TW201529726A - Liquid-crystal alignment agent, liquid-crystal alignment film, and liquid-crystal display element - Google Patents

Abstract

This liquid-crystal alignment agent contains a polymer, a polymerizable compound, and a solvent. The polymerizable compound has a polymerizable unsaturated bonding group, a functional group that forms a hydrogen bond, and at least one aromatic ring near said functional group. The functional group forms intermolecular hydrogen bonds so as to form a mesogenic structure.

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment film obtained by using a liquid crystal alignment agent and a liquid crystal alignment agent used for producing a liquid crystal alignment film, and a liquid crystal display element.

In a liquid crystal display device used for a liquid crystal television, a liquid crystal display or the like, a liquid crystal alignment film used for controlling a liquid crystal alignment state is usually provided in the element.

At present, according to the most common method in the industry, the liquid crystal alignment film is a surface of a film formed of a polylysine formed on an electrode substrate and/or a polyimide which is imidized by a ruthenium. The cloth such as nylon or polyester is rubbed in one direction, that is, the one produced by the so-called rubbing treatment can impart an alignment property to the liquid crystal alignment film by the rubbing treatment.

However, with the increasing performance of high-performance, high-definition, and large-scale liquid crystal display elements, the effects of friction treatment on the surface of the liquid crystal alignment film, such as scratches, dust, mechanical force, or static electricity, even alignment Various problems such as unevenness in the processing plane have gradually become clear.

One of the techniques which does not apply the rubbing treatment is known as a photo-alignment method (for example, Patent Document 1). In the photo-alignment method, the polymer contained in the liquid crystal alignment film is caused to cause a photoisomerization reaction or a photodimerization reaction by irradiating the liquid crystal alignment film with polarized ultraviolet rays, thereby imparting an alignment ability to the liquid crystal alignment film. The optical alignment method is applicable to liquid crystal display elements of IPS (In-Plane Switching) or FFS (Fringe Field Switching) in the demand for high definition and high-grade liquid crystal display elements (for example, patents). Literature 2). Further, in the IPS method, in recent years, a method of developing a combination of a PSA method (Polymer sustained Alignment) using a liquid crystal containing a polymerizable compound has been developed because the alignment ability can be further improved.

On the other hand, other techniques that do not apply a rubbing treatment are known, for example, in a VA (vertical) mode. In the VA method, an MVA (Multi Vertical Alignment) method in which a protrusion is formed on a TFT substrate color filter substrate for controlling a liquid crystal collapse direction is known, or a slit is formed on an ITO electrode of a substrate, and an electric field is used to control liquid crystal collapse. PVA (Patterned Vertical Alignment) mode, or known PSA mode. In the VA method, the PSA method has been attracting attention in recent years.

In the PSA method, a polymerizable compound which can be polymerized by light or heat is added to the liquid crystal, and after the liquid crystal cell is produced, UV is irradiated while the liquid crystal is tilted in an applied electric field. Thus, the polymerizable compound can be polymerized or crosslinked, and the liquid crystal can be aligned in the oblique direction. According to the PSA method, a slit is formed on the side electrode of the liquid crystal cell as a structure, and In the electrode pattern on the side, the MVA-like protrusion or the PVA-like gap is not provided, and an operation can be performed (for example, Patent Document 3).

In addition, when the polymerizable compound is added to the liquid crystal alignment film without being added to the liquid crystal alignment film, the response speed of the liquid crystal display element can be increased (for example, refer to Non-Patent Document 1).

However, the polymerizable compound to be added to the liquid crystal alignment agent has a problem of low solubility and precipitation stability in which a polymerizable compound is precipitated during storage of the liquid crystal alignment agent.

Further, in the liquid crystal display device, when the unreacted polymerizable compound remains as an impurity, a phenomenon such as image sticking tends to occur, and when the unreacted polymerizable compound is reduced, the amount of ultraviolet rays is increased, and ultraviolet rays are caused. The problem of damage caused by the liquid crystal or the member is increased, and the reliability of the liquid crystal display element is lowered. Therefore, in order to enhance the sensitivity of light, it is necessary to absorb from the ultraviolet light to the long wavelength side, and the conjugated bond of the polymerizable compound is longer, and the liquid crystal (mesogenic) structure is larger, and the ring structure is straight. The increase in structure, etc., causes a problem that the solubility of the liquid crystal alignment agent is further lowered.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2004-163646

[Patent Document 2] JP-A-2013-080193

[Patent Document 3] JP-A-2004-302061

[Non-patent literature]

[Non-Patent Document 1] K.H Y.-J, Lee, SID 09 DIGEST, P666-668

In view of the above, the present invention has been made in an effort to provide a liquid crystal alignment film obtained by a liquid crystal alignment agent having a high sensitivity alignment fixing ability and a liquid crystal alignment film obtained by a liquid crystal alignment agent, and a liquid crystal display element.

The inventors of the present invention conducted intensive studies and found a liquid crystal alignment agent containing at least one or more aromatic groups having a polymerizable unsaturated bond group, a hydrogen-bonded functional group, and a functional group. In the ring, this function is extremely effective in achieving the above object based on the formation of a polymerizable compound having a liquid crystal (mesogenic) structure by hydrogen bonding between molecules, and thus the present invention has been completed.

The present invention is as follows, the main contents are as follows.

(1) A liquid crystal alignment agent comprising a polymer, a polymerizable compound, and a solvent, wherein the polymerizable compound has a polymerizable unsaturated bond group and a hydrogen-bonded functional group. At least one or more aromatic rings in the vicinity of the functional group are formed by a hydrogen bond between the molecules to form a mesogenic structure.

(2) The liquid crystal alignment agent according to (1) above, wherein the functional group is a carboxyl group.

(3) The liquid crystal alignment agent according to the above (1) or (2), wherein the polymerizable compound is at least one selected from the following formulas [1-1] to [1-4].

(T is an ether, an ester, a guanamine bond, S is an alkylene group having 2 to 11 carbon atoms, R is a hydrogen atom or a methyl group, n = 1 or 2)

(4) The liquid crystal alignment agent of any one of (1) to (3), wherein the polymerizable compound is at least one selected from the following formulas [2-1] to [2-6].

(5) The liquid crystal alignment agent according to any one of the above (1), wherein the polymer has a liquid crystal in a side chain and a vertical alignment.

(6) The liquid crystal alignment agent according to (5) above, wherein the polymer further has a photopolymerizable group in a side chain.

(7) The liquid crystal aligning agent of the above (6), wherein the photopolymerizable group is at least one selected from the following formulas [3-1] to [3-7],

(wherein Me represents a methyl group).

(8) The liquid crystal alignment agent according to any one of the above (1), wherein the polymer is a photoreactive group.

(9) The liquid crystal alignment agent according to the above (8), wherein the photoreactive group is at least one selected from the following formulas [4-1] to [4-5].

(10) A liquid crystal according to any one of the above (1) to (9) An alignment agent, wherein the polymer is at least one selected from the group consisting of a polyimine precursor and a polyimine obtained by hydrazine imidization, a polyoxyalkylene or a poly(meth)acrylate .

(11) A liquid crystal alignment film obtained by the step of irradiating ultraviolet rays with an applied voltage by using the liquid crystal alignment agent of any one of the above (5) to (7).

(12) A liquid crystal display element comprising the liquid crystal alignment film of the above (11).

(13) A liquid crystal alignment film obtained by the step of irradiating a polarized ultraviolet ray by using the liquid crystal alignment agent of the above (8) or (9).

(14) A liquid crystal display device comprising the liquid crystal alignment film of the above (13).

According to the present invention, a polymerizable compound having a functional group having a liquid crystal (mesogenic) structure bonded by hydrogen bonding can be used, and a liquid crystal alignment agent capable of improving the solubility of a polymerizable compound and having high sensitivity alignment immobilization ability can be realized. A liquid crystal alignment film obtained by a liquid crystal alignment agent and a liquid crystal display element.

[Formation of the Invention]

Hereinafter, the present invention will be described in detail.

<Polymerizable compound>

The liquid crystal alignment agent of the present invention contains a polymerizable compound. The polymerizable compound contains a polymerizable unsaturated bond group, a hydrogen-bonded functional group, and at least one or more aromatic rings in the vicinity of the functional group, and the hydrogen-bonded function is based on hydrogen bond formation between molecules. The liquid crystal structure is formed.

The polymerizable unsaturated bond group means an ethylenically unsaturated double bond group which provides photopolymerization or photocrosslinking reaction via stimulation by heat or ultraviolet rays or the like. Specific examples thereof include radical polymerization of a vinyl group, a (meth) acrylonitrile group, an isopropenyl group, an allyl group, a styryl group, and an α-methyl-γ-butyl lactone group. Base.

Further, the term "hydrogen bonding" as used in the present invention means a hydrogen atom which is a functional group, and an electron offset generated by a difference in electronegativity between atoms having high electronegativity adjacent to the hydrogen atom, and a liquid crystal alignment agent. In the solvent or in the liquid crystal alignment film, a gravitational interaction between a hydrogen atom and other highly electronegative atoms is formed, and a bond formed between the molecules via a hydrogen atom is intended. The functional group having hydrogen bonding means that a hydrogen bonding group is formed between molecules in a liquid crystal alignment film or a solvent of a liquid crystal alignment agent. The hydrogen-bonded functional groups mainly form a dimer between the molecules in the liquid crystal alignment film or the solvent of the liquid crystal alignment agent. Since these polymerizable compounds have a highly polar group such as a carboxyl group or a hydroxyl group, they exhibit extremely high solubility when compared with a general polymerizable compound or the like. Therefore, the solubility of the polymerizable compound in the solvent can be improved. Therefore, when the liquid crystal alignment agent is stored (for example, in a frozen storage state), precipitation of the polymerizable compound or the like is not easily caused.

In addition, hydrogen-bonded functional groups are formed via intermolecular formation. A liquid crystal structure is formed by means of hydrogen bonding. The mesogenic structure refers to a rigid structure which is formed to produce liquid crystallinity. The formation of the liquid crystal structure bonded by the hydrogen, that is, the result of forming the rigid structure, in addition to improving the sensitivity of the liquid crystal alignment film to light, can also improve the alignment fixing ability of the liquid crystal alignment film.

Further, the functional group having hydrogen bonding is not particularly limited, and examples thereof include a carboxyl group, a hydroxyl group, a urea group, a decylamino group, and a quinone imine group. Among these, a dimer is easily formed, and a carboxyl group is preferred.

Further, since at least one or more aromatic rings of the polymerizable compound are rigid, they are formed in a liquid crystal structure together with the functional group when they are provided in the vicinity of a hydrogen-bonded functional group. Since these liquid crystal structures have a structure of a pseudo-large liquid crystal, the conjugate (body) can be made wider, and the absorption peak is still obtained up to the ultraviolet region on the long wavelength side (for example, 365 nm). Therefore, since high-intensity ultraviolet light irradiation also has high sensitivity, the ultraviolet irradiation of weak energy can also be aligned and fixed. The aromatic ring may, for example, be a benzene ring, or an aromatic hydrocarbon ring such as a naphthalene ring or an anthracene ring, or a pyridine ring or a pyridyl group. a heterocyclic ring such as a ring or a pyrrole ring. The number of aromatic rings is not particularly limited, and it is preferably 1 to 4. Further, the aromatic rings may have a substituent.

When the polymerizable compound described above is exemplified, the polymerizable compound represented by the above formula [1-1] to [1-4] having a carboxyl group or the above formulas [2-1] to [2-6] may be mentioned. Wait. Since the hydrogen atom adjacent to the hydrogen atom has a large negative electron difference due to the hydrogen atom of the carboxyl group, when the polymerizable compound is used, a stronger hydrogen bond is interposed between the molecules. The junction forms a dimer. Since the molecules of the polymerizable compounds are very small, the molecules of the respective dimers are also very small. Thus, the solubility of the polymerizable compound in the solvent can be further increased, and the sensitivity of the liquid crystal alignment film to light can be further increased. Further, the polymerizable compound represented by the above formula [1-1] to [1-4] or the above formulas [2-1] to [2-6] has a liquid crystal structure together with the carboxyl group in the vicinity of a carboxyl group. More than one aromatic ring. In this way, in addition to increasing the sensitivity of the liquid crystal alignment film to light, the alignment fixing ability can be further improved.

In addition, the addition ratio of the polymerizable compound to the liquid crystal alignment agent may be 0.1 to 30% by mass based on the liquid crystal alignment agent.

<Liquid alignment agent>

The liquid crystal alignment agent contains the above-mentioned polymerizable compound used for producing a liquid crystal alignment film, a polymer, and a solvent. The liquid crystal alignment agent of the present invention is a liquid crystal display element having a vertical alignment mode, that is, a vertical electric field driving method, or 2) ultraviolet light (polarized ultraviolet light) which is irradiated with polarized light, which is obtained by irradiating ultraviolet rays with a voltage applied to a liquid crystal cell. In the step of producing a liquid crystal cell, and then irradiating the liquid crystal cell with ultraviolet rays, a horizontal alignment method such as an IPS method (In-Plane Switching) or an FFS method (Fringe Field Switching), that is, a liquid crystal driven by a horizontal electric field The user of the display component.

a liquid crystal alignment agent in a case where a liquid crystal display element of a vertical alignment type is used, which is a group having a side chain having a liquid crystal which is a vertical alignment The polymer acts as a polymer. Further, these polymers may also be those having a photoreactive group or a photoradical generating group in a side chain. In the case of using a polymer having a side chain having such a photoreactive group or a photoradical generating group, photopolymerization or photocrosslinking reaction is more likely to occur upon irradiation with ultraviolet rays, and the alignment fixing ability can be improved.

As the liquid crystal alignment agent used in the case of the liquid crystal display element of the horizontal alignment type, a photoreactive substrate can be used as the polymer. When a photoreactive group is provided, when a polarized ultraviolet ray is irradiated, a photoreaction such as a photoisomerization reaction is caused, and the horizontal alignment ability (so-called photoalignment) can be imparted to the liquid crystal alignment film without the need of a rubbing treatment. Hereinafter, the liquid crystal vertical alignment group, the photopolymerizable group, and the photoreactive group will be respectively described.

<Liquid crystal is the basis of vertical alignment>

In the case where the liquid crystal display element is in the vertical alignment mode, the polymer contained in the liquid crystal alignment agent has a liquid crystal which is vertically aligned in the side chain. The basis of the liquid crystal in the vertical alignment means that the liquid crystal molecules have a basis for the vertical alignment ability of the substrate, and the structure is not particularly limited as long as it has such ability. The liquid crystal is a group of a vertical alignment, and examples thereof include a linear alkyl group, a linear fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, and a cholesteryl group. Specifically, for example, it is represented by the following formula [5].

R ¹ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or a hydrocarbon having 1 to 3 carbon atoms. Base-ether group (-CCO-). Among these, from the viewpoint of easiness of synthesis, -O-, -COO-, -CONH-, or an alkyl-ether group having 1 to 3 carbon atoms is preferred. The above R ² , R ³ and R ⁴ each independently represent a phenyl group or a cycloalkyl group. From the viewpoints of easiness of synthesis and ability of the liquid crystal to be vertically aligned, a combination of a, b, c, R ² , R ³ and R ⁴ shown in Table 1 is preferred.

R ⁵ represents a hydrogen atom, an alkyl group having 2 to 24 carbon atoms, preferably 5 to 8 or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring, or a large cyclic group formed therefrom. When at least one of a, b and c is 1, the structure of R ⁵ is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms, or a fluorine-containing alkyl group having 2 to 14 carbon atoms, more preferably a hydrogen atom. The carbon number is 2 to 12, and the most preferred is an alkyl group of 2 to 10 or a fluorine-containing alkyl group.

Further, when a, b and c are both o, the structure of R ⁵ is preferably a carbon number of 12 to 22, more preferably an alkyl group of 12 to 20 or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring. Or a large cyclic group formed by the above, more preferably an alkyl group having 12 to 20 carbon atoms, most preferably 12 to 18 carbon atoms or a fluorine-containing alkyl group.

Moreover, the liquid crystal is a side chain of a vertical alignment group, and can be polymerized The main chain of the object is directly bonded, and it can also be bonded by a suitable bonding group. As described above, the method of introducing the liquid crystal into the side chain of the vertical alignment is not particularly limited.

In addition, the liquid crystal is a sufficient amount of the vertical alignment, and the sensitivity and the alignment fixing ability of the light can be increased as long as it is in a range in which the alignment can be fixed, as long as it does not affect other characteristics. When the range is as much as possible, the better.

<Photopolymerizable group>

The polymer contained in the liquid crystal alignment agent of the present invention may further have a photopolymerizable group in the side chain. The photopolymerizable group is a group which causes a polymerization reaction by irradiating light such as ultraviolet rays, for example, by irradiating light such as ultraviolet rays to generate a polymerization group (hereinafter also referred to as a photopolymerizable group) or a photocrosslinking group (hereinafter also When it is called a photo-crosslinkable group, it is not particularly limited, and at least one selected from the photopolymerizable groups represented by the above formulas [3-1] to [3-7] is preferably used. By.

The liquid crystal alignment film obtained by using the liquid crystal alignment agent containing these polymers is a photopolymerizable group. When a liquid crystal display element containing a photopolymerizable group in a liquid crystal alignment film is irradiated with light such as ultraviolet rays, a photopolymerizable group located on a surface where the liquid crystal alignment film is in contact with the liquid crystal, or a polymerizable unsaturated bond group of the polymerizable compound, The photopolymerization or photocrosslinking reaction is caused, and the alignment of the liquid crystal provided on the surface of the liquid crystal alignment film can be more efficiently immobilized.

a photopolymerizable group introduced into a polymer side chain (hereinafter, also a photopolymerizable side chain) having a side containing at least one selected from a methacrylic group, an acrylic group, a vinyl group, an allyl group, a styryl group, and an α-methyl-γ-butyrolactone group. The chain is better.

The photopolymerizable side chains may be directly bonded to the main chain of the polymer, or may be bonded via a suitable bonding group. As described above, the method of introducing the photopolymerizable side chain is not particularly limited. The side chain of photopolymerization is represented by the following formula [6].

In the formula [6], R ⁶ represents a single bond or -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N ( Any of CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, R ⁷ represents a single bond, or an alkylene having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom. The alkyl group-CH ₂ - may be optionally substituted by -CF ₂ - or -CH=CH-, and any of the groups listed below may be in the case of not being bonded to each other, or may be Substituted; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, a divalent heterocyclic ring. R ⁸ represents a methacrylic group, an acrylic group, a vinyl group, an allyl group, a styryl group, and an α-methyl-γ-butyrolactone group.

Further, R ⁶ in the above formula [6] can be produced by a general organic synthesis method, and in view of easiness of synthesis, -CH ₂ -, -O-, -COO-, -NHCO-, -NH -, -CH ₂ O- is preferred.

Further, a carbon ring or a heterocyclic ring which may be a divalent carbocyclic ring or a divalent heterocyclic ring of any of -CH ₂ - which may be substituted for R ⁷ may, for example, be specifically exemplified by the following structures, but not limited thereto herein.

R ⁸ is preferably a methacrylic group, an acrylic group, a vinyl group or an α-methyl-γ-butyrolactone group from the viewpoint of photopolymerizability.

The amount of the side chain of photopolymerization is reflected by irradiation with light such as ultraviolet rays to form a covalent bond, and it is preferable that the range of the alignment can be fixed, and the sensitivity to light and the ability to fix the alignment are further improved. The point of view, as long as it does not affect the scope of other features, as much as possible.

<Photoreactive group>

In the case of a horizontal alignment method such as an IPS method or an FFS method in which a liquid crystal display element is irradiated with a polarized ultraviolet ray, a liquid crystal alignment agent can be introduced into a polymer contained in a liquid crystal alignment agent to introduce a polarized ultraviolet ray. The photoreactive base is preferred.

The liquid crystal alignment film obtained by irradiating the liquid crystal alignment agent containing the photoreactive group-containing polymer is irradiated with polarized ultraviolet light to carry out photoreaction, and is oriented in the same direction as the polarizing direction or perpendicular to the polarizing direction. The liquid crystal is aligned. Examples of the photoreaction include photodimerization, photoisomerization, and the like. The photoreactive group is preferably one having an unsaturated bond, particularly a double bond, and examples thereof include an acrylic group, a vinyl group, a methacryl group, a decyl group, a chalcone group, and a couma bean. Ordinary, diphenylvinyl, maleimide, cinnamyl and the like.

In the case of a specific example, for example, the structure at the time of photodimerization reaction, for example, the structure represented by the above formula [4-1] to [4-3], etc., can be mentioned. In addition, the structure at the time of performing a photoisomerization reaction is, for example, the structure represented by the above formula [4-4], [4-5]. Further, a photoreactive group having a structure selected from the above formulas [4-1] to [4-5], for example, an arbitrary number is removed from the structures of the formulae [4-1] to [4-5] The group obtained by H, the group in which the bond bond in the above formula [4-1] is O, or the structure in which the structure is bonded to another structure (for example, an alkyl group or the like).

Further, these photoreactive groups may be introduced into the main chain of the polymer or may be introduced into the side chain. The method of introducing the photoreactive group is not particularly limited. Further, the polymer may have a base of the above-mentioned liquid crystal in a vertical alignment together with the photoreactive group.

Further, the amount of the photoreactive group is preferably such a range as to cause a photoreaction or a fixed alignment, and the viewpoint of the sensitivity to light and the ability to fix the alignment is improved as long as it does not affect other characteristics. When you are surrounded, try to be as much as possible.

<polymer>

The polymer contained in the liquid crystal alignment agent of the present invention is suitable for use in addition to the polyimide precursor and the polyimine obtained by imidization of the oxime, polyoxyalkylene or poly(meth)acrylate. By. Among them, the polyimine precursor system refers to polyamic acid (Polyamic acid), or polyamidolate. Further, in the liquid crystal alignment agent, the different polymers may be contained at the same time, and the content ratios thereof may be variously selected in accordance with the characteristics of the liquid crystal display device. The total amount of the polymer contained in the liquid crystal alignment agent is preferably from 0.1 to 20% by mass. Further, the polymer of the polyimine precursor, the polyimine, the polyoxyalkylene or the poly(meth)acrylate contained in the liquid crystal alignment agent of the present invention must be a solvent soluble in the liquid crystal alignment agent. By. Each polymer will be described below.

<Polyimide precursor and its quinone imidized polyimine>

In the case where the polymer contained in the liquid crystal alignment agent of the present invention contains a polyimide precursor, the polyimide precursor has, for example, a repeating unit (structural unit) represented by the following formula [7].

In the formula [7], R ₁ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. From the viewpoint of facilitating the imidization by heating, a hydrogen atom or a methyl group is particularly preferable. X ₂ is a tetravalent organic group, and its structure is not particularly limited. In the case of a specific example, for example, the following formulas [X-1] to [X-43] and the like can be given. From the viewpoint of liquid crystal alignment, X _{2 is} preferably [X-1] to [X-10], [X-26] to [X-28], or [X-31] to [X-37].

In the formula [X-1], R ₂ , R ₃ , R ₄ and R ₅ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an alkenyl group. , or phenyl. From the viewpoint of liquid crystal alignment, R ₂ , R ₃ , R ₄ , and R _{5 are} preferably a hydrogen atom, a halogen atom, a methyl group or an ethyl group, preferably a hydrogen atom or a methyl group, more preferably a lower one. At least one selected from the group consisting of the structures represented by the formulae [X1-1] to [X1 - 2].

The liquid crystal alignment agent of the present invention is used in the case of a liquid crystal display element obtained by irradiating a polarized ultraviolet ray, and preferred structures of X ₂ are, for example, [X1-1], [X1-2], [X-2]. , [X-3], [X-5], [X-6], [X-7], [X-8], [X-9], [X-10], etc., and [X1-1 ], [X1-2] and [X-6] are particularly good.

In the above formula [7], Y ₂ is a divalent organic group, and the structure thereof is not particularly limited. Specific examples of Y ₂ include, for example, the following formulas [Y-1] to [Y-73].

(wherein Me represents a methyl group).

It is expected that the solubility of an organic solvent such as a polyimide precursor or a polyimine may be increased to have [Y-8], [Y-20], [Y-21], [Y-22]. The structural unit of the structure of [], [Y-28], [Y-29] or [Y-30] is preferred.

The polyimine precursor of the liquid crystal alignment agent of the present invention may, for example, be a diamine component (for example, a diamine having a liquid crystal in a side chain of a vertical alignment and a diamine having a photopolymerizable side chain, which will be described later). Or a diamine (diamine such as a diamine having a photoreactive group) and a tetracarboxylic dianhydride component (for example, a tetracarboxylic dianhydride, a tetracarboxylic acid diester dichloride or a tetracarboxylic acid diester described later) are reacted. By. Polyimine precursors, for example, polylysine or polyphthalate. Specifically, for example, polylysine is obtained by reacting a diamine component with a tetracarboxylic dianhydride. Polyurethane is obtained by reacting a diamine component with a tetracarboxylic acid diester dichloride in the presence of a base, or reacting a diamine component with a tetracarboxylic acid diester in the presence of a suitable condensing agent or a base. By. Further, the polyimine is used to dehydrate the poly-proline, or to make the polyamidolate Heating the closed loop. Any of the polyamic acid, polyphthalate, and polyimine is suitable as a polymer used for producing a liquid crystal alignment film.

<Diamine having a liquid crystal which is a side chain of a vertical alignment>

The diamine having a side chain in which the liquid crystal is vertically aligned may, for example, be a long-chain alkyl group, a group having a ring structure or a branched structure in the middle of a long-chain alkyl group, a hydrocarbon group such as a cholesteryl group, or a hydrogen having such a group. A diamine in which a part or all of an atom is replaced by a fluorine atom is a diamine of a side chain, a diamine having a side chain represented by the above formula [5], or the like. More specifically, for example, a diamine having a hydrocarbon group having a hydrogen atom which may be substituted with fluorine and having a hydrocarbon number of 8 to 30, or a diamine represented by the following formulas [8] to [11], but not only Limited to this.

(The definitions of a, b, c, and R ¹ to R ⁵ in the formula [8] are the same as those in the above formula [5]).

(In the formula [9] and the formula [10], A ₁₀ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH-, A ₁₁ represents a single bond or a phenyl group, and a ₁₀ represents a structure in which the side chain which is perpendicularly aligned with the liquid crystal represented by the above formula [5] is the same, and a ₁₀ ' represents a liquid crystal which is perpendicular to the liquid crystal represented by the above formula [5]. The side chain of the alignment is the same structure, and the divalent group of the structure after removing one element such as hydrogen).

(In the formula [11], A ₁₄ is an alkyl group having 3 to 20 carbon atoms which is substituted by a fluorine atom, A ₁₅ is a 1,4-cyclohexyl group, or 1,4-phenylene group, and A ₁₆ is an oxygen atom. Or -COO-* (where the bond key labeled "*" is bonded to A ₁₅ ), A ₁₇ is an oxygen atom, or -COO-* (where the bond key labeled "*" is (CH) ₂ ) a ₂ bond). Further, a ₁ is 0, or an integer of 1, a ₂ is an integer of 2 to 10, a ₃ is 0, or an integer of 1).

The bonding position of the amine group (-NH ₂ ) of two of the formula [8] is not particularly limited. Specifically, for example, the bonding group with respect to the side chain is a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, and a position of 3, 4 Location, location of 3, 5, etc. Among them, from the viewpoint of the reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferable. It is preferable to add a position of 2, 4 or 3, 5 in addition to the viewpoint of easiness in synthesizing a diamine.

The specific structure of the formula [8] can be, for example, a diamine represented by the following formula [A-1] to the formula [A-24], but is not limited thereto.

(In the formula [A-1] to the formula [A-5], A ₁ is an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group).

(In the formula [A-6] and the formula [A-7], A ₂ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and A ₃ is carbon. Alkyl groups of 1 to 22, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups).

(In the formula [A-8] to the formula [A-10], A ₄ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, or -CH ₂ -, A ₅ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [A-11] and the formula [A-12], A ₆ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O -, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, A ₇ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, Ethyloxy, or hydroxy).

(In the formula [A-13] and the formula [A-14], A ₈ is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexylene group is a trans isomer thereof. ).

(In the formula [A-15] and the formula [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexylene group is a trans isomer thereof. ).

Specific examples of the diamine represented by the formula [9] can be, for example, the following The diamine represented by the formula [A-25] to the formula [A-30], etc., is not limited thereto.

(In the formula [A-25] to the formula [A-30], A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or - NH-, A ₁₃ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

Specific examples of the diamine represented by the formula [10] include, for example, a diamine represented by the following formula [A-31] to the formula [A-32], but are not limited thereto.

Among these, [A-1], [A-2], [A-3], [A-4], [A-5] are also used in terms of the ability of the liquid crystal to vertically align and the response speed of the liquid crystal. Preferably, a diamine such as [A-25], [A-26], [A-27], [A-28], [A-29] or [A-30] is preferred.

The diamine may be used in combination with one type or two or more types of liquid crystal alignment, pretilt angle, voltage holding characteristics, and charge accumulation as a liquid crystal alignment film.

<Diamine having photopolymerizable side chain>

When the liquid crystal alignment agent of the present invention is used for a liquid crystal display device of a vertical alignment type, it is preferred that a diamine component which is a raw material of the polyimide precursor contained in the liquid crystal alignment agent is introduced with a photopolymerizable side chain. The diamine having a photopolymerizable side chain is at least one selected from the group consisting of a methacryl group, an acryl group, a vinyl group, an allyl group, a styryl group, and an α-methyl-γ-butyrolactone group. For example, a diamine or the like having a side chain represented by the above formula [6] can be mentioned. More specifically, a diamine or the like represented by the following general formula [12] can be mentioned, but it is not limited thereto.

(The definitions of R ⁶ , R ⁷ and R ⁸ in the formula [12] are the same as those in the above formula [6]).

The bonding position of the amine group (-NH ₂ ) of two of the formula [12] is not particularly limited. Specifically, for example, the bonding group with respect to the side chain is a position of 2, 3 on the benzene ring, a position of 2, 4, a position of 2, 5, a position of 2, 6, and a position of 3, 4 Location, location of 3, 5, etc. Among them, from the viewpoint of the reactivity in synthesizing polyamic acid, the position of 2, 4, the position of 2, 5, or the position of 3, 5 is preferable. It is preferable to add a position of 2, 4 or 3, 5 in addition to the viewpoint of easiness in synthesizing a diamine.

a diamine having a photopolymerizable side chain containing at least one selected from the group consisting of a methacrylic group, an acryl group, a vinyl group, an allyl group, a styryl group, and an α-methyl-γ-butyrolactone group, specifically The following compounds and the like are exemplified, but are not limited thereto.

(wherein R ₆ represents a group selected from -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-. R ₇ is a carbon a alkyl group, a divalent carbocyclic ring or a heterocyclic ring formed by a number of 1 to a carbon number of 30, and a hydrogen atom of one or more of the alkyl group, the divalent carbocyclic ring or the heterocyclic ring may be a fluorine atom or Further, in the case of R ₇ , in the case where any of the groups listed below are not adjacent to each other, -CH ₂ - may be substituted by the groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ₈ represents -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO- Any of -NH-, -CO-, or a single bond. R ₉ represents a cinnamyl group. R ₁₀ is a single bond, or an alkyl group or a divalent carbon formed from a carbon number of 1 to a carbon number of 30. a ring or a heterocyclic ring, wherein one or more of the hydrogen atoms of the alkylene group, the divalent carbocyclic ring or the heterocyclic ring may be substituted by a fluorine atom or an organic group. Further, in R ₁₀ , any of the following may be mentioned. In the case where the groups are not adjacent to each other, -CH ₂ - may be substituted by the groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, - NHCONH-, -CO- R ₁₁ represents the light selected from an acrylic group, methacrylic group according to any one of the polymerizable group).

(X is a bond group selected by a single bond, or -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or unsubstituted or substituted by a fluorine atom, carbon number 1-20 Alkyl).

a diamine having a photopolymerizable side chain containing at least one selected from the above methacrylic group, acryl group, vinyl group, allyl group, styryl group, and α-methyl-γ-butyrolactone group It can be used as a liquid crystal alignment film, a sensitivity to light, a pretilt angle, a voltage holding characteristic, an accumulated charge, etc., and a liquid crystal response speed when used as a liquid crystal display element, and can be used in one type. Or mix 2 or more types use.

Further, it has a photopolymerizable side chain containing at least one selected from the group consisting of methacrylic groups, acrylic groups, vinyl groups, allyl groups, styryl groups, and α-methyl-γ-butyrolactone groups. The diamine is preferably used in an amount of 10 to 70 mol%, preferably 20 to 60 mol%, and particularly preferably 30%, based on the total amount of the diamine component used in the synthesis of the polyamic acid. 50% by mole.

<Diamine having photoreactive group>

The liquid crystal alignment agent of the present invention is used in the case of a liquid crystal display device obtained by irradiating polarized ultraviolet light, and the diamine component contained in the liquid crystal alignment agent as a raw material of the polyimide precursor is introduced into a photoreactive substrate. good.

In the case of an alignment treatment method in which photodimerization reaction or photoisomerization reaction is carried out by irradiation of polarized ultraviolet rays to cause anisotropy, the above formula [4-1] is introduced into the polymer main chain or side chain. ~[4-5] structure can be.

The polymer contained in the liquid crystal alignment agent is used in the case of using a polyimine precursor and a polyimide obtained by imidization thereof, for example, using a main chain or a branched chain containing the above formula [4-1]~ The method of tetracarboxylic dianhydride or diamine of the structure of [4-5], in view of easiness of synthesis, a diamine having a structure in which the side chain contains the above formula [4-1] to [4-5] It is better. Further, the side chain of the diamine means a structure branched from a structure in which two amine groups in the diamine are bonded to each other. Specific examples of the diamines include compounds represented by the following formulas, but are not limited thereto.

(wherein X is a bond selected by a single bond, or -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or a carbon number which is unsubstituted or substituted by a fluorine atom An alkyl group of 1 to 20, R represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which is unsubstituted or substituted by a fluorine atom, or an alkyl ether group).

(wherein X is a bond selected by a single bond, or -O-, -COO-, -NHCO-, -NH-, Y represents a single bond, or a carbon number which is unsubstituted or substituted by a fluorine atom An alkyl group of 1 to 20, R represents a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms which is unsubstituted or substituted by a fluorine atom, or an alkyl ether group).

<tetracarboxylic dianhydride>

The tetracarboxylic dianhydride which reacts with the diamine component to produce the polyaminic acid contained in the liquid crystal alignment agent of the present invention is not particularly limited. Specifically, for example, the contents listed below.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include, for example, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3. , 4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -naphthalene succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3 , 3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclo octa-1,5-di Alkene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-di Anhydride, Hexacyclo[6.6.0.1 ^2,7 .0 ^3,6 .1 ^9,14 .0 ^10,13 ] Hexadecane-4,5,11,12-tetracarboxylic acid-4,5:11,12 - dianhydride, 4-(2,5-dionetetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride.

Further, when the aromatic tetracarboxylic dianhydride is used in addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, the liquid crystal alignment property can be improved, and the accumulated charge of the liquid crystal cell can be lowered. And is better. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyltetra Carboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4-benzophenone Tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, and the like.

The tetracarboxylic dianhydride can be used in combination with a liquid crystal alignment film, a sensitivity to light, a pretilt angle, a voltage holding property, and an accumulated charge, and can be used in combination of two types or two or more types. can.

The polyphthalate ester of the polyimine precursor contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as the dicarboxylic acid dialkyl ester is reacted with the diamine component. Specifically, for example, the contents listed below.

Specific examples of the aliphatic tetracarboxylic acid diester include, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-ring. Butane tetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2 , 3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1 , 2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetra Hydrogen-1-naphthalene succinate dialkyl ester, 1,2,3,4-butane tetracarboxylic acid dialkyl ester, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylate Acid dialkyl ester, 3,3',4,4'-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutyl Cyclohepta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]nonane-3,4,7,8-tetracarboxylic acid- 3,4: 7,8-dialkyl, six-ring ^12,7 [6.6.0 ^3,6 .1 ^9,14 .0 ^10,13 .0.] hexadecane -4,5,11,12- Tetracarboxylic acid-4,5:11,12-dialkyl ester, 4-(2,5-dionetetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylate Dialkyl esters and the like.

Examples of the aromatic tetracarboxylic acid dialkyl esters include, for example, dialkyl pyromellitic acid, dialkyl 3,3',4,4'-biphenyltetracarboxylate, 2,2',3,3'- Dialkyl biphenylate, dialkyl 2,3,3',4-biphenyltetracarboxylate, dialkyl 3,3',4,4'-benzophenonetetracarboxylate, 2, 3,3',4-dibenzophenone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4-dicarboxyphenyl)decane dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, and the like.

<polyoxane>

When the polymer contained in the liquid crystal alignment agent contains a polyoxyalkylene oxide, the polyoxyalkylene can be obtained by reacting an alkoxydecane component in an organic solvent (for example, a polycondensation reaction). The alkoxydecane component means an alkoxydecane having 1 to 4 alkoxy groups in the molecule. For example, a polyoxyalkylene can be obtained by reacting an alkoxydecane component represented by the following formula [14].

[化40]R ¹¹ Si (OR ¹² ) ₃    [14]

In the formula [14], R ¹¹ represents a monovalent organic group, and R ¹² is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R ¹² is a methyl group or an ethyl group.

<Alkoxydecane having a side chain of vertical alignment>

In the formula [14], R ¹¹ is a long-chain alkyl group, a long-chain alkyl group having a ring structure or a branched structure, and a cholesteryl group, and alkoxy decane having a liquid crystal in a side chain of a vertical alignment. And a hydrocarbyl group, or a group having a part or all of a hydrogen atom having such a group substituted with a fluorine atom as a side chain alkoxydecane, a diamine having a side chain represented by the above formula [5], or the like . More specifically, for example, a diamine having a hydrocarbon group having a hydrogen atom substituted with fluorine and having a hydrocarbon group of 8 to 30 or the like, or an alkoxydecane represented by the following formula [15], is not limited thereto. .

(The definitions of a, b, c, and R ¹ to R ^{5 in} the formula [15] are the same as those in the above formula [5]. In the formula [15], R ⁹ represents a single bond or -(CH ₂ ) _n O- (n is an alkyl group having 0 to 5 carbon atoms), and R ¹² represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms.

In the following, the following formulas [14-1] to [14-13] which are specific examples of the alkoxydecane having a side chain structure represented by the formula [14], are not limited thereto. Further, the following formula [14-1] ~ [14-13] of the R ^12, with the formula [14] wherein R ¹² is the same, and R ⁹ in the formula [15] R ⁹ is the same as the contents.

(In the formula [14-7] to the formula [14-9], R ¹³ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [14-10] and the formula [14-11], R ¹⁴ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an ethyl group, an ethoxy group or Hydroxyl).

(In the formula [14-12] and the formula [14-13], R ¹⁵ is an alkyl group having 3 to 12 carbon atoms, and a cis-trans isomer of 1,4-cyclohexylene group is a trans isomer thereof. ).

The alkoxy decane represented by the formula [14] can be used as a solvent for the solubility of a solvent, a liquid crystal alignment property as a liquid crystal alignment film, and a sensitivity to light, when it is used as a siloxane polymer (polysiloxane). The pretilt angle, the voltage holding characteristics, the characteristics of the accumulated charges, and the like, the response speed of the liquid crystal as the liquid crystal display element, and the like are used in combination of one type or two types or more. Further, an alkoxydecane having a long-chain alkyl group having 10 to 18 carbon atoms may be used in combination.

The alkoxy decane represented by the above formula [14] can be produced, for example, by a known method described in JP-A-61-286393.

<Alkoxydecane having a photopolymerizable side chain>

Further, in order to obtain the alkoxydecane component to be used for the polyoxyalkylene, for example, an alkoxysilane having a photopolymerizable group represented by the following formula [16] can also be used.

[Chem. 46] R ^{twenty one} Si (OR ^{twenty two} ) ₃    [16]

In the formula [16], R ²¹ is an alkyl group in which a hydrogen atom is substituted by an acryl group, a propylene group, a methacryl group, a methacryloxy group or a styryl group. The number of hydrogen atoms to be substituted may be one or more, preferably one. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 20, most preferably from 1 to 10. R ²² is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

The following is a specific example of the alkoxydecane represented by the formula [16], but it is not limited thereto. For example, 3-methacryloxypropyltrimethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, methacryloxymethyltrimethoxydecane, methacryloxymethyloxymethyl Triethoxy decane, 3-propenyloxypropyltrimethoxydecane, 3-propenyloxypropyltriethoxydecane, propyleneoxyethyltrimethoxydecane, propyleneoxyethyltriethoxydecane, styrene Alkyltrimethoxydecane, styrylethyltriethoxydecane, 3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxydecane, and the like.

<Other alkoxy decane>

Further, for the alkoxydecane component to be used for the polyoxyalkylene, for example, an alkoxydecane represented by the following formula [17] can also be used.

[47] (R ^{twenty three} ) _N2 Si (OR ^{twenty four} ) _4-n2    [17]

R ²³ of the alkoxydecane represented by the formula [17] is a hydrogen atom or a hydrogen atom may be substituted by a hetero atom, a halogen atom, an amine group, a glycidoxy group, a thiol group, an isocyanate group or a urea group. The hydrocarbon group having 1 to 10 carbon atoms is preferably an amine group, a glycidyl group or a urea group. R ²⁴ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n 2 is 0 to 3, preferably an integer of 0 to 2.

The following is a specific example of the alkoxydecane represented by the above formula [17], but is not limited thereto. For example, 3-(2-aminoethylaminopropyl)trimethoxydecane, 3-(2-aminoethylaminopropyl)triethoxydecane, 2-aminoethylaminomethyltrimethoxy Baseline, 2-(2-aminoethylthioethyl)triethoxydecane, 3-hydrothiopropyltriethoxydecane, thiomethyltrimethoxydecane, vinyltriethoxy Base decane, 3-isocyanate propyl triethoxy decane, trifluoropropyltrimethoxy decane, chloropropyl triethoxy decane, bromopropyltriethoxy decane, 3-hydrothiopropyltrimethoxy Base decane, dimethyl diethoxy decane, dimethyl dimethoxy decane, diethyl diethoxy decane, diethyl dimethoxy decane, diphenyl dimethoxy decane, diphenyl Diethoxy decane, 3-aminopropyl methyl diethoxy decane, 3-aminopropyl dimethyl ethoxy decane, trimethyl ethoxy decane, trimethyl methoxy decane And γ-guanidinopropyl triethoxy decane, γ-ureidopropyl trimethoxy decane, and γ-guanidinopropyl tripropoxy decane.

In the alkoxydecane represented by the formula [17], the alkoxydecane wherein n2 is 0 is a tetraalkoxydecane. Tetraalkoxy decane, with its easy It is preferred to carry out a polycondensation reaction with the alkoxydecane represented by the above formulas [14] to [16] to obtain a polyoxyalkylene.

In the formula [17], the alkoxy decane wherein n2 is 0 is preferably tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane or tetrabutoxy decane, especially in the case of Oxydecane or tetraethoxydecane is preferred.

The method for producing the polyoxyalkylene to be contained in the liquid crystal alignment agent is not particularly limited. For example, the alkoxydecane component containing the alkoxydecane represented by the above formula [14] to formula [17] is used. It can be obtained by carrying out a reaction (for example, a polycondensation reaction) in an organic solvent. Usually, the polyoxyalkylene can be obtained by subjecting the alkoxydecane components to polycondensation and then uniformly dissolving the solution in an organic solvent. Further, in the alkoxydecane component containing the alkoxydecane of the above formulas [14] to [17], the addition ratio of the alkoxydecane is not particularly limited.

A method for polycondensing an alkoxydecane to produce a polyoxyalkylene, for example, by subjecting an alkoxydecane to an organic solvent such as an alcohol or ethylene glycol for hydrolysis. Condensation and other methods. At this point, hydrolysis. The condensation reaction may be either partial hydrolysis or complete hydrolysis.

The polyoxyalkylene described above is a case where the liquid crystal alignment agent is used in a liquid crystal display device of a vertical alignment type, and it may be a group in which a liquid crystal is vertically aligned in a side chain or a photopolymerizable group in a side chain. Further, when the liquid crystal alignment agent is used for a liquid crystal display element of a horizontal alignment type, it may have a photoreactive group. Therefore, in the alkoxydecane component as a monomer, a liquid crystal is a vertical alignment group or a photopolymerizable group is introduced into a side chain, and a light is reversed. It is preferred that the basic group is introduced into the main chain or the side chain. These liquid crystals are a vertical alignment group, a photopolymerizable group, or a polyoxyalkylene having a photoreactive group, and are suitable as a polymer which can be used for a liquid crystal alignment film having a liquid crystal alignment fixing ability.

<Poly(meth)acrylate>

When the polymer contained in the liquid crystal alignment agent contains a poly(meth) acrylate, the poly(meth) acrylate can polymerize a monomer such as an acrylate compound or a methacrylate compound with a polymerization initiator or the like. Produced by reaction.

Acrylate compounds, for example, methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, methacrylate, methacrylate, phenyl acrylate, 2, 2,2-Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isodecyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2 -ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate Ester, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, and the like.

A methacrylate compound, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, methacrylic acid armor Ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isophthalic acid methacrylate Ester, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate And 8-ethyl-8-tricyclodecyl methacrylate or the like.

In the case where the liquid crystal alignment agent is used in a liquid crystal display device of a vertical alignment type, the poly(meth) acrylate described above may have a liquid crystal having a vertical alignment in a side chain or a photopolymerizable group in a side chain. By. Further, when the liquid crystal alignment agent is used for a liquid crystal display element of a horizontal alignment type, it may have a photoreactive group. Therefore, in the acrylate compound or the methacrylate compound as a monomer, it is preferred that the liquid crystal is a vertical alignment group or a photopolymerizable group is introduced into a side chain, and a photoreactive group is introduced into a main chain or a side chain. These liquid crystals are a vertical alignment group, a photopolymerizable group or a poly(meth)acrylate having a photoreactive group, and are suitable as a polymer which can be used for a liquid crystal alignment film having a liquid crystal alignment fixing ability.

In particular, the acrylate compound having a side chain or a methacrylate compound may, for example, be an acrylate compound having a side chain represented by the above formula [5], or a methacrylate compound. More specifically, for example, the acrylate compound or the methacrylate compound represented by the following formula [18] and the following formulas [19-1] to [19-3] are not limited thereto.

(The definition of a, b, c, R ¹ to R ⁵ in the formula [18] is the same as the above formula [5]. R is a hydrogen atom or a methyl group, and S is an alkylene group having 2 to 11 carbon atoms. ).

(R is a hydrogen atom or a methyl group, S is an alkylene group having 2 to 11 carbon atoms, X is an ether, an ester, a guanamine bond, R ¹⁰ is a hydrogen atom, or a carbon which is unsubstituted or substituted by a fluorine atom Number 1 to 5 alkyl).

<solvent>

The solvent contained in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can uniformly dissolve the polymer or the polymerizable compound contained in the liquid crystal alignment agent. Specific examples thereof include, for example, a polymer In the case of using a polyimine precursor or polyimine, it is N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N -methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl Yttrium, dimethyl hydrazine, γ-butyrolactone, 1,3-dimethyl-tetrahydroimidazolidone, 3-methoxy-N,N-dimethylpropane decylamine, and the like. Further, in the case where a polysiloxane is used as the polymer, examples thereof include a polyol compound such as ethylene glycol or 1,2-propylene glycol, N-methylformamide, N,N-dimethylformamide, and the like. Amidoxime compound or the like. Further, in the case where the polymer is a poly(meth)acrylate, an alcohol compound, a ketone compound, a guanamine compound or an ester compound or other aprotic compound may, for example, be mentioned. These may be used alone or in combination of two or more. In addition, even if it is a solvent which cannot melt|dissolve a polymer or a polymeric compound separately, it can mix with the above-mentioned organic solvent as long as it is not the range of a polymer or a polymeric compound.

The liquid crystal alignment agent of the present invention may contain a solvent used for improving the uniformity of the coating film when the liquid crystal alignment agent is applied to the substrate, in addition to the solvent used for dissolving the polymer or the polymerizable compound. The solvent is generally a solvent which has a lower surface tension than the above organic solvent. Specific examples thereof include ethyl cellosolve, cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, and 1 -Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol Diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, butyl cellosolve acetate Ester, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, and the like. These solvents can be used in combination of two or more types.

In addition to the above, the liquid crystal alignment agent of the present invention may further contain a polymer other than the polymer as long as it does not impair the effects of the present invention, for example, to change electrical properties such as dielectric constant or conductivity of the liquid crystal alignment film. a silane coupling agent for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, and a compound capable of improving film thickness uniformity or surface smoothness when the liquid crystal alignment agent is applied, for the purpose of the dielectric material or the conductive material, and the silane coupling agent for improving the adhesion between the liquid crystal alignment film and the substrate A cross-linking compound for the purpose of improving the hardness or density of the film as a liquid crystal alignment film, and for the purpose of efficiently performing the ruthenium imidization of the polyimide precursor during the sintering of the coating film. Amidoxime accelerator and the like.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and an aprotic surfactant. More specifically, F-TOP EF301, EF303, EF352 (made by Dow Chemical Manufacturing Co., Ltd.), Megfried F171, F173, R-30 (made by Dainippon Paint Co., Ltd.), FLUORAD FC430, FC431 (Sumitomo) 3M company), ASAHIGARD AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). In the case of using these surfactants, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

a compound which improves the adhesion between the liquid crystal alignment film and the substrate, For example, a compound containing a functional decane or a compound containing an epoxy group can be mentioned. For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N- (2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-anthracene Trimethoxy decane, 3-ureido propyl triethoxy decane, N-ethoxycarbonyl-3-aminopropyl trimethoxy decane, N-ethoxycarbonyl-3-aminopropyl three Ethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxymethyl decyl-1 ,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxyformamido-3,6-diazepine Acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3 -Aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxo) Ethyl)-3-aminopropyltrimethoxydecane, N - bis(oxoethyl)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl Ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl Glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1, 3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-( N-allyl-N-glycidol) aminopropyl Trimethoxydecane, 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. Further, in order to further enhance the film strength of the liquid crystal alignment film, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetrakis(methoxymethyl)diphenol may be added. Phenolic compounds. In the case of using these compounds, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the polymer contained in the liquid crystal alignment agent.

<Liquid alignment film>

In the liquid crystal alignment film used in the liquid crystal display device of the present invention, the liquid crystal alignment agent may be applied to a substrate, and if necessary, after drying, the surface of the coating film obtained by sintering may be subjected to an alignment treatment.

The substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, a tantalum nitride substrate, an acrylic substrate or a polycarbonate substrate can be used. Liquid crystal driving is preferred, and it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode or the like is formed to simplify the process. Further, when the reflective liquid crystal display element is only a single-sided substrate, an opaque object such as a germanium wafer may be used. In this case, a material such as aluminum that reflects light may be used.

The method of applying the liquid crystal alignment agent is not particularly limited, and industrially, it is generally carried out by using screen printing, lithography, letterpress printing, or inkjet method. The other coating method may, for example, be a dipping method, a roll coating method, a slit coating method, a spinning method or a spray method, and may be appropriately used in accordance with the purpose.

After the liquid crystal alignment agent is applied onto the substrate, a heating means such as a hot plate, a heat cycle type oven, or an IR (infrared) type oven may be used, and the solvent used for the liquid crystal alignment agent may be used at 30 to 300 ° C, preferably 30. The solvent is evaporated at a temperature of ~250 ° C to form a liquid crystal alignment film. The thickness of the liquid crystal alignment film after sintering is not favorable in terms of the power consumption of the liquid crystal display element when it is too thick, and the case where the reliability of the liquid crystal display element is lowered when it is too thin, it is preferably 5 to 300 nm, more preferably 10~100nm.

<Vertical alignment type liquid crystal display element>

The liquid crystal display element of the vertical alignment type of the present invention can be obtained by producing a liquid crystal cell by a known method after preparing a substrate having a liquid crystal alignment film containing a polymerizable compound. Specifically, for example, a liquid crystal alignment agent is applied onto two substrates, and a liquid crystal alignment film is formed by sintering so that the liquid crystal alignment film is disposed so as to face the two substrates. A liquid crystal composition containing liquid crystal is injected between the substrates to form a liquid crystal layer. Subsequently, the liquid crystal layer and the liquid crystal alignment film are irradiated with ultraviolet rays at an applied voltage to obtain a liquid crystal display element having a vertical alignment mode of the liquid crystal cell. Further, the liquid crystal composition may also contain a polymerizable compound.

When the step of irradiating ultraviolet rays by application of a voltage causes photopolymerization or photocrosslinking reaction of a polymerizable unsaturated bond group which the polymerizable compound has, it is possible to control the alignment state of molecules of the liquid crystal layer. In this manner, the alignment of the liquid crystals provided on the surface of the liquid crystal alignment film can be fixed in a state of being slightly inclined with respect to the vertical direction even without performing rubbing treatment.

<Horizontal alignment type liquid crystal display element>

The liquid crystal display element of the horizontal alignment type refers to a liquid crystal display element in which an electric field is applied in a horizontal direction (lateral direction) with respect to a substrate to cause liquid crystal molecules to respond. The liquid crystal display element of the horizontal alignment type such as the IPS method or the FFS method of the present invention can be obtained by preparing a liquid crystal cell by a known method after preparing a substrate having a liquid crystal alignment film containing a polymer compound. Specifically, for example, a liquid crystal alignment agent is applied onto two substrates, and after sintering, a rubbing treatment is carried out as necessary, and then a liquid crystal alignment film is formed by irradiating polarized ultraviolet rays. Next, the liquid crystal alignment film is placed in a pair of opposite substrates, and a liquid crystal composition containing liquid crystal is injected between the two substrates to form a liquid crystal layer. Subsequently, the liquid crystal layer and the liquid crystal alignment film are irradiated with polarized ultraviolet rays to obtain a liquid crystal display element having a horizontal alignment mode of the liquid crystal cell. Further, the liquid crystal composition may also contain a polymerizable compound.

The step of irradiating the liquid crystal layer and the liquid crystal alignment film with ultraviolet rays, that is, the step of irradiating the ultraviolet rays to the outside of the element after the element is formed, thereby causing photopolymerization or photocrosslinking of the polymerizable unsaturated bonding group of the polymerizable compound. reaction. In this manner, the liquid crystals provided on the surface of the liquid crystal alignment film can be fixed in such a manner as to be aligned in the horizontal direction.

The liquid crystal display element of the vertical alignment method or the horizontal alignment method of the present invention described above is a liquid crystal alignment film obtained by including a polymerizable compound liquid crystal alignment agent. Since the polymerizable compound in the liquid crystal alignment agent has the above-described hydrogen-bonded functional group, it can be hydrogen-bonded to form a dimer in the liquid crystal alignment film or the liquid crystal alignment agent. Moreover, due to the present invention The polymerizable compound used has a rigid aromatic ring, so that the hydrogen-bonded functional group can form a liquid crystal structure via hydrogen bonding. The liquid crystal structure has a quasi-large liquid crystal structure due to hydrogen bonding, and absorbs on the long wavelength side of the ultraviolet region, so that the sensitivity to light can be improved. Therefore, the liquid crystal display element including the liquid crystal alignment films can improve the sensitivity to light as shown in the later-described embodiment, so that the response speed of the ultraviolet light on the long wavelength side is extremely fast and has excellent alignment fixation. Ability.

[Examples]

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

The abbreviations used in the production of the liquid crystal alignment agent described below are as follows.

<Manufacture of liquid crystal alignment agent>

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

DBA: 3,5-diamino benzoic acid

m-PCH7: 1,3-diamino-5-((4-(4-heptylcyclohexyl)phenoxy)methyl)benzene represented by the following formula

PCH7: 1,3-diamino-4-[4-(4-heptylcyclohexyl)phenoxy]benzene represented by the following formula

BEM-S: 2-(methacryloxy)ethyl 3,5-diaminobenzoate represented by the following formula

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve (cellosolve)

<additive>

3AMP: 3-picolylamine

<Polymerizable compound>

The polymerizable compounds [RM1] to [RM7] added to the liquid crystal alignment agent have the following structures. Further, the polymerizable compounds [RM1] to [RM6] are the same as those of the polymerizable compounds of the above formulas [2-1] to [2-6].

<Synthesis Example 1> Synthesis of polymerizable compound [RM1]

4-bromo-4'-hydroxybiphenyl [A] (150 g, 0.60 mol), tert-butyl acrylate [B] (162 g, 1.3 mol), and palladium acetate (2.7 g, in a 4-liter four-neck flask. 12 mmol), tris(o-methylphenyl)phosphine (7.3 g, 24 mmol), tributylamine (334 g, 1.8 mol), N,N-dimethylacetamide (hereinafter also abbreviated as DMAc) (750 g), Heating and stirring were carried out at 100 °C. The reaction was traced by HPLC, and after confirming completion of the reaction, the reaction solution was cooled to room temperature, and 1.8 L of a 1 M aqueous hydrochloric acid solution was poured. Ethyl acetate (1 L) was added thereto, and a liquid separation operation was carried out to remove the aqueous layer. The organic layer was washed twice with 1 L of a 10% aqueous hydrochloric acid solution and 1 L of saturated brine, and the organic layer was dried over magnesium sulfate. Subsequently, the solvent was distilled off through a filtrate and a solvent to give 174 g (yield: 98%) of Compound (c) as an oily compound.

The results of nuclear magnetic resonance (NMR) measurement of the compound [C] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 9.68 (1H, s), 7.72 (2H, d), 7.63 (2H, d), 7.59-7.55 (9H, m), 6.87-6.85 (2H, m), 1.44 (9H, s).

The above-obtained compound [C] (174 g, 0.59 mol), 6-chloro-1-hexanol (96.7 g, 0.71 mol), and potassium carbonate were added to a 2 L four-necked flask equipped with a mechanical stirrer and a stirring blade. 163 g, 1.2 mol), potassium iodide (9.8 g, 59 mmol), and N,N-dimethylformamide (hereinafter, also referred to as DMF) (1600 g) were heated and stirred at 80 °C. The reaction was traced by HPLC. After confirming the completion of the reaction, the reaction solution was cooled to near room temperature, and 2 L of distilled water was poured into the reaction solution. After the precipitated solid was filtered off, a methanol/distilled water (1:1) solution was poured and filtered. The obtained solid was dried under reduced pressure to give Compound 221 g (yield: 95%).

The results of nuclear magnetic resonance (NMR) measurement of the compound [D] are shown below.

^{1 H-NMR (400MHz, CDCl} 3, δppm): 7.61 (1H, d), 7.56-7.52 (6H, m), 6.98-6.95 (2H, m), 6.38 (1H, d), 4.02 (2H, t ), 3.67 (2H, t), 1.84-1.44 (17H, m).

The compound [D] (221 g, 0.56 mol), triethylamine (67.7 g, 0.67 mol), and tetrahydrofuran (hereinafter, also referred to as THF) (1800 g) obtained above were added to a three-liter four-necked flask to prepare a reaction solution. cool down. A solution of methacrylic acid chloride (70.0 g, 0.67 mmol) in THF (200 g) was carefully added dropwise thereto at an internal temperature of not more than 10 °C. After completion of the dropwise addition, the reaction solution was allowed to reach 23 ° C, and then the reaction was carried out. The reaction was traced by HPLC, and after confirming the completion of the reaction, 6 L of distilled water was poured into the reaction solution, and 2 L of ethyl acetate was added thereto, followed by liquid separation operation. To remove the water layer. Subsequently, the organic layer was washed successively with a 5% aqueous potassium hydroxide solution, 1M aqueous hydrochloric acid and brine, and the organic layer was dried over magnesium sulfate. Subsequently, the solvent was distilled off using an evaporator to obtain a crude product. The obtained crude product was washed with 100 g of 2-propanol (hereinafter, also referred to as IPA), and filtered and dried to give 127 g (yield: 49%).

The results of nuclear magnetic resonance (NMR) measurement of the compound [E] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 7.73 (2H, d), 7.70-7.63 (4H, m), 7.58 (1H, d), 7.02-7.00 (2H, m), 6.53 (1H, d), 6.03-6.02 (1H, m), 5.67-5.66 (1H, m), 4.11 (2H, t), 4.00 (2H, t), 1.88-1.87 (3H, m), 1.79-1.25 (17H, m).

The compound [E] (81 g, 0.17 mol) and formic acid (400 g) obtained above were added to a 1 L four-necked flask, and the mixture was stirred under heating at 40 °C. The reaction was traced by HPLC, and after confirming completion of the reaction, 3 L of distilled water was poured into the reaction solution, followed by filtration. The obtained solid was washed with 200 g of methanol, and the solid was dried to give a polymer compound [RM1] (yield: 79%).

The results of nuclear magnetic resonance (NMR) measurement of the polymerizable compound [RM1] are shown below.

^{1 H-NMR (400MHz, CDCl} 3, δppm): 7.81 (1H, d), 7.60 (4H, s), 7.55 (2H, d), 6.97 (2H, d), 6.47 (2H, d), 6.11- 6.10(1H,m), 5.56-5.52(1H,m), 4.17(2H,t), 4.00(2H,t),1.95-1.94(2H, m),1.85-1.82(3H,m),1.75- 1.71 (2H, m), 1.55-1.48 (4H, m).

<Synthesis Example 2> Synthesis of polymerizable compound [RM2]

The same procedure as in Example 1 was carried out except that 6-chloro-1-hexanol used in the synthesis of the compound [D] of the intermediate of the polymerizable compound [RM1] was changed to 8-chloro-1-hexanol. The polymerizable compound [RM2] was obtained in an amount of 40.82 g.

The results of nuclear magnetic resonance (NMR) measurement of the polymerizable compound [RM2] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 7.70-7.56 (7H, m), 6.97 (2H, d), 6.51 (1H, d), 5.98 (1H, s), 5.62 (1H, s) , 4.04 (2H, t), 3.94 (2H, t), 1.83 (3H, s), 1.70-1.10 (12H).

<Synthesis Example 3> Synthesis of polymerizable compound [RM3]

To a 2 L four-necked flask, 6-bromo-2-naphthol [H] (150 g, 672 mol), tert-butyl acrylate [B] (103.4 g, 807 mmol), palladium acetate (3.02 g, 13,5 mmol) were added. ), tris(o-methylphenyl)phosphine (8.19 g, 26.9 mmol), tripropylamine (289.0 g, 2.02 mol), and DMAc (700 g) were heated and stirred at 100 °C. The reaction was traced by HPLC, and after confirming completion of the reaction, the reaction solution was cooled to room temperature, and 3 L of a 1 M aqueous hydrochloric acid solution was poured. Thereto, ethyl acetate (2 L) was added, and a liquid separation operation was performed to remove the water layer. The organic layer was washed twice with 1 L of a 10% aqueous hydrochloric acid solution and 1 L of saturated brine, and the organic layer was dried over magnesium sulfate. Subsequently, the solvent was distilled off through a filtrate and an evaporator to obtain 181 g (yield: 99%) of Compound [I].

The measurement result of the compound [I] by nuclear magnetic resonance (NMR) is as follows.

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 10.01 (1H, s), 8.04 (1H, s), 7.81-7.74 (2H, m), 7.70-7.63 (2H, m), 7.14-7.10 ( 2H, m), 6.54 (1H, d), 1.51-1.48 (9H, m).

In a 2L four-necked flask equipped with a mechanical stirrer and agitating blades, The compound [I] (181 g, 672 mmol) obtained above, 6-chloro-1-hexanol (110.2 g, 806 mol), potassium carbonate (111.5 g, 806 mmol), potassium iodide (1.12 g, 6.7 mmol), DMF (900 g) ), heating and stirring at 80 ° C. The reaction was traced by HPLC. After confirming the completion of the reaction, 2 L of distilled water was poured into the reaction solution, and ethyl acetate (2 L) was added thereto to carry out a liquid separation operation to remove the aqueous layer. Then, the organic layer was washed twice with saturated brine (1 L), and the organic layer was dried over magnesium sulfate. After filtration, the solvent was evaporated to give a crude product. The obtained crude product was recrystallized from ethyl acetate/hexane mixed solvent to give 185 g (yield: 74%) of Compound [J].

The results of nuclear magnetic resonance (NMR) measurement of the compound [J] are shown below.

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.06 (1H, s), 7.80 (1H, d), 7.77-7.76 (2H, m), 7.62 (1H, d), 7.34 (1H, d) , 7.15 (1H, dd), 6.53 (1H, d), 4.34 (1H, t), 4.05 (2H, t), 3.39-3.33 (2H, m), 1.73 (2H, t), 1.46-1.31 (15H , m).

The compound [J] (130.5 g, 352 mmol), triethylamine (42.76 g, 423 mmol) and THF (950 g) obtained above were added to a three-liter four-neck flask, and the reaction solution was cooled. A solution of methacrylic acid chloride (44.2 g, 423 mmol) in THF (100 g) was carefully added dropwise thereto at an internal temperature of not more than 10 °C. After completion of the dropwise addition, the reaction solution was allowed to reach 23 ° C, and then the reaction was carried out. After the reaction was traced by HPLC, it was confirmed that 6 L of distilled water was poured into the reaction solution, and 2 L of ethyl acetate was added thereto, followed by a liquid separation operation to remove the aqueous layer. Then, use 5 in order The organic layer was washed with an aqueous solution of potassium hydroxide, a 1M aqueous solution of hydrochloric acid, and brine, and the organic layer was dried over magnesium sulfate. Thereafter, the solvent was distilled off by filtration, and the compound [K] was obtained (yield: 92%).

The results of nuclear magnetic resonance (NMR) measurement of the compound [K] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 8.09 (1H, s), 7.83 (1H, d), 7.80-7.79 (2H, m), 7.66 (1H, d), 7.33 (1H, d) , 7.18 (1H, dd), 6.57 (1H, d), 6.02-6.01 (1H, m), 5.66-5.65 (1H, m), 4.12-4.06 (4H, m), 1.88-1.87 (3H, m) , 1.84-1.42 (15H, m).

The compound [K] (140.9 g, 321 mmol) and formic acid (700 g) obtained above were added to a three-liter four-necked flask, and the mixture was stirred under heating at 40 °C. The reaction was traced by HPLC, and after confirming completion of the reaction, 4.5 L of distilled water was poured into the reaction solution, followed by filtration. The obtained solid was washed with an IPA/hexane mixed solvent, and the solid was dried to give 95.9 g (yield: 78%) of the polymer compound (RM3).

The results of nuclear magnetic resonance (NMR) measurement of the polymerizable compound [RM3] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 12.4 (1H, brs), 8.10 (1H, s), 7.84 (1H, d), 7.81-7.80 (2H, m), 7.70 (1H, d) , 7.35 (1H, d), 7.19 (1H, dd), 6.59 (1H, d), 6.03-6.02 (1H, m), 5.67-5.65 (1H, m), 4.13-4.07 (4H, m), 1.88 -1.87 (3H, m), 1.83-1.41 (8H, m).

<Synthesis Example 4> Synthesis of polymerizable compound [RM4]

The same procedure as in Example 1 except that the intermediate of the polymerizable compound [RM3] was changed to 6-chloro-1-hexanol used in the synthesis of the compound [J]. In the same manner, 171 g of a polymerizable compound [RM4] was obtained.

The measurement results of the polymerizable compound [RM4] by nuclear magnetic resonance (NMR) are as follows.

¹ H-NMR (400 MHz, CDCl 3 , δ ppm): 12.4 (1H, brs), 7.94-7.88 (2H, m), 7.77-7.71 (2H, m), 7.70-7.63 (1H, m), 7.17 (1H, Dd), 7.12-7.11 (1H, m), 6.51 (1H, d), 6.11-6.10 (1H, m), 5.55-5.54 (1H, m), 4.17-4.06 (4H, m), 1.95-1.94 ( 3Hm), 1.87-1.40 (12H, m).

<Synthesis Example 5>

A polymerizable compound represented by the following formula is used as the polymerizable compound [RM5].

<Synthesis Example 6> Synthesis of polymerizable compound [RM6]

To a 2 L four-necked flask, 6-hydroxy-2-naphthalenecarboxylic acid [N] (300 g, 1.59 mol), potassium hydroxide (205 g, 3.66 mol), and distilled water (1200 g) were added, and the mixture was heated and stirred at 100 ° C. . 6-Chloro-1-hexanol (261 g, 1.91 mol) was added dropwise thereto. After completion of the dropwise addition, the reaction was traced by HPLC. After confirming the completion of the reaction, the reaction solution was cooled to near room temperature, and then the reaction solution was poured into ice water (3 L), and neutralized by adding 35% hydrochloric acid. Then, the precipitated solid was washed with distilled water and filtered, and the solid was dried under reduced pressure to give 275 g (yield: 60%).

The results of nuclear magnetic resonance (NMR) measurement of the compound [O] are shown below.

¹ H-NMR (400 MHz, DMSO-d6, δ ppm): 8.53 - 8.52 (1H, m), 8.06-7.87 (3H, m), 7.40 (1H, d), 7.27-7.23 (1H, m), 4.32 ( 1H, t), 4.12 (2H, m), 3.44-3.33 (2H, m), 1.82-1.76 (2H, m), 1.51-1.3 (6H).

The above-obtained compound [O] (50.00 g, 173 mmol), dimethylaminophenol (46.23 g, 382 mmol), nitrobenzene (2.13 g, 17.3 mmol), and THF (500 g) were added to a 2-liter four-neck flask. After substituting with nitrogen, stirring was carried out under reflux with heating. A solution of methacrylic acid chloride (38.1 g, 361 mmol) in THF (100 g) was slowly added dropwise thereto. After completion of the dropwise addition, the reaction was traced by HPLC, and after confirming completion of the reaction, the reaction solution was cooled to room temperature. Thereafter, the reaction solution was poured into 3 L of a 1 M aqueous hydrochloric acid solution, and the precipitated solid was filtered to give a crude product. Next, the obtained crude product was washed with an ethanol/hexane mixed solvent and then acetone, and dried under reduced pressure to give 38.4 g (yield: 62%) of the polymerizable compound [RM6].

The results of nuclear magnetic resonance (NMR) measurement of the polymerizable compound [RM6] are shown below.

^{1 H-NMR (400MHz, DMSO} -d6, δppm): 8.63 (1H, s), 8.08 (1H, dd), 7.87 (1H, d), 7.76 (1H, d), 7.22-7.19 (1H, m) , 7.16-7.15 (1H, m), 6.11-6.10 (1H, m), 5.56-5.54 (1H, m), 4.20-4.10 (4H, m), 1.97-1.95 (3H, m), 1.92-1.85 ( 2H, m), 1.78-1.71 (2H, m), 1.60-1.47 (4HH, m).

<Synthesis Example 7> Synthesis of polymerizable compound [RM7]

To a 500 ml eggplant type flask equipped with a cooling tube, 14.9 g (80.0 mmol) of diphenol, 35 g (167.0 mmol) of 5-bromopentyl acetate, 41.5 g (300 mmol) of potassium carbonate, and 250 ml of acetone were added as a mixture. The mixture was stirred at a temperature of 60 ° C for 48 hours to carry out a reaction. After the completion of the reaction, 600 ml of pure water was poured into the reaction liquid to obtain 33.6 g of a compound [P] as a white solid (yield: 95%).

The results of nuclear magnetic resonance (NMR) measurement of the compound [P] are shown below.

¹ H-NMR (CDCl ₃ ) δ: 1.57 (m, 4H), 1.74 (m, 4H), 1.86 (m, 4H), 2.06 (s, 6H), 4.02 (t, 4H), 4.12 (t, 4H) ), 6.95 (d, 4H), 7.47 (d, 4H).

To a 1 L eggplant type flask equipped with a cooling tube, 250 ml of ethanol, 18.0 g (41 mmol) of the obtained compound [P], and 100 ml of a 10% aqueous sodium hydroxide solution were added as a mixture, and the mixture was stirred at a temperature of 85 ° C for 5 hours. Carry out the reaction. After the reaction, in a 1000ml beaker After adding 500 ml of water and the reaction liquid, the mixture was stirred at room temperature for 30 minutes, and then 80 ml of a 10% aqueous HCl solution was added dropwise thereto, followed by filtration to obtain 12.2 g (yield: 83%) of Compound (Q) as a white solid.

The results of nuclear magnetic resonance (NMR) measurement of the compound [Q] are shown below.

¹ H-NMR (DMSO-d6) δ: 1.46 (m, 8H), 1.71 (m, 4H), 3.41 (m, 4H), 3.98 (m, 4H), 4.39 (m, 2H), 6.96 (m, 4H), 7.51 (m, 4H).

5.0 g (14.0 mmol) of the obtained compound [Q] and 3.2 g of triethylamine and a small amount of 2,6-di-tert-butyl-p-cresol (BHT) were dissolved in 30 ml of THF at room temperature. After stirring, a solution obtained by dissolving 20 ml of THF (3.3 mmol) of propylene glycol chloride (3.3 mmol) was added dropwise over 15 minutes using a water bath under cooling. After the dropwise addition, the mixture was stirred for 30 minutes, and the water bath was removed and returned to room temperature for continuous stirring overnight. After completion of the reaction, the reaction solution was poured into 200 ml of pure water, and filtered to give a white solid. The solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2 / 1) to afford 2.6 g (yield: 38%) of the polymer compound (RM7) as a white solid.

Polymeric compound [RM7] by nuclear magnetic resonance (NMR) The measurement results are as follows.

¹ H-NMR (CDCl ₃ ) δ: 1.56 (m, 4H), 1.74 (m, 4H), 1.82 (m, 4H), 1.97 (s, 6H), 4.03 (m, 4H), 4.20 (m, 4H) ), 5.55 (m, 2H), 6.10 (m, 2H), 6.94 (d, 4H), 7.45 (d, 4H).

<Measurement of molecular weight of polyimine]

The molecular weight measurement conditions of the polyimine are as follows.

Device: room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by SENSHE Scientific Co., Ltd.

Column: Shodex pipe column (KD-803, KD-805)

Column temperature: 50 ° C

Dissolution: N,N'-dimethylformamide (additive is lithium bromide-water and (LiBr.H ₂ O) is 30 mmol / L, phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol / L, tetrahydrofuran ( THF) is 10ml/L

Flow rate: 1.0ml/min

Standard sample for the production of calibration lines: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight of approximately 9,000,000, 150,000, 100,000, 30,000), and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Research.

Further, the imidization ratio of polyimine was measured in the following manner. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sample standard test tube manufactured by Kusano Scientific Co., Ltd. 5) 1.0 ml of dihydrogenated dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS mixture) was added, and ultrasonic waves were applied to completely dissolve it. The proton NMR of the solution at 500 MHz was measured using a NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The imidization ratio of ruthenium is determined by the proton generated by the unaltered structure before and after imidization as the reference proton, and the peak value of the proton is used, and the NH of proline is present near 9.5 to 10.0 ppm. The peak value of the proton wave generated by the base is obtained by the following formula. Further, in the following formula, x is a proton peak product value generated by an NH group of valine acid, y is a peak product integrated value of a reference proton, and α is a polyproline (a sulfhydrylation ratio of 0%). In the case, the number of the reference protons is proportional to one proton of the NH group of the proline.

醯 imidization rate (%) = (1-α.x/y) × 100

(Example 1)

BODA (10.0 g, 40.0 mmol), DBA (6.09 g, 40.0 mmol), PCH7 (11.5 g, 30.0 mmol), BEM-S (7.93 g, 30.0 mmol) were dissolved in NMP (140.7 g) at 60 ° C After reacting for 5 hours, CBDA (11.37 g, 58.0 mmol) and NMP (46.9 g) were added, and the reaction was carried out for 10 hours at 40 ° C to obtain polylysine. liquid. After the NMP was diluted to 6% by mass in this polyamic acid solution (200 g), acetic anhydride (17.4 g) as a ruthenium amide catalyst and pyridine (67.6 g) were added, and the reaction was carried out at 50 ° C. hour. The reaction solution was poured into methanol (3000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (A). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 12,000, and a weight average molecular weight of 26,000.

To the obtained polyimine powder (A) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment composition (B).

In addition, 0.06 g (10% by mass based on the solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 was added to 10.0 g of the liquid crystal alignment composition (B), and the mixture was stirred at room temperature for 3 hours to be dissolved. A liquid crystal alignment agent (B1) was obtained.

(Example 2)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM2] obtained in Synthesis Example 2, and liquid crystal alignment was obtained. Agent (B2).

(Example 3)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM3] obtained in Synthesis Example 3, and liquid crystal alignment was obtained. Agent (B3).

(Example 4)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM4] obtained in Synthesis Example 4, and liquid crystal alignment was obtained. Agent (B4).

(Example 5)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM5] obtained in Synthesis Example 5, and liquid crystal alignment was obtained. Agent (B5).

(Example 6)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM6] obtained in Synthesis Example 6, and liquid crystal alignment was obtained. Agent (B6).

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (B) was replaced with [RM7] obtained in Synthesis Example 7, and liquid crystal alignment was obtained. Agent (B7).

(Example 7)

BODA (10.0 g, 40.0 mmol), DBA (5.3 g, 35.0 mmol), m-PCH7 (12.0 g, 30.0 mmol), and BEM-S (9.2 g, 35.0 mmol) were dissolved in NMP (144.5 g). After reacting at 60 ° C for 5 hours, CBDA (11.5 g, 58.5 mmol) and NMP (48.2 g) were added, and the mixture was reacted at 40 ° C for 10 hours to obtain a polyamidonic acid solution. After the NMP was diluted to 6% by mass in this polyamic acid solution (200 g), acetic anhydride (17.0 g) as a ruthenium amide catalyst and pyridine (65.8 g) were added, and the reaction was carried out at 50 ° C. hour. The reaction solution was poured into methanol (3000 ml), and the resulting precipitate was filtered. This precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (C). The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 14,000, and a weight average molecular weight of 47,000.

To the obtained polyimine powder (C) (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g), and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment composition (D).

Further, 10.0 g of the above liquid crystal alignment composition (D) was added. 0.06 g (10% by mass based on the solid content) of the polymerizable compound [RM1] obtained in Synthesis Example 1 was added, and the mixture was stirred at room temperature for 3 hours to be dissolved to obtain a liquid crystal alignment agent (D1).

(Example 8)

The same procedure as in Example 7 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (D) was replaced with [RM2] obtained in Synthesis Example 2, and liquid crystal alignment was obtained. Agent (D2).

(Example 9)

The same procedure as in Example 7 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (D) was replaced with [RM3] obtained in Synthesis Example 3, and liquid crystal alignment was obtained. Agent (D3).

(Embodiment 10)

The same procedure as in Example 7 was carried out except that the polymerizable compound [RM1] used for the liquid crystal alignment composition (D) was replaced with [RM4] obtained in Synthesis Example 4, and liquid crystal alignment was obtained. Agent (D4).

(Comparative Example 2)

In addition to the polymerization property used for the liquid crystal alignment composition (D) The liquid crystal alignment agent (D5) was obtained by the same operation as in Example 7 except that [RM7] obtained in Synthesis Example 7 was used instead.

<Save stability test>

The liquid crystal alignment agents obtained in Examples 1 to 10, Comparative Example 1, and Comparative Example 2 were stored in a freezer at -20 ° C for one week, and then visually confirmed whether or not a precipitate or the like was observed. No precipitates or the like were found at all, indicating that they have good preservation stability. In Table 2, the results of the structure and storage stability test of the liquid crystal alignment agent are indicated.

As shown in Table 2, the liquid crystal alignment agents (B1) to (B6) of Examples 1 to 6 containing the polymerizable compounds [RM1] to [RM6] in the liquid crystal alignment composition (B) have no liquid phase alignment agent (B1) to (B6) at all. Since precipitates and the like were confirmed, it was confirmed to have good preservation stability. On the other hand, in the liquid crystal alignment agent (B7) of Comparative Example 1 containing the polymerizable compound [RM7] in the liquid crystal alignment composition (B), precipitates were produced.

Similarly, in the liquid crystal alignment composition (D), the liquid crystal alignment agents (D1) to (D4) of Examples 7 to 10 of the polymerizable compounds [RM1] to [RM4] have no precipitates at all. In the liquid crystal alignment agent (D5) of Comparative Example 2 containing the polymerizable compound [RM7] in the liquid crystal alignment agent (D), precipitates were produced.

From the above results, it is presumed that the liquid crystal alignment agents of Examples 1 to 10 contain a functional group having hydrogen bonding, that is, a polymerizable compound having a carboxyl group [RM1] to [RM6], so Dissolve The solubility of the agent was extremely high, and even after storage for one week in a freezer at -20 ° C, precipitates and the like were not generated at all. Therefore, it has been confirmed that the polymerizable compound used for the liquid crystal alignment agent is a polymerizable compound having a hydrogen-bonded functional group such as a carboxyl group, so that the liquid crystal alignment agent can have good storage stability.

Further, the polymerizable compound [RM1] to [RM6] having a carboxyl group forms a large liquid crystal (mesogenic) structure by hydrogen bonding between molecules, so that the absorption can be extended to the long wavelength side of the ultraviolet region, and the ultraviolet light can be enhanced. The sensitivity is predicted to be faster in the measurement of the response speed described later.

<Production of liquid crystal cell> (Example 11)

Using the liquid crystal alignment agent (B1) obtained in Example 1, the production of the liquid crystal cell was carried out in the order shown below.

The liquid crystal alignment agent (B1) obtained in Example 1 was spin-coated on an ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a surface of 5 μm, respectively, and heated at 80 ° C. After drying the plate for 90 seconds, it was sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.

Further, the liquid crystal alignment agent (B1) was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, and then sintered in a hot air circulating oven at 200 ° C for 30 minutes to form a film. A liquid crystal alignment film having a thickness of 100 nm.

A 4 μm particle spacer was spread on the liquid crystal alignment film of the substrate of one of the two substrates, and then a blocking agent (solvent-type thermosetting epoxy resin) was printed thereon. Next, after the surface on the side of the liquid crystal alignment film on the other side of the substrate is bonded to the front substrate, the sealing agent is cured to obtain an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Mark Co., Ltd.) was injected into the empty cell by a vacuum injection method to obtain a liquid crystal cell.

(Embodiment 12)

The same operation as in Example 11 was carried out except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B2), and a liquid was obtained. Crystal cell.

(Example 13)

A liquid crystal cell was obtained by the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B3).

(Example 14)

A liquid crystal cell was obtained by performing the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B4).

(Example 15)

A liquid crystal cell was obtained by performing the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B5).

(Embodiment 16)

A liquid crystal cell was obtained by performing the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B6).

(Example 17)

In addition to the liquid crystal alignment agent (B1) to use liquid crystal alignment agent (D1) Other than the generation, the same operation as in Example 11 was carried out to prepare a liquid crystal cell.

(Embodiment 18)

A liquid crystal cell was obtained by the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (D2).

(Embodiment 19)

A liquid crystal cell was obtained by the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (D3).

(Embodiment 20)

A liquid crystal cell was obtained by performing the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (D4).

(Comparative Example 3)

A liquid crystal cell was obtained by the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (B7).

(Comparative Example 4)

A liquid crystal cell was obtained by performing the same operation as in Example 11 except that the liquid crystal alignment agent (B1) was replaced with a liquid crystal alignment agent (D5).

<Method for measuring response speed>

The response speed of the liquid crystal cell obtained in Examples 11 to 20, Comparative Example 3, and Comparative Example 4 to UV irradiation can be measured by the following method.

First, in a measuring device comprising a backlight and a group of polarizing plates and a light amount detector in a state of a quadrature polarizer, a liquid crystal cell is disposed between a group of polarizing plates. At this time, the pattern of the ITO electrode forming the line/space was set to an angle of 45° with respect to the orthogonal polarizer. Then, a rectangular wave having a voltage of ±6 V and a number of cycles of 1 KHz is applied to the liquid crystal cell, and the change from the brightness observed by the light amount detector to saturation is performed using an oscilloscope, and the luminance is 0% when no voltage is applied, and ±4 V is added. The voltage and saturation brightness values are 100%, and the time taken for the brightness to change from 10% to 90% is observed as the response speed.

Thereafter, the liquid crystal cell was in a state of applying a DC voltage of 10 V, whereby the outside of the liquid crystal cell was irradiated with a UV line of 10 J through a 365 nm band pass filter. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. Table 3 shows the measurement results indicating the response speed.

<Measurement of pretilt angle>

The results obtained in Examples 11 to 20, Comparative Example 3 and Comparative Example 4 were obtained. The liquid crystal cell was measured for the pretilt angle of the pixel portion after UV irradiation. The measuring device was an LCD analyzer LCA-LUV42A manufactured by Mingling Technology. Table 3 shows the results of the measurement of the pretilt angle.

As shown in Table 3, the liquid crystal cell of Examples 11 to 20 is a liquid crystal alignment agent containing a hydrogen-bonded functional group, that is, a polymerizable compound having a carboxyl group [RM1] to [RM6]. Since the liquid crystal cell has a hydrogen bond which can cause a carboxyl group, a large mesogenic structure can be formed in the liquid crystal alignment film. The liquid crystal cells of Examples 11 to 20 are affected by the large liquid crystal structure and have sensitivity to ultraviolet light (365 nm) on the long wavelength side, so that even when irradiated with ultraviolet light of 365 nm, extremely fast can be achieved. Response speed (17~35msec). Further, since the liquid crystal cells of Examples 11 to 20 have a higher pretilt angle, it is known that the liquid crystal alignment agent used for the production of the liquid crystal cells can impart excellent alignment fixing ability.

On the other hand, the liquid crystal cell of Comparative Example 3 and Comparative Example 4 was obtained by adding a liquid crystal alignment agent of a polymerizable compound [RM7] having no functional group having hydrogen bonding. In the liquid crystal cell, since the liquid crystal portion in the liquid crystal alignment film is only a simple biphenyl structure, it has almost no sensitivity to ultraviolet light (365 nm) on the long wavelength side, so that it cannot be obtained even when irradiated with ultraviolet light of 365 nm. Full response speed.

Further, since the polymerizable compound [RM7] does not have a hydrogen-bonded functional group in the molecule, it has low solubility in a solvent, and a polymerizable compound [RM7] precipitates during freezing.

From the above results, when the polymerizable compound [RM1] to [RM6] having a carboxyl group is contained, an extremely fast response speed can be achieved even in the ultraviolet light on the long wavelength side, and excellent alignment fixation can be imparted. A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

Further, since the polymerizable compound [RM1] to [RM6] having a carboxyl group does not remain in the solvent, it is known that, in addition to the polymerizable compound, the liquid crystal alignment agent can have good storage stability. It can also increase the sensitivity to ultraviolet light.

[Industrial use]

The liquid crystal alignment agent of the present invention contains a highly soluble polymer Since the compound is compatible, a liquid crystal alignment film having excellent alignment sensitivity of light sensitivity can be obtained. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment agent of the present invention is excellent in reliability, and is suitable for use in a large-screen, high-definition liquid crystal television or the like, and is applied to a vertical electric field driving method (VA). Various liquid crystal display elements such as a mode, a TN method, an OCB method, or the like, or a horizontal electric field drive method (IPS method, FFS method) are useful. In particular, it is useful for a liquid crystal display element having a liquid crystal alignment film that controls the alignment of liquid crystals by irradiation of ultraviolet rays or polarized ultraviolet rays.

Claims (14)

A liquid crystal alignment agent comprising a polymer, a polymerizable compound, and a solvent, wherein the polymerizable compound has a polymerizable unsaturated bond group, a hydrogen-bonded functional group, and the aforementioned functional group At least one or more aromatic rings in the vicinity of the group, the aforementioned functional groups form a liquid crystal structure by hydrogen bonding between molecules. The liquid crystal alignment agent of claim 1, wherein the functional group is a carboxyl group. The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is at least one selected from the following formulas [1-1] to [1-4]. (T is an ether, an ester, a guanamine bond, S is an alkylene group having 2 to 11 carbon atoms, R is a hydrogen atom or a methyl group, and n is 1 or 2). The liquid crystal alignment agent of claim 1, wherein the polymerizable compound is at least one selected from the following formulas [2-1] to [2-6], The liquid crystal alignment agent of claim 1, wherein the polymer has a liquid crystal in a side chain and a vertical alignment. The liquid crystal alignment agent of claim 5, wherein the polymer further has a photopolymerizable group in a side chain. The liquid crystal alignment agent of claim 6, wherein the photopolymerizable group is at least one selected from the following formulas [3-1] to [3-7], (wherein Me represents a methyl group). The liquid crystal alignment agent of claim 1, wherein the polymer is a photoreactive group. The liquid crystal alignment agent of claim 8, wherein the photoreactive group is at least one selected from the following formulas [4-1] to [4-5], The liquid crystal alignment agent according to any one of claims 1 to 9, wherein the polymer is contained, and the polyimide precursor and its ruthenium imidization At least one selected from the group consisting of polyamidones, polyoxyalkylene or poly(meth)acrylate. A liquid crystal alignment film which is produced by using the liquid crystal alignment agent of claim 5 and which is irradiated with ultraviolet rays by applying a voltage. A liquid crystal display element comprising the liquid crystal alignment film of claim 11. A liquid crystal alignment film produced by using the liquid crystal alignment agent of claim 8 and obtained by irradiating a polarized ultraviolet ray. A liquid crystal display element comprising the liquid crystal alignment film of claim 13.