JP5967391B2 - Polymerizable compound, liquid crystal display element, and method for producing liquid crystal display element - Google Patents

Description

The present invention relates to a polymerizable compound, a liquid crystal display element, and a method for producing a liquid crystal display element, which can be used in the production of a liquid crystal display element of a vertical alignment type produced by irradiating ultraviolet rays with voltage applied to liquid crystal molecules. .

  A liquid crystal display element usually has an electrode on which a liquid crystal alignment film for aligning liquid crystals is formed and a liquid crystal. As materials for the liquid crystal alignment agent for forming this liquid crystal alignment film, organic liquid crystal alignment film materials such as polyimide and polysiloxane liquid crystal alignment film materials obtained by polycondensation of alkoxysilane are known. (See Patent Document 1 and Patent Document 2). As a display method of such a liquid crystal display element, there is a method (also referred to as a vertical alignment (VA) method) in which liquid crystal molecules aligned perpendicular to a substrate are responded by an electric field. Some manufacturing processes include a step of irradiating ultraviolet rays while applying a voltage to liquid crystal molecules.

  In such a vertical alignment type liquid crystal display element, a photopolymerizable compound is added to a liquid crystal composition in advance and used together with a vertical alignment film such as polyimide to irradiate ultraviolet rays while applying a voltage to a liquid crystal cell. A technique for increasing the response speed of liquid crystals (see, for example, Patent Document 3, Patent Document 4, and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display). Usually, the direction in which the liquid crystal molecules tilt in response to an electric field is controlled by protrusions provided on the substrate or slits provided on the display electrode, but a liquid crystal composition is added with a photopolymerizable compound. By irradiating ultraviolet rays while applying voltage to the cell, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film. It is said that the response speed of the liquid crystal display element is faster than the control method.

  Further, it has been reported that the response speed of the liquid crystal display element is increased by adding a photopolymerizable compound to the liquid crystal alignment film instead of the liquid crystal composition (SC-PVA liquid crystal display) (for example, Non-patent document 2).

JP 09-281502 A JP 2005-250244 A JP 2003-307720 A JP 2004-302061 A

K. Hanaoka, SID 04 DIGEST, P.1200-1202 K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

  However, it is desired to further increase the response speed of the liquid crystal display element. It is possible to increase the response speed of the liquid crystal display element by increasing the addition amount of the photopolymerizable compound, but if this photopolymerizable compound remains unreacted in the liquid crystal, it becomes an impurity (contamination), A polymerizable compound capable of increasing the response speed with a small addition amount is desirable because it causes a decrease in the reliability of the liquid crystal display element.

An object of the present invention is to solve the above-described problems of the prior art, and a polymerizable compound , a liquid crystal display element, and a liquid crystal display element that can improve the response speed of a vertical alignment type liquid crystal display element It is to provide a method.

  The polymerizable compound of the present invention that solves the above problems is represented by the following formula (1).

[Chemical 1]

(In the formula (1), V is a single bond or -R ¹ O-, R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, and W is a single bond or -OR ^2-. R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, provided that when one of V and W is a single bond, the other is a single bond or —R ¹ O— or —OR ² —. R ¹ or R ² is a linear or branched alkylene group having 1 to 3 carbon atoms.

The liquid crystal display element of the present invention is produced by containing the polymerizable compound in a liquid crystal or a liquid crystal alignment film, and irradiating ultraviolet rays while applying a voltage thereto to form a polymer of the polymerizable compound. The liquid crystal cell is provided.

The method for producing a liquid crystal display element of the present invention is characterized in that the polymerizable compound is contained in a liquid crystal or a liquid crystal alignment film, and a liquid crystal cell is produced by irradiating ultraviolet rays while applying a voltage thereto. To do.

Hereinafter, the present invention will be described in detail. The polymerizable compound of the present invention is represented by the above formula (1). In the above formula (1), V is represented by a single bond or —R ¹ O—, and R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, preferably represented by —R ¹ O—. R ¹ is a linear or branched alkylene group having 2 to 6 carbon atoms. W represents a single bond or —OR ² —, and R ² represents a linear or branched alkylene group having 1 to 10 carbon atoms, and preferably represents —OR ² — and R ² represents a straight chain or It is a branched alkylene group having 2 to 6 carbon atoms. V and W may be the same or different, but if they are the same, synthesis is easy.

  Since the polymerizable compound represented by the above formula (1) is a compound having a specific structure having α-methylene-γ-butyrolactone groups which are polymerizable groups at both ends, the polymer has a rigid structure and has a liquid crystal structure. The response speed can be improved by using it for the production of vertical alignment type liquid crystal display elements such as PSA type liquid crystal display and SC-PVA type liquid crystal display, as shown in the examples described later. It can be greatly improved. In the present invention, the polymerizable group at both ends must be an α-methylene-γ-butyrolactone group, such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, and an epoxy group described in Patent Document 1. In the case of the compound having a polymerizable group, the response speed of the liquid crystal display element of the vertical alignment type cannot be significantly improved by addition of a small amount like the compound represented by the above formula (1) of the present invention. In general, the process of forming the liquid crystal alignment film includes a step of baking at a high temperature to completely remove the solvent. However, a polymerizable group such as an acrylate group, a methacrylate group, a vinyl group, a vinyloxy group, or an epoxy group is added. The compounds that are possessed have poor thermal stability and are difficult to withstand firing at high temperatures. On the other hand, the polymerizable compound represented by the above formula (1) of the present invention can sufficiently withstand a high temperature, for example, a firing temperature of 200 ° C. or higher, because of its poor thermal polymerizability.

The polymerizable compound of the present invention represented by the above formula (1) can be synthesized by combining techniques in organic synthetic chemistry, and the synthesis method is not particularly limited. For example, taraga and the like represented by the following reaction formula are prepared by the method proposed by P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990) using SnCl ₂ and 2- (bromomethyl) acrylic acid. It can be synthesized by reacting (2- (bromomethyl) propenoic acid) with aldehyde or ketone. Amberlyst 15 is a strongly acidic ion exchange resin manufactured by Rohm and Haas.

[Chemical 2]

 (In the formula, R ′ represents a monovalent organic group.)

  In addition, 2- (bromomethyl) acrylic acid is represented by the following reaction formula: K. Ramarajan, K. Kamalingam, DJO'Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). It can be synthesized by the method proposed in.

[Chemical 3]

As a specific synthesis example, when synthesizing a polymerizable compound represented by the above formula (1) in which V is —R ¹ O—, W is —OR ² —, and R ¹ and R ² are the same, There are two methods shown in the following reaction formula.

[Chemical 4]

[Chemical 5]

Moreover, when synthesizing the polymerizable compound represented by the above formula (1) in which R ¹ and R ² are different, a method represented by the following reaction formula is exemplified.

[Chemical 6]

  And when synthesize | combining the polymeric compound represented by the said Formula (1) whose V and W are single bonds, the method shown by following Reaction Formula is mentioned.

[Chemical 7]

  The polymerizable compound represented by the above formula (1) can be contained in the liquid crystal aligning agent. Specifically, the liquid crystal aligning agent of this invention has the polymeric compound represented by the said Formula (1), the polymer which forms the liquid crystal aligning film which orientates a liquid crystal vertically, and a solvent. For example, a polymerizable compound represented by the above formula (1) is added to a known liquid crystal aligning agent for vertical alignment. The liquid crystal alignment agent is a solution for forming a liquid crystal alignment film, and the liquid crystal alignment film is a film for aligning liquid crystals in a predetermined direction, in the present invention, in the vertical direction.

 The polymer that forms the liquid crystal alignment film that aligns the liquid crystal vertically is not particularly limited as long as the liquid crystal on the liquid crystal alignment film formed on the substrate can be aligned perpendicular to the substrate. An organic liquid crystal alignment film material such as a polyimide obtained by imidizing the precursor or the polyimide precursor may be a polyester, (meth) acryloyl, or polysiloxane liquid crystal alignment film material. It is preferable that the polymer has a side chain that is aligned in the direction of, for example, a polyimide precursor having a side chain that aligns liquid crystal vertically, a polyimide obtained by imidizing the polyimide precursor, and a liquid crystal vertically. Examples thereof include at least one selected from polysiloxanes having side chains to be oriented. The polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal may be only one type or two or more types. Examples of the polyimide precursor include polyamic acid (also referred to as polyamic acid) and polyamic acid ester.

  The side chain for vertically aligning the liquid crystal is not limited as long as the liquid crystal can be aligned vertically with respect to the substrate. For example, a long chain alkyl group, a ring structure or a branch in the middle of the long chain alkyl group may be used. Examples thereof include a group having a structure, a hydrocarbon group such as a steroid group, and a group in which some or all of the hydrogen atoms of these groups are replaced with fluorine atoms. Of course, you may have the side chain which orientates two or more types of liquid crystal vertically. The side chain for vertically aligning the liquid crystal may be directly bonded to the main chain of the polymer such as polyimide precursor, polyimide or polysiloxane, that is, polyamic acid skeleton, polyimide skeleton or polysiloxane skeleton, You may couple | bond together through a suitable coupling group. Examples of the side chain for vertically aligning the liquid crystal include a hydrocarbon group having 8 to 30 carbon atoms, preferably 8 to 22 carbon atoms in which hydrogen atoms may be substituted with fluorine, specifically alkyl groups, fluoro Examples thereof include an alkyl group, an alkenyl group, a phenethyl group, a styrylalkyl group, a naphthyl group, and a fluorophenylalkyl group. Examples of the side chain for vertically aligning other liquid crystals include those represented by the following formula (a).

[Chemical 8]

(In the formula (a), l, m and n each independently represents an integer of 0 or 1, and R ³ represents an alkylene group having 2 to 6 carbon atoms, —O—, —COO—, —OCO—, —NHCO—. , -CONH-, or an alkylene ether group having 1 to 3 carbon atoms, R ⁴ , R ⁵ and R ⁶ each independently represent a phenylene group or a cycloalkylene group, R ⁷ is a hydrogen atom, 24 represents an alkyl group or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent heterocyclic ring, or a monovalent macrocyclic substituent comprising them.)

R ³ in the above formula (a) is preferably —O—, —COO—, —CONH—, or an alkylene ether group having 1 to 3 carbon atoms from the viewpoint of ease of synthesis.

R ⁴ , R ⁵ and R ⁶ in the formula (a) are l, m, n, R ⁴ and R ⁵ shown in Table 1 below from the viewpoint of ease of synthesis and ability to align liquid crystals vertically. And a combination of R ⁶ is preferred.

[table 1]

When at least one of l, m and n is 1, R ⁷ in formula (a) is preferably a hydrogen atom, an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, more preferably A hydrogen atom, an alkyl group having 2 to 12 carbon atoms, or a fluorine-containing alkyl group. When l, m, and n are all 0, R ⁷ is preferably an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, a monovalent aromatic ring, a monovalent aliphatic ring, a monovalent Heterocycles and monovalent macrocyclic substituents made of them, more preferably alkyl groups having 12 to 20 carbon atoms or fluorine-containing alkyl groups.

  The amount of the side chain that vertically aligns the liquid crystal is not particularly limited as long as the liquid crystal alignment film can align the liquid crystal vertically. However, in the liquid crystal display element having the liquid crystal alignment film, the amount of side chains that vertically align the liquid crystal is possible within a range that does not impair the display characteristics of the element such as voltage holding ratio and accumulation of residual DC voltage. As few as possible is preferable.

  The ability of a polymer having side chains for vertically aligning liquid crystals to align liquid crystals vertically varies depending on the structure of the side chains for vertically aligning liquid crystals, but in general, the side chains for vertically aligning liquid crystals. As the amount increases, the ability to align the liquid crystal vertically increases, and as the amount decreases, it decreases. Moreover, when it has a cyclic structure, compared with what does not have a cyclic structure, there exists a tendency for the capability to orientate a liquid crystal vertically.

  Moreover, it is preferable that the polymer which forms the liquid crystal aligning film which aligns a liquid crystal vertically has a photoreactive side chain. When it has a photoreactive side chain, the response speed can be further improved. The photoreactive side chain is a side chain having a functional group (hereinafter also referred to as a photoreactive group) that can react by irradiation with light such as ultraviolet rays (UV) to form a covalent bond. If it has, the structure is not limited. Examples of photoreactive side chains include vinyl groups, acrylic groups, methacryl groups, allyl groups, styryl groups, cinnamoyl groups, chalconyl groups, coumarin groups, maleimide groups, epoxy groups, vinyloxy groups, acryloxy groups as photoreactive groups. And the like, for example, these photoreactive groups themselves, and alkyl groups in which hydrogen atoms are substituted with these photoreactive groups. The number of substituted hydrogen atoms is one or more, preferably one. The number of carbon atoms of the alkyl group in which a hydrogen atom is substituted with a photoreactive group is preferably 1-30, more preferably 1-10, and still more preferably 1-5, from the viewpoint of response speed and vertical alignment. . Of course, you may have two or more types of photoreactive side chains. The photoreactive side chain may be directly bonded to the main chain of a polymer such as a polyimide precursor, polyimide or polysiloxane, or may be bonded via an appropriate bonding group. Examples of the photoreactive side chain include those represented by the following formula (b).

[Chemical 9]

(In the formula (b), R ⁸ is a single bond or —CH ₂ —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH ₂ O—, —N It represents any one of (CH ₃ ) —, —CON (CH ₃ ) —, —N (CH ₃ ) CO—, and R ⁹ is a single bond, unsubstituted or substituted with a fluorine atom. Represents an alkylene group of ˜20, and —CH ₂ — of the alkylene group may be optionally replaced by —CF ₂ — or —CH═CH—, and when any of the following groups is not adjacent to each other: , may be substituted with these groups; -O -, - COO -, - OCO -, - NHCO -, - CONH -, - NH-, a divalent carbocyclic, divalent heterocyclic ^{.R 10} Is vinyl group, acrylic group, methacryl group, allyl group, styryl group,- _(CH 2 CHCH ₂₎ represents a _2, or represented by the following formula structure.)

[Chemical 10]

R ⁸ in the above formula (b) can be formed by a general organic synthetic method, but from the viewpoint of ease of synthesis, —CH ₂ —, —O—, —COO—, —NHCO. _{-, - NH -, - CH} 2 O- are preferable.

Specific examples of the divalent carbocycle or divalent heterocycle carbocycle or heterocycle for replacing any —CH ₂ — in R ⁹ include the following structures, but are not limited thereto. Is not to be done.

[Chemical 11]

R ¹⁰ is preferably a vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, —N (CH ₂ CHCH ₂ ) ₂ or a structure represented by the following formula from the viewpoint of photoreactivity.

[Chemical 12]

  The above formula (b) is more preferably the following structure.

[Chemical 13]

  The amount of the photoreactive side chain is preferably within a range in which the response speed of the liquid crystal can be increased by reacting with ultraviolet irradiation to form a covalent bond. In order to further increase the response speed of the liquid crystal As many as possible are preferable as long as other characteristics are not affected.

  The polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal may have other side chains other than the side chain for vertically aligning the liquid crystal and the photoreactive side chain. Examples of the other side chain include a hydrogen atom, or a hydrocarbon group having 1 to 6 carbon atoms which may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. It is done. When polysiloxane having these groups is used, the adhesion of the obtained liquid crystal alignment film to the substrate and the affinity with liquid crystal molecules can be improved.

  A method for producing a polymer for forming a liquid crystal alignment film for vertically aligning such liquid crystals is not particularly limited. For example, in the case of producing a polyamic acid having a side chain for vertically aligning liquid crystals, diamine and tetra In a method of obtaining a polyamic acid by reaction with a carboxylic dianhydride, a method of copolymerizing a diamine having a side chain for vertically aligning a liquid crystal or a tetracarboxylic dianhydride having a side chain for vertically aligning a liquid crystal Convenient. In addition, when a polymer forming a liquid crystal alignment film for vertically aligning liquid crystals contains a photoreactive side chain, a diamine having a photoreactive side chain or a tetracarboxylic acid having a photoreactive side chain A dianhydride may be copolymerized.

  Examples of the diamine having a side chain for vertically aligning the liquid crystal include a long chain alkyl group, a group having a ring structure or a branched structure in the middle of the long chain alkyl group, a hydrocarbon group such as a steroid group, and the hydrogen of these groups. A diamine having a side chain with a group in which some or all of the atoms are replaced with fluorine atoms, for example, a diamine having a side chain represented by the above formula (a) can be mentioned. More specifically, for example, a diamine having a hydrocarbon group having 8 to 30 carbon atoms in which a hydrogen atom may be substituted with fluorine, or the following formulas (2), (3), (4), (5 The diamine represented by this can be mentioned, However, It is not limited to this.

[Chemical 14]

(The definitions of l, m, n, and R ^{3 to} R ⁷ in Formula (2) are the same as those in Formula (a) above.)

[Chemical 15]

(Equation (3) and the formula _(4), A 10 is -COO -, - OCO -, - CONH -, - NHCO -, - CH 2 -, - O -, - CO-, or -NH- and represents , A ₁₁ represents a single bond or a phenylene group, a represents the same structure as a side chain for vertically aligning the liquid crystal represented by the above formula (a), and a ′ is represented by the above formula (a). (This represents a divalent group having a structure in which one element such as hydrogen is removed from the same structure as the side chain that vertically aligns the liquid crystal.)

[Chemical 16]

(In the formula _{(5), A 14} is a fluorine atom may be substituted, an alkyl group having 3 to 20 carbon _{atoms, A 15} is 1,4-cyclohexylene group, or 1,4 A phenylene group, A ₁₆ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A ₁₅ ), and A ₁₇ is an oxygen atom or —COO — * ( However, "*" is a bond marked with a _(CH 2) binds to _{a 2.).} Further, _{a 1} is 0, or an integer 1, _{a 2} is an integer from 2 to 10, a ₃ is 0 or an integer of 1.

Binding positions of the two amino group (-NH ₂₎ in equation (2) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

  Specific examples of the structure of the formula (2) include diamines represented by the following formulas [A-1] to [A-24], but are not limited thereto.

[Chemical 17]

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

[Chemical 18]

(In Formula [A-6] and Formula [A-7], A ₂ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and ₃ is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

[Chemical 19]

(In formula [A-8] to formula [A-10], A ₄ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH _2. O—, —OCH ₂ —, or —CH ₂ — is shown, and 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.

[Chemical 20]

(In Formula [A-11] and 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— is shown, and A ₇ is fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy Group or hydroxyl group.)

[Chemical 21]

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

[Chemical 22]

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

[Chemical 23]

  Specific examples of the diamine represented by the formula (3) include diamines represented by the following formulas [A-25] to [A-30], but are not limited thereto.

[Chemical 24]

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

Specific examples of the diamine represented by the formula (4) include diamines represented by the following formulas [A-31] to [A-32], but are not limited thereto.

[Chemical 25]

  Among these, [A-1], [A-2], [A-3], [A-4], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5], [A-5] The diamines of A-25], [A-26], [A-27], [A-28], [A-29], and [A-30] are preferable.

  The diamine may be used alone or in combination of two or more depending on the liquid crystal alignment properties, pretilt angle, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

  The diamine having a side chain for vertically aligning the liquid crystal is preferably used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, more preferably 10 to 40 mol% of the diamine component. Is a diamine having a side chain for vertically aligning the liquid crystal, particularly preferably 15 to 30 mol%. When the diamine having a side chain for vertically aligning the liquid crystal is used in an amount of 5 to 50 mol% of the diamine component used for the synthesis of the polyamic acid, it is particularly excellent in terms of improving the response speed and the ability to fix the alignment of the liquid crystal. .

  Examples of diamines having photoreactive side chains include vinyl, acryl, methacryl, allyl, styryl, cinnamoyl, chalcone, coumarin, maleimide, epoxy, vinyloxy, and acryloxy groups. Examples thereof include diamines having a reactive group as a side chain, such as diamines having a side chain represented by the above formula (b). More specifically, examples include diamines represented by the following general formula (6), but are not limited thereto.

[Chemical 26]

(The definitions of R ⁸ , R ⁹ and R ¹⁰ in Formula (6) are the same as those in Formula (b) above.)

The bonding position of the two amino groups (—NH ₂ ) in Formula (6) is not limited. Specifically, with respect to the linking group of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring, 3, 4 position, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine, the positions 2, 4 or 3, 5 are more preferable.

  Specific examples of the diamine having a photoreactive side chain include, but are not limited to, the following compounds.

[Chemical 27]

(In the formula, X is a single bond or a linking group selected from —O—, —COO—, —NHCO—, and —NH—, Y is a single bond, or carbon that is unsubstituted or substituted by a fluorine atom. Represents an alkylene group of the number 1-20.)

  The diamine having the photoreactive group depends on the liquid crystal orientation when used as a liquid crystal alignment film, the pretilt angle, voltage holding characteristics, characteristics such as stored charge, the response speed of the liquid crystal when used as a liquid crystal display element, One type or a mixture of two or more types can also be used.

  Further, the diamine having such a photoreactive side chain is preferably used in an amount of 10 to 70 mol%, more preferably 20 to 60 mol%, particularly preferably diamine components used for the synthesis of polyamic acid. Is 30 to 50 mol%.

  In addition, as long as the polyamic acid does not impair the effect of the present invention, other diamines other than the diamine having a side chain for vertically aligning the liquid crystal and the diamine having a photoreactive side chain are used as a diamine component. Can be used together. Specifically, for example, p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′- Diaminobiphenyl, 3,3′-difluoro-4,4′-biphenyl, 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-diaminobiphenyl, 2,3′-diaminobiphenyl, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2′-diaminodiphenylmethane, 2, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4 ' -Sulphonyldianiline, 3,3'-sulfonyl Dianiline, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4′-thiodianiline, 3 , 3′-thiodianiline, 4,4′-diaminodiphenylamine, 3,3′-diaminodiphenylamine, 3,4′-diaminodiphenylamine, 2,2′-diaminodiphenylamine, 2,3′-diaminodiphenylamine, N-methyl ( 4,4'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) Amine, N-methyl (2,3′-diaminodiphenyl) amine, 4,4′-dia Nobenzophenone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2′-diaminobenzophenone, 2,3′-diaminobenzophenone, 1,5-diaminonaphthalene, 1, , 6-Diaminonaphthalene, 1,7-diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2 -Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, , 4-bis (4-aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis ( 3,5-diethyl-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 4,4 ′-[1,4 -Phenylenebis (methylene)] dianiline, 4,4 '-[1,3-phenylenebis (methylene)] dianiline, 3,4'-[1,4-phenylenebis (methylene)] dianiline, 3,4'- [1,3-phenylenebis (methylene)] dianiline, 3,3 ′-[1,4-phenylenebis (methylene)] dianiline, 3,3 ′-[1,3-phenylenebis (methylene)] di Aniline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4 -Aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3- Aminophenyl) isophthalate, N, N ′-(1,4-phenylene) bis (4-aminobenza) ), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3-aminobenzamide), N, N ′-(1 , 3-phenylene) bis (3-aminobenzamide), N, N′-bis (4-aminophenyl) terephthalamide, N, N′-bis (3-aminophenyl) terephthalamide, N, N′-bis ( 4-aminophenyl) isophthalamide, N, N′-bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4′-bis (4-aminophenoxy) diphenylsulfone 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2,2′-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, , 2′-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis (3-aminophenyl) hexafluoropropane, 2,2′-bis (3-amino-4-methylphenyl) hexafluoropropane 2,2′-bis (4-aminophenyl) propane, 2,2′-bis (3-aminophenyl) propane, 2,2′-bis (3-amino-4-methylphenyl) propane, 3,5 -Diaminobenzoic acid, 2,5-diaminobenzoic acid, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) Butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, , 6-bis (4-aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7- (3-aminophenoxy) Heptane, 1,8-bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-amino) Phenoxy) nonane, 1,10- (4-aminophenoxy) decane, 1,10- (3-aminophenoxy) decane, 1,11- (4-aminophenoxy) undecane, 1,11- (3-aminophenoxy) Aromatic diamines such as undecane, 1,12- (4-aminophenoxy) dodecane, 1,12- (3-aminophenoxy) dodecane, bis (4-aminocyclohexane) Sil) methane, alicyclic diamines such as bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diamino Aliphatic diamines such as xane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane .

  The above-mentioned other diamines can be used alone or in combination of two or more according to properties such as liquid crystal orientation, pretilt angle, voltage holding property, and accumulated charge when the liquid crystal alignment film is formed.

  The tetracarboxylic dianhydride to be reacted with the diamine component in the synthesis of polyamic acid is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2, 3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetra Carboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxy) Phenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphe) Nyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3 , 4-dicarboxyphenyl) pyridine, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3 4-cyclobutanetetracarboxylic acid, oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexane Tetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4 Cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0 ] Decane-2,4,7,9-tetracarboxylic acid, bicyclo [4,4,0] decane-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6 >] Ndecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydraphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3, Examples include 5,6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid and 1,2,4,5-cyclohexanetetracarboxylic acid. Of course, tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.

  In obtaining a polyamic acid by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent. The reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

  The organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid dissolves. Furthermore, even if it is an organic solvent in which a polyamic acid does not melt | dissolve, you may mix and use the said solvent in the range which the produced | generated polyamic acid does not precipitate. In addition, since the water | moisture content in an organic solvent inhibits a polymerization reaction and also causes the produced polyamic acid to hydrolyze, it is preferable to use what dehydrated and dried the organic solvent. Examples of the organic solvent used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2- Pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl Rosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether , Propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, dioxane, n-hexane, n-pentane, n-octane, Diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, Methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl -2-pentanone, 2-ethyl-1-hexanol and the like. These organic solvents may be used alone or in combination.

  When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or in an organic solvent. A method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component. The method of adding alternately etc. is mentioned, You may use any of these methods. In addition, when the diamine component or tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. The body may be mixed and reacted to form a high molecular weight body.

  The temperature at the time of making a diamine component and a tetracarboxylic dianhydride component react can select arbitrary temperatures, for example, -20 degreeC-150 degreeC, Preferably it is the range of -5 degreeC-100 degreeC. Moreover, reaction can be performed by arbitrary density | concentrations, for example, the total amount of a diamine component and a tetracarboxylic dianhydride component is 1-50 mass% with respect to the reaction liquid, Preferably it is 5-30 mass%.

  The ratio of the total number of moles of the tetracarboxylic dianhydride component with respect to the total number of moles of the diamine component in the polymerization reaction can be selected according to the molecular weight of the polyamic acid to be obtained. Similar to the normal polycondensation reaction, the molecular weight of the polyamic acid produced increases as the molar ratio approaches 1.0. If it shows a preferable range, it is 0.8 to 1.2.

  The method for synthesizing the polyamic acid used in the present invention is not limited to the above-described method, and in the same manner as the general polyamic acid synthesis method, instead of the tetracarboxylic dianhydride, a tetracarboxylic acid having a corresponding structure is used. The corresponding polyamic acid can also be obtained by reacting by a known method using a tetracarboxylic acid derivative such as acid or tetracarboxylic acid dihalide.

  Examples of the method for imidizing the polyamic acid to form a polyimide include thermal imidization in which a polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution. The imidation ratio from polyamic acid to polyimide is not necessarily 100%.

  The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and is preferably performed while removing water generated by the imidation reaction from the system.

The catalytic imidation of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

The polyamic acid ester is a reaction of a tetracarboxylic acid diester dichloride with a diamine similar to the synthesis of the polyamic acid, a suitable condensing agent with a diamine similar to the synthesis of the tetracarboxylic acid diester and the polyamic acid, It can be produced by reacting in the presence of a base or the like. Alternatively, it can also be obtained by previously synthesizing a polyamic acid by the above method and esterifying the carboxylic acid in the amic acid using a polymer reaction. Specifically, for example, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 hour. A polyamic acid ester can be synthesized by reacting for ˜4 hours. The polyimide can also be obtained by heating the polyamic acid ester at a high temperature to promote dealcoholization and ring closure.

  When recovering the polyimide precursor or polyimide such as polyamic acid and polyamic acid ester produced from the polyimide precursor or polyimide reaction solution such as polyamic acid and polyamic acid ester, the reaction solution is poured into a poor solvent and precipitated. You can do it. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating. Moreover, when the polymer which carried out precipitation collection | recovery is re-dissolved in an organic solvent and the operation which carries out reprecipitation collection | recovery is repeated 2 to 10 times, the impurity in a polymer can be decreased. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.

  The method for producing a polysiloxane having a side chain for vertically aligning the liquid crystal is not particularly limited. For example, it can be produced by polycondensing alkoxysilane or a condensate of alkoxysilane. The alkoxysilane condensate is a multimer of alkoxysilane such as a dimer of alkoxysilane. If an alkoxysilane having a side chain for vertically aligning the liquid crystal is used as the alkoxysilane, a polysiloxane having a side chain for vertically aligning the liquid crystal can be formed. In addition, when the polysiloxane that vertically aligns the liquid crystal contains a photoreactive side chain, an alkoxysilane having a photoreactive side chain or a condensate thereof may be used.

Examples of alkoxysilanes having side chains for vertically aligning liquid crystals include long-chain alkyl groups, groups having a ring structure or a branched structure in the middle of long-chain alkyl groups, hydrocarbon groups such as steroid groups, and the like of these groups. Examples include alkoxysilanes having a group in which part or all of the hydrogen atoms are replaced with fluorine atoms as side chains, for example, alkoxysilanes represented by the above formula (7). In the above formula (7), R ¹¹ is preferably an alkyl group or a fluoroalkyl group, and particularly preferably an alkyl group. R ¹² is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R ¹² is a methyl group or an ethyl group.

  Specific examples of the alkoxysilane represented by the above formula (7) include, for example, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. , Hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltri Ethoxysilane, undecyltrimethoxysilane, 21-docosenyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane Heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, isooctyltriethoxysilane, phenethyltriethoxysilane, pentafluorophenylpropyltrimethoxysilane, (1-naphthyl) triethoxysilane, (1-naphthyl) trimethoxy Silane etc. are mentioned. Among them, octyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane , Heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, undecyltriethoxysilane, or undecyltrimethoxysilane, triethoxyvinylsilane, trimethoxyvinylsilane, Triethoxyallylsilane, trimethoxyallylsilane, triethoxystyrylsilane, and trimethoxystyrylsilane are preferable.

  Examples of the alkoxysilane having a side chain for vertically aligning the liquid crystal include an alkoxysilane having a side chain represented by the above formula (a).

  An alkoxysilane having a side chain that vertically aligns a liquid crystal such as an alkoxysilane represented by the above formula (7) or an alkoxysilane having a side chain represented by the above formula (a) has good liquid crystal orientation. In order to obtain, in all the alkoxysilanes used for obtaining polysiloxane, 0.1 mol% or more is preferable, More preferably, it is 0.5 mol% or more, More preferably, it is 1 mol% or more. Moreover, in order for the liquid crystal aligning film formed to acquire sufficient hardening characteristics, 30 mol% or less is preferable, More preferably, it is 22 mol% or less.

Examples of the alkoxysilane having a photoreactive side chain include a vinyl group, an acrylic group, a methacryl group, an allyl group, a styryl group, a cinnamoyl group, a chalcone group, a coumarin group, a maleimide group, an epoxy group, a vinyloxy group, and an acryloxy group. A side chain having a photoreactive group such as, for example, these photoreactive groups themselves, or an alkoxysilane having, as a side chain, an alkyl group in which a hydrogen atom is substituted with these photoreactive groups, And alkoxysilanes represented by the above formula (8). In the above formula (8), the number of hydrogen atoms substituted with R ¹³ is one or more, preferably one. The number of carbon atoms in the alkyl group of R ¹³ is preferably 1 to 30, more preferably 1 to 10, more preferably from 1 to 5. R ¹⁴ is preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. More preferably, R ¹⁴ is a methyl group or an ethyl group.

  Specific examples of the alkoxysilane represented by the above formula (8) include, for example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltrimethyl. Examples include ethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, acryloxyethyltrimethoxysilane, and acryloxyethyltriethoxysilane.

  Examples of other alkoxysilanes having photoreactive side chains include alkoxysilanes having side chains represented by the above formula (b).

  An alkoxysilane having a photoreactive side chain such as an alkoxysilane represented by the above formula (8) or an alkoxysilane having a side chain represented by the above formula (b) is sufficient to form a liquid crystal alignment film. In order to cure it, it is preferably 60 mol% or less in all alkoxysilanes used to obtain polysiloxane, but from the viewpoint of vertical alignment, if it is contained in an amount of 60 mol% or more, there is a concern that the content will decrease. 50 mol% is preferable.

  Further, other alkoxysilanes may be used. Examples of other alkoxysilanes include alkoxysilanes represented by the following formula (9). By using one or a plurality of alkoxysilanes represented by the following formula (9), the adhesion with the substrate and the affinity with the liquid crystal molecules can be improved.

(R ¹⁵ ) _n Si (OR ¹⁶ ) _4-n (9)
(In the formula (9), R ¹⁵ is a carbon atom having 1 to 6 carbon atoms which may be substituted with a hydrogen atom, a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. A hydrogen group, R ¹⁶ is an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 3.)

In the alkoxysilane of the above formula (9), specific examples when R ¹⁵ is a hydrogen atom include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane and the like.

Further, in the alkoxysilane of the above formula (9), R ¹⁵ may be substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group or a ureido group. Specific examples of the hydrogen group include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methyltripropoxysilane, and 3-aminopropyl. Trimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, 3- (2-aminoethylamino) Propyl) trimethoxysila 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltri Methoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxy Silane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethyl Tokishishiran, trimethyl silane, trimethyl silane, .gamma.-ureidopropyltriethoxysilane, .gamma.-ureidopropyltrimethoxysilane and .gamma.-ureidopropyl tripropoxysilane, and the like.

  In the alkoxysilane represented by the above formula (9), the alkoxysilane in which n is 0 is tetraalkoxysilane. Tetraalkoxysilane is preferably used because it easily polycondenses with the alkoxysilane represented by the above formula (7) and the alkoxysilane represented by the above formula (8). As the alkoxysilane in which n is 0 in the above formula (9), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.

  When the alkoxysilane represented by the above formula (9) is used, the amount of the alkoxysilane represented by the above formula (9) is 10 to 99.8 mol in all alkoxysilanes used for obtaining the polysiloxane. %, More preferably 35-96.9 mol%.

  Examples of a method for polycondensing such alkoxysilane and its condensate include a method of hydrolyzing and condensing alkoxysilane and its condensate in a solvent such as alcohol or glycol. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, it is theoretically necessary to add 0.5 moles of water of all alkoxy groups in the alkoxysilane or its condensate, but usually an excess of water is added in excess of 0.5 moles. Is preferred. In the present invention, the amount of water used in the above reaction can be appropriately selected as desired, but it is usually preferably 0.5 to 2.5 moles of all alkoxy groups in the alkoxysilane.

  Usually, for the purpose of promoting hydrolysis / condensation reaction, acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, formic acid, succinic acid, maleic acid, fumaric acid; alkalis such as ammonia, methylamine, ethylamine, ethanolamine, triethylamine A metal salt such as hydrochloric acid, sulfuric acid or nitric acid; In addition, it is also common to further promote the hydrolysis / condensation reaction by heating the solution in which the alkoxysilane is dissolved. At that time, the heating temperature and the heating time can be appropriately selected as desired. For example, heating and stirring at 50 ° C. for 24 hours, heating and stirring for 1 hour under reflux, and the like can be mentioned.

  As another method, for example, a method of polycondensation by heating a mixture of alkoxysilane, its condensate, solvent and oxalic acid can be mentioned. Specifically, oxalic acid is added to alcohol in advance to obtain an alcohol solution of oxalic acid, and then the alkoxysilane and its condensate are mixed while the solution is heated. At that time, the amount of succinic acid used is preferably 0.2 to 2 mol with respect to 1 mol of all alkoxy groups contained in the alkoxysilane or its condensate. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. Preferably, it is a method of heating for several tens of minutes to several tens of hours under reflux so that evaporation or volatilization of the liquid does not occur.

  When using multiple types of alkoxysilane and its condensate when obtaining polysiloxane, the alkoxysilane and its condensate may be mixed as a premixed mixture, or multiple types of alkoxysilane and its condensate are sequentially added. You may mix.

  The solvent used for polycondensation of alkoxysilane and its condensate (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it dissolves alkoxysilane and its condensate. Moreover, even if alkoxysilane and its condensate do not melt | dissolve, what is necessary is just to melt | dissolve with progress of the polycondensation reaction of alkoxysilane and its condensate. In general, since an alcohol is generated by a polycondensation reaction of alkoxysilane or its condensate, alcohols, glycols, glycol ethers, or organic solvents having good compatibility with alcohols are used.

  Specific examples of such a polycondensation solvent include alcohols such as methanol, ethanol, propanol, butanol, and diacetone alcohol: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, and 1,3-propanediol. 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, Glycols such as 1,5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Glycol ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone , Dimethyl sulfoxide, tetramethylurea, hexamethylphosphotriamide, m-cresol and the like. A plurality of polymerization solvents may be used as a mixture.

The polysiloxane polymerization solution (hereinafter, also referred to as polymerization solution) obtained by the above method is a concentration obtained by converting silicon atoms of all alkoxysilanes used as raw materials into SiO ₂ (hereinafter referred to as SiO ₂ conversion concentration). ) Is preferably 20% by mass or less, more preferably 5 to 15% by mass. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous solution can be obtained.

  In the present invention, the polymerization solution obtained by the above method may be contained in the liquid crystal aligning agent as it is, or the polysiloxane may be precipitated and contained as a solid in the liquid crystal aligning agent. The solution obtained by the above method may be concentrated, diluted by adding a solvent, or substituted with another solvent and contained in the liquid crystal aligning agent. In that case, the solvent to be used (hereinafter also referred to as additive solvent) may be the same as the polymerization solvent, or may be another solvent. The additive solvent is not particularly limited as long as the polysiloxane is uniformly dissolved, and one kind or plural kinds can be arbitrarily selected and used. Specific examples of such an additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent described above, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as methyl acetate, ethyl acetate, and ethyl lactate. Can be mentioned. These solvents can improve the coating property when the liquid crystal aligning agent is applied onto the substrate by adjusting the viscosity of the liquid crystal aligning agent, or by spin coating, flexographic printing, ink jetting or the like.

  As long as the liquid crystal aligning agent of the present invention has the polymerizable compound represented by the above formula (1), the polymer forming the liquid crystal aligning film for vertically aligning the liquid crystal, and the solvent as described above. Well, the mixing ratio is not particularly limited, but the content of the polymerizable compound represented by the above formula (1) is based on 100 parts by mass of the polymer that forms the liquid crystal alignment film that aligns the liquid crystal vertically. It is preferable that it is 1-50 mass parts, More preferably, it is 5-30 mass parts. The content of the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal contained in the liquid crystal aligning agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably. 3% by mass to 10% by mass.

  Moreover, the liquid crystal aligning agent of this invention may contain other polymers other than the polymer which forms the liquid crystal aligning film which orientates a liquid crystal vertically. In that case, 0.5 mass%-15 mass% are preferable, and, as for content of this other polymer in a polymer whole component, More preferably, they are 1 mass%-10 mass%.

  The molecular weight of the polymer of the liquid crystal aligning agent is determined based on GPC (Gel Permeation Chromatography) in consideration of the strength of the liquid crystal aligning film obtained by applying the liquid crystal aligning agent, workability during coating film formation, and uniformity of the coating film. ) Is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000 in terms of weight average molecular weight measured by the method.

  There is no particular limitation on the solvent contained in the liquid crystal aligning agent, and it is possible to dissolve or disperse the components such as the polymerizable compound represented by the above formula (1) and the polymer that forms the liquid crystal alignment film that vertically aligns the liquid crystal. Anything is acceptable. For example, organic solvents as exemplified in the above synthesis of polyamic acid, polymerization solvents and additive solvents shown in the synthesis of polysiloxane can be mentioned. Among these, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methoxy-N, N-dimethylpropanamide are soluble. To preferred. Of course, two or more kinds of mixed solvents may be used.

  Moreover, it is preferable to mix and use the solvent which improves the uniformity and smoothness of a coating film in the solvent with the high solubility of the component of a liquid crystal aligning agent. Solvents that improve the uniformity and smoothness of the coating include, for example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol Tolu, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether , Dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, dii Butylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, acetic acid Ethyl, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 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, dipropylene glycol, 2- (2- Ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester, 2-ethyl-1-hexanol and the like. A plurality of these solvents may be mixed. When using these solvents, it is preferable that it is 5-80 mass% of the whole solvent contained in a liquid crystal aligning agent, More preferably, it is 20-60 mass%.

  The liquid crystal aligning agent may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.

  Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.). When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the total amount of the polymer contained in the liquid crystal aligning agent. 1 part by mass.

  Specific examples of compounds that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′ , N′-tetraglycidyl-4, 4′-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like. . In order to further increase the film strength of the liquid crystal alignment film, a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added. When using these compounds, it is preferable that it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of the polymer contained in a liquid crystal aligning agent, More preferably, it is 1-20 mass parts.

  In addition to the above, the liquid crystal aligning agent is added with a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant or conductivity of the liquid crystal aligning film as long as the effects of the present invention are not impaired. May be.

  Further, the liquid crystal aligning agent may contain inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, surfactants, and the like.

  As the inorganic fine particles, fine particles such as silica fine particles, alumina fine particles, titania fine particles, and magnesium fluoride fine particles are preferable, and those in the state of a colloidal solution are particularly preferable. This colloidal solution may be a dispersion of inorganic fine particles in a dispersion medium, or a commercially available colloidal solution. In the present invention, the inclusion of inorganic fine particles makes it possible to impart the surface shape of the formed cured film and other functions. The inorganic fine particles preferably have an average particle size of 0.001 to 0.2 μm, more preferably 0.001 to 0.1 μm. When the average particle diameter of the inorganic fine particles exceeds 0.2 μm, the transparency of the cured film formed using the prepared coating liquid may be lowered.

  Examples of the dispersion medium for the inorganic fine particles include water and organic solvents. As a colloidal solution, it is preferable that pH or pKa is adjusted to 1-10 from the viewpoint of the stability of the coating liquid for forming a film. More preferably, it is 2-7.

  Examples of the organic solvent used for the dispersion medium of the colloidal solution include alcohols such as methanol, propanol, butanol, ethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, diethylene glycol, dipropylene glycol, and ethylene glycol monopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; esters such as ethyl acetate, butyl acetate and γ-butyrolactone; Examples include ethers such as tetrahydrofuran and 1,4-dioxane. Of these, alcohols or ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.

  As the metalloxane oligomer and metalloxane polymer, single or composite oxide precursors such as silicon, titanium, aluminum, tantalum, antimony, bismuth, tin, indium, and zinc are used. The metalloxane oligomer or metalloxane polymer may be a commercially available product or may be obtained from a monomer such as a metal alkoxide, nitrate, hydrochloride, or carboxylate by a conventional method such as hydrolysis.

  Specific examples of commercially available metalloxane oligomers and metalloxane polymers include siloxane oligomers or siloxanes such as methyl silicate 51, methyl silicate 53A, ethyl silicate 40, ethyl silicate 48, EMS-485, and SS-101 manufactured by Colcoat. Examples thereof include titanoxane oligomers such as a polymer and titanium-n-butoxide tetramer manufactured by Kanto Chemical Co., Inc. You may use these individually or in mixture of 2 or more types.

  Moreover, a leveling agent, surfactant, etc. can use a well-known thing, and since a commercial item is easy to acquire especially, it is preferable.

  The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. If the polymerizable compound represented by the above formula (1), the polymer forming the liquid crystal alignment film for vertically aligning the liquid crystal, and other components added as needed are mixed uniformly. Good. For example, since polysiloxane is usually polycondensed in a solvent as described above, it is convenient to use the polysiloxane solution as it is or to add other components to the polysiloxane solution as necessary. . Furthermore, the most convenient method is to use the polysiloxane polymerization solution as it is.

  In addition, when adjusting the content of the polymer that forms the liquid crystal alignment film that vertically aligns the liquid crystal in the liquid crystal aligning agent, an organic solvent such as exemplified in the synthesis of the polyamic acid described above, or polymerization of polysiloxane is used. A solvent selected from the group consisting of a solvent and an additive solvent can be used.

  By applying and baking this liquid crystal aligning agent on a substrate, a liquid crystal alignment film for vertically aligning liquid crystals can be formed. Since the liquid crystal aligning agent of this invention has a polymeric compound represented by the said Formula (1), it can make the response speed of the liquid crystal display element using the obtained liquid crystal aligning film quick.

  For example, after apply | coating the liquid crystal aligning agent of this invention to a board | substrate, after drying as needed, the cured film obtained by baking can also be used as a liquid crystal aligning film as it is. In addition, the cured film is rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as a PSA alignment film It is also possible to irradiate with UV. In particular, it is useful to use as an alignment film for PSA.

  At this time, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, Plastic substrates such as trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.

  The method for applying the liquid crystal aligning agent is not particularly limited, and examples thereof include screen printing, offset printing, flexographic printing, and other printing methods, ink jet methods, spray methods, roll coating methods, dip, roll coater, slit coater, and spinner. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.

  The drying process after applying the liquid crystal aligning agent is not necessarily required, but if the time from application to baking is not constant for each substrate, or if baking is not performed immediately after application, the drying process is performed. It is preferable. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transporting the substrate or the like. For example, a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C., for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes.

  The coating film formed by applying the liquid crystal aligning agent by the above method can be baked to obtain a cured film. The baking temperature of the coating film formed by applying a liquid crystal aligning agent is not limited, For example, it can carry out at arbitrary temperatures of 100-350 degreeC. When the liquid crystal aligning agent contains a polyimide precursor having a side chain for vertically aligning liquid crystal or a polyimide obtained by imidizing the polyimide precursor, the temperature is preferably 120 ° C to 300 ° C, more preferably 150 ° C. C. to 250.degree. Moreover, when the liquid crystal aligning agent contains polysiloxane having a side chain for vertically aligning the liquid crystal, it is preferably 140 ° C to 300 ° C, more preferably 150 ° C to 230 ° C, and further preferably 160 ° C to 220 ° C. ° C. Firing can be performed at an arbitrary time of 5 minutes to 240 minutes. Preferably it is 10 minutes-90 minutes, More preferably, it is 20 minutes-90 minutes. Heating can be performed by a generally known method, for example, a hot plate, a hot air circulating furnace, an infrared furnace, an IR oven, a belt furnace, or the like.

  The polysiloxane in the liquid crystal alignment film undergoes polycondensation in this baking step. However, in the present invention, it is not necessary to completely polycondense unless the effects of the present invention are impaired. However, firing is preferably performed at a temperature higher by 10 ° C. or more than the heat treatment temperature required for the liquid crystal cell production process, such as curing of the sealant.

  The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 nm or more, more preferably 10 nm or more because the reliability of the liquid crystal display element can be easily obtained. Further, since the power consumption of the liquid crystal display element does not become extremely large, the thickness of the liquid crystal alignment film is preferably 300 nm or less, more preferably 150 nm or less, and further preferably 100 nm or less.

  And the liquid crystal display element of this invention can produce a liquid crystal cell by a well-known method, after forming a liquid crystal aligning film in a board | substrate by said method. Specific examples of the liquid crystal display element include two substrates disposed so as to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal aligning agent provided between the substrate and the liquid crystal layer. A vertical alignment type liquid crystal display device comprising a liquid crystal cell having the above-described liquid crystal alignment film. Specifically, the liquid crystal aligning agent of the present invention is applied onto two substrates and baked to form a liquid crystal aligning film, and the two substrates are arranged so that the liquid crystal aligning films face each other. A liquid crystal layer composed of liquid crystal is sandwiched between two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer. This is a vertical alignment type liquid crystal display device including a liquid crystal cell to be manufactured. Thus, using the liquid crystal aligning film formed with the liquid crystal aligning agent of the present invention, the polymerizable compound represented by the above formula (1) is polymerized by irradiating ultraviolet rays while applying voltage to the liquid crystal aligning film and the liquid crystal layer. By doing so, a liquid crystal display element excellent in response speed is obtained.

  The substrate used in the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving liquid crystal is formed. As a specific example, the thing similar to the board | substrate described with the said liquid crystal aligning film can be mentioned. A substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, a polymerizable compound represented by the above formula (1) as a liquid crystal aligning agent for forming a liquid crystal aligning film. Since the liquid crystal aligning agent of the present invention having the above is used, it is possible to operate even in a structure in which a line / slit electrode pattern of 1 to 10 μm, for example, is formed on one side substrate and no slit pattern or projection pattern is formed on the opposite substrate The liquid crystal display element having this structure can simplify the manufacturing process and obtain high transmittance.

  As a high-performance element such as a TFT type element, an element in which an element such as a transistor is formed between an electrode for driving a liquid crystal and a substrate is used.

  In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above. However, in a reflective liquid crystal display element, if only one substrate is used, an opaque substrate such as a silicon wafer may be used. Is possible. At that time, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

  The liquid crystal alignment film is formed by applying the liquid crystal aligning agent of the present invention on this substrate and baking it, and the details are as described above.

  The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and a liquid crystal material used in a conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Can be used.

  As a method of sandwiching the liquid crystal layer between two substrates, a known method can be exemplified. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate so that the surface on which the liquid crystal alignment film is formed is on the inside. Then, the other substrate is bonded, and liquid crystal is injected under reduced pressure to seal. Also, a pair of substrates on which a liquid crystal alignment film is formed are prepared, and spacers such as beads are dispersed on the liquid crystal alignment film on one substrate, and then liquid crystal is dropped, and then the surface on which the liquid crystal alignment film is formed A liquid crystal cell can also be produced by a method in which the other substrate is bonded to the inside so as to be inside and sealed. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

  The step of producing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer includes, for example, applying an electric field between the electrodes installed on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer. And applying ultraviolet rays while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is improved.

  Thus, when ultraviolet rays are irradiated while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound represented by the above formula (1) reacts to form a polymer, and the liquid crystal molecules are formed by this polymer. Since the tilt direction is stored, the response speed of the obtained liquid crystal display element can be increased.

  Although the liquid crystal display element produced by making the liquid crystal aligning agent which forms a liquid crystal aligning film contain the polymeric compound represented by the said Formula (1) was demonstrated above, the liquid crystal display element of this invention is liquid crystal. It may be prepared by containing a polymerizable compound represented by the above formula (1). Specifically, a vertical cell comprising a liquid crystal cell having two substrates arranged to face each other, a liquid crystal layer provided between the substrates, and a liquid crystal alignment film provided between the substrate and the liquid crystal layer. An alignment type liquid crystal display element, in which a liquid crystal alignment film is formed by applying and baking a liquid crystal alignment agent on two substrates, and the two substrates are arranged so that the liquid crystal alignment films face each other. A liquid crystal layer composed of a liquid crystal containing a polymerizable compound represented by the above formula (1) is sandwiched between the two substrates, and is produced by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer. The liquid crystal display element is a vertical alignment type liquid crystal display device including a liquid crystal cell. Thus, the polymerizable compound represented by the above formula (1) is polymerized by irradiating the liquid crystal layer containing the polymerizable compound represented by the above formula (1) of the present invention with ultraviolet rays while applying a voltage. As a result, a liquid crystal display device excellent in response speed is obtained.

  The substrate is the same as the above-mentioned liquid crystal display element produced by containing the polymerizable compound represented by the above formula (1) in the liquid crystal aligning agent that forms the liquid crystal aligning film.

  The liquid crystal alignment film is formed by removing the polymerizable compound represented by the above formula (1) from the liquid crystal aligning agent of the present invention, for example, by applying a conventional liquid crystal aligning agent and baking it. The liquid crystal alignment film can be formed by the same operation as described above.

  And what contains the polymeric compound represented by the said Formula (1) is used as a liquid crystal which comprises a liquid-crystal layer. Content of the polymeric compound represented by the said Formula (1) is 0.01 mass part-0.10 mass part with respect to 100 mass parts of liquid crystals, for example. Thus, even if the content of the polymerizable compound to be contained in the liquid crystal is small, the response speed of the liquid crystal display element is sufficiently improved because the compound represented by the above formula (1) is used in the present invention. be able to. As the liquid crystal material, a liquid crystal material used in a conventional vertical alignment method such as negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck can be used.

  The method of sandwiching the liquid crystal layer between two substrates includes the liquid crystal display element prepared by adding a polymerizable compound represented by the above formula (1) to a liquid crystal aligning agent that forms a liquid crystal alignment film. It is the same.

  The process of manufacturing a liquid crystal cell by irradiating ultraviolet rays while applying a voltage to the liquid crystal layer is applied, for example, by applying a voltage between the electrodes placed on the substrate to maintain this electric field. And a method of irradiating with ultraviolet rays. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The irradiation amount of ultraviolet rays is, for example, 1 to 60 J, preferably 40 J or less, and the smaller the irradiation amount of ultraviolet rays, the lowering of reliability caused by the destruction of members constituting the liquid crystal display element can be suppressed, and the irradiation time of ultraviolet rays can be reduced. This is preferable because the manufacturing efficiency is improved.

  Thus, when ultraviolet rays are applied while applying a voltage to the liquid crystal layer, the polymerizable compound represented by the above formula (1) reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by this polymer. As a result, the response speed of the obtained liquid crystal display element can be increased.

  In addition, the liquid crystal aligning agent which forms a liquid crystal aligning film is made to contain the polymeric compound represented by the said Formula (1), and the liquid crystal is made to contain the polymeric compound represented by the said Formula (1). A liquid crystal display element may be used. In addition, both of the liquid crystal alignment films formed on the two substrates may be liquid crystal alignment films formed using a liquid crystal alignment agent containing the polymerizable compound represented by the above formula (1). Only the liquid crystal alignment film is formed using a liquid crystal aligning agent containing the polymerizable compound represented by the above formula (1), and the other liquid crystal alignment film is a polymerization represented by the above formula (1). It is good also as what was formed using the liquid crystal aligning agent which does not contain an ionic compound.

  The liquid crystal aligning agent is not only useful as a liquid crystal aligning agent for producing a vertical alignment type liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by rubbing treatment or photo-alignment treatment. It can also be suitably used for applications of the liquid crystal alignment film to be produced.

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

<Synthesis of polymerizable compound>
Example 1
Synthesis of polymerizable compound (RM1) In a 300 ml eggplant flask with a condenser tube, 6.7 g (35.9 mmol) of 4,4′-biphenol, 15.0 g of 2- (4-bromobutyl) -1,3-dioxolane (71. 7 mmol), 19.8 g (143 mmol) of potassium carbonate, and 150 ml of acetone were added to form a mixture, which was reacted at 60 ° C. for 48 hours with stirring. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Then, this solid and 200 ml of water were mixed and extracted by adding 80 ml of chloroform. Extraction was performed three times.

The separated organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. The solid was purified by recrystallization (hexane / chloroform = 4/1 (volume ratio)) to obtain 14.6 g of a white solid. The result of having measured the obtained white solid by NMR is shown below. The obtained solid was dissolved in deuterated chloroform (CDCl ₃ ) and measured at 300 MHz using a nuclear magnetic resonance apparatus (manufactured by Diol). From this result, it was confirmed that this white solid was an intermediate compound (RM1-A) represented by the following reaction formula. The yield was 92%.

¹ H-NMR (CDCl ₃ ) δ: 1.65 (m, 4H), 1.74 (m, 4H), 1.87 (m, 4H), 3.86 (m, 4 H), 3.97 (m, 8H), 4.89 (t, 2H), 6.92 (m, 4H), 7.44 (m, 4H).

[Chemical 28]

  Next, in a 500 ml eggplant flask equipped with a cooling tube, 13.3 g (30 mmol) of the intermediate compound (RM1-A) obtained above, 11.6 g (70 mmol) of 2- (bromomethyl) acrylic acid, 10% hydrochloric acid (aq ) 50 ml, tetrahydrofuran (THF) 160 ml, tin (II) chloride 13.2 g (70 mmol) was added to form a mixture, and the mixture was stirred at 70 ° C. for 20 hours for reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and extracted with 100 ml of dichlorochloro. Extraction was performed three times.

  To the separated organic layer, anhydrous magnesium sulfate was added and dried, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was purified by recrystallization (hexane / chloroform = 2/1) to obtain 9.4 g of a white solid. As a result of measuring the obtained white solid by NMR in the same manner as described above, it was confirmed that the white solid was the target polymerizable compound (RM1) represented by the following formula. The yield was 64%.

¹ H-NMR (CDCl ₃ ) δ: 1.69 (m, 12H), 2.61 (m, 2H), 3.09 (m, 2H), 4.00 (t, 4 H), 4.57 (m, 2H), 5.64 (m, 2H), 6.24 (m, 2H), 6.92 (d, 4H), 7.45 (m, 4H).

[Chemical 29]

(Example 2) Synthesis of polymerizable compound (RM2) In a 300 ml eggplant flask equipped with a cooling tube, 5.0 g (23.8 mmol) of 4,4′-biphenyldicarboxaldehyde, 7.9 g of 2- (bromomethyl) acrylic acid ( (47.6 mmol), 33 ml of 10% hydrochloric acid (aq), 100 ml of tetrahydrofuran (THF), and 9.5 g (50 mmol) of tin (II) chloride were added to form a mixture, and the reaction was stirred at 70 ° C. for 20 hours. After completion of the reaction, the reaction solution was poured into 300 ml of pure water to obtain a white solid. The obtained solid was separated and purified by recrystallization (hexane / chloroform = 2/1) to obtain 3.5 g of a white solid. As a result of measuring this solid by NMR, it was confirmed that this white solid was the target polymerizable compound (RM2) represented by the following formula. The yield was 72%.

¹ H-NMR (CDCl ₃ ) δ: 2.99 (m, 2H), 3.42 (m, 2H), 5.60 (m, 2H), 5.74 (m, 2 H), 6.36 (m, 2H), 7.42 (m, 4H), 7.60 (m, 4 H).

[Chemical 30]

(Comparative Example 1) Polymerizable compound (RM3)
A known polymerizable compound represented by the following formula was designated as RM3.

[Chemical 31]

Example 3 Synthesis of Polymerizable Compound (RM4) In a 500 ml eggplant flask equipped with a cooling tube, 11.2 g (60 mmol) of 4,4′-biphenol, 25.0 g of 2- (2-bromoethyl) -1,3-dioxolane (138 mmol), 35.9 g (260 mmol) of potassium carbonate, and 200 ml of acetone were added to form a mixture, which was reacted at 60 ° C. with stirring for 48 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a yellow wet solid. Thereafter, this solid was mixed with 200 ml of water, and extracted with 100 ml of chloroform. Extraction was performed three times.

The separated organic layer was dried by adding anhydrous magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure to obtain a yellow solid. This solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2/1) to obtain 17.6 g of a white solid. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was a compound (RM4-A) shown by the following reaction formula. The yield was 76%.
¹ H-NMR (CDCl ₃ ) δ: 2.19 (m, 4H), 3.89 (m, 4H), 4.01 (m, 4H), 4.16 (m, 4 H), 5.11 (m, 2H), 6.95 (m, 4H), 7.45 (m, 4H).

[Chemical 32]

   Next, in a 500 ml eggplant flask equipped with a condenser tube, 10.0 g (26 mmol) of the compound (RM4-A) obtained above, 10.0 g (60.6 mmol) of 2- (bromomethyl) acrylic acid, 10% HCl (aq ) 32 ml, tetrahydrofuran (THF) 140 ml, and tin (II) chloride 11.4 g (60.6 mmol) were added to form a mixture, which was stirred at 70 ° C. for 20 hours for reaction. After completion of the reaction, the reaction solution was filtered under reduced pressure, mixed with 200 ml of pure water, and extracted with 100 ml of chloroform. Extraction was performed three times.

The organic layer after extraction was dried by adding anhydrous magnesium sulfate, and the solvent was distilled off from the solution after filtration under reduced pressure to obtain a white solid. This solid was dissolved in chloroform and precipitated with hexane (hexane / chloroform = 2/1) to obtain a white solid. After this solid was washed with methanol, 4.7 g of a white solid was obtained. The result of having measured this solid by NMR is shown below. From this result, it was confirmed that this white solid was the target polymerizable compound (RM4) represented by the following reaction formula. The yield was 42%.
¹ H-NMR (CDCl ₃ ) δ: 2.18 (m, 4H), 2.76 (m, 2H), 3.16 (m, 2H), 4.18 (m, 4 H), 4.84 (m, 2H), 5.67 (m, 2H), 6.27 (m, 2H), 6.95 (d, 4H), 7.46 (m, 4H).

[Chemical 33]

<Preparation of liquid crystal aligning agent>
The abbreviations used in the preparation of the following liquid crystal aligning agents are as follows. BODA: bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride TCA: represented by the following formula 2,3,5-tricarboxycyclopentylacetic acid-1,4: 2,3-dianhydride

[Chemical 34]

m-PDA: m-phenylenediamine p-PDA: p-phenylenediamine PCH: 1,3-diamino-4- [4- (4-heptylcyclohexyl) phenoxy] benzene DBA: 3,5-diaminobenzoic acid DA-1 : 2- (methacryloyloxy) ethyl 3,5-diaminobenzoate represented by the following formula

[Chemical 35]

^{DA-2: N 1, N} 1 of the following formula - diallyl benzene-1,2,4-triamine

[Chemical 36]

 DA-3: Cholestanyl 3,5-diaminobenzoate represented by the following formula

[Chemical 37]

3-AMP: 3-aminomethylpyridine NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve

Moreover, the molecular weight measurement conditions of polyimide are as follows. Apparatus: Room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. Column: Columns manufactured by Shodex (KD-803, KD-805) Column temperature: 50 ° C. Eluent: N, N′-dimethyl Formamide (as additives, lithium bromide-hydrate (LiBr · H ₂ O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1.0 ml / min. Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (manufactured by Polymer Laboratories) Molecular weight about 12,000, 4,000, 1,000).

Moreover, the imidation ratio of polyimide was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), add 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture), and apply ultrasonic waves. To dissolve completely. 500 MHz proton NMR was measured for this solution with the NMR measuring device by the JEOL datum company (JNW-ECA500). The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing near 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value. In the following formula, x is the proton peak integrated value derived from the NH group of the amic acid, y is the peak integrated value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidation rate is 0%). This is the ratio of the number of reference protons to one.
Imidation ratio (%) = (1−α · x / y) × 100

Example 4
BODA (28.15 g, 112.5 mmol), m-PDA (4.86 g, 45 mmol), PCH (11.42 g, 30 mmol), DBA (11.41 g, 75 mmol) were mixed in NMP (187.8 g). After reacting at 80 ° C. for 5 hours, CBDA (6.77 g, 36 mmol) and NMP (62.6 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (313 g) and diluting to 6% by mass, acetic anhydride (79.1 g) and pyridine (30.7 g) were added as an imidization catalyst, and the mixture was reacted at 100 ° C. for 3 hours. This reaction solution was poured into methanol (4000 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (A). The imidation ratio of this polyimide was 70%, the number average molecular weight was 18000, and the weight average molecular weight was 59000.

  NMP (40.2 g) was added to the obtained polyimide powder (A) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. To this solution was added a 5.0 wt% NMP solution (6.0 g) of 3-AMP (0.3 g as 3-AMP), NMP (27.9 g), and BCS (20.0 g) at 50 ° C. The liquid crystal aligning agent (A1) was obtained by stirring for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred at room temperature for 3 hours. The liquid crystal aligning agent (A2) was prepared. Similarly, 0.18 g (30% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (A1), and the mixture was stirred at room temperature for 3 hours. By dissolving, a liquid crystal aligning agent (A3) was prepared.

(Example 5)
BODA (8.76 g, 35.0 mmol), p-PDA (3.78 g, 35.0 mmol), PCH (5.33 g, 14.0 mmol), DA-1 (5.55 g, 21.0 mmol) were added to NMP ( 90.0 g), and after reacting at 80 ° C. for 5 hours, CBDA (6.59 g, 33.6 mmol) and NMP (30.0 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (140.0 g) and diluting to 6% by mass, acetic anhydride (20.0 g) and pyridine (25.8 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1800 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (B). The imidation ratio of this polyimide was 50%, the number average molecular weight was 22000, and the weight average molecular weight was 77000.

  NMP (74.0 g) was added to the obtained polyimide powder (B) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (B1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (B1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (B2).

(Example 6)
BODA (3.13 g, 12.5 mmol), p-PDA (1.08 g, 10 mmol), PCH (1.90 g, 5 mmol), DA-1 (2.64 g, 10 mmol) in NMP (33.3 g). After mixing and reacting at 80 ° C. for 5 hours, CBDA (2.35 g, 12 mmol) and NMP (11.1 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (55.5 g) and diluting to 6% by mass, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (710 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (C). The imidation ratio of this polyimide was 48%, the number average molecular weight was 26000, and the weight average molecular weight was 102000.

  NMP (74.0 g) was added to the obtained polyimide powder (C) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (C1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (C1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (C2).

(Example 7)
BODA (3.13 g, 12.5 mmol), p-PDA (0.81 g, 7.5 mmol), PCH (1.90 g, 5 mmol), DA-1 (3.30 g, 12.5 mmol) and NMP (34. 5 g), the mixture was reacted at 80 ° C. for 5 hours, CBDA (2.35 g, 12 mmol) and NMP (11.5 g) were added, and the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (57.5 g) and diluting to 6% by mass, acetic anhydride (7.7 g) and pyridine (9.9 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (730 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (D). The imidation ratio of this polyimide was 50%, the number average molecular weight was 23000, and the weight average molecular weight was 63000.

  NMP (74.0 g) was added to the obtained polyimide powder (D) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0 g) was added to this solution, and the liquid crystal aligning agent (D1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (D1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (D2).

(Example 8)
BODA (5.00 g, 20 mmol), p-PDA (0.87 g, 8 mmol), PCH (3.05 g, 8 mmol), DA-1 (6.34 g, 24 mmol) were mixed in NMP (57.1 g). After reacting at 80 ° C. for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (19.0 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. After adding NMP to this polyamic acid solution (95.5 g) and diluting to 6% by mass, acetic anhydride (12.3 g) and pyridine (15.9 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (1200 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (E). The imidation ratio of this polyimide was 51%, the number average molecular weight was 31000, and the weight average molecular weight was 111000.

  NMP (74.0 g) was added to the obtained polyimide powder (E) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (E1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (E1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (E2).

Example 9
BODA (5.00 g, 20.0 mmol), p-PDA (2.16 g, 20.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (2.44 g, 12.0 mmol) were added to NMP ( 49.2 g), and after reacting at 80 ° C. for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (16.4 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (75.0 g) and diluting to 6% by mass, acetic anhydride (9.33 g) and pyridine (14.6 g) were added as an imidization catalyst and reacted at 50 ° C. for 3 hours. It was. This reaction solution was poured into methanol (950 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (F). The imidation ratio of this polyimide was 47%, the number average molecular weight was 20100, and the weight average molecular weight was 106000.

  NMP (74.0 g) was added to the obtained polyimide powder (F) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (F1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (F1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (F2).

(Example 10)
BODA (5.00 g, 20.0 mmol), p-PDA (0.87 g, 8.0 mmol), PCH (3.04 g, 8.0 mmol), DA-2 (4.88 g, 24.0 mmol) were added to NMP ( 52.7 g), and after reacting at 80 ° C. for 5 hours, CBDA (3.77 g, 19.2 mmol) and NMP (17.56 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (75g) and diluting to 6 mass%, acetic anhydride (8.7g) and pyridine (13.5g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (950 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (G). The imidation ratio of this polyimide was 50%, the number average molecular weight was 20000, and the weight average molecular weight was 86000.

  NMP (74.0 g) was added to the obtained polyimide powder (G) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (G1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM1 obtained in Example 1 was added to 10.0 g of the liquid crystal aligning agent (G1), and the mixture was stirred and dissolved at room temperature for 3 hours. Liquid crystal aligning agent (G2).

(Example 11)
TCA (3.36 g, 15.0 mmol), p-PDA (1.30 g, 12.0 mmol), DA-3 (3.14 g, 6.0 mmol), DA-1 (3.17 g, 12.0 mmol). After mixing in NMP (41.6 g) and reacting at 60 ° C. for 5 hours, CBDA (2.88 g, 14.7 mmol) and NMP (13.9 g) were added and reacted at 40 ° C. for 10 hours to polyamic acid. A solution was obtained. After adding NMP to this polyamic acid solution (68g) and diluting to 6 mass%, acetic anhydride (6.0g) and pyridine (11.7g) were added as an imidation catalyst, and it was made to react at 50 degreeC for 3 hours. This reaction solution was poured into methanol (850 ml), and the resulting precipitate was separated by filtration. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (H). The imidation ratio of this polyimide was 50%, the number average molecular weight was 18000, and the weight average molecular weight was 58,000.

  NMP (74.0 g) was added to the obtained polyimide powder (H) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (H1) was obtained by stirring at 50 degreeC for 5 hours.

  Further, 0.06 g of RM1 (10 wt% with respect to the solid content) was added to 10.0 g of the liquid crystal aligning agent (H1), and the mixture was stirred and dissolved at room temperature for 3 hours to prepare a liquid crystal aligning agent (H2). .

(Example 12)
BODA (6.01 g, 24.0 mmol), p-PDA (2.60 g, 24.0 mmol), PCH (6.85 g, 18.0 mmol), DA-1 (4.76 g, 18.0 mmol) and NMP ( 81.5 g), and after reacting at 80 ° C. for 5 hours, CBDA (6.94 g, 35.4 mmol) and NMP (27.2 g) were added and reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution. Obtained. After adding NMP to this polyamic acid solution (135 g) and diluting to 6% by mass, acetic anhydride (18.3 g) and pyridine (23.6 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was poured into methanol (1700 ml), and the resulting precipitate was filtered off. This deposit was wash | cleaned with methanol, and it dried under reduced pressure at 100 degreeC, and obtained the polyimide powder (I). The imidation ratio of this polyimide was 60%, the number average molecular weight was 12000, and the weight average molecular weight was 39000.

  NMP (74.0 g) was added to the obtained polyimide powder (I) (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 12 hours. BCS (20.0g) was added to this solution, and the liquid crystal aligning agent (I1) was obtained by stirring at 50 degreeC for 5 hours.

  0.06 g (10% by mass with respect to the solid content) of the polymerizable compound (RM4) obtained above was added to 10.0 g of the liquid crystal aligning agent (I1) and dissolved by stirring at room temperature for 3 hours. A liquid crystal aligning agent (I2) was prepared.

<Preparation of liquid crystal containing polymerizable compound>
A liquid crystal containing a polymerizable compound was prepared as follows. 0.0147 g (3 × 10 ⁻⁵ mol) of the polymerizable compound RM1 obtained in Example 1 was added to 20 g of MLC-6608 (trade name, manufactured by Merck), and the mixture was stirred and dissolved at 80 ° C. for 3 hours. Liquid crystal 1 was prepared.

Similarly, 0.0097 g (3 × 10 ⁻⁵ mol) of the polymerizable compound RM2 obtained in Example 2 was added to 20 g of MLC-6608, and the mixture was stirred and dissolved at 80 ° C. for 3 hours. Prepared.

Further, 0.0097 g (3 × 10 ⁻⁵ mol) of the polymerizable compound RM3 obtained in Comparative Example 1 was added to 20 g of MLC-6608, and the mixture was stirred and dissolved at 80 ° C. for 3 hours to prepare liquid crystal 3. did.

  In addition, as for the liquid crystal 1, the liquid crystal 2, and the liquid crystal 3, it confirmed that the polymeric compound was melt | dissolving in the liquid crystal material MLC-6608, respectively, and a polymeric compound did not precipitate even after 1 month of refrigeration storage.

<Production of liquid crystal cell>
(Example 13)
Using the liquid crystal aligning agent (A1) obtained in Example 4, a liquid crystal cell was prepared according to the procedure shown below. The liquid crystal aligning agent (A1) obtained in Example 4 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, and the temperature was 80 ° C. After drying for 90 seconds on this hot plate, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

  Moreover, after spin-coating the liquid crystal aligning agent (A1) on the ITO surface in which the electrode pattern is not formed, and drying for 90 seconds on a hot plate at 80 ° C., baking is performed in a hot air circulation oven at 200 ° C. for 30 minutes, A liquid crystal alignment film having a thickness of 100 nm was formed.

  After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. The liquid crystal 1 was injected into this empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (realignment treatment of liquid crystal by heating) in an oven at 120 ° C., thereby producing a liquid crystal cell.

  The response speed immediately after production of the obtained liquid crystal cell was measured by the following method. After that, in a state where a voltage of 20 Vp-p was applied to the liquid crystal cell, UV irradiation through a band-pass filter of 313 nm was irradiated from the outside of the liquid crystal cell at 5 J. Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Table 2 shows the results of the response speed immediately after the production of the liquid crystal cell (initial stage) and after UV irradiation (after UV irradiation).

"Response speed measurement method"
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave with a voltage of ± 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0% and ± 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.

(Example 14)
The same operation as in Example 13 was performed except that the liquid crystal 2 was used in place of the liquid crystal 1, and the response speeds before and after UV irradiation were compared.

(Comparative Example 2)
Except that the liquid crystal 3 was used instead of the liquid crystal 1, the same operation as in Example 13 was performed to compare the response speed before and after UV irradiation.

(Example 15)
The same operation as in Example 13 except that the liquid crystal aligning agent (A2) was used instead of the liquid crystal aligning agent (A1), MLC-6608 was used instead of the liquid crystal 1, and 20 J irradiation was performed instead of UV irradiation at 5 J. The response speed before and after UV irradiation was compared.

(Example 16)
Except for using the liquid crystal aligning agent (A3) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed to compare the response speed before and after UV irradiation.

(Comparative Example 3)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (A1) was used instead of the liquid crystal aligning agent (A2).

(Example 17)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (B2) was used instead of the liquid crystal aligning agent (A2).

(Comparative Example 4)
Except for using the liquid crystal aligning agent (B1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.

(Example 18)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (C2) was used instead of the liquid crystal aligning agent (A2).

(Comparative Example 5)
Except that the liquid crystal aligning agent (C1) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.

(Example 19)
Except that the liquid crystal aligning agent (D2) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.

(Comparative Example 6)
Except for using the liquid crystal aligning agent (D1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.

(Example 20)
Except that the liquid crystal aligning agent (E2) was used instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speed before and after UV irradiation was compared.

(Comparative Example 7)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (E1) was used instead of the liquid crystal aligning agent (A2).

(Example 21)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (F2) was used instead of the liquid crystal aligning agent (A2).

(Comparative Example 8)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (F1) was used instead of the liquid crystal aligning agent (A2).

(Example 22)
Except for using the liquid crystal aligning agent (G2) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.

(Comparative Example 9)
Except for using the liquid crystal aligning agent (G1) instead of the liquid crystal aligning agent (A2), the same operation as in Example 15 was performed, and the response speeds before and after UV irradiation were compared.

(Example 23)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (H2) was used instead of the liquid crystal aligning agent (A2).

  As a result, as shown in Table 2, Example 13 and Example 14 in which the polymerizable compound represented by the above formula (1) was contained in the liquid crystal showed a response speed after ultraviolet irradiation with respect to a response speed before ultraviolet irradiation. The improvement rate of was significantly higher than that of Comparative Example 2 containing a conventional polymerizable compound. Therefore, it was confirmed that the response speed can be greatly improved by containing the polymerizable compound represented by the above formula (1) in the liquid crystal even if the amount of the polymerizable compound added to the liquid crystal is small.

  And Example 13 using the polymerizable compound in which V and W are oxyalkylene groups in the above formula (1) is an example using the polymerizable compound in which V and W are single bonds in the above formula (1). The response rate improvement rate was significantly higher than 14.

  Further, in Examples 15 to 23 in which the polymerizable compound represented by the above formula (1) was contained in the liquid crystal aligning agent, the improvement rate of the response speed before and after the ultraviolet irradiation was expressed by the above formula (1). Compared with Comparative Examples 3 to 9 which did not contain the represented polymerizable compound, it was significantly higher. Therefore, it was confirmed that the response speed can be significantly improved by incorporating the polymerizable compound represented by the above formula (1) into the liquid crystal aligning agent. And in any of Examples 15-23 which changed the kind of polyimide, it was confirmed that the improvement rate of a response speed becomes high compared with the corresponding comparative example.

  Further, Example 16 in which the addition amount of the polymerizable compound represented by the above formula (1) was 30% by mass had a higher response speed improvement rate than Example 15 in which the addition amount was 10% by mass. . Therefore, it was confirmed that the response speed was improved as the amount of the polymerizable compound represented by the formula (1) was increased.

  In Examples 17 to 23 using a polyimide having a photoreactive group, the response speed is remarkably improved as compared with Example 15 using a polyimide having no photoreactive group. It was confirmed that the response speed was further improved by using a polyimide having.

[Table 2]

(Example 24)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM2 obtained in Example 2 was added to 10.0 g of the liquid crystal aligning agent (D1), and stirred and dissolved at room temperature for 3 hours. A liquid crystal aligning agent (D3) was prepared.

(Comparative Example 10)
0.06 g (10% by mass with respect to the solid content) of the polymerizable compound RM3 of Comparative Example 1 is added to 10.0 g of the liquid crystal aligning agent (D1), and the mixture is stirred and dissolved at room temperature for 3 hours. (D4) was prepared.

(Example 25)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 19 except that the liquid crystal aligning agent (D3) was used instead of the liquid crystal aligning agent (D2). The results are shown in Table 3.

(Example 26)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 25 except that the baking in the heat circulation oven was performed at 200 ° C. for 30 minutes instead of 30 minutes at 160 ° C.

(Comparative Example 11)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 25 except that the liquid crystal aligning agent (D4) was used instead of the liquid crystal aligning agent (D3).

(Comparative Example 12)
The response speed before and after UV irradiation was compared by performing the same operation as in Comparative Example 11 except that the baking in the heat circulating oven was performed at 200 ° C. for 30 minutes instead of 30 minutes at 160 ° C.

(Example 27)
The response speed before and after UV irradiation was compared by performing the same operation as in Example 15 except that the liquid crystal aligning agent (I2) was used instead of the liquid crystal aligning agent (A2).

(Example 28)
Except for changing the baking temperature from 200 ° C. to 140 ° C., the same operation as in Example 27 was performed, and the response speed before and after UV irradiation was compared.

(Comparative Example 13)
Except for using the liquid crystal aligning agent (I1) instead of the liquid crystal aligning agent (I2), the same operation as in Example 27 was performed to compare the response speed before and after UV irradiation.

(Comparative Example 14)
Except for changing the firing temperature from 200 ° C. to 140 ° C., the same operation as in Comparative Example 13 was performed to compare the response speed before and after UV irradiation.

  As a result, in Examples 25 to 28 using the liquid crystal aligning agent containing the polymerizable compound represented by the above formula (1), it was confirmed that sufficient response speed was improved by UV irradiation regardless of the firing temperature. It was. On the other hand, in the comparative example using the liquid crystal aligning agent containing RM3 which is a conventional polymerizable compound, in the comparative example 11 having a baking temperature of 160 ° C., a sufficient response speed is improved by UV irradiation. In Comparative Example 12 in which the temperature was 200 ° C., the improvement rate of the response speed was significantly reduced. Moreover, in Comparative Example 13 and Comparative Example 14 using a liquid crystal aligning agent to which no polymerizable compound was added, the response speed before and after the ultraviolet irradiation was almost the same at any firing temperature.

[Table 3]

Abbreviations used below are as follows.
TEOS: tetraethoxysilane C18: octadecyltriethoxysilane ACPS: 3-acryloxypropyltrimethoxysilane UPS: 3-ureidopropyltriethoxysilane MPMS: 3-methacryloxypropyltrimethoxysilane VTES: triethoxyvinylsilane NMP: N-methyl -2-pyrrolidone HG: 2-methyl-2,4-pentanediol (also known as hexylene glycol)
BCS: 2-butoxyethanol

<Production of polysiloxane-based liquid crystal aligning agent>
(Comparative Example 15)
A solution of alkoxysilane monomer was prepared by mixing 24.5 g of BCS, 32.4 g of TEOS, and 1.34 g of C18 in a 100 mL four-neck reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by previously mixing 12.3 g of BCS, 8.65 g of water and 0.14 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and a mixed solution of methanol solution having a UPS content of 92% by mass and 0.44 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.

38.0 g of the obtained polysiloxane solution, 3.63 g of BCS, and 49.6 g of NMP were mixed to obtain a liquid crystal aligning agent (a) having a SiO ₂ equivalent concentration of 5 mass%.

(Example 29)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 10% by mass and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Example 30)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 20% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Example 31)
The polymerizable compound RM2 was added to the liquid crystal aligning agent (a) obtained in Comparative Example 15 so as to be 10% by mass and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Comparative Example 16)
In a 100 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 24.5 g of BCS, 25.7 g of TEOS, 1.33 g of C18, and 6.09 g of VTES were mixed to prepare a solution of an alkoxysilane monomer. A solution prepared by previously mixing 12.3 g of BCS, 8.64 g of water and 0.72 g of oxalic acid as a catalyst was added dropwise to this solution at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and a mixed solution of methanol solution having a UPS content of 92% by mass and 0.44 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.

38.0 g of the obtained polysiloxane solution, 3.63 g of BCS, and 49.6 g of NMP were mixed to obtain a liquid crystal aligning agent (b) having a SiO ₂ equivalent concentration of 5 mass%.

(Example 32)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (b) obtained in Comparative Example 16 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Example 33)
The polymerizable compound RM2 was added to the liquid crystal aligning agent (b) obtained in Comparative Example 16 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Comparative Example 17)
A solution of alkoxysilane monomer was prepared by mixing 23.3 g of BCS, 22.3 g of TEOS, 1.33 g of C18, and 11.3 g of ACPS in a 100 mL four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution prepared by previously mixing 11.6 g of BCS, 8.64 g of water and 0.72 g of oxalic acid as a catalyst was added dropwise at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and a mixed solution of methanol solution having a UPS content of 92% by mass and 0.44 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.

38.0 g of the obtained polysiloxane solution, 4.24 g of BCS, and 49.0 g of NMP were mixed to obtain a liquid crystal aligning agent (c) having a SiO ₂ equivalent concentration of 5 mass%.

(Example 34)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (c) obtained in Comparative Example 17 so as to be 5% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Example 35)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (c) obtained in Comparative Example 17 so as to be 10% by mass, and the mixture was stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Comparative Example 18)
Polymerizable compound RM3 was added to the liquid crystal aligning agent (c) obtained in Comparative Example 17 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Comparative Example 19)
A solution of an alkoxysilane monomer was prepared by mixing 23.4 g of BCS, 25.7 g of TEOS, 1.33 g of C18, and 7.95 g of MPMS in a 100 mL four-necked reaction flask equipped with a thermometer and a reflux tube. To this solution, a solution in which 11.7 g of BCS, 8.64 g of water and 0.58 g of oxalic acid as a catalyst were mixed in advance was added dropwise at room temperature over 30 minutes. The solution was stirred for 30 minutes and then refluxed for 30 minutes, and a mixed solution of methanol solution having a UPS content of 92% by mass and 0.44 g of BCS was added in advance. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution having a SiO ₂ equivalent concentration of 12% by mass.

38.0 g of the obtained polysiloxane solution, 4.20 g of BCS, and 49.0 g of NMP were mixed to obtain a liquid crystal aligning agent (d) having a SiO ₂ equivalent concentration of 5 mass%.

(Example 36)
The polymerizable compound RM1 was added to the liquid crystal aligning agent (d) obtained in Comparative Example 19 so as to be 5% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Example 37)
Polymerizable compound RM1 was added to the liquid crystal aligning agent (d) obtained in Comparative Example 19 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

(Comparative Example 20)
Polymerizable compound RM3 was added to the liquid crystal aligning agent (d) obtained in Comparative Example 19 so as to be 10% by mass, and stirred at room temperature for 5 hours to prepare a varnish (liquid crystal aligning agent).

<Production of liquid crystal cell>
(Example 38)
Using the varnish (liquid crystal aligning agent) obtained in Example 29, a liquid crystal cell was prepared according to the procedure shown below. First, the varnish obtained in Example 29 was spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm was formed, and a hot plate at 80 ° C. After drying for 5 minutes, baking was performed in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

  The liquid crystal aligning agent (a) obtained in Comparative Example 15 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on an 80 ° C. hot plate for 5 minutes, and then heated at 200 ° C. in a hot air circulation oven. Was baked for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

  After spraying a 6 μm bead spacer on the liquid crystal alignment film of one of the two substrates, a sealant (solvent type thermosetting epoxy resin) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was faced inward and bonded to the previous substrate, and then the sealing agent was cured to produce an empty cell. Liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected into the empty cell by a reduced pressure injection method, and was subjected to Isotropic treatment (liquid crystal realignment treatment by heating) in an oven at 120 ° C., thereby producing a liquid crystal cell.

  The response speed immediately after production of the obtained liquid crystal cell was measured by the following method. After that, with a voltage of 20 Vp-p applied to the liquid crystal cell, 10 J UV irradiation through a 313 nm band pass filter was applied from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after UV irradiation was compared. Table 4 shows the results of response speed immediately after the production of the liquid crystal cell (initial stage), after UV irradiation for 5J (after UV5J) and after UV irradiation for 10J (after UV10J).

"Response speed measurement method"
First, a liquid crystal cell was arranged between a pair of polarizing plates in a measuring device configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector. At this time, the ITO electrode pattern in which the line / space was formed was at an angle of 45 ° with respect to the crossed Nicols. Then, a rectangular wave with a voltage of ± 4 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the change until the luminance observed by the light amount detector is saturated is captured by an oscilloscope, and the luminance when no voltage is applied is obtained. A voltage of 0% and ± 4 V was applied, the saturated luminance value was set to 100%, and the time taken for the luminance to change from 10% to 90% was defined as the response speed.

(Example 39)
The same operation as in Example 38 was performed except that the varnish obtained in Example 30 was used instead of the varnish obtained in Example 29.

(Example 40)
The same operation as in Example 38 was performed except that the varnish obtained in Example 31 was used instead of the varnish obtained in Example 29.

(Example 41)
The same operation as in Example 38 was performed except that the varnish obtained in Example 32 was used instead of the varnish obtained in Example 29.

(Example 42)
The same operation as in Example 38 was performed except that the varnish obtained in Example 33 was used instead of the varnish obtained in Example 29.

(Example 43)
The same operation as in Example 38 was performed except that the varnish obtained in Example 34 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.

(Example 44)
The same operation as in Example 38 was performed except that the varnish obtained in Example 35 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.

(Example 45)
The same operation as in Example 38 was performed except that the varnish obtained in Example 36 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.

(Example 46)
The same operation as in Example 38 was performed except that the varnish obtained in Example 37 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.

(Comparative Example 21)
The same operation as in Example 38 was performed except that the liquid crystal aligning agent (a) obtained in Comparative Example 15 was used instead of the varnish obtained in Example 29.

(Comparative Example 22)
The same operation as in Example 38 was performed except that the liquid crystal aligning agent (b) obtained in Comparative Example 16 was used instead of the varnish obtained in Example 29.

(Comparative Example 23)
The same procedure as in Example 38 was performed, except that the liquid crystal aligning agent (c) obtained in Comparative Example 17 was used instead of the varnish obtained in Example 29, and 5 J was irradiated instead of 10 J with UV irradiation. It was.

(Comparative Example 24)
The same operation as in Example 38 was performed except that the varnish obtained in Comparative Example 18 was used instead of the varnish obtained in Example 29, and 5 J was irradiated instead of 10 J with UV irradiation.

(Comparative Example 25)
The same procedure as in Example 38 was performed, except that the liquid crystal aligning agent (d) obtained in Comparative Example 19 was used instead of the varnish obtained in Example 29, and 5 J was irradiated instead of 10 J with UV irradiation. It was.

(Comparative Example 26)
The same operation as in Example 38 was performed except that the varnish obtained in Comparative Example 20 was used in place of the varnish obtained in Example 29 and that 5J was irradiated instead of 10J with UV irradiation.

  As a result, as shown in Table 4, in Examples 38 to 46 using the liquid crystal aligning agent containing the polymerizable compound represented by the above formula (1), the response rate improvement rate before and after the ultraviolet irradiation was Comparative Examples 21 to 23 and 25 using a liquid crystal aligning agent not containing a polymerizable compound and comparison using a liquid crystal aligning agent containing a polymerizable compound which is not a polymerizable compound represented by the above formula (1) Compared to Examples 24 and 26, it was significantly higher. Therefore, it was confirmed that the response speed can be significantly improved by incorporating the polymerizable compound represented by the above formula (1) into the liquid crystal aligning agent. And in any of Examples 38-46 which changed the kind of polysiloxane, it was confirmed that the improvement rate of a response speed becomes high compared with the corresponding comparative example.

  It was also confirmed that the response speed was improved as the amount of the polymerizable compound represented by the formula (1) was increased.

  And Examples 41-46 using the polysiloxane which has a photoreactive group have improved the response speed notably compared with Examples 38-40 using the polysiloxane which does not have a photoreactive group, It was confirmed that the response speed was further improved by using a polysiloxane having a photoreactive group.

  Thus, by using the liquid crystal aligning agent of the present invention containing the polymerizable compound represented by the above formula (1), it is confirmed that the response speed can be increased without including the polymerizable compound in the liquid crystal. It was. And in this liquid crystal aligning agent of this invention, even if it did not add a polymeric compound in large quantities, and it was also confirmed that a response speed can be made quick enough, without increasing the irradiation amount of an ultraviolet-ray. .

[Table 4]

ADVANTAGE OF THE INVENTION According to this invention, the novel polymeric compound which can improve the response speed of the liquid crystal display element of a vertical alignment system can be provided. By using this polymerizable compound, it is possible to provide a vertical alignment type liquid crystal display element having a high response speed. And in this liquid crystal aligning agent, even when the addition amount of a polymeric compound is small, or even when the irradiation amount of an ultraviolet-ray is small, a response speed can fully be improved.
The liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention is a liquid crystal capable of obtaining characteristics equivalent to those of the PSA method even when a liquid crystal to which no polymerizable compound is added is used in the PSA method. A display element can be provided. As a result, it is useful for PSA TFT (Thin Film Transistor) liquid crystal display elements, TN (Twisted Nematic) liquid crystal display elements, VA liquid crystal display elements, and the like.

Claims (3)

A polymerizable compound represented by the following formula (1):

(In the formula (1), V is a single bond or -R ¹ O-, R ¹ is a linear or branched alkylene group having 1 to 10 carbon atoms, and W is a single bond or -OR ^2-. R ² is a linear or branched alkylene group having 1 to 10 carbon atoms, provided that when one of V and W is a single bond, the other is a single bond or —R ¹ O— or —OR ² —. R ¹ or R ² is a linear or branched alkylene group having 1 to 3 carbon atoms.) A liquid crystal cell produced by containing the polymerizable compound according to claim 1 in a liquid crystal or a liquid crystal alignment film, and irradiating ultraviolet rays while applying a voltage thereto to form a polymer of the polymerizable compound. A liquid crystal display element. A method for producing a liquid crystal display element , comprising incorporating the polymerizable compound according to claim 1 in a liquid crystal or a liquid crystal alignment film, and irradiating ultraviolet rays while applying a voltage thereto to produce a liquid crystal cell.