TW201311743A - Photoreactive liquid crystal alignment agent, liquid crystal alignment element and preparation method thereof - Google Patents

Abstract

The purpose of present invention is to provide a novel photoreactive liquid crystal alignment agent and a liquid crystal display element having a photoalignment layer formed by the photoreactive liquid crystal alignment agent. The present invention provides a photoreactive liquid crystal alignment agent containing the polymer represented by formula (1-1), an alignment layer formed by the photoreactive liquid crystal alignment agent and a liquid crystal element having the photoalignment layer. (In formula, Y1 and Y2 respectively represent a hydrogen atom, etc.; R2 and R4 respectively represent a C1-C2 alkoxyl group, etc.; p, q and r respectively represent a mole ratio of individual structure unit to whole structure unit and satisfy the relationship: 0.25<p≰1, 0≰q<0.75 and 0≰r<0.75).

Description

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

The present invention relates to a photoreactive liquid crystal alignment agent, a liquid crystal alignment element, and a method of manufacturing the same.

A flat panel display (FPD) includes an optically anisotropic optical anisotropic layer (alignment layer) such as a polarizing plate and a phase difference plate as members. Such optically anisotropic layers are typically formed by two methods. The first method is a method of extending a polymer to form an optically anisotropic layer, and the second method is a method of forming an optically anisotropic layer from a coating film obtained by coating an alignment agent. In particular, the latter method is advantageous in that the optically anisotropic layer formed of the alignment agent is easy to control the direction of the optical axis thereof; and the optical film formed by aligning and immobilizing the liquid crystal compound on the optically anisotropic layer ( The liquid crystal alignment element) is essentially a film; it can be continuously produced by a Roll to Roll process.

For example, Non-Patent Document 1 discloses that a liquid crystal alignment element can be obtained by applying a solution containing a polymerizable liquid crystal compound (trade name: LC242, manufactured by BASF Corporation) represented by the following formula to an alignment layer. Thereafter, the polymerizable liquid crystal compound is polymerized to obtain a polarizing layer. However, the photoalignment layer having the alignment energy of the polymerizable liquid crystal compound in the nematic phase and the higher order stratified phase, and the photoalignment agent capable of forming the photoalignment layer are not known.

[Previous Technical 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 Ultrath in Optical Films", SID Symposium Digest of Technical Papers, 2006, Volume 37, p.1673

The present invention has an optical alignment layer having an alignment energy of a polymerizable liquid crystal compound which is a nematic phase and a higher order stratified phase, and a novel photoalignment agent capable of forming the photoalignment layer (photoreaction) Liquid crystal alignment agent).

The present invention includes the following [1] to [12].

[1] A photoreactive liquid crystal alignment agent comprising the polymer represented by the formula (1-1): [In the formula (1-1), n and m each independently represent 0 or 1; v and w each independently represent an integer of 1 to 3; and S ¹ and S ² each independently represent a fluorine atom or a cyano group; An alkanediyl group having 1 to 12 carbon atoms; and S ³ represents an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group; and 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; Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group; and R ¹ and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; a group or alkoxy group having 1 to 4 carbon atoms; R ² and R ⁴ each independently represent an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of them are present. R ^{2 is the} same or different, and when w is 2 or 3, a plurality of R ^{4 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 each represent The molar fraction of the structural unit relative to all structural units, and satisfies 0.25<p 1,0 q<0.75 and 0 r<0.75 relationship].

[2] The photoreactive liquid crystal alignment agent according to [1] above, wherein the polymer is a polymer wherein q of the above formula (1-1) is 0.

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

[4] The above [1] to [3] according to any one of the light reactive liquid crystal alignment agent, wherein said polymer is R in the above formula (1-1) of ¹ and R ² are each independently methoxy or B A polymer of oxy groups.

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

[6] A liquid crystal alignment layer obtained by forming a coating film of the photoreactive liquid crystal alignment agent according to any one of the above [1] to [5], and subjecting the coating film to polarized light irradiation.

[7] A liquid crystal alignment element comprising the liquid crystal alignment layer and the polarizing layer according to [6] above, wherein the polarizing layer is obtained by coating a solution containing a polymerizable liquid crystal compound on the liquid crystal alignment layer. The coating film is formed by polymerizing the polymerizable liquid crystal compound contained in the coating film by polarized light irradiation.

[8] The liquid crystal alignment element according to [7] above, wherein the polymerizable liquid crystal compound is a compound which exhibits a liquid crystal state of a smectic phase.

[9] The liquid crystal alignment element according to [7] above, wherein the polymerizable liquid crystal compound is a compound exhibiting a liquid crystal state of a high-order layer phase.

[10] The liquid crystal alignment element according to [7] above, wherein the polymerizable liquid crystal compound is a compound which directly displays a liquid crystal state of a nematic phase from a liquid crystal state of an isotropic phase.

[11] The liquid crystal alignment element according to [10] above, wherein the polymerizable liquid crystal compound is represented by the formula (2): [In the formula (2), Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group; and D ¹ and D ² each independently represent a single a bond or a divalent linking group; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group may pass through a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, 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 substituted with -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; and A ¹ and A ² each independently represent a divalent group; An alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. An oxy group, a cyano group or a nitro group; the hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted by a fluorine atom; k and l each independently represent 0. An integer of ~3; when k is 2 or more, there are a plurality of A ¹ phases The same or different, there are a plurality of B ^{1 which are the} same or different from each other; when l is 2 or more, there are a plurality of A ^{2 which are the} same or different from each other, and there are a plurality of B ^{2 which are} identical or different from each other; F ¹ and F ² Each independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom to constitute -CH ₂ - of the alkanediyl group. It may be substituted with -O- or -CO-; P ¹ and P ² each independently represent a hydrogen atom, a propylene methoxy group or a methacryloxy group, but there is no case where both P ¹ and P ² are hydrogen atoms] .

[12] a compound represented by the formula (1-3), [In the formula (1-3), n represents 0 or 1; v represents an integer of 1 to 3; and S ¹ represents an alkanediyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group; and X ¹ and X ³ each Independently represents 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 a carbon number of 1 to 4 Alkoxy; R ² represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ^{2 are the} same or different; R ⁵ represents a hydrogen atom or a base].

According to the photoreactive liquid crystal alignment agent of the present invention, an optical alignment layer having an alignment energy of a polymerizable liquid crystal compound which is a nematic phase and a higher order stratified phase can be formed.

<Photoreactive liquid crystal alignment agent>

The photoreactive liquid crystal alignment agent of the present invention contains a photoreactive liquid crystal alignment agent of a polymer represented by the formula (1-1) (hereinafter referred to as "polymer (1-1)").

In the formula (1-1), n and m each independently represent 0 or 1.

v and w each independently represent an integer of 1 to 3.

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

S ³ represents an alkyl group having 1 to 12 carbon atoms which may contain 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.

Y ¹ and Y ² 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 having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ^{2 are the} same or different, and w is 2 or 3 In the case, there are a plurality of R ^{4 which 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 molar fraction of each structural unit with respect to all structural units, and satisfy 0.25<p 1,0 q<0.75 and 0 r<0.75 relationship.

In the above formula (1-1), the dotted line connecting the respective structural units means that the copolymerization mode of each of the structural units is not particularly limited, and is a random copolymerization, a block copolymerization, an alternating copolymerization, and a combination thereof.

The so-called S ¹ and S ² may contain carbon number of fluorine atom or a cyano alkanediyl group of 1 to 12, a portion of hydrogen atoms contained in two alkyl group means, the alkanediyl group or a fluorine atom and / or Cyano substituted group. The alkanediyl group may be linear or branched. S ¹ and S ^{2 are} preferably an unsubstituted (no fluorine atom or a cyano group) and a linear alkyl group having 1 to 12 carbon atoms, more preferably an alkyl 2 group having 2 to 11 carbon atoms. It is an ethylenediyl group, a butyldiyl group, a hexamethylene group and an undecanediyl group.

The alkyl group having 1 to 12 carbon atoms which may contain a fluorine atom or a cyano group of S ³ means a group in which an alkyl group or a hydrogen atom 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. S ^{3 is} preferably an unsubstituted (containing no fluorine atom or a cyano group) and a linear alkyl group having 1 to 12 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a octyl group. Base, fluorenyl, undecyl and dodecyl.

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

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

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

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

R ⁵ , R ⁶ and R ^{7 are} particularly preferably a methyl group.

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

As described above, p, q and r each represent the molar fraction of each structural unit with respect to all structural units of the polymer (1-1).

q preferably satisfies 0 The relationship of q < 0.25 is particularly preferably q = 0.

r preferably satisfies 0 The relationship of r < 0.25 is particularly preferably r = 0.

p preferably satisfies 0.75<p In the relationship of 1, since p=1, the formed light alignment layer is excellent in solvent resistance, and therefore it is particularly preferable. The polymer (1-1) satisfying the relationship of q=0, r=0, and p=1 substantially includes the structural unit represented by the formula (1-2).

(All symbols in the formula have the same meaning as above)

Here, a method of producing the polymer (1-1) substantially including the structural unit represented by the formula (1-2) will be described. The polymer (1-1) can be produced by polymerizing a monomer represented by the formula (1-3) (hereinafter referred to as "monomer (1-3)").

(All symbols in the formula have the same meaning as above)

The monomer (1-3) is a novel and useful compound for the production of the polymer (1-1), and the invention also includes the invention of the monomer (1-3).

Specific examples of the monomer (1-3) are, for example, the formula (M1-1-1) to the formula (M1-1-13). The compound represented, etc.

In one embodiment of the production method of the monomer (1-3), the monomer represented by the formula (1-3A) wherein X ¹ is a carbonyloxy group and Y ¹ is an oxygen atom ( 1-3)] is explained as an example. The monomer (1-3) can be produced by reacting a compound represented by the formula (1-3B) and a compound represented by the formula (1-3C). If the reaction is represented by the reaction formula, it is as follows.

In the reaction formula, X represents a halogen atom such as a chlorine atom or a bromine atom, and the meanings of the other symbols are the same as described above. The compound represented by the formula (1-3C) can be produced by a known production method according to the desired S ¹ , R ¹ , R ² and X ³ or the like. The compound represented by the formula (1-3B) is, for example, (meth)acrylofluorene chloride, (meth)acrylonitrile bromide or the like, which can be easily obtained from the market.

This reaction is usually carried out in a solvent. The solvent may be inactive to the reaction, and may have sufficient solubility for the compound represented by the formula (1-3B) and the compound represented by the formula (1-3C), and for example, chloroform or the like may be used. Methyl chloride, toluene, xylene, tetrahydrofuran and dimethylacetamide.

Further, the reaction is preferably carried out in the presence of an oxygen scavenger such as a base. The base is, for example, triethylamine, diisopropylethylamine, pyridine or dimethylaminopyridine.

Next, a method of polymerizing the monomer (1-3) to produce the polymer (1-1) will be described.

The polymerization of the polymer (1-1) produced from the monomer (1-3) is an addition polymerization such as an anionic polymerization or a radical polymerization. The embodiment of the radical polymerization may be any one of solution polymerization, bulk polymerization, emulsion polymerization, and soap-free emulsion polymerization. Among them, in view of the stability or melting point of the monomer (1-3), solution polymerization is preferred.

As the polymerization solvent in the case of solution polymerization, it is preferred to use a solvent which does not deactivate the radical activity such as benzene, dichloromethane, tetrahydrofuran or diethyl ether. Among these, in view of the solubility of the monomer (1-3), it is particularly preferred to use tetrahydrofuran as a polymerization solvent.

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

As the polymerization initiator, a thermal initiator such as a peroxide or an azo compound can be used, and the following photoinitiator can also be used. The hot starter is generally classified into a low temperature starter, a medium temperature starter, and a high temperature starter depending on the radical generation temperature. The polymerization of the monomers (1-3) may be carried out using any of the initiators, or the initiators may be used in combination, since it is easy to obtain a polymer (1-1) having a high degree of polymerization, and it is difficult to obtain A side reaction occurs, so that it is more preferably a medium temperature initiator, and further preferably an azo compound. Among the azo compounds, azobisisobutyronitrile (AIBN) is particularly preferable since it can be easily obtained.

High polymerization degree can be produced by using the above azo compound as a polymerization initiator Polymer (1-1), but in order to produce the desired molecular weight polymer (1-1), that is, in order to control the molecular weight of the polymer (1-1), a chain transfer agent may be suitably used, and atom transfer freely Base polymerization.

After the polymerization, in order to remove unreacted monomers and the like, it is preferred to carry out reprecipitation purification. Examples of the solvent used for the reprecipitation purification include water, an alcohol solvent, an ether solvent, a saturated hydrocarbon solvent, an aromatic hydrocarbon solvent, or a mixed solvent thereof, depending on the kind of the polymerization solvent used for the polymerization, and the monomer (1). 3) The type and the like are appropriately selected as a preferred solvent.

Examples of the alcohol solvent include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether. Among them, methanol, ethanol, and isopropyl alcohol are more preferable. The ether solvent may, for example, be tetrahydrofuran or dimethoxyethane, and more preferably tetrahydrofuran. Examples of the saturated hydrocarbon solvent include n-pentane, n-heptane, and cyclohexane, and more preferably n-heptane. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and chlorobenzene, and toluene and xylene are preferred. The solvent may be appropriately selected according to its safety, etc., and more preferably methanol, ethanol, isopropanol, toluene, toluene/heptane mixed solvent, water/methanol mixed solvent, water/ethanol mixed solvent, and water/tetrahydrofuran. A mixed solvent is more preferably methanol, ethanol or isopropanol.

The molecular weight of the polymer (1-1) is represented by a polystyrene-equivalent weight average molecular weight determined by, for example, a gel permeation method (GPC method), and is preferably in the range of 1 × 10 ³ to 1 × 10 ⁷ . However, when the molecular weight is too high, the solubility in a solvent is lowered, the preparation of the photoreactive liquid crystal alignment agent of the present invention becomes difficult, or the sensitivity to light irradiation tends to be lowered, so the molecular weight is preferably 1 ×10 ⁴ ~1×10 ⁶ range. Further, the analysis conditions of the GPC method for determining the molecular weight are described in the examples of the present application.

The polymer (1-1) can be produced by polymerization of the monomer (1-3) described above. Further, in the polymerization of the monomer (1-3), the polymer (1-1) of the copolymer can be produced by using the following monomers in combination. In the case where the following monomer is used, it is necessary to adjust the monomer (1-3) and the monomer shown below in such a manner that the molar fraction of each structural unit of the polymer (1-1) satisfies the above relationship. The amount of each use.

(All symbols in the formula have the same meaning as above) <Photoreactive liquid crystal alignment agent>

The photoreactive liquid crystal alignment agent of the present invention (hereinafter referred to as "the present liquid crystal alignment agent") contains the polymer (1-1), and more preferably the photoalignment layer is formed by the following photoalignment layer formation method. Contains polymer (1-1) and solvent. In order to prepare such a liquid crystal alignment agent, the polymer (1-1) is first dissolved in a solvent. The solvent can be appropriately selected from the range of the liquid crystal alignment agent which can dissolve the polymer (1-1) and obtain a precise viscosity, and examples thereof include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, and B. Alcohol solvents such as glycol methyl ether, ethylene glycol butyl hydrazine and propylene glycol monomethyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone or propylene glycol methyl ether acetate and lactic acid Ester solvent such as ethyl ester; ketone solvent such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; fat such as pentane, hexane and heptane Aromatic hydrocarbon solvent; aromatic hydrocarbon solvent such as toluene and xylene; nitrile solvent such as acetonitrile; ether solvent such as tetrahydrofuran and dimethoxyethane; chlorine solvent such as chloroform and chlorobenzene; N-methylpyrrolidone, N, A guanamine-based solvent such as N-dimethylformamide, γ-butyrolactone or dimethylacetamide. These solvents may be used alone or in combination of plural kinds.

The concentration of the polymer (1-1) relative to the liquid crystal alignment agent may be appropriately adjusted depending on the kind or solubility of the polymer (1-1), and is expressed as a solid content concentration, preferably at least 0.2 mass. %, particularly preferably in the range of 0.3 to 10% by mass. Further, the liquid crystal alignment agent may contain a polymer material such as polyvinyl alcohol or polyimine or a photosensitizer such as ruthenium.

The liquid crystal alignment agent prepared by dissolving the polymer (1-1) in a solvent can be used to form a photoalignment layer directly or, if necessary, after filtration or the like.

<Photoalignment layer formation method>

A method of forming a photoalignment layer (photoalignment layer formation method) using the liquid crystal alignment agent containing a polymer (1-1) and a solvent will be described. First, the present liquid crystal alignment agent is applied to a specific support substrate. The support substrate is preferably a transparent support substrate. As a method of coating the liquid crystal alignment agent on a transparent support substrate, the following known methods can be employed: spin coating method, extrusion coating method, gravure coating method, die coating method, bar coating method, and dressing. A coating method such as a coating method, or a printing method such as a soft plate method.

Next, the coating film formed by applying the liquid crystal alignment agent on the transparent supporting substrate removes the solvent to form a dried film. The removal of the solvent can be carried out by heating at a suitable temperature to dry the solvent (heating method); or by sealing in a suitable pressure-resistant container, The pressure in the vessel is set to a reduced pressure state, whereby the solvent is removed by drying (decompression method); air drying (ventilation method); natural drying; or a combination of the methods. It is more preferably a heating method since it can be carried out in a continuous form in the form of a Roll to Roll.

The thickness of the dried film containing the polymer (1-1) formed on the transparent supporting 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 dried film can be adjusted by adjusting the concentration of the solid component relative to the liquid crystal alignment agent (especially the solid content of the polymer (1-1)) and the coating conditions of the transparent substrate of the liquid crystal alignment agent. And to control. In the above manner, a laminate having a dry film containing the polymer (1-1) can be obtained on the transparent supporting substrate.

Then, by irradiating the dry film of the laminate with polarized UV (ultraviolet light) (polarized ultraviolet light), the polymer (1-1) is aligned to impart liquid crystal alignment energy (hereinafter referred to as "optical alignment operation" ) to form a photoalignment layer. In the light alignment operation, when the polarized light UV is applied to the laminated body, the form of the polarized UV (form (A)) may be directly applied from the dry film side of the laminated body, or the transparent base may be applied to the laminated body. The material side is irradiated with polarized light UV, and the polarized light is transmitted through the transparent substrate to irradiate the dried film with a form of polarized UV (form (B)). In any of these forms, the polarized light UV to be irradiated may be either linearly polarized UV or elliptically polarized UV, but for efficient optical alignment operation, it is preferred to use an elliptically polarized UV that is close to linear polarized light. Or quench the relatively high linear polarized UV. Further, it is particularly preferable that the polarized UV is substantially parallel light. Wherein, in the case of the photo-alignment operation by the form (B), the transparent substrate in the laminate used The higher the transparency, the better.

The polarized light UV to be irradiated is preferably a wavelength region in which the photoreactive group (cinna thiophene) of the polymer (1-1) contained in the dried film absorbs light energy. Specifically, UV (ultraviolet rays) having a wavelength in the range of 250 to 400 nm is particularly preferable. As the light source for the light alignment operation, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, an ultraviolet laser such as KrF or ArF, and the like can be cited. The light source for the light alignment operation is preferably a high pressure mercury lamp, an ultra high pressure mercury lamp and a metal halide lamp. The reason for this is that the illuminating intensity of ultraviolet rays having a wavelength of 313 nm is relatively large. When the light from the light source is irradiated to the laminated body through an appropriate polarizing element, the laminated body is irradiated with the polarized light UV. As the polarizing element, a polarizing mirror or a polarizing element such as Glan-Thompson or Gülen-Taylor or a wire grid type polarizing element can be used.

When the polarized film UV is applied to the dried film of the laminate, the direction of irradiation of the polarized light is not necessarily perpendicular to the plane direction of the layered body, and the direction of irradiation of the polarized light UV may be inclined with respect to the plane direction of the layered body. The irradiation direction of the polarized light UV with respect to the surface direction of the laminated body is set so that the obtained optical alignment layer has a desired absorption axis depending on the type of the light source used for the photoalignment operation and the type of the polarizing element.

By using the above-mentioned method or the like, a composition containing a polymerizable liquid crystal compound can be applied onto the photo-alignment layer in the photo-alignment layer formed by the liquid crystal alignment agent, and the polymerizable liquid crystal compound can be made into a nematic phase or higher. The liquid crystal state (polymerizable liquid crystal) of the smectic phase. The liquid alignment layer obtained by the liquid crystal alignment agent is such that the polymerizable liquid crystal compound is in such a liquid crystal state (polymerizable liquid crystal) and the liquid alignment layer can form a photo alignment layer. Use, this opinion is unique to the inventors and others.

When a polymerizable liquid crystal compound which can form a liquid crystal state in a smectic layer is used as the polymerizable liquid crystal compound, the polymerizable smectic liquid crystal compound can be obtained by mainly combining a dichroic dye to form a polarized light on the photoalignment film. Layered liquid crystal alignment component. In the case where a polymerizable nematic liquid crystal compound having a liquid crystal state in a smectic layer is used as the polymerizable liquid crystal compound, a liquid crystal alignment element in which a retardation layer is formed on the photoalignment film can be obtained. When a polarizing layer or a retardation layer is provided on the optical alignment layer in the above manner, the solution containing the polymerizable liquid crystal compound may be applied and dried to carry out photopolymerization. Hereinafter, the methods are classified into the case of using a polymerizable smectic liquid crystal compound and the case of using a polymerizable nematic liquid crystal compound. In the above 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 "phase difference layer forming composition".

<Liquid alignment element using a polymerizable smectic liquid crystal compound>

The polymerizable smectic liquid crystal compound is a compound having a polymerizable group and exhibiting a liquid crystal phase in a layer. The polymerizable group means a group which participates in the polymerization reaction of the polymerizable smectic liquid crystal compound.

The liquid crystal phase exhibited by the above polymerizable smectic liquid crystal compound is preferably a higher order smectic phase. Here, the high-order smectic phase is a smectic B phase, a smectic D phase, a smectic E phase, a smectic F phase, a smectic G phase, a smectic H phase, a smectic I phase, and a smectic phase J phase. , the smectic K phase and the smectic L phase, wherein the smectic B phase, the smectic F phase, the smectic I phase, the slanted smectic F phase, and the slanted smectic phase I phase are preferred. For the tier B phase. When the stratified liquid crystal phase exhibited by the polymerizable layer liquid crystal compound is high, a polarizing layer having a higher alignment degree can be formed, and a polarizing layer having higher performance can be obtained.

As a preferable polymerizable smectic liquid crystal composition, for example, a compound represented by the formula (3-1) (hereinafter referred to as "compound (3-1)") may be mentioned.

In ^{U 1 -V 1 -W 1 -E 1} -J 1 -E 2 -J 2 -E 3 -W 2 -V 2 -U 2 (3-1) [ formula (3-1), E ^1, E ² and E ³ independently of each other represent a para-phenyl group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. Wherein at least one of E ¹ , E ² and E ³ is a para-phenyl group which may have a substituent.

J ¹ and J ² independently of each other represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a 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 independently of each other represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² independently of each other represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group may be substituted by -O-, -S- or -NH-].

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

Preferably, the above-mentioned para-phenylene group is unsubstituted. The above cyclohexane-1,4-diyl group is preferably a transcyclohexane-1,4-diyl group, which is more preferably unsubstituted.

Examples of the substituent optionally contained in the above-mentioned p-phenylene group or the above cyclohexane-1,4-diyl group include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a butyl group; a cyano group; and a halogen atom. Wait. Further, -CH ₂ - constituting the cyclohexane-1,4-diyl group may be substituted with -O-, -S- or -NR ⁷ -. R ⁷ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

J ^{1 of the} 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, and is preferably a polymerizable group. That is, it is preferred that both U ¹ and U ² are a polymerizable group, and it is preferably a photopolymerizable group. Here, the photopolymerizable group means a group which can participate in a polymerization reaction by using an active radical or an acid generated from a photopolymerization initiator described below. When a polymerizable smectic liquid crystal compound having a photopolymerizable group is used, it is advantageous in that the polymerizable smectic liquid crystal compound can be polymerized under lower temperature conditions.

In the 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 groups. Examples of the photopolymerizable group include a vinyl group, a vinyloxy group, a 1-chlorovinyl group, an isopropenyl group, a 4-vinylphenyl group, an acryloxy group, a methacryloxy group, and an oxirane group. Oxetane and the like. Among them, an acryloxy group, a methacryloxy group, a vinyloxy group, an oxiranyl group, and an oxetanyl group are preferred, and an acryloxy group is more preferred.

Examples of the alkanediyl group of V ¹ and V ² include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group. Pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, Tetradecan-1,14-diyl and eicosane-1,20-diyl and the like. V ¹ and V ^{2 are} preferably an alkanediyl group having 2 to 12 carbon atoms, more preferably an alkanediyl group having 6 to 12 carbon atoms.

Examples of the substituent optionally contained in the alkanediyl group include a cyano group and a halogen atom. However, the alkanediyl group is preferably unsubstituted, and more preferably an unsubstituted and linear alkanediyl group.

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

The compound (3-1) may, for example, be a compound represented by any one of the formula (3-1-1) to the formula (3-1-24). When the specific example of the compound (3-1) has a cyclohexane-1,4-diyl group, it is preferred that the cyclohexane-1,4-diyl group is a trans group.

The exemplified compound (3-1) is referred to as "a compound according to the formula (3-1-1)" and so on.

The exemplified compound (3-1) can be used singly or in the form of a polymerizable smectic liquid crystal mixture in which two or more kinds are mixed. Further, it is also possible to use two or more kinds of polymerizable smectic compounds and at least one of the two or more polymerizable smectic compounds is the compound (3-1). In the following description, a case where a single type of polymerizable smectic liquid crystal compound is used and a case where two or more types of polymerizable smectic liquid crystal compounds are used 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 determined in advance, and the compound (3-1) for removing the composition for forming a polarizing layer is adjusted. The component other than the liquid crystal compound] is such that the compound (3-1) can be polymerized at a temperature which does not reach the phase transition temperature. Examples of such a component capable of controlling the polymerization temperature include the following photopolymerization initiators, photosensitizers, and polymerization inhibitors. The polymerization temperature of the compound (3-1) can be controlled by appropriately adjusting the kind and amount of the materials. In the case where a mixture of two or more kinds of the compound (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, After the phase transition temperature of the polymerizable layer-column liquid crystal composition, the polymerization temperature was controlled in the same manner as in the case of the polymerizable smectic liquid crystal compound.

Among the exemplified compounds (3-1), preferred are formula (3-1-3), formula (3-1-6), formula (3-1-7), formula (3-1-12), Any one of the formula (3-1-13) and the formula (3-1-23). Since the compound (3-1) is mixed or interacts with a photopolymerization initiator used in common, it is easy to transfer to the phase Under the temperature condition of the temperature, that is, the supercooled state is directly obtained in the liquid crystal state in which the high-order smectic phase is sufficiently maintained, the compound (3-1) can be polymerized. More specifically, by the interaction with the photopolymerization initiator, the compound (3-1) can be sufficiently maintained at a temperature higher than 70 ° C, preferably 60 ° C or lower. Directly polymerize in the liquid crystal state of the column.

As described above, the above compound (3-1) may be a single species or a plurality of species, and preferably a plurality of species. In the composition for forming a polarizing layer, it is preferred to use two or more kinds of polymerizable smectic liquid crystal compositions, preferably two or more kinds of compounds (3-1).

The content ratio of the compound (3-1) in the composition for forming a polarizing layer is preferably from 70 to 99.9% by mass, and more preferably from 90 to 99.9% by mass, based on the solid content of the composition for forming a polarizing layer. When the content ratio of the compound (3-1) is within the above range, the alignment of the compound (3-1) tends to be improved. Here, the solid content component refers to the total amount of components from which the volatile component such as a solvent is removed from the composition for forming a polarizing layer. In the case where the polarizing layer-forming composition contains a plurality of compounds (3-1), the total content ratio may be in the above range.

The composition for forming a polarizing layer preferably contains a leveling agent. The leveling agent is a function of adjusting the fluidity of the polymerizable liquid crystal composition and making the coating film obtained by applying the composition for forming a polarizing layer to be more flat, and examples thereof include a surfactant. Further preferably, the leveling agent is at least one selected from the group consisting of a leveling agent containing a polyacrylate compound as a main component and a leveling agent containing a fluorine atom-containing compound as a main component.

As a leveling agent containing a polyacrylate compound as a main component, it can be enumerated BYK-350, BYK-352, BYK-353, BYK-354, BYK-355, BYK-358N, BYK-361N, BYK-380, BYK -381" and "BYK-392" [BYK Chemie] etc.

Examples of the leveling agent containing a fluorine atom-containing compound as a main component include "MEGAFAC R-08", "MEGAFAC R-30", "MEGAFAC R-90", "MEGAFAC F-410", and "MEGAFAC F-" 411", "MEGAFAC F-443", "MEGAFAC F-445", "MEGAFAC F-470", "MEGAFAC F-471", "MEGAFAC F-477", "MEGAFAC F-479", "MEGAFAC F-482" ""MEGAFAC F-483" [DIC Co., Ltd.]; "SURFLON S-381", "SURFLON S-382", "SURFLON S-383", "SURFLON S-393", "SURFLON SC-101", "SURFLON SC-105", "KH-40" and "SA-100" [AGC Seimi Chemical Co., Ltd.]; "E1830", "E5844" [Daikin Fine Chemical Institute]; "EFTOP EF301", "EFTOP EF303", "EFTOP EF351" and "EFTOP EF352" [Mitsubishi Materials Electronic Chemicals Co., Ltd.].

When the leveling agent is contained in the composition for forming a polarizing layer, the content thereof is preferably 0.3 parts by mass or more and 5 parts by mass or less, more preferably 0.5% by mass based on 100 parts by mass of the polymerizable smectic liquid crystal compound. More than 3 parts by weight. When the content of the leveling agent is in the above range, the polymerizable smectic liquid crystal compound tends to be aligned horizontally, and the formed polarizing layer tends to be smoother. If the content of the leveling agent relative to the polymerizable layer liquid crystal compound exceeds the above range, the obtained polarizing layer is liable to be produced. The tendency of both. Further, the composition for forming a polarizing layer may contain two or more kinds of leveling agents.

The composition for forming a polarizing layer contains a solvent. The solvent is 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 which does not significantly affect the polymerization reaction of the polymerizable layer liquid crystal compound is preferred. Such a solvent is the same as exemplified as a solvent for preparing the liquid crystal alignment agent composition. The solvent for preparing the composition for forming a polarizing layer may be used singly or in combination of plural kinds.

The content of the solvent in the composition for forming a polarizing layer is preferably from 50 to 98% by mass based on the total amount of the composition for forming a polarizing layer. On the other hand, when the solid content component of the composition for forming a polarizing layer is 50% by mass or less, the viscosity of the composition is lowered, so that the thickness of the coating film is substantially uniform. Further, the solid component can be determined in such a manner that the polarizing layer reaches a desired thickness.

The composition for forming a polarizing layer preferably contains a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator in terms of starting a polymerization reaction of the polymerizable layer-column liquid crystal compound in order to start the polymerization reaction under a lower temperature condition. Specifically, a compound which can generate an active radical or an acid by the action of light under such temperature conditions can be used as a photopolymerization initiator. Among the photopolymerization initiators, those which generate radicals by the action of light are more preferred.

Examples of the photopolymerization initiator include a benzoin compound, a benzophenone compound, an alkylphenol compound, a mercaptophosphine oxide compound, and the like. Compounds, strontium salts and strontium salts.

Specific examples of the photopolymerization initiator are listed below.

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

Examples of the benzophenone compound include benzophenone, methyl phthalic acid benzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl sulfide. 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenol compound include diethoxyacetophenone and 2-methyl-2- Lolinyl-1-(4-methylthienyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane- 1-ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2- An oligomer of methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one or the like.

Examples of the fluorenylphosphine oxide compound include (2,4,6-trimethylbenzylidene)diphenylphosphine oxide and bis(2,4,6-trimethylbenzhydrazide)phenylphosphine oxide. .

As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Wait.

The photopolymerization initiator can also be used as it is readily available from the market. Examples of commercially available photopolymerization initiators include "Irgacure 907", "Irgacure 184", "Irgacure 651", "Irgacure 819", "Irgacure 250", and "Irgacure 369" (Ciba Japan Co., Ltd.); "Seikuol BZ", "Seikuol Z", "Seikuol BEE" (Seiko Chemical Co., Ltd.); "Kayacure BP100" (Japan Chemical Pharmaceutical Co., Ltd.); "Kayacure UVI-6992" (manufactured by Dow); "Adeka Optomer SP-152", "Adeka Optomer SP-170" (ADEKA Co., Ltd.); "TAZ-A", "TAZ-PP" (Nihon Siber Hegner); and "TAZ-104" (Sanwa Chemical).

When the composition for forming a polarizing layer contains a polymerization initiator, the content thereof can be appropriately adjusted depending on the kind and amount of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer, for example, relative to polymerization. The total amount of the polymerization initiator is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, even more preferably from 0.5 to 8 parts by mass, per 100 parts by mass of the liquid crystal compound. When the content of the polymerizable initiator is within this range, the alignment of the polymerizable smectic liquid crystal compound can be prevented from being polymerized, so that the polymerizable smectic liquid crystal compound can maintain the liquid crystal state of the high-order layer phase directly. polymerization.

Further, when the composition for forming a polarizing layer contains a photopolymerization initiator, the composition may further contain a photosensitizer. As the photosensitizer, for example, Ketone and 9-oxosulfur Wait Ketone compounds (eg 2,4-diethyl-9-oxosulfur 2-isopropyl-9-oxosulfur And other compounds such as anthracene and alkoxy-containing anthracene (e.g., dibutoxyanthracene); And red fluorene and the like.

When the composition for forming a polarizing layer is 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 promoted. The amount of the photosensitizer to be used may be appropriately adjusted depending on the kind and amount of the photopolymerization initiator and the polymerizable smectic liquid crystal compound to be used together, for example, 100 parts by mass based on the total of the polymerizable stratified liquid crystal compound, preferably 0.1. ~30 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass.

The above-mentioned composition for forming a polarizing layer contains a photosensitizer, and the polymerization reaction of the polymerizable smectic liquid crystal compound can be promoted. Although the polymerization reaction has been described above, the polarizing layer can be made to stably carry out the polymerization reaction. The composition for forming contains a polymerization inhibitor as appropriate. The degree of progress of the polymerization reaction of the polymerizable smectic liquid crystal compound can be controlled by containing a polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, alkoxy-containing hydroquinone, alkoxy-containing catechol (for example, butyl catechol), and pyrogallol. A radical scavenger such as 2,2,6,6-tetramethyl-1-piperidinyloxy radical; thiophenols; β-naphthylamines and β-naphthols.

When the composition for forming a polarizing layer contains a polymerization inhibitor, the content thereof may be appropriately adjusted depending on the kind and amount of the polymerizable stratified liquid crystal compound to be used, the amount of the photosensitizer used, and the like, for example, relative to polymerization. The total amount of the polymerization inhibitor is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 10 parts by mass, even more preferably from 0.5 to 8 parts by mass, based on 100 parts by mass of the liquid crystal compound. When the content of the polymerization inhibitor is within this range, the polymerizable layer liquid crystal contained in the composition for forming a polarizing layer can be prevented from being disturbed. Since the polymerizable layer is polymerized, the polymerizable layer-aligned liquid crystal compound can be directly polymerized by maintaining the liquid crystal state of the high-order layer phase more satisfactorily.

The composition for forming a polarizing layer described above is applied onto a photo-alignment layer of a laminate (first laminate) provided with a transparent support substrate and a photo-alignment layer to obtain a coating film, and a coating film is obtained in the coating film. The polymerizable smectic liquid crystal compound is dried without being polymerized to form a dried film for forming a polarizing layer, thereby obtaining a second layered product.

The method (coating method) and the drying method of applying the composition for forming a polarizing layer to the first laminate are the same as those described for the method of applying the liquid crystal alignment agent to a transparent support substrate. . The thickness of the coating film formed in the above manner is preferably in the range of 0.5 to 10 μm, and more preferably in the range of 0.5 to 3 μm. The thickness of the coating film is determined in such a manner that the obtained polarizing layer reaches a desired thickness. Further, the thickness of the polarizing layer is determined by measurement by an interference film thickness meter, a laser microscope or a stylus type film thickness meter.

Furthermore, the polymerizable smectic liquid crystal compound contained in the dried coating film (the dried film for forming a polarizing layer) of the second layered product is photopolymerized, and the polymerizable layer liquid crystal compound retains the smectic phase, It is preferred to directly polymerize in the liquid crystal state of the high-order layer phase as exemplified, and as a result, the dried film is added to the polarizing layer.

<Liquid alignment element using a polymerizable nematic liquid crystal compound>

Next, a method of forming a retardation layer on a photo-alignment film formed of the liquid crystal alignment agent using a composition for forming a retardation layer (a solution containing a polymerizable nematic liquid crystal compound) will be described.

The polymerizable nematic liquid crystal compound to be contained in the composition for forming a retardation layer is, for example, a compound represented by the formula (20) (hereinafter referred to as "compound (20)").

P ¹¹ -E ¹¹ -(B ¹¹ -A ¹¹ ) _t -B ¹² -G (20) [In the formula (20), A ¹¹ represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent a heterocyclic group, the divalent aromatic hydrocarbon group, the divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the divalent heterocyclic group may have a halogen atom, an alkyl group having 1 to 6 carbon atoms, and a carbon number An alkoxy group of 1 to 6 , an N-alkylamino group having 1 to 6 carbon atoms, an N,N-dialkylamino group having 2 to 12 carbon atoms, a nitro group, a cyano group or a thio group.

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 bonded to form an alkanediyl 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 alkanediyl group having 1 to 12 carbon atoms. The hydrogen atom contained in the alkanediyl group 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.

P ¹¹ represents a polymerizable group.

G is a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, an N-alkylamino group having 1 to 13 carbon atoms, N,N-dialkylamino, cyano, nitro, or a carbon number of 2 to 26 carbon atoms A polymerizable group bonded to an alkanediyl group of 1 to 12, and a hydrogen atom contained in the alkanediyl 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.

t represents an integer from 1 to 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 the polymerizable group in P ¹¹ and G include a vinyl group, a vinyloxy group, a styryl group, a p-(2-phenylvinyl)phenyl group, an acryloyl group, an acryloxy group, and a methacryl group. , methacryloxyloxy group, carboxyl group, ethyl hydrazino group, hydroxyl group, amine carbaryl group, amine group, N-alkylamino group having 1 to 4 carbon atoms, epoxy group, oxetanyl group, formazan group Base, -N=C=O and N=C=S, etc. Among them, in terms of high photopolymerization reactivity, a radical polymerizable group or a cationic polymerizable group is preferred, and propylene is preferred because it is easy to handle and the liquid crystal compound is easier to manufacture. Oxy, methacryloxy or vinyloxy.

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

The compound (20) is, for example, a compound represented by the formula (20-1) and a compound represented by the 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 the formulas (20-1) and (20-2), P ¹¹ , E ¹¹ , B ¹¹ , A ¹¹ and B ¹² have the same meaning as described above.

F ¹¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 13 carbon atoms, an alkoxy group having 1 to 13 carbon atoms, a fluoroalkyl group having 1 to 13 carbon atoms, and an N-alkylamino group having 1 to 13 carbon atoms. An N,N-dialkylamino group having a carbon number of 2 to 26, a cyano group or a nitro group.

E ¹² represents an alkanediyl group having 1 to 12 carbon atoms, and the alkanediyl 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.

P ¹² represents a polymerizable group.

t ¹ and t ² each independently represent an integer of 1 to 5].

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

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 the formulae (I) to (V), A ¹² ~ A ¹⁵ have the same meaning as A ¹¹ , B ¹³ ~ B ¹⁶ has the same meaning as B ¹¹ ].

Further, among the compounds represented by the formula (20-1), the formula (20-2), the formula (I), the formula (II), the formula (III), the formula (IV) and the formula (V), P ¹¹ and E ^{11 is} preferably bonded via an ether bond or an ester bond, and P ¹² and E ^{12 are} preferably bonded via an ether bond or an ester bond.

Specific examples of the polymerizable nematic liquid crystal compound include compounds represented by formula (I-1) to formula (I-5), formula (B1) to formula (B20), and formula (C1) to formula (C4). a compound represented by the formula (I); a compound represented by the formula (II) represented by the formula (II-1) to the formula (II-6); a compound represented by the formula (II); (III-19) to (III-19) The compound represented by the formula (III); the formula (IV-1) to the formula (IV-14) The compound represented by the formula (IV); the compound represented by the formula (V-1) to the formula (V-5) and the compound represented by the formula (V). Furthermore, in the formula, k represents an integer from 1 to 11, and the * symbol represents a bond key. It is preferred that these polymerizable nematic liquid crystal compounds are relatively easy to manufacture or are commercially available from the market.

(The two * in the formula (B1) are bonded to any one of (B1-1) to (B1-8).)

(The two * in the formula (B2) are bonded to any one of (B2-1) to (B2-8).)

(The two * in the formula (B3) are bonded to any one of (B3-1) to (B3-8).)

(The two * in the formula (B4) are bonded to any one of (B4-1) to (B4-8).)

(Two of the formulas (B5) are bonded to any one of (B5-1) to (B5-8).)

(The two of the formulas (B6) are bonded to any one of (B6-1) to (B6-8).)

(The two * in the formula (B7) are bonded to any one of (B7-1) to (B7-8).)

(The two * in the formula (B8) are bonded to any one of (B8-1) to (B8-8).)

(The two * in the formula (B9) are bonded to any one of (B9-1) to (B9-8).)

(The two * in the formula (B10) are bonded to any one of (B10-1) to (B10-8).)

(The two * in the formula (B11) are bonded to any one of (B11-1) to (B11-8).)

(The two * in the formula (B12) are bonded to any one of (B12-1) to (B12-8).)

(Two of the formulas (B13) are bonded to any one of (B13-1) to (B13-8).)

(The two * in the formula (B14) are bonded to any one of (B14-1) to (B14-8).)

(The two of the formulas (B15) are bonded to any one of (B15-1) to (B15-8).)

(The two * in the formula (B16) are bonded to any one of (B16-1) to (B16-8).)

(Two of the formulas (B17) are bonded to any one of (B17-1) to (B17-8).)

(Two of the formulas (B18) are bonded to any one of (B18-1) to (B18-8).)

(The two * in the formula (B19) are bonded to any one of (B19-1) to (B19-8).)

(Two of the formulas (B20) are bonded to any one of (B20-1) to (B20-8).)

(The two * in the formula (C1) are bonded to any one of (C1-1) to (C1-8).)

(The two * in the formula (C2) are bonded to any one of (C2-1) to (C2-8).)

(The two * in the formula (C3) are bonded to any one of (C3-1) to (C3-8).)

(The two * in the formula (C4) are bonded to any one of (C4-1) to (C4-8).)

In the same manner as the compound (20), the polymerizable nematic liquid crystal compound represented by the formula (2) (hereinafter referred to as "compound (2)") may be used as the composition for forming a retardation layer. The user forms a phase difference layer on the light alignment layer.

[In the formula (2), Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group, or a substituted or unsubstituted polycyclic aromatic heterocyclic group; and D ¹ and D ² are each independently represented. a single bond or a divalent linking group; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group may pass through a halogen atom and an alkyl group having 1 to 4 carbon atoms. a fluoroalkyl group having 1 to 4 carbon atoms, 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 substituted with -O-, -S- or -NH-; E ¹ and E ² each independently represent a single bond or a divalent linking group; and B ¹ and B ² each independently represent a single bond or a divalent linking group; and A ¹ and A ² each independently represent 2 The alicyclic hydrocarbon group or the divalent aromatic hydrocarbon group, the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, an alkyl group having 1 to 4 carbon atoms, and a carbon number of 1 to 4. Alkoxy, cyano or nitro substituted; the hydrogen atom contained in the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms may be substituted by a fluorine atom; k and l are each independently represented an integer of 0 to 3; K is the case when 2 or more, presence of a plurality of A ¹ interoperability Are the same or different, there are a plurality of B ¹ are the same or different from each other; when l is 2 or more the case, the presence of a plurality of A ² each are the same or different, there are a plurality of B ² are the same or different from each other; F ¹ and F ² Each independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom to constitute -CH ₂ - of the alkanediyl group. It may be substituted with -O- or -CO-; P ¹ and P ² each independently represent a hydrogen atom, a propylene methoxy group or a methacryloxy group, but there is no case where both P ¹ and P ² are hydrogen atoms] .

Specific examples of Q ¹ include a group represented by any one 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 bond.

In the formula (2), D ¹ and D ² each independently represent a single bond or a divalent linking group. Examples of the divalent linking group 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 having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, etc.). ). R ⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, butyl group, etc.).

Among these, it is preferred that D ¹ and D ² are each independently *-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) The bond key of one of the indicated bases. Preferably, R ⁴ , R ⁵ , R ⁶ and R ⁷ each independently represent 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. R ^{8 is} preferably a hydrogen atom, a methyl group or an ethyl group.

The divalent alicyclic hydrocarbon group of G ¹ and G ² is preferably a group having a number of atoms (ring-forming atoms) constituting the ring in the range of 3 to 10. When the ring-forming atom contains a hetero atom, the number of the hetero atom is 2 or less. Specific examples of the alicyclic hydrocarbon group are those represented by any one of the formulae (g-1) to (g-10). Among them, the divalent alicyclic hydrocarbon group of G ¹ and G ² is more preferably a 5-membered ring or a 6-membered ring alicyclic hydrocarbon group.

(where * indicates a keying key)

The hydrogen atom contained in the group represented by any one of the above formulas (g-1) to (g-10) may be substituted with a substituent such as a methyl group, an ethyl group, an isopropyl group or a t-butyl group. An alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group; a fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; and a carbon number such as a trifluoromethoxy group a fluoroalkoxy group of 1 to 4; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

G ¹ and G ^{2 are} preferably a group represented by the formula (g-1), further preferably a 1,4-cyclohexanediyl group, and particularly preferably a trans 1,4-cyclohexanediyl group.

Examples of the divalent linking group of E ¹ and E ² include -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, and -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 -, and the like. 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 the divalent linking group of B ¹ and B ² include -CR ⁹ R ¹⁰ -, -CH ₂ -CH ₂ -, -O-, -S-, -CO-O-, and -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 -, and the like.

From the viewpoint of easier production, it is preferred that B ¹ and B ² are each independently -CH ₂ -CH ₂ -, -CO-O-, -O-CO-, -CO-NH-, -NH-CO. -, -O-CH ₂ -, -CH ₂ -O- or a single bond, and -CO-O- or -O-CO- is preferable in terms of the compound (2) showing particularly high liquid crystallinity.

Further, in terms of the compound (2) which can be produced more easily, it is preferred that B ¹ is the same as B ² .

Specific examples of the divalent alicyclic hydrocarbon group or the divalent aromatic hydrocarbon group in A ¹ and A ² include the formula (g-1) to the formula (g-10) shown by G ¹ and G ² . The group represented by any one of them is an aromatic hydrocarbon group having a carbon number of 6 to 20 represented by any one of the following formulas (a-1) to (a-8).

The hydrogen atom contained in the group represented by the above formula (a-1) to formula (a-8) may be substituted with a substituent such as a methyl group, an ethyl group, an isopropyl group or a third butyl group; Alkyl group of ~4; alkoxy group having 1 to 4 carbon atoms such as methoxy group and ethoxy group; fluoroalkyl group having 1 to 4 carbon atoms such as trifluoromethyl group; carbon number 1 to 4 such as trifluoromethoxy group a fluoroalkoxy group; a cyano group; a nitro group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom.

Among them, as A ¹ and A ² , a 1,4-phenylene group or a 1,4-cyclohexanediyl group is preferable, and in terms of production of the compound (2), it is more preferably 1,4. - Stretch phenyl. Further, in terms of making the compound (2) easier to manufacture, it is preferred that A ¹ is the same as A ² .

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

The alkanediyl 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 -, -(CH ₂ ) ₄ -, -(CF ₂ ) ₆ -, - (CF ₂ ) ₈ -, more preferably -(CH ₂ ) ₄ -, -(CH ₂ ) ₆ -.

Preferably, B ¹ and B ² are each independently -O-, -CO-O-, -O-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or a single bond.

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but there is no case where the same hydrogen atom is present. That is, at least one of P ¹ and P ² is a polymerizable group. In the aspect of the tendency that the hardness of the phase difference layer obtained from the compound (2) is excellent, it is more preferable that both P ¹ and P ² are a polymerizable group.

The polymerizable group may be any group which can participate in the polymerization reaction of the compound (2). The polymerizable group of U ¹ and U ^{2 in} the above compound (3-1) is repeated, but specific examples of the polymerizable group include a vinyl group, a vinyloxy group, a styryl group, and a p-(2-benzene group). Phenyl, phenyl fluorenyl, methacryl fluorenyl, propylene decyloxy, methacryloxycarbonyl, carboxyl, ethyl hydrazino, hydroxy, amine carbhydryl, N- to 1-4 An alkylamino group, an amine group, an epoxy group, an oxetanyl group, a decyl group, an isocyanate group, an isothiocyana group or the like. Among them, in terms of photopolymerization, a radical polymerizable group and a cationic polymerizable group are preferable, and in terms of easy handling and easy production of the compound (2), propylene oxide is more preferable. Or a methacryloxy group, more preferably an acryloxy group.

The polymerizable group may be directly bonded to F ¹ and F ² , but is preferably bonded via one or more divalent linking groups (for example, a linking group of two of B ¹ and B ² described above).

As -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 thereof include the groups represented by the formula (R-1) to the formula (R-134). * indicates The bond key of one of the indicated bases.

The compound (2) is a compound represented by the formula (A1) to the formula (A73). (The two * in the formula (A1) are bonded to any one of (A1-1) to (A1-8).)

(The two * in the formula (A2) are bonded to any one of (A2-1) to (A2-8).)

(The two * in the formula (A3) are bonded to any one of (A3-1) to (A3-8).)

(The two * in the formula (A4) are bonded to any one of (A4-1) to (A4-8).)

(The two * in the formula (A5) are bonded to any one of (A5-1) to (A5-8).)

(The two * in the formula (A6) are bonded to any one of (A6-1) to (A6-8).)

(The two * in the formula (A7) are bonded to any one of (A7-1) to (A7-8).)

(The two * in the formula (A8) are bonded to any one of (A8-1) to (A8-8).)

(The two * in the formula (A9) are bonded to any one of (A9-1) to (A9-8).)

(The two * in the formula (A10) are bonded to any one of (A10-1) to (A10-8).)

(The two * in the formula (A11) are bonded to any one of (A11-1) to (A11-8).)

(The two * in the formula (A12) are bonded to any one of (A12-1) to (A12-8).)

(The two * in the formula (A13) are bonded to any one of (A13-1) to (A13-8).)

(The two * in the formula (A14) are bonded to any one of (A14-1) to (A14-8).)

(The two * in the formula (A15) are bonded to any one of (A15-1) to (A15-8).)

(The two * in the formula (A16) are bonded to any one of (A16-1) to (A16-8).)

(The two * in the formula (A17) are bonded to any one of (A17-1) to (A17-8).)

(The two * in the formula (A18) are bonded to any one of (A18-1) to (A18-8).)

(The two * in the formula (A19) are bonded to any one of (A19-1) to (A19-8).)

(The two * in the formula (A20) are bonded to any one of (A20-1) to (A20-8).)

(The two * in the formula (A21) are bonded to any one of (A21-1) to (A21-8).)

(The two * in the formula (A22) are bonded to any one of (A22-1) to (A22-8).)

(The two * in the formula (A23) are bonded to any one of (A23-1) to (A23-8).)

(The two * in the formula (A24) are bonded to any one of (A24-1) to (A24-8).)

(The two * in the formula (A25) are bonded to any one of (A25-1) to (A25-8).)

(The two * in the formula (A26) are bonded to any one of (A26-1) to (A26-8).)

(The two * in the formula (A27) are bonded to any one of (A27-1) to (A27-8).)

(The two * in the formula (A28) are bonded to any one of (A28-1) to (A28-8).)

(The two * in the formula (A29) are bonded to any one of (A29-1) to (A29-8).)

(The two * in the formula (A30) are bonded to any one of (A30-1) to (A30-8).)

(The two * in the formula (A31) are bonded to any one of (A31-1) to (A31-8).)

(The two * in the formula (A32) are bonded to any one of (A32-1) to (A32-8).)

(The two * in the formula (A33) are bonded to any one of (A33-1) to (A33-8).)

(The two * in the formula (A34) are bonded to any one of (A34-1) to (A34-8).)

(The two * in the formula (A35) are bonded to any one of (A35-1) to (A35-8).)

(The two * in the formula (A36) are bonded to any one of (A36-1) to (A36-8).)

(The two * in the formula (A37) are bonded to any one of (A37-1) to (A37-8).)

(The two * in the formula (A38) are bonded to any one of (A38-1) to (A38-8).)

(The two * in the formula (A39) are bonded to any one of (A39-1) to (A39-8).)

(The two * in the formula (A40) are bonded to any one of (A40-1) to (A40-8).)

(The two * in the formula (A41) are bonded to any one of (A41-1) to (A41-8).)

(The two * in the formula (A42) are bonded to any one of (A42-1) to (A42-8).)

(The two * in the formula (A43) are bonded to any one of (A43-1) to (A43-8).)

(The two * in the formula (A44) are bonded to any one of (A44-1) to (A44-8).)

(The two * in the formula (A45) are bonded to any one of (A45-1) to (A45-8).)

(The two * in the formula (A46) are bonded to any one of (A46-1) to (A46-8).)

(The two * in the formula (A47) are bonded to any one of (A47-1) to (A47-8).)

(The two * in the formula (A48) are bonded to any one of (A48-1) to (A48-8).)

(The two * in the formula (A49) are bonded to any one of (A49-1) to (A49-8).)

(The two * in the formula (A50) are bonded to any one of (A50-1) to (A50-8).)

(The two * in the formula (A51) are bonded to any one of (A51-1) to (A51-8).)

(The two * in the formula (A52) are bonded to any one of (A52-1) to (A52-8).)

(The two * in the formula (A53) are bonded to any one of (A53-1) to (A53-8).)

(The two * in the formula (A54) are bonded to any one of (A54-1) to (A54-8).)

(The two * in the formula (A55) are bonded to any one of (A55-1) to (A55-8).)

(The two * in the formula (A56) are bonded to any one of (A56-1) to (A56-8).)

(The two * in the formula (A57) are bonded to any one of (A57-1) to (A57-8).)

(The two * in the formula (A58) are bonded to any one of (A58-1) to (A58-8).)

(The two * in the formula (A59) are bonded to any one of (A59-1) to (A59-8).)

(The two * in the formula (A60) are bonded to any one of (A60-1) to (A60-8).)

(The two * in the formula (A61) are bonded to any one of (A61-1) to (A61-8).)

(The two * in the formula (A62) are bonded to any one of (A62-1) to (A62-8).)

(The two * in the formula (A63) are bonded to any one of (A63-1) to (A63-8).)

(The two * in the formula (A64) are bonded to any one of (A64-1) to (A64-8).)

(The two * in the formula (A66) are bonded to any one of (A66-1) to (A66-8).)

(The two * in the formula (A67) are bonded to any one of (A67-1) to (A67-8).)

(The two * in the formula (A68) are bonded to any one of (A68-1) to (A68-8).)

(The two * in the formula (A69) are bonded to any one of (A69-1) to (A69-8).)

(The two * in the formula (A70) are bonded to any one of (A70-1) to (A70-8).)

(The two * in the formula (A71) are bonded to any one of (A71-1) to (A71-8).)

(The two * in the formula (A72) are bonded to any one of (A72-1) to (A72-8).)

(The two * in the formula (A73) are bonded to any one of (A73-1) to (A73-8).)

The polymerizable nematic liquid crystal compound used for forming the retardation layer may be the compound (2) exemplified exemplified, or two or more kinds thereof may be appropriately mixed. In particular, when a compound represented by any one of the formulae (A1) to (A73) is used, the obtained retardation layer is preferably a reverse wavelength dispersion retardation layer. The compound (2) is also preferable in terms of its wavelength dispersion property showing a more desirable reverse wavelength dispersion property.

It is preferable that the composition for forming a retardation layer further contains a polymerization initiator. A suitable polymerization initiator is the same as those exemplified as the preferred polymerization initiator in the composition for forming a polarizing layer. Again, with the above bias In the same manner, in order to further promote polymerization of a polymerizable liquid crystal compound (polymerizable nematic liquid crystal compound), the phase difference layer forming composition may further contain a photosensitizer or a polymerization inhibitor for controlling polymerization. . The photosensitizer or polymerization inhibitor is as described above for the composition for forming a polarizing layer. Further, similarly to the composition for forming a polarizing layer, the composition for forming a retardation layer may further contain a leveling agent.

In terms of fluidity, it is preferred that the composition for forming a phase difference layer contains a solvent, particularly an organic solvent. The organic solvent can be appropriately selected depending on the type and amount of the polymerizable nematic liquid crystal compound used in the composition for forming a retardation layer, and specific examples thereof include methanol, ethanol, ethylene glycol, and isopropanol. Alcohol solvent such as propylene glycol, ethylene glycol methyl ether or ethylene glycol butyl ether; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, lactate B Ester ester solvent; acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone and other ketone solvents; pentane, hexane, heptane and other non-chlorinated aliphatic Hydrocarbon solvent; non-chlorinated aromatic hydrocarbon solvent such as toluene, xylene or phenol; nitrile solvent such as acetonitrile; ether solvent such as propylene glycol monomethyl ether, tetrahydrofuran or dimethoxyethane; chlorinated hydrocarbon solvent such as chloroform or chlorobenzene; Phenol; etc. These organic solvents may be used singly or in combination of plural kinds. More preferred are alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents, and non-chlorinated aromatic hydrocarbon solvents.

When the organic solvent is used in the composition for forming a phase difference layer, the content thereof is from 10 to 10,000 parts by mass, preferably from 100 to 5,000 parts by mass, per 100 parts by mass of the polymerizable nematic liquid crystal compound. There is a tendency that it becomes difficult to cause unevenness in the film thickness of the formed retardation layer. The composition for forming the retardation layer has a viscosity of 0.1 to 10 mPa·s, preferably 0.1 to 7 mPa·s. Therefore, the kind and amount (content) of the organic solvent used in the composition for forming a phase difference layer can be determined in such a manner as to achieve such a preferable viscosity.

Moreover, the solid content concentration in the composition for forming a phase difference layer is in the range of 2 to 50% by mass, preferably 5 to 50% by mass. When the solid content concentration is 2% by mass or more, the retardation layer does not become too thin, and the tendency to obtain a retardation layer which is a birefringence necessary for optical compensation of a liquid crystal panel of a liquid crystal display device is easily obtained. . In addition, when the concentration of the solid content component is 50% by mass or less, the viscosity of the composition for forming a retardation layer does not become too small, and the viscosity is moderate. Therefore, it is difficult to produce a film thickness of the phase difference layer. The tendency of both. In addition, the solid content component is a component which removes a volatile component, such as an organic solvent, from the composition for forming a phase difference layer.

The phase difference layer is used to convert linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converts circularly polarized or elliptically polarized light into linearly polarized light.

The retardation layer can be obtained by polymerizing the polymerizable nematic liquid crystal compound contained in the composition for forming a phase difference layer.

The composition for forming a phase difference layer is applied onto the photoalignment layer formed of the liquid crystal alignment agent, and dried to obtain an unpolymerized film (a dried film for forming a retardation layer). In addition, the coating method or the drying method is the same as that described in the method of obtaining a coating film for forming a polarizing layer and drying a film from the coating film for forming a polarizing layer.

The polymerizable nematic liquid crystal in the unpolymerized film is brought into a liquid crystal state of the nematic phase, and then polymerized, whereby the phase difference layer obtained exhibits birefringence due to single domain alignment.

The film of the phase difference layer can be controlled by appropriately adjusting the solid content concentration of the phase difference layer forming composition, the content of the organic solvent, and the coating amount of the phase difference layer forming composition on the support substrate. thick. When the content of the polymerizable nematic liquid crystal compound contained in the composition for forming a phase difference layer is fixed, the phase difference (delay value, Re(λ)) of the phase difference layer obtained is based on the formula (7). Re(λ)=d×Δn(λ) (7) (wherein, Re(λ) represents the phase difference of the wavelength λ nm, d represents the film thickness, and Δn(λ) represents the birefringence of the wavelength λ nm rate)

Therefore, in order to obtain the desired Re (λ), it is only necessary to adjust the film thickness d and Δn (λ).

The method of polymerizing the polymerizable nematic liquid crystal compound in the unpolymerized film can be appropriately determined depending on the kind of the polymerizable nematic liquid crystal compound. In the case where the polymerizable nematic liquid crystal compound contains a photopolymerizable group as a polymerizable group, a photopolymerization method is used, and in the case where the polymerizable group is a thermally polymerizable group, a thermal polymerization method is used. The polymerizable nematic liquid crystal compound can be polymerized at a low temperature by a photopolymerization method, and it is preferable to use light in terms of a wide selection of heat resistance of the support substrate and industrial production. A polymerizable nematic liquid crystal compound having a polymerizable polymerizable group. Further, photopolymerization is also preferable from the viewpoint of film formability. The polymerization of photopolymerization is carried out by irradiating the unpolymerized film with visible light, ultraviolet light or laser light. get on. In terms of ease of operation, it is especially preferred for ultraviolet light. Light irradiation can also be carried out at a temperature at which the compound of the present invention is a liquid crystal phase. At this time, the polymer film may be patterned by masking or the like.

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

The retardation layer obtained in the above manner is thinner than the stretched film obtained by stretching the polymer to obtain a phase difference. Further, by combining with the light alignment layer formed of the liquid crystal alignment agent, the direction of the patterning or the phase advance axis (slow phase axis) can be freely controlled.

Further, the retardation layer is excellent in transparency, and the thickness of the retardation layer used as a film for various displays is different depending on the phase difference of the optical film as described above, and preferably 0.1 to 10 μm, thereby reducing light. In terms of elasticity, it is preferably 0.2 to 5 μm, and particularly preferably 0.5 to 3 μm.

The phase difference value of the phase difference layer exhibiting birefringence is about 50 to 500 nm, preferably 100 to 300 nm.

Such a phase difference layer can achieve the same polarization conversion in a wider wavelength region. Therefore, the liquid crystal alignment element in which the retardation layer and the light alignment layer formed of the liquid crystal alignment agent are combined can be used as an optical compensation film in all liquid crystal panels or FPDs such as organic EL (Electro Luminescence).

The above retardation layer can be used as a broadband λ/4 plate or a λ/2 plate. When it is used as a broadband λ/4 plate or a λ/2 plate, the content of the polymer formed of the polymerizable nematic liquid crystal compound in the retardation layer may be appropriately selected. When using a λ/4 plate, the Re (550) of the obtained liquid crystal alignment element is used. The film thickness can be adjusted to reach 113 to 163 nm, preferably 135 to 140 nm, and more preferably about 137.5 nm. When the λ/2 plate is used, the obtained liquid crystal alignment element is Re (550). The film thickness can be adjusted by 250 to 300 nm, preferably 273 to 277 nm, and particularly preferably about 275 nm.

The retardation layer can also be used as an optical film for a VA (Vertical Alignment) mode. When it is used as the optical film for VA mode, the content of the polymer formed of the polymerizable nematic liquid crystal compound in the retardation layer may be appropriately selected. The film thickness can be adjusted so that the Re (550) of the obtained optical film is preferably 40 to 100 nm, more preferably 60 to 80 nm.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise stated, the "%" and "parts" in the examples are % by mass and parts by mass.

Example 1: 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. To the obtained solution, 10 g of sulfuric acid was added at room temperature, and the mixture was heated until the solvent was refluxed, and then reacted under reflux for 2 hours. After cooling the obtained reaction solution, Add 150 g of ice and 150 g of water. The supernatant was removed by decantation, and further 150 g of water at 5 ° C was added to crystallize it. The obtained white crystals were filtered, washed with a 1 M aqueous solution of sodium hydrogencarbonate and water, and then dried in vacuo to obtain 22.2 g of compound (a1-1-1). Based on ferulic acid, the yield was 83%.

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

25 g (120 mmol) of the compound (a1-1-1) was dissolved in 250 g of dimethylacetamide. To the obtained solution, 33.19 g (240 mmol) of potassium carbonate and 1.99 g (12 mmol) of potassium iodide were added. To the obtained dispersion, 6-chlorohexanol was added dropwise, and the mixture was stirred at room temperature for 1 hour, and then stirred 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, and the mixture was stirred, allowed to stand, and liquid-separated to collect the organic layer. 200 g of water was added to the recovered organic layer, and the stirring, standing, and liquid-washing operations were repeated twice. The solvent was removed from the recovered organic layer by vacuum distillation using an evaporator to obtain a crude product of compound (b1-1-1).

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

The entire amount of the crude product of the above compound (b1-1-1) was dissolved in 185 g of ethanol. To the obtained solution, 92 g of water and 14.41 g (360 mmol) of sodium hydroxide were added, and the mixture was stirred at 80 ° C for 1 hour. After cooling the reaction solution to about 3 ° C, a 2 M aqueous hydrochloric acid solution was added while maintaining the temperature at 5 ° C or lower to adjust the pH to 2. The white precipitate of the acid precipitation was filtered, and washed twice with a mixed solution of 100 g of water and 80 g of methanol, and dried under vacuum to obtain 30.4 g of the compound (c1-1-1). Based on compound (a1-1-1) The yield is 86%.

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

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

[Synthesis of Compound (M1-1-1) (Other Methods)]

Compound (c1-1-1) 27.46 g (93 mmol) was dissolved in 280 g of chloroform. To the obtained solution, 8.00 g of BHT (di-t-butyl-hydroxytoluene), 11.16 g of p-toluenesulfonic acid and 44.63 g of methacrylic acid were added as a polymerization inhibitor, and water was removed by azeotropic dehydration. Reaction for 8 hours. After cooling the reaction solution to 5 ° C or lower, 200 g of water was added, and the organic layer was recovered by stirring, standing, and liquid separation. To the obtained organic layer, 5.7 g of dimethylaminopyridine and 190 g of water were added, and the mixture was stirred at room temperature for 12 hours. The organic layer of the obtained reaction liquid was recovered, and the organic layer was washed twice with 100 g of a 2 N aqueous hydrochloric acid solution. The organic layer was recovered, 300 g of n-heptane was added, and filtered. Take the precipitated crystals. After washing twice with a mixed solvent containing 100 g of water and 80 g of methanol, vacuum drying was carried out to obtain 18.3 g of the compound (M1-1-1). The yield was 54% based on the compound (c1-1-1).

Example 2 (Production of a polymer containing a photoreactive group)

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

Compound (M1-1-1) 1.00 g (2.76 mmol) and 10 g of tetrahydrofuran were added to the Schlenk tube, and after deoxidation, azobisisobutyronitrile (AIBN) 2.27 mg was added while introducing nitrogen gas. Stir at 60 ° C for 72 hours. The obtained reaction solution was added to 200 g of toluene. The precipitate was collected by filtration, washed with heptane, and dried under vacuum, whereby 0.75 g of polymer 1 was obtained. The yield was 75% based on the compound (M1-1-1). The molecular weight of the obtained polymer was determined by GPC to be a polystyrene standard, and the number average molecular weight was 28,200, which showed Mw/Mn of 1.82 and a monomer content of 0.5%. This polymer was designated as a polymer (1-1-1).

Further, a GPC analysis for determining the number average molecular weight of the polymer (1-1-1) based on polystyrene standards was measured under the following conditions.

Device: HLC-8220GPC (manufactured by Tosoh Co., Ltd.)

Protection column: TSK guardcolumn 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: 1.0 mL/min

Injection volume: 50 μL

Detector: IR, UV

Determination of sample concentration: 0.6% by mass (solvent: THF)

Standard materials for calibration: TSK STANDARD POLYSTYRENE (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.)

Example 3: Manufacture of photoreactive liquid crystal alignment agent

The polymer (1-1-1) was dissolved in cyclopentanone at a concentration of 5% by mass to prepare a photoreactive liquid crystal alignment agent.

Evaluation Example 1 [Preparation of Composition for Polarizing Layer Formation]

The components described below were mixed and stirred at 80 ° C for 1 hour, whereby a polymerizable liquid crystal composition was obtained.

[Measurement of phase transition temperature]

The phase transition temperature was confirmed by texture observation using a polarizing microscope. The temperature of the polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was raised to 120 ° C, and the solvent was removed and dried. Then, when the temperature was lowered, the phase was transferred to a nematic phase at 110 ° C, and the phase was transferred to a layer at 104 ° C. Column A phase is phase shifted to a smectic B phase at 83 °C.

[Production of light alignment layer]

The photoreactive liquid crystal alignment agent obtained in Example 3 was applied onto a polyethylene terephthalate substrate (PET substrate) by a bar coating method, and dried at 60 ° C for 1 minute to form a thickness of 100 nm. Dry film. Then, the surface of the obtained dried film was subjected to a polarized UV irradiation treatment to form a photoalignment layer. The polarized UV treatment was carried out under the conditions of an intensity of 100 mJ measured at a wavelength of 365 nm using a UV irradiation apparatus (SPOT CURE SP-7, manufactured by Ushio Electric Co., Ltd.).

[Production of polarizing layer]

The composition for forming a polarizing layer was applied onto the photo-alignment film by a bar coating method, and dried by heating 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 Ushio Electric Co., Ltd.), the layer formed of the composition for forming a polarizing layer was irradiated with ultraviolet rays having an exposure amount of 1200 mJ/cm ² (based on 365 nm). This forms a polarizing layer, thereby manufacturing a liquid crystal alignment element. The film thickness of the polarizing layer at this time was measured by a laser microscope (manufactured by Olympus Co., Ltd., OLS3000) and found to be 1.6 μm.

[X-ray diffraction measurement]

The obtained polarizing layer was subjected to X-ray diffraction measurement using an X-ray diffraction apparatus X' Pert PRO MPD (manufactured by Spectris Co., Ltd.). Using Cu as a target, X-rays generated under conditions of X-ray tube current of 40 mA and X-ray tube voltage of 45 kV are incident from the rubbing direction by a fixed divergence slit of 1/2° in the scanning range of 2θ=4.0~40.0°. In the range of 2θ=0.01671°, the measurement is performed, and as a result, a steep diffraction peak of FWHM (full width at half maximum)=about 0.187° is obtained in the vicinity of 2θ=20.22° (Prague crest). Also, the same result is obtained by the incidence of self-friction in the vertical direction. The order period (d) obtained from the peak position is about 4.4 Å, and it is known that a structure reflecting the high-order layer phase is formed.

[Measurement of two-color ratio]

A device equipped with a holder for a polarizing element on a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150) is used to measure the absorbance (A ¹ ) and the absorption axis in the transmission axis direction at the maximum absorption wavelength by the two-beam method. Absorbance of the direction (A ² ). The reference side of the holder is provided with a grid that cuts off 50% of the light. (A ²⁾ values were calculated from the measured absorbance of the transmission (A ¹⁾ and the axial direction of the absorption axis direction of the absorbance ratio (A ² / A ¹⁾ as the dichroic ratio. The results are shown in the table. It can be considered that the higher the dichroic ratio, the more useful as the polarizing layer. The measurement results of the two color ratios are shown in Table 1.

[Observation of alignment status]

The alignment state of the obtained polarizing layer was confirmed by a polarizing microscope observation. A sample was inserted between the polarizing microscope orthogonal polarizers in a direction of approximately 45°, and observation was performed in a state of light leakage. When it is aligned in the vertical direction, no light leakage occurs, and a dark field state is observed. In the case of horizontal alignment, light leakage occurs, and observation is performed in a bright field state. The case where the bright field is obtained in the entire screen is set to "○", and the case where the dark field is obtained in the entire screen is set to "x", and the evaluation is performed using the two levels. The results are shown in Table 1.

[Measurement of haze value]

The haze value of the obtained polarizing element was measured using a haze meter (HZ-2, manufactured by Suga Test Instruments Co., Ltd.). The haze value is expressed by the following formula.

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

When the alignment regulating force of the polarizing layer using the photoalignment layer is insufficient, the polymerizable smectic liquid crystal which is a main component of the polarizing layer has a defect of discontinuity. Since light scattering occurs at the discontinuous defect interface, the haze value becomes a large value. That is, it is considered that the smaller the haze value, the better the alignment property. Here, it is better than 3%. The results are shown in Table 1.

Evaluation Example 2

The dichroic dye was changed from azo pigment (G205, manufactured by Hayashibara Biochemical Research Institute) to azo dye (NKX2029, manufactured by Hayashibara Biochemical Research Institute) In the same manner as in Evaluation Example 1, a liquid crystal alignment element was produced.

[Measurement of phase transition temperature]

The phase transfer behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer of Evaluation Example 2 was measured in the same manner as in Evaluation Example 1. After the temperature was raised to 120 ° C, the solvent was removed and dried. After cooling, it was confirmed that the phase was transferred to a nematic phase at 113 ° C, the phase was transferred to a smectic phase A at 107 ° C, and the phase was converted to a smectic phase B at 83 ° C. .

The dichroic ratio measurement, the alignment state observation, and the haze value measurement of the produced liquid crystal alignment element were carried out in the same manner as in Evaluation Example 1. 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 the compound (3-1-6) and 25 parts of the compound (3-1-7) to the compound (3-1-6) 75. A liquid crystal alignment element was produced in the same manner as in Evaluation Example 1 except that a mixture of the compound and the compound (3-1-8) was used in an amount of 25 parts.

[Measurement of phase transition temperature]

The phase transfer behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer of Evaluation Example 3 was measured in the same manner as in Evaluation Example 1. After the temperature was raised to 120 ° C, the solvent was removed and dried. After cooling, it was confirmed that the phase was transferred to a nematic phase at 111 ° C, the phase was transferred to a smectic phase A at 105 ° C, and the phase was transferred to a smectic column B at 82 ° C. phase.

The dichroic ratio measurement, the alignment state observation, and the haze value measurement of the produced liquid crystal alignment element were carried out in the same manner as in Evaluation Example 1. 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 the compound (3-1-6) and 25 parts of the compound (3-1-7) to the compound (3-1-6) 75. A liquid crystal alignment element was produced in the same manner as in Evaluation Example 1, except that a mixture of 25 parts of the compound and the compound (3-1-13) was used.

[Measurement of phase transition temperature]

The phase transfer behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer of Example 4 was measured in the same manner as in Evaluation Example 1. After the temperature was raised to 130 ° C and the solvent was removed and dried, it was confirmed that the phase was transferred to a nematic phase at 119 ° C when the temperature was lowered, and the phase was transferred to a smectic phase A at 111 ° C, and the phase was converted to a smectic phase B at 82 ° C. .

The dichroic ratio measurement, the alignment state observation, and the haze value measurement of the produced polarizing element were carried out in the same manner as in Evaluation Example 1. 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 the compound (3-1-6) and 25 parts of the compound (3-1-7) to the compound (3-1-6) 75. A liquid crystal alignment element was produced in the same manner as in Evaluation Example 1, except that a mixture of 25 parts of the compound and the compound (3-1-14) was used.

[Measurement of phase transition temperature]

The phase transfer behavior of the polymerizable liquid crystal composition contained in the composition for forming a polarizing layer of Example 5 was measured in the same manner as in Evaluation Example 1. After the temperature was raised to 130 ° C and the solvent was removed and dried, it was confirmed that the phase was transferred to a nematic phase at 118 ° C when the temperature was lowered, and the phase was transferred to a smectic phase A at 109 ° C, and the phase was converted to a smectic phase B at 79 ° C. .

The dichroic ratio of the produced liquid crystal alignment element was carried out in the same manner as in Evaluation Example 1. Measurement, alignment state observation, and haze value measurement. The results are shown in Table 1.

Evaluation Example 6

A polymerizable nematic liquid crystal compound which can align a rubbing film of polyvinyl alcohol (for example, 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) in place of the polymerizable liquid crystal (1-6) of Evaluation Example 1, (1- 7), and preparing a composition for forming a retardation layer which does not use a dichroic dye, and applying it to the photoalignment layer shown in Evaluation Example 1, and heating the mixture to a nematic phase transition temperature to obtain the polymerizable nematic The liquid crystal compound is polymerized, whereby a liquid crystal alignment element of a nematic liquid crystal phase can be formed on the photoalignment layer. The liquid crystal alignment element can adjust the thickness so that the liquid crystal phase reaches a desired phase difference, and functions as a phase difference layer.

[Industrial availability]

According to the photoreactive liquid crystal alignment agent of the present invention, a liquid crystal alignment element (for example, a polarizing layer or a retardation layer) using nematic liquid crystal or smectic liquid crystal can be formed. The alignment layer obtained by using the photoreactive liquid crystal alignment agent of the present invention has the advantages of less dust and easier patterning with a mask due to formation of an alignment layer in a non-contact system, and is superior to the prior friction step. Obtained alignment layer.

Claims (12)

A photoreactive liquid crystal alignment agent comprising the polymer represented by the formula (1-1): [In the formula (1-1), n and m each independently represent 0 or 1; v and w each independently represent an integer of 1 to 3; and S ¹ and S ² each independently represent a fluorine atom or a cyano group; An alkanediyl group having 1 to 12 carbon atoms; and S ³ represents an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group; and 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; Y ¹ and Y ² each independently represent a single bond, an oxygen atom or a carbonyloxy group; and R ¹ and R ³ each independently represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms; a group or alkoxy group having 1 to 4 carbon atoms; R ² and R ⁴ each independently represent an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of them are present. R ^{2 is the} same or different, and when w is 2 or 3, a plurality of R ^{4 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 each represent The molar fraction of the structural unit relative to all structural units, and satisfies 0.25<p 1,0 q<0.75 and 0 r<0.75 relationship]. The photoreactive liquid crystal alignment agent of claim 1, wherein the polymer is a polymer wherein q of the above formula (1-1) is 0. The photoreactive liquid crystal alignment agent according to claim 1 or 2, wherein the polymer is a polymer in which r of the above formula (1-1) is 0. The photoreactive liquid crystal alignment agent according to any one of claims 1 to 3, wherein the polymer is a polymer of each of R ¹ and R ^{2 in the} above formula (1-1) independently of a methoxy group or an ethoxy group. The photoreactive liquid crystal alignment agent according to any one of claims 1 to 4, wherein the polymer is a polymer in which n and m of the above formula (1-1) are 0. A liquid crystal alignment layer formed by forming a coating film from the photoreactive liquid crystal alignment agent according to any one of claims 1 to 5, and subjecting the coating film to polarized light. A liquid crystal alignment element comprising the liquid crystal alignment layer and the polarizing layer of claim 6, wherein the polarizing layer obtains a coating film by applying a composition solution containing a polymerizable liquid crystal compound on the liquid crystal alignment layer. The polymerizable liquid crystal compound contained in the coating film is polymerized by polarized light irradiation to form it. The liquid crystal alignment element according to claim 7, wherein the polymerizable liquid crystal compound is a compound which exhibits a liquid crystal state of a layer phase. The liquid crystal alignment element of claim 7, wherein the polymerizable liquid crystal compound The compound exhibits a liquid crystal state of the high-order layer phase. The liquid crystal alignment element according to claim 7, wherein the polymerizable liquid crystal compound is a compound which directly displays a liquid crystal state of a nematic phase from a liquid crystal state of an isotropic phase. The liquid crystal alignment element of claim 10, wherein the polymerizable liquid crystal compound is represented by the formula (2): [In the formula (2), Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group; and D ¹ and D ² each independently represent a single a bond or a divalent linking group; G ¹ and G ² each independently represent a divalent alicyclic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group may pass through a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, 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 -O-, -S- or -NH -Substitution; 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; and A ¹ and A ² each independently represent a divalent group; An alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, wherein the alicyclic hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may pass through a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkyl group having 1 to 4 carbon atoms. An oxy group, a cyano group or a nitro group; the hydrogen atom 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 a fluorine atom; k and l each independently represent 0. An integer of ~3; when k is 2 or more, there are a plurality of A ¹ phases The same or different, there are a plurality of B ^{1 which are the} same or different from each other; when l is 2 or more, there are a plurality of A ^{2 which are the} same or different from each other, and there are a plurality of B ^{2 which are} identical or different from each other; F ¹ and F ² Each independently represents an alkanediyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkanediyl group may be substituted with an alkoxy group having 1 to 5 carbon atoms or a halogen atom to constitute -CH ₂ - of the alkanediyl group. It may be substituted with -O- or -CO-; P ¹ and P ² each independently represent a hydrogen atom, a propylene methoxy group or a methacryloxy group, but there is no case where both P ¹ and P ² are hydrogen atoms] . a compound of the formula (1-3), [In the formula (1-3), n represents 0 or 1; v represents an integer of 1 to 3; and S ¹ represents an alkanediyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group; and X ¹ and X ³ each Independently represents 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 a carbon number of 1 to 4 Alkoxy; R ² represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, a plurality of R ^{2 are the} same or different; R ⁵ represents a hydrogen atom or a base].