KR101945053B1 - Photoreactive liquid crystal aligning agent, and liquid crystal alignment device and method for production thereof - Google Patents

Abstract

[상기 화학식 (1-1)에서,
Y¹ 및 Y²는 산소 원자 등을 나타낸다.
R² 및 R⁴는 탄소수 1∼2의 알콕시기 등을 나타낸다.
p, q 및 r은 전체 구조 단위에 대한 각 구조 단위의 몰분률을 나타내고, 0.25＜p≤1, 0≤q＜0.75 및 0≤r＜0.75의 관계를 만족한다.]An object of the present invention is to provide a novel photoreactive liquid crystal aligning agent and a liquid crystal display element having a photo alignment layer formed from the photoreactive liquid crystal aligning agent.
The present invention provides a photoreactive liquid crystal aligning agent comprising a polymer represented by the following formula (1-1), an orientation layer formed from the photoreactive liquid crystal aligning agent, and a liquid crystal display element having the photo alignment layer.

[In the above formula (1-1)
Y ¹ and Y ² represent an oxygen atom or the like.
R ² and R ⁴ represent an alkoxy group having 1 to 2 carbon atoms.
p, q and r represent molar fractions of the respective structural units with respect to the total structural units, and satisfy a relationship of 0.25 <p? 1, 0? q <0.75 and 0? r <0.75.

Description

TECHNICAL FIELD [0001] The present invention relates to a photoreactive liquid crystal aligning agent, and a liquid crystal aligning element and a method of manufacturing the same. BACKGROUND ART [0002]

The present invention relates to a photoreactive liquid crystal aligning agent, and a liquid crystal aligning element and a process for producing the same.

In a flat panel display (FPD), an optically anisotropic optically anisotropic layer (orientation layer) such as a polarizing plate and a retardation plate is included as a member. Such an optically anisotropic layer is generally formed by two methods. The method is a method in which an optically anisotropic layer is first formed by stretching a polymer, and a method in which an optically anisotropic layer is formed from a coating film obtained by applying an orientation agent secondly. Particularly, in the latter method, the optically anisotropic layer formed from the alignment agent can easily control the direction of the optical axis, and the optical film (liquid crystal alignment element) formed by aligning and fixing the liquid crystal compound on the optically anisotropic layer is essentially It is advantageous because it can be continuously produced by a roll-to-roll process.

For example, in Non-Patent Document 1, a solution containing a polymerizable liquid crystal compound (trade name: LC242, manufactured by BASF) represented by the following formula is applied on an alignment layer, and then the polymerizable liquid crystal compound is polymerized, Is obtained by a manufacturing method in which a liquid crystal alignment layer is obtained. However, the photo-alignment layer in which the polymerizable liquid crystal compound has a nematic phase and an alignment ability to become a polymeric liquid crystal in a higher order of a smectic phase, and a photo-dispersing agent capable of forming the photo-alignment layer are not known.

[Non-Patent Document 1] Cordula Mock-Knoblauch, Olivier S. Enger, Ulrich D. Schalkowsky, "L-7 Novel Polymerisable Liquid Crystalline Acrylates for the Manufacturing of Ultrathes in Optical Films", SlD Symposium Digest of Technical Papers, 37, p.1673

It is preferable that the polymerizable liquid crystal compound has a photo-alignment layer having a nematic phase and an orientation ability to become a polymeric liquid crystal in a higher order of a steric structure, and a novel photo-alignment agent capable of forming the photo- ) Is required.

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

[1] A photoreactive liquid crystal aligning agent comprising a polymer represented by the general 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;

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

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

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

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, plural R ^{2 s} present may be the same or different and w is 2 or 3 , Plural R ⁴ present may be 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 molar fractions of the respective structural units with respect to the total structural units, and satisfy a relationship of 0.25 <p? 1, 0? q <0.75 and 0? r <0.75.

[2]

The photoreactive liquid crystal aligning agent according to the above [1], wherein q in the formula (1-1) is 0.

[3] The polymer according to [

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

[4]

The photoreactive liquid crystal aligning agent according to any one of [1] to [3], wherein R ¹ and R ² in the above formula (1-1) are each independently a methoxy group or an ethoxy group.

[5]

The photoreactive liquid crystal aligning agent according to any one of [1] to [4], wherein the n and m in the above formula (1-1) are all 0's.

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

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

Wherein the polarizing layer is formed by applying a composition solution containing a polymerizable liquid crystal compound on the liquid crystal alignment layer to obtain a coating film,

And the polymerizable liquid crystal compound contained in the coating film is polymerized by polarized light irradiation.

[8] The liquid crystal alignment element according to the above-mentioned [7], wherein the polymerizable liquid crystal compound is a compound exhibiting a liquid crystal state in a smectic phase.

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

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

[11] The liquid crystal alignment element according to the above-mentioned [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.

D ¹ and D ² each independently represent 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 is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, 4 alkoxy group, cyano group or 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.

A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group, a cyano group or a nitro group. The alkyl group having 1 to 4 carbon atoms and the hydrogen atom contained in the 1 to 4 carbon alkoxy group may be substituted with a fluorine atom.

k and l each independently represent an integer of 0 to 3; When k is 2 or more, plural A ^{1 s} are the same or different from each other, and plural B ^{1 s} are the same or different from each other. When l is 2 or more, a plurality of A ^{2 s} are the same or different from each other and a plurality of B ^{2 s} present are the same or different from each other.

F ¹ and F ² each independently represent 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, -CH ₂ - may be substituted with -O- or -CO-.

P ¹ and P ² each independently represent a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, but P ¹ And P &lt; ² &gt; are not 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;

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

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

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

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

R ² represents an alkoxy group having 1 to 2 carbon atoms, a cyano group or a halogen atom, and when v is 2 or 3, plural R ^{2 s} present are the same or different.

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

According to the photoreactive liquid crystal aligning agent of the present invention, it is possible to form a photo-alignment layer having a nematic phase of the polymerizable liquid crystal compound and an aligning ability of becoming a polymeric liquid crystal in a higher-order steric phase.

&Lt; Photoreactive liquid crystal aligning agent >

The photoreactive liquid crystal aligning agent of the present invention is a photoreactive liquid crystal aligning agent comprising a polymer represented by the formula (1-1) (hereinafter occasionally 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 have a fluorine atom or a cyano group.

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

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

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, plural R ^{2 s} present may be the same or different and w is 2 or 3 , Plural R ⁴ present may be 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 molar fractions of respective structural units with respect to the total structural units, and satisfy a relationship of 0.25 <p? 1, 0? q <0.75 and 0? r <0.75.

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

The alkanediyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group as S ¹ and S ² is a group in which a part of the hydrogen atoms contained in the alkanediyl group or the alkanediyl group is a fluorine atom and / Substituted &quot; Such an alkanediyl group may be linear or branched. S ¹ And S ² is preferably an unsubstituted (having no fluorine atom and no cyano group), and a straight-chain alkanediyl group having 1 to 12 carbon atoms, more preferably an alkanediyl group having 2 to 11 carbon atoms, , Butane diaryl group, hexanediyl group and undecanediyl group are particularly preferable.

The alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group of S ³ means an alkyl group or a group in which a part of the hydrogen atoms contained in the alkyl group is substituted with a fluorine atom and / or a cyano group. These alkyl groups may be linear or branched. S ³ is preferably an unsubstituted (having no fluorine atom or cyano group) or straight-chain alkyl group having 1 to 12 carbon atoms, more preferably a methyl, ethyl, propyl, butyl, hexyl, More preferably an undecyl group and a dodecyl group.

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

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

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

R ² and R ⁴ are each independently 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.

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

q is preferably satisfying a relation of 0 &lt; q &lt; 0.25, and particularly preferably q = 0.

It is preferable that r satisfies the relationship of 0? r &lt; 0.25, and it is particularly preferable that r = 0.

p satisfies the relationship of 0.75 &lt; p &lt; = 1, and p = 1 is particularly preferable because the optical alignment layer formed is excellent in solvent resistance. The polymer (1-1) satisfying the relationship of q = 0, r = 0 and p = 1 substantially comprises the structural unit represented by the formula (1-2).

In the above formula, all the symbols are the same as above.

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

In the above formula, all the symbols are the same as above.

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

Specific examples of the monomer (1-3) include compounds represented by the formulas (M1-1-1) to (M1-1-12).

One embodiment of the method for producing the monomer (1-3) is a method for producing a monomer (1-3) represented by the formula (1-3A) wherein X ¹ is a carbonyloxy group and Y ¹ is an oxygen atom, 3)] will be described as an example. The monomer (1-3) can be produced by reacting a compound represented by the formula (1-3B) with a compound represented by the formula (1-3C). This reaction can be expressed in the form of a reaction formula as follows.

In this reaction formula, X represents a halogen atom such as a chlorine atom and a bromine atom, and all other symbols are the same as above. The compound represented by the formula (1-3C) can be prepared by reacting the desired S ¹ , R ¹ , R ² and X ³ Or the like, by a known production method. The compounds represented by the general formula (1-3B) are, for example, (meth) acrylic acid chloride and (meth) acrylic acid bromide, and they are readily available on the market.

This reaction is usually carried out in a solvent. Examples of such a solvent include those which are inert to this reaction and which are sufficiently soluble in the compound represented by the general formula (1-3B) and the compound represented by the general formula (1-3C), and examples thereof include chloroform, dichloromethane, toluene , Xylene, tetrahydrofuran, and dimethylacetamide.

The reaction is preferably carried out in the presence of a deoxidizer such as an alkali. Examples of the alkali include triethylamine, diisopropylethylamine, pyridine, and dimethylaminopyridine.

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

Addition polymerization such as anionic polymerization or radical polymerization is employed as the polymerization for producing the polymer (1-1) from the monomer (1-3). Embodiments of the radical polymerization may be any of solution polymerization, bulk polymerization, emulsion polymerization and soap-free emulsion polymerization. However, in consideration 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 preferable to use a solvent which does not deactivate the radical activity such as benzene, dichloromethane, tetrahydrofuran and diethyl ether. Of these, tetrahydrofuran is particularly preferable as a polymerization solvent from the viewpoint of the solubility of the monomer (1-3).

The polymerization temperature can be appropriately adjusted in the range of -20 占 폚 to 200 占 폚 depending on the kind and amount of the polymerization initiator used and the stability of the monomer (1-3), but is more preferably in the range of 20 占 폚 to 120 占 폚 , 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 may be used, or a photoinitiator described later may be used. Thermal initiators are usually classified as low-temperature initiators, mid-temperature initiators, and high-temperature initiators, depending on the radical generating temperature. In the polymerization of the monomer (1-3), any of these initiators may be used, or these initiators may be used in combination. However, the polymer (1-1) having a high degree of polymerization can be easily obtained, A mid-temperature initiator is more preferable, and an azo compound is more preferable. Of these azo compounds, azobisisobutyronitrile (AIBN) is particularly preferable because it is readily available.

The polymer (1-1) having a high degree of polymerization can be produced by using the above-described azo compound as a polymerization initiator. In order to prepare the polymer (1-1) having a desired molecular weight, that is, It is also possible to employ atom transfer radical polymerization by appropriately using a chain transfer agent.

After the polymerization, reprecipitation purification is preferably carried out to remove unreacted monomers and the like. Examples of the solvent used in the reprecipitation purification include water, an alcohol solvent, an ether solvent, a saturated hydrocarbon solvent, an aromatic hydrocarbon solvent or a mixed solvent thereof. The kind of the polymerization solvent used for the polymerization, the kind of the monomer (1-3) Suitable solvents can be selected according to the conditions, etc.

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. As the ether solvent, tetrahydrofuran and dimethoxyethane can be mentioned, and tetrahydrofuran is more preferable. As the saturated hydrocarbon solvent, n-pentane, n-heptane and cyclohexane are exemplified, and n-heptane is more preferable. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and chlorobenzene, and toluene and xylene are preferable. Such a solvent may be appropriately selected depending on its safety and the like, and may be suitably selected from the group consisting of methanol, ethanol, isopropyl alcohol, toluene, toluene / heptane mixed solvent, water / methanol mixed solvent, water / ethanol mixed solvent and water / tetrahydro Furan mixed solvents are more preferable, and methanol, ethanol and isopropyl alcohol are particularly preferable.

The molecular weight of the polymer (1-1) is preferably in the range of 1 × 10 ^{3 to} 1 × 10 ⁷ , which is expressed by a weight average molecular weight in terms of polystyrene, which can be obtained, for example, by gel permeation method (GPC method). However, when the molecular weight is too high, the solubility in a solvent is lowered to make it difficult to prepare the photoreactive liquid crystal aligning agent of the present invention, or the sensitivity to light irradiation tends to be lowered. ^{4 to} 1 x 10 &lt; ⁶ &gt; is preferable. The analysis conditions of the GPC method for obtaining the molecular weight are described in the Examples of the present application.

The polymer (1-1) can be produced by the polymerization of the monomers (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 of using the following monomers, the molar fractions of the respective structural units of the polymer (1-1) must satisfy the above-mentioned relationship, and the amounts of the monomers (1-3) and the monomers shown below should be adjusted.

All the symbols in the above equations are the same as above.

&Lt; Photoreactive liquid crystal aligning agent >

The photoreactive liquid crystal aligning agent of the present invention (hereinafter referred to as &quot; present liquid crystal aligning agent &quot; in some cases) includes the polymer (1-1), more preferably, In order to form an orientation layer, it contains a polymer (1-1) and a solvent. To prepare such a liquid crystal aligning agent, first, the polymer (1-1) is dissolved in a solvent. Such a solvent can be appropriately selected within a range in which the liquid crystal aligning agent capable of dissolving the polymer (1-1) and having an appropriate viscosity can be obtained, and examples thereof include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol , Alcohol solvents such as ethylene glycol methyl ether, ethylene glycol butyl ether and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone or propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene; And amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide,? -Butyrolactone and dimethylacetamide. These solvents may be used singly or in combination of plural kinds.

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

The present liquid crystal aligning agent prepared by dissolving the polymer (1-1) in a solvent is used as it is or after filtration if necessary, and then used for forming a photo alignment layer.

&Lt; Optical alignment layer formation method >

A method of forming a photo alignment layer (photo alignment layer formation method) using the present liquid crystal aligning agent containing a polymer (1-1) and a solvent will be described. First, this liquid crystal aligning agent is applied on a predetermined supporting substrate. Such a supporting substrate is preferably a transparent supporting substrate. Examples of a method of applying the present liquid crystal aligning agent on a transparent support substrate include a coating method such as a spin coating method, an extrusion method, a gravure coating method, a die coating method, a bar coating method and an applicator method, A known method such as a printing method of printing is employed.

Next, the solvent is removed from the coating film formed by applying the present liquid crystal aligning agent on the transparent supporting substrate to form a dried coating film. For removal of the solvent, a method of drying and removing the solvent by heating at a suitable temperature (heating method), a method of drying the solvent by removing the solvent by reducing the pressure in the container after sealing it in a suitable pressure- , Air drying (ventilation method), natural drying, or a combination of these methods. The heating method is more preferable because it can be carried out in a continuous roll-to-roll type.

The thickness of the dry film containing the polymer (1-1) formed on the transparent support substrate is, for example, in the range of 1 nm to 10000 nm, preferably in the range of 10 nm to 1000 nm. The thickness of such a dry film can be controlled by adjusting the solid content concentration of the present liquid crystal aligning agent (particularly, the solid content concentration of the polymer (1-1)) and the application condition of the liquid crystal aligning agent to the transparent substrate. Thus, a layered product in which a dry film containing the polymer (1-1) is formed on a transparent support substrate can be obtained.

Subsequently, the polymer (1-1) is oriented by applying polarized UV (polarized ultraviolet light) to the dried film of the laminate, and the liquid crystal aligning ability is imparted (hereinafter referred to as &quot; Thereby forming a photo alignment layer. In order to irradiate the laminated body with the polarized light UV in the photo alignment operation, it is also possible to irradiate the laminated body with polarized UV light directly from the side of the dried film of the laminated body in the form of polarized UV (Form A) (Mode (B)) in which polarized UV is irradiated to the dry film by irradiating UV light and transmitting the polarized UV through the transparent substrate. In any of these formats, the polarized light UV to be irradiated may be either linearly polarized UV or elliptically polarized UV, but in order to perform the optical alignment operation efficiently, it is preferable to use an elliptically polarized light (UV) close to linearly polarized light or an extinction ratio It is preferable to use a high linearly polarized UV. It is particularly preferable that the polarized UV is substantially parallel light. However, when the photo alignment operation is carried out by the type (B), the transparent substrate in the laminate to be used preferably has higher transparency.

The polarized UV to be irradiated is preferably a wavelength region in which the photoreactive group (cinnamoyl group) of the polymer (1-1) contained in the dried coating can absorb light energy. Specifically, UV (ultraviolet ray) having a wavelength in the range of 250 nm to 400 nm is particularly preferable. As the light source used for the photo-alignment operation, a xenon lamp; High pressure mercury lamp; Ultra high pressure mercury lamp; Metal halide lamp; And ultraviolet laser such as KrF and ArF. High-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps are more preferable as the light source used in the photo-alignment operation. This is because these lamps have a large emission intensity of ultraviolet rays having a wavelength of 313 nm. When the light from the light source is irradiated to the laminate after passing through a suitable polarizer, the laminated body is irradiated with the polarized UV. As such a polarizer, a polarizing prism such as a polarizing filter, Glan Thomson, or Glan Taylor, or a wire grid type polarizer can be used.

It is not always necessary that the irradiation direction of the polarized UV is substantially perpendicular to the plane direction of the laminated body in irradiating the dried film of the laminated body with the polarized UV, May be oblique. The irradiation direction of the polarized UV with respect to the plane direction of the laminate is determined so that the obtained photo-alignment layer has a desired absorption axis depending on the light source used for the photo-alignment operation and the kind of the polarizer.

The photo-alignment layer formed from the present liquid crystal aligning agent can be formed by applying a composition containing a polymerizable liquid crystal compound on the photo alignment layer by the above-described method, and forming the polymerizable liquid crystal compound in a nematic phase or a higher- (Polymerizable liquid crystal). The liquid crystal aligning agent obtained from this liquid crystal aligning agent is very useful as a liquid crystal aligning agent capable of forming a photo alignment layer using such a liquid crystal state (polymerizable liquid crystal) as a polymerizable liquid crystal compound. .

When a polymerizable smectic liquid crystal compound capable of forming a smectic liquid crystal state is used as the polymerizable liquid crystal compound, the polymerizable smectic liquid crystal compound can be obtained by combining a dichroic dye mainly with a polarizing layer on the photo alignment layer To thereby obtain a liquid crystal alignment element. When a polymerizable nematic liquid crystal compound capable of forming a smectic liquid crystal state is used as the polymerizable liquid crystal compound, a liquid crystal alignment element formed by forming a phase difference layer on the photo alignment film can be obtained. When the polarizing layer or the retardation layer is formed on the photo alignment layer, the solution containing the polymerizable liquid crystal compound may be applied and dried to be photopolymerized. Hereinafter, these methods will be described separately for the case of using a polymerizable smectic liquid crystal compound and the case of using a polymerizable nematic liquid crystal compound. In this description, a solution containing a polymerizable smectic liquid crystal compound is referred to as a &quot; composition for forming a polarizing layer &quot;, and a solution containing a polymerizable nematic liquid crystal compound is referred to as a &quot; composition for forming a retardation layer &quot;.

&Lt; Liquid crystal alignment element using polymerizable smectic liquid crystal compound >

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

The liquid crystal phase represented by the polymerizable smectic liquid crystal compound is preferably a high-order smectic phase. The high-order smectic phase referred to herein 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, The steric B phase, the steric F phase, the steric I phase, the inclined smectic F phase, and the inclined smectic I phase are preferable, and the smectic B phase is more preferable . When the polymerizable smectic liquid crystal compound exhibits a higher order of the smectic liquid crystal phase, a polarizing layer having a higher degree of alignment 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 &quot; compound (3-1) &quot;

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

In the above formula (3-1)

E ¹ , E ² and E ³ independently represent a p-phenylene group which may have a substituent or a cyclohexane-1,4-diyl group which may have a substituent. However, E ¹ , E ² And E ³ Is a p-phenylene group which may have a substituent.

J ¹ and J ² each independently represent -CH ₂ CH ₂ -, -CH ₂ O-, -COO-, -OCOO-, a single bond, -N = N-, -CR ^a = CR ^b -, -C≡ C- or -CR &^lt; ^a &gt; = N-. R ^a and R ^b 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 represent a single bond, -O-, -S-, -COO- or -OCOO-.

V ¹ and V ² independently represent an alkanediyl group having 1 to 20 carbon atoms which may have a substituent, and -CH ₂ - constituting the alkanediyl group is substituted with -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, but at least two of them are substituents Or a p-phenylene group which may be substituted.

The p-phenylene group is preferably an amorphous group. The cyclohexane-1,4-diyl group is preferably a trans-cyclohexane-1,4-diyl group, more preferably an indeterminate group.

Examples of the substituent optionally having a p-phenylene group or a 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; Cyano; Halogen atoms and the like. 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 in 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, preferably a polymerizable group. That is, all of U ¹ and U ² are preferably a polymerizable group, and all of them are preferably a photopolymerizable group. Here, the photopolymerizable group means a group capable of participating in the polymerization reaction by an active radical or an acid generated from a photopolymerization initiator described later. Use of a polymerizable smectic liquid crystal compound having a photopolymerizable group is also advantageous in that the polymerizable smectic liquid crystal compound can be polymerized at a lower temperature.

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

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, a butane- A heptane-1,7-diyl group, an octane-1,8-diyl group, a decane-1,10-diyl group, a tetradecane-1,14-diyl group, An acid-1,20-diyl group 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.

As the substituent optionally present in the alkanediyl group, a cyano group, a halogen atom and the like can be mentioned. However, the alkanediyl group is preferably an amorphous group, more preferably an unsubstituted or straight-chain alkanediyl group.

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

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

The exemplified compound (3-1) is hereinafter referred to as &quot; compound (3-1-1) &quot;

The exemplified compound (3-1) can be used alone or as a polymerizable smectic liquid crystal mixture in which two or more kinds are mixed. In addition, two or more polymerizable stymic compounds may be used, and at least one of the two or more polymerizable stymatic compounds may be a compound (3-1). In the following description, the case where a polymerizable smectic liquid crystal compound of a single species is used and the case where two or more polymerizable smectic liquid crystal compounds are used is sometimes referred to as a "polymerizable smectic liquid crystal compound" as a whole.

When the compound (3-1) is used in a composition for forming a polarizing layer, the phase transition temperature of the compound (3-1) is determined in advance and the compound (3-1) can polymerize under the temperature condition below the phase transition temperature , Components other than the compound (3-1) [polymerizable smectic liquid crystal compound] of the composition for forming a polarizing layer are adjusted. Examples of the component capable of controlling the polymerization temperature include a photopolymerization initiator, a photosensitizer and a polymerization inhibitor which will be described later. The polymerization temperature of the compound (3-1) can be controlled by suitably controlling the kind and amount thereof. Further, even when a mixture of two or more compounds (3-1) [polymerizable smectic liquid crystal composition], that is, a polymerizable smectic liquid crystal composition, is used in the composition for forming a polarizing layer, After the phase transition temperature is obtained, the polymerization temperature is controlled in the same manner as in the case of the polymerizable smectic liquid crystal compound.

Among the exemplified compounds (3-1), the compounds represented by formulas (3-1-3), (3-1-6), (3-1-7), (3-1-12) 1-13) and (3-1-23). These compounds (3-1) can be easily obtained by mixing or under a temperature condition in which the phase transition temperature is easily lowered by interaction with a photopolymerization initiator used together, that is, a supercooled state , The compound (3-1) can be polymerized. More specifically, by interacting with the photopolymerization initiator, these compounds (3-1) can be polymerized under polymerization conditions of a high-order smectic liquid crystal state at a temperature of 70 ° C or lower, preferably 60 ° C or lower, .

As described above, the compound (3-1) may be a single species or a plurality of species, but it is preferable that the compounds (3-1) are plural species. That is, as the composition for forming a polarizing layer, it is preferable to use two or more polymerizable smectic liquid crystal compositions, preferably two or more compounds (3-1).

The content of the compound (3-1) in the composition for forming a polarizing layer is preferably 70 to 99.9 mass%, more preferably 90 to 99.9 mass%, with respect to the solid content of the composition for forming a polarizing layer. If the content of the compound (3-1) is within the above range, the orientation of the compound (3-1) tends to be high. Here, the solid content refers to the total amount of components excluding the volatile component such as a solvent from the composition for forming a polarizing layer. When plural kinds of compounds (3-1) are contained in the composition for forming a polarizing layer, the total content ratio may be within the above-mentioned range.

The composition for forming a polarizing layer preferably contains a leveling agent. The leveling agent has 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 more flat, and examples thereof include a surfactant and the like. The leveling agent is more preferably 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, there may be mentioned "BYK-350", "BYK-352", "BYK-353", "BYK-354", "BYK- 381 ", " BYK-381 ", and " BYK-392 " [BYK Chemie Co., Ltd.].

As a leveling agent containing a fluorine atom-containing compound as a main component, "Megapack R-08", "Megapack R-30", "Megapack R-90", "Megafac F- , "Megapack F-477", "Megapack F-479", "Megapack F-471", "Megapack F- &Quot; Megapack F-482 " and " Megapack F-483 " [DIC Co., Ltd.]; Surfron S-381, Surfron S-382, Surfron S-383, Surfron S-393, Surfron SC-101, Surfron SC- -40 " and " SA-100 " [AGC Seiyam Chemical Co., Ltd.]; &Quot; E1830 ", " E5844 " [Daikin Fine Chemical Co., Ltd .; "EF Top EF301", "EF Top EF303", "EF Top EF351" and "EF Top EF352" (manufactured by Mitsubishi Materials Corporation).

When the leveling agent is contained in the composition for forming a polarizing layer, the content thereof is preferably not less than 0.3 parts by mass and not more than 5 parts by mass, more preferably not less than 0.5 parts by mass and not more than 3 parts by mass based on 100 parts by mass of the polymerizable smectic liquid crystal compound Is more preferable. If the content of the leveling agent is within the above range, it is easy to horizontally orient the polymerizable smectic liquid crystal compound, and the polarizing layer to be formed tends to become smoother. If the content of the leveling agent in the polymerizable smectic liquid crystal compound exceeds the above range, unevenness tends to occur in the obtained polarizing layer. 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. This solvent can be selected as appropriate and preferable in consideration of the solubility and the like of the polymerizable smectic liquid crystal compound to be used. However, it is preferably an inert solvent which does not significantly interfere with the progress of the polymerization reaction of the polymerizable smectic liquid crystal compound. Such a solvent is the same as that exemplified for the solvent for preparing the present liquid crystal aligning agent composition. The solvent for preparing a composition for forming a polarizing layer may be used alone or in combination of plural kinds.

The content of the solvent in the composition for forming a polarizing layer is preferably 50 to 98 mass% with respect to the total amount of the composition for forming a polarizing layer. On the other hand, when the solid content of the composition for forming a polarizing layer is 50 mass% or less, the viscosity of the composition is lowered, so that the thickness of the coating film becomes substantially uniform. Such a solid content can be determined so that the polarizing layer has a desired thickness.

The composition for forming a polarizing layer preferably contains a polymerization initiator. The polymerization initiator is preferably a photopolymerization initiator since it is a compound capable of initiating polymerization reaction of a polymerizable smectic liquid crystal compound and can initiate the polymerization reaction under a lower temperature condition. Specifically, a compound capable of generating an active radical or an acid under the action of light under this temperature condition is used as a photopolymerization initiator. Among these photopolymerization initiators, it is more preferable that radicals are generated by the action of light.

Examples of the photopolymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts, and sulfonium salts.

Specific examples of the photopolymerization initiator are described 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 o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Peroxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 2-methyl-1-phenylpropan-1-one, 1,2-diphenyl-2,2-dimethoxyethane-1-one, 2 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) And oligomers of 4- (1-methylvinyl) phenyl] propan-1-one.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis - [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- ) Ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-tri Azine, and the like.

As the photopolymerization initiator, those readily available on the market may be used. Examples of commercially available photopolymerization initiators include Irgacure 907, Irgacure 184, Irgacure 651, Irgacure 819, Irgacure 250, Irgacure 369 [Chiba Japan week)]; "Seake All BZ", "Seake All Z", "Seake All BEE" [Seiko Kagaku Co., Ltd.]; "Kayacure BP100" [Nippon Kayaku Co., Ltd.]; &Quot; Kayacure-UVI-6992 " (manufactured by Dow Chemical Company); &Quot; Adeka Optomer SP-152 ", " Adeka Optomer SP-170 " &Quot; TAZ-A ", " TAZ-PP " (Nippon Shibel Hegner); And " TAZ-104 " (manufactured by Sanwa Chemical Co., Ltd.).

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, The content of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass per 100 parts by mass of the total sum of the smectic liquid crystal compounds. If the content of the polymerizable initiator is within the range, polymerization can be carried out without disturbing the orientation of the polymerizable smectic liquid crystal compound. Therefore, the polymerizable smectic liquid crystal compound can be polymerized while maintaining the liquid state of the higher-order smectic have.

When the composition for polarizing layer contains a photopolymerization initiator, the composition may contain a photosensitizer. Examples of the photosensitizer include xanthene compounds such as xanthone and thioxanthone (e.g., 2,4-diethylthioxanthone, 2-isopropylthioxanthone, etc.); Anthracene compounds such as anthracene and alkoxy group-containing anthracene (e.g., dibutoxyanthracene); Phenothiazine, rubrene, and the like.

When the composition for forming a polarizing layer contains a photopolymerization initiator and a photosensitizer, the polymerization reaction of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer can be further promoted. The amount of such a photosensitizer to be used can be appropriately adjusted depending on the kind and amount of the photopolymerization initiator and the polymerizable smectic liquid crystal compound to be used in combination. For example, the amount of the photosensitizer is preferably 0.1 to 100 parts by mass, More preferably 0.5 to 10 parts by mass, still more preferably 0.5 to 8 parts by mass.

It has been described that the polymerization reaction of the polymerizable stymatic liquid crystal compound can be promoted by containing a photosensitizer in the composition for forming a polarizing layer. However, in order to stably proceed the polymerization reaction, The inhibitor may be appropriately contained. By containing the polymerization inhibitor, the progress of the polymerization reaction of the polymerizable smectic liquid crystal compound can be controlled.

Examples of the polymerization inhibitor include hydroquinone, alkoxy group-containing hydroquinone, alkoxy group-containing catechol (e.g., butyl catechol), pyrogallol, 2,2,6,6-tetramethyl-1-piperidinyloxy radical Radical supplements; Thiophenols; β-naphthyl amines, β-naphthols, and the like.

When the composition for forming a polarizing layer contains a polymerization inhibitor, the content thereof can be appropriately adjusted depending on the type and amount of the polymerizable smectic liquid crystal compound to be used, the amount of the photosensitizer used, and the like, The content of the polymerization inhibitor is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 10 parts by mass, and still more preferably 0.5 to 8 parts by mass per 100 parts by mass of the total sum of the smectic liquid crystal compounds. When the content of the polymerization inhibitor is within the above range, the alignment of the polymerizable smectic liquid crystal compound contained in the composition for forming a polarizing layer can be polymerized without cluttering, so that the polymerizable smectic liquid crystal compound has a higher The polymerization can be carried out while maintaining the liquid crystal state of the methic phase satisfactorily.

The composition for forming a polarizing layer described above was applied on the photo-alignment layer of a laminate (first laminate) on which a transparent supporting substrate and a photo-alignment layer were formed to obtain a coated film, and the polymerizable smectic liquid crystal By drying under the condition that the compound does not polymerize, a dry film for forming a polarizing layer is formed, and a second laminate can be obtained.

The method (coating method) for applying the composition for forming a polarizing layer to the first laminate and the drying method are the same as those described for the method of applying the present liquid crystal aligning agent on a transparent supporting substrate. The thickness of the coating film thus formed is preferably in the range of 0.5 탆 to 10 탆, more preferably in the range of 0.5 탆 to 3 탆. The thickness of the coating film is determined so that the obtained polarizing layer has a desired thickness. The thickness of the polarizing layer is determined by measurement of an interference film thickness meter, a laser microscope or a needle contact type film thickness meter.

The polymerizable smectic liquid crystal compound contained in the dried film (the dry film for forming a polarizing layer) of the second laminate is subjected to photopolymerization to form a polymerizable smectic liquid crystal compound in a smectic phase, , Polymerization is carried out while maintaining the liquid crystal state of the high-order smectic phase as already exemplified, and as a result, the dry film is added to the polarizing layer.

&Lt; Liquid crystal alignment element using polymerizable nematic liquid crystal compound >

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

Examples of the polymerizable nematic liquid crystal compound contained in the composition for forming a retardation layer include a compound represented by the formula (20) [hereinafter referred to as &quot; compound (20) &quot;

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

In the above formula (20)

A ¹¹ represents a divalent aromatic hydrocarbon group, a divalent alicyclic hydrocarbon group or a divalent heterocyclic group, and the hydrogen atom contained in the divalent aromatic hydrocarbon group, the divalent alicyclic hydrocarbon group and the divalent heterocyclic group is , A halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an N-alkylamino group having 1 to 6 carbon atoms, an N, N-dialkylamino group having 2 to 12 carbon atoms, a nitro group, Or may be substituted with a 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 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 Represents a single bond. R ¹⁴ and R ¹⁵ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ and R ¹⁵ may be connected to form an 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 with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogen atom.

P ¹¹ represents a polymerizable group.

G represents a hydrogen atom, a halogen atom, an alkyl group 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, A dialkylamino group, a cyano group, a nitro group, or a polymerizable group which is bonded through an alkandiyl group having 1 to 12 carbon atoms, and the hydrogen atom contained in the alkandiyl group is an alkyl group having 1 to 6 carbon atoms, An alkoxy group having 1 to 6 carbon atoms or a halogen atom.

t represents an integer of 1 to 5; When t is an integer of 2 or more, a plurality of A ¹¹ are the same or different and a 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-phenylethenyl) phenyl group, an acryloyl group, an acryloyloxy group, a methacryloyl group, An amino group, an N-alkylamino group having 1 to 4 carbon atoms, an epoxy group, an oxetanyl group, a formyl group, -N = C = O and N = C = S, . Among them, a radically polymerizable group or a cationic polymerizable group is preferable from the viewpoint of high photopolymerization reactivity. In view of ease of handling and easy production of a liquid crystal compound, acryloyloxy group, methacryloyloxy group, A vinyloxy group is more preferable.

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

Examples of the compound (20) include 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 ) _{t 1} -B ¹² -E ¹² -P ¹² (20-1)

P ¹¹ -E ¹¹ - (B ¹¹ -A ¹¹ ) _{t 2} -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 are the same 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, an N-alkylamino group having 1 to 13 carbon atoms, An N-dialkylamino group, 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;

The compound represented by the formula (I), the formula (II), the formula (III), the formula (IV) or the formula (V) may be used as the compound represented by the formula (20-1) .

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 above formulas (I) to (V)

A ^{12 to} A ¹⁵ are the same as A ^11, and B ^{13 to} B ¹⁶ are the same as B ¹¹ .

Further, in the compound represented by the formula (20-1), the formula (20-2), the formula (I), formula (II), formula (III), formula (IV) and formula (V), and P ¹¹ It is preferable that E ¹¹ is bonded through an ether bond or an ester bond, and it is preferable that P ¹² and E ¹² are bonded through an ether bond or an ester bond.

Specific examples of the polymerizable nematic liquid crystal compound include compounds represented by the formulas (I-1) to (I-5), the compounds represented by the formulas (B1) to (B20) (I); A compound represented by the formula (II) such as a compound represented by the formula (II-1) to (II-6); A compound represented by the formula (III) such as a compound represented by the formulas (III-1) to (III-19); A compound represented by the formula (IV) such as a compound represented by the formula (IV-1) to (IV-14); And compounds represented by the formula (V) such as the compounds represented by the formulas (V-1) to (V-5). In the formulas, k represents an integer of 1 to 11, and an asterisk represents a number of bonds. These polymeric nematic liquid crystal compounds are preferable because they can be produced relatively easily or are easily available from the market.

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).

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

The two * in the formula (B5) are bonded to any one of (B5-1) to (B5-8).

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

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

Two of the * 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).

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

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

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

The two * in the formula (B13) are bonded to any one of (B13-1) to (B13-8).

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

The two * in the formula (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 * in the formula (B17) are bonded to any one of (B17-1) to (B17-8).

The two * in the formula (B18) are bonded to any one of (B18-1) to (B18-8).

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

The two * in the formula (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).

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

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

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

The polymerizable nematic liquid crystal compound represented by the formula (2) [hereinafter referred to as &quot; compound (2) &quot;, as the case may be) is also used as a composition for forming a retardation layer, similarly to the compound (20) The retardation layer can be formed on the orientation layer.

In the above formula (2)

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

D ¹ and D ² each independently represent 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 is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, 4 alkoxy group, cyano group or 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.

A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group, a cyano group or a nitro group. The alkyl group having 1 to 4 carbon atoms and the hydrogen atom contained in the 1 to 4 carbon alkoxy group may be substituted with a fluorine atom.

k and l each independently represent an integer of 0 to 3; When k is 2 or more, plural A ^{1 s} are the same or different from each other, and plural B ^{1 s} are the same or different from each other. When l is 2 or more, a plurality of A ^{2 s} are the same or different from each other and a plurality of B ^{2 s} present are the same or different from each other.

F ¹ and F ² each independently represent 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, -CH ₂ constituting a - may be substituted with -O- or -CO-.

P ¹ and P ² each independently represent a hydrogen atom, an acryloyloxy group or a methacryloyloxy group, but P ¹ And P ² are not all hydrogen atoms.

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

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

Among them, D ¹ and D ² each independently represents a group represented by * -O-CO-, * -OC (= S) -, * -O-CR ⁴ R ⁵ -, * -NR ⁸ -CR ⁴ R ⁵ - -NR ⁸ -CO-, more preferably * -O-CO-, * -OC (= S) - or -NR ⁸ -CO-. Here, * represents the number of carbon atoms of the compound (2)

Represents the number of bonds to one side of the group represented by *. R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently preferably 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 bivalent alicyclic hydrocarbon group of G ¹ and G ² is preferably a group in which the number of atoms (ring constituting atoms) constituting the ring is in the range of 3 to 10. When a ring constituent atom contains a hetero atom, the number of the hetero atom is 2 or less. Specific examples of such alicyclic hydrocarbon groups are represented by any one of formulas (g-1) to (g-10). Among them, the bivalent alicyclic hydrocarbon group of G ¹ and G ² is more preferably a 5-membered or 6-membered alicyclic hydrocarbon group.

In the above formula, * represents the number of bonds.

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

G ¹ and G ² are preferably a group represented by the formula (g-1), more 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-, -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 -. 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 -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-, -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 -.

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 that the compound (2) exhibits particularly high liquid crystallinity.

From the viewpoint that the compound (2) can be more easily produced, B ¹ and B ¹² are preferably the same.

Specific examples of the divalent alicyclic hydrocarbon group or divalent aromatic hydrocarbon group in A ¹ and A ² are represented by any one of the formulas (g-1) to (g-10) shown in the description of G ¹ and G ² And a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by any one of the following formulas (a-1) to (a-8).

The hydrogen atom contained in the groups represented by the formulas (a-1) to (a-8) is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group and a tert- An alkoxy group having 1 to 4 carbon atoms such as methoxy group and ethoxy group; A fluoroalkyl group having 1 to 4 carbon atoms such as a trifluoromethyl group; A fluoroalkoxy group having 1 to 4 carbon atoms such as a trifluoromethoxy group; Cyano; A nitro group; And may be substituted with a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom.

Among them, A ¹ and A ² are preferably a 1,4-phenylene group or a 1,4-cyclohexanediyl group, and from the viewpoint that the production of the compound (2) is easy, More preferable. In addition, from the viewpoint that the preparation of the compound (2) is easier, it is preferable that A ¹ and A ² are the same.

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.

F ¹ and F ² of Al having 1 to 12 carbon atoms in the alkanediyl group is _{- (CH 2) 3 -,} - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, - _{(CH 2) 7 -, -} (CH 2) 8 -, - (CH 2) 9 -, - (CH 2) 10 -, - (CF 2) 4 -, - (CF 2) 6 -, - (CF ₂ ) ₈ - is preferable, and - (CH ₂ ) ₄ - and - (CH ₂ ) ₆ - are more preferable.

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

P ¹ and P ² each independently represent a hydrogen atom or a polymerizable group, but they are not all hydrogen atoms. That is, at least one of P ¹ and P ² is a polymerizable group. From the viewpoint that the hardness of the retardation layer obtained from the compound (2) tends to be excellent, it is more preferable that P ¹ and P ² are both polymerizable groups.

The polymerizable group may be a group capable of participating in the polymerization reaction of the compound (2). The compound (3-1), U ¹ and U ^2, but the redundancy of the polymerizable groups of, for a specific example of the polymerizable group, a vinyl group, vinyloxy group, styryl group, p- (2-phenylethenyl) phenyl , An acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, a carboxy group, an acetyl group, a hydroxy group, a carbamoyl group, an N-alkylamino group having 1 to 4 carbon atoms, an amino group, an epoxy group, A formyl group, an isocyanate group and an isothiocyanate group. Among them, a radically polymerizable group and a cationic polymerizable group are preferable from the viewpoint of being suitable for photopolymerization, and an acryloyloxy group or a methacryloyloxy group is preferable because it is easy to handle and the compound (2) More preferably an acryloyloxy group is particularly preferable.

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 divalent linking group in B ¹ and B ² ).

-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 groups represented by formulas (R-1) to (R-134). *silver

Quot; * &quot; of the group denoted by &quot; * &quot;.

Examples of the formula (2) include compounds represented by the formulas (A1) to (A73).

Two of the * in formula (A1) are bonded to any one of (A1-1) to (A1-8).

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

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

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

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

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

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

Two of the * 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).

Two of the * 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).

Two of the * 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).

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

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

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

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

Two of the * 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).

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

Two of the * 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).

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

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

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

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

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

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

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

Two of the * 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).

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

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

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

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

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

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

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

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

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

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

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

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

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

Two of the * 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).

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

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

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

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

Two of * 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).

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

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

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

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

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

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

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

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

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

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).

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

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

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

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

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

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

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

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

As the polymerizable nematic liquid crystal compound used for forming the retardation layer, the exemplified compound (2) may be used singly or two or more kinds may be appropriately mixed. In particular, when a compound represented by any one of formulas (A1) to (A73) is used, the resulting retardation layer is more preferable because it is an inverse wavelength dispersed phase difference layer. These compounds (2) are also preferable in that they exhibit reverse wavelength dispersion properties in which the wavelength dispersion property is more ideal.

It is preferable that the composition for forming a retardation layer further contains a polymerization initiator. Suitable polymerization initiators are the same as those exemplified as preferred polymerization initiators optionally contained in the composition for forming a polarizing layer. Further, in the composition for forming a retardation layer, in order to further promote the polymerization of the polymerizable liquid crystal compound (polymerizable nematic liquid crystal compound) in the same manner as the composition for forming the polarizing layer, a polymerization inhibitor . The photosensitizer and the polymerization inhibitor are as described for the composition for forming a polarizing layer. The composition for forming a retardation layer may contain a leveling agent in the same manner as the composition for forming a polarizing layer.

The retardation layer forming composition preferably contains a solvent, particularly an organic solvent, from the viewpoint of its flowability. The organic solvent may be appropriately selected depending on the type and amount of the polymerizable nematic liquid crystal compound used in the composition for forming the retardation layer and the like. Specific examples thereof include methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, Alcohol solvents such as ethylene glycol methyl ether and ethylene glycol butyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate,? -Butyrolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Non-chlorinated aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Non-chlorinated aromatic hydrocarbon solvents such as toluene, xylene, and phenol; Nitrile solvents such as acetonitrile; Ether solvents such as propylene glycol monomethyl ether, tetrahydrofuran and dimethoxyethane; Chlorinated hydrocarbon solvents such as chloroform and chlorobenzene; Phenol and the like. These organic solvents may be used alone or in combination of two or more. Especially, alcohol solvents, ester solvents, ketone solvents, non-chlorinated aliphatic hydrocarbon solvents and non-chlorinated aromatic hydrocarbon solvents are preferable.

When an organic solvent is used for the retardation layer forming composition, the content thereof is 10 to 10,000 parts by mass, preferably 100 to 5,000 parts by mass based on 100 parts by mass of the polymerizable nematic liquid crystal compound. The viscosity of the composition for forming a retardation layer is from 0.1 to 10 mPa · s, preferably from 0.1 to 7 mPa · s, from the standpoint that unevenness of film thickness of the retardation layer to be formed tends to become unlikely to occur. Therefore, the kind and amount (content) of the organic solvent used in the composition for forming a retardation layer can be determined in such a manner that such a suitable viscosity is obtained.

The solid content concentration in the retardation layer-forming composition is in the range of 2 to 50 mass%, preferably in the range of 5 to 50 mass%. When the solid content concentration is 2% by mass or more, the retardation layer is not excessively thin, and a retardation layer having a birefringence required for optical compensation as a liquid crystal panel of a liquid crystal display tends to be easily obtained. When the solid concentration is 50% by mass or less, the viscosity of the composition for forming a retardation layer is not too small, and the above-mentioned appropriate viscosity is obtained, so that the film thickness of the retardation layer tends to become unlikely to occur. The term "solid component" refers to a component excluding the volatile component such as an organic solvent from the composition for forming a retardation layer.

The retardation layer is used for converting linearly polarized light into circularly polarized light or elliptically polarized light, or conversely converting circularly polarized light or elliptically polarized light into linearly polarized light.

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

The composition for forming a retardation layer is coated on the photo alignment layer formed from the liquid crystal aligning agent and dried to obtain an unpolymerized film (dry film for forming a retardation layer). The application method and the drying method are the same as those described in the method for obtaining the polarizing layer-forming coating film and the dry coating film from the polarizing layer-forming coating film.

The retardation layer obtained by polymerizing a polymerizable nematic liquid crystal in a nematic liquid crystal state in an unpolymerized film exhibits birefringence due to monodomain alignment.

The film thickness of the retardation layer can be controlled by appropriately adjusting the solid content concentration of the retardation layer forming composition, the content of the organic solvent, and the application amount of the composition for forming the retardation layer on the supporting substrate. When the content of the polymerizable nematic liquid crystal compound contained in the retardation layer forming composition is constant, the retardation value (retardation value, Re ()) of the obtained retardation layer is determined according to the formula (7) (?), the film thickness d and? n (?) may be adjusted.

Re (?) = D x? N (?) (7)

In the above formula, Re (?) Represents the retardation value at the wavelength? Nm, d represents the film thickness, and? N (?) Represents the birefringence at the wavelength? Nm.

The method of polymerizing the polymerizable nematic liquid crystal compound in the un polymerized film may be appropriately determined depending on the kind of the polymerizable nematic liquid crystal compound. When the polymerizable nematic liquid crystal compound is a polymerizable group, a photopolymerizable group is used, and when the polymerizable group is a heat-polymerizable group, a thermal polymerization method is used. According to the photopolymerization method, it is possible to polymerize the polymerizable nematic liquid crystal compound at a low temperature, to broaden the selection range of the heat resistance of the supporting substrate, and from the viewpoint that it is industrially easy to manufacture, It is preferable to use a sane nematic liquid crystal compound. Also, photopolymerization is preferable from the viewpoint of film formability. The polymerization reaction according to the photopolymerization method is carried out by irradiating visible light, ultraviolet light or laser light to the unpolymerized film. Ultraviolet light is particularly preferable because it is easy to handle. The light irradiation may be performed at a temperature at which the compound of the present invention takes a liquid crystal phase. At this time, the polymerized film may be patterned by masking or the like.

The birefringence? N (?) Can be adjusted so as to give a desired retardation by suitably adjusting the amount of exposure, heating temperature and heating time during polymerization.

The resulting retardation layer becomes thinner in film thickness as compared with a stretched film which gives a retardation by stretching the polymer. And further combined with the photo-alignment layer formed from this liquid crystal aligning agent, the direction of the patterning or the phase-advance axis (slow axis) can be freely controlled.

The retardation layer is excellent in transparency and the thickness of the retardation layer used for various display films is different depending on the retardation value of the optical film as described above. However, it is preferably 0.1 to 10 占 퐉, More preferably 0.2 m to 5 m, and particularly preferably 0.5 m to 3 m.

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

Such a retardation layer can perform the same polarization conversion in a wider wavelength region. Therefore, this phase difference layer can be used as an optical compensation film in FPDs of all liquid crystal panels, organic EL, etc. in combination with a photo alignment layer formed from this liquid crystal aligning agent.

The retardation layer can be used as a wide-band? / 4 plate or a? / 2 plate. When used as a wide-band lambda / 4 plate or a lambda / 2 plate, the content of the polymer formed from the polymerizable nematic liquid crystal compound in the retardation layer may be appropriately selected. In the case of the lambda / 4 plate, the film thickness can be adjusted to Re (550) of the obtained liquid crystal aligning element to 113 nm to 163 nm, preferably 135 nm to 140 nm, particularly preferably about 137.5 nm, In the case of the second plate, the film thickness may be adjusted so that Re (550) of the obtained liquid crystal aligning element is 250 nm to 300 nm, preferably 273 nm to 277 nm, particularly preferably about 275 nm.

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

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, &quot;% &quot; and &quot; part &quot; are parts by mass and parts by mass unless otherwise specified.

Example 1: Synthesis of compound (M1-1-1)

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

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

50 g (258 mmol) of ferric acid was dissolved in 360 g of methanol. To the obtained solution, 10 g of sulfuric acid was added at room temperature. After the temperature of the solvent was raised to reflux, the reaction was carried out for 2 hours under reflux. After the obtained reaction solution was cooled, 150 g of ice and 150 g of water were added. The supernatant was removed by decantation, and 150 g of water at 5 캜 was further added to crystallize. The obtained white crystals were filtered. The filtered white crystals were further washed with 1M aqueous sodium hydrogencarbonate solution and water, followed by vacuum drying to obtain 22.2 g of a compound (a1-1-1). The yield was 83% based on ferric acid.

[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 resulting solution, 33.19 g (240 mmol) of potassium carbonate and 1.99 g (12 mmol) of potassium iodide were added. To the resulting dispersion, 6-chlorohexanol was added dropwise, and the mixture was stirred at room temperature for 1 hour and then at 70 ° C for 8 hours. The resulting reaction solution was filtered to remove insolubles. To the filtrate, 200 g of methyl isobutyl ketone and 300 g of water were added, and the mixture was stirred, allowed to stand, separated, and the organic layer was recovered. 200 g of water was added to the recovered organic layer, and the washing operation of stirring, setting and separating was repeated twice. From the recovered organic layer, the solvent was removed by distillation under reduced pressure using an evaporator to obtain a crude product of the compound (b1-1-1).

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

The total amount of the crude product of the 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 占 폚 for 1 hour. After the reaction solution was cooled to about 3 캜, a 2M hydrochloric acid aqueous solution was added thereto while maintaining the temperature at 5 캜 or lower. A white precipitate obtained by acid precipitation was collected by filtration, further washed twice with a mixed solution of 100 g of water and 80 g of methanol, and vacuum dried to obtain 30.4 g of a compound (c1-1-1). The yield was 86% based on the compound (a1-1-1).

[Synthesis of Compound (M1-1-1)

27.46 g (93 mmol) of the compound (c1-1-1) was dissolved in 280 g of chloroform. To the obtained solution, 2.06 g of BHT (ditert-butyl-hydroxytoluene) as a polymerization inhibitor and 37.73 g (373 mmol) of triethylamine were added, and the mixture was stirred under ice cooling. 29.26 g (260 mmol) of methacrylic acid chloride was added dropwise to the reaction solution, and the mixture was stirred at 5 ° C or lower for 5 hours. To the reaction solution obtained, 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 2N hydrochloric acid aqueous solution was added to this organic layer, and the washing operation of stirring, standing and separating was repeated twice. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. Washed twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, and then dried under vacuum 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) (different method)]

27.46 g (93 mmol) of the compound (c1-1-1) was dissolved in 280 g of chloroform. To the obtained solution, 8.00 g of BHT (ditert-butyl-hydroxytoluene) as a polymerization inhibitor, 11.16 g of para-toluenesulfonic acid and 44.63 g of methacrylic acid were added and reacted for 8 hours while removing water by azeotropic dehydration. After the reaction solution was cooled to 5 캜 or less, 200 g of water was added, and the organic layer was recovered by stirring, standing, and liquid separation. 5.7 g of dimethylaminopyridine and 190 g of water were added to the obtained organic layer, and the mixture was stirred at room temperature for 12 hours. The obtained organic layer of the reaction solution was recovered, and this organic layer was washed twice with 100 g of 2N hydrochloric acid aqueous solution. The organic layer was recovered, 300 g of n-heptane was added, and the precipitated crystals were collected by filtration. Washed twice with a mixed solvent consisting of 100 g of water and 80 g of methanol, and then dried under vacuum to obtain 18.3 g of a compound (M1-1-1). The yield was 54% based on the compound (c1-1-1).

Example 2 (Production of polymer having photoreactive group)

The polymer having the photoreactive group from the above compound (M1-1-1) was produced as follows.

1.00 g (2.76 mmol) of the compound (M1-1-1) and 10 g of tetrahydrofuran were added to the Schlenk tube and deoxidized. Then, while nitrogen was flowing, 2.27 mg of azobisisobutyronitrile (AIBN) was added And the mixture was stirred at 60 DEG 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 then vacuum-dried to obtain 0.75 g of polymer 1. The yield was 75% based on the compound (M1-1-1). From the GPC measurement, the obtained polymer had a number average molecular weight of 28200 and an Mw / Mn of 1.82 as a polystyrene standard, and a monomer content thereof was 0.5%. This polymer is referred to as polymer (1-1-1).

Further, GPC analysis of the number average molecular weight of the polymer (1-1-1) as a polystyrene standard was measured under the following conditions.

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

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

column; TSK-gel MultiporeH _XL- M (trade name)

TSK-gel MultiporeH _XL- M (trade name)

TSK-gel MultiporeH _XL- M (trade name)

      (The column was connected in series).

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 ml / min

Dose; 50 μl

Detector; IR, UV

Sample concentration; 0.6% by mass (solvent: THF)

Calibration standards; TSK STANDARD POLYSTYRENE

                  A-500, A-1000, A-2500, A-5000, F-1, F-2, F-

                  F-20, F-40, F-80, F-128, F-288, F-380

                  (Trade name, manufactured by Tosoh Corporation)

Example 3: Preparation of photoreactive liquid crystal aligning agent

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

Evaluation example 1

[Preparation of Composition for Polarizing Layer]

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

A polymerizable liquid crystal compound; Compound (3-1-6) 75 parts

                    Compound (3-1-7) 25 parts

Dichroic dye; Azo dye (G205; manufactured by Hayashibara Seibutsukagaku Kenkou Sho)

3.0 parts

A polymerization initiator; 6 parts of 1-hydroxycyclohexyl phenyl ketone (Irgacure 184; manufactured by Ciba Specialty Chemicals)

Leveling agents; 1.5 parts of a polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

solvent; Cyclopentanone 250 parts

[Measurement of phase transition temperature]

The phase transition temperature was confirmed by a texture observation by a polarizing microscope. The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was phase-shifted to a nematic phase at 110 캜 and phase-transitioned to a smectic A phase at 104 캜 at the time of temperature lowering by raising the temperature to 120 캜, , It was confirmed that the phase transition occurred at 83 DEG C into a smectic B phase.

[Fabrication of photo-alignment layer]

The photoreactive liquid crystal aligning agent obtained in Example 3 was applied to a polyethylene terephthalate substrate (PET substrate) by a bar coating method and dried at 60 占 폚 for 1 minute to form a dried coating film having a thickness of 100 nm. Subsequently, the surface of the obtained dried film was subjected to polarized UV irradiation treatment to form a photo alignment layer. The polarizing UV treatment was performed under the condition that the intensity measured at a wavelength of 365 nm was 100 mJ by using a UV irradiator (SPOT CURE SP-7; manufactured by Usuo Denki K.K.).

[Production of polarizing layer]

On the photo alignment layer, a composition for forming a polarizing layer was applied by a bar coating method, heated and dried in a drying oven at 120 캜 for 1 minute, and then cooled to room temperature. UV rays having an exposure dose of 1200 mJ / cm 2 (based on 365 nm) were irradiated to a layer formed from the composition for forming a polarizing layer using a UV irradiator (SPOT CURE SP-7, manufactured by Ushio Inc.) to form a polarizing layer To prepare a liquid crystal alignment element. The film thickness of the polarizing layer at this time was measured by a laser microscope (OLS3000, manufactured by Olympus Corporation) and found to be 1.6 탆.

[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 Spectrty Corporation). Using Cu as a target, X-rays generated under conditions of an X-ray tube current of 40 mA and an X-ray tube voltage of 45 kV were made incident from the rubbing direction through the fixed diverging slit 1/2 °, = 0.01671 [deg.] Step. As a result, a sharp diffraction peak (black peak) having a peak half-value width FWHM = about 0.187 deg. Was obtained in the vicinity of 2? = 20.22 deg. In addition, the same results were obtained when incidence from the rubbing vertical direction. It can be seen that the ordered period (d) obtained from the peak position is about 4.4 Å and forms a structure reflecting the high order smectic phase.

[Measurement of dichroic ratio (dichroic ratio)] [

The absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction at the maximum absorption wavelength were set to a folder in which a polarizer was attached to a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation) And measured by a double beam method using one apparatus. In this folder, the reference side has a mesh that cuts 50% of the light amount. The ratio (A ² / A ¹ ) was calculated from the measured values of the absorbance (A ¹ ) in the transmission axis direction and the absorbance (A ² ) in the absorption axis direction. The results are shown in the table. The higher the dichroic ratio, the more useful it is as a polarizing layer. Table 1 shows the measurement results of the dichroic ratio.

[Observation of alignment state]

The alignment state of the obtained polarizing layer was confirmed by observation with a polarizing microscope. A sample was inserted between the polarizing microscope Cross-Nicol in the direction of about 45 占 and observation was made in the state of light leakage. When aligned in the vertical direction, the light leakage does not occur and the dark field state is observed. In the case where the light is horizontally aligned, light leakage occurs and is observed in the bright field state. A case where a bright field was obtained over the entire screen was evaluated as &quot;? &Quot;, and a case where a dark field was obtained over the entire screen was evaluated as two levels. The results are shown in Table 1.

[Measurement of Haze Value]

The haze value of the obtained polarizer was measured using a haze meter (HZ-2; manufactured by Suga Shikenki K.K.). The haze value is expressed by the following equation.

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

When the alignment regulating force of the polarizing layer by the photo-alignment layer is insufficient, a discontinuous defect occurs in the polymerizable smectic liquid crystal which is the main component of the polarizing layer. Since light scattering occurs at the discontinuous defect interface, the haze value becomes large. That is, the smaller the haze value is, the better the orientation property can be. In this case, 3% or less was considered good. The results are shown in Table 1.

Evaluation example 2

A liquid crystal alignment element was prepared in the same manner as in Evaluation Example 1 except that the dichroic dye was changed from an azo dye (G205; Hayashibara Seibutsukagaku Kagaku Sho) to an azo dye (NKX2029; Hayashibara Seibutsuka Kagaku Kyusho).

[Measurement of phase transition temperature]

The phase transition 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 to remove the solvent and dried, the phase transition occurred at 113 ° C in a nematic phase at 107 ° C and the smectic A phase transition at 83 ° C, .

As in Evaluation Example 1, dichroic ratio measurement, alignment state observation and haze value measurement of the produced liquid crystal aligning device were performed. The results are shown in Table 1.

Evaluation example 3

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was prepared from a mixture of 75 parts of the compound (3-1-6) and 25 parts of the compound (3-1-7), 75 parts of the compound (3-1-6) (3-1-8) was changed to a mixture of 25 parts by weight, to prepare a liquid crystal aligning element.

[Measurement of phase transition temperature]

The phase transition 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 to remove the solvent and dried, phase transition occurred at 111 ° C in a nematic phase at 105 ° C, phase transition to a smectic A phase at 82 ° C, and phase transition to a smectic B phase at 82 ° C .

As in Evaluation Example 1, dichroic ratio measurement, alignment state observation and haze value measurement of the produced liquid crystal aligning device were performed. The results are shown in Table 1.

Evaluation example 4

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was prepared from a mixture of 75 parts of the compound (3-1-6) and 25 parts of the compound (3-1-7), 75 parts of the compound (3-1-6) (3-1-13) was changed to a mixture of 25 parts by weight of the liquid crystal aligning element.

[Measurement of phase transition temperature]

The phase transition behavior of the polymerizable liquid crystal composition contained in the composition for polarizing layer of Example 4 was measured in the same manner as in Evaluation Example 1. After the temperature was raised to 130 ° C to remove the solvent, the solvent was phase-transformed into a nematic phase at 119 ° C at the time of cooling down, a phase transition from 111 ° C to a smectic A phase, and a phase transition to a smectic B phase at 82 ° C .

As in Evaluation Example 1, the dichroic ratio measurement, the alignment state observation, and the haze value measurement of the produced polarizing element were performed. The results are shown in Table 1.

Evaluation Example 5

The polymerizable liquid crystal compound contained in the composition for forming a polarizing layer was prepared from a mixture of 75 parts of the compound (3-1-6) and 25 parts of the compound (3-1-7), 75 parts of the compound (3-1-6) (3-1-14) was changed to a mixture of 25 parts by weight, to prepare a liquid crystal aligning element.

[Measurement of phase transition temperature]

The phase transition 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 to remove the solvent, the solvent was phase-transformed into a nematic phase at 118 ° C at the time of cooling down, a phase transition at 109 ° C to a smectic A phase, and a phase transition to a skeletal B phase at 79 ° C .

As in Evaluation Example 1, dichroic ratio measurement, alignment state observation and haze value measurement of the produced liquid crystal aligning device were performed. The results are shown in Table 1.

Evaluation example 6

A polymerizable nematic liquid crystal compound (for example, A1-1, A5-1, A6-1) which can be oriented in a rubbing film of polyvinyl alcohol instead of the polymerizable liquid crystals (1-6) and (1-7) , 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), and a composition for forming a retardation layer without using a dichroic dye was prepared. The composition was applied on the photo alignment layer shown in Evaluation Example 1 and heated to the nematic phase transition temperature. Thereafter, the polymerizable nematic By polymerizing the liquid crystal compound, a nematic liquid crystal alignment element can be formed on the photo alignment layer. This liquid crystal alignment element functions as a retardation layer when the thickness of the liquid crystal phase is adjusted to be a desired retardation.

According to the photoreactive liquid crystal aligning agent of the present invention, it is possible to form a liquid crystal aligning element (for example, a polarizing layer and a retardation layer) using a nematic liquid crystal or a smectic liquid crystal. The orientation layer obtained by the photoreactive liquid crystal aligning agent of the present invention is advantageous in that the orientation layer is formed in the noncontact system and therefore dust is small and masking is easily performed in combination with the mask. Layer.

Claims (12)

A liquid crystal alignment element comprising a liquid crystal alignment layer formed by forming a coating film from a photoreactive liquid crystal aligning agent comprising a polymer represented by the following formula (1-1), and polarizing the coating film, and a polarizing layer or a phase difference layer,
Wherein the polarizing layer or the retardation layer is formed by applying a composition solution containing a polymerizable liquid crystal compound on the liquid crystal alignment layer to obtain a coating film and polymerizing the polymerizable liquid crystal compound contained in the coating film by polarized irradiation Lt; / RTI &
Wherein the polymerizable group of the polymerizable liquid crystal compound is an acryloyloxy group.

[In the above 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 have a fluorine atom or a cyano group.
S ³ represents an alkyl group having 1 to 12 carbon atoms which may have a fluorine atom or a cyano group.
X ¹ , X ² , X ³ , X ⁴ and X ⁵ each independently represent a single bond, an oxygen atom, a carbonyloxy group or a methylene group.
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, plural R ^{2 s} present may be the same or different and w is 2 or 3 , Plural R ⁴ present may be 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 molar fractions of the respective structural units with respect to the total structural units, and satisfy a relationship of 0.25 <p? 1, 0? q <0.75 and 0? r <0.75. The liquid crystal alignment element according to claim 1, wherein the polymer is a polymer having q of 0 in the formula (1-1). The liquid crystal alignment element according to claim 1 or 2, wherein the polymer is a polymer in which r in the formula (1-1) is 0. The liquid crystal alignment element according to claim 1 or 2, wherein the polymer is a polymer in which R ¹ and R ² in the formula (1-1) are each independently a methoxy group or an ethoxy group. The liquid crystal alignment element according to claim 1 or 2, wherein the polymer is a polymer in which n and m in the formula (1-1) are both 0. delete delete The liquid crystal alignment element according to claim 1, wherein the polymerizable liquid crystal compound is a compound exhibiting a smectic liquid crystal state. The liquid crystal alignment element according to claim 1, wherein the polymerizable liquid crystal compound is a compound exhibiting a high-order smectic liquid crystal state. The liquid crystal alignment element according to claim 1, wherein the polymerizable liquid crystal compound is a compound which exhibits a nematic liquid crystal state directly from an isotropic liquid crystal state. The liquid crystal alignment element according to claim 10, wherein the polymerizable liquid crystal compound is represented by the following formula (2).

[In the above formula (2)
Q ¹ represents a substituted or unsubstituted polycyclic aromatic hydrocarbon group or a substituted or unsubstituted polycyclic aromatic heterocyclic group.
D ¹ and D ² each independently represent 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 is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, 4 alkoxy group, cyano group or 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.
A ¹ and A ² each independently represent a divalent alicyclic hydrocarbon group or a divalent aromatic hydrocarbon group, and the hydrogen atom contained in the alicyclic hydrocarbon group and the alicyclic hydrocarbon group is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkoxy group, a cyano group or a nitro group. The alkyl group having 1 to 4 carbon atoms and the hydrogen atom contained in the 1 to 4 carbon alkoxy group may be substituted with a fluorine atom.
k and l each independently represent an integer of 0 to 3; When k is 2 or more, plural A ^{1 s} are the same or different from each other, and plural B ^{1 s} are the same or different from each other. When l is 2 or more, a plurality of A ^{2 s} are the same or different from each other and a plurality of B ^{2 s} present are the same or different from each other.
F ¹ and F ² each independently represent 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, -CH ₂ - may be substituted with -O- or -CO-.
P ¹ and P ² each independently represent a hydrogen atom or an acryloyloxy group, but P ¹ and P ² are not both hydrogen atoms. delete