CN102863967B - Photoreactivity aligning agent for liquid crystal, and liquid crystal aligning element and manufacture method thereof - Google Patents

Abstract

Provided are a novel photoreactive liquid crystal aligning agent, and a liquid crystal display element having a photoalignment layer formed from the photoreactive liquid crystal aligning agent. Formula (1? 1) [In the formula (1-1), Y ¹ and Y ² represent an oxygen atom or the like. R ² and R ⁴ represent an alkoxy group having 1 to 2 carbon atoms or the like. p, q, and r represent the mole fraction of each structural unit relative to the total structural units, and satisfy the relationships of 0.25<p≦1, 0≦q<0.75, and 0≦r<0.75. ] provide a photoreactive liquid crystal aligning agent containing the polymer, an alignment layer formed from the photoreactive liquid crystal aligning agent, and a liquid crystal display element having the photoalignment layer.

Description

Photoreactive liquid crystal aligning agent, and liquid crystal aligning element and manufacturing method thereof

technical field

The invention relates to a photoreactive liquid crystal alignment agent, a liquid crystal alignment element and a manufacturing method thereof.

Background technique

In a flat panel display (FPD), an optically anisotropic layer (orientation layer) having optical anisotropy such as a polarizing plate and a retardation plate is included as a member. Such an optically anisotropic layer is generally formed by two methods. Among the methods, the first is a method of stretching a polymer to form an optically anisotropic layer, and the second is a method of forming an optically anisotropic layer from a coating film obtained by coating an alignment agent.

Especially the latter method, because the optical axis direction of the optical anisotropic layer formed by the alignment agent is easy to control, and the optical film formed by aligning and immobilizing the liquid crystal compound on the optical anisotropic layer (liquid crystal alignment element) It is advantageous in that it is a film in nature and can be produced continuously by a roll-to-roll (Roll to Roll) process.

For example, in Non-Patent Document 1, it is described that after applying a solution containing a polymerizable liquid crystal compound represented by the following formula (trade name: LC242, manufactured by BASF Corporation) on an alignment layer, the polymerizable liquid crystal compound is polymerized to obtain polarization. The manufacturing method of an optical layer obtains a liquid crystal alignment element by this manufacturing method. However, a photo-alignment layer having alignment ability in which the polymerizable liquid crystal compound becomes a polymerizable liquid crystal in a nematic phase or a higher-order smectic phase, and a photo-alignment agent capable of forming the photo-alignment layer are not known.

prior art literature

non-patent literature

Non-Patent Document 1

Cordula Mock-Knoblauch, Olivier S. Enger, Ulrich D. Schalkowsky, "L-7 Novel Polymerisable Liquid Crystalline Acrylates for the Manufacturing of Ultrathin Optical Films", SID Symposium Digest of Technical Papers, 2006, Vol. 37, p.1673

Contents of the invention

Problems to be solved by the present invention

A photo-alignment layer capable of aligning a polymeric liquid crystal that forms a nematic phase and a higher-order smectic phase from a polymerizable liquid crystal compound, and a new type of photo-alignment agent (photoreactive liquid crystal alignment agent) that can form the photo-alignment layer ) is expected.

Solution to the problem

The present invention consists of the following [1] to [12].

[1] A photoreactive liquid crystal aligning agent containing a polymer represented by formula (1-1).

[In formula (1-1),

n and m each independently represent 0 or 1.

v and w each independently represent the integer of 1-3.

S ¹ and S ² each independently represent an alkylene group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.

S ³ represents an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.

^Y1 and ^Y2 each independently represent a single bond, an oxygen atom or a carbonyloxy group.

R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

R ² and R ⁴ each independently represent an alkoxy group, a cyano group or a halogen atom with 1 to 2 carbon atoms, when v is 2 or 3, there are multiple R ² that are the same or different, and when w is 2 or 3 When, there are multiple R ⁴ that are the same or different.

R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group.

p, q, and r represent the mole fraction of each structural unit relative to the total structural units, and satisfy the relationships of 0.25<p≦1, 0≦q<0.75, and 0≦r<0.75. ]

[2] The photoreactive liquid crystal aligning agent as described in said [1] whose said polymer is a polymer whose q in said formula (1-1) is 0.

[3] The photoreactive liquid crystal aligning agent according to the above [1] or [2], wherein the polymer is a polymer in which r in the formula (1-1) is 0.

[4] The photoreactive liquid crystal aligning agent according to any one of the above-mentioned [1] to [3], wherein the above-mentioned polymer is such that R ¹ and R ² in the above-mentioned formula (1-1) are each independently a methoxy group or ethoxylated polymers.

[5] The photoreactive liquid crystal aligning agent according to any one of the above [1] to [4], wherein the polymer is a polymer in which both n and m in the formula (1-1) are 0.

[6] A liquid crystal alignment layer formed by forming a coating film from the photoreactive liquid crystal aligning agent according to any one of the above [1] to [5] and irradiating the coating film with polarized light.

[7] A liquid crystal alignment element comprising the liquid crystal alignment layer and the polarizing layer described in [6] above,

The above-mentioned polarizing layer is a coating film obtained by coating a composition solution containing a polymerizable liquid crystal compound on the above-mentioned liquid crystal alignment layer,

The above-mentioned polymerizable liquid crystal compound contained in the above-mentioned coating film is irradiated with polarized light and polymerized.

[8] The liquid crystal aligning device according to the above [7], wherein the polymerizable liquid crystal compound is a compound exhibiting a smectic liquid crystal state.

[9] The liquid crystal aligning device according to the above [7], wherein the polymerizable liquid crystal compound is a compound exhibiting a high-order smectic liquid crystal state.

[10] The liquid crystal aligning device according to the above [7], wherein the polymerizable liquid crystal compound is a compound that directly assumes a nematic liquid crystal state from an isotropic liquid crystal state.

[11] The liquid crystal aligning device according to the above [10], wherein the polymerizable liquid crystal compound is represented by formula (2).

[In formula (2),

Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group, or a substituted or unsubstituted polycyclic aromatic heterocyclic group.

D1 and ^D2 each independently represent ^a single bond or a divalent linking group.

^G1 and G2 each independently represent a divalent alicyclic hydrocarbon group, and the ^hydrogen atom contained in the alicyclic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 4 carbon atoms, or a fluorine group with 1 to 4 carbon atoms. Substituted by an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and -CH ₂ - constituting the alicyclic hydrocarbon group may be replaced by -O-, -S- or -NH-.

E ¹ and E ² each independently represent a single bond or a divalent linking group.

B ¹ and B ² each independently represent a single bond or a divalent linking group.

A1 and A2 each independently represent ^a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the ^hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group can be replaced by a halogen atom, a carbon number of 1 to 4 Substituted by an alkyl group, an alkoxy group with 1 to 4 carbon atoms, a cyano group or a nitro group. Hydrogen atoms contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with fluorine atoms.

k and l each independently represent the integer of 0-3. When k is 2 or more, a plurality of A ^1s are the same or different from each other, and a plurality of B ^1s are the same or different from each other. When l is ² or more, a plurality of A2s are the same or different from each other, and a plurality of ^B2s are the same or different from each other.

F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted by an alkoxy group or a halogen atom having 1 to 5 carbon atoms to form the alkylene group. The radical -CH ₂ - may be replaced by -O- or -CO-.

Although P1 and P2 each independently represent ^{a hydrogen} atom, an acryloyloxy group or ^a methacryloyloxy group, P1 and P2 cannot be a ^hydrogen atom at the same time. ]

[12] A compound represented by formula (1-3).

[In formula (1-3),

n represents 0 or 1. v represents an integer of 1-3.

S ¹ represents an alkylene group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.

X1 and ^X3 each independently represent ^a single bond, an oxygen atom, a carbonyloxy group or a methylene group.

Y ¹ represents a single bond, an oxygen atom or a carbonyloxy group.

R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

R ² represents an alkoxy group with 1 to 2 carbon atoms, a cyano group, or a halogen atom, and when v is 2 or 3, there are multiple R ² that are the same or different.

R ⁵ represents a hydrogen atom or a methyl group. ]

Invention effect

According to the photoreactive liquid crystal aligning agent of this invention, the photo-alignment layer which has orientation ability in which a polymeric liquid crystal compound becomes a nematic phase and a smectic phase polymeric liquid crystal of a higher order can be formed.

detailed description

＜Photoreactive liquid crystal aligning agent＞

The photoreactive liquid crystal aligning agent of this invention is a photoreactive liquid crystal aligning agent containing the polymer represented by formula (1-1) (it may be called "polymer (1-1)" hereafter.).

In formula (1-1),

n and m each independently represent 0 or 1.

v and w each independently represent the integer of 1-3.

S ¹ and S ² each independently represent an alkylene group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.

S ³ represents an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.

^Y1 and ^Y2 each independently represent a single bond, an oxygen atom or a carbonyloxy group.

R ¹ and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

R ² and R ⁴ each independently represent an alkoxy group, a cyano group or a halogen atom with 1 to 2 carbon atoms, when v is 2 or 3, there are multiple R ² that are the same or different, and when w is 2 or 3 When, there are multiple R ⁴ that are the same or different.

R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a methyl group.

p, q, and r represent the mole fraction of each structural unit relative to the total structural units, and satisfy the relationships of 0.25<p≦1, 0≦q<0.75, and 0≦r<0.75.

In the above formula (1-1), the dotted line connecting each structural unit indicates that the copolymerization form of each structural unit is not particularly limited, and is random copolymerization, block copolymerization, alternating copolymerization and combinations thereof.

An alkylene group having ¹ to 12 carbon atoms that may have a fluorine atom or ^a cyano group in S1 and S2 means that the alkylene group or a part of the hydrogen atoms contained in the alkylene group is replaced by a fluorine atom and/or a cyano group substituted groups. Such an alkylene group may be linear or branched. S ¹ and S ² are preferably unsubstituted (without fluorine atoms and cyano groups), and straight-chain alkylene groups having 1 to 12 carbon atoms, more preferably alkylene groups having 2 to 11 carbon atoms, particularly preferably alkylene groups Ethyl, butylene, hexylene and undecylene.

The alkyl group having ¹ to 12 carbon atoms which may have a fluorine atom or a cyano group in S3 refers to an alkyl group or a group in which a part of hydrogen atoms contained in the alkyl group is substituted with a fluorine atom and/or a cyano group. Such an alkyl group may be linear or branched. S3 is preferably an unsubstituted (without a fluorine atom or a cyano group), and a linear alkyl group with ¹ to 12 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, or a decyl group. base, undecyl and dodecyl.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ are preferably each independently a single bond or a carbonyloxy group, particularly preferably a carbonyloxy group.

Y ¹ and Y ² are preferably each independently an oxygen atom or a carbonyloxy group, particularly preferably an oxygen atom.

R ¹ and R ³ are more preferably each independently a hydrogen atom, a methyl group and a methoxy group, particularly preferably a hydrogen atom.

R ² and R ⁴ are preferably each independently a methoxy group, an ethoxy group, a cyano group or a fluorine atom, more preferably a methoxy group or an ethoxy group, particularly preferably a methoxy group.

R ⁵ , R ⁶ and R ⁷ are particularly preferably methyl.

n and m are preferably 0, and v and w are preferably 1 or 2 each independently.

As mentioned above, p, q, and r respectively represent the mole fraction of each structural unit of the polymer (1-1) with respect to the total structural units.

q preferably satisfies the relationship of 0≦q<0.25, particularly preferably q=0.

r preferably satisfies the relationship of 0≦r<0.25, particularly preferably r=0.

p preferably satisfies the relationship of 0.75<p≦1, and p=1 is particularly preferable since the formed photo-alignment layer has excellent solvent resistance. The polymer (1-1) satisfying the relationship of q=0, r=0, and p=1 is substantially composed of the structural unit represented by the formula (1-2).

(All the symbols in the formula have the same meanings as above.)

Here, the manufacturing method of the polymer (1-1) which consists substantially of the structural unit represented by formula (1-2) is demonstrated. The polymer (1-1) can be produced by polymerizing a monomer represented by formula (1-3) (hereinafter also referred to as "monomer (1-3)" as the case may be).

(All the symbols in the formula have the same meanings as above.)

The monomer (1-3) is a novel and useful compound for producing the polymer (1-1), and the present invention also includes the invention related to the monomer (1-3).

Specific examples of the monomer (1-3) include compounds represented by formula (M1-1-1) to formula (M1-1-12), and the like.

For one embodiment of the production method of monomer (1-3), enumerate X ¹ is carbonyloxy group, Y ¹ is the monomer (1-3) [the monomer shown in formula (1-3A) that is oxygen atom (1-3)] as an example for illustration. The monomer (1-3) can be prepared by reacting a compound represented by formula (1-3B) with a compound represented by formula (1-3C). The related reactions are shown below in the form of equations.

In this reaction formula, X represents a chlorine atom and a halogen atom such as a bromine atom, and other symbols have the same meanings as above. The compound represented by the formula (1-3C) may be produced by a known production method according to desired S ¹ , R ¹ , R ² , X ³ , and the like. The compound represented by formula (1-3B) is, for example, (meth)acryloyl chloride, (meth)acryloyl bromide, etc., and these can be purchased from the market.

This reaction is usually carried out in a solvent. The solvent involved is inactive to this reaction, as long as it has sufficient solubility for the compound shown in the formula (1-3B) and the compound shown in the formula (1-3C), for example, chloroform, dichloromethane, Toluene, xylene, tetrahydrofuran and dimethylacetamide, etc.

In addition, this reaction is preferably carried out in the presence of a deoxidizing agent such as a base. The base is, for example, triethylamine, diisopropylethylamine, pyridine, dimethylaminopyridine and the like.

Next, a method for producing the polymer (1-1) by polymerizing the monomer (1-3) will be described.

Polymerization to produce the polymer (1-1) from the monomer (1-3) can be carried out by addition polymerization such as anionic polymerization or radical polymerization. The implementation of radical polymerization can be any one of solution polymerization, bulk polymerization, emulsion polymerization and soap-free emulsion polymerization. However, solution polymerization is preferred in view of the stability or melting point of the monomer (1-3).

As a polymerization solvent in solution polymerization, solvents that do not deactivate radical activity, such as benzene, dichloromethane, tetrahydrofuran, and diethyl ether, are preferably used. Among them, tetrahydrofuran is particularly preferable as a polymerization solvent from the viewpoint of the solubility of the monomer (1-3).

The polymerization temperature can be appropriately adjusted in the range of -20°C to 200°C, more preferably in the range of 20°C to 120°C, depending on the type and amount of the polymerization initiator used, the stability of the monomer (1-3), etc. , more preferably in the range of 30°C to 100°C, particularly preferably in the range of 50°C to 75°C.

As the polymerization initiator, thermal initiators such as peroxides and azo compounds can be used, and photoinitiators described later can also be used. Thermal initiators are generally classified into low-temperature initiators, medium-temperature initiators, and high-temperature initiators according to the temperature at which free radicals are generated. In the polymerization of the monomer (1-3), any one of these initiators, or a combination of these initiators can be used, but based on the fact that the polymer (1-1) with a high degree of polymerization is easily obtained, side reactions are less likely to occur From the point of view, a medium-temperature initiator is more preferred, and an azo compound is further preferred. Among the azo compounds, azobisisobutyronitrile (AIBN) is particularly preferable in terms of availability.

By using the above-mentioned azo compound as a polymerization initiator, although it is possible to produce a polymer (1-1) with a high degree of polymerization, if it is desired to produce a polymer (1-1) with a desired molecular weight, it is necessary to control the polymer (1-1) ) molecular weight, then a chain transfer agent can be used appropriately, and atom transfer radical polymerization can be adopted.

After the polymerization, it is preferable to carry out reprecipitation purification in order to remove unreacted monomers and the like. The used solvent of reprecipitation purification can enumerate, water, alcoholic solvent, ether solvent, saturated hydrocarbon solvent, aromatic hydrocarbon solvent or their mixed solvent, can according to the kind of the used polymerization solvent of polymerization, monomer (1-3 ) type, etc., select the solvent appropriately.

Alcohol solvents include methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether, among which methanol, ethanol, and isopropanol are more preferred. . Examples of ether solvents include tetrahydrofuran and dimethoxyethane, more preferably tetrahydrofuran. Examples of saturated hydrocarbon solvents include n-pentane, n-heptane and cyclohexane, more preferably n-heptane. Examples of aromatic hydrocarbon-based solvents include benzene, toluene, xylene, and chlorobenzene, among which toluene and xylene are preferred. The solvent involved can be properly selected according to its safety, etc., more preferably methanol, ethanol, isopropanol, toluene, toluene/heptane mixed solvent, water/methanol mixed solvent, water/ethanol mixed solvent and water/tetrahydrofuran Mixed solvents are particularly preferably methanol, ethanol and isopropanol.

The molecular weight of the polymer (1-1) is represented by, for example, a polystyrene-equivalent weight average molecular weight obtained by gel permeation chromatography (GPC method), and is preferably in the range of 1×10 ³ to 1×10 ⁷ . However, if the molecular weight is too high, the solubility in solvents will decrease, it will be difficult to prepare the photoreactive liquid crystal aligning agent of the present invention, and the sensitivity to light irradiation will tend to decrease. Therefore, the molecular weight is preferably 1×10 ⁴ to 1× 10 ⁶ range. In addition, the analysis conditions of the GPC method for obtaining the molecular weight will be described in the examples of the present application.

Polymer (1-1) can be produced by polymerizing monomer (1-3) as above. In addition, in the polymerization of the monomer (1-3), the following monomers are used in combination to produce the polymer (1-1) which is a copolymer. However, when using the following monomers, the mole fraction of each structural unit of the polymer (1-1) needs to satisfy the above-mentioned relationship, and adjust the respective usage amounts of the monomers (1-3) and the following monomers.

(All the symbols in the formula have the same meanings as above.)

＜Photoreactive liquid crystal aligning agent＞

The photoreactive liquid crystal aligning agent of the present invention (hereinafter also referred to as "this liquid crystal aligning agent" as the case may be) contains a polymer (1-1), and in order to form a photo-alignment layer by the photo-alignment layer forming method described later, it is more preferable to contain Polymer (1-1) and solvent. When preparing such this liquid crystal aligning agent, first, polymer (1-1) is melt|dissolved in a solvent. The solvent involved can be appropriately selected within the range of the present liquid crystal aligning agent capable of dissolving the polymer (1-1) and obtaining a suitable viscosity, for example, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol Alcohol solvents such as methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, or propylene glycol methyl ether Ester solvents such as acid esters and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; pentane, hexane and heptane, etc. Aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and xylene, nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorinated solvents such as chloroform and chlorobenzene; N-methylpyrrolidone, N, N -amide-based solvents such as dimethylformamide, γ-butyrolactone, and dimethylacetamide, etc. These solvents may be used alone or in combination.

The concentration of the polymer (1-1) with respect to this liquid crystal aligning agent can also be adjusted appropriately according to the type or solubility of the polymer (1-1), but it is preferably at least 0.2% by mass in terms of solid content concentration, especially The range of 0.3-10 mass % is preferable. Moreover, this liquid crystal aligning agent may contain photosensitizers, such as polymer materials, such as polyvinyl alcohol and polyimide, and anthracene.

This liquid crystal aligning agent prepared by dissolving a polymer (1-1) in a solvent can be used for formation of a photo-alignment layer as it is, or after filtering etc. as needed.

＜Photo alignment layer formation method＞

The formation method (photo-alignment layer formation method) of the photo-alignment layer using this liquid crystal aligning agent containing a polymer (1-1) and a solvent is demonstrated. First, this liquid crystal aligning agent is apply|coated on the predetermined support base material. The support substrate involved is preferably a transparent support substrate. The method for coating this liquid crystal aligning agent on the transparent support substrate can adopt coating methods such as spin coating-dip coating method, extrusion method, gravure coating method, die coating method, rod coating method and coating method, or Well-known methods, such as printing methods, such as a flexo method, can be used.

Next, the present liquid crystal aligning agent is coated on a transparent support substrate to form a coating film, and the solvent is removed from the coating film to form a dry film. The removal of the solvent can be carried out by heating at an appropriate temperature to dry and remove the solvent (heating method), or after sealing in an appropriate pressure-resistant container, the pressure in the container can be used to dry and remove the solvent under reduced pressure. method (depressurization method), ventilation drying (ventilation method), natural drying, or a combination of these methods to implement. The heating method is more preferred from the point that it can be carried out in a continuous form in a roll-to-roll format.

The thickness of the dry film containing the polymer (1-1) formed on the transparent support substrate is, for example, in the range of 1 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm. The thickness of the dry film can be controlled by adjusting the solid content concentration of this liquid crystal aligning agent (especially the solid content concentration of polymer (1-1)), and the coating conditions of this liquid crystal aligning agent to a transparent substrate. In this way, a laminate in which the dry film containing the polymer (1-1) is provided on the transparent support substrate can be obtained.

Next, by irradiating polarized light UV (polarized light ultraviolet ray) on the dry film of the laminate, the polymer (1-1) is oriented, and liquid crystal alignment capability is imparted (hereinafter also referred to as "photo-alignment operation" depending on the case), forming photo-alignment layer. In the photo-alignment operation, when irradiating polarized light UV to the laminated body, a form (form (A)) in which polarized light UV is directly irradiated from the above-mentioned dry film side of the laminated body, or the laminated body One side of the above-mentioned transparent substrate is irradiated with polarized light UV, the polarized light UV is transmitted through the transparent substrate, and the dried film is irradiated with polarized light UV (form (B)). In any of these forms, the irradiated polarized light UV can be any of linearly polarized light UV or elliptically polarized light UV. In order to perform photo-alignment operations with high efficiency, it is preferable to use elliptically polarized light UV close to linearly polarized light. Or linearly polarized UV with high extinction ratio. Furthermore, the polarized light UV is particularly preferably almost parallel light. However, when the photo-alignment operation is performed according to the aspect (B), it is preferable that the transparency of the transparent base material in the laminate used is as high as possible.

The wavelength of polarized light UV to be irradiated should just be in the wavelength range which the photoreactive group (cinnamoyl group) of the polymer (1-1) contained in a dry film can absorb light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. The light source used for the photo-alignment operation includes xenon lamp; high-pressure mercury lamp; ultrahigh-pressure mercury lamp; metal halide lamp; ultraviolet lasers such as KrF and ArF, and the like. The light source used for the photo-alignment operation is more preferably a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp. The reason is that these lamps have a high emission intensity of ultraviolet rays with a wavelength of 313 nm. The laminated body can be irradiated with polarized light UV after passing the light emitted from the above-mentioned light source through a suitable polarizer and then irradiating the laminated body. The related polarizer can be a polarizing filter, a polarizing prism such as Glan Thompson, Glan Taylor, or a wire grid polarizer.

When irradiating polarized light UV to the dried film of the laminate, it is not necessarily required that the irradiation direction of the polarized light UV is slightly perpendicular to the plane direction of the laminate, and the irradiation direction of the polarized UV can be inclined to the plane of the laminate direction. The irradiation direction of polarized UV with respect to the planar direction of the laminate can be determined so that the obtained photo-alignment layer has a desired absorption axis according to the type of light source and polarizer used in the photo-alignment operation.

By the above method, etc., the photo-alignment layer formed by this liquid crystal aligning agent can be coated with a composition containing a polymerizable liquid crystal compound on the photo-alignment layer, so that the polymerizable liquid crystal compound can exhibit a nematic phase, or a higher-order near phase. Crystalline liquid crystal state (polymerizable liquid crystal). For the photo-alignment layer obtained from this liquid crystal aligning agent, this liquid crystal aligning agent that can form a photo-alignment layer by making a polymerizable liquid crystal compound into such a liquid crystal state (polymerizable liquid crystal) is extremely useful, and the relevant knowledge and insights are the present invention. peculiar to man.

As the polymerizable liquid crystal compound, when using a polymerizable smectic liquid crystal compound capable of forming a smectic liquid crystal state, the polymerizable smectic liquid crystal compound can be formed by forming a polarizing layer on a photoalignment film mainly by combining a dichroic dye. Liquid crystal alignment element. In addition, when a polymerizable nematic liquid crystal compound capable of forming a smectic liquid crystal state is used as the polymerizable liquid crystal compound, a liquid crystal aligning device in which a retardation layer is formed on a photoalignment film can be obtained. When a polarizing layer or a retardation layer is provided on a photo-alignment layer in this way, it may be applied and dried with a solution containing a polymerizable liquid crystal compound to be photopolymerized. Hereinafter, these methods will be described separately for the case of using a polymerizable smectic liquid crystal compound and the case of using a polymerizable nematic liquid crystal compound. In addition, in the related description, a solution containing a polymerizable smectic liquid crystal compound is referred to as a "polarizing layer forming composition", and a solution containing a polymerizable nematic liquid crystal compound is referred to as a "retardation layer forming composition".

<Liquid crystal aligning device using polymerizable smectic liquid crystal compound>

The polymerizable smectic liquid crystal compound refers to a compound that has a polymerizable group and exhibits a smectic liquid crystal phase. The polymerizable group refers to a group that participates in the polymerization reaction of the polymerizable smectic liquid crystal compound.

The liquid crystal phase exhibited by the polymerizable smectic liquid crystal compound is preferably a high-order smectic phase. The high-order smectic phases mentioned here are smectic B phase, smectic D phase, smectic E phase, smectic F phase, smectic G phase, smectic H phase, smectic I phase, and smectic J phase , smectic K phase and smectic L phase, among which, smectic B phase, smectic F phase, smectic I phase, oblique smectic F phase and oblique smectic I phase are preferred, and smectic B phase is more preferred. If the smectic liquid crystal phase displayed by the polymerizable smectic liquid crystal compound is of higher order, a polarizing layer with a higher degree of orientation order can be formed, and a polarizing layer with higher performance can be obtained.

Preferable polymerizable smectic liquid crystal compositions include, for example, compounds represented by formula (3-1) (hereinafter also referred to as "compound (3-1)" as the case may be).

U ¹ -V ¹ -W ¹ -E ¹ -J ¹ -E ² -J ² -E ³ -W ² -V ² -U ² (3-1)

[In formula (3-1),

E ¹ , E ² and E ³ each independently represent a p-phenylene group which may have a substituent or a 1,4-cyclohexanediyl group which may have a substituent. Among them, at least one of E ¹ , E ² and E ³ is a p-phenylene group which may have a substituent.

J ¹ and J ² each independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, single bond, -N=N-, -CR ^a =CR ^b -, -C≡ C- or -CR ^a =N-. R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

U ¹ represents a hydrogen atom or a polymerizable group.

U ² represents a polymerizable group.

W ¹ and W ² each independently represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² each independently represent an optionally substituted alkylene group having 1 to 20 carbon atoms, and -CH ₂ - constituting the alkylene group may be replaced by -O-, -S- or -NH-. ]

In compound (3-1), as described above, at least one of E ¹ , E ² and E ³ is 1,4-phenylene which may have a substituent, but preferably at least two of them are substituted The p-phenylene group of the base.

The above-mentioned p-phenylene group is preferably unsubstituted. The aforementioned 1,4-cyclohexanediyl group is preferably trans-1,4-cyclohexanediyl group, and is also more preferably unsubstituted.

Examples of substituents optionally possessed by the above-mentioned p-phenylene group or the above-mentioned 1,4-cyclohexanediyl group include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and butyl groups; cyano groups; halogen atoms, and the like. In addition, -CH ₂ - constituting 1,4-cyclohexanediyl may be replaced by -O-, -S- or -NR ⁷ -. R ⁷ is an alkyl group or phenyl group having 1 to 6 carbon atoms.

J ¹ of compound (3-1) is preferably -CH ₂ CH ₂ -, -COO- or a single bond, and J ² is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

U ² is a polymerizable group. U ¹ is a hydrogen atom or a polymerizable group, preferably a polymerizable group. That is, ^U1 and ^U2 are preferably polymerizable groups at the same time, preferably photopolymerizable groups at the same time. Here, the photopolymerizable group refers to a group capable of participating in a polymerization reaction by an active radical generated by a photopolymerization initiator described later, an acid, or the like. Using a polymerizable smectic liquid crystal compound having a photopolymerizable group is advantageous in that the polymerizable smectic liquid crystal compound can be polymerized at a lower temperature.

In compound (3-1), the photopolymerizable groups of U ¹ and U ² may be different from each other, but are preferably the same type of group. Examples of photopolymerizable groups include vinyl, vinyloxy, 1-chlorovinyl, isopropenyl, 4-vinylphenyl, acryloyloxy, methacryloyloxy, oxiranyl and Oxetanyl, etc. Among them, acryloyloxy, methacryloyloxy, vinyloxy, oxiranyl and oxetanyl are preferred, and acryloyloxy is more preferred.

^The alkylene groups ^of V1 and V2 include methylene, ethylene, 1,3-propylene, 1,3-butylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,10-decylene, 1,14-tetradecylene and 1,20-eicosylene Wait. V ¹ and V ² are preferably an alkylene group having 2 to 12 carbon atoms, more preferably an alkylene group having 6 to 12 carbon atoms.

Examples of substituents that the alkylene group optionally has include cyano groups, halogen atoms, and the like, and the alkylene group is preferably unsubstituted, more preferably an unsubstituted straight-chain alkylene group.

W ¹ and W ² are each independently preferably a single bond or -O-.

Examples of the compound (3-1) include compounds represented by any of the formulas (3-1-1) to (3-1-24). When a specific example of the compound (3-1) has a 1,4-cyclohexanediyl group, the 1,4-cyclohexanediyl group is preferably a trans form.

The listed compound (3-1) is numbered according to its structural formula, and is hereinafter referred to as "compound (3-1-1)" and the like.

The listed compound (3-1) can be used alone or as a mixture of two or more kinds of polymerizable smectic liquid crystals. In addition, two or more polymerizable smectic compounds are used, and at least one of the two or more polymerizable smectic compounds is in the form of compound (3-1). In the following description, the case of using one kind of polymerizable smectic liquid crystal compound and the case of using two or more kinds of polymerizable smectic liquid crystal compounds may be collectively referred to as “polymerizable smectic liquid crystal compound”.

When the compound (3-1) is used in the composition for forming a polarizing layer, the phase transition temperature of the compound (3-1) is obtained in advance, and the temperature for forming the polarizing layer is adjusted at a temperature lower than the phase transition temperature. Components other than the compound (3-1) [polymerizable smectic liquid crystal compound] of the composition, the compound (3-1) is polymerized. As a component which can control such a polymerization temperature, the photoinitiator mentioned later, a photosensitizer, a polymerization inhibitor, etc. are mentioned. The polymerization temperature of the compound (3-1) can be controlled by appropriately adjusting the types and amounts of these compounds. In addition, when a mixture of two or more compounds (3-1) [polymerizable smectic liquid crystal composition], that is, a polymerizable smectic liquid crystal composition, is used in the composition for forming a polarizing layer, the polymerization After the phase transition temperature of the polymerizable smectic liquid crystal composition is determined, the polymerization temperature is controlled as in the case of the polymerizable smectic liquid crystal compound.

Among the listed compounds (3-1), preferred formula (3-1-3), formula (3-1-6), formula (3-1-7), formula (3-1-12), formula ( 3-1-13) and any compound represented by formula (3-1-23). These compounds (3-1) can easily maintain a sufficient high-order smectic phase at a temperature lower than the phase transition temperature by mixing or interacting with a photopolymerization initiator used at the same time. In the case of a liquid crystal state, a supercooled state is obtained, whereby the compound (3-1) is polymerized. More specifically, these compounds (3-1) can be polymerized while maintaining a sufficient high-order smectic liquid crystal state at a temperature of 70° C. or lower, preferably 60° C. or lower, by interacting with a photopolymerization initiator.

The above-mentioned compound (3-1) may be one or more kinds as described above, but preferably two or more kinds. That is, in this composition for polarizing layer formation, it is preferable to use 2 or more types of polymerizable smectic liquid crystal compositions, and it is preferable to use 2 or more types of compounds (3-1).

The content of the compound (3-1) in the composition for forming a polarizing layer is preferably 70 to 99.9% by mass, more preferably 90 to 99.9% by mass based on the solid content of the composition for forming a polarizing layer. There exists a tendency for the orientation of a compound (3-1) to become high that the content rate of a compound (3-1) exists in the said range. Here, the solid content refers to the total amount of components after excluding volatile components such as solvents from the composition for forming a polarizing layer. Moreover, when several types of compounds (3-1) are contained in this composition for polarizing layer formation, the total content ratio should just be in the said range.

The composition for forming a polarizing layer preferably contains a leveling agent. The leveling agent can adjust the fluidity of the polymerizable liquid crystal composition and has a function of making the coating film obtained by coating the above-mentioned composition for forming a polarizing layer flatter, and examples thereof include surfactants and the like. More preferably, the leveling agent is at least one selected from a leveling agent mainly composed of a polyacrylate compound and a leveling agent mainly composed of a fluorine atom-containing compound.

The leveling agents mainly composed of polyacrylate compounds include "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK-355", "BYK-358N" , "BYK-361N", "BYK-380", "BYK-381" and "BYK-392" [BYK Chemie], etc.

Leveling agents mainly composed of fluorine-containing compounds include "Megaface R-08", same as "R-30", same as "R-90", same as "F-410", same as "F-411", Same as "F-443", Same as "F-445", Same as "F-470", Same as "F-471," Same as "F-477", Same as "F-479", Same as "F-482" and Same as "F-483"" [DIC (Co., Ltd.)]; ", the same as "SC-105", "KH-40" and "SA-100" [AGC Seimi Chemical Co., Ltd.]; EF301", the same as "EF303", the same as "EF351" and the same as "EF352" [Mitsubishi Material Electronics Co., Ltd.], etc.

When the composition for forming a polarizing layer contains a leveling agent, the content thereof is preferably 0.3 to 5 parts by mass, more preferably 0.5 to 3 parts by mass based on 100 parts by mass of the polymerizable smectic liquid crystal compound. When content of a leveling agent exists in the said range, it will become easy to horizontally align a polymerizable smectic liquid crystal compound, and there exists a tendency for the formed polarizing layer to become smoother. When content of a leveling agent with respect to a polymerizable smectic liquid crystal compound exceeds the said range, it exists in the tendency which becomes easy to generate|occur|produce unevenness in the polarizing layer obtained. Moreover, this composition for polarizing layer formation may contain 2 or more types of leveling agents.

The said composition for polarizing layer formation contains a solvent. As the solvent, an ideal solvent can be appropriately selected in consideration of the solubility of the polymerizable smectic liquid crystal compound to be used, and the like. Among them, an inert solvent that does not significantly hinder the progress of the polymerization reaction of the polymerizable smectic liquid crystal compound is preferable. Such a solvent is the same as the solvent listed as the solvent for preparing this liquid crystal aligning agent composition. The solvents for preparing the composition for forming a polarizing layer can also be used alone or in combination of multiple types.

The content of the solvent in the composition for forming a polarizing layer is preferably 50 to 98% by mass relative to the total amount of the composition for forming a polarizing layer. On the other hand, when the solid content of the composition for forming a polarizing layer is 50 mass % or less, since the viscosity of the composition becomes low, the thickness of the coating film becomes slightly uniform. In addition, the relevant solid content can be determined according to the desired thickness of the polarizing layer.

It is preferable that the said composition for polarizing layer formation contains a polymerization initiator. The polymerization initiator is a compound capable of starting the polymerization reaction of the polymerizable smectic liquid crystal compound, and is preferably a photopolymerization initiator from the point of view that the polymerization reaction can be started at a lower temperature. Specifically, under the temperature conditions, a compound capable of generating active radicals or acids by the action of light is used as a photopolymerization initiator. Among the photopolymerization initiators, those that generate radicals by the action of light are more preferable.

As said photoinitiator, a benzoin compound, a benzophenone compound, a phenyl ketone compound, an acyl phosphine oxide compound, a triazine compound, an iodonium salt, a sulfonium salt, etc. are mentioned, for example.

Specific examples of the photopolymerization initiator are given below.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone, etc.

Phenyl ketone compounds include, for example, diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylthiophenyl)-1-propanone, 2-benzyl-2 -Dimethylamino-1-(4-morpholinephenyl)-1-butanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1,2-diphenyl-2, 2-Dimethoxy-1-ethanone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]-1-propanone, 1-hydroxycyclohexyl phenyl ketone And 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]-1-propanone oligomers, etc.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

Triazine compounds include, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) )-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3, 4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc.

As a photopolymerization initiator, what is easy to obtain from a market can be used. Examples of commercially available photopolymerization initiators include “Irgacure 907”, “Irgacure 184”, “Irgacure 651”, “Irgacure 819”, “Irgacure 250”, and “Irgacure 369” (Chiba Japan Co., Ltd.). ; "Seikour BZ", "Seikold Z", "Seiko Chemical Co., Ltd." (Seiko Chemical Co., Ltd.); "Kayacure BP100" (Nippon Kayaku Co., Ltd.); -6992" (manufactured by Dow Corporation); "アデカオプトマ-SP-152", "アデカオプトマ-SP-170" ((strain) ADEKA); "TAZ-A", "TAZ-PP" (Japan シイべルへグナ- Society); and "TAZ-104" (Sanwa Chemical Corporation), etc.

When the above-mentioned composition for forming a polarizing layer contains a polymerization initiator, its content can be appropriately adjusted according to the type and amount of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer, for example, relative to The total amount of the polymerizable smectic liquid crystal compound is 100 parts by mass, and the content of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass. If the content of the polymerizable initiator is within this range, the polymerizable smectic liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable smectic liquid crystal compound, so the polymerizable smectic liquid crystal compound can maintain a high-order smectic phase liquid crystal state. Polymerize below.

Moreover, when the said composition for polarizing layer formation contains a photoinitiator, this composition may contain a photosensitizer. Examples of the photosensitizer include xanthone compounds such as xanthone and thioxanthone (for example, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); anthracene and Anthracene compounds such as alkoxy-containing anthracene (for example, dibutoxyanthracene, etc.); phenothiazine, rubrene, etc.

When the composition for forming a polarizing layer contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer can be further accelerated. The usage amount of the relevant photosensitizer can be appropriately adjusted according to the type and amount of the photopolymerization initiator and the polymerizable smectic liquid crystal compound used in combination, but it is preferably 100% relative to the total amount of the polymerizable smectic liquid crystal compound, for example. The mass part is 0.1-30 mass parts, More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts.

Although it has been demonstrated that the polymerization reaction of the polymerizable smectic liquid crystal compound can be accelerated by making the above-mentioned composition for forming a polarizing layer contain a photosensitizer, in order to stably proceed the polymerization reaction, the composition for forming a polarizing layer Inhibitors may be suitably contained. By containing the polymerization inhibitor, the progress of the polymerization reaction of the polymerizable smectic liquid crystal compound can be controlled.

The above-mentioned polymerization inhibitors include, for example, hydroquinone, alkoxy hydroquinone, alkoxy catechol (for example, butyl catechol, etc.), pyrogallol, 2,2,6 , 6-tetramethyl-1-piperidinyloxy radical and other free radical scavengers; thiophenols; β-naphthylamines and β-naphthols, etc.

When the above-mentioned composition for forming a polarizing layer contains a polymerization inhibitor, its content can be appropriately adjusted according to the type and amount of the polymerizable smectic liquid crystal compound used, and the amount of the photosensitizer used, etc., but preferably such as , Content of a polymerization inhibitor is 0.1-30 mass parts with respect to 100 mass parts of total amounts of a polymerizable smectic liquid crystal compound, More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. When the content of the polymerization inhibitor is within this range, the polymerizable smectic liquid crystal compound can be polymerized without disturbing the orientation of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer. The polymerization was performed satisfactorily while maintaining the high-order smectic liquid crystal state further.

The composition for forming a polarizing layer described above was coated on the photo-alignment layer of a laminate (first laminate) provided with a transparent support substrate and a photo-alignment layer to obtain a coating film. The above-mentioned polymerizable smectic liquid crystal compound contained in the cloth film is dried to form a dry film for forming a polarizing layer under the condition that the polymerizable smectic liquid crystal compound does not polymerize, and a second laminate is obtained.

The method (coating method) and drying method of coating the composition for polarizing layer formation on the said 1st laminated board can employ the same method as the method of coating this liquid crystal aligning agent on the transparent support base material demonstrated. The thickness of the coating film thus formed is preferably in the range of 0.5 to 10 μm, more preferably in the range of 0.5 to 3 μm. The thickness of the coating film can be set according to the desired thickness of the polarizing layer. In addition, the thickness of this polarizing layer is the value calculated|required by the measurement of an interference film thickness meter, a laser microscope, or a stylus type film thickness meter.

Furthermore, by photopolymerizing the polymerizable smectic liquid crystal compound contained in the dry coating film (dry coating film for forming a polarizing layer) of the above-mentioned second laminate, the polymerizable smectic liquid crystal compound maintains a smectic phase, preferably already The liquid crystal state of the listed high-order smectic phase is polymerized, and finally the dry film is added to the polarizing layer.

<Liquid crystal alignment device using polymerizable nematic liquid crystal compound>

Next, the method of forming a phase difference layer using the composition for phase difference layer formation (solution containing a polymerizable nematic liquid crystal compound) on the photo-alignment film formed from this liquid crystal aligning agent is demonstrated.

Examples of the polymerizable nematic liquid crystal compound contained in the composition for forming a retardation layer include compounds represented by formula (20) (hereinafter also referred to as "compound (20)" as the case may be) and the like.

P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t -B ¹² -G (20)

[In formula (20),

A represents a ² -valent aromatic hydrocarbon group, a 2-valent alicyclic hydrocarbon group, or a 2-valent heterocyclic group, and the hydrogen atoms contained in the 2-valent aromatic hydrocarbon group, the 2-valent alicyclic hydrocarbon group, and the 2-valent heterocyclic group can be replaced by Halogen atom, alkyl group with 1 to 6 carbon atoms, alkoxy group with 1 to 6 carbon atoms, N-alkylamino group with 1 to 6 carbon atoms, N,N-dioxane with 2 to 12 carbon atoms Amino, nitro, cyano or sulfanyl substitution.

B ¹¹ and B ¹² each independently represent -CR ¹⁴ R ¹⁵ -, -C≡C-, -CH=CH-, -CH ₂ -CH ₂ -, -O-, -S-, -C(=O) -, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=S)-, -C(=S)-O-, -OC (=S)-, -CH=N-, -N=CH-, -N=N-, -C(=O)-NR ¹⁶ -, -NR ¹⁶ -C(=O)-, -OCH ₂ - , -OCF ₂ -, -NR ¹⁶ -, -CH ₂ O-, -CF ₂ O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH- or single key. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be connected to form an alkylene group having 4 to 7 carbon atoms. R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E ¹¹ represents an alkylene group having 1 to 12 carbon atoms. The hydrogen atoms contained in the alkylene group may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.

P ¹¹ represents a polymerizable group.

G represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 13 carbon atoms, an alkoxy group with 1 to 13 carbon atoms, a fluoroalkyl group with 1 to 13 carbon atoms, or an N-alkane with 1 to 13 carbon atoms Amino groups, N, N-dialkylamino groups with 2 to 26 carbon atoms, cyano groups, nitro groups, or polymerizable groups connected through alkylene groups with 1 to 12 carbon atoms, the alkylene groups The contained hydrogen atoms may be substituted by an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.

t represents an integer of 1-5. When t is an integer of 2 or more, the plurality of A ¹¹ are the same or different from each other, and the plurality of B ¹¹ are the same or different from each other. ]

Examples of polymerizable groups in P11 and G include vinyl, vinyloxy, styryl, p-( ² -phenylvinyl)phenyl, acryloyl, acryloyloxy, methacryloyl, Methacryloyloxy group, carboxyl group, acetyl group, hydroxyl group, carbamoyl group, amino group, N-alkylamino group with 1 to 4 carbon atoms, epoxy group, oxetanyl group, formyl group, -N=C =O and N=C=S etc. Among them, radically polymerizable groups or cationically polymerizable groups are preferred because of high photopolymerization reactivity, and acryloyloxy groups and methacryloyloxy groups are more preferred because of ease of handling and relatively easy production of liquid crystal compounds. or ethyleneoxy.

In addition, the number of carbon atoms in the divalent aromatic hydrocarbon group, divalent alicyclic hydrocarbon group and divalent heterocyclic group of A ¹¹ is, for example, in the range of 3-18, preferably in the range of 5-12, particularly preferably 5 or 6.

Compound (20) includes, for example, a compound represented by formula (20-1) and a compound represented by formula (20-2).

P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t1 -B ¹² -E ¹² -P ¹² (20-1)

P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t2 -B ¹² -F ¹¹ (20-2)

[In formula (20-1) and formula (20-2),

P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ and B ¹² have the same meanings as above.

F ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 13 carbon atoms, an alkoxy group with 1 to 13 carbon atoms, a fluoroalkyl group with 1 to 13 carbon atoms, an N- Alkylamino, N,N-dialkylamino with 2 to 26 carbon atoms, cyano or nitro.

E12 represents an alkylene group having 1 to ¹² carbon atoms, and the alkylene group may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.

^P12 represents a polymerizable group.

^t1 and ^t2 each independently represent the integer of 1-5. ]

Further, the compounds represented by these formulas (20-1) and (20-2) may include compounds represented by formula (I), formula (II), formula (III), formula (IV) or formula (V) .

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -A ¹⁵ -B ¹⁶ -E ¹² -P ¹² (I)

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -A ¹⁴ -B ¹⁵ -E ¹² -P ¹² (II)

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -E ¹² -P ¹² (III)

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -A ¹³ -B ¹⁴ -F ¹¹ (IV)

P ¹¹ -E ¹¹ -B ¹¹ -A ¹¹ -B ¹² -A ¹² -B ¹³ -F ¹¹ (V)

[In formula (I)～formula (V),

The meanings of A ¹² to A ¹⁵ are the same as those of A ¹¹ , and the meanings of B ¹³ to B ¹⁶ are the same as those of B ¹¹ . ]

In addition, among the compounds represented by formula (20-1), formula (20-2), formula (I), formula (II), formula (III), formula (IV) and formula (V), preferably P ¹¹ It is connected to ^E11 through an ether bond or an ester bond, and preferably ^P12 is connected to ^E12 through an ether bond or an ester bond.

Specific examples of polymerizable nematic liquid crystal compounds include compounds represented by formula (I-1) to formula (I-5), formula (B1) to formula (B20), formula (C1) to formula (C4), etc. The compound shown in (I); the compound shown in the compound shown in formula (II-1) ~ formula (II-6); The compound shown in formula (II); Shown in formula (III-1) ~ formula (III-19) Compounds shown in formula (III) such as compounds; compounds shown in formula (IV-1) to formula (IV-14); compounds shown in formula (IV); formula (V-1) to formula (V Compounds represented by -5) Compounds represented by formula (V), etc. In addition, in the formula, k represents an integer of 1 to 11, and * denotes a bonding position. These polymerizable nematic liquid crystal compounds are preferred because they are relatively easy to manufacture or easy to obtain from the market.

(Two * in the formula (B1) form a bond with any * in (B1-1) to (B1-8).)

(Two * in the formula (B2) form a bond with any * in (B2-1) to (B2-8).)

(Two * in the formula (B3) form a bond with any * in (B3-1) to (B3-8).)

(Two * in the formula (B4) form a bond with any * in (B4-1) to (B4-8).)

(Two * in the formula (B5) form a bond with any * in (B5-1) to (B5-8).)

(Two * in the formula (B6) form a bond with any * in (B6-1) to (B6-8).)

(Two * in the formula (B7) form a bond with any * in (B7-1) to (B7-8).)

(Two * in the formula (B8) form a bond with any * in (B8-1) to (B8-8).)

(Two * in the formula (B9) form a bond with any * in (B9-1) to (B9-8).)

(Two * in the formula (B10) form a bond with any * in (B10-1) to (B10-8).)

(Two * in the formula (B11) form a bond with any * in (B11-1) to (B11-8).)

(Two * in formula (B12) form a bond with any * in (B12-1) to (B12-8).)

(Two * in the formula (B13) form a bond with any * in (B13-1) to (B13-8).)

(Two * in the formula (B14) form a bond with any * in (B14-1) to (B14-8).)

(Two * in formula (B15) form a bond with any * in (B15-1) to (B15-8).)

(Two * in the formula (B16) form a bond with any * in (B16-1) to (B16-8).)

(Two * in the formula (B17) form a bond with any * in (B17-1) to (B17-8).)

(Two * in the formula (B18) form a bond with any * in (B18-1) to (B18-8).)

(Two * in the formula (B19) form a bond with any * in (B19-1) to (B19-8).)

(Two * in the formula (B20) form a bond with any * in (B20-1) to (B20-8).)

(Two * in the formula (C1) form a bond with any * in (C1-1) to (C1-8).)

(Two * in the formula (C2) form a bond with any * in (C2-1) to (C2-8).)

(Two * in the formula (C3) form a bond with any * in (C3-1) to (C3-8).)

(Two * in the formula (C4) form a bond with any * in (C4-1) to (C4-8).)

Like the compound (20), the polymerizable nematic liquid crystal compound represented by the formula (2) (hereinafter also referred to as "compound (2)" as the case may be) can also be used as a compound used in the composition for retardation layer formation, A retardation layer is formed on the photo-alignment layer.

[In formula (2),

Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.

D1 and ^D2 each independently represent ^a single bond or a divalent linking group.

^G1 and G2 each independently represent a divalent alicyclic hydrocarbon group, and the ^hydrogen atoms contained in the alicyclic hydrocarbon group can be replaced by a halogen atom, an alkyl group with 1 to 4 carbon atoms, or a fluorine group with 1 to 4 carbon atoms. Substituted by an alkyl group, an alkoxy group having 1 to 4 carbon atoms, a cyano group or a nitro group, and -CH ₂ - constituting the alicyclic hydrocarbon group may be replaced by -O-, -S- or -NH-.

E ¹ and E ² each independently represent a single bond or a divalent linking group.

B ¹ and B ² each independently represent a single bond or a divalent linking group.

A1 and A2 each independently represent ^a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the ^hydrogen atoms contained in the alicyclic hydrocarbon group and the aromatic hydrocarbon group can be replaced by a halogen atom, a carbon number of 1 to 4 Substituted by an alkyl group, an alkoxy group with 1 to 4 carbon atoms, a cyano group or a nitro group. Hydrogen atoms contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted with fluorine atoms.

k and l each independently represent the integer of 0-3. When k is 2 or more, a plurality of A ^1s are the same or different from each other, and a plurality of B ^1s are the same or different from each other. When l is ² or more, a plurality of A2s are the same or different from each other, and a plurality of ^B2s are the same or different from each other.

F ¹ and F ² each independently represent an alkylene group having 1 to 12 carbon atoms, and the hydrogen atoms contained in the alkylene group may be substituted by an alkoxy group or a halogen atom having 1 to 5 carbon atoms to form the alkylene group. The radical -CH ₂ - may be replaced by -O- or -CO-.

P1 and P2 each independently represent ^{a hydrogen} atom, acryloyloxy group or methacryloyloxy group, but ^P1 and P2 are not ^hydrogen atoms at the same time. ]

Specific examples of Q ¹ include groups represented by any of the formulas (ar-1) to (ar-840). In the following groups, Me represents a methyl group, Et represents an ethyl group, and * represents a bonding position.

In formula (2), D ¹ and D ² each independently represent a single bond or a divalent linking group. Examples of such divalent linking groups include -CO-O-, -O-CO-, -C(=S)-O-, -OC(=S)-, -CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -CR ⁶ R ⁷ -, -O-CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -O-, -CR ⁴ R ⁵ -O-CR ⁶ R ⁷ -, -CR ⁴ R ⁵ -O- CO-, -O-CO-CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -O-CO-CR ⁶ R ⁷ -, -CR ⁴ R ⁵ -CO-O-CR ⁶ R ⁷ -, -NR ⁸ - CR ⁴ R ⁵ -, -CR ⁴ R ⁵ -NR ⁸ -, -CO-NR ⁸ -, -NR ⁸ -CO-, -O-, -S-, -NR ⁸ - and -CR ⁴ =CR ⁵ - Wait. Here, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group with 1 to 4 carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl Wait). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (such as methyl, ethyl, propyl, isopropyl, butyl, etc.).

Among them, D ¹ and D ² are each independently preferably *-O-CO-, *-OC(=S)-, *-O-CR ⁴ R ⁵ -, *-NR ⁸ -CR ⁴ R ⁵ - or * -NR ⁸ -CO-, more preferably *-O-CO-, *-OC(=S)- or *-NR ⁸ -CO-. Here, * means relative to compound (2)

Bonding position of a * in the indicated group. Preferably, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group. Preferably R ⁸ is a hydrogen atom, methyl or ethyl.

^The divalent alicyclic hydrocarbon groups of ^G1 and G2 preferably have 3-10 atoms constituting the ring (ring-forming atoms). When the ring-forming atoms contain heteroatoms, the number of heteroatoms is 2 or less. Specific examples of related alicyclic hydrocarbon groups include groups represented by any of formula (g-1) to formula (g-10). Among them, it is more preferable that the divalent alicyclic hydrocarbon groups of ^G1 and G2 are ⁵ -membered or 6-membered alicyclic hydrocarbon groups.

(In the formula, * indicates the bonding position.)

The hydrogen atoms contained in the groups shown in any of the above formulas (g-1) to (g-10) can be replaced by alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, isopropyl and tert-butyl. ; alkoxy groups with 1 to 4 carbon atoms such as methoxy and ethoxy; fluoroalkyl groups with 1 to 4 carbon atoms such as trifluoromethyl; fluorine with 1 to 4 carbon atoms such as trifluoromethoxy Alkoxy; cyano; nitro; halogen atoms such as fluorine atom, chlorine atom and bromine atom are substituted.

G ¹ and G ² are preferably groups represented by formula (g-1), more preferably 1,4-cyclohexanediyl, particularly preferably trans-1,4-cyclohexanediyl.

Examples of divalent linking groups for E ¹ and E ² include -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S-, -NR ¹¹ - and -CR ⁹ =CR ¹⁰ -, etc. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

E ¹ and E ² are preferably -CO-O-, -O-CO-, -O-CO-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -CH ₂ -O-, -CH ₂ -S- or a single bond, more preferably -CO-O-.

Examples of divalent linking groups for B ¹ and B ² include -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, -O-CO-, -O-CO-O-, -C(=S)-O-, -OC(=S)-, -OC(=S)-O-, -CO-NR ¹¹ -, -NR ¹¹ -CO-, -O-CH ₂ -, -CH ₂ -O-, -S-CH ₂ -, -CH ₂ -S-, -NR ¹¹ - and -CR ⁹ =CR ¹⁰ -, etc.

From the viewpoint of easier production, B1 and B2 are preferably each independently ^{-CH2 -} CH2-, -CO _{- O-} , -O-CO-, -CO-NH-, -NH-CO-, - O—CH ₂ —, —CH ₂ —O—, or a single bond is preferably —CO—O— or —O—CO— based on the fact that compound (2) exhibits particularly high liquid crystallinity.

In addition, it is preferable that B1 and B2 are the same from the point of view that ^compound ( ² ) can be produced more easily.

Specific examples of the divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group in A1 and A2 include any of the formulas ( ^g - ¹ ) to ( ^g -10) listed in the description of ^G1 and G2. the group shown, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by any of the following formulas (a-1) to (a-8).

The hydrogen atoms contained in the groups represented by the above formulas (a-1) to (a-8) can be replaced by alkyl groups with 1 to 4 carbon atoms such as methyl, ethyl, isopropyl and tert-butyl; Alkoxy groups with 1 to 4 carbon atoms such as methoxy and ethoxy; fluoroalkyl groups with 1 to 4 carbon atoms such as trifluoromethyl; fluorocarbons with 1 to 4 carbon atoms such as trifluoromethoxy Oxygen; cyano; nitro; halogen atoms such as fluorine atom, chlorine atom and bromine atom are substituted.

Among them, as A ¹ and A ² , 1,4-phenylene or 1,4-cyclohexanediyl is preferable, and 1,4-phenylene is more preferable from the viewpoint of easy production of compound (2). Furthermore, it is preferable that A1 and A2 are the same from the point of view of making ^compound ( ² ) easier to produce.

From the viewpoint of the liquid crystallinity of the compound (2), k and 1 are preferably 0, 1 or 2. The sum of k and 1 is preferably 5 or less, more preferably 4 or less.

The alkylene group having 1 to 12 carbon atoms in F ¹ and F ² is preferably -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ) ₅ -, -(CH ₂ ) ₆ -, -(CH ₂ ) ₇ -, -(CH ₂ ) ₈ -, -(CH ₂ ) ₉ -, -(CH ₂ ) ₁₀ -, -(CF ₂ ) ₄ -, -(CF ₂ ) ₆ -, -( CF ₂ ) ₈ -, more preferably -(CH ₂ ) ₄ -, -(CH ₂ ) ₆ -.

Preferably, B1 and B2 are each independently -O-, -CO ^{- O-} , -O-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or a single bond.

Although P1 and P2 each independently represent ^{a hydrogen} atom or a polymerizable group, they are not hydrogen atoms at the same time. That is, at least ^one of P1 and ^P2 is a polymerizable group. From the point that the retardation layer obtained from the compound ( ² ) tends to have excellent hardness, it is more preferable that ^both P1 and P2 are polymerizable groups.

The polymerizable group should just be a group which can participate in the polymerization reaction of compound (2). Although it overlaps with the polymerizable groups of U1 and U2 ^of the above ^- mentioned compound (3-1), specific examples of the polymerizable group include vinyl, vinyloxy, styryl, p-(2-benzene (vinyl) phenyl, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, carboxyl, acetyl, hydroxyl, carbamoyl, N-alkylamino with 1 to 4 carbon atoms , amino, epoxy, oxetanyl, formyl, isocyanate and isothiocyanate, etc. Among them, radically polymerizable groups and cationically polymerizable groups are preferable because they are suitable for photopolymerization, and acryloyloxy groups or methacryloyl groups are more preferable because they are easy to handle and the production of compound (2) is also easy. Oxygen, particularly preferably acryloyloxy.

^The polymerizable group may be directly bonded to F1 and F2, but is preferably bonded via ^one or more divalent linking groups (for example, the above ^- mentioned divalent linking groups in B1 and B2, etc. ⁾ .

-D ¹ -G ¹ -E ¹ -(A ¹ -B ¹ ) _k -F ¹ -P ¹ and -D ² -G ² -E ² -(A ² -B ² ) ₁ -F ² -P ² Specific examples include groups represented by formula (R-1) to formula (R-134). * means with

One* bonding position for the indicated group.

As compound (2), the compound represented by formula (A1) - a formula (A73) is mentioned.

(Two * in the formula (A1) form a bond with any * in (A1-1) to (A1-8).)

(Two * in the formula (A2) form a bond with any * in (A2-1) to (A2-8).)

(Two * in the formula (A3) form a bond with any * in (A3-1) to (A3-8).)

(Two * in the formula (A4) form a bond with any * in (A4-1) to (A4-8).)

(Two * in formula (A5) form a bond with any * in (A5-1) to (A5-8).)

(Two * in the formula (A6) form a bond with any * in (A6-1) to (A6-8).)

(Two * in the formula (A7) form a bond with any * in (A7-1) to (A7-8).)

(Two * in the formula (A8) form a bond with any * in (A8-1) to (A8-8).)

(Two * in formula (A9) form a bond with any * in (A9-1) to (A9-8).)

(Two * in the formula (A10) form a bond with any * in (A10-1) to (A10-8).)

(Two * in formula (A11) form a bond with any * in (A11-1) to (A11-8).)

(Two * in formula (A12) form a bond with any * in (A12-1) to (A12-8).)

(Two * in formula (A13) form a bond with any * in (A13-1) to (A13-8).)

(Two * in formula (A14) form a bond with any * in (A14-1) to (A14-8).)

(Two * in formula (A15) form a bond with any * in (A15-1) to (A15-8).)

(Two * in the formula (A16) form a bond with any * in (A16-1) to (A16-8).)

(Two * in formula (A17) form a bond with any * in (A17-1) to (A17-8).)

(Two * in formula (A18) form a bond with any * in (A18-1) to (A18-8).)

(Two * in formula (A19) form a bond with any * in (A19-1) to (A19-8).)

(Two * in formula (A20) form a bond with any * in (A20-1) to (A20-8).)

(Two * in formula (A21) form a bond with any * in (A21-1) to (A21-8).)

(Two * in formula (A22) form a bond with any * in (A22-1) to (A22-8).)

(Two * in formula (A23) form a bond with any * in (A23-1) to (A23-8).)

(Two * in the formula (A24) form a bond with any * in (A24-1) to (A24-8).)

(Two * in formula (A25) form a bond with any * in (A25-1) to (A25-8).)

(Two * in formula (A26) form a bond with any * in (A26-1) to (A26-8).)

(Two * in the formula (A27) form a bond with any * in (A27-1) to (A27-8).)

(Two * in the formula (A28) form a bond with any * in (A28-1) to (A28-8).)

(Two * in formula (A29) form a bond with any * in (A29-1) to (A29-8).)

(Two * in the formula (A30) form a bond with any * in (A30-1) to (A30-8).)

(Two * in formula (A31) form a bond with any * in (A31-1) to (A31-8).)

(Two * in formula (A32) form a bond with any * in (A32-1) to (A32-8).)

(Two * in formula (A33) form a bond with any * in (A33-1) to (A33-8).)

(Two * in formula (A34) form a bond with any * in (A34-1) to (A34-8).)

(Two * in formula (A35) form a bond with any * in (A35-1) to (A35-8).)

(Two * in formula (A36) form a bond with any * in (A36-1) to (A36-8).)

(Two * in formula (A37) form a bond with any * in (A37-1) to (A37-8).)

(Two * in formula (A38) form a bond with any * in (A38-1) to (A38-8).)

(Two * in formula (A39) form a bond with any * in (A39-1) to (A39-8).)

(Two * in the formula (A40) form a bond with any * in (A40-1) to (A40-8).)

(Two * in formula (A41) form a bond with any * in (A41-1) to (A41-8).)

(Two * in formula (A42) form a bond with any * in (A42-1) to (A42-8).)

(Two * in formula (A43) form a bond with any * in (A43-1) to (A43-8).)

(Two * in formula (A44) form a bond with any * in (A44-1) to (A44-8).)

(Two * in formula (A45) form a bond with any * in (A45-1) to (A45-8).)

(Two * in formula (A46) form a bond with any * in (A46-1) to (A46-8).)

(Two * in formula (A47) form a bond with any * in (A47-1) to (A47-8).)

(Two * in formula (A48) form a bond with any * in (A48-1) to (A48-8).)

(Two * in formula (A49) form a bond with any * in (A49-1) to (A49-8).)

(Two * in the formula (A50) form a bond with any * in (A50-1) to (A50-8).)

(Two * in formula (A51) form a bond with any * in (A51-1) to (A51-8).)

(Two * in formula (A52) form a bond with any * in (A52-1) to (A52-8).)

(Two * in formula (A53) form a bond with any * in (A53-1) to (A53-8).)

(Two * in formula (A54) form a bond with any * in (A54-1) to (A54-8).)

(Two * in formula (A55) form a bond with any * in (A55-1) to (A55-8).)

(Two * in formula (A56) form a bond with any * in (A56-1) to (A56-8).)

(Two * in the formula (A57) form a bond with any * in (A57-1) to (A57-8).)

(Two * in formula (A58) form a bond with any * in (A58-1) to (A58-8).)

(Two * in formula (A59) form a bond with any * in (A59-1) to (A59-8).)

(Two * in the formula (A60) form a bond with any * in (A60-1) to (A60-8).)

(Two * in formula (A61) form a bond with any * in (A61-1) to (A61-8).)

(Two * in the formula (A62) form a bond with any * in (A62-1) to (A62-8).)

(Two * in formula (A63) form a bond with any * in (A63-1) to (A63-8).)

(Two * in formula (A64) form a bond with any * in (A64-1) to (A64-8).)

(Two * in the formula (A66) form a bond with any * in (A66-1) to (A66-8).)

(Two * in formula (A67) form a bond with any * in (A67-1) to (A67-8).)

(Two * in formula (A68) form a bond with any * in (A68-1) to (A68-8).)

(Two * in formula (A69) form a bond with any * in (A69-1) to (A69-8).)

(Two * in the formula (A70) form a bond with any * in (A70-1) to (A70-8).)

(Two * in formula (A71) form a bond with any * in (A71-1) to (A71-8).)

(Two * in formula (A72) form a bond with any * in (A72-1) to (A72-8).)

(Two * in formula (A73) form a bond with any * in (A73-1) to (A73-8).)

As the polymerizable nematic liquid crystal compound used to form the retardation layer, the listed compound (2) may be used alone or in admixture of two or more of them as appropriate. In particular, use of a compound represented by any of the formulas (A1) to (A73) is more preferable because the obtained retardation layer is a reverse wavelength dispersion retardation layer. These compounds (2) are preferred because the wavelength dispersibility exhibits more desirable reverse wavelength dispersibility.

In the said composition for retardation layer formation, it is more preferable to contain a polymerization initiator. Suitable polymerization initiators are the same as those listed as preferable polymerization initiators which are arbitrarily contained in the above-mentioned composition for forming a polarizing layer. In addition, like the above-mentioned composition for forming a polarizing layer, the composition for forming a retardation layer may also contain a photosensitizer for accelerating the polymerization of a polymerizable liquid crystal compound (polymerizable nematic liquid crystal compound), or a photosensitizer for Inhibitor to control polymerization. About this photosensitizer or polymerization inhibitor, it is the same as what was demonstrated about the said composition for polarizing layer formation. Furthermore, this composition for retardation layer formation may contain a leveling agent similarly to the said composition for polarizing layer formation.

The composition for forming a phase difference layer preferably contains a solvent, especially an organic solvent, from the viewpoint of its fluidity. The organic solvent can be appropriately selected according to the type and amount of the polymerizable nematic liquid crystal compound used in the composition for forming a retardation layer, and specifically, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, Alcohol solvents such as ethylene glycol methyl ether and ethylene glycol butyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, Ester solvents such as ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; non-chlorinated solvents such as pentane, hexane, and heptane Aliphatic hydrocarbon solvents; non-chlorinated aromatic hydrocarbon solvents such as toluene, xylene, and phenol; nitrile solvents such as acetonitrile; ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran, and dimethoxyethane; chlorinated solvents such as chloroform and chlorobenzene Hydrocarbon solvents; phenol, etc. These organic solvents may be used alone or in combination of multiple types. In particular, alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents, and non-chlorinated aromatic hydrocarbon solvents are preferable.

When an organic solvent is used in the composition for forming a retardation layer, the content thereof is 10 to 10,000 parts by mass, preferably 100 to 5,000 parts by mass relative to 100 parts by mass of the polymerizable nematic liquid crystal compound. The viscosity of the composition for forming a retardation layer is 0.1 to 10 mPa·s, preferably 0.1 to 7 mPa·s, based on the point that the film thickness of the formed retardation layer is less likely to become uneven. Therefore, the kind and quantity (content) of the organic solvent used for the said composition for phase difference layer formation can be determined in consideration of making it have such an appropriate viscosity.

Moreover, the solid content concentration in the said composition for retardation layer formation is the range of 2-50 mass %, Preferably it is the range of 5-50 mass %. When the solid content concentration is 2% by mass or more, the retardation layer does not become too thin, and it is easy to obtain a retardation layer having birefringence necessary for optical compensation of a liquid crystal panel as a liquid crystal display device. In addition, if the solid content concentration is 50% by mass or less, the viscosity of the composition for forming a retardation layer will not become too low, and since it has the above-mentioned suitable viscosity, the film thickness of the retardation layer is less likely to be uneven. tendency. In addition, a solid content means the component which removed the volatile components, such as an organic solvent, from the said composition for phase difference layer formation.

The aforementioned retardation layer is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or vice versa.

The said retardation layer is obtained by polymerizing the polymerizable nematic liquid crystal compound contained in the said retardation layer forming composition.

On the photo-alignment layer formed from this liquid crystal aligning agent, a non-polymerized film (dry film for retardation layer formation) can be obtained by apply|coating and drying the said composition for retardation layer formation. In addition, the coating method and the drying method are the same as those described in the method of obtaining a coating film for forming a polarizing layer and a drying film from the coating film for forming a polarizing layer described above.

After the polymerizable nematic liquid crystal in the unpolymerized film is brought into a nematic liquid crystal state, the retardation layer obtained through polymerization exhibits birefringence by monodomain alignment.

The film thickness of the retardation layer can be controlled by appropriately adjusting the solid content concentration and organic solvent content of the retardation layer-forming composition and the coating amount of the retardation layer-forming composition on the support substrate. When the content of the polymerizable nematic liquid crystal compound contained in the composition for forming a retardation layer is constant, the retardation value (Retardation value, Re(λ)) of the obtained retardation layer is determined by the formula (7) , so in order to obtain the desired Re(λ), just adjust the film thickness d and Δn(λ).

Re(λ)=d×Δn(λ) (7)

(In the formula, Re(λ) represents the retardation value at the wavelength of λnm, d represents the film thickness, and Δn(λ) represents the birefringence at the wavelength of λnm.)

The method for polymerizing the polymerizable nematic liquid crystal compound in the unpolymerized film may be appropriately determined according to the type of the polymerizable nematic liquid crystal compound. When the polymerizable nematic liquid crystal compound contains a photopolymerizable group as the polymerizable group, a photopolymerization method is used, and when the polymerizable group is a thermal polymerizable group, a thermal polymerization method is used. According to the photopolymerization method, the polymerizable nematic liquid crystal compound can be polymerized at a low temperature, and it is preferable to use a photopolymerizable polymerizable group from the point of wide selection of the heat resistance of the support substrate and the point of industrial ease of manufacture. polymerizable nematic liquid crystal compounds. In addition, photopolymerization is also preferable from the viewpoint of film-forming properties.

The polymerization reaction involved in the photopolymerization method is performed by irradiating an unpolymerized film with visible light, ultraviolet light or laser light. Ultraviolet light is particularly preferred from the point of view of ease of handling. Light irradiation can be performed at a temperature at which the compound of the present invention is in a liquid crystal phase. At this time, the polymeric film may be patterned by photolithography masking or the like.

The birefringence Δn(λ) can be manufactured to obtain a desired phase difference by appropriately adjusting the exposure amount, heating temperature, and heating time during polymerization.

The retardation layer obtained as above has a thinner film thickness than a stretched film in which a retardation is obtained by stretching a polymer. Furthermore, patterning and the direction of a fast axis (slow axis) can be freely controlled by combining it with the photo-alignment layer formed from this liquid crystal aligning agent.

Furthermore, the transparency of the retardation layer is excellent, and the thickness of the retardation layer used as a film for various displays varies depending on the retardation value of the optical film as described above, but is preferably 0.1 to 10 μm, From the point of reducing photoelasticity, it is more preferably 0.2 to 5 μm, particularly preferably 0.5 to 3 μm.

The retardation value of the retardation layer exhibiting birefringence is on the order of 50 to 500 nm, preferably 100 to 300 nm.

Such a phase difference layer can perform the same polarization conversion in a wider wavelength range. Therefore, the liquid crystal aligning element which combines this retardation layer and the photo-alignment layer which consists of this liquid crystal aligning agent can be used as an optical compensation film for FPDs, such as all liquid crystal panels and organic EL.

The retardation layer mentioned above can be used as a broadband λ/4 plate or a λ/2 plate. When using it as a broadband λ/4 plate or a λ/2 plate, the content of the polymer comprising a polymerizable nematic liquid crystal compound in the retardation layer may be appropriately selected. In the case of a λ/4 plate, adjust the film thickness so that the Re(550) of the obtained liquid crystal alignment element is 113 to 163 nm, preferably 135 to 140 nm, and particularly preferably about 137.5 nm. In the case of a λ/2 plate Next, what is necessary is just to adjust film thickness so that Re(550) of the obtained liquid crystal aligning element may be 250-300 nm, Preferably it is 273-277 nm, Most preferably, it is about 275 nm.

The said retardation layer can also be used as an optical film for VA (Vertical Alingment, vertical alignment) mode. When using as an optical film for VA mode, content in the retardation layer of the polymer which consists of a polymerizable nematic liquid crystal compound should just be selected suitably. The film thickness may be adjusted so that Re(550) of the obtained optical film is preferably 40 to 100 nm, more preferably 60 to 80 nm.

[Example]

The present invention will be described in more detail through examples below. Unless otherwise specified, "%" and "part" in an example are mass % and a mass part.

Embodiment 1: the synthesis of compound (M1-1-1)

Compound (1-1-1) was synthesized according to the following scheme.

[Synthesis of compound (a1-1-1)]

50 g (258 mmol) of ferulic acid was dissolved in 360 g of methanol. 10 g of sulfuric acid was added to the resulting solution at room temperature, and the reaction was carried out under reflux for 2 hours after the temperature was raised until the solvent began to reflux. After cooling the obtained reaction solution, 150 g of ice and 150 g of water were added. The supernatant was removed by decantation, and 150 g of water at 5° C. was added to crystallize. The obtained white crystals were filtered, and the filtered white crystals were further washed with a 1M aqueous sodium bicarbonate solution and water, and then vacuum-dried to obtain 22.2 g of compound (a1-1-1). The yield was 83% based on ferulic acid.

[Synthesis of compound (b1-1-1)]

25 g (120 mmol) of compound (a1-1-1) was dissolved in 250 g of dimethylacetamide. To the obtained solution were added 33.19 g (240 mmol) of potassium carbonate and 1.99 g (12 mmol) of potassium iodide. 6-Chlorohexanol was added dropwise to the obtained dispersion, and stirred at room temperature for 1 hour, and then at 70° C. for 8 hours. The obtained reaction solution was filtered to remove insoluble matter. 200 g of methyl isobutyl ketone and 300 g of water were added to the filtrate, stirred, left to stand, and the organic layer was recovered after liquid separation. 200 g of water was added to the recovered organic layer, stirred, left to stand, and liquid-separated, and this water washing operation was repeated twice. The solvent was removed from the recovered organic layer by distillation under reduced pressure using an evaporator to obtain a crude product of compound (b1-1-1).

[Synthesis of compound (c1-1-1)]

All the crude product of the above-mentioned compound (b1-1-1) was dissolved in 185 g of ethanol. 92 g of water and 14.41 g (360 mmol) of sodium hydroxide were added to the obtained solution, followed by stirring at 80° C. for 1 hour. After cooling the reaction solution to about 3°C, while keeping the temperature below 5°C, 2M hydrochloric acid aqueous solution was added to adjust the pH to 2. The acid precipitate was collected by filtration to obtain a white precipitate, which was further washed twice with a mixed solution of 100 g of water and 80 g of methanol, and dried in vacuum to obtain 30.4 g of compound (c1-1-1). The yield was 86% based on compound (a1-1-1).

[Synthesis of compound (M1-1-1)]

27.46 g (93 mmol) of compound (c1-1-1) was dissolved in 280 g of chloroform. To the obtained solution, 2.06 g of BHT (di-tert-butyl-hydroxytoluene) and 37.73 g (373 mmol) of triethylamine were added as a polymerization inhibitor, followed by stirring under ice cooling. 29.26 g (260 mmol) of methacryloyl chlorides were dripped at the reaction solution, and it stirred at 5 degreeC or less for 5 hours. To the obtained reaction solution were added 5.7 g of dimethylaminopyridine and 190 g of water, followed by stirring at room temperature for 12 hours. After standing still, the organic layer was recovered, 100 g of 2N hydrochloric acid aqueous solution was added to the organic layer, stirring, standing and liquid separation were repeated twice. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. After washing twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, it was vacuum-dried to obtain 22.0 g of compound (M1-1-1). The yield was 65% based on compound (c1-1-1).

[Synthesis of compound (M1-1-1) (another method)]

27.46 g (93 mmol) of compound (c1-1-1) was dissolved in 280 g of chloroform. 8.00 g of BHT (di-tert-butyl-hydroxytoluene) as a polymerization inhibitor, 11.16 g of p-toluenesulfonic acid, and 44.63 g of methacrylic acid were added to the obtained solution, and they were reacted while removing water by azeotropic dehydration. 8 hours. After cooling the reaction solution to below 5° C., 200 g of water was added, stirred, left to stand, and liquid-separated, and the organic layer was recovered. To the obtained organic layer were added 5.7 g of dimethylaminopyridine and 190 g of water, followed by stirring at room temperature for 12 hours. The organic layer of the obtained reaction solution was recovered, and the organic layer was washed twice with 100 g of 2N aqueous hydrochloric acid solution. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. After washing twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, it was vacuum-dried to obtain 18.3 g of compound (M1-1-1). The yield was 54% based on compound (c1-1-1).

Example 2 (production of polymers with photoreactive groups)

The production of a polymer having a photoreactive group from the above-mentioned compound (M1-1-1) is carried out as follows.

Add 1.00 g (2.76 mmol) of compound (M1-1-1) and 10 g of tetrahydrofuran to the Schlenk tube. After deoxygenation, add 2.27 mg of azobisisobutyronitrile (AIBN) while flowing nitrogen, and place at 60° C. Stirred for 72 hours. The obtained reaction solution was added to 200 g of toluene. The precipitate was collected by filtration, washed with heptane, and then vacuum-dried to obtain 0.75 g of polymer 1 . The yield was 75% based on compound (M1-1-1). The molecular weight of the obtained polymer was determined by GPC, with polystyrene as the standard, showing a number average molecular weight of 28200, Mw/Mn of 1.82, and a monomer content of 0.5%.

This polymer is referred to as polymer (1-1-1).

In addition, GPC analysis for obtaining the number average molecular weight of the polymer (1-1-1) based on polystyrene was measured under the following conditions.

Device: HLC-8220GPC (manufactured by Tosoh Corporation)

Guard column: TSKguardcolumn MP (XL) (trade name)

Column: TSK-gel MultiporeH _XL -M (trade name)

TSK-gel MultiporeH _XL -M (trade name)

TSK-gel MultiporeH _XL -M (trade name)

(Connect the above columns in series.)

Column temperature: 40°C

Solvent: THF

Flow rate: 1.0mL/min

Injection volume: 50μL

Detectors: IR, UV

Measurement sample concentration: 0.6% by mass (solvent: THF)

Standard material for calibration: TSK STANDARD POLYSTYRENE

A-500, A-1000, A-2500, A-5000,

F-1, F-2, F-4, F-10, F-20, F-40,

F-80, F-128, F-288, F-380

(trade name, manufactured by Tosoh Co., Ltd.)

Embodiment 3: the manufacture of photoreactive liquid crystal aligning agent

The polymer (1-1-1) was dissolved in cyclopentanone so that the concentration would be 5% by mass, and it was set as a photoreactive liquid crystal aligning agent.

Evaluation Example 1

[Preparation of composition for forming polarizing layer]

The following components were mixed and stirred at 80° C. for 1 hour to obtain a polymerizable liquid crystal composition.

Polymeric liquid crystal compound: 75 parts of compound (3-1-6)

Compound (3-1-7) 25 parts

Dichroic dye: Azo dye (G205: manufactured by Hayashibara Biochemical Research Institute) 3.0 parts

Polymerization initiator: 6 parts of 1-hydroxycyclohexyl phenyl ketone (Ilgacyua 184: manufactured by Ciba Specialty Chemical Co., Ltd.)

Leveling agent: polyacrylate compound (BYK-361N: manufactured by BYK-Chemie) 1.5 parts

Solvent: 250 parts of cyclopentanone

[Measurement of Phase Transition Temperature]

The phase transition temperature was confirmed by observing the structure using a polarizing microscope. The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was heated to 120°C to remove the solvent and dried, and then it was confirmed that the phase transition was to a nematic phase at 110°C and to a smectic phase at 104°C while the temperature was lowered. Phase A, phase transition to smectic B phase at 83°C.

〔Production of photo-alignment layer〕

The photoreactive liquid crystal aligning agent obtained in Example 3 was coated on a polyethylene terephthalate substrate (PET substrate) by a bar coating method, and dried at 60°C for 1 minute to form a 100nm-thick liquid crystal aligning agent. Dry the film. Next, the surface of the obtained dried film was irradiated with polarized light UV to form a photo-alignment layer. The polarized UV treatment was performed using a UV irradiation device (SPOT CURE SP-7: manufactured by Usio Electric Co., Ltd.), under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ.

〔Production of polarizing layer〕

The composition for forming a polarizing layer was applied on the photo-alignment film by a bar coating method, heated and dried in a drying oven at 120° C. for 1 minute, and then cooled to room temperature. Using a UV irradiation device (SPOT CURE SP-7: manufactured by Usio Electric Co., Ltd.), the layer formed of the composition for forming a polarizing layer was irradiated with ultraviolet light at an exposure amount of 1200 mJ/cm ² (based on 365 nm), thereby forming a polarizing layer , made of liquid crystal alignment elements. When the film thickness of the polarizing layer at this time was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation), it was 1.6 μm.

〔X-ray diffraction measurement〕

X-ray diffraction measurement was performed on the obtained polarizing layer using an X-ray diffractometer X'Pert PRO MPD (manufactured by Spectris Co., Ltd.). Using Cu as the target, the X-rays generated under the conditions of X-ray tube current 40mA and X-ray tube voltage 45kV pass through the fixed divergence slit 1/2° along the friction (rabing) direction, and the scanning range 2θ=4.0～40.0 ° range, the step width 2θ=0.01671° was scanned, and as a result of measurement, a sharp diffraction peak (Bragg peak) with half maximum width (FWHM)=about 0.187° was obtained around 2θ=20.22°. In addition, the same results were obtained from the incidence perpendicular to the rubbing direction. The lattice period (order period) (d) obtained from the position of the peak is approximately It can be seen that a structure reflecting a high-order smectic phase is formed.

〔Measurement of dichromatic ratio〕

Using a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) equipped with a holder with a polarizer, the absorbance (A ¹ ) and the absorbance of the maximum absorption wavelength in the direction of the transmission axis were measured by the two-ray method. Absorbance in axial direction (A ² ). The reference side of the holder was provided with a mesh that reduces the amount of light by 50%. The ratio (A ² /A ¹ ) was calculated from the measured values of absorbance (A ¹ ) in the direction of the transmission axis and absorbance (A ² ) in the direction of the absorption axis, and was defined as a dichromatic ratio. The results are shown in the table. The higher the dichroic ratio, the more useful it is as a polarizing layer. The measurement results of the dichroic ratio are shown in Table 1.

[Observation of orientation state]

The orientation state of the obtained polarizing layer was confirmed by polarizing microscope observation. Insert the sample between the crossed polarizers of the polarizing microscope along the direction of about 45°, and observe it in the state of light leakage. When aligned in the vertical direction, no light leakage occurred, and a dark field state was observed. When aligned horizontally, light leakage occurred, and a bright field state was observed. The evaluation was performed on two levels, when the whole screen was in bright field and was marked as "○", and when the whole screen was in dark field was marked as "×". The results are shown in Table 1.

〔Determination of Haze value〕

About the obtained polarizer, the haze value was measured using the haze meter (HZ-2: Suga test machine Co., Ltd. product). The haze value is represented by the following formula.

Haze value (%)=scattering transmittance (%)/total light transmittance (%)×100

If the anchoring force to the polarizing layer by the photo-alignment layer is insufficient, the polymerizable smectic liquid crystal which is the main component of the polarizing layer will generate a defect of discontinuity. The haze value increases due to light scattering at the interface of the discontinuity defect. That is, the smaller the haze value, the better the orientation. Here, 3% or less is good. The results are shown in Table 1.

Evaluation example 2

A liquid crystal alignment device was produced in the same manner as in Evaluation Example 1 except that the dichroic dye was changed from an azo dye (G205: manufactured by Hayashibara Biochemical Research Institute) to an azo dye (NKX2029: manufactured by Hayashibara Biochemical Research Institute). .

[Measurement of Phase Transition Temperature]

In the same manner as in Evaluation Example 1, the state of phase transition of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation Example 2 was measured. After the temperature was raised to 120°C to remove the solvent and dried, it was confirmed that the phase transition was to nematic phase at 113°C, to smectic A phase at 107°C, and to smectic B phase at 83°C during cooling down.

Similar to Evaluation Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement were performed on the produced liquid crystal aligning element.

The results are shown in Table 1.

Evaluation example 3

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is changed from a mixture of 75 parts of compound (3-1-6) and 25 parts of compound (3-1-7) to compound (3-1-6) Except the mixture of 75 parts and 25 parts of compounds (3-1-8), it carried out similarly to Evaluation Example 1, and the liquid crystal aligning element was obtained.

[Measurement of Phase Transition Temperature]

In the same manner as in Evaluation Example 1, the state of phase transition of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation Example 3 was measured. After the temperature was raised to 120°C to remove the solvent and dried, it was confirmed that the phase transition was to nematic phase at 111°C, to smectic A phase at 105°C, and to smectic B phase at 82°C during cooling down.

Similar to Evaluation Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement were performed on the produced liquid crystal aligning element.

The results are shown in Table 1.

Evaluation example 4

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is changed from a mixture of 75 parts of compound (3-1-6) and 25 parts of compound (3-1-7) to compound (3-1-6) Except the mixture of 75 parts and 25 parts of compounds (3-1-13), it carried out similarly to Evaluation Example 1, and the liquid crystal aligning element was obtained.

[Measurement of Phase Transition Temperature]

In the same manner as in Evaluation Example 1, the state of phase transition of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation Example 4 was measured. After the temperature was raised to 130°C to remove the solvent and dried, it was confirmed that the phase transition was to nematic phase at 119°C, to smectic A phase at 111°C, and to smectic B phase at 82°C during cooling down.

Similar to Evaluation Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement were performed on the produced liquid crystal aligning element.

The results are shown in Table 1.

Evaluation Example 5

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer is changed from a mixture of 75 parts of compound (3-1-6) and 25 parts of compound (3-1-7) to compound (3-1-6) Except the mixture of 75 parts and 25 parts of compounds (3-1-14), it carried out similarly to Evaluation Example 1, and the liquid crystal aligning element was obtained.

[Measurement of Phase Transition Temperature]

In the same manner as in Evaluation Example 1, the state of phase transition of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer in Evaluation Example 5 was measured. After raising the temperature to 130°C to remove the solvent and dry it, it was confirmed that the phase transition was to nematic phase at 118°C, to smectic A phase at 109°C, and to smectic B phase at 79°C during cooling down.

Similar to Evaluation Example 1, dichroic ratio measurement, orientation state observation, and haze value measurement were performed on the produced liquid crystal aligning element.

The results are shown in Table 1.

[Table 1]

Evaluation example 6

Use polymerizable nematic liquid crystal compounds (such as A1-1, A5-1, A6-1, A7-1, A9-1, A10-1, A11-1, A15-1, A21-1, A25-1, A63-1, A69-1, A70-1, A71-1, A72-1 or A73-1), instead of the polymerizable liquid crystal (1-6) and (1- 7), without using a dichroic dye, it is formulated into a composition for forming a retardation layer, coated on the photo-alignment layer shown in Evaluation Example 1, heated to the nematic phase transition temperature, and the polymerizability is changed to The nematic liquid crystal phase liquid crystal alignment element can be made on the photo-alignment layer by polymerizing the nematic liquid crystal compound. This liquid crystal aligning element has a function as a retardation layer, and this retardation layer can make a liquid crystal phase into a desired retardation by adjusting thickness.

Industrial availability

According to the photoreactive liquid crystal aligning agent of this invention, the liquid crystal aligning element (for example, a polarizing layer, retardation layer) using a nematic liquid crystal or a smectic liquid crystal can be formed. The alignment layer made by the photoreactive liquid crystal alignment agent of the present invention has the advantages of less dust and easy patterning with a mask because the alignment layer is formed by a non-contact system, which is better than the existing method obtained by rubbing. orientation layer.

Claims (14)

1. liquid crystal aligning element, has liquid crystal aligning layer and polarization photosphere,

Described liquid crystal aligning layer is to be formed coated film by containing the photoreactivity aligning agent for liquid crystal of polymer shown in formula (1-1), right This coated film carries out polarizing light irradiation and forms,

Described polarization photosphere is by being formed as follows:

On described liquid crystal aligning layer, the coating composition solution containing polymerizable liquid crystal compound obtains coated film,

The described polymerizable liquid crystal compound contained in described coated film is carried out polarizing light irradiation be allowed to be polymerized,

In formula (1-1),

N and m represents 0 or 1 independently of one another,

V and w represents the integer of 1～3 independently of one another,

S¹And S²Represent the alkylidene of the carbon number 1～12 with or without fluorine atom or cyano group independently of one another,

S³Represent the alkyl of the carbon number 1～12 with or without fluorine atom or cyano group,

X¹、X²、X³、X⁴And X⁵Represent singly-bound, oxygen atom, carbonyl acyloxy or methylene independently of one another,

Y¹And Y²Represent singly-bound, oxygen atom or carbonyl acyloxy independently of one another,

R¹And R³Represent hydrogen atom, the alkyl of carbon number 1～4 or the alkoxyl of carbon number 1～4 independently of one another,

R²And R⁴Represent alkoxyl, cyano group or the halogen atom of carbon number 1～2 independently of one another, when v is 2 or 3, exist many Individual R²Identical or different, when w is 2 or 3, there is multiple R⁴It is identical or different,

R⁵、R⁶And R⁷Represent hydrogen atom or methyl independently of one another,

P, q and r represent each construction unit mole fraction relative to general construction unit, and it meets 0.25 ＜ p 1,0 q ＜ The relation of 0.75 and 0 r ＜ 0.75.

Liquid crystal aligning element the most according to claim 1, described polymer is the polymerization that q is 0 in described formula (1-1) Thing.

Liquid crystal aligning element the most according to claim 1, described polymer is the polymerization that r is 0 in described formula (1-1) Thing.

Liquid crystal aligning element the most according to claim 1, described polymer is the R in described formula (1-1)¹And R²The most solely It it is on the spot the polymer of methoxy or ethoxy.

Liquid crystal aligning element the most according to claim 1, described polymer is that n and m in described formula (1-1) is 0 Polymer.

Liquid crystal aligning element the most according to claim 1, described polymerizable liquid crystal compound is to present smectic liquid crystal shape The compound of state.

Liquid crystal aligning element the most according to claim 1, described polymerizable liquid crystal compound is to present high dimension smectic phase The compound of mesomorphic state.

8. liquid crystal aligning element, has liquid crystal aligning layer and inverse wave length dispersion phase separation layer,

Described liquid crystal aligning layer is to be formed coated film by containing the photoreactivity aligning agent for liquid crystal of polymer shown in formula (1-1), right This coated film carries out polarizing light irradiation and forms,

Described phase separation layer is by being formed as follows:

On described liquid crystal aligning layer, the coating composition solution containing polymerizable liquid crystal compound obtains coated film,

The described polymerizable liquid crystal compound contained in described coated film is carried out polarizing light irradiation be allowed to be polymerized,

In formula (1-1),

N and m represents 0 or 1 independently of one another,

V and w represents the integer of 1～3 independently of one another,

S¹And S²Represent the alkylidene of the carbon number 1～12 with or without fluorine atom or cyano group independently of one another,

S³Represent the alkyl of the carbon number 1～12 with or without fluorine atom or cyano group,

X¹、X²、X³、X⁴And X⁵Represent singly-bound, oxygen atom, carbonyl acyloxy or methylene independently of one another,

Y¹And Y²Represent singly-bound, oxygen atom or carbonyl acyloxy independently of one another,

R¹And R³Represent hydrogen atom, the alkyl of carbon number 1～4 or the alkoxyl of carbon number 1～4 independently of one another,

R²And R⁴Represent alkoxyl, cyano group or the halogen atom of carbon number 1～2 independently of one another, when v is 2 or 3, exist many Individual R²Identical or different, when w is 2 or 3, there is multiple R⁴It is identical or different,

R⁵、R⁶And R⁷Represent hydrogen atom or methyl independently of one another,

P, q and r represent each construction unit mole fraction relative to general construction unit, and it meets 0.25 ＜ p 1,0 q ＜ The relation of 0.75 and 0 r ＜ 0.75.

Liquid crystal aligning element the most according to claim 8, described polymer is the polymerization that q is 0 in described formula (1-1) Thing.

Liquid crystal aligning element the most according to claim 8, described polymer is the polymerization that r is 0 in described formula (1-1) Thing.

11. liquid crystal aligning elements according to claim 8, described polymer is the R in described formula (1-1)¹And R²The most solely It it is on the spot the polymer of methoxy or ethoxy.

12. liquid crystal aligning elements according to claim 8, described polymer is that n and m in described formula (1-1) is 0 Polymer.

13. liquid crystal aligning elements according to claim 8, described polymerizable liquid crystal compound is from isotropic phase liquid crystal State directly presents the compound of nematic liquid crystal state.

14. liquid crystal aligning elements according to claim 13, described polymerizable liquid crystal compound by formula (2) Suo Shi,

In formula (2),

Q¹Represent replacement or unsubstituted polycycle aromatic hydrocarbyl or replacement or unsubstituted polycycle aromatic heterocycle,

D¹And D²Represent singly-bound or the linking group of divalent independently of one another,

G¹And G²Represent the ester ring type alkyl of divalent independently of one another, this hydrogen atom contained by ester ring type alkyl by halogen atom, The alkyl of carbon number 1～4, the fluoroalkyl of carbon number 1～4, carbon number 1～4 alkoxyl, cyano group or nitro replace or nothing Replace, constitute-the CH of this ester ring type alkyl₂-replaced or without replacing by-O-,-S-or-NH-,

E¹And E²Represent singly-bound or the linking group of divalent independently of one another,

B¹And B²Represent singly-bound or the linking group of divalent independently of one another,

A¹And A²Represent ester ring type alkyl or the aromatic hydrocarbyl of divalent of divalent, this ester ring type alkyl and this fragrance independently of one another Hydrogen atom contained by race's alkyl is by halogen atom, the alkyl of carbon number 1～4, carbon number 1～4 alkoxyl, cyano group or nitre Base replaces or unsubstituted, and the hydrogen atom contained by the alkyl of this carbon number 1～4 and this carbon number 1～4 alkoxyl is former by fluorine Son replaces or replaces,

K and l represents the integer of 0～3 independently of one another, when k is more than 2, there is multiple A¹It is the most identical or different, There is multiple B¹The most identical or different, when l is more than 2, there is multiple A²The most identical or different, deposit At multiple B²It is the most identical or different,

F¹And F²Representing the alkylidene of carbon number 1～12 independently of one another, the hydrogen atom contained by this alkylidene is by carbon number The alkoxy or halogen atom of 1～5 replaces or unsubstituted, constitutes-the CH of this alkylidene₂-replaced or without replacing by-O-or-CO- Change,

P¹And P²Represent hydrogen atom, acryloxy or methacryloxy independently of one another, but P¹And P²It is asynchronously that hydrogen is former Son.