WO2014196540A1

WO2014196540A1 - Alkoxysilane compound, liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element

Info

Publication number: WO2014196540A1
Application number: PCT/JP2014/064767
Authority: WO
Inventors: 大輔佐久間; 章吾檜森
Original assignee: 日産化学工業株式会社
Priority date: 2013-06-06
Filing date: 2014-06-03
Publication date: 2014-12-11
Also published as: KR102344233B1; CN105452262A; TWI620753B; TW201509952A; JP6398973B2; JPWO2014196540A1; KR20160018597A

Abstract

Provided are an alkoxysilane that is used as a material for liquid crystal alignment films or the like, and a method for producing said alkoxysilane. An alkoxysilane represented by formula (1), wherein a ring structure is linked by an amide bond. (In the formula, Z¹, Z² and Z³ each represent a linear or branched C1-4 hydrocarbon group or the like; Z⁴ represents H, a methyl group or the like; Y¹ represents a single bond, -C(CH₃)=CH- or the like; Cy¹ represents a phenylene group or the like; Cy² represents a phenylene group or the like; Z⁵ represents H, a linear or branched C1-18 hydrocarbon group or the like; a represents an integer of 1-18; m represents 1 or 2; and n represents 0, 1 or 2.)

Description

Alkoxysilane compound, liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to an alkoxysilane compound, a method for producing the same, a liquid crystal aligning agent containing the alkoxysilane compound, a liquid crystal alignment film, and a liquid crystal display element.

In recent years, among liquid crystal display elements, vertical alignment (VA) liquid crystal display elements are widely used for large-screen liquid crystal televisions and high-definition mobile applications (displays for digital cameras and mobile phones). ing. The VA method includes an MVA method (Multi-Vertical Alignment) in which protrusions for controlling the direction in which the liquid crystal is tilted are formed on the TFT substrate or the color filter substrate, and a direction in which the liquid crystal is tilted by forming an slit in the ITO electrode of the substrate. There is known a PVA (Patterned Vertical Alignment) method for controlling the above. Another alignment method is a PSA (Polymer Sustained Alignment) method.

Among the VA methods, the PSA method is a technology that has attracted attention in recent years. This method increases the response speed of the liquid crystal by adding a photopolymerizable compound to the liquid crystal composition and applying a voltage to the liquid crystal panel to irradiate the liquid crystal with ultraviolet rays after the liquid crystal panel is tilted. Technology (see Patent Document 1). When a liquid crystal cell prepared using a liquid crystal composition containing a photopolymerizable compound and a liquid crystal alignment film made of polyimide or the like was irradiated with ultraviolet rays while applying a voltage, a photopolymerization reaction occurred and the liquid crystal molecules were tilted. A polymer structure in which the direction is memorized is formed on the liquid crystal alignment film. As a result, the alignment direction of the liquid crystal is fixed and a pretilt is generated, so that a liquid crystal display element having a better response speed can be obtained as compared with the method of controlling the inclination direction of the liquid crystal molecules only by the protrusions and slits.

This PSA method can be operated even in a structure in which a slit is formed in one electrode constituting a liquid crystal panel, and a protrusion such as MVA or a slit such as PVA is not provided in the opposite electrode pattern. It has a feature that simplification and excellent panel transmittance can be obtained (see Patent Document 2).

However, the PSA type liquid crystal display element has a problem that the solubility of the photopolymerizable compound added to the liquid crystal is low, and when the addition amount is increased, it is precipitated at a low temperature. On the other hand, if the addition amount of the photopolymerizable compound is reduced, a good alignment state and response speed cannot be obtained. In addition, the unreacted photopolymerizable compound remaining in the liquid crystal becomes an impurity in the liquid crystal, which causes a problem of reducing the reliability of the liquid crystal display element.

Therefore, a liquid crystal alignment agent using a polymer in which a photoreactive side chain is introduced into a polymer molecule is applied to a substrate, and a liquid crystal layer in contact with the liquid crystal alignment film obtained by baking is provided. A method has been developed in which a liquid crystal display element can be obtained by irradiating ultraviolet rays while applying a voltage to obtain a liquid crystal display element having a high response speed without adding a photopolymerizable compound to the liquid crystal. .

On the other hand, as a material for the liquid crystal alignment film, an inorganic liquid crystal alignment film material is known together with a conventionally used organic liquid crystal alignment film material such as polyimide. For example, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, trialkoxysilane, alcohol, and oxalic acid has been proposed as a material for a coating-type inorganic alignment film. It is reported that a liquid crystal alignment film having excellent vertical alignment properties, heat resistance and uniformity is formed (see Patent Document 4).

In addition, a liquid crystal aligning agent composition containing a reaction product of tetraalkoxysilane, specific trialkoxysilane and water and a specific glycol ether solvent has been proposed. By using such a liquid crystal aligning agent composition, display defects are prevented, afterimage characteristics are good even after long-time driving, the ability to align the liquid crystal does not decrease, and the decrease in voltage holding ratio against light and heat is small. Forming a liquid crystal alignment film has been reported (see Patent Document 5).

It is known that polysiloxane obtained by polycondensation of an alkoxysilane compound can be used as a component of a liquid crystal alignment film material. In particular, it has been reported that in a VA liquid crystal display element, good vertical alignment can be imparted by using an alkoxysilane compound having a ring structure (see Patent Documents 6, 7, and 8).

The alkoxysilane compound having this ring structure has a part containing one or more phenylene group, cyclohexylene group, etc., and the part and the alkoxysilyl group are directly connected or connected through an ether bond. What you are doing. As a method for producing such a compound, a Grignard reaction between a cyclic compound having a halide site and an alkoxysilane, a hydrosilylation reaction between a cyclic compound having a carbon-carbon unsaturated bond site and a hydrosilane, or the like is used. (See Patent Documents 6 and 7).

However, all of these reactions involve generation of impurities derived from by-products and reaction reagents. Therefore, complicated purification operations must be performed to isolate the target product with high purity, and production efficiency is low. There's a problem. For example, when the target product is liquid, distillation is often performed as a purification operation, but the boiling point difference between the target product and the by-product is not so large, and it takes a lot of time to separate the by-product. It is a difficult point that a thing and a yield fall. In addition, the target product having a large molecular weight does not reach the boiling point even under high vacuum and high temperature conditions, and distillation itself is physically impossible. I have to do it.

On the other hand, when the target product is solid, recrystallization is usually performed as a purification operation. However, as a general property of the alkoxysilane compound, crystallinity is remarkably low. Product removal is extremely difficult. Therefore, as described above, column chromatography with extremely low production efficiency must be performed as a purification operation.

Japanese Unexamined Patent Publication No. Sho 61-286393 WO2012-165354 Japanese Unexamined Patent Publication No. 2012-159826 Japanese Unexamined Patent Publication No. 09-281502 Japanese Unexamined Patent Publication No. 2005-250244 Japanese Unexamined Patent Publication No. 2003-307720 Japanese Unexamined Patent Publication No. 2004-302061 WO2010 / 074269

The present invention has been made in view of such circumstances, an alkoxysilane compound having high production efficiency and excellent vertical alignment when used as a component of a liquid crystal alignment film material, a method for producing the same, and It aims at providing the liquid crystal aligning agent obtained by using this alkoxysilane compound, a liquid crystal aligning film, and a liquid crystal display element.

As a result of intensive studies to achieve the above object, the present inventors have obtained a novel alkoxysilane compound in which the ring structure is linked by an amide bond, and a carboxylic acid having a ring structure as a method for producing the compound. By reacting the acid chloride obtained by the treatment with a chlorinating agent and an amino group-containing alkoxysilane compound, almost no by-products are generated, and no purification is performed. A method for obtaining the product was found. Furthermore, when the said compound was used as a structural component of liquid crystal aligning film material, it discovered that favorable vertical alignment property was exhibited, and came to complete this invention.

The present invention is based on such knowledge and has the following gist.
1. An alkoxysilane compound represented by the following formula [1] and having a ring structure linked by an amide bond.

(In the formula [1], Z ¹ , Z ² and Z ³ are each independently R ¹ , OR ¹ or OCOR ¹ (R ¹ is a linear or branched hydrocarbon having 1 to 4 carbon atoms) Group except that Z ¹ , Z ² and Z ³ are all R ^1. a is an integer of 1 to 18. m is 1 or 2. Z ⁴ is H, .Y ¹ is a methyl group or a phenyl group, a single ^{^{bond, -R 2 O -, - R}} 2 OCO -, - R 2 COO -, - CH = CH -, - C (CH 3) = CH- or - C≡C— (R ² is a linear or branched hydrocarbon group having 1 to 3 carbon atoms) Cy ¹ is a divalent cyclic group selected from a phenylene group, a naphthylene group, and a cyclohexylene group. or .Cy ² is an organic group having a carbon number of 12-40 with a steroid skeleton, a phenylene group, a naphthylene group and a cyclohexylene group Divalent any hydrogen atom present on the cyclic group [Cy ¹ and Cy ² in the selected La, F, CN, OH, ^{R 3} and ^OR 3 ^{(R 3} is a straight-chain having 1 to 4 carbon atoms Or may be substituted with a group selected from a branched hydrocarbon group or a linear or branched fluorine-containing hydrocarbon group having 1 to 4 carbon atoms.] N is 0, 1 or 2 Z ⁵ is H, CN, R ⁴ or OR ⁴ (R ⁴ is a linear or branched hydrocarbon group having 1 to 18 carbon atoms, or a linear or branched fluorine atom having 1 to 18 carbon atoms. (However, when Cy ¹ is a C 12-40 organic group having a steroid skeleton, n is 0 and Z ⁵ is unsubstituted.)
2. 2. The alkoxysilane compound according to 1 above, wherein a is 3 and m is 1.
3. 2. The alkoxysilane compound according to 1 above, wherein a is 3, m is 1, Z ⁴ is H, and Y ¹ is a single bond.
4). By treating the carboxylic acid represented by the following formula [2] with a chlorinating agent to obtain an acid chloride represented by the following formula [3], the acid chloride and the following formula [4] are represented. The method for producing an alkoxysilane compound according to the above 1, wherein the alkoxysilane compound is reacted in the presence of a base.

In consideration of industrial applicability, it is preferable that a is 3 and m is 1 which is manufactured from an industrially inexpensive and available raw material. In addition, it is manufactured in a short synthesis step. More preferably, a is 3, m is 1, Z ⁴ is H, and Y ¹ is a single bond.

(In formula [2], Y ¹ , Cy ¹ , Cy ² , Z ⁵ and n have the same meaning as described above.)

(In formula [3], Y ¹ , Cy ¹ , Cy ² , Z ⁵ and n represent the same meaning as described above.)

(In the formula [4], Z ¹ , Z ² , Z ³ , Z ⁴ , a and m have the same meaning as described above.)

5. 5. The production method according to 4 above, wherein a is 3 and m is 1.
6). 5. The production method according to 4 above, wherein a is 3, m is 1, Z ⁴ is H, and Y ¹ is a single bond.
7). A polysiloxane obtained by polycondensation of the alkoxysilane compound described in 1 above.
8). 8. The polysiloxane as described in 7 above, wherein the content of the alkoxysilane described in 1 is 1 to 30 mol% in the total alkoxysilane.
9. 9. A liquid crystal aligning agent containing the polysiloxane as described in 7 or 8 above.
10. 10. The liquid crystal aligning agent according to 9 above, wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO ₂ concentration.
11. The liquid crystal aligning film obtained by apply | coating the liquid crystal aligning agent of said 9 or 10 to a board | substrate, drying and baking.
12 12. A liquid crystal display device having the liquid crystal alignment film as described in 11 above.
13. 11. A liquid crystal display element obtained by irradiating a liquid crystal cell, in which a liquid crystal is sandwiched between two substrates fired by applying the liquid crystal aligning agent described in 9 or 10 above, with ultraviolet rays applied to a liquid crystal cell.
14 A method for producing a liquid crystal display element, wherein the liquid crystal aligning agent according to 9 or 10 above is applied, the liquid crystal is sandwiched between two baked substrates, and ultraviolet rays are irradiated in a state where a voltage is applied.

According to the present invention, an alkoxysilane compound having a ring structure can be obtained with high production efficiency, and when the alkoxysilane compound is used as a constituent component of a liquid crystal alignment film material, it is equivalent to a similar compound that has been conventionally used. The vertical alignment of Moreover, the alkoxysilane compound obtained by this invention and the polysiloxane obtained by using the same can be suitably used not only for liquid crystal alignment film materials but also for various functional materials.

Hereinafter, the present invention will be described in more detail.
<Alkoxysilane compound>
As shown in the following [Reaction Formula 1], the alkoxysilane compound of the present invention represented by the formula [1] (alkoxysilane compound [1]) converts a carboxylic acid [2] having a ring structure into a chlorinating agent. It can be produced by derivatization to the corresponding acid chloride [3] by chlorination reaction with an alkoxy group [4] containing an amino group and an amidation reaction in the presence of a base.

(In the formula, Y ¹ , Cy ¹ , Cy ² , Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , a, m, and n represent the same meaning as described above.)

<Chlorination reaction>
Hereinafter, the reaction conditions in the chlorination reaction of [Reaction Formula 1] and details of the post-treatment operation will be described.
Examples of the chlorinating agent include thionyl chloride, oxalyl chloride, phosgene, chlorine, phosphorus oxychloride, phosphorus pentachloride, etc., preferably thionyl chloride, oxalyl chloride, or phosgene, more preferably thionyl chloride. It is. The amount of the chlorinating agent is usually 1 to 100 times mol, preferably 1 to 30 times mol, more preferably 2 to 15 times mol with respect to the carboxylic acid [2].

The chlorination reaction can be carried out without a solvent, but a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl Examples include ethers such as ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof. , Hexane, heptane, or toluene, more preferably toluene.

The chlorination reaction proceeds without a catalyst, but the progress can be accelerated by adding a catalyst. Examples of the catalyst include organic bases such as triethylamine, pyridine, quinoline, N, N-dimethylaniline or N, N-dimethylformamide, and metal alkoxides such as sodium methoxide, potassium methoxide or potassium t-butoxide. Preferred is triethylamine, pyridine, or N, N-dimethylformamide, and more preferred is N, N-dimethylformamide. The amount of the catalyst is usually 0 to 10 times mol, preferably 0.001 to 1 times mol, more preferably 0.005 to 0.1 times mol, relative to the carboxylic acid [2].

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −30 to 100 ° C., more preferably 50 to 80 ° C.
The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 20 hours, more preferably 0.5 to 5 hours.

The acid chloride [3] obtained as described above can be isolated by distilling off the chlorinating agent and the solvent remaining in the reaction solution under reduced pressure. The isolated acid chloride [3] has a sufficiently good purity, but in the case of liquid, it can be purified by distillation, and in the case of solid, it can be further purified by washing or recrystallization using a solvent. You can also

The solvent used for washing is not particularly limited. For example, hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4 -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof, preferably hexane, heptane or toluene And more preferably heptane.

The solvent used for recrystallization is not particularly limited as long as the acid chloride [3] dissolves upon heating and precipitates upon cooling. For example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1,2-dichloroethane or chlorobenzene Halogenated hydrocarbons such as, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and These mixtures are mentioned, Preferably they are hexane, heptane, or toluene, More preferably, it is heptane.

<Amidation reaction>
Hereinafter, the reaction conditions in the amidation reaction of [Reaction Formula 1] and details of the post-treatment operation will be described.
Examples of the alkoxysilane compound [4] include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3 -Aminopropyldiethoxymethylsilane, bis [3- (trimethoxysilyl) propyl] amine and the like, preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3- Aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane are preferable, and 3-aminopropyltrimethoxysilane is more preferable.

The amount of the alkoxysilane compound [4] is usually 0.8 to 2.0 times mol, preferably 1 to 1.2 times mol, more preferably 1 to 1.05 times mol with respect to the acid chloride [3]. It is.
Examples of the base include organic bases such as triethylamine, diisopropylethylamine, tributylamine, pyridine, quinoline or collidine, and inorganic salts such as sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate or potassium phosphate, preferably triethylamine. , Pyridine and potassium carbonate, more preferably triethylamine.

The solvent used in the amidation reaction is not particularly limited as long as it is inert to the reaction. For example, hydrocarbons such as hexane, heptane or toluene, halogens such as chloroform, 1,2-dichloroethane or chlorobenzene Hydrocarbons, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof Preferably, it is hexane, heptane, or toluene, More preferably, it is toluene.

The amidation reaction proceeds even without a catalyst, but can be accelerated by adding a catalyst. Examples of the catalyst include organic bases such as triethylamine, pyridine, quinoline, N, N-dimethylaniline or N, N-dimethylformamide, and metal alkoxides such as sodium methoxide, potassium methoxide or potassium t-butoxide. Preferred is triethylamine, pyridine, or N, N-dimethylformamide, and more preferred is N, N-dimethylformamide. The amount of the catalyst is usually 0 to 10 times mol, preferably 0.001 to 1 times mol, more preferably 0.005 to 0.1 times mol, relative to the carboxylic acid [2].

The alkoxysilane compound [1] obtained as described above is obtained by removing the organic salt or inorganic salt remaining in the reaction solution by filtration, diluting the filtrate with a solvent, washing this with pure water, The phase can be extracted and the solvent can be isolated by distillation under reduced pressure.

Examples of the solvent used for diluting the filtrate include hydrocarbons such as hexane, heptane and toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane and chlorobenzene, diethyl ether, tetrahydrofuran and 1,4-dioxane. Ethers such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof, preferably toluene, 1,2-dichloroethane or Ethyl acetate, more preferably ethyl acetate.

The organic phase after washing with pure water may be dehydrated using magnesium sulfate, sodium sulfate or the like.

The isolated alkoxysilane compound [1] has sufficiently good purity, but in the case of a solid, it can be further purified by washing or recrystallization using a solvent.

The solvent used for washing is not particularly limited. For example, hydrocarbons such as hexane, heptane or toluene, halogenated hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, diisopropyl ether, tetrahydrofuran or Examples include ethers such as 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, and mixtures thereof, preferably heptane, toluene Or it is diisopropyl ether, More preferably, it is diisopropyl ether.

The solvent used for recrystallization is not particularly limited as long as the alkoxysilane compound [1] dissolves upon heating and precipitates upon cooling. For example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1,2-dichloroethane, Halogenated hydrocarbons such as chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile And mixtures thereof, preferably heptane, toluene or diisopropyl ether, more preferably diisopropyl ether.

<Carboxylic acid having a ring structure>
Examples of the carboxylic acid [2] having a ring structure include the following compounds.

(In the formula, Z ⁵ represents the same meaning as described above. R ⁵ and R ⁶ each independently represent H or CH _3. )

The carboxylic acid containing a carbon-carbon double bond such as the above [2-7] to [2-11] is, for example, an aromatic halide (or triflate) as shown in [Reaction Formula 2] below. It can be obtained by Heck reaction with (meth) acrylic acid.

(In the formula, X ² represents Cl, Br, I or OTf (triflate), R ⁵ represents H or CH ₃ , and Z ⁵ represents the same as described above.)

In addition, the carboxylic acid containing a carbon-carbon triple bond such as the above [2-12] to [2-16] is, for example, an aromatic halide (or triflate) as shown in [Reaction Formula 3] below. It can be produced by Sonogashira reaction with propiolic acid.

(In the formula, X ² and Z ⁵ represent the same as described above.)

A carboxylic acid containing an ether bond with the ring structure such as the above [2-17] to [2-24] is a base such as potassium carbonate as shown in the following [Reaction Scheme 4]. In the presence, it can be produced by subjecting a ring structure compound containing a carboxylic acid group to an ester having a leaving group at the α-position, followed by a hydrolysis reaction using an acid or a base. .

Wherein X ³ is Cl, Br, I, OMs (mesylate) or OTs, R ⁴ is H or CH ₃ , R ⁵ is CH ₃ , C ₂ H ₅ , iso-propyl group, iso-butyl group or tert -Butyl group, Z ⁵ is the same as defined above.

A carboxylic acid having an ester bond with a ring structure such as the above [2-25] to [2-28] is a base such as potassium carbonate as shown in [Reaction Formula 5] below, for example. In the presence, a ring structure compound containing a carboxylic acid group is subjected to a nucleophilic substitution reaction with a tert-butyl ester having a leaving group at the α-position, and then tert-butyl using an acid such as formic acid or trifluoroacetic acid. It can be produced by subjecting only the ester moiety to a hydrolysis reaction.

(Wherein X ³ represents Cl, Br, I, OMs or OTs, and Z ⁵ represents the same as described above.)

In addition, a carboxylic acid containing an ester bond with a ring structure such as [2-29] to [2-35] above is a ring containing a hydroxyl group, as shown, for example, in [Reaction Scheme 6] below. It can be produced by reacting a structural compound with succinic anhydride.

(In the formula, Z ⁵ represents the same as described above.)

In addition, a carboxylic acid containing an ester bond with a ring structure such as the above [2-36] to [2-42] is a ring containing a hydroxyl group as shown in, for example, [Reaction Scheme 7] below. It can be produced by reacting a compound having a structure with glutaric anhydride.

(In the formula, Z ⁵ represents the same as described above.)

<Polysiloxane>
The polysiloxane of the present invention is a polysiloxane obtained by polycondensation of an alkoxysilane compound represented by the above formula [1].
In addition to the alkoxysilane compound represented by the above formula [1], the polysiloxane of the present invention may further contain other alkoxysilane as a constituent component. Examples of the other alkoxysilane include an alkoxysilane represented by the following formula (1), an alkoxysilane represented by the following formula (3), an alkoxysilane represented by the following formula (4), and an alkoxy represented by the following formula (5). Examples thereof include silane, alkoxysilane represented by the following formula (6), and alkoxysilane represented by the following formula (7).

R ¹⁰¹ Si (OR ¹⁰² ) ₃ (1)
(R ¹⁰¹ represents the structure of the following formula (2), and R ¹⁰² represents an alkyl group having 1 to 5 carbon atoms.)

(In Formula (2), Y ¹ is a single bond, — (CH ₂ ) _b — (b is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. Y ² is a straight or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or — (CR ¹¹⁷ R ¹¹⁸ ) _c — (c is an integer of 1 to 15) R ¹¹⁷ and R ¹¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) Y ³ is a single bond, — (CH ₂ ) _d — (d is 1 to 15 is an integer of 15), —O—, —CH ₂ O—, —COO— or —OCO—, wherein Y ⁴ is selected from the group consisting of a single bond, a benzene ring, a cyclohexyl ring, and a heterocyclic ring. Or a divalent organic group having 17 to 51 carbon atoms having a steroid skeleton, and these cyclic groups The above optional hydrogen atom is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has a carbon number N1 may be substituted with an alkyl group having 1 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y ⁶ is an integer of 0 to 4. Y ⁶ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or fluorine having 1 to 18 carbon atoms. Containing alkoxyl group Represent.)

(In Formula (3), R ²¹ , R ²² , and R ²³ are each independently —OCH ₃ , —OC ₂ H ₅ , —OCH (CH ₃ ) ₂ , —OC (CH ₃ ) ₃ , —CH ₃ , —Ph, —Cl, —OCOCH ₃ , —OH, —H, or a combination thereof, R ²⁴ represents a hydrogen atom or a methyl group, Y ²¹ represents a single bond, or A straight-chain or branched hydrocarbon group having 1 to 8 carbon atoms which may contain a double bond, Y ²² represents a single bond, —O—, —CO—, —COO—, —OCO—. , —NH—, —N (CH ₃ ) —, —NPh—, —NHCO—, —N (CH ₃ ) CO—, —NPhCO—, —NHSO ₂ —, —N (CH ₃ ) SO ₂ —, — _{_{NPhSO 2 -, - S -,}} - SO 2 -, - NHCONH, -N (CH 3) CONH-, NPhCONH -, - NHCOO-, and ^{.Y 23} is a single bond represents a bond group selected from -OCONH-, or ^{.Y 24} is a single bond representing a linear or branched hydrocarbon group having 1 to 8 carbon atoms Or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, Y ²⁵ represents a single bond, —O—, or —NZ ₂ —, Z ₂ is a hydrogen atom, and has 1 to 18 carbon atoms. Represents a linear or branched hydrocarbon group, an aromatic ring group, or an aliphatic ring group, wherein Cy represents a divalent cyclic group selected from the following and formed by bonding at an arbitrary substitution position. Any hydrogen atom on the cyclic group may be substituted with a group selected from an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, and a chlorine atom.

(Z ₁ represents a linear or branched divalent hydrocarbon group having 1 to 18 carbon atoms which may contain an aromatic ring group or an aliphatic ring group.)

R ¹⁰³ Si (OR ¹⁰⁴ ) ₃ (4)
(R ¹⁰³ is an alkyl group having 1 to 30 carbon atoms in which an arbitrary hydrogen atom is substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group, and R ¹⁰⁴ is an alkyl group having 1 to 5 carbon atoms. Represents a group.)

Si (OR ¹⁵ ) ₄ (5)
(R ¹⁵ represents an alkyl group having 1 to 5 carbon atoms.)

(R ¹³ ) _n2 Si (OR ¹⁴ ) _4-n (6)
(In formula (6), R ¹³ is a hydrogen atom or a carbon in which any hydrogen atom 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. A hydrocarbon group having 1 to 10 carbon atoms, R ¹⁴ is an alkyl group having 1 to 5 carbon atoms, and n2 represents an integer of 0 to 3.)

R ¹⁶ Si (OR ¹⁷ ) ₃ (7)
(R ¹⁶ is an alkyl group having 1 to 5 carbon atoms, and R ¹⁷ is an alkyl group having 1 to 5 carbon atoms.)

In Formula (2), Y ¹ is a single bond, — (CH ₂ ) _b — (b is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among these, a single bond, — (CH ₂ ) _b — (b is an integer of 1 to 15), —O—, —CH ₂ O— or —COO— is a viewpoint that facilitates the synthesis of the side chain structure. To preferred. Further, a single bond, — (CH ₂ ) _b — (b is an integer of 1 to 10), —O—, —CH ₂ O— or —COO— is more preferable.

In formula (2), Y ² is a straight or branched hydrocarbon group having 3 to 8 carbon atoms containing a single bond or a double bond, or — (CR ¹¹⁷ R ¹¹⁸ ) _c — (c is 1 And R ¹¹⁷ and R ¹¹⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Of these, — (CH ₂ ) _c — (c is an integer of 1 to 10) is preferable from the viewpoint of significantly improving the response speed of the liquid crystal display device.

In the formula (2), Y ³ is a single bond, — (CH ₂ ) _d — (d is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO—. . Among them, a single bond, — (CH ₂ ) _d — (d is an integer of 1 to 15), —O—, —CH ₂ O—, —COO— or —OCO— is used to synthesize the side chain structure. It is preferable from the viewpoint of facilitating. Further, a single bond, — (CH ₂ ) _d — (d is an integer of 1 to 10), —O—, —CH ₂ O—, —COO— or —OCO— is more preferable.

In formula (2), Y ⁴ is a single bond or a cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. It may be substituted with an alkyl group having 3 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Further, Y ⁴ may be a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton. Of these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring, or a steroid skeleton is preferable.

In Formula (2), Y ⁵ is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 to It may be substituted with a 3 alkyl group, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
In the formula (2), n1 is an integer of 0 to 4. Preferably, it is an integer of 0-2.

In formula (2), Y ⁶ is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. . Among these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.

R ¹⁰² of the alkoxysilane represented by the formula (1) is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, R ² is a methyl group or an ethyl group.

Specific examples of the alkoxysilane represented by the formula (1) include formulas [1-1] to [1-31], but are not limited thereto. Note that R ² in the following formulas [1-1] to [1-31] is the same as R ¹⁰² in the formula (1).

(In the formulas [1-19] to [1-21], R ¹⁰⁵ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ — or —CH ₂ OCO—, and R ¹⁰⁶ represents (It is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.)

(In the formulas [1-22] to [1-24], R ¹⁰⁷ represents a single bond, —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, — (CH ₂ ) _n O— ( n represents an integer of 1 to 5), —OCH ₂ — or —CH ₂ —, and R ¹⁰⁸ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.

(In the formulas [1-25] and [1-26], R ¹⁰⁹ represents —COO—, —OCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, — CH ₂ - or -O- are ^{shown, R 110} is a fluorine group, a cyano group, trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).

(In Formula [1-27] and Formula [1-28], R ¹¹¹ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. )

(In Formula [1-29] and Formula [1-30], R ¹¹² is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. .)

(In the formula [1-31], B ₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and B ₃ is a 1,4-cyclohexylene group or a 1,4-phenylene group. B ₂ is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to B ₃ ), and B ₁ is an oxygen atom or —COO— * (where “*” ”Is a bond with (CH ₂ ) a ₂ ). A ₁ is an integer of 0 or 1, a ₂ is an integer of 2 to 10, and a ₃ is an integer of 0 or 1. )

The alkoxysilane represented by the formula (1) is soluble in a solvent when a siloxane polymer (polysiloxane) is used, liquid crystal alignment when a liquid crystal alignment film is used, pretilt angle characteristics, voltage holding ratio, accumulated charge. Depending on the characteristics such as, one kind or a mixture of two or more kinds may be used. Further, it can be used in combination with an alkoxysilane containing a long-chain alkyl group having 10 to 18 carbon atoms.

Such an alkoxysilane represented by the formula (1) can be produced by a known method as described in, for example, JP-A-61-286393.

R ²¹ , R ²² , and R ²³ of the alkoxysilane represented by the formula (3) are each independently —OCH ₃ , —OC ₂ H ₅ , —OCH (CH ₃ ) ₂ , —OC (CH ₃ ). ₃ , —CH ₃ , —Ph (ie, —C ₆ H ₅ ), —Cl, —OCOCH ₃ , —OH, —H, or a combination thereof. Preferably, R ²¹ , R ²² , and R ²³ are each independently —OCH ₃ or —OC ₂ H ₅ .

R ²⁴ is a hydrogen atom or a methyl group.

Y ²¹ of the alkoxysilane represented by the formula (3) is a linear or branched hydrocarbon group having 1 to 8 carbon atoms which may contain a single bond or a double bond. Preferably, Y ²¹ is a single bond or a linear hydrocarbon group having 3 to 5 carbon atoms.

Y ²² of the alkoxysilane represented by the formula (3) is a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —N (CH ₃ ) —, —NPh—, _{_{-NHCO -, - N (CH 3}} ) CO -, - NPhCO -, - NHSO 2 -, - N (CH 3) SO 2 -, - NPhSO 2 -, - S -, - SO 2 -, - NHCONH, - The bonding group is selected from N (CH ₃ ) CONH—, —NPhCONH—, —NHCOO—, and —OCONH—. Preferably, Y ²² is a single bond.

Y ²³ is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, preferably a single bond.

Y ²⁴ is a single bond or a linear or branched hydrocarbon group having 1 to 8 carbon atoms, preferably a single bond or a linear hydrocarbon group having 1 to 3 carbon atoms.

Y ²⁵ is a single bond, —O—, or —NZ ₂ —. Here, Z ₂ is a hydrogen atom, a linear or branched hydrocarbon group having 1 to 18 carbon atoms, an aromatic ring group, or an aliphatic ring group. Preferred is a single bond, —O—, or —NH—.

Cy of the alkoxysilane represented by the formula (3) represents a divalent cyclic group selected from the following and formed by bonding at any substitution position, and any hydrogen atom on these cyclic groups has 1 carbon atom. It may be substituted with an alkyl group having 3 to 3, an alkoxy group having 1 to 3 carbon atoms, a cyano group, a fluorine atom, and a chlorine atom. Preferably, Cy is a benzene ring or a biphenyl ring. In addition, “a divalent cyclic group formed by bonding at an arbitrary substitution position” means that the position of two bonds of the following cyclic group may be arbitrary.

R ¹⁰³ of the alkoxysilane represented by the formula (4) is an alkyl group in which an arbitrary hydrogen atom is substituted with an acryl group, an acryloxy group, a methacryl group, a methacryloxy group, or a styryl group. The number of substituted hydrogen atoms is one or more, preferably one. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. More preferably, it is 1-10.

R ¹⁰⁴ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

Although the specific example of the alkoxysilane represented by Formula (4) is given, it is not limited to these. For example, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxy Silane, acryloxyethyltrimethoxysilane, acryloxyethyltriethoxysilane, styrylethyltrimethoxysilane, styrylethyltriethoxysilane, or 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane.

R ¹³ of the alkoxysilane represented by the formula (6) has a hydrogen atom or an arbitrary hydrogen atom substituted with a hetero atom, a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, or a ureido group. Or a hydrocarbon group having 1 to 10 carbon atoms, preferably an amino group, a glycid group, or a ureido group. R ¹⁴ represents an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and n2 represents an integer of 0 to 3, preferably 0 to 2. )

R ¹³ of the alkoxysilane represented by the formula (6) is a hydrogen atom or an organic group having 1 to 10 carbon atoms. Examples of R ¹³ which is an organic group having 1 to 10 carbon atoms include ring structures such as aliphatic hydrocarbons, aliphatic rings, aromatic rings and heterocyclic rings having 1 to 10 carbon atoms, These may contain an unsaturated bond, a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom, and may be linear or branched. The number of carbon atoms is preferably 1-6. In addition, any hydrogen atom of the hydrocarbon group may be substituted with a halogen atom, an amino group, a glycidoxy group, a mercapto group, an isocyanate group, a ureido group, or the like.

Specific examples of the alkoxysilane represented by the formula (6) are given below, but are not limited thereto. For example, 3- (2-aminoethylaminopropyl) trimethoxysilane, 3- (2-aminoethylaminopropyl) triethoxysilane, 2-aminoethylaminomethyltrimethoxysilane, 2- (2-aminoethylthioethyl) Triethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, vinyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, trifluoropropyltrimethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, diphenyl Diethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane and γ-ureidopropyltri And propoxysilane.

In the alkoxysilane represented by the formula (6), the alkoxysilane in which n2 is 0 is tetraalkoxysilane. Tetraalkoxysilane easily undergoes a polycondensation reaction with the alkoxysilane represented by the formula (1), (3) or (4).

As the alkoxysilane of the formula (6), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.

As the alkoxysilane represented by the formula (5), tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane or tetrabutoxysilane is preferable, and tetramethoxysilane or tetraethoxysilane is particularly preferable.

R ¹⁶ of the alkoxysilane represented by the formula (7) is an alkyl group having 1 to 5 carbon atoms. The alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms.

R ¹⁷ is an alkyl group having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms, and particularly preferably 1 to 2 carbon atoms.

Although the specific example of the alkoxysilane represented by Formula (7) is given, it is not limited to these. For example, methyltriethoxysilane, methyltrimethoxysilane, dimethyltrimethoxysilane, dimethyltriethoxysilane, n-propyltrimethoxysilane, or n-propyltriethoxysilane.

Since the polysiloxane contained in the liquid crystal aligning agent of the present invention is less expensive than an expensive polyimide, the liquid crystal aligning agent of the present invention can be manufactured at low cost and has high versatility.

The molecular weight of the polysiloxane of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000 in terms of weight average molecular weight. The number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.

The proportion of the alkoxysilane compound represented by the formula [1] is 1 mol% or more in order to obtain good liquid crystal alignment in all alkoxysilane components (100 mol%) used to obtain polysiloxane. Preferably, 1.5 mol% or more is more preferable, and 2 mol% or more is more preferable. Further, in order to obtain sufficient curing characteristics of the liquid crystal alignment film to be formed, 30 mol% or less is preferable, and 25 mol% or less is more preferable.

<Method for producing polysiloxane>
The method for obtaining the polysiloxane of the present invention is not particularly limited, and a known method can be used. As a method of polycondensation of alkoxysilane in order to obtain polysiloxane, for example, a method of hydrolyzing and condensing alkoxysilane in a solvent such as alcohol or glycol can be mentioned. At that time, the hydrolysis / condensation reaction may be either partial hydrolysis or complete hydrolysis. In the case of complete hydrolysis, theoretically, it is sufficient to add 0.5 times mole of water of all alkoxy groups in the alkoxysilane, but it is usually preferable to add an excess amount of water more than 0.5 times mole.

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 times mol of all alkoxy groups in the alkoxysilane. More preferably, it is 5 to 2 moles.

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, and alkalis such as ammonia, methylamine, ethylamine, ethanolamine, Metal salts such as hydrochloric acid, sulfuric acid and nitric acid are used as catalysts. 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, a method of heating / stirring at 50 ° C. for 24 hours or heating / stirring under reflux for 1 hour can be mentioned.

As another method, for example, a method of heating and polycondensing a mixture of alkoxysilane, a solvent and oxalic acid can be mentioned. Specifically, after adding oxalic acid to alcohol in advance to obtain an alcohol solution of oxalic acid, the alkoxysilane is mixed while the solution is heated. In this case, the amount of succinic acid used is preferably 0.2 to 2 mol, more preferably 0.5 to 2 mol, relative to 1 mol of all alkoxy groups contained in the alkoxysilane. Heating in this method can be performed at a liquid temperature of 50 to 180 ° C. A method of heating for several tens of minutes to several tens of hours under reflux is preferred so that the liquid does not evaporate or volatilize.

In the present invention, when obtaining polysiloxane, a plurality of types of alkoxysilanes can be used. In that case, alkoxysilanes may be mixed in advance as a mixture, or a plurality of types of alkoxysilanes may be sequentially mixed. May be. That is, there is no limitation on the order in which the alkoxysilane components are reacted. For example, the alkoxysilane components may be reacted at once, or after some alkoxysilanes are reacted, other alkoxysilanes are added. You may make it react.

The solvent used for polycondensation of alkoxysilane (hereinafter also referred to as polymerization solvent) is not particularly limited as long as it can dissolve alkoxysilane. Moreover, even when alkoxysilane does not melt | dissolve, what melt | dissolves as the polycondensation reaction of alkoxysilane progresses is sufficient. In general, since an alcohol is generated by a polycondensation reaction of alkoxysilane, an alcohol, a glycol, a glycol ether, or an organic solvent having good compatibility with the alcohol is used.

Specific examples of such a polymerization solvent include alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1 , 5-pentanediol, 2,4-pentanediol, 2,3-pentanediol, 1,6-hexanediol and other glycols, 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 , 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.
In the present invention, a plurality of the above polymerization solvents may be mixed and used.

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 charged as raw materials into SiO ₂ (hereinafter referred to as SiO ₂ conversion concentration). ), 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.

<Polysiloxane solution>
In the present invention, the polysiloxane polymerization solution obtained by the above method may be used as a polymer component as it is. If necessary, the solution obtained by the above method is concentrated or a solvent is added. The polymer component may be diluted with another solvent or substituted with another solvent.
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 the additive solvent include, in addition to the solvents mentioned as examples of the polymerization solvent, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and esters such as methyl acetate, ethyl acetate, and ethyl lactate. It is done. These solvents can adjust the viscosity of the liquid crystal aligning agent, and further improve the coating property when the liquid crystal aligning agent is applied on the substrate by spin coating, flexographic printing, ink jetting or the like.

<Other ingredients>
In the present invention, as long as the effects of the present invention are not impaired, other components other than polysiloxane, for example, inorganic fine particles, metalloxane oligomers, metalloxane polymers, leveling agents, and further components such as surfactants are included. It may be.
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. 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 of the inorganic fine particles include water or an organic solvent. As the colloidal solution, it is preferable that the pH or pKa is adjusted to 1 to 10 from the viewpoint of the stability of the coating solution for film formation. 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; And 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 or 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, carboxylate or the like by a conventional method such as hydrolysis. .

Specific examples of commercially available metalloxane oligomers or metalloxane polymers include siloxane oligomers 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 siloxane polymers and titanoxane oligomers such as 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.
Moreover, the method of mixing the above-mentioned other components with the polysiloxane may be simultaneous with or after the polysiloxane, and is not particularly limited.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is a solution containing the polysiloxane mentioned above and other components as needed. In this case, as the solvent, a solvent selected from the group consisting of the above-mentioned polysiloxane polymerization solvent and additive solvent is used. The content of polysiloxane in the liquid crystal aligning agent is preferably 0.5 to 15% by mass, more preferably 1 to 6% by mass in terms of SiO ₂ equivalent concentration. Be in the range of such terms of SiO ₂ concentration, easy to obtain a desired film thickness by a single coating, easy pot life sufficient solution is obtained.

The method for preparing the liquid crystal aligning agent of the present invention is not particularly limited. The polysiloxane used in the present invention may be in a state where other components added as necessary are uniformly mixed. Since polysiloxane is usually polycondensed in a solvent, 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.
Moreover, when adjusting content of polysiloxane in a liquid crystal aligning agent, the solvent chosen from the group which consists of the polymerization solvent and addition solvent of the polysiloxane mentioned above can be used.

The content of the organic solvent contained in the liquid crystal aligning agent of the present invention is preferably 90 to 99% by mass and more preferably 92 to 97% by mass in the liquid crystal aligning agent from the viewpoint of forming a uniform thin film by coating. These contents can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.

Also, in organic solvents, for the purpose of improving the uniformity of the coating film, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monopentyl ether, ethylene glycol mono Hexyl 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, diethylene glycol monoethyl ether acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy- 2-propanol, 1- Toxi-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, di Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2- (2-ethoxypropoxy) propanol, diacetone alcohol, methyl lactate, ethyl lactate, It is preferable to contain a solvent having a low surface tension such as lactic acid n-propyl ester, lactic acid n-butyl ester, and lactyl isoamyl ester.

<Liquid crystal alignment film>
The liquid crystal aligning film of this invention is obtained using the liquid crystal aligning agent mentioned above. After applying the liquid crystal aligning agent to the substrate, the cured film obtained by drying and baking is used as it is as the liquid crystal alignment film, or after being subjected to the alignment treatment by rubbing treatment or light irradiation, the liquid crystal alignment film is used. Can be used.

In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate; a plastic substrate such as an acrylic substrate or a polycarbonate substrate; Furthermore, it is preferable from the viewpoint of simplification of the process to use a substrate on which an ITO for driving a liquid crystal or an IZO (Indium Zinc Oxide) electrode is formed. In the reflection type liquid crystal display element, an opaque material such as a silicon wafer can be used as long as only one substrate is used. In this case, a material that reflects light such as metal aluminum can be used as the electrode.

Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri Examples thereof include a substrate in which a transparent electrode is formed on a plastic plate such as acetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.

The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. From the standpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

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, a drying process is included. Is preferred. 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 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

Firing after applying the liquid crystal aligning agent can be performed at an arbitrary temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., More preferably, it is 160 ° C to 220 ° C. The firing time can be any time of 5 to 240 minutes, preferably 10 to 90 minutes, more preferably 20 to 80 minutes. For the heating, a generally known method such as a hot plate, a hot air circulation oven, an IR oven, a belt furnace or the like can be used.

The polysiloxane in the liquid crystal alignment film undergoes polycondensation in the firing 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 that is 10 ° C. or more higher than the heat treatment temperature required for the manufacturing process of the liquid crystal cell, such as sealing agent curing.
The thickness of the cured film can be selected as necessary, but is preferably 5 nm or more, more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained. Moreover, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, which is suitable.

<Liquid crystal display element>
The liquid crystal display element of the present invention is formed of 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 liquid crystal display element 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 display element including a liquid crystal cell manufactured by sandwiching a liquid crystal layer composed of liquid crystal between two substrates and irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film and the liquid crystal layer.

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 the 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 The liquid crystal cell can also be manufactured by a method in which the other substrate is attached and sealed so that the inner side is on the inside. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.
The method for injecting the liquid crystal is not particularly limited, and examples thereof include a vacuum method for injecting liquid crystal after the inside of the manufactured liquid crystal cell is decompressed, and a dropping method for sealing after dropping the liquid crystal.

By irradiating ultraviolet rays with a voltage applied between the electrodes on both sides of the liquid crystal cell in which liquid crystal is introduced, crosslinkable groups such as acrylic and methacrylic groups in the liquid crystal alignment film are polymerized in situ and crosslinked. As a result, the response speed of the liquid crystal display is increased.
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 a voltage between the electrodes installed on the substrate to thereby apply the voltage to the liquid crystal alignment film and the liquid crystal layer. There is a method of applying a voltage and irradiating ultraviolet rays while maintaining this voltage. Here, the voltage applied between the electrodes is, for example, 5 to 80 Vp-p, preferably 5 to 60 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 the 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.

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. Specific examples thereof include the same substrates as those described in the above <Liquid crystal alignment film>. 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, the liquid crystal aligning agent of the present invention is used as the liquid crystal aligning agent for forming the liquid crystal aligning film. Therefore, operation is possible even in a structure in which a line / slit electrode pattern of 1 to 10 μm is formed on one side substrate, and a slit pattern or projection pattern is not formed on the opposite substrate. This process can be simplified and high transmittance can be obtained.

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 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 Alternatively, MLC-2041 or the like can be used.

EXAMPLES Hereinafter, although an Example is hung up and this invention is demonstrated in detail, this invention is limited to these Examples and is not interpreted.
The conditions for ¹ H-NMR analysis used for identification of the compounds synthesized in Synthesis Examples 1 to 3 are shown below.
Apparatus: Varian NMR System 400 NB (400 MHz)
Measuring solvent: CDCl ₃
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

Synthesis of Compound [1] A 300 ml four-necked flask equipped with a magnetic stirrer was charged with 30.00 g (0.0992 mol) of 4- (trans-4-heptylcyclohexyl) benzoic acid and 120 g (1.00087 mol) of thionyl chloride. Then, 0.07 g (0.0010 mol) of N, N-dimethylformamide was charged and stirred at an internal temperature of 50 ° C. for 2 hours. Thereafter, thionyl chloride was distilled off from the reaction solution under reduced pressure to obtain 31.80 g (0.0991 mol) of compound [1] (yield: 100%, property: yellow oil).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.89 ppm (t, J = 7.0 Hz, 3H), 0.98-1.12 ppm (m, 2H), 1.18-1.39 ppm (m, 13H), 1.40-1.53 ppm (m , 2H), 1.83-1.93ppm (m, 4H), 2.51-2.62ppm (m, 1H), 7.32ppm (d, J = 8.2 Hz, 2H), 8.03ppm (d, J = 8.2 Hz, 2H)

Synthesis of Compound [2] In a 1 L four-necked flask equipped with a magnetic stirrer, 31.80 g (0.0991 mol) of compound [1] and 190.8 g of toluene were charged, and in an ice bath (internal temperature 5 ° C.). While stirring, a solution prepared by dissolving 18.12 g (0.0111 mol) of 3-aminopropyltrimethoxysilane and 11.03 g (0.1090 mol) of triethylamine in 127.2 g of toluene was added dropwise over 30 minutes. Then, the mixture was further stirred at room temperature for 17 hours. Thereafter, triethylamine hydrochloride precipitated in the reaction solution was filtered, and the filtrate was diluted with 192 g of ethyl acetate. Next, this filtrate was washed with 200 g of pure water three times, and then 5 g of sodium sulfate was added to the organic phase for dehydration treatment. Subsequently, after filtering this, the solvent was completely distilled off from the filtrate under reduced pressure to obtain 44.49 g (0.0959 mol) of Compound [2] (yield: 97%, property: white crystals). .
¹ H-NMR (400 MHz) in CDCl ₃ : 0.70-0.75 ppm (m, 2H), 0.89 ppm (t, J = 7.0 Hz, 3H), 0.99-1.10 ppm (m, 2H), 1.18-1.39 ppm (m , 13H), 1.40-1.52ppm (m, 2H), 1.74ppm (m, 2H), 1.84-1.92ppm (m, 4H), 2.45-2.55ppm (m, 1H), 3.45ppm (q, J = 6.9 Hz, 2H), 3.57ppm (s, 9H), 6.39-6.44ppm (m, 1H), 7.25ppm (d, J = 8.2 Hz, 2H), 7.68ppm (d, J = 8.2 Hz, 2H)

Synthesis of Compound [3] In a 500 ml four-necked flask equipped with a magnetic stirrer, 4-heptylbenzoic acid (40.00 g, 0.1816 mol), thionyl chloride (160 g, 1.3449 mol), and N, N-dimethylformamide 0.13 g (0.0019 mol) was charged and stirred at an internal temperature of 50 ° C. for 2 hours. Thereafter, thionyl chloride was distilled off from the reaction solution under reduced pressure to obtain 43.23 g (0.1811 mol) of Compound [3] (yield: 100%, property: orange oil).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.88 ppm (t, J = 6.9 Hz, 3H), 1.21-1.39 ppm (m, 8H), 1.57-1.69 ppm (m, 2H), 2.69 ppm (t, J = 7.8 Hz, 2H), 7.30 ppm (d, J = 8.5 Hz, 2H), 8.01 ppm (d, J = 8.5 Hz, 2H)

Synthesis of Compound [4] A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 15.00 g (0.0628 mol) of compound [3] and 90 g of toluene and stirred in an ice bath (internal temperature 5 ° C.). However, a solution prepared by dissolving 11.49 g (0.0641 mol) of 3-aminopropyltrimethoxysilane and 6.99 g (0.0690 mol) of triethylamine in 60 g of toluene was added dropwise over 30 minutes, and then at room temperature. For 1 hour. Thereafter, triethylamine hydrochloride precipitated in the reaction solution was filtered, and the filtrate was diluted with 90 g of ethyl acetate. Next, this filtrate was washed with 90 g of pure water three times, and then 2.3 g of sodium sulfate was added to the organic phase for dehydration treatment. Subsequently, after filtration, the solvent was completely distilled off from the filtrate under reduced pressure to obtain 22.32 g (0.0585 mol) of compound [4] (yield: 93%, property: pale yellow oil). ).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.69-0.78 ppm (m, 2H), 0.89 ppm (t, J = 6.9 Hz, 3H), 1.20-1.37 ppm (m, 8H), 1.54-1.66 ppm (m , 2H), 1.69-1.80ppm (m, 2H), 2.64ppm (t, J = 7.7Hz, 2H), 3.45ppm (q, J = 6.8Hz, 2H), 3.58ppm (s, 9H), 6.38- 6.48ppm (m, 1H), 7.22ppm (d, J = 8.3 Hz, 2H), 7.68ppm (d, J = 8.3 Hz, 2H)

Synthesis of Compound [5] A 500 ml four-necked flask equipped with a magnetic stirrer was charged with 15.00 g (0.0628 mol) of compound [3] and 90 g of toluene and stirred in an ice bath (internal temperature 5 ° C.). However, a solution prepared by dissolving 16.37 g (0.0641 mol) of N-phenyl-3-aminopropyltrimethoxysilane and 6.97 g (0.0689 mol) of triethylamine in 60 g of toluene was added dropwise over 30 minutes. And stirred at room temperature for 1 hour. Thereafter, triethylamine hydrochloride precipitated in the reaction solution was filtered, and the filtrate was diluted with 90 g of ethyl acetate. Next, this filtrate was washed with 90 g of pure water three times, and 2.5 g of sodium sulfate was added to the organic phase for dehydration treatment. Subsequently, after filtration, the solvent was completely distilled off from the filtrate under reduced pressure to obtain 28.39 g (0.0620 mol) of compound [5] (yield: 99%, property: pale yellow oil). ).
¹ H-NMR (400 MHz) in CDCl ₃ : 0.64-0.71 ppm (m, 2H), 0.86 ppm (t, J = 7.1 Hz, 3H), 1.15-1.34 ppm (m, 8H), 1.45-1.54 ppm (m , 2H), 1.69-1.80ppm (m, 2H), 2.49ppm (t, J = 7.8 Hz, 2H), 3.53ppm (s, 9H), 3.90ppm (t, J = 8.0 Hz, 2H), 6.93ppm (d, J = 8.2 Hz, 2H), 7.02 ppm (d, J = 8.2 Hz, 2H), 7.10-7.28 ppm (m, 5H)

"Synthesis of polysiloxane"
The names of the compounds described in abbreviated names in Synthesis Examples 4 to 9 below are as follows.
TEOS: tetraethoxysilane C18: octadecyltriethoxysilane ACPS: 3-acryloxypropyltrimethoxysilane MPMS: 3-methacryloxypropyltrimethoxysilane M8MS: 3-methacryloxyoctyltrimethoxysilane MTES: methyltriethoxysilane HG: 2 -Methyl-2,4-pentanediol (also known as hexylene glycol)
BCS: 2-butoxyethanol UPS: 3-ureidopropyltriethoxysilane XS-18: 1- (trans-4-n-pentylcyclohexyl) -4- (3-trimethoxysilylpropanoxy) benzene XS-91: 2 -Methoxy-4- [3-triethoxysilyl) propyl] phenyl methacrylate

<Synthesis Example 4>
In a 200 mL four-neck reaction flask equipped with a thermometer and a reflux tube, 9.9 g of HG, 3.3 g of BCS, 17.6 g of TEOS, and 2 of the compound [2] obtained in Synthesis Example 1 were used. 0.1 g was mixed to prepare an alkoxysilane monomer solution. To this solution, 4.8 g of HG, 1.6 g of BCS, 4.9 g of water, and 0.2 g of oxalic acid as a catalyst were added dropwise over 30 minutes at room temperature, and further 30 minutes at room temperature. Stir. After heating using an oil bath and refluxing for 30 minutes, a prepared mixture of 0.3 g of a UPS content 92 mass% methanol solution, 0.1 g HG and 0.1 g BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (A) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (A) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent (K1) having a SiO ₂ equivalent concentration of 4% by mass.

<Synthesis Example 5>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 9.9 g of HG, 3.3 g of BCS, 17.6 g of TEOS, and 1.8 g of XS-18 were mixed to obtain an alkoxysilane monomer. A solution of was prepared. A solution in which 5.0 g of HG, 1.7 g of BCS, 4.9 g of water, and 0.2 g of oxalic acid as a catalyst were mixed dropwise into this solution over 30 minutes at room temperature, and further 30 minutes at room temperature. Stir. After heating using an oil bath and refluxing for 30 minutes, a prepared mixture of 0.3 g of a UPS content 92 mass% methanol solution, 0.1 g HG and 0.1 g BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (B) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (B) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent (L1) having a SiO ₂ equivalent concentration of 4% by mass.

<Synthesis Example 6>
In a 200 mL four-necked reaction flask equipped with a thermometer and reflux tube, 7.7 g of HG, 2.6 g of BCS, 5.8 g of TEOS, 7.8 g of MPMS, and 5.35 g of XS-91 Then, 3.3 g of compound [2] obtained in Synthesis Example 1 and 1.3 g of VTMS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by mixing 3.8 g of HG, 1.3 g of BCS, 4.9 g of water and 0.8 g of oxalic acid as a catalyst in advance was added dropwise over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a prepared mixed solution of 0.1 g of a methanol solution with a UPS content of 92% by mass, 0.1 g of HG and 0.2 g of BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (C) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (C) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent intermediate (S1) having a SiO ₂ equivalent concentration of 4% by mass.

In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 8.6 g of HG, 2.9 g of BCS, 14.4 g of TEOS, 0.7 g of XS-18, and 7 of XS-91 0.1 g was mixed to prepare an alkoxysilane monomer solution. A solution prepared by previously mixing 4.3 g of HG, 1.4 g of BCS, 4.9 g of water, and 0.3 g of oxalic acid as a catalyst was added dropwise to this solution over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. Thereafter, the mixture was heated using an oil bath and refluxed for 30 minutes, and a prepared mixed solution of 0.3 g of a methanol solution having a UPS content of 92% by mass, 0.1 g of HG, and 0.1 g of BCS was added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (D) having a SiO ₂ equivalent concentration of 12% by mass.
The resulting polysiloxane solution (D) 10.0 g, and were mixed BCS20.0G, give in terms of SiO ₂ concentration of the liquid crystal aligning agent intermediates 4% by weight of (U1).

Thereafter, the liquid crystal aligning agent intermediate (S1) and the liquid crystal aligning agent intermediate (U1) are mixed at a mass ratio of 3: 7 to obtain a liquid crystal aligning agent [K2] having a SiO ₂ equivalent concentration of 4% by mass. It was.

<Synthesis Example 7>
In a 200 mL four-necked reaction flask equipped with a thermometer and reflux tube, 7.7 g of HG, 2.6 g of BCS, 5.8 g of TEOS, 7.8 g of MPMS, 5.4 g of XS-91 Then, 3.3 g of compound [2] obtained in Synthesis Example 1 and 1.3 g of VTMS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by mixing 3.8 g of HG, 1.3 g of BCS, 4.9 g of water and 0.8 g of oxalic acid as a catalyst in advance was added dropwise over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. After heating using an oil bath and refluxing for 30 minutes, a prepared mixture of 0.3 g of a UPS content 92 mass% methanol solution, 0.1 g HG and 0.1 g BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (E) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (E) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent intermediate (S2) having a SiO ₂ equivalent concentration of 4% by mass.

Thereafter, the liquid crystal aligning agent intermediate (S2) and the liquid crystal aligning agent intermediate (U1) are mixed at a mass ratio of 3: 7 to obtain a liquid crystal aligning agent [K3] having a SiO ₂ conversion concentration of 4% by mass. It was.

<Synthesis Example 8>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, HG 8.2 g, BCS 2.7 g, TEOS 5.8 g, MPMS 7.8 g, and XS-91 5.4 g. Then, 2.5 g of compound [2] obtained in Synthesis Example 1 and 1.3 g of VTMS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by previously mixing 4.1 g of HG, 1.4 g of BCS, 4.8 g of water, and 0.8 g of oxalic acid as a catalyst was added dropwise over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. After heating using an oil bath and refluxing for 30 minutes, a prepared mixture of 0.3 g of a UPS content 92 mass% methanol solution, 0.1 g HG and 0.1 g BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (F) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (F) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent intermediate (S3) having a SiO ₂ equivalent concentration of 4% by mass.

Thereafter, the liquid crystal aligning agent intermediate (S3) and the liquid crystal aligning agent intermediate (U1) are mixed at a mass ratio of 3: 7 to obtain a liquid crystal aligning agent [K4] having a SiO ₂ equivalent concentration of 4% by mass. It was.

<Synthesis Example 9>
In a 200 mL four-necked reaction flask equipped with a thermometer and a reflux tube, 9.9 g of HG, 2.5 g of BCS, 5.1 g of TEOS, 7.8 g of MPMS, 5.4 g of XS-91 Then, 4.4 g of XS-18 and 1.3 g of VTMS were mixed to prepare an alkoxysilane monomer solution. To this solution, a solution prepared by mixing 3.8 g of HG, 1.3 g of BCS, 4.9 g of water and 0.8 g of oxalic acid as a catalyst in advance was added dropwise over 30 minutes at room temperature, and further stirred at room temperature for 30 minutes. After heating using an oil bath and refluxing for 30 minutes, a prepared mixture of 0.3 g of a methanol solution with a UPS content of 92% by mass, 0.1 g of HG and 0.2 g of BCS was prepared. added. The mixture was further refluxed for 30 minutes and then allowed to cool to obtain a polysiloxane solution (G) having a SiO ₂ equivalent concentration of 12% by mass.
10.0 g of the obtained polysiloxane solution (G) and 20.0 g of BCS were mixed to obtain a liquid crystal aligning agent intermediate (S4) having a SiO ₂ equivalent concentration of 4% by mass.

Thereafter, the liquid crystal aligning agent intermediate (S4) and the liquid crystal aligning agent intermediate (U1) are mixed at a mass ratio of 3: 7 to obtain a liquid crystal aligning agent [L2] having a SiO ₂ equivalent concentration of 4% by mass. It was.

-Evaluation of liquid crystal cell <Example 1>
The liquid crystal aligning agent [K1] obtained in Synthesis Example 4 was spin-coated on the ITO surface on which no electrode pattern was formed. After drying for 2 minutes on a hot plate at 80 ° C., 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. Two substrates thus obtained were prepared, and 4 μm bead spacers were sprayed on the liquid crystal alignment film surface of one of the substrates, and a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate was placed inside and bonded together, and then the sealing agent was cured to produce an empty cell. A liquid crystal cell 1 was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck) into the empty cell by vacuum injection. The vertical alignment property of the liquid crystal cell 1 was evaluated by the method described later.

The above liquid crystal cell 1 was annealed in a circulation oven at 100 ° C. for 30 minutes. The extracted liquid crystal cell was observed with a microscope in a state where the polarizing plate was in a crossed Nicol state, and the state of the domain, which was an alignment disorder of the liquid crystal, was observed. At this time, when no domain was observed, it was evaluated that the vertical alignment was good, and when many domains were observed, it was evaluated that the vertical alignment was not good (the results are shown in Table 1).

<Comparative Example 1>
A liquid crystal cell was prepared in the same manner as in Example 1 except that the liquid crystal aligning agent [K1] was changed to the liquid crystal aligning agent [L1] obtained in Synthesis Example 5, and the state of the domain after annealing was observed (results) In Table 1).

<Example 2>
The liquid crystal aligning agent [K2] obtained in Synthesis Example 6 was spin-coated on the ITO surface of the ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 × 300 μm and a line / space of 5 μm was formed. After drying for 2 minutes on a hot plate at 80 ° C., 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. In addition, the liquid crystal aligning agent [K2] obtained in Example 2 was spin-coated on the ITO surface on which no electrode pattern was formed, dried on an 80 ° C. hot plate for 2 minutes, and then heated at 200 ° C. in the same manner as the above substrate. Firing was performed in a hot air circulation oven for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

These two substrates were prepared, 4 μm bead spacers were sprayed on the liquid crystal alignment film surface of one substrate, and a sealant was printed thereon. The liquid crystal alignment film surface of the other substrate was placed inside and bonded together, and then the sealing agent was cured to produce an empty cell. Liquid crystal cell 2 was prepared by injecting liquid crystal MLC-6608 (trade name, manufactured by Merck) into the empty cell by vacuum injection. The response speed of the liquid crystal cell 2 was measured by the method described later.

(Response speed measurement)
In the measurement apparatus configured in the order of a backlight, a set of polarizing plates in a crossed Nicol state, and a light amount detector, the liquid crystal cell produced as described above was placed between the pair of polarizing plates. 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.

Next, in a state where a DC voltage of 20 V was applied to the liquid crystal cell 2, ultraviolet rays were irradiated from the outside of the liquid crystal cell by 5J. Thereafter, the response speed was measured again (results are listed in Table 2).

On the other hand, the liquid crystal cell 2 (that is, a liquid crystal cell not irradiated with 5 J of ultraviolet rays from the outside of the liquid crystal cell in a state where a DC voltage of 20 V was applied) was annealed in a circulation oven at 100 ° C. for 30 minutes. The extracted liquid crystal cell was observed with a microscope in a state where the polarizing plate was in a crossed Nicol state, and the state of the domain, which was an alignment disorder of the liquid crystal, was observed. At this time, when no domain was observed, it was evaluated that the vertical alignment was good, and when many domains were observed, it was evaluated that the vertical alignment was not good (the results are shown in Table 2).

<Example 3>
A liquid crystal cell was produced in the same manner as in Example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K3] obtained in Synthesis Example 7, and the state of the domain after annealing was observed. Moreover, the response speed was measured (the result is described in Table 2).

<Example 4>
A liquid crystal cell was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [K4] obtained in Synthesis Example 8, and the state of the domain after annealing was observed. Moreover, the response speed was measured (the result is described in Table 2).

<Comparative example 2>
A liquid crystal cell was prepared in the same manner as in Example 2 except that the liquid crystal aligning agent [K2] was changed to the liquid crystal aligning agent [L2] obtained in Synthesis Example 9, and the state of the domain after annealing was observed. Moreover, the response speed was measured (the result is described in Table 2).

Domain observation result after annealing △: Many domains are observed,
○: About 1 to 3 domains are observed (good),
A: No domain is observed at all (very good).

As can be seen from Table 1, in the liquid crystal cells of Example 1 and Comparative Example 1, no domain that is a disorder of alignment of the liquid crystal was observed after annealing.

Judgment of response speed; ◎: very fast (very good), ○: fast (good), x: slow (bad).
Domain observation result after annealing △: Many domains are observed,
○: About 1 to 3 domains are observed (good),
A: No domain is observed at all (very good).

As can be seen from Table 2, in the liquid crystal cells of Examples 3 and 4, the response speed after ultraviolet irradiation was as fast as about 30 ms, and in Example 3, the state of the domain after annealing was also good. This means that the vertical alignment property and the response speed are equivalent to those of the liquid crystal cell of Comparative Example 2.

As described above, the liquid crystal cell produced using the liquid crystal aligning agent comprising the alkoxysilane compound of the present invention as a constituent component is perpendicular to the case of a similar compound conventionally used such as XS-18. It was confirmed that the orientation was equivalent. Moreover, it was confirmed that the response speed after ultraviolet irradiation is also equivalent.

The alkoxysilane compound of the present invention can be synthesized in a high yield and high purity without performing a purification operation such as distillation, and a liquid crystal alignment film produced using a liquid crystal alignment agent comprising the alkoxysilane compound as a constituent component Can provide a liquid crystal display element having excellent pretilt angle stability, and is useful for a vertical alignment type liquid crystal display element.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-120053 filed on June 6, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

An alkoxysilane compound represented by the following formula [1] and having a ring structure linked by an amide bond.

(In the formula [1], Z 1 , Z 2 and Z 3 are each independently R 1 , OR 1 or OCOR 1 (R 1 is a linear or branched hydrocarbon having 1 to 4 carbon atoms) Group except that Z 1 , Z 2 and Z 3 are all R 1. a is an integer of 1 to 18. m is 1 or 2. Z 4 is H, .Y 1 is a methyl group or a phenyl group, a single bond, -R 2 O -, - R 2 OCO -, - R 2 COO -, - CH = CH -, - C (CH 3) = CH- or - C≡C— (R 2 is a linear or branched hydrocarbon group having 1 to 3 carbon atoms) Cy 1 is a divalent cyclic group selected from a phenylene group, a naphthylene group, and a cyclohexylene group. or .Cy 2 is an organic group having a carbon number of 12-40 with a steroid skeleton, a phenylene group, a naphthylene group and a cyclohexylene group Divalent any hydrogen atom present on the cyclic group [Cy 1 and Cy 2 in the selected La, F, CN, OH, R 3 and OR 3 (R 3 is a straight-chain having 1 to 4 carbon atoms Or may be substituted with a group selected from a branched hydrocarbon group or a linear or branched fluorine-containing hydrocarbon group having 1 to 4 carbon atoms.] N is 0, 1 or 2 Z 5 is H, CN, R 4 or OR 4 (R 4 is a linear or branched hydrocarbon group having 1 to 18 carbon atoms, or a linear or branched fluorine atom having 1 to 18 carbon atoms. (However, when Cy 1 is a C 12-40 organic group having a steroid skeleton, n is 0 and Z 5 is unsubstituted.)
The alkoxysilane compound according to claim 1, wherein a is 3 and m is 1.
a is 3, m is 1, Z 4 is H, alkoxy silane compound according to claim 1 Y 1 is a single bond.
By treating the carboxylic acid represented by the following formula [2] with a chlorinating agent to obtain an acid chloride represented by the following formula [3], the acid chloride and the following formula [4] are used. The method for producing an alkoxysilane compound according to claim 1, wherein the alkoxysilane compound represented is reacted in the presence of a base.

(In formula [2], Y 1 , Cy 1 , Cy 2 , Z 5 and n have the same meaning as described above.)

(In formula [3], Y 1 , Cy 1 , Cy 2 , Z 5 and n represent the same meaning as described above.)

(In the formula [4], Z 1 , Z 2 , Z 3 , Z 4 , a and m have the same meaning as described above.)
The production method according to claim 4, wherein a is 3 and m is 1.
The production method according to claim 4, wherein a is 3, m is 1, Z 4 is H, and Y 1 is a single bond.
Polysiloxane containing the alkoxysilane compound according to claim 1 as a constituent component.
The polysiloxane according to claim 7, wherein the content of the alkoxysilane according to claim 1 is 1 to 30 mol% in the total alkoxysilane.
A liquid crystal aligning agent containing the polysiloxane according to claim 7 or 8.
The liquid crystal aligning agent according to claim 9, wherein the polysiloxane content is 0.5 to 15% by mass in terms of SiO 2 concentration.
A liquid crystal alignment film obtained by applying the liquid crystal aligning agent according to claim 9 or 10 to a substrate, drying and baking.
A liquid crystal display element having the liquid crystal alignment film according to claim 11.
A liquid crystal display element obtained by irradiating an ultraviolet ray in a state where a voltage is applied to a liquid crystal cell in which the liquid crystal is sandwiched between two substrates that are coated with the liquid crystal aligning agent according to claim 9 and baked.
A method for producing a liquid crystal display element, wherein the liquid crystal aligning agent according to claim 9 or 10 is applied, the liquid crystal is sandwiched between two baked substrates, and ultraviolet rays are irradiated with a voltage applied.