TW201402701A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crytal display device - Google Patents

Abstract

A purpose of this invention is to provide a liquid crystal alignment agent capable of forming an in-plane switching type or fringe field switching type liquid crystal display device which has excellent properties such as high-speed responsivity, and the in-plane switching type or fringe field switching type liquid crystal display device having a liquid crystal alignment film formed by the liquid crystal alignment agent. The liquid crystal alignment agent for forming the liquid crystal alignment film in the in-plane switching type or fringe field switching type liquid crystal display device is characterized in containing [A] a compound having a group represented by the following formula (1) (hereinafter also called ''a compound [A]''). In formula (1), R1 is a group having at least two single-ring structures, R2 is a connection group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom, and a is an integer of 0 to 1.

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

In recent years, liquid crystal display elements have advantages such as low power consumption, ease of miniaturization, and planarization. Therefore, they are used in a wide range of applications from small liquid crystal display devices such as mobile phones to large-screen liquid crystal display devices such as liquid crystal televisions. .

At present, as a driving mode of a liquid crystal display device, a twisted nematic (TN), a super twisted nematic (Super Twisted Nematic), and a coplanar switching are known in accordance with changes in the alignment (arrangement) state of liquid crystal molecules. In-Plane Switching (IPS), Fringe Field Switching (FFS), Vertical Alignment (VA), and the like.

Among these driving modes, it is known that the electrode pair is arranged in a comb-tooth shape in one substrate surface, and the driving direction of the liquid crystal when an electric field is applied is only an IPS (In-Plane Switching) type liquid crystal display element in the in-plane direction of the substrate. FFS (Fringe) that changes the IPS type electrode structure and increases the aperture ratio of the display element portion to increase the brightness The Field Switching type liquid crystal display element has excellent viewing angle characteristics (refer to Japanese Patent Laid-Open No. Hei 56-91277, U.S. Patent No. 5,928,733, and Japanese Patent Laid-Open No. Hei No. No. 2008-216572). Further, it is known that since liquid crystal is always aligned in parallel with respect to the substrate, liquid crystal disturbance caused by pressure from the outside is small, and display defects such as spots are less likely to occur. Therefore, the application of the IPS method or FFS in applications such as mobile phones and tablet personal computers equipped with a touch screen function is expanding.

However, in recent years, a mobile phone or a tablet computer is being used as an animation display device, and as a characteristic required for a liquid crystal display device, in order to smoothly display an animation and suppress the afterimage as much as possible, it is required to further increase the response speed of the liquid crystal.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. SHO 56-91277

[Patent Document 2] U.S. Patent No. 5,928,733

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2008-216572

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal alignment agent comprising an IPS method or an FFS liquid crystal display element comprising a liquid crystal alignment film formed of the liquid crystal alignment agent, the liquid crystal alignment agent An IPS method or an FFS liquid crystal display element which satisfies the liquid crystal alignment property which is generally required for a liquid crystal display element and which is excellent in liquid crystal responsiveness can be formed.

The invention completed to solve the above problem is a liquid crystal alignment agent, which A liquid crystal alignment agent for forming a liquid crystal alignment film in an IPS method or an FFS liquid crystal display device, which comprises [A] a compound having a group represented by the following formula (1) (hereinafter also referred to as "[A] compound").

In the formula (1), R ¹ is a group having at least two monocyclic structures. R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom. a is an integer from 0 to 1.

The liquid crystal alignment agent contains the compound [A], and the alignment controllability of the liquid crystal molecules is excellent, and the compound [A] has the group having a dielectric anisotropy. Therefore, the liquid crystal molecules of the IPS method or the FFS liquid crystal display element having the liquid crystal alignment film formed using the liquid crystal alignment agent are excellent in the alignment property, and the response time can be shortened.

The compound [A] preferably includes a moiety derived from a polyorganosiloxane having an epoxy group, and a compound derived from a carboxyl group represented by the following formula (2) (hereinafter, also referred to as "specific carboxylic acid" )part.

In the formula (2), R ¹ , R ² and a have the same meanings as in the above formula (1). R ³ is a methylene group or an alkylene group having a carbon number of 2 to 30, a phenyl group or a cyclohexylene group, and these groups may further have a substituent.

According to the liquid crystal alignment agent, by utilizing the reactivity of an epoxy group and a carboxyl group, As the compound [A], a structure having a dielectric anisotropy represented by the above formula (1) as a side chain can be easily introduced into a polyorganosiloxane as a main chain. Therefore, the liquid crystal alignment agent can effectively impart high-speed responsiveness to the obtained liquid crystal display element.

The R ¹ is preferably a group represented by the following formula (3).

In the formula (3), R ⁴ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group. R ⁵ and R ⁷ are each independently a pendant phenyl group, a stretched biphenyl group, an extended naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylphenyl group or a heterocyclic ring, and these groups may further have a substituent. R ⁶ is an alkylene group having 1 to 10 carbon atoms and a linking group containing a double bond, a triple bond, an ether bond, an ester bond, and a hetero ring, and these groups may further have a substituent. b is an integer from 1 to 9. When b is 2 or more, a plurality of R ^{4 's} may be the same or different. c is an integer from 0 to 1. d is an integer from 1 to 2. When d is 2, a plurality of R ⁶ , R ⁷ and c may be the same or different from each other.

By introducing the structure represented by the above formula (3) into the compound [A] of the liquid crystal alignment agent, the responsiveness of the obtained liquid crystal display element can be increased.

The epoxy group is preferably a group represented by the following formula (X ¹ -1) or (X ¹ -2).

[Chemical 4]

In the formula (X ¹ -1), A is an oxygen atom or a single bond. h is an integer from 1 to 3. i is an integer from 0 to 6. Wherein, when i is 0, A is a single bond.

In the formula (X ¹ -2), j is an integer of 0-6.

By including the group represented by the formula (X ¹ -1) or the formula (X ¹ -2) in the polyorganosiloxane, it is easy to introduce the group represented by the formula (1) to The liquid crystal alignment agent is a compound of [A].

The liquid crystal alignment agent preferably further includes [B] at least one polymer selected from the group consisting of polylysine and polyimine (hereinafter also referred to as "[B] polymer"). When a liquid crystal alignment film is formed using a liquid crystal alignment agent containing a [B] polymer, a liquid crystal display element in which liquid crystal alignment property is further improved can be obtained.

The liquid crystal display element of the present invention is an IPS method or an FFS liquid crystal display element including a liquid crystal alignment film formed of the liquid crystal alignment agent. According to the liquid crystal display device, the liquid crystal alignment film is formed of the liquid crystal alignment agent, whereby the liquid crystal alignment property is high, and excellent high-speed response can be exhibited.

As described above, the liquid crystal alignment agent of the present invention can form an IPS method or an FFS liquid crystal display element having various characteristics such as high-speed responsiveness. In addition, the liquid crystal display element of the present invention is used as an element of the IPS mode or the FFS mode. It can be used for high responsiveness.

10‧‧‧ glass

20‧‧‧Alignment film

30‧‧‧Transparent top electrode

40‧‧‧Transparent bottom electrode

50‧‧‧ nitride

1 is a cross-sectional view showing the structure of a liquid crystal display element produced in Examples and Comparative Examples.

2 is a schematic view (plan view) showing an electrode structure of a liquid crystal display element produced in Examples and Comparative Examples.

Hereinafter, the form of the liquid crystal alignment agent and liquid crystal display element of the present invention will be described in detail.

<Liquid alignment agent>

The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent for forming a liquid crystal alignment film in an IPS method or an FFS liquid crystal display element, and is characterized by containing the compound [A]. Further, the liquid crystal alignment agent may contain a "other polymer" to be described later, such as a [B] polymer. Further, the liquid crystal alignment agent may contain other optional components within the range which does not impair the effects of the present invention. Hereinafter, each component will be described in detail.

<[A] compound>

The compound [A] is a compound having a group represented by the above formula (1). The group represented by the formula (1) has dielectric anisotropy, and the liquid crystal molecules of the liquid crystal alignment agent containing the [A] compound are excellent in alignment controllability. Therefore, an IPS method or an FFS liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal alignment agent The alignment of the liquid crystal molecules of the device is good, and the response time can be shortened.

In the formula (1), R ¹ is a group having at least two single ring structures, and preferably exhibits positive or negative dielectric anisotropy. The single ring structure refers to a structure in which one ring structure exists independently of the other ring structures, and a bond of one ring structure and other ring structures do not have a so-called condensed ring structure. Further, the monocyclic structure may be any of an alicyclic structure, an aromatic ring structure, or a heterocyclic structure, or these structures may be combined and contained.

R ¹ is not particularly limited as long as it has at least two monocyclic structures, but R ¹ is preferably a group represented by the above formula (3). By introducing the structure represented by the above formula (3) into the side chain of the [A] compound of the liquid crystal alignment agent, the liquid crystal response speed of the obtained liquid crystal alignment element can be increased.

In the formula (3), R ⁴ is any one of a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group, and an alkoxy group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group; and examples of the alkyl group include a carbon such as a methyl group, an ethyl group, a propyl group, a n-butyl group, and an isobutyl group. The number is a linear or branched alkyl group of 1 to 20, and the like, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

In the formula (3), when a plurality of R ⁴ are present, R ⁴ different from each other may be used in combination. As a combination with a plurality of R ⁴ , in order to stably exhibit a desired dielectric anisotropy, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, and a combination of a cyano group and an alkyl group are preferable. Furthermore, b is an integer from 0 to 9.

In the formula (3), R ⁵ and R ⁷ are each independently a stretching phenyl group, a stretching phenyl group, a stretching naphthyl group, a cyclohexylene group, a dicyclohexyl group, a cyclohexylene group or a hetero ring. Examples of the hetero ring include a pyridine ring, a pyridazine ring, and a pyrimidine ring.

In the formula (3), R ⁶ is an alkylene group having 1 to 10 carbon atoms, and contains a double bond, a triple bond, an ether bond, an ester bond, and a hetero ring, and links R ⁵ and R ⁷ . Further, these groups (alkyl or heterocyclic) may further have a substituent. It can be suitably selected corresponding to the orientation or dielectric anisotropy required for the [A] compound. Further, c is an integer of 0 or 1, and therefore may contain R ⁶ or may not contain R ⁶ .

In the formula (3), d is an integer of 1 to 2. When d is 2, a plurality of R ⁶ , R ⁷ and c may be the same or different from each other.

Examples of the group represented by the formula (3) include a group represented by the following formula (D-1) to formula (D-116).

[Chemical 5]

[Chemical 6]

[Chemistry 7]

[Chemistry 9]

[化10]

[11]

In the formula (D-1) to the formula (D-116), R is an alkyl group having 1 to 20 carbon atoms (methyl, ethyl, propyl, n-butyl, isobutyl, n-pentyl, n-hexyl) Or) alkoxy (methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.).

In the formula (1), R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom. R ^{2 may} contain any of the above-mentioned bonds, but each of the bonds may be combined and contained. Further, when R ^{3 to} be described later is a phenylene group or a cyclohexylene group, R ² preferably contains a carbon number of 1 to 30 from the viewpoint of the alignment property of the alignment film formed or the solubility in a solvent. alkyl. Furthermore, a is an integer from 0 to 1.

The compound [A] is not particularly limited as long as it has a group represented by the above formula (1), but a polymer having a group represented by the formula (1) in a side chain is preferable, and in terms of electrical properties, More preferably, polyorganosiloxane, polyimine, polyglycolic acid, polyacrylate, polymethacrylate, poly(styrene-phenylmethylene iodide) derivative, fiber Derivatives, polyesters, polyamines, polystyrene derivatives, The polyglycolate is a compound having a main chain structure, and in terms of light resistance, a compound having a polyorganosiloxane as a main chain structure is more preferable.

The compound [A] having a polyorganosiloxane as a main chain structure preferably includes a moiety derived from a polyorganosiloxane having an epoxy group, and a source derived from the specific carboxylic acid represented by the formula (2). Part of the compound. A liquid crystal display element having a liquid crystal alignment film formed using the liquid crystal alignment agent, wherein the [A] compound in the liquid crystal alignment agent has a specific structural unit and a structure having a dielectric anisotropy is introduced into the side chain. Further reduce response time. Further, by utilizing the reactivity between the epoxy group and the carboxyl group, the structure having the dielectric anisotropy represented by the above formula (1) as a side chain can be easily introduced into the polyorganism as a main chain. In the oxime.

When the [A] compound includes a moiety derived from a polyorganosiloxane having an epoxy group, and a moiety derived from the specific carboxylic acid, it can be considered as an epoxy group of a polyorganosiloxane and a specific carboxylic acid. Obtained as a reactant of a carboxyl group, but in order to facilitate the subsequent description, it is conveniently divided into a portion derived from a polyorganosiloxane having an epoxy group (and a derivative thereof), and a specific carboxylic acid. The part is to explain the [A] compound.

[Derived from a portion of a polyorganosiloxane having an epoxy group]

The concept of this part includes the structure of the compound [A], a polyorganosiloxane skeleton as a polymer main chain, and an epoxy group-containing skeleton as a side chain extending from the polyorganosiloxane main chain. . As described above, in the compound [A], it is considered that most of the epoxy groups react with a specific carboxylic acid without having an initial structure, but it is also possible that a specific carboxylic acid is bonded to a portion other than the epoxy group. Case. therefore, The form including both in the present invention is referred to as "a portion derived from a polyorganosiloxane having an epoxy group".

When the [A] compound has an epoxy group such as a glycidyl group, a glycidoxy group or an epoxycyclohexyl group-containing group, the alignment property or high-speed responsiveness and the isoelectric characteristics of the liquid crystal alignment agent are further improved. As the epoxy group, a group represented by the above formula (X ¹ -1) or formula (X ¹ -2) is preferred. By poly siloxane-containing organic silicon group represented by (X ¹ -1) or Formula (X ¹ -2) represented by the formula in [A] compounds, is easy to use by the specific carboxylic acids of formula ( 1) The indicated group is introduced into the side chain.

Among the above formula (X ¹ -1) or formula (X ¹ -2), a group represented by the following formula is preferable.

The polyorganosiloxane having an epoxy group has a polystyrene-equivalent weight average molecular weight measured by Gel Permeation Chromatography (GPC) of preferably 500 to 100,000, more preferably 1,000 to 50,000, particularly preferably 1,000. 20,000.

[Synthesis method of polyorganosiloxane having epoxy group]

Such an epoxy group-containing polyorganosiloxane can be synthesized by preferably, in the presence of a suitable organic solvent, water and a catalyst, a decane compound having an epoxy group or having an epoxy group. Decane compounds and other decaneization The mixture of the compounds is hydrolyzed or hydrolyzed. condensation.

Examples of the decane compound having an epoxy group include 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, and 3-glycidoxypropyl group. Methyldimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyldimethylmethoxydecane, 3-glycidoxypropyldimethyl Ethoxy decane, 2-glycidoxyethyl trimethoxy decane, 2-glycidoxyethyl triethoxy decane, 2-glycidoxyethyl methyl dimethoxy decane, 2 - glycidoxyethyl methyldiethoxy decane, 2-glycidoxyethyl dimethyl methoxy decane, 2-glycidoxyethyl dimethyl ethoxy decane, 4-shrinkage Glyceroxybutyltrimethoxydecane, 4-glycidoxybutyltriethoxydecane, 4-glycidoxybutylmethyldimethoxydecane, 4-glycidoxybutylmethyldiethoxy矽, 4-glycidoxybutyl dimethyl methoxy decane, 4-glycidoxy butyl dimethyl ethoxy decane, 2-(3,4-epoxy ring Hexyl)ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, 3-(3,4-epoxycyclohexyl)propyltrimethoxydecane, 3- (3,4-epoxycyclohexyl)propyltriethoxydecane, and the like. These decane compounds may be used alone or in combination of two or more.

Examples of the other decane compound include tetrachloromethane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetra-isopropoxy decane, and tetra-n-butoxy decane. , tetra-butoxy decane, trichlorodecane, trimethoxy decane, triethoxy decane, tri-n-propoxy decane, tri-isopropoxy decane, tri-n-butoxy decane, three - second butoxy decane, fluorotrichloro decane, fluorotrimethoxy decane, fluorine Triethoxy decane, fluorotri-n-propoxy decane, fluorotri-isopropoxy decane, fluorotri-n-butoxy decane, fluorotri- 2 -butoxy decane, methyl trichloro decane, A Trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl tri-isopropoxy decane, methyl tri-n-butoxy decane, methyl tri-second Butoxy decane, 2-(trifluoromethyl)ethyltrichlorodecane, 2-(trifluoromethyl)ethyltrimethoxydecane, 2-(trifluoromethyl)ethyltriethoxydecane, 2-(Trifluoromethyl)ethyltri-n-propoxydecane, 2-(trifluoromethyl)ethyltris-isopropoxydecane, 2-(trifluoromethyl)ethyltri-n-butyl Oxydecane, 2-(trifluoromethyl)ethyltri-t-butoxydecane, 2-(perfluoro-n-hexyl)ethyltrichlorodecane, 2-(perfluoro-n-hexyl)ethyltrimethyl Oxydecane, 2-(perfluoro-n-hexyl)ethyltriethoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-hexyl)ethyl Tris-isopropoxydecane, 2-(perfluoro-n-hexyl)ethyltri-n-butoxydecane, 2-(perfluoro-n-hexyl)ethyltri-t-butoxydecane, 2- (all Fluorine-n-octyl)ethyltrichlorodecane, 2-(perfluoro-n-octyl)ethyltrimethoxydecane, 2-(perfluoro-n-octyl)ethyltriethoxydecane, 2-( Perfluoro-n-octyl)ethyltri-n-propoxydecane, 2-(perfluoro-n-octyl)ethyltris-isopropoxydecane, 2-(perfluoro-n-octyl)ethyltri - n-butoxydecane, 2-(perfluoro-n-octyl)ethyltri-t-butoxydecane, methylol trichloromethane, hydroxymethyltrimethoxydecane, hydroxyethyltrimethoxydecane , hydroxymethyl tri-n-propoxy decane, methylol tris-isopropoxy decane, hydroxymethyl tri-n-butoxy decane, hydroxymethyl tri-second butoxy decane, 3-(A Base) propylene methoxy propyl trichloro decane, 3-(methyl) propylene methoxy propyl trimethoxy decane, 3-(methyl) propylene methoxy propyl triethoxy decane, 3- ( Methyl) propylene methoxy propyl tri-n-propoxy decane, 3-(methyl) propylene methoxy propyl tri-isopropoxy decane, 3-(methyl) propylene oxime Propyltri-n-butoxydecane, 3-(methyl)propenyloxypropyltri-t-butoxydecane, 3-mercaptopropyltrichlorodecane, 3-mercaptopropyltrimethoxydecane , 3-mercaptopropyltriethoxydecane, 3-mercaptopropyltri-n-propoxyoxydecane, 3-mercaptopropyltris-isopropoxydecane, 3-mercaptopropyltri-n-butoxydecane , 3-mercaptopropyltri-t-butoxydecane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, vinyltrichloromethane, vinyltrimethoxydecane, vinyltriethoxy Base decane, vinyl tri-n-propoxy decane, vinyl tri-isopropoxy decane, vinyl tri-n-butoxy decane, vinyl tri-second butoxy decane, allyl trichloro decane , allyl trimethoxy decane, allyl triethoxy decane, allyl tri-n-propoxy decane, allyl tri-isopropoxy decane, allyl tri-n-butoxy decane , allyl tri-second butoxy decane, phenyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl tri-n-propoxy decane, phenyl tri-isopropyl Oxydecane, Phenyl tri-n-butoxy decane, phenyl tri-second butoxy decane, methyl dichlorodecane, methyl dimethoxy decane, methyl diethoxy decane, methyl di-n-propoxy Base decane, methyl di-isopropoxy decane, methyl di-n-butoxy decane, methyl di-second butoxy decane, dimethyl dichloro decane, dimethyl dimethoxy decane, Dimethyldiethoxydecane, dimethyldi-n-propoxydecane, dimethyldi-isopropoxydecane, dimethyldi-n-butoxydecane, dimethyldi-second Oxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dichlorodecane, (methyl)[2-(perfluoro-n-octyl)ethyl]dimethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]diethoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-propoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-isopropoxydecane, (methyl)[2-(perfluoro-n-octyl)ethyl]di-n-butoxy Decane, (methyl) [2- (all Fluoro-n-octyl)ethyl]di-second butoxydecane, (methyl)(3-mercaptopropyl)dichlorodecane, (methyl)(3-mercaptopropyl)dimethoxydecane, (methyl)(3-mercaptopropyl)diethoxydecane, (methyl)(3-mercaptopropyl)di-n-propoxydecane, (methyl)(3-mercaptopropyl)di-iso Propoxy decane, (methyl) (3-mercaptopropyl) di-n-butoxy decane, (methyl) (3-mercaptopropyl) bis-second butoxy decane, (methyl) (ethylene Dichloromethane, (meth) (vinyl) dimethoxy decane, (methyl) (vinyl) diethoxy decane, (methyl) (vinyl) di-n-propoxy decane, (methyl)(vinyl)di-isopropoxydecane, (methyl)(vinyl)di-n-butoxydecane, (methyl)(vinyl)di-secondbutoxydecane, two Vinyl chlorin, divinyl dimethoxy decane, divinyl diethoxy decane, divinyl di-n-propoxy decane, divinyl di-isopropoxy decane, divinyl bis - n-butoxydecane, divinyldi-second butoxydecane, diphenyldichlorodecane, diphenyldimethoxydecane, diphenyldiethoxydecane, Phenyl di-n-propoxy decane, diphenyl di-isopropoxy decane, diphenyl di-n-butoxy decane, diphenyl di-second butoxy decane, chlorodimethyl decane, Methoxy dimethyl decane, ethoxy dimethyl decane, chlorotrimethyl decane, bromotrimethyl decane, iodine trimethyl decane, methoxy trimethyl decane, ethoxy trimethyl decane, N-propoxy trimethyl decane, isopropoxy trimethyl decane, n-butoxy trimethyl decane, second butoxy trimethyl decane, third butoxy trimethyl decane, (chlorine) (vinyl) dimethyl decane, (methoxy) (vinyl) dimethyl decane, (ethoxy) (vinyl) dimethyl decane, (chloro) (methyl) diphenyl decane, ( A decane compound having one ruthenium atom such as (methoxy)(methyl)diphenyl decane or (ethoxy)(methyl)diphenyl decane.

As a commercial item, for example, KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X- 22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40- 9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (above, Shin-Etsu Chemical Co., Ltd.); Glass Resin (Showa Denko); SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, SR2420 (above, Toray Dow Corning); FZ3711, FZ3722 (above, Nippon Unicar); DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS -S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-22 7. PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso); methyl decanoate MS51, methyl decanoate MS56 (above, Mitsubishi Chemical Corporation); Ethyl citrate 28, ethyl decanoate 40, ethyl decanoate 48 (above, Colcoat); partial condensates such as GR100, GR650, GR908, GR950 (above, Showa Denko).

Among these other decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, and methyl triethyl are preferable from the viewpoint of the alignment property and storage stability of the liquid crystal alignment agent to be obtained. Oxydecane, 3-(meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyl triethyl Oxydecane, allyltrimethoxydecane, allyltriethoxydecane, phenyltrimethoxydecane, phenyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropane Triethoxy decane, mercaptomethyltrimethoxydecane, mercaptomethyltriethoxydecane, dimethyldimethoxydecane, dimethyldiethoxydecane.

The polyorganosiloxane having an epoxy group which can be preferably used in the present invention is preferably introduced in a sufficient amount to introduce a side chain having a dielectric anisotropy, preferably having an epoxy equivalent of from 100 g/m<0> to 10,000 g/mole. It is preferably 150 g/mole to 1,000 g/mole, particularly preferably 150 g/mole to 300 g/mole. Therefore, when synthesizing a precursor of a polyorganosiloxane having an epoxy group, it is preferred to prepare a decane compound in such a manner that the epoxy equivalent of the obtained polyorganosiloxane having an epoxy group is in the above range. Ratio of use to other decane compounds. When synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is more preferred to use only a decane compound instead of other decane compounds.

As organic which can be used in the synthesis of polyorganosiloxanes having epoxy groups Examples of the solvent include a hydrocarbon compound, a ketone compound, an ester compound, an ether compound, and an alcohol compound.

Examples of the hydrocarbon include toluene and xylene; and examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, diethyl ketone, and cyclohexanone. And examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate, and the like; Examples of the alcohol include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Among these organic solvents, a water-insoluble organic solvent is preferred. These organic solvents may be used singly or in combination of two or more.

The amount of the organic solvent used is preferably 10 parts by mass to 10,000 parts by mass, more preferably 50 parts by mass to 1,000 parts by mass, based on 100 parts by mass of all the decane compounds. The amount of water used in the production of the polyorganosiloxane having an epoxy group is preferably from 0.5 to 100 moles, more preferably from 1 to 30 moles, relative to all of the decane compound.

As the catalyst, for example, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound or the like can be used.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.

Examples of the organic base include ethylamine, diethylamine, piperazine, and piperazine. a primary organic amine such as pyridine, pyrrolidine or pyrrole, a secondary organic amine; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc. Grade organic amine; tetrabasic organic amine such as tetramethylammonium hydroxide. Among these organic bases, in view of the fact that the reaction proceeds smoothly, a tertiary organic amine such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine or 4-dimethylaminopyridine is preferred; A quaternary organic amine such as a quaternary ammonium.

As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferred. By using an alkali metal compound or an organic base as a catalyst, a side reaction such as ring opening of an epoxy group can be produced without high hydrolysis. Since the condensation rate is obtained as the target polyorganosiloxane, the production stability is excellent and it is preferable. Further, the liquid crystal alignment agent containing a reaction product of an epoxy group-containing polyorganosiloxane and a specific carboxylic acid synthesized by using an alkali metal compound or an organic base as a catalyst is excellent in storage stability and is therefore suitable. The reason is presumed to be as follows: as indicated in Chemical Reviews, 95, p1409 (1995), if an alkali metal compound or an organic base is used as a catalyst in the hydrolysis or condensation reaction, a random structure is formed. In the ladder structure or the cage structure, a polyorganosiloxane having a small content of a stanol group can be obtained. It is presumed that since the content ratio of the stanol group is small, the condensation reaction between the stanol groups is suppressed, and further, when the liquid crystal alignment agent is a liquid crystal alignment agent containing another polymer described later, the condensation of the decyl alcohol group with another polymer Since the reaction is suppressed, it is excellent in storage stability.

As the catalyst, an organic base is particularly preferred. The amount of the organic base to be used varies depending on the type of the organic base, the reaction conditions such as the temperature, and the like, and should be appropriately set, for example, relative Preferably, from 0.01 moles to 3 moles, more preferably from 0.05 moles to 1 moles, of all decane compounds.

Hydrolysis or hydrolysis when producing polyorganosiloxanes with epoxy groups. The condensation reaction is preferably carried out by dissolving a decane compound having an epoxy group and, if necessary, another decane compound in an organic solvent, mixing the solution with an organic base and water, and heating the mixture with, for example, an oil bath.

In hydrolysis. In the condensation reaction, the heating temperature of the oil bath is preferably 130 ° C or lower, more preferably 40 ° C to 100 ° C, and preferably 0.5 to 12 hours, more preferably 1 hour to 8 hours. heating. The mixture may be stirred during heating or placed under reflux.

After completion of the reaction, the organic solvent layer separated from the reaction liquid is preferably washed with water. At the time of the cleaning, it is preferable to use a water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by mass or the like, to facilitate the cleaning operation. After the cleaning is carried out until the water layer after the cleaning is made neutral, the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve as necessary, and the solvent is removed, whereby the desired epoxy group can be obtained. Polyorganosiloxane.

In the present invention, a commercially available product sold as a polyorganosiloxane having an epoxy group can also be used. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21, and EMS-32 (above, Chisso Corporation).

The [A] compound may also contain a moiety derived from a hydrolyzate produced by hydrolysis of a polyorganosiloxane having an epoxy group itself, or a polyorgano group having an epoxy group. A portion of a hydrolysis condensate obtained by hydrolyzing and condensing a siloxane with each other. The hydrolyzate or hydrolysis condensate which is a constituent material of the portion may be prepared in the same manner as the hydrolysis and condensation conditions of the polyorganosiloxane having an epoxy group.

[part of a specific carboxylic acid]

The portion derived from the specific carboxylic acid represented by the formula (2) corresponds to a side chain mainly extending from the polyorganosiloxane main chain among the structures of the [A] compound contained in the liquid crystal alignment agent. In the structure, the side chain structure will serve as a starting point for a carboxyl group-derived structure bonded to an epoxy group-derived structure. However, in the present invention, the case where a specific carboxylic acid is bonded to a portion other than the epoxy group is also referred to as "a portion derived from a specific carboxylic acid".

² the same (2) in the formula, R ¹ and R and R (1) and R ¹ in the formula ^2.

R ³ of the formula (2) is a methylene group or an alkylene group having a carbon number of 2 to 30, a phenyl group or a cyclohexylene group, and these groups may further have a substituent.

Examples of the alkylene group having a carbon number of 2 to 30 include an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a hydrazine group, a hydrazine group, and an undecane group. Base, extended dodecyl, tetradecyl, hexadecyl, octadecyl, hexadecyl, eicosyl, eicosyl, tetradecane Base, thirteenthylene, tetracosyl, tetradecyl, hexadecyl, hexadecyl, octadecyl, hexadecyl And stretching thirty alkyl groups. Among these alkylene groups, in order to stably exhibit liquid crystal alignment, it is preferred to extend a pentyl group, a hexyl group, a octyl group, a decyl group, a decyl group, an undecyl group, a dodecyl group, and a tetradecene group. alkyl The alkyl group having a carbon number of 5 or more and 20 or less, such as a hexadecyl group, an octadecyl group, an extended octadecyl group, and an eicosyl group.

Examples of the compound having a carboxyl group represented by the above formula (2) include compounds represented by the following formulas (E-1) to (E-25).

In the formula (E-1) to the formula (E-25), the meaning of R ^{1 is} the same as the above formula (2). m is an integer from 1 to 30.

[Synthesis method of specific carboxylic acid]

The synthesis procedure of the specific carboxylic acid is not particularly limited, and a conventionally known method can be combined and carried out. As a typical synthesis procedure, for example, the following method and the like can be exemplified: (1) a compound having a phenol skeleton is reacted with a compound in which an alkyl chain moiety of a higher fatty acid ester is substituted with a halogen under basic conditions to form a compound. a method in which a hydroxyl group of a phenol skeleton is bonded to a carbon substituted with a halogen, followed by reduction of the ester to form a specific carboxylic acid; (2) reacting a compound having a phenol skeleton with ethylene carbonate to form a terminal alcohol compound, and then The hydroxyl group of the terminal alcohol compound is reacted with the halogenated benzenesulfonium chloride to be activated, and then the activated moiety is reacted with the hydroxyl group-containing methyl benzoate to partially liberate the sulfonyl group, and the hydroxyl group of the terminal alcohol compound is formed. A method of forming a specific carboxylic acid by bonding a hydroxyl group of methyl benzoate having a hydroxyl group as a substituent, followed by reduction of the ester. However, the synthesis procedure of a specific carboxylic acid is not limited to these methods.

<Method for synthesizing [A] compound>

The method for synthesizing the [A] compound is not particularly limited, and can be synthesized by a generally known method. When the compound of [A] includes a moiety derived from a polyorganosiloxane having an epoxy group and a moiety derived from a specific carboxylic acid, it is preferable to make a polyorganosiloxane having an epoxy group and a specific carboxylic acid preferably The reaction is carried out in the presence of a catalyst to synthesize.

Here, the specific carboxylic acid is preferably used in an amount of from 0.001 mol to 10 mol, more preferably 0.01 mol to 5 mol, and more preferably 0.05 mol, based on 1 mol of the epoxy group of the polyorganosiloxane. Ears ~ 2 moles.

In the present invention, a part of the specific carboxylic acid may be used instead of a compound represented by the following formula (4) within the range which does not impair the effects of the present invention. In this case, the synthesis of the [A] compound can be carried out by reacting a polyorganosiloxane having an epoxy group with a mixture of a specific carboxylic acid and a compound represented by the following formula (4).

[14] A ¹ -L ⁰ -L ¹ -Z (4)

In the formula (4), A ¹ is a linear or branched alkyl group having 1 to 30 carbon atoms, and the carbon number may be 3 to 10 by an alkyl group or an alkoxy group having 1 to 20 carbon atoms. Cycloalkyl. Here, a part or all of the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a substituent such as a cyano group, a fluorine atom or a trifluoromethyl group.

L ⁰ is a single bond, *-O-, *-COO- or *-OCO-. With "*" is a bond and A ¹ are bonded.

L ¹ is a single bond, an alkyl group having a carbon number of 1 to 20, a phenyl group, a phenyl group, a phenylene group, a cyclohexylene group or a formula (L ¹ -1) or (L ¹ - 2) The base represented.

Z is a monovalent organic group which can react with an epoxy group in the [A] polyorganosiloxane compound to form a binding group.

Wherein, when L ¹ is a single bond, L ⁰ is a single bond.

[化15]

The bond of formula (L ¹ -1) and formula (L ¹ -2), the with "*" are bonded with Z.

Z is preferably a carboxyl group.

Examples of the linear or branched alkyl group having 1 to 30 carbon atoms represented by A ¹ in the formula (4) include methyl group, ethyl group, n-propyl group, isopropyl group and n-butyl group. Base, second butyl, tert-butyl, n-pentyl, 3-methylbutyl, 2-methylbutyl, 1-methylbutyl, 2,2-dimethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3-dimethylbutyl, 2,3-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,1-dimethylbutyl, n-glycol , 5-methylhexyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl, 4,4-dimethylpentyl, 3,4-dimethylpentyl Base, 2,4-dimethylpentyl, 1,4-dimethylpentyl, 3,3-dimethylpentyl, 2,3-dimethylpentyl, 1,3-dimethylpentyl Base, 2,2-dimethylpentyl, 1,2-dimethylpentyl, 1,1-dimethylpentyl, 2,3,3-trimethylbutyl, 1,3,3- Trimethylbutyl, 1,2,3-trimethylbutyl, n-octyl, 6-methylheptyl, 5-methylheptyl, 4-methylheptyl, 3-methylheptyl, 2-methylheptyl, 1-methyl Heptyl, 2-ethylhexyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexa Alkyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and the like.

As the carbon number which can be substituted by an alkyl group or an alkoxy group having 1 to 20 carbon atoms, it is 3 Examples of the cycloalkyl group of ～10 include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclodecyl group, a cyclododecyl group, and the like.

A ¹ in the above formula (4) is preferably a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a fluoroalkyl group having 1 to 20 carbon atoms.

The compound represented by the formula (4) is preferably a compound represented by any one of the following formulas (4-1) to (4 to 5).

In the formula (4-1) to the formula (4-5), u is an integer of 1 to 5. v is an integer from 1 to 18. w is an integer from 1 to 20. k is an integer from 1 to 5. p is 0 or 1. q is an integer from 0 to 18. r is an integer from 0 to 18. s and t are each independently an integer of 0~2.

Among these compounds, a compound represented by the following formula (4-6) to formula (4-11) is more preferable.

[化18]

In the present specification, the compound represented by the above formula (4) is sometimes referred to as "another carboxylic acid compound".

In the present invention, when a specific carboxylic acid and another carboxylic acid compound are used in combination, the total use ratio of the specific carboxylic acid and the other carboxylic acid compound is preferably 0.001 mol with respect to the epoxy group 1 mol of the polyorganosiloxane. The ear is ~1.5 moles, more preferably 0.01 moles to 1 mole, and even more preferably 0.05 moles to 0.9 moles. In this case, the other carboxylic acid compound is used in a range of preferably 40 mol% or less, more preferably 20 mol% or less, based on the total amount of the specific carboxylic acid. When the ratio of use of other pretilt angle developing compounds exceeds 40%, the viewing angle characteristics of the liquid crystal display element may be adversely affected.

As the catalyst used for the reaction of the epoxy group in the polyorganosiloxane and the other carboxylic acid compound, a known compound which is a so-called curing accelerator which is an organic base or a reaction which promotes the reaction of an epoxy compound and an acid anhydride can be used.

Examples of the organic base include ethylamine, diethylamine, piperazine, and piperazine. a primary organic amine such as pyridine, pyrrolidine or pyrrole, a secondary organic amine; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, etc. Grade organic amine; tetrabasic organic amine such as tetramethylammonium hydroxide. Among these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and tetramethylammonium hydroxide are preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, cyclohexyldimethylamine, and triethanolamine; Imidazole, 2-n-heptyl imidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyanoethyl)-2-methylimidazole, 1-(2- Cyanoethyl)-2-n-undecylimidazole, 1-(2-cyanoethyl)-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4- Methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-bis(hydroxymethyl)imidazole, 1-(2-cyanoethyl)-2 -Phenyl-4,5-bis[(2'-cyanoethoxy)methyl]imidazole, 1-(2-cyanoethyl)-2-n-undecylimidazolium trimellitate , 1-(2-cyanoethyl)-2-phenylimidazolium trimellitate, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazolium trimellitic acid Salt, 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-(2'-positive eleven Alkyl imidazolyl)ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'- Methylimidazolyl-(1')]ethyl-s-triazine, isomeric cyanuric acid addition of 2-methylimidazole, isomeric cyanuric acid addition of 2-phenylimidazole, 2,4 An imidazole compound such as an isomeric cyanuric acid adduct of diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine; Organic phosphorus compounds such as diphenylphosphine, triphenylphosphine, and triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, and bromide b Triphenylsulfonium, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium O, O -diethyldithiophosphate, tetra-n-butylphosphonium benzotriazole salt, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-butylphosphonium tetraphenylborate, tetraphenylphosphonium tetra a quaternary phosphonium salt such as a phenylborate; a diazabicycloalkenyl such as 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof; zinc octoate, tin octylate, aluminum acetonate An organometallic compound such as a complex compound; a tetra-ammonium salt such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride or tetra-n-butylammonium chloride; boron trifluoride, A boron compound such as triphenyl borate; a metal halogen compound such as zinc chloride or tin chloride; a high melting point dispersion type latent hardening promotion such as an amine addition accelerator such as dicyandiamide or an amine and an epoxy resin addition product; Coating the imidazole with a polymer Microcapsule latent hardening accelerator formed on the surface of a hardening accelerator such as a compound, an organophosphorus compound or a quaternary phosphonium salt; an amine salt type latent hardening accelerator; Lewis acid salt, Bronsted A latent curing accelerator such as a high temperature dissociating type thermal cationic polymerization type latent curing accelerator such as a Bronsted Acid salt.

Among these catalysts, tetraethylammonium bromide and tetra-n-butylammonium bromide are preferred. A quaternary ammonium salt such as tetraethylammonium chloride or tetra-n-butylammonium chloride.

The catalyst is used in an amount of preferably 100 parts by mass or less, more preferably 0.01 parts by mass to 100 parts by mass, still more preferably 0.1 parts by mass to 20 parts by mass, per 100 parts by mass of the polyorganosiloxane having an epoxy group.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C. The reaction time is preferably from 0.1 to 50 hours, more preferably from 0.5 to 20 hours.

The synthesis reaction of the [A] compound can be carried out in the presence of an organic solvent as needed. Examples of the organic solvent include a hydrocarbon compound, an ether compound, an ester compound, a ketone compound, a guanamine compound, and an alcohol compound. Among these organic solvents, an ether compound, an ester compound, and a ketone compound are preferred from the viewpoints of solubility of a raw material and a product, and ease of purification of the product. The solvent is preferably a solid content concentration (a ratio of the mass of the component other than the solvent in the reaction solution to the total mass of the solution) of 0.1% by mass or more and 70% by mass or less, more preferably 5% by mass or more, and 50% by mass. The amount below % is used.

The weight average molecular weight in terms of styrene in terms of gel permeation chromatography of the compound [A] obtained in the above manner is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 20,000. By being in such a molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

The [A] compound introduces a structure derived from a specific carboxylic acid onto a polyorganosiloxane having an epoxy group by ring-opening addition of a carboxylate moiety of a specific carboxylic acid to an epoxy group. This production method is simple and can be an extremely suitable method from the viewpoint of improving the introduction rate of a structure derived from a specific carboxylic acid.

<arbitrary component>

In addition to the compound of the above [A], the liquid crystal alignment agent may contain, for example, a polymer other than the compound [A] (hereinafter sometimes referred to as "other polymer"), a curing agent, or the like, as long as the effects of the present invention are not impaired. The curing catalyst, the curing accelerator, a compound having at least one epoxy group in the molecule (hereinafter sometimes referred to as "epoxy compound"), a functional decane compound, a surfactant, and the like are optional.

[Other polymers]

Other polymers can be used to further improve the solution characteristics of the liquid crystal alignment agent and the electrical characteristics of the obtained liquid crystal display element. The other polymer may, for example, be at least one polymer selected from the group consisting of polylysine and polyimine ([B] polymer); and is selected from the group consisting of the following formula (5) At least one of a group consisting of a polyorganosiloxane, a hydrolyzate thereof, and a condensate of a hydrolyzate thereof (hereinafter sometimes referred to as "other polyorganosiloxane"); a polyglycolate, Polyester, polyamine, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene-phenylmethylene iodide) derivative, poly(meth)acrylate, and the like.

In the formula (5), X ¹ is a hydroxyl group, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms. Y ¹ is a hydroxyl group or an alkoxy group having 1 to 10 carbon atoms.

<[B]polymer>

The [B] polymer is at least one polymer selected from the group consisting of polylysine and polyimine. Hereinafter, polylysine and polyimine are described in detail.

[polyglycolic acid]

Polylysine can be obtained by reacting a tetracarboxylic dianhydride with a diamine compound. Examples of the tetracarboxylic dianhydride which can be used for the synthesis of poly-proline are, for example, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1, 2, 3, 4 - cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid Anhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro- 5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b - hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-8-methyl-naphtho[1,2-c]-furan-1,3-dione, 5- (2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5, 6-tetracarboxylic dianhydride, an aliphatic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by the following formula (F-1) to formula (F-14), or an alicyclic tetracarboxylic dianhydride; [Chemistry 20]

Pyromellitic dianhydride, 3,3',4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylnonane tetracarboxylic dianhydride, 3, 3',4,4'-tetraphenylnonanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) Diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl phthalic anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl Propane dianhydride, 3,3',4,4'-perfluoroextension isopropyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(o-phenylene) Formic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, meta-phenyl-bis(triphenylphthalic acid) dianhydride, bis(triphenyl) Phthalic acid)-4,4'-diphenyl ether dianhydride, double (three An aromatic tetracarboxylic dianhydride such as phenylphthalic acid)-4,4'-diphenylmethane dianhydride.

Among these tetracarboxylic dianhydrides, preferably 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1] ,2-c]-furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)- 8-methyl-naphtho[1,2-c]-furan-1,3-dione, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, butane tetracarboxylic dianhydride, 1,3 - dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3' , 4,4'-biphenylfluorene tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', Tetracarboxylic dianhydride represented by 4,4'-biphenyl ether tetracarboxylic dianhydride. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Examples of the diamine compound which can be used for the synthesis of poly-proline are, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'. -diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2 '-Bis(trifluoromethyl)biphenyl, 2,7-diaminostilbene, 4,4'-diaminodiphenyl ether, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-double (4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylenedi-isopropyl)diphenylamine, 4,4'-(meta-phenylenedi-isopropyl)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2,6-diaminopyridine, 3,4-diamine Pyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl -3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, N,N'-double (4-Aminophenyl)-N,N'-dimethylbenzidine, 1,4-bis-(4-aminophenyl)-piperazine, 3,5-diaminobenzoic acid , dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4-diaminobenzene, pentadecyloxy-2,4-diaminobenzene, heptadecyloxy Base-2,4-diaminobenzene, octadecyloxy-2,4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5 -diaminobenzene, pentadecyloxy-2,5-diaminobenzene, cetyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene , cholestyloxy-3,5-diaminobenzene, cholesteneoxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholestene oxygen Base-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, 3,5-diaminobenzoic acid Lanthanide, 3,6-bis(4-aminobenzylideneoxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'- Trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-di Amino benzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminobenzene) Methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenoxy)) Phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2 ,4-diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine-4-carboxylate Acid, 4-(morpholin-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω- Aminophenylalkylene, 4-aminophenyl=4-aminobenzoate, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4 -diylamine]diphenylamine, di-4-aminophenylphenyl ether, diaminotetraphenylthiophene, etc. heteroatom-containing aromatic diamine; m-xylylenediamine, 1,3 -propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, ninamethylenediamine, 4,4 -diamine heptamethylenediamine, 1,4-diaminocyclohexane, cyclohexane bis(methylamine), isophoronediamine, tetrahydrobicyclopentadienylethyldiamine, Hexahydro-4,7-bridged methylene-extended succinyldimethylenediamine, tricyclo[6.2.1.0 ^2,7 ]-e-undecyldimethyldiamine, 4,4'- Aliphatic or alicyclic two such as methyl bis(cyclohexylamine) ; Hexamethyl diamine siloxane and the like silicon organic silicon siloxane diamine and the like.

Among these diamine compounds, preference is given to p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, cyclohexane. Bis(methylamine), 1,5-diaminonaphthalene, 2,7-diaminopurine, 4,4'-diaminodiphenyl ether, 4,4'-(p-phenylene isopropyl) Diphenylamine, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-double [4-(4-Amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-bis[(4-amino-2-trifluoromethyl)phenoxy]-octafluorobiphenyl, 1-hexadecyloxy-2,4-diaminobenzene, 1-ten Octacooxy-2,4-diaminobenzene, 1-cholesteryl-2,4-diaminobenzene, 1-cholestyloxy-2,4-diaminobenzene, hexadecane Oxy (3,5-diaminobenzimidyl), octadecyloxy (3,5-diaminobenzylidene), cholesteryloxy (3,5-diaminobenzimidamide) , cholesteryloxy (3,5-diaminobenzimidyl), 4-aminophenyl=4-aminobenzoate, 4,4'-[4,4'-propane a diamine represented by -1,3-diylbis(piperidine-1,4-diyl)]diphenylamine or diethylene glycol (di-4-aminophenyl)ether . These diamines may be used alone or in combination of two or more.

The ratio of the tetracarboxylic dianhydride to the diamine compound to be used in the synthesis reaction of the polyamic acid is preferably 0.2 equivalent to 2 equivalents to the tetracarboxylic dianhydride based on 1 equivalent of the amine group contained in the diamine compound. The ratio of the equivalent amount is more preferably such that the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.3 equivalent to 1.2 equivalent.

The synthesis reaction of polylysine is preferably in an organic solvent, and preferably at -20 ° C It is more preferably from 0.5 to 24 hours, more preferably from 2 to 10 hours, at a temperature of from 0 ° C to 100 ° C. Here, the organic solvent is not particularly limited as long as it is an organic solvent capable of dissolving the synthesized polyamic acid, and examples thereof include N-methyl-2-pyrrolidone and N,N-dimethylacetamidine. Amine, N,N-dimethylformamide, N,N-dimethylimidazolidinone, dimethyl hydrazine, γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, etc. Proton-based polar solvent; phenolic solvent such as m-cresol, xylenol, phenol, halogenated phenol. The amount (a) of the organic solvent to be used is preferably such an amount that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is preferably 0.1% by mass based on the total amount (a+b) of the reaction solution. 50% by mass, more preferably 5% by mass to 30% by mass.

Further, in the organic solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, a hydrocarbon or the like which is a poor solvent of polyphthalic acid may be used in combination within a range in which the produced polyamine does not precipitate. Examples of the poor solvent include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, and ethylene glycol monomethyl ether. , ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethoxy Ethyl propyl propionate, propylene carbonate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl Ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether , diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutyl Alkane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, and the like. These poor solvents may be used singly or in combination of two or more.

A reaction solution obtained by dissolving polylysine was obtained in the manner described. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be used for the preparation of the liquid crystal alignment agent after the polyamic acid contained in the reaction solution is isolated, or may be subjected to the isolated polyamic acid. After purification, it is supplied to the preparation of the liquid crystal alignment agent. Separation of polylysine can be carried out by injecting the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure; or, using an evaporator A method of distilling off the reaction solution under reduced pressure. Further, the polyproline may be purified by dissolving the polylysine in an organic solvent and then precipitating it with a poor solvent; or by distilling off under reduced pressure using an evaporator. The steps are performed one or several times.

[polyimine]

The polyimine can be produced by dehydration ring closure of the proline structure of the polyamic acid obtained in the manner described. In this case, the entire proline structure may be subjected to dehydration ring closure and completely ruthenium imidization, or a part of the proline structure may be dehydrated and closed to form a portion in which the proline structure and the quinone imine structure coexist. Yttrium imide.

The dehydration ring closure of polylysine can be carried out by: (i) a method of heating polylysine; or (ii) dissolving polylysine in an organic solvent, adding a dehydrating agent to the solution. And a method of dehydrating the closed-loop catalyst and heating as needed.

The reaction temperature in the method of heating the polyamic acid of the above (i) is preferably from 50 ° C to 200 ° C, more preferably from 60 ° C to 170 ° C. By setting the reaction temperature to 50 ° C or higher, the dehydration ring-closure reaction can be sufficiently carried out, and by setting the reaction temperature to 200 ° C or lower, the decrease in the molecular weight of the obtained ruthenium-imided polymer can be suppressed. The reaction time in the method of heating the polyproline is preferably from 0.5 to 48 hours, more preferably from 2 to 20 hours.

On the other hand, in the method of adding a dehydrating agent and a dehydration ring-closure catalyst to the solution of the poly-proline in the above (ii), as the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent used is preferably set to 0.01 mol to 20 mol with respect to the polyamic acid structural unit 1 mol. Further, as the dehydration ring-closure catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, lutidine or triethylamine can be used. However, it is not limited to these dehydration ring-closing catalysts. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction is exemplified as the organic solvent exemplified as the organic solvent used in the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C, and the reaction time is preferably from 0.5 to 20 hours, more preferably from 1 to 8 hours.

In the method (ii), a reaction solution containing a polyimine is obtained in the manner described. The reaction solution may be directly supplied to the preparation of the liquid crystal alignment agent, or may be prepared for the liquid crystal alignment agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution, or may be supplied to the liquid crystal alignment after segregation of the polyimine. The preparation of the agent or the preparation of the liquid crystal alignment agent may also be carried out after refining the isolated polyimine. When from When the dehydrating agent and the dehydration ring-closure catalyst are removed from the reaction solution, for example, a method such as solvent replacement can be applied. Segregation and purification of the polyimine can be carried out by the same operation as that described for the method of separation and purification as polyglycine.

[Other polyorganosiloxanes]

The liquid crystal alignment agent may contain other polyorganosiloxanes in addition to the [A] compound containing a portion derived from polyorganosiloxane. The other polyorganosiloxane is preferably selected from at least one selected from the group consisting of polyorganooxane represented by the above formula (5), a hydrolyzate thereof, and a condensate thereof. Further, when the liquid crystal alignment agent contains another polyorganosiloxane, most of the other polyorganosiloxanes are present independently of the [A] compound, and a part thereof may exist as a condensate with the [A] compound.

In the X ¹ and Y ¹ in the formula (5), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl group, and a n-hexyl group. N-heptyl, n-octyl, n-decyl, n-decyl, n-lauryl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, Examples are n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, and the like; and examples of the alkoxy group having 1 to 16 carbon atoms include a methoxy group and an ethoxy group; Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and the like.

The other polyorganosiloxane may be synthesized, for example, by a group selected from the group consisting of an alkoxydecane compound and a halogenated decane compound, preferably in a suitable organic solvent and in the presence of water and a catalyst. At least one decaneization The compound (hereinafter sometimes referred to as "raw material decane compound") is hydrolyzed or hydrolyzed. condensation.

Examples of the raw material decane compound which can be used herein include tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane, tetra-isopropoxy decane, and tetra-n-butoxy decane. Tetra-second butoxy decane, tetra-butoxy decane, tetrachloro decane; methyl trimethoxy decane, methyl triethoxy decane, methyl tri-n-propoxy decane, methyl three - isopropoxy decane, methyl tri-n-butoxy decane, methyl tri-second butoxy decane, methyl tri-tert-butoxy decane, methyl triphenyloxy decane, methyl three Chlorodecane, ethyltrimethoxydecane, ethyltriethoxydecane, ethyltri-n-propoxydecane, ethyltris-isopropoxydecane, ethyltri-n-butoxydecane, ethyl Tri-t-butoxy decane, ethyl tri-t-butoxy decane, ethyl trichloro decane, phenyl trimethoxy decane, phenyl triethoxy decane, phenyl trichloro decane; dimethyl Dimethoxy decane, dimethyl diethoxy decane, dimethyl dichloro decane; trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl chloro decane, and the like. Among these raw material decane compounds, tetramethoxy decane, tetraethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, Dimethyldimethoxydecane, dimethyldiethoxydecane, trimethylmethoxydecane, trimethylethoxydecane.

When another polyorganosiloxane is synthesized, examples of the organic solvent that can be used arbitrarily include an alcohol compound, a ketone compound, a guanamine compound or an ester compound, or other aprotic compounds. These organic solvents may be used singly or in combination of two or more.

Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, third butanol, n-pentanol, isoamyl alcohol, and 2-methyl group. Butanol, second pentanol, third pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, second hexanol, 2-ethylbutanol, second heptanol, heptanol -3, n-octanol, 2-ethylhexanol, second octanol, n-nonanol, 2,6-dimethylheptanol-4, n-nonanol, twenty-first alcohol, trimethylnonanol a monohydric alcohol compound such as a tetradecyl alcohol, a twenty-seventh alcohol, a phenol, a cyclohexanol, a methylcyclohexanol, a 3,3,5-trimethylcyclohexanol, a benzyl alcohol or a diacetone alcohol; Glycol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2 , 4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol and other polyol compounds; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Alcohol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl a partial ether of a polyol compound such as ether, dipropylene glycol monoethyl ether or dipropylene glycol monopropyl ether. These alcohol compounds may be used alone or in combination of two or more.

Examples of the ketone compound include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, and methyl-n-pentane. Ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethyl fluorenone, cyclohexanone, 2-hexanone, methyl ring a monoketone compound such as ketone, 2,4-pentanedione, acetonylacetone, acetophenone or anthrone; acetamidine acetone, 2,4-hexanedione, 2,4-heptanedione, 3,5- Heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-decanedione, 3,5-nonanedione, 5-methyl-2,4-hexanedione, 2 a β-diketone compound such as 2,6,6-tetramethyl-3,5-heptanedione or 1,1,1,5,5,5-hexafluoro-2,4-heptanedione or the like. These ketone compounds may be used alone or in combination of two or more.

As the guanamine compound, for example, formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-diethyl A can be mentioned. Indoleamine, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-methylpropyl Indoleamine, N-methylpyrrolidone, N-methylmercaptomorpholine, N-methylpyridylpiperidine, N-methylpyridylpyrrolidine, N-ethylmercaptomorpholine, N-ethylhydrazinopiperidine, N - Ethyl pyrrolidine and the like. These guanamine compounds may be used alone or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, and isopropyl acetate. , n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate , 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl ethyl acetate, ethyl acetate, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl acetate Ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, ethylene glycol diacetate, Methoxy triethylene glycol acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate Ester, n-amyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. These ester compounds may be used alone or in combination of two or more.

Examples of the other aprotic compound include acetonitrile, dimethyl hydrazine, N, N, N', N'-tetraethyl thiodecylamine, trimethylamine hexamethylphosphate, and N-methylmorpholine. Ketone, N-methylpyrrole, N-ethylpyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N,N-dimethylpiperazine, N -methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-Dimethyltetrahydro-2(1H)-pyrimidinone or the like. Among these solvents, a polyhydric alcohol compound, a partial ether or an ester compound of a polyhydric alcohol compound is particularly preferable.

The amount of water used in the synthesis of the other polyorganosiloxane is 1 mol, preferably 0.01 mol to 100 mol, more preferably 0.1 mol, based on the total amount of the alkoxy group and the halogen atom which the starting decane compound has. The ear is ~30 moles, and more preferably 1 mole to 1.5 moles.

Examples of the catalyst which can be used in the synthesis of other polyorganosiloxanes include metal chelate compounds, organic acids, inorganic acids, organic bases, ammonia, and alkali metal compounds.

As the metal chelate compound, for example, triethoxy group can be mentioned. Single (acetonitrile) titanium, tri-n-propoxy. Single (acetonitrile) titanium, tri-isopropoxy. Single (acetonitrile) titanium, tri-n-butoxy. Single (acetonitrile) titanium, tri-second butoxy. Single (acetonitrile) titanium, tri-tert-butoxy. Single (acetonitrile) titanium, diethoxy. Bis(acetonitrile) titanium, Di-n-propoxy. Bis (acetylacetone) titanium, di-isopropoxy. Bis(acetylacetone) titanium, di-n-butoxy. Bis (acetylacetone) titanium, di-second butoxy. Bis (acetylacetone) titanium, di-tert-butoxy. Double (acetonitrile) titanium, monoethoxy. Tris(acetonitrile) titanium, mono-n-propoxy. Tris(acetonitrile) titanium, mono-isopropoxy. Tris(acetonitrile) titanium, mono-n-butoxy. Tris(acetonitrile) titanium, mono-second butoxy. Tris(acetonitrile) titanium, mono-tert-butoxy. Tris(acetonitrile) titanium, tetrakis(acetonitrile) titanium, triethoxy. Single (ethyl acetate) titanium, tri-n-propoxy. Single (ethyl acetate) titanium, tri-isopropoxy. Single (ethyl acetate) titanium, tri-n-butoxy. Single (ethyl acetate) titanium, tri-second butoxy. Single (ethyl acetate) titanium, tri-tert-butoxy. Single (ethyl acetate) titanium, diethoxy. Bis(ethyl acetate) titanium, di-n-propoxy. Bis(ethyl acetate) titanium, di-isopropoxy. Bis(ethyl acetate) titanium, di-n-butoxy. Bis(ethyl acetate) titanium, di-second butoxy. Bis(ethyl acetate) titanium, di-t-butoxy. Bis(ethyl acetate) titanium, monoethoxy. Tris(ethyl acetate) titanium, mono-n-propoxy. Tris(ethyl acetate) titanium, mono-isopropoxy. Tris(ethyl acetate) titanium, mono-n-butoxy. Tris(ethyl acetate) titanium, mono-second butoxy. Tris(ethyl acetate) titanium, mono-tert-butoxy. Tris(ethyl acetate) titanium, tetrakis(ethyl acetate) titanium, mono(acetonitrile) tris(ethyl acetate) titanium, bis(acetonitrile) bis(ethyl acetate) Titanium, tris(acetonitrile) mono(ethylene acetate) titanium and other titanium chelate compounds; triethoxy. Single (acetonitrile) zirconium, tri-n-propoxy. Single (acetonitrile) zirconium, tri-isopropoxy. Single (acetonitrile) zirconium, tri-n-butoxy. Single (acetonitrile) zirconium, tri-second butoxy. Single (acetonitrile) zirconium, tri-tert-butoxy. Single (acetonitrile) zirconium, diethoxy. Bis(acetylacetone) zirconium, di-n-propoxy. Bis(acetylacetone)zirconium, di-isopropyl Oxygen. Bis (acetylacetone) zirconium, di-n-butoxy. Bis (acetylacetone) zirconium, di-second butoxy. Bis(acetylacetone) zirconium, di-t-butoxy. Bis(acetyl acetonide) zirconium, monoethoxy. Tris(acetonitrile) zirconium, mono-n-propoxy. Tris(acetonitrile) zirconium, mono-isopropoxy. Tris(acetonitrile) zirconium, mono-n-butoxy. Tris(acetonitrile) zirconium, mono-second butoxy. Tris(acetonitrile) zirconium, mono-tert-butoxy. Tris(acetonitrile)zirconium, tetrakis(acetonitrile)zirconium, triethoxy. Single (ethyl acetate) zirconium, tri-n-propoxy. Single (ethyl acetate) zirconium, tri-isopropoxy. Single (ethyl acetate) zirconium, tri-n-butoxy. Single (ethyl acetate) zirconium, tri-second butoxy. Single (ethyl acetate) zirconium, tri-tert-butoxy. Single (ethyl acetate) zirconium, diethoxy. Bis(ethyl acetate) zirconium, di-n-propoxy. Bis(ethyl acetate) zirconium, di-isopropoxy. Bis(ethyl acetate) zirconium, di-n-butoxy. Bis(ethyl acetate) zirconium, di-second butoxy. Bis(ethyl acetate) zirconium, di-t-butoxy. Bis(ethyl acetate) zirconium, monoethoxy. Tris(ethyl acetate) zirconium, mono-n-propoxy. Tris(ethyl acetate) zirconium, mono-isopropoxy. Tris(ethyl acetate) zirconium, mono-n-butoxy. Tris(ethyl acetate) zirconium, mono-second butoxy. Tris(ethyl acetate) zirconium, mono-tert-butoxy. Zirconium triacetate, ethyl zirconium tetrakis(ethyl acetate), zirconium mono(acetonitrile) tris(ethyl acetate), bis(acetonitrile) bis(ethyl acetate) Zirconium chelate compound such as zirconium, tris(acetonitrile)aluminum mono(acetate ethyl acetate) zirconium; aluminum chelate compound such as tris(acetonitrile)aluminum, tris(ethylacetate)aluminum or the like.

Examples of the organic acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, capric acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, and Diacid, azelaic acid, gallic acid, butyric acid, mellitic acid, peanut four Alkenoic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid , monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, and the like.

Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of the organic base include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, and monomethyldiene. Ethanolamine, triethanolamine, diazabicyclooctene, diazabicyclononane, diazabicycloundecene, tetramethylammonium hydroxide, and the like.

Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. These catalysts may be used alone or in combination of two or more.

Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred. As the metal chelate compound, a titanium chelate compound is more preferable.

The amount of the catalyst used is preferably 0.001 part by mass to 10 parts by mass, more preferably 0.001 part by mass to 1 part by mass, per 100 parts by mass of the raw material decane compound.

The catalyst may be added to the decane compound as a raw material or a solution obtained by dissolving the decane compound in an organic solvent, or may be dissolved or dispersed in the added water.

The water added when synthesizing other polyorganosiloxanes may be added intermittently or continuously to the decane compound as a raw material, or the decane compound may be dissolved in the organic solvent. In the solution formed in the agent.

The reaction temperature at the time of synthesis of another polyorganosiloxane is preferably from 0 ° C to 100 ° C, more preferably from 15 ° C to 80 ° C. The reaction time is preferably from 0.5 to 24 hours, more preferably from 1 to 8 hours.

When the liquid crystal alignment agent is a liquid crystal alignment agent containing the compound of [A] and another polymer, the content of the other polymer is preferably 10,000 parts by mass or less based on 100 parts by mass of the [A] compound. A more preferable content of the other polymer differs depending on the kind of other polymers.

When the liquid crystal alignment agent contains the [A] compound and the [B] polymer in a preferred ratio of use, the total amount of the [B] polymer is preferably 100 parts by mass to 5,000 based on 100 parts by mass of the [A] compound. The parts by mass are more preferably 200 parts by mass to 3,000 parts by mass.

On the other hand, when the liquid crystal alignment agent is a liquid crystal alignment agent containing a compound [A] and another polyorganosiloxane, a preferred use ratio of the liquid crystal alignment agent to 100 parts by mass of the [A] compound The amount of oxyalkylene is from 100 parts by mass to 2,000 parts by mass.

When the liquid crystal alignment agent is a liquid crystal alignment agent containing the compound [A] and another polymer, as the other polymer, a [B] polymer or other polyorganosiloxane is preferable.

[hardener, hardening catalyst and hardening accelerator]

The hardener and the hardening catalyst can be contained in the liquid crystal alignment agent for the purpose of making the crosslinking reaction of the compound [A] stronger. Hardening accelerator can promote The liquid crystal alignment agent is included for the purpose of the hardening reaction by the curing agent.

As the curing agent, a curing agent which is usually used for curing of a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. Examples of such a curing agent include polyamines, polycarboxylic anhydrides, and polycarboxylic acids.

Examples of the polycarboxylic acid anhydride include an anhydride of cyclohexanetricarboxylic acid and other polycarboxylic acid anhydrides.

Examples of the cyclohexane tricarboxylic anhydride include cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride and cyclohexane-1,3,5-tricarboxylic acid-3,5-. Anhydride, cyclohexane-1,2,3-tricarboxylic acid-2,3-anhydride, and the like. Examples of the other polycarboxylic acid anhydride include 4-methyltetrahydrophthalic anhydride, methyl nadic anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, and phthalic anhydride. And trimellitic acid, a compound represented by the following formula (6), and a tetracarboxylic dianhydride generally used for the synthesis of polyglycine, and examples thereof include α-terpinene and berylate. Diels-Alder reaction products of alicyclic compounds having a conjugated double bond and maleic anhydride, and their hydrides and the like.

In the formula (6), x is an integer of 1 to 20.

As the hardening catalyst, for example, ruthenium hexafluoride compound or hexafluoride can be used. Phosphorus compound, aluminum triacetate, and the like. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

Examples of the hardening accelerator include an imidazole compound, a quaternary phosphorus compound, a quaternary amine compound, and a diazo such as 1,8-diazabicyclo[5.4.0]undecene-7 or an organic acid salt thereof. Heterobicycloalkenes; organometallic compounds such as zinc octoate, tin octoate, acetoacetate aluminum complex; boron compounds such as boron trifluoride and triphenyl borate; metal halogen compounds such as zinc chloride and tin chloride; A high-melting-point-dispersion latent hardening accelerator such as an amine addition accelerator such as an amine or an amine or an epoxy resin; or a microcapsule-type latent hardening obtained by coating a surface of a quaternary phosphonium salt with a polymer Promoter; amine salt type latent hardening accelerator; high temperature dissociation type thermal cationic polymerization latent hardening accelerator such as Lewis acid salt or Bronsted acid salt.

[epoxy compound]

The liquid crystal alignment agent may contain the epoxy compound from the viewpoint of enhancing the adhesion of the formed liquid crystal alignment film to the surface of the substrate.

As the epoxy compound, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl glycol is preferable. Ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2, 4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,-diglycidyl-benzylamine, N,N-diglycidyl- Aminomethylcyclohexane.

When the liquid crystal alignment agent contains an epoxy compound, the content ratio thereof is preferably 0.01 parts by mass to 40 parts by mass based on 100 parts by mass of the total of the [A] polyorganosiloxane compound and any other polymer used arbitrarily. The parts below are more preferably 0.1 part by mass to 30 parts by mass.

Further, when the liquid crystal alignment agent contains an epoxy compound, a base catalyst such as 1-benzyl-2-methylimidazole may be used in combination in order to efficiently produce a crosslinking reaction.

[functional decane compound]

The functional decane compound can be used for the purpose of improving the adhesion between the obtained liquid crystal alignment film and the substrate. Examples of the functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltri Ethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Decane, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl- 3-Aminopropyltriethoxydecane, N-triethoxycarbamidopropyltriethylenetriamine, N-trimethoxymethylidenepropyltriethylenetriamine, 10-trimethoxyformane Base-1,4,7-triazadecane, 10-triethoxycarbamimidyl-1,4,7-triazadecane, 9-trimethoxyformamido-3,6-di Azaindenyl acetate, 9-triethoxycarbamido-3,6-diazadecyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl- 3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(oxygen) Ethylene)-3-amino group Trimethoxy Silane, N- bis (oxyethylene) -3-aminopropyl triethoxysilane Silane, 3-glycidoxypropyl trimethoxy silicon Alkane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, etc., and further, tetracarboxylic dianhydride and decane having an amine group described in JP-A-63-291922 The reactants of the compound and the like.

When the liquid crystal alignment agent contains a functional decane compound, the content ratio thereof is preferably 50 parts by mass or less, more preferably 20 parts by mass, based on 100 parts by mass of the total of the [A] compound and any other polymer used arbitrarily. the following.

[Surfactant]

Examples of the surfactant include a nonionic surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, an anthrone surfactant, a polyalkylene oxide surfactant, a fluorine-containing surfactant, and the like. .

When the liquid crystal alignment agent contains a surfactant, the content ratio thereof is preferably 10 parts by mass or less, and more preferably 1 part by mass or less based on 100 parts by mass of the entire liquid crystal alignment agent.

<Preparation method of liquid crystal alignment agent>

As described above, the liquid crystal alignment agent contains the [A] compound as an essential component, and may optionally contain other optional components. However, it is preferably prepared as a solution-like composition obtained by dissolving each component in an organic solvent.

As the organic solvent which can be used for the preparation of the liquid crystal alignment agent, a solvent which dissolves the [A] compound and other components arbitrarily used, and does not react with them is preferable. The organic solvent which can be preferably used for the liquid crystal alignment agent differs depending on the kind of other polymer to be added.

Preferred as the liquid crystal alignment agent containing the [A] compound and the [B] polymer Examples of the organic solvent include the organic solvents exemplified as the organic solvent used in the synthesis of polyglycine. In this case, it may be used in combination as a poor solvent exemplified as the poor solvent used in the synthesis of the polyamic acid of the present invention. These organic solvents may be used singly or in combination of two or more.

On the other hand, when the liquid crystal alignment agent contains only the [A] compound as a polymer or a preferred organic solvent when the [A] compound and other polyorganosiloxane are contained, for example, 1-ethoxy- 2-propanol, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monoacetate, dipropylene glycol methyl ether, dipropylene glycol ether, dipropylene glycol propyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether , ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, diethylene glycol, methyl cellosolve Acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol, ethyl carbitol, propyl carbitol, butyl carbitol, acetic acid N-propyl ester, isopropyl acetate, n-butyl acetate, isobutyl acetate, dibutyl acetate, n-amyl acetate, second amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate , 2-ethyl butyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate , amyl acetate, isoamyl acetate and the like. Among these organic solvents, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, second butyl acetate, n-amyl acetate, and second amyl acetate are preferable.

A preferred solvent to be used for the preparation of the liquid crystal alignment agent can be obtained by combining one or more kinds of the organic solvents, depending on the presence or absence of other polymers and their types. Such a solvent is used in a liquid crystal alignment agent at a preferred solid concentration concentration described below. The solvent contained in the range in which the surface tension of the liquid crystal alignment agent is 25 mN/m to 40 mN/m is not precipitated.

The solid content concentration of the liquid crystal alignment agent, that is, the ratio of the weight of all components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent is selected in consideration of viscosity, volatility, etc., but is preferably 1% by mass. ~10% by mass range. When the liquid crystal alignment agent is applied to the surface of the substrate to form a coating film which is a liquid crystal alignment film, when the solid content concentration is 1% by mass or more, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration is 10% by mass or less, the film thickness of the coating film can be prevented from becoming excessively large, and a favorable liquid crystal alignment film can be obtained, and the viscosity of the liquid crystal alignment agent can be prevented from increasing and the coating property can be changed. Good. The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is coated on the substrate. For example, in the case of using the rotator method, a range of 1.5% by mass to 4.5% by mass is particularly preferable. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% by mass to 9% by mass, thereby making the solution viscosity 12 mPa. s~50 mPa. The scope of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by mass to 5% by mass, thereby making the solution viscosity 3 mPa. s~15 mPa. The scope of s. The temperature at which the liquid crystal alignment agent is prepared is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

<Liquid crystal display element>

The liquid crystal display element of the present invention is an IPS method or an FFS liquid crystal display element including a liquid crystal alignment film formed of the liquid crystal alignment agent. According to the liquid crystal display element, a liquid crystal alignment film is formed from the liquid crystal alignment agent, whereby liquid crystal alignment property, High voltage retention and excellent high-speed response. Hereinafter, an embodiment of a liquid crystal display element will be described.

Hereinafter, a method for producing a liquid crystal display device of the present invention will be described, and a method for producing the liquid crystal alignment film of the present invention will be described in the same description. The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3).

[Step (1): Formation of coating film]

First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. The liquid crystal alignment agent of the present invention is applied to each of a substrate provided with an electrode pair patterned into a comb-shaped type, a substrate provided with an insulating layer between the electrode pairs, and a surface of the opposite substrate not provided with the electrode pair, and then Each coated surface is heated to form a coating film. Preferably, the liquid crystal alignment agent of the present invention is applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method, respectively, and then each coated surface is heated (preferably including preheating (prebaking) and A two-stage heating of calcination (post-baking), thereby forming a coating film. Here, as the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly (aliphatic) may be used. A transparent substrate of plastic such as olefin). As the transparent conductive film provided on one side of the substrate, a NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and an oxidation containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) can be used. Indium Tin Oxide (ITO) film, chromium, etc., when a patterned electrode is to be obtained, for example, a method of forming a pattern by photolithography after forming an electrode film without a pattern can be used. A method of using a mask having a desired pattern when forming an electrode film. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the electrode film and the coating film, the surface of the substrate on which the coating film is to be formed may be coated with a functional decane compound or a functional titanium compound. Pre-processing.

Then, the coated surface after the application of the liquid crystal alignment agent is preheated (prebaked), and further calcined (post-baking) to form a coating film. The prebaking conditions are, for example, pre-baking at 40 ° C to 120 ° C for 0.1 minutes to 5 minutes, and the post-baking conditions are preferably 120 ° C to 300 ° C, more preferably 150 ° C to 250 ° C, preferably 5 Minutes to 200 minutes, more preferably 10 minutes to 100 minutes of post-baking. After the liquid crystal alignment agent is applied onto the substrate, the organic solvent is removed to form a coating film to be an alignment film. In this case, in the case where the polymer contained in the liquid crystal alignment agent of the present invention is a polyaminic acid or a ruthenium iodide polymer having a quinone ring structure and a phthalic acid structure, the coating may be formed. After the film is further heated, a dehydration ring-closure reaction is carried out to prepare a coating film which is further imidized. The film thickness of the formed coating film is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

[Step (2): Friction treatment]

When a liquid crystal display element is manufactured, a rubbing treatment is performed in which a coating film formed in the above manner is rubbed in a fixed direction by, for example, a roll on which a cloth including fibers of nylon, rayon, cotton or the like is wound. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film.

[Step (3): Construction of liquid crystal cell]

Two pairs of substrates formed with the liquid crystal alignment film in the manner described The rubbing direction of the liquid crystal alignment film of the substrate is reversed so as to be opposed to each other via a gap (cell gap), and the peripheral portion of the two substrates is bonded together using a sealant, and the unit is divided toward the surface of the substrate and the sealant. After the filling liquid crystal is injected into the gap, the injection hole is sealed to constitute a liquid crystal cell. Then, the polarizing plate is bonded to the outer surface of the liquid crystal cell such that the polarizing direction thereof is aligned or orthogonal to the rubbing direction of the liquid crystal alignment film formed on each of the substrates, whereby a liquid crystal display element can be obtained.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used.

The liquid crystal may be a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferably used, for example, a Schiff base liquid crystal, an azoxy liquid crystal, or a biphenyl liquid crystal. Phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cetane liquid crystal, or the like. Further, for example, the following compounds may be added to these liquid crystals: cholesteric liquid crystals such as cholesteryl cholesteryl, cholesteryl phthalate, and cholesteryl carbonate; as the trade names "C-15" and "CB-15" (a chiral agent sold by Merck); a ferroelectric liquid crystal such as p-oxybenzylidene-p-amino-2-methylbutyl cinnamate or the like.

The polarizing plate to be bonded to the outer surface of the liquid crystal cell includes a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film, or a polarizing plate including the H film itself. The H film is a polarizing film in which polyvinyl alcohol is stretched to one side to absorb iodine.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited to these Examples.

The weight average molecular weight (Mw) of the polyorganosiloxane having the epoxy group and the compound [A] obtained in the following examples is a polystyrene equivalent value measured by GPC of the following specifications.

Column: Tosoh, TSKgelGRCXLII

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68 kgf/cm ²

In addition, the required amount of the raw material compound and the polymer used in the following examples is ensured by repeating the synthesis of the raw material compound and the polymer at the synthesis scale shown in the following synthesis examples as needed. .

The viscosity of the polyamic acid obtained in the following examples and the ruthenium imidization ratio of the polyimine were measured in the following manner.

[Solid viscosity of polymer solution]

The solution viscosity (mPa.s) of the polymer solution was determined by adjusting the polymer concentration to 10 wt% using a predetermined solvent, and measuring it at 25 ° C using an E-type rotational viscometer.

[醯Iminization rate of polyimine]

The solution of the polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine, and tetramethyl decane is used as a reference substance in the room. ¹ H-NMR was measured at a temperature. From the ¹ H-NMR spectrum obtained, the oxime imidization ratio was determined by the formula represented by the following formula (1).

醯 imidization rate (%) = (1-A ¹ /A ² ×α)×100...(1)

In the formula (1), A ¹ is the peak area of the proton derived from the NH group which occurs near the chemical shift of 10 ppm, A ² is the peak area derived from other protons, and α is the precursor of the polymer (poly The ratio of the number of other protons in the amine acid to the number of one proton of the NH group.

<Synthesis of polyorganosiloxane having an epoxy group>

[Synthesis Example 1]

Add 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (ECETS) 100.0 g, methyl isobutyl ketone 500 g to a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux cooling tube. And 10.0 g of triethylamine, and mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and then mixed under reflux, and reacted at 80 ° C for 6 hours. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing became neutral. Then, the solvent and water were distilled off under reduced pressure to obtain an epoxy having a viscous transparent liquid. Polyorganosiloxane.

As a result of ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, an epoxy group-based peak was obtained as the theoretical intensity near the chemical shift (δ) = 3.2 ppm, and it was confirmed that no reaction occurred in the reaction. A side reaction of an epoxy group.

<Synthesis of specific carboxylic acids>

The specific carboxylic acid 1 was synthesized according to the following reaction scheme.

[Synthesis Example 2]

To a 500 mL three-necked flask equipped with a cooling tube, 6.3 g of 4-cyano-4'-hydroxybiphenyl, 10 g of methyl 11-bromoundecanoate, 14.2 g of potassium carbonate, N,N-dimethyl Toluidine 200 mL was stirred and heated at 160 ° C for 5 hours. After confirming the completion of the reaction by Thin Layer Chromatography (TLC), the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, and mixed and stirred. The precipitated white solid was collected by filtration and further washed with water. The obtained solid was vacuum dried at 80 ° C, whereby 11 g of Compound 1 was obtained.

[Synthesis Example 3]

Then, 10 g of Compound 1, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was stirred under heating at 80 ° C for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. Filtration of the precipitated solids, then The water and ethanol are washed sequentially. The obtained solid was vacuum dried at 80 ° C, whereby 8 g of a specific carboxylic acid 1 was obtained.

The specific carboxylic acid 2 was synthesized according to the following reaction scheme.

[Synthesis Example 4]

To a 500 mL three-necked flask equipped with a cooling tube, 15 g of 4-cyano-4'-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB), N,N-dimethyl Baseamylamine 300 mL was stirred and heated at 150 ° C for 9 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was subjected to liquid separation washing using a mixed solution of 300 mL of ethyl acetate and 100 mL of a 1 N-aqueous sodium hydroxide solution. After the organic layer was extracted, the liquid separation was carried out in the order of 100 mL of a 1 N-aqueous sodium hydroxide solution and 100 mL of water. After the organic layer was dried over magnesium sulfate, the organic solvent was distilled off. Vacuum drying the obtained solid After drying, recrystallization was carried out using 100 mL of ethanol/250 mL of hexane, whereby 13.1 g of Compound 2 was obtained.

[Synthesis Example 5]

To a 200 mL three-necked flask equipped with a cooling tube and a dropping funnel, 12 g of a compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated dichloromethane were added and mixed. In a state where the reaction solution was cooled with an ice bath, a solution of 6.6 g of triethylamine in 10 mL of dehydrated dichloromethane was added dropwise over 10 minutes. The mixture was stirred directly in an ice bath for 30 minutes, returned to room temperature, and further stirred for 6 hours. 150 mL of chloroform was added to the reaction solution, and the liquid separation was performed 4 times with 100 mL of water. The extracted organic layer was dried over magnesium sulfate, and then the organic solvent was distilled off. The obtained solid was washed with ethanol, whereby 16.1 g of Compound 3 was obtained.

[Synthesis Example 6]

Add 15 g of compound 3, methyl 4-hydroxybenzoate 11 g, potassium carbonate 12.5 g, N,N-dimethylformamide 180 mL to a 300 mL three-necked flask equipped with a cooling tube at 80 ° C. Stir under heating for 9 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, and mixed and stirred. The precipitated white solid was collected by filtration and further washed with ethanol. The obtained solid was vacuum dried at 80 ° C, whereby 10 g of Compound 4 was obtained.

[Synthesis Example 7]

9.5 g of compound 4, lithium hydroxide monohydrate 1.6 g, methanol 30 mL, tetrahydrofuran 15 mL, water were added to a 100 mL three-necked flask equipped with a cooling tube. 15 mL and stirred under heating at 80 ° C for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. The precipitated solid was filtered, and then washed in the order of water and ethanol. The obtained solid was vacuum dried at 80 ° C, whereby 9 g of a specific carboxylic acid 2 was obtained.

The specific carboxylic acid 3 was synthesized according to the following reaction scheme.

[Synthesis Example 8]

In Synthesis Example 2, 10.7 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used instead of 4-cyano-4'-hydroxybiphenyl, thereby obtaining 13.7 g of a compound. 5.

[Synthesis Example 9]

In Synthesis Example 3, 13.5 g of Compound 5 was used instead of Compound 1, whereby 11.2 g of a specific carboxylic acid 3 was obtained.

The specific carboxylic acid 4 was synthesized according to the following reaction scheme.

[Synthesis Example 10]

In Synthesis Example 4, 25.5 g of 2,3,5,6-tetrafluoro-4-(pentafluorophenyl)phenol was used instead of 4-cyano-4'-hydroxybiphenyl, thereby obtaining 23.1 g of a compound. 6.

[Synthesis Example 11]

In Synthesis Example 5, 18.9 g of Compound 6 was used instead of Compound 2, whereby 24.1 g of Compound 7 was obtained.

[Synthesis Example 12]

In Synthesis Example 6, 20 g of Compound 7 was used instead of Compound 3, whereby 15.4 g of Compound 8 was obtained.

[Synthesis Example 13]

In Synthesis Example 7, 13 g of Compound 8 was used instead of Compound 4, whereby 11.4 g of a specific carboxylic acid 4 was obtained.

The specific carboxylic acid 5 was synthesized according to the following reaction scheme.

[Synthesis Example 14]

In the same manner as the synthesis of the specific carboxylic acid 1, 15 g of a specific carboxylic acid 5 in which the number of methylene groups was changed from 10 to 5 was synthesized.

The specific carboxylic acid 6 was synthesized according to the following reaction scheme.

[化29]

[Synthesis Example 15]

Add 2,2',3,3'-tetrafluoro-4'-propyl-4-hydroxybiphenyl 10.1 g, methyl 11-bromoundecanoate 10 g to a 500 mL three-necked flask equipped with a cooling tube Potassium carbonate 14.2 g, N,N-dimethylformamide 200 mL, and stirred under heating at 160 ° C for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was poured into 500 mL of water, and mixed and stirred. The precipitated white solid was collected by filtration and further washed with water. The obtained solid was vacuum dried at 80 ° C, whereby 10.8 g of Compound 9 was obtained.

[Synthesis Example 16]

Then, 10 g of Compound 9, 1.6 g of lithium hydroxide monohydrate, 30 mL of methanol, and 15 mL of water were added to a 200 mL three-necked flask equipped with a cooling tube, and the mixture was stirred under heating at 80 ° C for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. Dilute hydrochloric acid was slowly added dropwise to the reaction solution while the reaction solution was stirred. Filtration of the precipitated solids, then The water and ethanol are washed sequentially. The obtained solid was vacuum dried at 80 ° C, whereby 6 g of a specific carboxylic acid 6 was obtained.

<[A] Synthesis of Compounds>

[Synthesis Example 17]

To the 100 mL three-necked flask, 9.8 g of an epoxy group-containing polyorganosiloxane, 28 g of methyl isobutyl ketone, and 5.0 g of the obtained epoxy group obtained in Synthesis Example 1 were added. Specific carboxylic acid 1, 3.3 g of 4-octyloxybenzoic acid represented by formula (4-10) exemplified as one of the compounds represented by the above formula (4), and UCAT 18X (triapura) San-Apro) quaternary amine salt) 0.20 g and stirred at 80 ° C for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After the solution was washed with water three times, the solvent was distilled off, thereby obtaining 14.5 g of white powder as a white powder. Compound A-1.

[A] The Mw of the compound A-1 was 6,500.

[Synthesis Example 18]

The white powder of [A] Compound A-2 was obtained in the same manner as in Synthesis Example 24 except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 7 was used instead of the specific carboxylic acid 1. [A] The Mw of the compound A-2 was 6,000.

[Synthesis Example 19]

In the same manner as in Synthesis Example 24 except that 6.8 g of the specific carboxylic acid 3 obtained in Synthesis Example 9 was used instead of the specific carboxylic acid 1, 14.7 g of a white powder of [A] Compound A-3 was obtained. [M] The Mw of the compound A-3 was 8,100.

[Synthesis Example 20]

The synthesis of the compound [A] was carried out in the same manner as in Synthesis Example 24 except that 5.6 g of the specific carboxylic acid 4 obtained in Synthesis Example 13 was used instead of the specific carboxylic acid 1. As a result, 15.0 g of a white powder of [A] Compound A-4 was obtained. [A] The Mw of the compound A-4 was 7,500.

[Synthesis Example 21]

To the 100 mL three-necked flask, 9.8 g of an epoxy group-containing polyorganosiloxane, 28 g of methyl isobutyl ketone, and 10 g of the obtained obtained in Synthesis Example 3 obtained in Synthesis Example 1 were obtained. The specific carboxylic acid 1 and UCAT 18X (the quaternary amine salt of Sanya Proc) were 0.20 g, and stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. After the solution was washed with water three times, the solvent was distilled off to obtain 16.0 g of [A] Compound A as a white powder. 5. [A] The Mw of the compound A-5 was 8,500.

[Synthesis Example 22]

The white powder of [A] Compound A-6 was obtained in the same manner as in Synthesis Example 21 except that the specific carboxylic acid 5 obtained in Synthesis Example 14 was used instead of the specific carboxylic acid 1. [A] The Mw of the compound A-6 was 6,200.

[Synthesis Example 23]

In place of the 4-octyloxy group, 3.6 g of 4-(4-pentylcyclohexyl)benzoic acid represented by the formula (4-11), which is exemplified as one of the compounds represented by the formula (4), is used. In the same manner as in Synthesis Example 21 except for benzoic acid, 13.4 g of white powder of [A] Compound A-7 was obtained. [A] The Mw of the compound A-7 was 7,900.

[Synthesis Example 24]

To the 100 mL three-necked flask, 9.8 g of an epoxy group-containing polyorganosiloxane, 28 g of methyl isobutyl ketone, and 8.0 g obtained in Synthesis Example 1 were added. Specific carboxylic acid 1, 1.4 g of 4-(4-pentylcyclohexyl)benzoic acid represented by the formula (4-11), and UCAT 18X (quaternary amine salt of Sanya Proc) 0.20 g, and Stir at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. The solution was washed with water three times, and then the solvent was distilled off to obtain 13.9 g of [A] Compound A as a white powder. 8. [A] The Mw of the compound A-8 was 8,900.

[Synthesis Example 25]

To the 100 mL three-necked flask, 9.8 g of an epoxy group-containing polyorganooxane, 28 g of methyl isobutyl ketone obtained in Synthesis Example 1, and 2.0 g of the obtained product of Synthesis Example 3 were obtained. Specific carboxylic acid 1, 5.8 g of 4-(4-pentylcyclohexyl)benzoic acid represented by the formula (4-11), and UCAT 18X (quaternary amine salt of Sanya Proc) 0.20 g, and Stir at 80 ° C for 12 hours. After completion of the reaction, reprecipitation was carried out by using methanol, and the precipitate was dissolved in ethyl acetate to obtain a solution. After the solution was washed with water three times, the solvent was distilled off, thereby obtaining 13.4 g of white powder as a white powder [A] Compound A-9. [A] The Mw of the compound A-9 was 7,600.

[Synthesis Example 26]

The white powder of [A] Compound A-10 was obtained in the same manner as in Synthesis Example 21 except that 6.1 g of the specific carboxylic acid 6 obtained in Synthesis Example 16 was used instead of the specific carboxylic acid 1. [A] The Mw of the compound A-10 was 7,300.

[Comparative Synthesis Example 1]

To the 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group, 28 g of methyl isobutyl ketone, 3.3 g of 4-octyloxybenzoic acid obtained in Synthesis Example 1, and UCAT 18X (a quaternary amine salt of Sanya Pro) was 0.10 g and stirred at 80 ° C for 12 hours. After completion of the reaction, the precipitate was reprecipitated with methanol, and the precipitate was dissolved in ethyl acetate. The solution was washed with water three times, and then the solvent was distilled off to obtain 9.6 g of the compound [A] as a white powder. 1. The Mw of the compound CA-1 was 6,000.

<Synthesis of polylysine>

[Synthesis Example 27]

11 g (0.05 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 190 g (0.95 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as diamine compound 4-aminophenyl=4-aminobenzoate 160 g (0.71 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1, 4-diyl)]diphenylamine 110 g (0.29 mol) was dissolved in N-methyl-2-pyrrolidone (NMP) 1300 g, γ-butyrolactone (γ-BL) 1300 g, and at 40 ° C The reaction was carried out for 6 hours to obtain a solid concentration of 15% and a solution viscosity of 420 mPa. Polysylamine of s (as a polylysine (PA-1)) solution.

[Synthesis Example 28]

40 g (0.20 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 160 g (0.80 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as diamine compound 4-aminophenyl=4-aminobenzoate 140 g (0.62 mol), 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1, 4-diyl)]diphenylamine 110 g (0.29 mol), diethylene glycol (di-4-aminophenyl) ether 26 g (0.09 mol) dissolved in N-methyl-2-pyrrolidone (NMP ) 1400 g, γ-butyrolactone (γ-BL) 1400 g, and reacted at 40 ° C for 6 hours, to obtain a solid concentration of 15%, the solution viscosity of 850 mPa. A solution of poly-proline (as a poly-proline (PA-2)).

[Synthesis Example 29]

200 g (0.90 mol) of pyromellitic dianhydride as tetracarboxylic dianhydride and 22 g (0.10 mol) of 1,2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a diamine compound Phenylenediamine 22 g (0.50 mol), 4,4-diaminodiphenyl ether 100 g (0.20 mol), 3,5-diaminobenzoic acid 46 g (0.30 mol) dissolved in N-methyl-2-pyrrolidone (NMP) 1100 g, γ-butyrolactone (γ-BL) 1100 g, and reacted at 40 ° C for 4 hours, to obtain a solid concentration of 15%, the solution viscosity of 410 mPa. Polysylamine of s (as a polylysine (PA-3)) solution.

<Synthesis of Polyimine>

[Synthesis Example 30]

220 g (1.00 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, p-phenylenediamine 87 g (0.80 mol), 2, 2 as a diamine compound '-Bis-trifluoromethyl-4,4'-diaminobiphenyl 32 g (0.10 mol), 4,4'-diaminodiphenylmethane 20 g (0.10 mol) dissolved in NMP 2700 g Medium and reacted at 60 ° C for 6 hours. A small amount of the obtained polyaminic acid solution was separated and extracted, and NMP was added to determine the viscosity as a solution having a solid concentration of 10%. The result was 35 mPa. s. Then, 2200 g of NMP was added to the obtained polyamic acid solution, and 160 g of pyridine and 200 g of acetic anhydride were added, followed by dehydration ring closure at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is replaced with a new NMP (by this operation) A solution of pyridine and acetic anhydride for the oxime imidization reaction was removed to the outside of the system, and a solution containing about 15% by weight of polyamidolimine (PI-1) having a ruthenium iodide ratio of about 78% was obtained. A small amount of the obtained polyaminic acid solution was separated and extracted, and the viscosity of the solution was determined to be 13 mPa as a solution having a concentration of 6.5 wt% of polyimine. s.

[Synthesis Example 31]

220 g (1.00 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as tetracarboxylic dianhydride, and 110 g (1.00 mol) of p-phenylenediamine as a diamine compound were dissolved in NMP 3000 In g, and reacted at 60 ° C for 4 hours. A small amount of the obtained polyaminic acid solution was separated and extracted, and NMP was added to determine the viscosity as a solution having a solid concentration of 10%. The result was 68 mPa. s. Then, 3300 g of NMP was added to the obtained polyamic acid solution, and 400 g of pyridine and 310 g of acetic anhydride were added, followed by dehydration ring closure at 110 ° C for 4 hours. After the imidization reaction, the solvent in the system is subjected to solvent replacement using a new NMP (by this operation, pyridine and acetic anhydride for the oxime imidization reaction are removed to the outside of the system), thereby obtaining ruthenium iodide. A solution of about 11% by weight of polyethylenimine (PI-2) of about 88%. A small amount of the obtained polyaminic acid solution was separated and extracted, and the viscosity of the solution was determined to be 32 mPa as a solution having a polyethylenimine concentration of 6.8 wt% after adding NMP. s.

<Preparation of liquid crystal alignment agent>

[Example 1]

The solution containing the poly-proline acid PA-1 obtained in Synthesis Example 27 was converted into the poly-proline acid PA-1 contained therein, and the amount corresponding to 1,000 parts by mass was added, and [A] Compound A-1 ( 100 parts by mass), further adding γ-butyrolactone, N-methyl-2-pyridyl The solvent composition is γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40:40:20 (mass ratio), and the solid content concentration is 4.0% by mass. The solution. This solution was filtered using a filter having a pore size of 0.45 μm to prepare a liquid crystal alignment agent S-1.

[Example 2 to Example 14 and Comparative Example 1 to Comparative Example 4]

The same procedure as in Example 1 was carried out except that the combination of the polyperuric acid or the polyimine which is the [B] polymer and the polyorganosiloxane compound as the component [A] was as described in Table 2. The liquid crystal alignment agent S-2 to liquid crystal alignment agent S-14 and the liquid crystal alignment agent CS-1 to liquid crystal alignment agent CS-4 were prepared.

[Example 15]

The solution containing the polyimine PI-1 obtained in Synthesis Example 30 was converted into the polyimine PI-1 contained therein and was taken in an amount equivalent to 800 parts by mass, and the obtained product obtained in Synthesis Example 29 was contained. The solution of the poly-proline acid PA-3 is converted into the poly-proline acid PA-3 contained therein, and is added in an amount corresponding to 200 parts by mass, and [A] compound A-1 (100 parts by mass) is added, and γ- is further added. Butyrolactone, N-methyl-2-pyrrolidone and butyl cellosolve, and the solvent composition is γ-butyrolactone: N-methyl-2-pyrrolidone: butyl cellosolve = 40:40:20 (mass ratio A solution having a solid concentration of 4.0% by mass. This solution was filtered using a filter having a pore size of 0.45 μm to prepare a liquid crystal alignment agent S-15.

[Example 16 and Comparative Example 5]

In addition, as shown in Table 2, the combination of the poly-proline and the polyamidene as the [B] polymer and the polyorganosiloxane compound as the component [A] are as described in Table 2. The same manner as in Example 15 was carried out to prepare a liquid crystal alignment agent S-16 and a liquid crystal alignment agent CS-5.

<Manufacture of liquid crystal display element>

As a liquid crystal display element using the liquid crystal alignment agent S-1, a schematic view of a substrate provided with a patterned electrode pair is shown in FIGS. 1 and 2. A flat glass in which an electrode film is not formed is used for the substrate on the opposite side. In Fig. 1, reference numeral 10 denotes glass, reference numeral 20 denotes an alignment film, reference numeral 30 denotes a transparent top electrode (slit structure), reference numeral 40 denotes a transparent bottom electrode, and reference numeral 50 denotes tantalum nitride (SiNx).

On these substrates, a liquid crystal alignment film was formed by a spin coating method using a liquid crystal alignment agent S-1, and calcined at 70 ° C for 80 seconds on a hot plate to perform prebaking, and was carried out at 230 ° C using a clean oven. Calcination was carried out for 15 minutes (under nitrogen) for post-baking. Further, the rubbing treatment was performed in the direction illustrated in Fig. 2 by using a cotton cloth. These substrates were bonded together with a spacer having a diameter of 3.5 μm so that the rubbing directions of the substrates became antiparallel to each other, thereby forming an empty cell in which liquid crystal was not injected. Liquid crystal MLC-6221 (manufactured by Merck) was injected into the unit. Further, the liquid crystal display element of Example 1 was produced by bonding the polarizing plates to the outer surfaces of the substrate so that the polarizing directions of the two polarizing plates were orthogonal to each other.

The liquid crystal alignment agent shown in Table 2 was used instead of the liquid crystal alignment agent S-1, and the same operation as described above was carried out to prepare liquid crystals using Examples 2 to 16 and Comparative Examples 1 to 5. A liquid crystal display element of an alignment agent.

<evaluation>

The following evaluation was performed on the manufactured liquid crystal display element. Summary of results And shown in Table 2.

[Orientation]

For the liquid crystal display element manufactured in the above manner, under the illumination of the backlight, it is visually observed whether there is light leakage in a state where no voltage is applied. The alignment is chaotic and there will be no light leakage. If the alignment disorder is set to "○", there will be light leakage in a part. In the case where the alignment disorder is set to "Δ", the case where the vertical alignment state is not obtained at all is set to "x".

[Response speed (photoelectric responsiveness when rising)]

The time of rise of the liquid crystal response was measured by a device including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed refers to a time required to change the transmittance from 10% to 90% when a voltage of 5 V is applied to the liquid crystal display element for a maximum of 1 second in a state where no voltage is applied. Msec.).

As is clear from the results of Table 1, it is understood that the liquid crystal display element including the liquid crystal alignment film produced by using the liquid crystal alignment agents of Examples 1 to 16 is excellent not only in the alignment property but also in comparison with the liquid crystal display device of the comparative example. The response speed of the liquid crystal is about 3/4 or more.

(industrial availability)

The liquid crystal alignment agent of the present invention can be suitably used for the production of an IPS method or an FFS liquid crystal display element having excellent high-speed response.

Claims (7)

A liquid crystal alignment agent which is a liquid crystal alignment agent for forming a liquid crystal alignment film in a liquid crystal display element of a coplanar switching method or a fringe field switching method, characterized in that: [A] has a formula (1) represented by the following formula (1) Base compound, In the formula (1), R ¹ is a group having at least two monocyclic structures; R ² is a linking group containing a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom; and a is an integer of 0 to 1. The liquid crystal alignment agent according to claim 1, wherein the [A] compound comprises: a moiety derived from a polyorganosiloxane having an epoxy group, and derived from having the following formula (2) a portion of a compound representing a carboxyl group, In the formula (2), R ¹ , R ² and a have the same meanings as in the above formula (1); R ³ is a methylene group or an alkylene group having a carbon number of 2 to 30, a phenyl group or a cyclohexyl group. These groups may further have a substituent. The liquid crystal alignment agent according to claim ¹ , wherein the R ¹ is a group represented by the following formula (3), In the formula (3), R ⁴ is a hydrogen atom, a cyano group, a fluorine atom, a trifluoromethyl group, an alkoxycarbonyl group, an alkyl group or an alkoxy group; and R ⁵ and R ⁷ are each independently a phenyl group and a biphenyl group. a group, an anthranyl group, a cyclohexylene group, a cyclohexylene group, a cyclohexylene group or a heterocyclic ring, these groups may further have a substituent; R ⁶ is an alkylene group having a carbon number of 1 to 10 and contains a double bond. a linking group of any one of a triple bond, an ether bond, an ester bond, and a hetero ring, wherein these groups may further have a substituent; b is an integer of 1 to 9; when b is 2 or more, a plurality of R ⁴ may be the same, It may be different; c is an integer of 0 to 1; d is an integer of 1 to 2; when d is 2, a plurality of R ⁶ , R ⁷ and c may be the same or different. The liquid crystal alignment agent according to claim 2, wherein the epoxy group is a group represented by the following formula (X ¹ -1) or (X ¹ -2), In the formula (X ¹ -1), A is a single bond or an oxygen atom; H is an integer of 1 to 3; i is an integer from 0 to 6; wherein, when i is 0, A is a single bond; the formula (X ¹ In -2), j is an integer from 0 to 6. The liquid crystal alignment agent according to any one of claims 1 to 4, further comprising [B] at least one polymerization selected from the group consisting of polyproline and polyimine. Things. A liquid crystal display element of a coplanar switching type, comprising: a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5. A liquid crystal display element of a fringe field switching type, comprising a liquid crystal alignment film formed by the liquid crystal alignment agent according to any one of claims 1 to 5.