may be used alone or in combination of two or more.

<Polyfunctional thiol compound>

The polyfunctional thiol compound can be obtained as an addition reaction product of a polyhydric alcohol with a monofunctional and/or polyfunctional thiol compound. Specific compounds include 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate, 1,3,5-tris(3-mercaptobutyryloxyethyl)-isocyanurate Trifunctional thiol compounds such as (Showa Denko Co., Ltd., Carens MT (registered trademark) NR1) and trimethylolpropane tris (3-mercaptopropionate); Tetrafunctional thiol compounds such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko, Carens MT (registered trademark) PEI); And hexafunctional thiol compounds such as dipentaerythritol hexakis (3-propionate).

<diamine>

The diamine component used is not particularly limited. It is as follows if the specific example is given.

Examples of the alicyclic diamines are 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'. -Dimethyldicyclohexylamine, isophoronediamine, and the like.

Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1 And 4-diamino-2-methoxybenzene, 2,5-diamino-p-xylene and 1,3-diamino-4-chlorobenzene.

Examples of aromatic-aliphatic diamines are 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-amino Phenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3 -Methylaminopropyl)aniline, 4-(3-methylaminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4 -(4-methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-methylaminopentyl)aniline, 4-(5-methylaminopentyl) Aniline, 2-(6-aminonaphthyl)methylamine, 3-(6-aminonaphthyl)methylamine, 2-(6-aminonaphthyl)ethylamine, 3-(6-aminonaphthyl)ethylamine, etc. Can be heard.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, and 1,7 -Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino -2,5-dimethylhexane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1, And 9-diamino-5-methylheptane.

<(A2) Compound (polymer) having two or more Michael donor sites>

When the compound (A2) having two or more Michael donor sites is a polymer (polymer compound), as the polymer (A2), the precursors of the polymer (A2) and the polymer (B2) described below are represented by the above formula (a1). Polymers etc. obtained by introducing a Michael donor site|region are mentioned as the method described in the introduction method of the group (Michael donor site|part) displayed.

On the other hand, when a liquid crystal alignment group is to be introduced into a polymer (A2) having two or more Michael donor sites, a liquid crystal alignment group is introduced into the precursors of the polymer (A2) and polymer (B2) described below, or the polymer is introduced. When producing the precursors of (A2) and polymer (B2), the monomer having the above-described liquid crystal alignment group may be copolymerized, and then the Michael donor site may be introduced by the above-described method.

<(B1) low molecular compound having one Michael acceptor site and a liquid crystal orientation group>

As one Michael acceptor site and a low molecular compound (B1) having a liquid crystal alignment group, the compound having the above photo alignment group and a hydroxyl group and an ester obtained using (meth)acrylic acid chloride, having the above vertical alignment group and a hydroxyl group And esters obtained using a compound and (meth)acrylic acid chloride.

<(B2) Compound having two or more Michael acceptor sites (low molecular compound)>

When the compound (B2) having two or more Michael acceptor sites is a low-molecular compound, polyfunctional (meth)acrylate, bismaleimide, and the like are exemplified as the low-molecular compound (B2).

[Polyfunctional urethane (meth)acrylate compound having three or more (meth)acryloyl groups]

(1) Trifunctional (has three (meth)acryloyl groups) Urethane (meth)acrylate

As a specific example of a commercial item of a polyfunctional urethane (meth)acrylate compound having three (meth)acryloyl groups, NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.); EBECRYL (Registered Trademark) 204, Dong 205, Dong 264, Dong 265, Dong 294/25HD, Dong 1259, Dong 4820, Dong 8311, Dong 8465, Dong 8701, Dong 9260, KRM(registered trademark) 8296, Dong 8667 [above] , All made by Daicel Allnex Co., Ltd.; And Shikou (registered trademark) UV-7550B, copper 7000B, copper 7510B, copper 7461TE, copper 2750B (above, all manufactured by Japan Synthetic Chemical Industries, Ltd.) and the like.

(2) 4-functional ((meth)acryloyl group has 4) urethane (meth)acrylate

As a specific example of a commercial item of a polyfunctional urethane (meth)acrylate compound having four (meth)acryloyl groups, EBECRYL (registered trademark) 8210, copper 8405, KRM (registered trademark) 8528 (above, all die cells All Nex Co., Ltd. product; And Shiko (registered trademark) UV-7650B (manufactured by Japan Synthetic Chemical Industry Co., Ltd.).

(3) Urethane (meth)acrylates with five or more functionalities (having five or more (meth)acryloyl groups)

As a polyfunctional urethane (meth)acrylate compound having 5 or more (meth)acryloyl groups (urethane (meth)acrylate having 5 or more functionalities), for example, pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate With urethane, pentaerythritol tri(meth)acrylate and toluene diisocyanate urethane, pentaerythritol tri(meth)acrylate with isophorone diisocyanate urethane, dipentaerythritol penta(meth)acrylate And urethanes with hexamethylene diisocyanate.

Commercially available products can be suitably used for the above-mentioned 5-functional urethane (meth)acrylate, for example

UA-306H, UA-306T, UA-306I, UA-510H (above, all manufactured by Kyoeisha Chemical Co., Ltd.); NK Oligo U-6LPA, Copper U-10HA, Copper U-10PA, Copper U-1100H, Copper U-15HA, Copper UA-53H, Copper UA-33H [above, all manufactured by Shin-Nakamura Chemical Industries, Ltd.]; EBECRYL (registered trademark) 220, copper 1290, copper 5129, copper 8254, copper 8301R, KRM (registered trademark) 8200, copper 8200AE, copper 8904, copper 8452 [all or more, manufactured by Daicel Allnex Co., Ltd.]; Shikou (registered trademark) UV-1700B, copper 6300B, copper 7600B, copper 7605B, copper 7610B, copper 7620EA, copper 7630B, copper 7640B, copper 7650B (above, all manufactured by Japan Synthetic Chemical Industries, Ltd.), etc. have.

(1) Trifunctional (having three (meth)acryloyl groups) compounds

As a compound having three (meth)acryloyl groups, 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate , Pentaerythritol tri(meth)acrylate, glycerin tri(meth)acrylate, and the like.

The compound having three (meth)acryloyl groups, commercially available products can be suitably used, for example, BisCoat #295, Copper #300 [above, all manufactured by Osaka Organic Chemical Industries, Ltd.]; Light acrylate TMP-A, copper PE-3A, light ester TMP [above, all manufactured by Kyoeisha Chemical Co., Ltd.]; NK ester A-9300, copper A-9300-1CL, copper A-TMM-3, copper A-TMM-3L, copper A-TMM-3LM-N, copper A-TMPT, copper TMPT [above, all Shinnakamura Chemical Industry Co., Ltd.]; PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 (above, all manufactured by Daicel Allnex Co., Ltd.) and the like.

(2) A tetrafunctional (having four (meth)acryloyl groups) compounds

Ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc. are mentioned as a compound which has four (meth)acryloyl groups.

As the compound having four (meth)acryloyl groups, commercially available products can be suitably used, for example, Biscoat #300 [manufactured by Osaka Organic Chemical Industries, Ltd.]; Light acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.); NK ester AD-TMP, copper A-TMMT [above, all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; EBECRYL (registered trademark) 140, copper 1142, copper 180 (all above, manufactured by Daicel Allnex Co., Ltd.) and the like.

(3) 5-functional or higher (having 5 or more (meth)acryloyl groups)

As a compound which has 5 or more (meth)acryloyl groups, dipentaerythritol penta (meth)acrylate, dipentaerythritol hexa (meth)acrylate, tripentaerythritol octa (meth)acrylate, etc. are mentioned.

As the compound having five or more (meth)acryloyl groups, commercially available products can be suitably used, for example, Biscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.); NK ester A-9550, copper A-DPH [above, all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.]; And DPHA (manufactured by Daicel Allnex Co., Ltd.).

<bismaleimide>

The bismaleimide compound used as the component (B2) in the present invention is represented by the following formula (3).

[Formula 15]

In the formula, R ³³ is an organic group consisting of an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or a combination of a plurality of organic groups selected from the group. In addition, R ³³ may contain a bond such as an ester bond, an ether bond, an amide bond or a urethane bond.

Examples of such bismaleimide compounds include N,N'-3,3-diphenylmethanebismaleimide, N,N'-(3,3-diethyl-5,5-dimethyl)-4, 4-diphenyl-methanebismaleimide, N,N'-4,4-diphenylmethanebismaleimide, 3,3-diphenylsulfonebismaleimide, 4,4-diphenylsulfonebismaleimide, N, N'-p-benzophenone bismaleimide, N,N'-diphenylethane bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-(methylenedi-ditetrahydrophenyl)bis Maleimide, N,N'-(3-ethyl)-4,4-diphenylmethanebismaleimide, N,N'-(3,3-dimethyl)-4,4-diphenylmethanebismaleimide, N ,N'-(3,3-diethyl)-4,4-diphenylmethanebismaleimide, N,N'-(3,3-dichloro)-4,4-diphenylmethanebismaleimide, N, N'-isophorone bismaleimide, N,N'-tolidinebismaleimide, N,N'-diphenylpropanebismaleimide, N,N'-naphthalenebismaleimide, N,N'-m-phenyl Renbismaleimide, N,N'-5-methoxy-1,3-phenylenebismaleimide, 2,2-bis(4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis (3-chloro-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis( 3-ethyl-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-propyl-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3- Isopropyl-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-butyl-4-(4-maleimidephenoxy)phenyl)propane, 2,2-bis(3-me Methoxy-4-(4-maleimidephenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidephenoxy)phenyl)ethane, 1,1-bis(3-methyl-4-(4 -Maleimidephenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimidephenoxy)phenyl)ethane, 1,1-bis(3-bromo-4-(4- Maleimidephenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidephenoxy)phenyl)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-(4-maleimidephenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dime Yl-4-(4-maleimidephenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dibromo-4-(4 -Maleimidephenoxy)phenyl)propane, N,N'-ethylenedimaleimide, N,N'-hexamethylenebismaleimide, N,N'-dodecamethylenebismaleimide, N,N'-m- Xylenebismaleimide, N,N'-p-xylenebismaleimide, N,N'-1,3-bismethylenecyclohexanebismaleimide, N,N'-2,4-tolylenebismaleimide , N,N'-2,6-tolylene bismaleimide, and the like. These bismaleimide compounds are not particularly limited to those described above. These can be used alone or in combination of two or more components.

<(B2) Compound (polymer) having two or more Michael acceptor sites>

When the compound having two or more Michael acceptor sites is a polymer (polymer compound), the polymer (B2) includes a polymer compound having a side chain in which one or more terminals are polymerizable unsaturated bonds in the molecule.

As a polymer compound having a side chain in which such a terminal is a polymerizable unsaturated bond, a polymer compound having a (meth)acryloyl group in two or more side chains in the molecule is preferably mentioned.

As the polymer compound, a polymer compound containing a (meth)acryloyl group such as urethane acrylic, epoxy acrylic, or various (meth)acrylates, in particular, a polyfunctional polymer containing three or more of the (meth)acryloyl groups And compounds.

As a polymer compound having a (meth)acryloyl group, which is a preferable example, commercially available products can be suitably used, for example, 8KX-077, 8KX-078 copper, 8KX-089 copper, 8KX-127 copper, Copper 8KX-128, Copper 8KX-012C, Copper 8KX-014C, Copper 8KX-018C, Copper 8KX-052C, Copper 8KQ-2001, Copper 8BR-600, Copper 8UH-1006, Copper 8UH-1012 [above, all Taisei Fine Chemical Co., Ltd.; And SMP-220A, SMP-250A, SMP-360A, and SMP-550A (all of which are manufactured by Kyoeisha Chemical Co., Ltd.).

In addition, as the polymer (B2) having two or more Michael acceptor sites, the aforementioned method of introducing a (meth)acrylic group or a maleimide group into the precursors of the polymer (A2) and the polymer (B2) described later. By using it, the polymer which introduce|transduced the Michael acceptor site is mentioned.

On the other hand, when a liquid crystal alignment group is to be introduced into a polymer (B2) having two or more Michael acceptor sites, a liquid crystal alignment group is introduced into the precursors of the polymer (A2) and the polymer (B2) described below by the method described above, When preparing the precursors of the polymer (A2) and the polymer (B2), the monomer having the above-described liquid crystal alignment group may be copolymerized, and then the Michael acceptor site may be introduced by the above-described method.

<Precursor of polymer (A2) and polymer (B2)>

When a side chain (specific side chain) having a liquid crystal orientation group or a Michael addition reaction site or the like is introduced into a polymer, specific side groups that are easy to react with each other (or with respect to a specific compound) are placed and reacted to generate specific side chains. Can. In the reaction for generating this specific side chain, preferred combinations of specific functional groups and combinations of specific functional groups and specific compounds include carboxyl groups, epoxy groups, hydroxyl groups and isocyanate groups, phenolic hydroxyl groups and epoxy groups, carboxyl groups and isocyanate groups, amino groups It is a combination of isocyanate group, hydroxy group and acid chloride. As a more specific preferable example, a carboxyl group and glycidyl (meth)acrylate, and a hydroxy group and isocyanate ethyl (meth)acrylate are mentioned.

The polymer having a specific functional group (also referred to as a specific copolymer) is a copolymer obtained by polymerizing a monomer having a functional group (specific functional group) for reacting with a specific compound as an essential component, the number average molecular weight of which is 2,000 to 25,000 It is. In that case, the monomer which has a specific functional group to be used may be individual, and if a specific functional group does not react during polymerization, multiple types may be used together.

Below, the specific example of the monomer which has a specific functional group is given, but it is not limited to these.

As the monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl)phthalate, mono-(2-(methacryloyloxy)ethyl)phthalate , N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

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

As a monomer which has a hydroxyl group other than a phenolic hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, for example Acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monoacrylate, And diethylene glycol monomethacrylate.

2-aminoethyl acrylate, 2-aminomethyl methacrylate, etc. are mentioned as a monomer which has the amino group which has active hydrogen.

Examples of the monomer having an epoxy group include glycidyl methacrylate, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and allyl glyc Dilether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, and the like.

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

Moreover, in this invention, when obtaining a specific copolymer, besides the monomer which has a specific functional group, other monomer copolymerizable with this monomer can be used together.

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 other monomers are given, but the present invention is not limited thereto.

Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2,3-dihydroxy Propyl acrylate, diethylene glycol monoacrylate, caprolactone 2-(acryloyloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, 5-acryloyloxy-6-hydroxynorbornene-2- Carboxylic-6-lactone, acrylic acid, mono-(2-(acryloyloxy)ethyl)phthalate, glycidylacrylate, isopropylacrylate, benzylacrylate, naphthylacrylate, anthrylacrylate, Anthrylmethylacrylate, phenylacrylate, glycidylacrylate, 2,2,2-trifluoroethylacrylate, tert-butylacrylate, cyclohexylacrylate, isobornylacrylate, 2-methoxyethyl Acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl Acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecylacrylate, and 8-ethyl-8-tricyclodecylacrylate.

Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, diethylene glycol monomethacrylate, caprolactone2-(methacryloyloxy)ethyl ester, 5-methacryloyloxy-6-hydroxynorbornene-2 -Carboxylic-6-lactone, glycidyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate , Glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethylmethacrylate, tetrahydrofurfurylmethacrylate, 3-methoxybutylmethacrylate, 2-methyl-2-a Damanyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecylmethacrylate, and, 8-ethyl-8-tri And cyclodecyl methacrylate.

Examples of the acrylamide compound include acrylamide, methacrylamide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N- (Hydroxyphenyl)acrylamide, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth) )Acrylamide and the like. On the other hand, (meth)acrylamide means both acrylamide and methacrylamide.

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

As said styrene compound, styrene, methyl styrene, chlorostyrene, bromostyrene, etc. are mentioned, for example.

Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-(hydroxyphenyl)maleimide, N-(hydroxyphenyl)maleimide, and N-(carboxy Phenyl) maleimide, N-cyclohexyl maleimide, and the like.

When a liquid crystal alignment group is introduced into the (A2) component or the (B2) component (polymer), the amount of each monomer used to obtain a specific copolymer is 25 to 90 mol% of the liquid crystal alignment group based on the total amount of the total monomers. A monomer having a monomer having a group for introducing it, or a monomer having a 10 to 75 mol% Michael addition reaction site (Michael donor site, Michael acceptor site) or a monomer having a group for introducing it, 0 to 65 mol% specific It is preferable that it is other monomer which does not have a functional group. Or, it is preferably a monomer having a liquid crystal orientation group of 25 to 100 mol% and a Michael addition reaction site, and a monomer having no specific functional group of 0 to 75 mol%.

When the liquid crystal orientation group is not introduced into the (A2) component or the (B2) component (polymer), the amount of each monomer used to obtain the specific copolymer is based on the total amount of the total monomers, based on the total amount of 5 to 100 mol% of Michael It is preferably a monomer having a reaction site or a monomer having a group for introducing it, and other monomers having no specific functional groups of 0 to 95 mol%.

The method for obtaining a specific copolymer used in the present invention is not particularly limited, but, for example, in a solvent in which a monomer having a specific functional group and other monomers having no specific functional group and a polymerization initiator are coexisted, as necessary, 50 to 110 Obtained by polymerization at a temperature of ℃. In that case, the solvent used is not particularly limited as long as it dissolves a monomer having a specific functional group, a monomer not having a specific functional group, a polymerization initiator, and the like, if necessary. As a specific example, it describes in <solvent> mentioned later.

The specific copolymer obtained by the above method is usually in a 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, then dried at room temperature or under reduced pressure at room temperature or under reduced pressure, and then It can be made into a powder of a copolymer. By the above operation, the polymerization initiator coexisting with the specific copolymer and unreacted monomer can be removed, and as a result, a powder of the purified specific copolymer is obtained. When purification cannot be sufficiently performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.

In the present invention, the specific copolymer may be used in the form of a powder or in the form of a solution in which the purified powder is redissolved in a solvent described later.

The acrylic copolymer used as the component (A2) or component (B2) of the present invention can be, for example, a copolymer having a weight average molecular weight of 3,000 to 200,000, or a copolymer having a weight of 4,000 to 150,000, for example. And a copolymer of 5,000 to 100,000. If the weight average molecular weight of the copolymer is more than 200,000, the solubility in the solvent may be reduced and handling properties may be deteriorated. If the weight average molecular weight is less than 3,000, the curing becomes insufficient during heat curing. Solvent resistance and heat resistance may fall.

Moreover, as a precursor of (A2) component or (B2) component, the polymer other than the above which has multiple hydroxyl groups can be used.

Polyether polyols, which are preferable examples of polymers having a plurality of hydroxy groups, include polypropylene glycol, polypropylene glycol, polypropylene glycol, propylene glycol, bisphenol A, triethylene glycol, sorbitol, polypropylene glycol, polyethylene glycol, polypropylene glycol, and the like. What was added is mentioned. As a specific example of the polyether polyol, Adeka Polyether P series, G series, EDP series, BPX series, FC series, CM series manufactured by Adeka Co., Ltd., Uniox (registered trademark) HC-40 manufactured by Nichiyu Co., Ltd. , 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 LT-221, ST-221, OT-221 and the like.

As a polyester polyol which is a preferable example of a polymer having a plurality of hydroxy groups, diols such as ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, and polypropylene glycol are added to polycarboxylic acids such as adipic acid, sebacic acid, and isophthalic acid. And those reacted. As a specific example of the polyester polyol, DIC Co., Ltd. polylite (trademark) OD-X-286, OD-X-102, OD-X-355, OD-X-2330, OD-X-240, OD -X-668, OD-X-2108, OD-X-2376, OD-X-2044, OD-X-688, OD-X-2068, OD-X-2547, OD-X-2420, OD-X -2523, OD-X-2555, OD-X-2560, Polyol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, manufactured by Kuraray Co., Ltd. F-510, F-1010, F-2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 and the like.

As a polycaprolactone polyol which is a preferable example of a polymer having a plurality of hydroxy groups, those obtained by ring-opening polymerization of ε-caprolactone as a polyhydric alcohol such as trimethylolpropane or ethylene glycol are used as initiators. Specific examples of the polycaprolactone polyol include Polylite (registered trademark) OD-X-2155, OD-X-640, OD-X-2568 manufactured by DIC Corporation, and Proxel (registered trademark) 205 manufactured by Daicel Corporation. L205AL, 205U, 208, 210, 212, L212AL, 220, 230, 240, 303, 305, 308, 312, 320, 410 and the like.

As a polycarbonate polyol which is a preferable example of a polymer having a plurality of hydroxy groups, those obtained by reacting polyhydric alcohols such as trimethylolpropane and ethylene glycol with diethyl carbonate, diphenyl carbonate, and ethylene carbonate. Specific examples of the polycarbonate polyol are Proxel (registered trademark) CD205, CD205PL, CD210, CD220, manufactured by Daicel Co., Ltd., C-590, C-1050, C-2050, C-2090, C manufactured by Kuraray Co., Ltd. -3090.

As a preferred example of a polymer having a plurality of hydroxy groups, cellulose, such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyalkyl celluloses, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose, and the like. Hydroxyalkyl alkylcelluloses and celluloses, and the like, for example, hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose are preferred.

Cyclodextrins, which are preferred examples of a polymer having a plurality of hydroxy groups, include cyclodextrins such as α-cyclodextrin, β-cyclodextrin and γcyclodextrin, methyl-α-cyclodextrin, methyl-β-cyclodextrin and methyl-γ -Methylated cyclodextrins such as cyclodextrin, hydroxymethyl-α-cyclodextrin, hydroxymethyl-β-cyclodextrin, hydroxymethyl-γ-cyclodextrin, 2-hydroxyethyl-α-cyclodextrin, 2-hydroxy Hydroxyethyl-β-cyclodextrin, 2-hydroxyethyl-γ-cyclodextrin, 2-hydroxypropyl-α-cyclodextrin, 2-hydroxypropyl-β-cyclodextrin, 2-hydroxypropyl-γ-cyclo Dextrin, 3-hydroxypropyl-α-cyclodextrin, 3-hydroxypropyl-β-cyclodextrin, 3-hydroxypropyl-γ-cyclodextrin, 2,3-dihydroxypropyl-α-cyclodextrin, 2 And hydroxyalkyl cyclodextrins such as ,3-dihydroxypropyl-β-cyclodextrin and 2,3-dihydroxypropyl-γ-cyclodextrin.

As a urethane-modified acrylic polymer, which is a preferred example of a polymer having a plurality of hydroxy groups, as commercially available products, Accret (registered trademark) 8UA-017, 8UA-239, 8UA-239H, 8UA-140, manufactured by Daisei Fine Chemical Co., Ltd., And 8UA-146, 8UA-585H, 8UA-301, 8UA-318, 8UA-347A, 8UA-347H, and 8UA-366.

As a phenol novolak resin which is a preferable example of the polymer which has multiple hydroxyl groups, a phenol-formaldehyde polycondensate etc. are mentioned, for example.

The content of the component (B) in the case where the component (B) is contained (in the case where the component (A2) and the component (B2) described later is not the same compound) is 1 per 100 parts by mass of the component (A). It is a mass part to 2000 mass parts, for example, 5 mass parts to 2000 mass parts, preferably 15 mass parts to 700 mass parts, or 1 mass part to 400 mass parts.

<When (A) component and (B) component become the same compound>

In such a case, a combination of the above-described introduction methods may be used to introduce both the liquid crystal alignment group as well as both the Michael donor site and the Michael acceptor site, as necessary. As such a method, for example, (meth)acrylic acid may be reacted with a polymer obtained by copolymerizing a monomer having an active methylene group, a monomer having an epoxy group, and a monomer having a liquid crystal alignment group as necessary.

<(C)Michael addition reaction catalyst>

The cured film-forming composition of the present invention, in addition to the components (A) and (B), may further contain a Michael addition reaction catalyst that promotes the Michael addition reaction as the component (C).

The Michael addition reaction catalyst may be, for example, a basic compound represented below, but is not limited to these. Examples of the basic compound include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; Alkoxides of alkali metals such as sodium methoxide and potassium ethoxide; Quaternary ammonium hydroxides such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide; Quaternary ammonium carbonates such as tetrabutyl ammonium carbonate, benzyl trimethyl ammonium carbonate, triethyl monomethyl ammonium 2-ethyl hexanoate, and tetrabutyl ammonium acetate; Quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; Quaternary ammonium tetrahydroborate, such as tetrabutylammonium tetrahydroborate and benzyl trimethylammonium tetrahydroborate; Tertiary amines such as tetramethylguanidine, 1,8-diazabicyclo[5,4,0]undecene-7 and diazabicyclo[4,3,0]nonen-5; And tertiary phosphine such as guanidine, azine, and triphenylphosphine.

An acidic compound may be added together with the Michael addition reaction catalyst for the purpose of further increasing the storage stability during storage. In particular, in the case of using a strongly basic compound having a high catalytic activity, the addition of an acidic compound is effective to increase storage stability. Examples of the acidic compound include low boiling point carboxylic acids such as acetic acid, formic acid and propionic acid, and high boiling point carboxylic acids such as monochloroacetic acid and octanoic acid.

As the component (C), from the viewpoint of reactivity and storage stability, quaternary ammonium carbonate, quaternary ammonium hydroxide, and tertiary amine are more preferable.

The content in the case where the component (C) in the cured film-forming composition of the present invention is contained is preferably 0.01 parts by mass to 20 parts by mass based on 100 parts by mass of the total of the components (A) and (B), More preferably, it is 0.1 mass part-15 mass parts, More preferably, it is 0.5 mass part-10 mass parts. (C) When content of a component is 0.01 mass part or more, sufficient thermosetting property and solvent resistance can be provided. However, when more than 20 parts by mass, the storage stability of the composition may be lowered.

<solvent>

The cured film-forming composition of the present invention is mainly used in a solution state dissolved in a solvent. The solvent used at that time may dissolve (A) component, (B) component, and (C) component as necessary, and other additives described later as necessary, and the type, structure, etc. are particularly limited. It does not become.

As specific examples of the solvent, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-methyl-1-butanol, n-pentanol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene 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, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentane On, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy 3-methyl methylbutanoate, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 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.

For example, when using the cured film-forming composition of the present invention to form a cured film on a resin film to prepare an alignment material, methanol, ethanol, n-propanol, isopropanol in that the resin film is a solvent exhibiting resistance. , n-butanol, 2-methyl-1-butanol, 2-heptanone, isobutyl methyl ketone, diethylene glycol, propylene glycol, propylene glycol monomethyl ether, cyclopentyl methyl ether, propylene glycol monomethyl ether acetate, ethyl acetate It is preferable to use butyl acetate or the like.

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

<Other additives>

Furthermore, the cured film-forming composition of the present invention, as long as it does not impair the effects of the present invention, if necessary, adhesion enhancer, silane coupling agent, surfactant, rheology modifier, pigment, dye, preservative stabilizer, antifoaming agent, Antioxidants, inorganic oxide particles, and the like.

<Preparation of cured film-forming composition>

The cured film-forming composition of the present invention includes (A) a component having a Michael donor site, (B) a component having a Michael acceptor site, and (C) a Michael addition reaction catalyst of the component, and further effects of the present invention. It is a composition that can contain other additives as long as it does not damage the. And usually, they are used in the form of a solution dissolved in a solvent.

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

[1]: 0.01 mass per 100 parts by mass of the total of (A) component and (B) component, containing the compound having the Michael donor portion of the component (A) and the Michael acceptor portion of the component (B) Cured film-forming composition containing from 20 parts by mass (C) component and a solvent.

When using the cured film-forming composition of the present invention as a solution, the blending ratio, preparation method, and the like are detailed below.

The ratio of the solid content in the cured film-forming composition of the present invention is not particularly limited as long as each component is uniformly dissolved in a solvent, but is 1% by mass to 60% by mass, preferably 2% by mass to 50% by mass It is mass %, More preferably, it is 2 mass%-20 mass %. Here, solid content means the thing remove|excluding the solvent from the whole component of a cured film formation composition.

The method for preparing the cured film-forming composition of the present invention is not particularly limited. As a preparation method, the (B) component and (C) component are mixed with the solution of the (A) component dissolved in the solvent at a predetermined ratio, and it is set as a uniform solution, or the appropriate steps of this preparation method are mentioned, for example. In, the method of mixing by adding another additive as needed is mentioned.

In the preparation of the cured film-forming composition of the present invention, a solution of a specific copolymer (polymer) obtained by polymerization in a solvent can be used as it is. In this case, for example, (A) component or (B) component and (C) component are put into the solution of the polymer of (A) component or (B) component, and it is set as a uniform solution. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the process of producing the polymer of the component (A) or the component (B) may be the same as or different from the solvent used to adjust the concentration of the cured film-forming composition.

In addition, it is preferable to use the solution of the prepared cured film-forming composition after filtration using a filter having a pore diameter of about 0.2 µm or the like.

<Cured film, alignment material and retardation material>

The solution of the cured film-forming composition of the present invention is a substrate (for example, a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, glass substrate, quartz substrate) , ITO substrate, etc.) or film substrate (for example, triacetyl cellulose (TAC) film, polycarbonate (PC) film, cycloolefin polymer (COP) film, cycloolefin copolymer (COC) film, polyethylene terephthalate (PET) ) Film, acrylic film, resin film such as polyethylene film), etc., coated with bar coat, rotating coating, spill coating, roll coating, slit coating, slit rotating coating, inkjet coating, printing, etc. to form a coating film. , After that, by heating and drying with a hot plate or an oven, a cured film can be formed. This cured film can be applied as an alignment material as it is.

Under the conditions of heating and drying, the crosslinking reaction by the crosslinking agent may be carried out so that the components of the cured film (orientation material) do not elute in the polymerizable liquid crystal solution applied thereon, for example, the temperature is 60°C to 200 A heating temperature and heating time appropriately selected from the range of ℃ and time from 0.4 minutes to 60 minutes are employed. The heating temperature and the heating time are preferably 70°C to 160°C and 0.5 minutes to 10 minutes.

The film thickness of the cured film (orientation material) formed using the curable composition of the present invention is, for example, 0.05 μm to 5 μm, and can be appropriately selected in consideration of the step difference, optical and electrical properties of the substrate to be used.

Since the alignment material formed from the cured film composition of the present invention has solvent resistance and heat resistance, it is possible to apply a phase difference material such as a polymerizable liquid crystal solution having vertical alignment on the alignment material and to align the alignment material. Then, by curing the retardation material in the aligned state as it is, a retardation material can be formed as a layer having optical anisotropy. In addition, when the substrate forming the alignment material is a film, it is useful as a retardation film.

Further, using two substrates having the alignment material of the present invention formed as described above, the alignment materials on both substrates are bonded to each other via spacers, and then liquid crystals are injected between the substrates to form liquid crystals. This oriented liquid crystal display element can also be used.

As described above, the cured film-forming composition of the present invention can be suitably used for the production of various phase difference materials (phase difference films), liquid crystal display devices, and the like.

Example

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

[Weak symbols used in Examples]

The meaning of the symbol used in the following examples is as follows.

<raw material>

GMA: glycidyl methacrylate

M100: 3,4-epoxycyclohexylmethylmethacrylate

EGAMA: Ethylene glycol monoacetoacetate monomethacrylate

LA: lauryl acrylate

HA: Hexyl acrylate

AIBN: α,α’-azobisisobutyronitrile

CIN1:

[Formula 16]

CIN2:

[Formula 17]

CIN3:

[Formula 18]

CIN4:

[Formula 19]

CIN5: (mixture of isomers below)

[Formula 20]

CIN6: (mixture of isomers below)

[Formula 21]

CIN7:

[Formula 22]

CIN8:

[Formula 23]

CIN9:

[Formula 24]

<A2 component>

TMPI: 1,3,5-tris(3-mercaptopropionyloxyethyl)-isocyanurate

[Formula 25]

TMBI: 1,3,5-tris(3-mercaptobutyryloxyethyl)-isocyanurate

[Formula 26]

<B2 ingredient>

DPHA: Dipentaerythritol hexaacrylate [A-DPH (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)]

UA: Urethane acrylate [UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.)]

SMP: Acrylic group-containing acrylic polymer [SMP-220A (manufactured by Kyoeisha Chemical Co., Ltd.)]

<C component>

UCAT: triethyl monomethylammonium 2-ethyl hexanoate [U-CAT18X (manufactured by Afro Corporation)]

TBAAc: Tetrabutylammonium Acetate

TBAH: tetrabutylammonium hydroxide

DBU: 1,8-diazabicyclo[5.4.0]-7-undecene

<Other ingredients (D ingredient)>

PGM-AC: Organosilica sol [PGM-AC-2140Z (manufactured by Nissan Chemical Industries, Ltd.)]

<solvent>

Each composition of Examples and Comparative Examples contained a solvent, and as the solvent, propylene glycol monomethyl ether (PM), propylene glycol monomethyl ether acetate (PMA), butyl acetate (BA), and ethyl acetate (EA) were used. .

<Measurement of molecular weight of polymer>

The molecular weight of the acrylic copolymer in the polymerization example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd., and columns (KD-803, KD-805) manufactured by Shodex. Was measured.

On the other hand, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene conversion values.

Column temperature: 40℃

Eluent: Tetrahydrofuran

Flow rate: 1.0 mL/min

Standard sample for calibration calibration: Standard polystyrene manufactured by Showa Denko Corporation (molecular weights about 197,000, 55,100, 12,800, 3,950, 1,260, 580).

<Synthesis of raw materials>

<Synthesis Example 1> Synthesis of CIN3

8.3 g of GMA, 20.7 g of 4-methoxy cinnamic acid, 0.2 g of dibutylhydroxytoluene, 0.3 g of triphenylethylphosphonium bromide, and 80 mL of 1.4-dioxane were mixed and heated at 90°C for 3 days. After completion of the reaction, 1.4-dioxane was distilled off under reduced pressure, and 150 mL of ethyl acetate was added to filter the insoluble matter, and then 100 mL of sodium bicarbonate water was added and washed 3 times to remove excess methoxy cinnamic acid. Ethyl acetate was distilled off under reduced pressure to obtain 16.5 g of the target product, CIN3.

<Synthesis Example 2> Synthesis of acetyl meldrum acid

After dissolving 18.3 g of meldrum acid and 20.0 g of pyridine in 150 mL of chloroform, the mixture was cooled to -20°C, and 13.5 g of acetyl chloride was added dropwise. After slowly heating up to room temperature, the reaction was performed for 20 hours. 40 mL of 2N hydrochloric acid and 150 mL of water were added, extracted and concentrated with a separatory funnel to obtain an orange solid. 100 mL of chloroform was added and bottom cut with a silica gel (neutral) short column and solvent distillation to obtain 20.5 g of acetyl meldrum acid shown below.

[Formula 27]

<Synthesis Example 3> Synthesis of CIN4

16.3 g of CIN3, 9.5 g of acetyl meldrum acid obtained in Synthesis Example 2 was dissolved in 80 mL of 1.4-dioxane, and heated at 80°C for 1 hour. CIN4 20.4g was obtained by distilling off 1.4-dioxane under reduced pressure.

<Synthesis Example 4> Synthesis of CIN5

4.9 g of M100, 8.9 g of 4-methoxy cinnamic acid, 0.1 g of dibutylhydroxytoluene, 0.18 g of triphenylethylphosphonium bromide, and 40 mL of 1.4-dioxane were heated at 90°C for 3 days. After completion of the reaction, 1.4-dioxane was distilled off under reduced pressure, 100 mL of ethyl acetate was added, the insoluble matter was filtered off, and then 100 mL of sodium bicarbonate was added and washed three times. Ethyl acetate was distilled off under reduced pressure to obtain 6.3 g of the target product, CIN5.

<Synthesis Example 5> Synthesis of CIN6

CIN5 5.0g, 2.4 g of acetylmeldrum acid obtained in Synthesis Example 2 was dissolved in 40 mL of 1.4-dioxane, and heated at 80°C for 1 hour. 7.1 g of dioxane was distilled off under reduced pressure to obtain 7.1 g of CIN6.

<Synthesis of A1 component>

<Synthesis Example 6> Synthesis of CIN8

5.0 g of CIN7, 3.3 g of acetylmeldrum acid obtained in Synthesis Example 2 were dissolved in 40 mL of 1.4-dioxane, and heated at 80°C for 1 hour. CIN8 8.0g was obtained by distilling off 1.4-dioxane under reduced pressure.

<Synthesis of A2 component>

<Synthesis Example 7>

CIN1 10.0g, EGAMA 4.3g, AIBN 0.43g as a polymerization catalyst was dissolved in 132.4g of PM, and reacted at 90°C for 20 hours to obtain an acrylic copolymer (A2-1) having an acetoacetyl group in the side chain. A solution containing 10% by mass was obtained. Mn of the obtained acrylic copolymer was 12,000, and Mw was 23,000.

<Synthesis Example 8>

A solution containing 10% by mass of acrylic copolymer (A2-2) having acetoacetyl group in the side chain by dissolving 10.0 g of CIN2, 2.5 g of EGAMA, 0.38 g of AIBN as a polymerization catalyst in 115.9 g of PM, and reacting at 80°C for 20 hours. Got Mn of the obtained acrylic copolymer was 18,000 and Mw was 35,000.

<Synthesis Example 9>

A solution containing 20% by mass of an acrylic copolymer (A2-3) having acetoacetyl groups in a side chain was obtained by dissolving 15.0 g of CIN4 and 0.3 g of AIBN as a polymerization catalyst in PM 61.2 g and reacting at 80°C for 20 hours. Mn of the obtained acrylic copolymer was 17,000, and Mw was 32,000.

<Synthesis Example 10>

A solution containing 20% by mass of an acrylic copolymer (A2-4) having acetoacetyl groups in the side chain was obtained by dissolving 15.0 g of CIN6 and 0.3 g of AIBN as a polymerization catalyst in PM 61.2 g and reacting at 80°C for 20 hours. Mn of the obtained acrylic copolymer was 23,000 and Mw was 40,000.

<Synthesis Example 11>

A compound having acetoacetyl group (A2) by dissolving 10.0 g of Fracel 410 (polycaprolactone tetraol manufactured by Daicel Co., Ltd.) and 6.3 g of acetacetic acid tert-butyl in 38.1 g of PMA and reacting at 130°C for 10 hours. -5) to obtain a solution containing 30% by mass.

<Synthesis Example 12>

EGAMA 8.0g, AIBN 0.3g as a polymerization catalyst was dissolved in 33.2g of PM and reacted at 80°C for 20 hours to obtain a solution containing 20% by mass of an acrylic copolymer (A2-6) having an acetoacetyl group in the side chain. Mn of the obtained acrylic copolymer was 10,000, and Mw was 22,000.

<Synthesis Example 13>

CIN3 10.0g, EGAMA 4.3g, AIBN 0.4g as a polymerization catalyst dissolved in PM 58.9g, and reacted at 80°C for 20 hours to contain 20% by mass of an acrylic copolymer (A2-7) having acetoacetyl groups in the side chains Got Mn of the obtained acrylic copolymer was 17,000, and Mw was 32,000.

<Synthesis Example 14>

CIN1 10.0g, EGAMA 3.3g, GMA 3.3g, AIBN 0.5g as a polymerization catalyst was dissolved in PM 68.7g, and reacted at 90°C for 20 hours to obtain an acrylic copolymer solution having acetoacetyl groups in the side chains. Next, acrylic acid was introduced into the side chain of the acrylic copolymer by adding 2.0 g of acrylic acid, 0.1 g of triphenylethylphosphonium bromide, and 0.2 g of dibutylhydroxytoluene, and reacting at 100°C for 18 hours. Then, by reprecipitation with hexane, an acrylic copolymer (A2-8) having an acetoacetyl group and an acrylic group in the side chain was obtained. Mn of the obtained acrylic copolymer was 23,000 and Mw was 42,000.

<Synthesis of B2 component>

<Synthesis Example 15>

An acrylic copolymer solution was obtained by dissolving 8.0 g of CIN1, 3.4 g of GMA, and 0.3 g of AIBN as a polymerization catalyst in 27.5 g of PM and reacting at 90°C for 20 hours. Next, acrylic acid was introduced into the side chain of the acrylic copolymer by adding 1.7 g of acrylic acid, 0.1 g of triphenylethylphosphonium bromide, and 0.2 g of dibutylhydroxytoluene, and reacting at 100°C for 18 hours. Then, by reprecipitation with hexane, an acrylic copolymer (B2-1) having an acrylic group in a side chain was obtained. Mn of the obtained acrylic copolymer was 12,000, and Mw was 32,000.

<Example 1>

(A-1) The amount equivalent to 100 parts by mass in terms of the acrylic copolymer (A2-1) (solid content) of a solution containing 10% by mass of the acrylic copolymer (A2-1) obtained in Synthesis Example 7 as a component. , (B) 30 parts by mass of DPHA as a component, and 3 parts by mass of UCAT as a component (C), PM and PMA are added thereto, and the solvent composition is PM:PMA = 80:20 (mass ratio), and the solid content concentration is 5.0. An orientation reforming composition (A-1) having a mass% was prepared.

<Examples 2 to 25 and Comparative Examples 1 to 4>

Alignment-reforming compositions A-2 to A-29 were respectively prepared in the same manner as in Example 1, except that the types and amounts of each component were as described in Table 1, respectively ((A) to ( D) All components are converted to solids).

[Table 1]

<Example 26>

[Evaluation of orientation]

The alignment reforming composition A-1 obtained in Example 1 was coated on a TAC film with a Wet film thickness of 4 μm using a bar coater. At a temperature of 110° C. for 2 minutes, heat-drying was performed in a heat-circulating oven to form a cured film on the TAC film. Each of the cured films was irradiated vertically with a linear polarization of 313 nm at an exposure amount of 20 mJ/cm ² to form an alignment material. On the alignment material on the TAC film, a polymerizable liquid crystal solution RMS03-013c (manufactured by Merck Corporation) was coated with a Wet film thickness of 6 μm using a bar coater. The coating film was heated and dried for 2 minutes on a hot plate set at a temperature of 65°C, and then exposed at 300 mJ/cm ² to prepare a phase difference material. The phase difference material on the produced substrate was sandwiched between a pair of polarizing plates, and the phase difference characteristics were observed in the phase difference material, where the phase difference was expressed without defects, and the phase difference was not expressed as ×. It described in the column of "orientation property" of 2.

<Examples 27 to 50 and Comparative Examples 5 to 8>

A retardation material was prepared in the same manner as in Example 26, except that the alignment material-forming composition and the heating temperature and heating time in the thermal cycle oven were as described in Table 2, respectively, to evaluate orientation. The evaluation results are summarized in Table 2 later.

[Table 2]

In Examples 26 to 50, a retardation material exhibiting good orientation by firing at a low temperature for a short time could be produced.

On the other hand, in Comparative Examples 5-8, the phase difference material which showed favorable orientation by baking at a low temperature for a short time could not be produced.

[Evaluation of adhesion]

<Examples 51-53>

In the retardation material on the film prepared in Examples 48 to 50, sheaths were placed with a cutter knife so as to be 10×10 squares with a 1 mm vertical and horizontal gap. A cellophane tape peeling test was conducted on this sheath using a Scotch (registered trademark) tape. After peeling off the tape, all of the 100 spaces were peeled off, and the ones peeled off were evaluated as ×. About the evaluation result, it shows collectively in the column of "initial" in Table 3 mentioned later.

[Evaluation of durability adhesion]

The retardation material produced in the same manner as in the evaluation of adhesion described above was placed in an oven set at a temperature of 80°C and a humidity of 90%, and left standing for 200 hours or more. Thereafter, the retardation material was taken out, and the adhesion was evaluated in the same manner as in the evaluation of the adhesion described above. About the evaluation result, it shows collectively in the column of "durability" in Table 3 mentioned later.

[Table 3]

From Examples 51 to 53, the produced retardation materials exhibited good adhesion with excellent durability.

<Synthesis of (A) component>

<Synthesis Example 16>

A solution containing 30% by mass of acrylic copolymer (A2-9) was obtained by dissolving 14.1 g of LA, 7.2 g of EGAMA, and 0.68 g of AIBN as a polymerization catalyst in 107.0 g of PM and reacting at 80°C for 16 hours. Mn of the obtained acrylic copolymer was 13,300 and Mw was 27,800.

<Synthesis Example 17>

A solution containing 30% by mass of acrylic copolymer (A2-10) was obtained by dissolving 14.1 g of HA, 7.2 g of EGAMA, and 0.68 g of AIBN as a polymerization catalyst in 107.0 g of PM and reacting at 80°C for 16 hours. Mn of the obtained acrylic copolymer was 13,300 and Mw was 27,800.

<Examples 54 to 57 and Comparative Examples 9 to 10>

Alignment-reforming compositions A-30 to A-35 were each prepared in the same manner as in Example 1, except that the types and amounts of each component were as described in Table 4, respectively ((A) to ( D) All components are converted to solids).

[Table 4]

<Example 58>

[Evaluation of vertical orientation]

The alignment reforming composition A-30 obtained in Example 54 was coated on a TAC film with a Wet film thickness of 4 μm using a bar coater. Heat-drying was performed in a thermocycle oven for 2 minutes at a temperature of 120°C to form an alignment material on the TAC film. On the alignment material on the TAC film, a polymerizable liquid crystal solution RMS03-015 (manufactured by Merck Co., Ltd.) was coated with a Wet film thickness of 6 μm using a bar coater. The coating film was heated and dried for 2 minutes on a hot plate set at a temperature of 65°C, and then exposed at 300 mJ/cm ² to prepare a phase difference material. The produced phase difference material was measured for dependence on the angle of incidence of the in-plane phase difference using a retardation measuring device RETS100 manufactured by Otsuka Electronics Co., Ltd. It was judged that the in-plane phase difference value at 0 degrees of incidence angle was 0, and the in-plane phase phase difference at ±50 degrees of incidence angle was in the range of 38±5 nm. The evaluation results are listed in the column of "Vertical orientation" in Table 5.

<Examples 59 to 61 and Comparative Examples 11 to 12>

A retardation material was produced in the same manner as in Example 58, except that the alignment material-forming composition was as described in Table 5, respectively, and vertical alignment properties were evaluated. The evaluation results are summarized in Table 5 later.

[Table 5]

In Examples 58 to 61, a retardation material exhibiting good vertical orientation by firing at a low temperature for a short time could be produced.

On the other hand, in Comparative Examples 11 to 12, a retardation material exhibiting good orientation by firing at a low temperature for a short time could not be produced.

Industrial availability

The cured film forming composition according to the present invention is very useful as a material for forming 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, in particular, IPS- It is suitable as a material for retardation of circular polarizing plates used as anti-reflection films for LCDs and organic EL displays.

Claims (11)

(A) As a component, a compound containing a Michael donor site,
(B) As a component, the compound containing the Michael acceptor site is included,
At least one of (A) component and (B) component contains a liquid crystal orientation group,
Cured film forming composition. According to claim 1,
Component (A) and component (B) are the same compound containing a Michael donor site, a Michael acceptor site and a liquid crystal alignment group,
Cured film forming composition. The method according to claim 1 or 2,
(A) At least one component selected from a compound (A2) having one Michael donor site, a low-molecular compound (A1) having a liquid crystal alignment group, and two or more Michael donor sites, and containing or containing a liquid crystal alignment group. Type 1,
(B) As a component, it is selected from the compound (B2) which has one Michael acceptor site, a low molecular compound (B1) having a liquid crystal orientation group, and two or more Michael acceptor sites and does not contain or contains a liquid crystal orientation group. It contains at least one kind,
(A2) component and (B2) component may be a low molecular compound or a high molecular compound,
Cured film forming composition. The method according to any one of claims 1 to 3,
(A) The cured film forming composition, wherein the Michael donor site of the component is an active methylene group or an active methine group. The method according to any one of claims 1 to 4,
(C) A cured film-forming composition further containing a Michael addition reaction catalyst. The method according to any one of claims 1 to 5,
Cured film forming composition, wherein the Michael acceptor site is an acrylic group. The method according to any one of claims 1 to 6,
(A) Cured film forming composition containing 1 mass part-2,000 mass parts (B) component with respect to 100 mass parts of component. The method according to any one of claims 5 to 7,
Cured film forming composition containing 0.01 mass part-20 mass parts (C) component with respect to 100 mass parts of (A) component and (B) component in total. The cured film obtained using the cured film forming composition in any one of Claims 1-8. An alignment material obtained by using the cured film-forming composition according to any one of claims 1 to 8. A retardation material formed using the alignment material according to claim 10.