JP5776152B2 - Liquid crystal aligning agent, liquid crystal display element, and polyorganosiloxane compound - Google Patents

Description

  The present invention is suitably used for a liquid crystal aligning agent suitable as a material for forming an alignment film of a liquid crystal display element (LCD), a liquid crystal display element having a liquid crystal aligning film formed from this liquid crystal aligning agent, and a liquid crystal aligning agent. It relates to the polyorganosiloxane compound.

  In recent years, liquid crystal display elements have advantages such as low power consumption and easy miniaturization and flattening. Therefore, liquid crystal display elements can be used from small liquid crystal display devices such as mobile phones to large screen liquid crystals such as liquid crystal televisions. It is applied to a wide range of uses up to display devices.

  As the driving mode of the liquid crystal display device, TN (Super Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), etc. are currently used according to the change in the alignment (alignment) state of liquid crystal molecules. It has been known. In VA mode, MVA (Multi domain Vertical Alignment) method and PVA (Patterned Vertical Alignment) method are adopted to increase the viewing angle by orientation division, further improving the high-speed response and panel aperture ratio to the liquid crystal. It has been studied to adopt a pre-tilt angle for use in an optical vertical alignment method, a PSA (Polymer Sustained Alignment) method, and the like. In any of the drive modes, the alignment state of the liquid crystal molecules is directly controlled by the liquid crystal alignment film, and the liquid crystal alignment film is responsible for the development and control of the functional characteristics of the liquid crystal display element.

  Since such a liquid crystal display device is expected as a moving image display device such as a mobile phone or a liquid crystal television, as a characteristic required for a liquid crystal display element, an electro-optic effect is required to suppress an afterimage as much as possible while smoothly displaying a moving image. A further increase in response time is required. In response to this requirement, a technique for improving the structure by imparting a structure that gives dielectric anisotropy to the polymer side chain used in the liquid crystal alignment film has been reported (Japanese Patent Publication No. 2007-521361 and Japanese Patent Publication No. 2007-521506). No. publication). However, this patent document does not describe electrical characteristics such as orientation, voltage holding ratio, and afterimage characteristics that are important in practical use other than speeding up the electro-optic response time.

  Under these circumstances, development of a liquid crystal aligning agent capable of forming a liquid crystal aligning element having a short electro-optic response time while satisfying electrical characteristics such as orientation and voltage holding ratio generally required as a liquid crystal aligning element is desired. Yes.

Special table 2007-521361 Special table 2007-521506 gazette

  The present invention has been made based on the circumstances as described above, and its purpose is to form a liquid crystal display element excellent in various performances such as voltage holding ratio and afterimage characteristics while realizing a high-speed response of the liquid crystal element. It is to provide a liquid crystal aligning agent that can be used, a liquid crystal display element such as a vertical type provided with a liquid crystal aligning film formed from the liquid crystal aligning agent, and a polyorganosiloxane compound suitably used for the liquid crystal aligning agent.

（式（１）中、Ｒ^１はメチレン基若しくは炭素数２〜３０のアルキレン基、フェニレン基又はシクロヘキシレン基である。これらの基は置換基を有していてもよい。Ｒ^２は二重結合、三重結合、エーテル結合、エステル結合及び酸素原子のいずれかを含む連結基である。Ｒ^３は少なくとも２つの単環構造を有する基である。ａは０〜１の整数である。） The invention made to solve the above problems is
[A] containing a polyorganosiloxane compound,
This [A] polyorganosiloxane compound is
A portion derived from a polyorganosiloxane having an epoxy group;
And a portion derived from a compound having a carboxyl group represented by the following formula (1) (hereinafter sometimes referred to as “specific carboxylic acid”).

(In Formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group, or a cyclohexylene group. These groups may have a substituent. R ² is double. A linking group containing any one of a bond, a triple bond, an ether bond, an ester bond, and an oxygen atom, R ³ is a group having at least two monocyclic structures, and a is an integer of 0 to 1.)

  Since the liquid crystal aligning agent contains a polyorganosiloxane compound, a liquid crystal display device including a liquid crystal aligning film formed using the liquid crystal aligning agent has good alignment properties and high voltage holding characteristics, and an afterimage. It has excellent characteristics and can shorten the response time (at the time of startup). Moreover, by having an epoxy group, the liquid crystal aligning agent further improves electrical characteristics such as orientation and voltage holding ratio. Further, a liquid crystal display element comprising a liquid crystal alignment film formed by using a structure having dielectric anisotropy in the side chain introduced by the liquid crystal alignment agent having a specific structural unit and using the liquid crystal alignment agent, Electrical characteristics and afterimage characteristics are improved, and response time is further shortened. 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 the side chain can be easily formed on the polyorganosiloxane as the main chain. Can be introduced.

（式（２）中、Ｒ^４及びＲ^６はそれぞれフェニレン基、ビフェニレン基、ナフタレン基、シクロヘキシレン基、ビシクロヘキシレン基、シクロへキシレンフェニレン基又は複素環であり、これらはさらに置換基を有していてもよい。Ｒ^５は置換基を有していてもよい炭素数１〜１０のアルキレン基、二重結合、三重結合、エーテル結合、エステル結合及び複素環のいずれかを含む連結基である。Ｒ^７は水素原子、シアノ基、フッ素原子、トリフルオロメチル基、アルコキシカルボニル基、アルキル基及びアルコキシ基のいずれかであり、Ｒ^６が複数の置換基を有する場合はそれぞれ同一の又は異なるものを組み合わせてもよい。ｂは０〜１の整数である。ｃは１〜９の整数である。） R ³ in the above formula (1) is preferably a group represented by the following formula (2).

(In formula (2), R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring, and these further have a substituent. R ⁵ is a linking group containing any one of an optionally substituted alkylene group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring. R ⁷ 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, and when R ⁶ has a plurality of substituents, they are the same or different. (B may be an integer of 0 to 1. c is an integer of 1 to 9.)

  By introducing the structure represented by the above formula (2) into the side chain of the polyorganosiloxane compound of the liquid crystal aligning agent, the electro-optical response of the obtained liquid crystal aligning element can be further accelerated.

（式（Ｘ^１−１）中、Ａは酸素原子又は単結合である。ｈは１〜３の整数である。ｉは０〜６の整数である。但し、ｉが０の場合、Ａは単結合である。「＊」は結合手であることを示す。） The epoxy group is preferably a group represented by the following formula (X ¹ -1) or (X ¹ -2).

(In the formula (X ¹ -1), A is an oxygen atom or a single bond. H is an integer of 1 to 3. i is an integer of 0 to 6. However, when i is 0, A is (It is a single bond. “*” Indicates a bond.)

By including the group represented by the above formula (X ¹ -1) or (X ¹ -2), the polyorganosiloxane compound of the liquid crystal aligning agent has a specific structure represented by the above formula (1). It becomes easy to introduce a side chain group derived from a compound.

  The liquid crystal aligning agent preferably further contains at least one polymer selected from the group consisting of [B] polyamic acid and polyimide (hereinafter sometimes referred to as “[B] polymer”). When a liquid crystal alignment film is produced using the polymer as described above, a liquid crystal display element with improved electrical characteristics can be obtained.

  The liquid crystal display element of this invention comprises the liquid crystal aligning film formed from the said liquid crystal aligning agent. As a result, a liquid crystal display element having excellent electrical characteristics such as orientation, voltage holding ratio, and afterimage characteristics and high-speed electro-optical response can be obtained.

  In the present invention, a liquid crystal display device comprising a transparent electrode and the liquid crystal alignment film laminated on the transparent electrode, and having a liquid crystal alignment mode of a vertical type and having two or more regions having different alignment directions is also suitable. included. Moreover, as a means having two or more regions having different orientation directions, a means using a transparent electrode patterned as the transparent electrode or a means for imparting an alignment division function to the liquid crystal alignment film is preferable. Such a liquid crystal display device can be suitably applied in drive modes such as TN, STN, IPS, and VA (including VA-MVA method, VA-PVA method, etc.), further improves contrast, and has high-speed response. More improved.

（式（３）中、Ｒ^２は二重結合、三重結合、エーテル結合、エステル結合又は酸素原子のいずれかを含む連結基である。Ｒ^３は少なくとも２つの単環構造を有する基である。ａは０〜１の整数である。「＊」は結合手であることを示す。） In the present invention, the liquid crystal alignment film in a liquid crystal display device comprising a transparent electrode and a liquid crystal alignment film laminated on the transparent electrode, wherein the liquid crystal alignment mode is a vertical type and has two or more regions having different alignment directions. A liquid crystal aligning agent which is a liquid crystal aligning agent for formation and contains a compound having a group represented by the following formula (3) is also preferably included. Further, as a means having two or more regions having different orientation directions, it is preferable to use a patterned transparent electrode or a liquid crystal alignment film having an alignment division function.

(In Formula (3), R ² is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond, or an oxygen atom. R ³ is a group having at least two monocyclic structures. a is an integer of 0 to 1. “*” indicates a bond.)

  The present invention relates to a liquid crystal display device having two or more regions having different liquid crystal orientation modes and different orientation orientations, including the liquid crystal aligning agent (compound having a group represented by the formula (3) above) The liquid crystal display element characterized by including the liquid crystal aligning film formed from the liquid crystal aligning agent characterized by the above is also contained suitably.

（式（１）中、Ｒ^１はメチレン基若しくは炭素数２〜３０のアルキレン基、フェニレン基又はシクロヘキシレン基である。これらの基は置換基を有していてもよい。Ｒ^２は二重結合、三重結合、エーテル結合、エステル結合及び酸素原子のいずれかを含む連結基である。Ｒ^３は少なくとも２つの単環構造を有する基である。ａは０〜１の整数である。）

（式（２）中、Ｒ^４及びＲ^６はそれぞれフェニレン基、ビフェニレン基、ナフタレン基、シクロヘキシレン基、ビシクロヘキシレン基、シクロへキシレンフェニレン基又は複素環であり、これらはさらに置換基を有していてもよい。Ｒ^５は置換基を有していてもよい炭素数１〜１０のアルキレン基、二重結合、三重結合、エーテル結合、エステル結合及び複素環のいずれかを含む連結基である。Ｒ^７は水素原子、シアノ基、フッ素原子、トリフルオロメチル基、アルコキシカルボニル基、アルキル基及びアルコキシ基のいずれかであり、Ｒ^６が複数の置換基を有する場合はそれぞれ同一の又は異なるものを組み合わせてもよい。ｂは０〜１の整数である。ｃは１〜９の整数である。） The polyorganosiloxane compound of the present invention is a compound derived from a polyorganosiloxane having an epoxy group and a compound having a carboxyl group represented by the following formula (1), or R ^{3 of the} formula (1) is represented by the following formula (2 And a portion derived from a compound having a carboxyl group represented by:

(In Formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group, or a cyclohexylene group. These groups may have a substituent. R ² is double. A linking group containing any one of a bond, a triple bond, an ether bond, an ester bond, and an oxygen atom, R ³ is a group having at least two monocyclic structures, and a is an integer of 0 to 1.)

(In formula (2), R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring, and these further have a substituent. R ⁵ is a linking group containing any one of an optionally substituted alkylene group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring. R ⁷ 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, and when R ⁶ has a plurality of substituents, they are the same or different. (B may be an integer of 0 to 1. c is an integer of 1 to 9.)

  The polyorganosiloxane compound can be suitably used as a liquid crystal aligning agent for constituting a liquid crystal display device having various properties such as an afterimage characteristic in addition to the orientation property, the high-speed response property, and the voltage property.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent which can form the liquid crystal display element which is excellent in various orientations, such as an orientation property and high-speed response, and excellent in various performances, such as a voltage characteristic and an afterimage characteristic, can be provided. Therefore, the liquid crystal display element can also be suitably applied in drive modes such as TN, STN, IPS, and VA (including VA-MVA method and VA-PVA method).

(A) It is a top view which shows one form of the patterned transparent electrode used for this invention. (B) It is an expanded sectional view of X-X 'in the said top view. It is a top view which shows one form of the patterned transparent electrode used for this invention. It is a top view which shows one form of the patterned transparent electrode used for this invention.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains a [A] polyorganosiloxane compound. Since the liquid crystal aligning agent contains [A] a polyorganosiloxane compound, a liquid crystal display device including a liquid crystal aligning film formed using the liquid crystal aligning agent has good alignment properties and high voltage holding characteristics. In addition, the afterimage characteristics are excellent and the response time can be shortened. Moreover, "B" polymer and other "other polymers" described later can be contained. Furthermore, you may contain another arbitrary component in the range which does not impair the effect of this invention. Hereinafter, each component will be described in detail.

<[A] polyorganosiloxane compound>
[A] The polyorganosiloxane compound has a part derived from a polyorganosiloxane having an epoxy group and a part derived from a specific carboxylic acid represented by the above formula (1). Since the liquid crystal aligning agent has a specific structural unit, a structure having dielectric anisotropy in the side chain is introduced, and a liquid crystal display device including a liquid crystal aligning film formed using this liquid crystal aligning agent further has electrical characteristics. In addition, the afterimage characteristics are improved and the response time is further shortened. 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 the side chain can be easily formed on the polyorganosiloxane as the main chain. Can be introduced.

  [A] It is considered that the polyorganosiloxane compound is mainly obtained as a reaction product between the epoxy group of the polyorganosiloxane and the carboxyl group of the specific carboxylic acid. The [A] polyorganosiloxane compound contained in the liquid crystal aligning agent will be described separately for a part derived from a polyorganosiloxane having an epoxy group (and its derivative) and a part derived from a specific carboxylic acid.

[Part derived from polyorganosiloxane having epoxy group]
This part is a concept including a polyorganosiloxane skeleton as a polymer main chain and an epoxy group-containing skeleton as a side chain extending from the polyorganosiloxane main chain in the structure of [A] polyorganosiloxane compound. is there. As described above, in the [A] polyorganosiloxane compound, it is considered that most of the epoxy groups do not have the initial structure by reacting with the specific carboxylic acid. In some cases, they may be combined. Therefore, in the present invention, both the embodiments are referred to as “parts derived from polyorganosiloxane having an epoxy group”.

[A] When the polyorganosiloxane compound has an epoxy group such as a group containing a glycidyl group, a glycidyloxy group, or an epoxycyclohexyl group, the liquid crystal aligning agent further improves electrical characteristics such as orientation and voltage holding ratio. The epoxy group is preferably a group represented by the above formula (X ¹ -1) or (X ¹ -2). The polyorganosiloxane having the structural unit represented by the above formula (1) contains the group represented by the above formula (X ¹ -1) or (X ¹ -2) to thereby form a polyorgano of the liquid crystal aligning agent. It becomes easy to introduce a side chain group derived from a compound having a specific structure represented by the above formula (1) into the siloxane compound.

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

（式（Ｘ^１−１−１）及び（Ｘ^１−２−１）中、「＊」は結合手であることを示す。）

(In formulas (X ¹ -1-1) and (X ¹ -2-1), “*” indicates a bond).

  The polystyrene-reduced weight average molecular weight of the polyorganosiloxane having an epoxy group measured by gel permeation chromatography (GPC) is preferably 500 to 100,000, more preferably 1,000 to 50,000, and 1,000 to 1,000. 20,000 is particularly preferred.

[Method for synthesizing polyorganosiloxane having epoxy group]
Such polyorganosiloxane having an epoxy group is preferably a silane compound having an epoxy group or a mixture of a silane compound having an epoxy group and another silane compound, preferably in the presence of a suitable organic solvent, water and a catalyst. It can be synthesized by hydrolysis or hydrolysis / condensation below.

  Examples of the silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxy. Silane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 2-glycidyloxyethylmethyldimethoxy Silane, 2-glycidyloxyethylmethyldiethoxysilane, 2-glycidyloxyethyldimethylmethoxysilane, 2-glycidyloxyethyldimethylethoxysilane, 4-glycidyloxybutyltrimethoxysilane, -Glycidyloxybutyltriethoxysilane, 4-glycidyloxybutylmethyldimethoxysilane, 4-glycidyloxybutylmethyldiethoxysilane, 4-glycidyloxybutyldimethylmethoxysilane, 4-glycidyloxybutyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 3- (3 4-epoxycyclohexyl) propyltriethoxysilane and the like. These may be used alone or in combination of two or more.

  Examples of the other silane compounds include tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, trichlorosilane, Trimethoxysilane, triethoxysilane, tri-n-propoxysilane, tri-i-propoxysilane, tri-n-butoxysilane, tri-sec-butoxysilane, fluorotrichlorosilane, fluorotrimethoxysilane, fluorotriethoxysilane, Fluorotri-n-propoxysilane, fluorotri-i-propoxysilane, fluorotri-n-butoxysilane, fluorotri-sec-butoxysilane, methyltrichlorosilane, methyltrimethoxysilane, Rutriethoxysilane, methyltri-n-propoxysilane, methyltri-i-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, 2- (trifluoromethyl) ethyltrichlorosilane, 2- (trifluoromethyl) ) Ethyltrimethoxysilane, 2- (trifluoromethyl) ethyltriethoxysilane, 2- (trifluoromethyl) ethyltri-n-propoxysilane, 2- (trifluoromethyl) ethyltri-i-propoxysilane, 2- (tri Fluoromethyl) ethyltri-n-butoxysilane, 2- (trifluoromethyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-hexyl) ethyltrichlorosilane, 2- (perfluoro-n-hexyl) ethyltri Methoxy Lan, 2- (perfluoro-n-hexyl) ethyltriethoxysilane, 2- (perfluoro-n-hexyl) ethyltri-n-propoxysilane, 2- (perfluoro-n-hexyl) ethyltri-i-propoxysilane 2- (perfluoro-n-hexyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-hexyl) ethyltri-sec-butoxysilane, 2- (perfluoro-n-octyl) ethyltrichlorosilane, 2 -(Perfluoro-n-octyl) ethyltrimethoxysilane, 2- (perfluoro-n-octyl) ethyltriethoxysilane, 2- (perfluoro-n-octyl) ethyltri-n-propoxysilane, 2- (perfluorosilane Fluoro-n-octyl) ethyltri-i-propoxysilane, 2- (Perful Olo-n-octyl) ethyltri-n-butoxysilane, 2- (perfluoro-n-octyl) ethyltri-sec-butoxysilane, hydroxymethyltrichlorosilane, hydroxymethyltrimethoxysilane, hydroxyethyltrimethoxysilane, hydroxymethyltri -N-propoxysilane, hydroxymethyltri-i-propoxysilane, hydroxymethyltri-n-butoxysilane, hydroxymethyltri-sec-butoxysilane, 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryl Loxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propoxysilane, 3- (meth) acryloxypropyltri-i-propo Sisilane, 3- (meth) acryloxypropyltri-n-butoxysilane, 3- (meth) acryloxypropyltri-sec-butoxysilane, 3-mercaptopropyltrichlorosilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3-mercaptopropyltri-n-propoxysilane, 3-mercaptopropyltri-i-propoxysilane, 3-mercaptopropyltri-n-butoxysilane, 3-mercaptopropyltri-sec-butoxysilane, mercapto Methyltrimethoxysilane, mercaptomethyltriethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-i-propoxy Vinyltri-n-butoxysilane, vinyltri-sec-butoxysilane, allyltrichlorosilane, allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propoxysilane, allyltri-i-propoxysilane, allyltri-n-butoxysilane Allyltri-sec-butoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-i-propoxysilane, phenyltri-n-butoxysilane, phenyltri-sec -Butoxysilane, methyldichlorosilane, methyldimethoxysilane, methyldiethoxysilane, methyldi-n-propoxysilane, methyldi-i-propoxysilane, methyldi-n-butoxy Silane, methyldi-sec-butoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-i-propoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, (Methyl) [2- (perfluoro-n-octyl) ethyl] dichlorosilane, (methyl) [2- (perfluoro-n-octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n- Octyl) ethyl] dimethoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-n-propoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-i -Propoxysilane, (methyl) [2- (perfluoro-n- (Cutyl) ethyl] di-n-butoxysilane, (methyl) [2- (perfluoro-n-octyl) ethyl] di-sec-butoxysilane, (methyl) (3-mercaptopropyl) dichlorosilane, (methyl) ( 3-mercaptopropyl) dimethoxysilane, (methyl) (3-mercaptopropyl) diethoxysilane, (methyl) (3-mercaptopropyl) di-n-propoxysilane, (methyl) (3-mercaptopropyl) di-i- Propoxysilane, (methyl) (3-mercaptopropyl) di-n-butoxysilane, (methyl) (3-mercaptopropyl) di-sec-butoxysilane, (methyl) (vinyl) dichlorosilane, (methyl) (vinyl) Dimethoxysilane, (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di n-propoxysilane, (methyl) (vinyl) di-i-propoxysilane, (methyl) (vinyl) di-n-butoxysilane, (methyl) (vinyl) di-sec-butoxysilane, divinyldichlorosilane, divinyldimethoxy Silane, divinyldiethoxysilane, divinyldi-n-propoxysilane, divinyldi-i-propoxysilane, divinyldi-n-butoxysilane, divinyldi-sec-butoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi -N-propoxysilane, diphenyldi-i-propoxysilane, diphenyldi-n-butoxysilane, diphenyldi-sec-butoxysilane, chlorodimethylsilane, methoxydimethylsilane, ethoxydimethylsilane Chlorotrimethylsilane, bromotrimethylsilane, iodotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, n-propoxytrimethylsilane, i-propoxytrimethylsilane, n-butoxytrimethylsilane, sec-butoxytrimethylsilane, t-butoxytrimethylsilane , (Chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) ( Examples thereof include silane compounds having one silicon atom such as methyl) diphenylsilane.

Examples of commercially available products include KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5586, 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 (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 Company);
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- 227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (above, Chisso);
Methyl silicate MS51, Methyl silicate MS56 (Mitsubishi Chemical Corporation);
Ethyl silicate 28, ethyl silicate 40, ethyl silicate 48 (above, Colcoat);
Examples include partial condensates such as GR100, GR650, GR908, and GR950 (shown above, Showa Denko).

  Among these other silane compounds, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxy from the viewpoint of the orientation and storage stability of the obtained liquid crystal display device. Propyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferred.

  Since the polyorganosiloxane having an epoxy group preferably used in the present invention introduces a sufficient amount of side chains having dielectric anisotropy, the epoxy equivalent is preferably from 100 to 10,000 g / mol, and from 150 to More preferably, it is 1,000 g / mol, and it is especially preferable that it is 150-300 g / mol. Therefore, when synthesizing a precursor of a polyorganosiloxane having an epoxy group, the use ratio of the silane compound and the other silane compound is set so that the epoxy equivalent of the polyorganosiloxane having an epoxy group is within the above range. It is preferable to prepare and set. In synthesizing the polyorganosiloxane having an epoxy group used in the present invention, it is more preferable to use only a silane compound and not to use another silane compound.

  Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane having an epoxy group include hydrocarbon compounds, ketone compounds, ester compounds, ether compounds, alcohol compounds, and the like.

Examples of the hydrocarbon include toluene and xylene; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone; Examples of the ester include ethyl acetate, n-butyl acetate, and acetic acid. i-amyl, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; as the ether, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; as the alcohol, for example, 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-pro Ether, ethylene glycol monobutyl -n- butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono -n- propyl ether. Of these, water-insoluble ones are preferred. These organic solvents may be used alone or in combination of two or more.

  The amount of the organic solvent used is preferably 10 to 10,000 parts by mass, and more preferably 50 to 1,000 parts by mass with respect to 100 parts by mass of the total silane compounds. The amount of water used in producing the polyorganosiloxane having an epoxy group is preferably 0.5 to 100 times mol, more preferably 1 to 30 times mol, based on the total silane compound.

  As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be used, for example.

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

  Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, Examples thereof include tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide, and the like. Of these organic bases, tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, etc. Quaternary organic amines such as methylammonium hydroxide are preferred.

  As a catalyst for producing a polyorganosiloxane having an epoxy group, an alkali metal compound or an organic base is preferable. By using an alkali metal compound or organic base as a catalyst, the desired polyorganosiloxane can be obtained at a high hydrolysis / condensation rate without causing side reactions such as ring opening of the epoxy group, so that production stability is achieved. This is preferable. In addition, the liquid crystal aligning agent containing a reaction product of a polyorganosiloxane having an epoxy group synthesized with an alkali metal compound or an organic base as a catalyst and a specific carboxylic acid is advantageous because it has excellent storage stability. . The reason is that, as pointed out in Chemical Reviews, Vol. 95, p1409 (1995), when an alkali metal compound or an organic base is used as a catalyst in a hydrolysis or condensation reaction, a random structure, a ladder structure or a cage structure is used. It is presumed that a structure is formed and a polyorganosiloxane having a low content of silanol groups is obtained. Since the content ratio of silanol groups is small, the condensation reaction between silanol groups is suppressed, and when the liquid crystal aligning agent contains other polymers described later, silanol groups and other polymers Since the condensation reaction is suppressed, it is presumed that the storage stability is excellent.

  As the catalyst, an organic base is particularly preferable. The amount of organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set appropriately. For example, it is preferably 0.01 to 3 times the moles of all silane compounds. More preferably, it is 0.05-1 times mole.

  Hydrolysis or hydrolysis / condensation reaction when producing polyorganosiloxane having an epoxy group is carried out by dissolving an epoxy group-containing silane compound and, if necessary, another silane compound in an organic solvent, and dissolving the solution in an organic base. And it is preferable to carry out by mixing with water and heating with, for example, an oil bath.

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

  After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by mass is preferred in that the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the target is removed by removing the solvent. A polyorganosiloxane having an epoxy group can be obtained.

  In the present invention, a commercially available polyorganosiloxane having an epoxy group may be used. As such a commercial item, DMS-E01, DMS-E12, DMS-E21, EMS-32 (above, Chisso) etc. are mentioned, for example.

  [A] The polyorganosiloxane compound is a part derived from a hydrolyzate produced by hydrolyzing an epoxy group-containing polyorganosiloxane itself, or a hydrolyzed condensate obtained by hydrolytic condensation of polyorganosiloxanes having an epoxy group. The part which originates may be included. These hydrolysates and hydrolysis condensates which are constituent materials of the part can also be prepared in the same manner as the hydrolysis and condensation conditions of polyorganosiloxane having an epoxy group.

[Part derived from specific carboxylic acid]
This part represented by the above formula (1) is mainly derived from an epoxy group extending from the polyorganosiloxane main chain in the structure of the polyorganosiloxane compound of [A] component contained in the liquid crystal aligning agent. It corresponds to a side chain structure starting from a structure derived from a carboxyl group bonded to the structure. However, in the present invention, the term “part derived from the specific carboxylic acid” includes the case where the specific carboxylic acid is bonded to a part other than the epoxy group.

R ^{1 in the} above formula (1) is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group or a cyclohexylene group, and these may further have a substituent.

  Examples of the alkylene group having 2 to 30 carbon atoms include ethylene group, propylene group, butylene group, pentylene group, hexylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, octadecylene group, Nonadecylene group, icosylene group, hencosylene group, docosylene group, tricosylene group, tetracosylene group, pentacosylene group, hexacosylene group, heptacosylene group, octacosylene group, nonacosylene group, triaconylene group and the like can be mentioned. Among these, in order to stably develop the liquid crystal alignment, the number of carbon atoms of octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tetradecylene group, hexadecylene group, octadecylene group, nonadecylene group, icosylene group, etc. The following alkylene groups are preferred.

R ² is a linking group containing any one of a double bond, a triple bond, an ether bond, an ester bond and an oxygen atom. Incidentally, R ² need only comprise one of the binding, but may contain a combination of the binding. When R ¹ is a phenylene group or a cyclohexylene group, R ² contains an alkylene group having 1 to 30 carbon atoms from the viewpoint of the orientation of the formed alignment film and the solubility in a solvent. It is preferable. In addition, a is an integer of 0-1.

R ³ is a group having at least two monocyclic structures, and preferably exhibits positive or negative dielectric anisotropy. A monocyclic structure is a structure that does not have a so-called fused ring structure, in which one ring structure exists independently of the other ring structure, and a bond of one ring structure is shared with another ring structure. is there. Moreover, as a monocyclic structure, any of an alicyclic structure, an aromatic ring structure, and a heterocyclic structure may be sufficient, and you may have combining these.

R ³ is not particularly limited as long as it is a group having at least two monocyclic structures. Typically, R ³ is preferably a group represented by the above formula (2). By introducing the structure represented by the above formula (2) into the side chain of the polyorganosiloxane compound of the liquid crystal aligning agent, the electro-optical response of the obtained liquid crystal aligning element can be further accelerated. In formula (2), R ⁴ and R ⁶ are each independently a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring. Examples of the heterocyclic ring include a pyridine ring, a pyridazine ring, and a pyrimidine ring.

In the above formula (2), R ⁵ includes any one of an optionally substituted alkylene group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond, and a heterocyclic ring. It is a linking group for linking R ⁴ and R ⁶ and can be appropriately selected according to the orientation and induced anisotropy required for the polyorganosiloxane compound. Since b is an integer of 0 or 1, R ⁵ may or may not be included in the side chain structure design.

In the above formula (2), R ⁷ 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. Examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, and an isobutyl group. Examples of the alkoxy group such as a linear or branched alkyl group include a methoxy group, an ethoxy group, and a propoxy group.

In the above formula (2), when R ⁶ has a plurality of substituents (R ⁷ ), different ones may be used in combination. In the case where R ⁶ has a plurality of substituents, in order to stably express desired dielectric anisotropy, a combination of a fluorine atom and a cyano group, a combination of a fluorine atom and an alkyl group, a cyano group And a combination of alkyl groups are preferred. In addition, c is an integer of 0-9.

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

（式（Ｄ−１）〜（Ｄ−２５）中、Ｒ^３は上記式（１）と同義である。ｍは１〜３０の整数である。）

(In the formulas (D-1) to (D-25), R ³ has the same meaning as the above formula (1). M is an integer of 1 to 30.)

Examples of the group represented by the formula (2) include groups represented by the following formulas (E-1) to (E-58).

（式（Ｅ−１）〜（Ｅ−５８）中、Ｒは炭素数１から２０のアルキル基（メチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等）又はアルコキシ基（メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基等）である。）

(In the formulas (E-1) to (E-58), R represents an alkyl group having 1 to 20 carbon atoms (methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, n-pentyl group, n- Hexyl group or the like) or alkoxy group (methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, etc.).

[Method for synthesizing specific carboxylic acid]
The procedure for synthesizing the specific carboxylic acid is not particularly limited, and can be performed by combining conventionally known methods. As a typical synthesis procedure, for example, (1) a compound having a phenol skeleton is reacted with a compound in which the alkyl chain portion of a higher fatty acid ester is substituted with a halogen under a basic condition, and the hydroxyl group of the phenol skeleton is substituted with a halogen. A method of forming a bond with the formed carbon and then reducing the ester to a specific carboxylic acid; (2) reacting a compound having a phenol skeleton with ethylene carbonate to form a terminal alcohol compound, the hydroxyl group and halogen It is activated by reacting with benzenesulfonyl chloride, and then reacting with methyl benzoate containing a hydroxyl group in the activated moiety, and with the elimination of the sulfonyl moiety, the hydroxyl group of the terminal alcohol compound and the methyl benzoate containing a hydroxyl group as a substituent Create a bond with a hydroxyl group,
Next, a method of reducing an ester to a specific carboxylic acid is exemplified. However, the synthesis procedure of the specific carboxylic acid is not limited to these.

<[A] Synthesis method of polyorganosiloxane compound>
[A] The method for synthesizing the polyorganosiloxane compound is not particularly limited, and can be synthesized by a generally known method. As a method for synthesizing the [A] polyorganosiloxane compound having an epoxy group, it can be synthesized by reacting a polyorganosiloxane having an epoxy group with a specific carboxylic acid, preferably in the presence of a catalyst.

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

  In the present invention, a part of the specific carboxylic acid may be replaced with a compound represented by the following formula (5) within a range not impairing the effects of the present invention. In this case, the synthesis of [A] polyorganosiloxane compound is 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).

In the above formula (4),
A ¹ represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxyl group, or a steroid skeleton. It is a hydrocarbon group having 17 to 51 carbon atoms. However, part or all of the hydrogen atoms of the alkyl group and 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—. Bond marked with "*" is bound to A ^1.
L ¹ is represented by a single bond, an alkylene group having 1 to 20 carbon atoms, a phenylene group, biphenylene group, cyclohexylene group, cyclohexylene group or the following formula bicyclo ^(L 1 -1) or ^(L 1 -2) It is a group.
Z is a monovalent organic group capable of reacting with an epoxy group in the [A] polyorganosiloxane compound to form a bonding group.
However, L ⁰ is a single bond when L ¹ is a single bond.

In the above formulas (L ¹ -1) and (L ¹ -2), the bonds marked with “*” are each bonded to 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 above formula (4) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3 -Methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1 , 2-dimethylbutyl group, 1,2-dimethylbutyl group, 1,1-dimethylbutyl group, n-heptyl group, 5-methylhexyl group, 4-methylhexyl group, 3-methylhexyl group, 2-methylhexyl group, 1-methylhexyl group, 4,4-dimethylpentyl group, 3,4-dimethylpentyl group, 2,4-dimethylpentyl group, 1,4-dimethylpentyl group, 3,3-dimethylpentyl Group, 2,3-dimethylpentyl group, 1,3-dimethylpentyl group, 2,2-dimethylpentyl group, 1,2-dimethylpentyl group, 1,1-dimethylpentyl group, 2,3,3-trimethylbutyl Group, 1,3,3-trimethylbutyl group, 1,2,3-trimethylbutyl group, n-octyl group, 6-methylheptyl group, 5-methylheptyl group, 4-methylheptyl group, 3-methylheptyl group 2-methylheptyl group, 1-methylheptyl group, 2-ethylhexyl group, n-nonanyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group Group, n- tetradecyl, n- heptadecyl group, n- hexadecyl group, n- heptadecyl group, n- octadecyl, n- nonadecyl group and the like.

  Examples of the cycloalkyl group having 3 to 10 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononanyl group, and a cyclodecyl group. And cyclododecyl group.

  Examples of the hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton include groups represented by the following formulas (A-1) to (A-3).

A ¹ in the above formula (4) is preferably a group selected from an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms and the above formula (A-1) or (A-3).

  As a compound represented by the said Formula (4), the compound represented by either of following formula (4-1)-(4-6) is preferable.

  In the above formulas (4-1) to (4-6), u is an integer of 1 to 5. v is an integer of 1-18. w is an integer of 1-20. k is an integer of 1-5. p is 0 or 1. q is an integer of 0-18. r is an integer of 0-18. s and t are each independently an integer of 0 to 2.

  Among these compounds, compounds represented by the following formulas (5-1) to (5-7) are more preferable.

  The compound represented by the above formula (4) is a compound that reacts with a polyorganosiloxane having an epoxy group together with a specific carboxylic acid and becomes a site that imparts pretilt angle expression to the obtained liquid crystal alignment film. In the present specification, the compound represented by the above formula (4) may be hereinafter referred to as “another pretilt angle-expressing compound”.

  In the present invention, when another pretilt angle-expressing compound is used together with the specific carboxylic acid, the total use ratio of the specific carboxylic acid and the other pretilt angle-expressing compound is 1 mol of the epoxy group of the polyorganosiloxane. Preferably it is 0.001-1.5 mol, More preferably, it is 0.01-1 mol, More preferably, it is 0.05-0.9 mol. In this case, the other compound having a pretilt angle is preferably used in a range of 75 mol% or less, more preferably 50 mol% or less, based on the total with the specific carboxylic acid. If the proportion of other pretilt angle-expressing compounds exceeds 75 mol%, the high-speed response of the liquid crystal may be adversely affected.

  The catalyst used for the reaction of the epoxy group in the polyorganosiloxane with the carboxylic acid group-containing compound represented by the above formula (4) and other compounds having a pretilt angle is an organic base or an epoxy compound and an acid anhydride. A known compound can be used as a so-called curing accelerator that accelerates the reaction with the compound.

  Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole; triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, And tertiary organic amines such as diazabicycloundecene; quaternary organic amines such as tetramethylammonium hydroxide. Of 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;
2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenyl Imidazole, 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-di (Hydroxymethyl) imidazole, 1- (2-cyanoethyl) -2-fur Nyl-4,5-di [(2′-cyanoethoxy) methyl] imidazole, 1- (2-cyanoethyl) -2-n-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Imidazolium trimellitate, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethyl-s -Triazine, 2,4-diamino-6- (2'-n-undecylimidazolyl) ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ' )] Ethyl-s-triazine, isocyanuric acid adduct of 2-methylimidazole, isocyanuric acid adduct of 2-phenylimidazole, 2,4-diamino-6- [2'-methyl] An imidazole compound such as an isocyanuric acid adduct of Louis-imidazolyl- (1 ′)] ethyl-s-triazine;
Organophosphorus compounds such as diphenylphosphine, triphenylphosphine, triphenyl phosphite; benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphine Phonium bromide, n-butyltriphenylphosphonium bromide, tetraphenylphosphonium bromide, ethyltriphenylphosphonium iodide, ethyltriphenylphosphonium acetate, tetra-n-butylphosphonium o, o- Diethylphosphorodithionate, tetra-n-butylphosphonium benzotriazolate, tetra-n-butylphosphonium tetrafluoroborate, tetra-n-buty Phosphonium tetraphenylborate, quaternary phosphonium salts such as tetraphenyl phosphonium tetraphenyl borate;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof;
Organometallic compounds such as zinc octylate, tin octylate, aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition accelerators such as dicyandiamide and adducts of amine and epoxy resin;
A microcapsule type latent curing accelerator in which the surface of a curing accelerator such as an imidazole compound, an organic phosphorus compound or a quaternary phosphonium salt is coated with a polymer;
An amine salt type latent curing accelerator;
Examples include latent curing accelerators such as high temperature dissociation type thermal cationic polymerization type latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

  Among these catalysts, quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride are preferable.

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

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

  [A] The synthesis reaction of the polyorganosiloxane compound can be carried out in the presence of an organic solvent, if necessary. Examples of the organic solvent include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, alcohol compounds, and the like. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products and ease of purification of the products. The solvent has a solid content concentration (the ratio of the mass of components other than the solvent in the reaction solution to the total mass of the solution), preferably 0.1% by mass to 70% by mass, more preferably 5% by mass to 50% by mass. % Is used in an amount of less than%.

  Although the weight average molecular weight in terms of styrene by gel permeation chromatography of the [A] polyorganosiloxane compound thus obtained is not particularly limited, it is preferably 1,000 to 200,000, preferably 2,000 to 20, More preferably, it is 000. By being in such a molecular weight range, it is possible to ensure good orientation and stability of the liquid crystal display element.

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

<Optional component>
The liquid crystal aligning agent is, for example, a polymer other than the [A] polyorganosiloxane compound (hereinafter referred to as “other polymer”) unless the effects of the present invention are impaired in addition to the above-mentioned [A] polyorganosiloxane compound. ), Curing agent, curing catalyst, curing accelerator, compound having at least one epoxy group in the molecule (hereinafter sometimes referred to as “epoxy compound”), functional silane compound, surfactant Other optional components such as may be contained.

[Other polymers]
Other polymers can be used to further improve the solution properties of the liquid crystal aligning agent and the electrical properties of the resulting liquid crystal aligning device. Examples of the other polymer include at least one polymer selected from the group consisting of polyamic acid and polyimide ([B] polymer);
At least one selected from the group consisting of a polyorganosiloxane represented by the following formula (5), a hydrolyzate thereof and a condensate of the hydrolyzate (hereinafter sometimes referred to as “other polyorganosiloxane”). );
Examples include polyamic acid esters, polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.

（式（５）中、Ｘ^１は水酸基、ハロゲン原子、炭素数１〜２０のアルキル基、炭素数１〜６のアルコキシ基又は炭素数６〜２０のアリール基である。Ｙ^１は水酸基又は炭素数１〜１０のアルコキシ基である。）

(In 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 carbon. (It is an alkoxy group of formula 1 to 10.)

<[B] polymer>
[B] The polymer is at least one polymer selected from the group consisting of polyamic acid and polyimide. Hereinafter, polyamic acid and polyimide will be described in detail.

[Polyamic acid]
A polyamic acid is obtained by reacting a tetracarboxylic dianhydride and a diamine compound. Examples of tetracarboxylic dianhydrides that can be used for the synthesis of polyamic acid include 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic 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- (tetrahydride) -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, the following formula (F-1) Aliphatic or alicyclic tetracarboxylic dianhydride such as tetracarboxylic dianhydride represented by ~ (F-14);

Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ', 4,4'-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide Dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′ , 4 4′-perfluoroisopropylidenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis ( Triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid)- Examples include 4,4′-diphenylmethane dianhydride and aromatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydrides represented by the following formulas (F-15) to (F-18).

  Of these, 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-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 2, , 6,7-Naphthalenetetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, the above formulas (F-1), (F-2), (F-15) ) To (F-18) are preferred tetracarboxylic dianhydrides. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

Examples of the diamine compound that can be used for the synthesis of polyamic acid include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and 4,4′-diaminodiphenyl sulfide. 4,4′-diaminodiphenyl sulfone, 3,3′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 4,4′-diamino-2 , 2′-dimethylbiphenyl, 1,5-diaminonaphthalene, 3,3-dimethyl-4,4′-diaminobiphenyl, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane 6-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodi Phenyl ether, 2,2-bis (4
-Aminophenoxy) propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis ( 4-aminophenyl) hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) ) Benzene, 1,3-bis (3-aminophenoxy) benzene, 9,9-bis (4-aminophenyl) -10-hydroanthracene, 2,7-diaminofluorene, 9,9-bis (4-aminophenyl) ) Fluorene, 4,4′-methylene-bis (2-chloroaniline), 2,2 ′, 5,5′-tetrachloro-4,4′-diaminobiphenyl 2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 4,4 ′-(p-phenyleneisopropylidene) Bisaniline, 4,4 ′-(m-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2 , 2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 6- (4-chalconyloxy) hexyloxy (2 , 4-diaminobenzene), 6- (4′-fluoro-4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 8- (4-chalcone) Ruoxy) octyloxy (2,4-diaminobenzene), 8- (4′-fluoro-4-chalconyloxy) octyloxy (2,4-diaminobenzene), 1-dodecyloxy-2,4-diaminobenzene, 1-tetradecyloxy-2,4-diaminobenzene, 1-pentadecyloxy-2,4-diaminobenzene, 1-hexadecyloxy-2,4-diaminobenzene, 1-octadecyloxy-2,4-diaminobenzene 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, dodecyloxy (3,5-diaminobenzoyl), tetradecyloxy (3,5-diaminobenzoyl), penta Decyloxy (3,5-diaminobenzoyl), hexadecyloxy (3,5-dia Nobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diaminobenzoyl), (2,4-diaminophenoxy) palmitate, (2 , 4-diaminophenoxy) stearylate, (2,4-diaminophenoxy) -4-trifluoromethylbenzoate, aromatic diamines such as diamine compounds represented by the following formulas (G-1) to (G-7);

An aromatic diamine having a heteroatom such as diaminotetraphenylthiophene;
Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, 1,4-diamino Cyclohexane, cyclohexanebis (methylamine), isophoronediamine, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylene methylenediamine, tricyclo [6.2.1.0 ^2,7 ] -undecylenedimethyl Aliphatic or alicyclic diamines such as diamine, 4,4′-methylenebis (cyclohexylamine);
And diaminoorganosiloxanes such as diaminohexamethyldisiloxane.

  Among these, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-2,2′-dimethylbiphenyl, cyclohexanebis (methylamine), 1,5-diaminonaphthalene, 2,7- Diaminofluorene, 4,4′-diaminodiphenyl ether, 4,4 ′-(p-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2-bis [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-octadecyloxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy- 2,4-diaminobenzene, hexadecyloxy (3,5-diaminobenzoyl), octadecyloxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), cholestanyloxy (3,5-diamino) Benzoyl) and diamines represented by the above formulas (G-1) to (G-7) are preferred. These diamines may be used alone or in combination of two or more.

  The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.

  The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 to 150 ° C., more preferably at a temperature of 0 to 100 ° C., preferably 0.5 to 24 hours, more preferably 2 to 10 Done for hours. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol . The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is preferably 0.1 to 50% by mass, more preferably 5%, based on the total amount (a + b) of the reaction solution. The amount is -30% by mass.

  In addition, the said organic solvent can use together the alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbons, etc. which are poor solvents of a polyamic acid in the range in which the polyamic acid to produce | generate does not precipitate. Examples of the poor solvent include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, diacetone alcohol, ethylene glycol monomethyl ether, ethyl lactate, and butyl lactate. , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, propylene carbonate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol Methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-pro 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-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like. These poor solvents may be used alone or in combination of two or more.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. Further, the polyamic acid can be purified by a method in which the polyamic acid is dissolved again in an organic solvent and then precipitated with a poor solvent, or a method in which the step of distilling off with an evaporator under reduced pressure is performed once or several times.

[Polyimide]
The polyimide can be produced by dehydrating and ring-closing the amic acid structure of the polyamic acid obtained as described above. At this time, all of the amic acid structure may be dehydrated and cyclized to completely imidize, or only a part of the amic acid structure may be dehydrated and cyclized to form a partially imidized product in which the amic acid structure and the imide structure coexist. Also good.

  The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.

  The reaction temperature in the method of heating the polyamic acid (i) is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. By setting the reaction temperature to 50 ° C. or higher, the dehydration ring-closing reaction can be sufficiently advanced, and by setting the reaction temperature to 200 ° C. or lower, it is possible to suppress a decrease in the molecular weight of the resulting imidized polymer. The reaction time in the method of heating the polyamic acid is preferably 0.5 to 48 hours, more preferably 2 to 20 hours.

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

  In the method (ii), a reaction solution containing polyimide is obtained as described above. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. May be used for the preparation of a liquid crystal aligning agent, or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydration ring closure catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

[Other polyorganosiloxanes]
The liquid crystal aligning agent may contain other polyorganosiloxane in addition to the [A] polyorganosiloxane compound. The other polyorganosiloxane is preferably at least one selected from the group consisting of the polyorganosiloxane represented by the above formula (5), a hydrolyzate thereof, and a condensate of the hydrolyzate. In addition, when the liquid crystal aligning agent contains other polyorganosiloxane, most of the other polyorganosiloxane exists independently from the [A] polyorganosiloxane compound, and a part thereof is [A It may exist as a condensate with a polyorganosiloxane compound.

In X ¹ and Y ¹ in the above formula (5),
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Nonyl group, n-decyl group, n-lauryl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n- Nonadecyl group, n-eicosyl group, etc .;
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.

  The other polyorganosiloxane is, for example, at least one silane compound selected from the group consisting of an alkoxysilane compound and a halogenated silane compound (hereinafter sometimes referred to as “raw silane compound”), preferably a suitable organic It can be synthesized by hydrolysis or hydrolysis / condensation in a solvent in the presence of water and a catalyst.

Examples of the raw material silane compound that can be used here include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, and tetra-tert-. Butoxysilane, tetrachlorosilane; methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane , Methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxy Run, ethyltri -n- butoxysilane, ethyltri -
sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltrichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane; trimethylmethoxysilane, trimethylethoxysilane And trimethylchlorosilane. Of these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane are preferred. .

  Examples of organic solvents that can optionally be used in the synthesis of other polyorganosiloxanes include alcohol compounds, ketone compounds, amide compounds or ester compounds, and other aprotic compounds. These may be used alone or in combination of two or more.

Examples of alcohol compounds include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec -Pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, Monoalcohol compounds such as phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2- Polyhydric alcohol compounds such as ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol 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 ether, dipropylene glycol monoethyl ether, partial ethers of a polyhydric alcohol compound and dipropylene glycol monopropyl ether, and the like. 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-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, and methyl-n-hexyl. Monoketone compounds such as ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, fencheon;
Acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4-nonanedione, 3,5-nonanedione, 5 -Methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1,1,5,5,5-hexafluoro-2,4-heptanedione, etc. Β-diketone compounds and the like. These ketone compounds may be used alone or in combination of two or more.

  Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-ethyl. Acetamide, N, N-diethylacetamide, N-methylpropionamide, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-acetylmorpholine, N-acetylpiperidine, N-acetylpyrrolidine, etc. Is mentioned. These amide compounds may be used alone or in combination of two or more.

Examples of the ester compound include diethyl carbonate, ethylene carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, and i-acetate. -Butyl, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-acetate -Nonyl, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diacetate Ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diethylene ether Glycol acetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-lactate Examples include amyl, diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester compounds may be used alone or in combination of two or more.

  Examples of other aprotic compounds include acetonitrile, dimethyl sulfoxide, N, N, N ′, N′-tetraethylsulfamide, hexamethylphosphoric triamide, N-methylmorpholone, N-methylpyrrole, and N-ethyl. Pyrrole, N-methyl-Δ3-pyrroline, N-methylpiperidine, N-ethylpiperidine, N, N-dimethylpiperazine, N-methylimidazole, N-methyl-4-piperidone, N-methyl-2-piperidone, N- Examples include methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyltetrahydro-2 (1H) -pyrimidinone. Of these solvents, polyhydric alcohol compounds, partial ethers of polyhydric alcohol compounds, or ester compounds are particularly preferred.

  The amount of water used in the synthesis of the other polyorganosiloxane is preferably 0.01 to 100 mol, more preferably 0, relative to 1 mol of the total amount of alkoxy groups and halogen atoms of the starting silane compound. 0.1 to 30 mol, and preferably 1 to 1.5 mol.

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

Examples of the metal chelate compound include triethoxy mono (acetylacetonato) titanium, tri-n-propoxy mono (acetylacetonato) titanium, tri-i-propoxy mono (acetylacetonato) titanium, tri-n- Butoxy mono (acetylacetonato) titanium, tri-sec-butoxy mono (acetylacetonato) titanium, tri-t-butoxy mono (acetylacetonato) titanium, diethoxybis (acetylacetonato) titanium, di- n-propoxy bis (acetylacetonato) titanium, di-i-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, di-sec-butoxy bis (acetylacetate) Natto) titanium, di-t-butoxy Su (acetylacetonato) titanium, monoethoxy-tris (acetylacetonato) titanium, mono-n-propoxy-tris (acetylacetonato) titanium, mono-i-propoxy-tris (acetylacetonato) titanium, mono-n -Butoxy-tris (acetylacetonato) titanium, mono-sec-butoxy-tris (acetylacetonato) titanium, mono-t-butoxy-tris (acetylacetonato) titanium, tetrakis (acetylacetonato) titanium, triethoxy mono (Ethyl acetoacetate) titanium, tri-n-propoxy mono (ethyl acetoacetate) titanium, tri-i-propoxy mono (ethyl acetoacetate) titanium, tri-n-butoxy mono (ethyl acetoacetate) titanium, tri -S c-butoxy mono (ethyl acetoacetate) titanium, tri-t-butoxy mono (ethyl acetoacetate) titanium, diethoxy bis (ethyl acetoacetate) titanium, di-n-propoxy bis (ethyl acetoacetate) titanium, Di-i-propoxy bis (ethyl acetoacetate) titanium, di-n-butoxy bis (ethyl acetoacetate) titanium, di-sec-butoxy bis (ethyl acetoacetate) titanium, di-t-butoxy bis ( Ethyl acetoacetate) titanium, monoethoxy tris (ethyl acetoacetate) titanium, mono-n-propoxy tris (ethyl acetoacetate) titanium, mono-i-propoxy tris (ethyl acetoacetate) titanium, mono-n-butoxy・ Tris (ethyl aceto Acetate) titanium, mono-sec-butoxy tris (ethyl acetoacetate) titanium, mono-t-butoxy tris (ethyl acetoacetate) titanium, tetrakis (ethyl acetoacetate) titanium, mono (acetylacetonate) tris (ethyl aceto) Titanium chelate compounds such as acetate) titanium, bis (acetylacetonato) bis (ethylacetoacetate) titanium, tris (acetylacetonato) mono (ethylacetoacetate) titanium;

Triethoxy mono (acetylacetonato) zirconium, tri-n-propoxy mono (acetylacetonato) zirconium, tri-i-propoxy mono (acetylacetonato) zirconium, tri-n-butoxy mono (acetylacetonate) Zirconium, tri-sec-butoxy mono (acetylacetonato) zirconium, tri-t-butoxy mono (acetylacetonato) zirconium, diethoxybis (acetylacetonato) zirconium, di-n-propoxybis (acetylacetate) Nato) zirconium, di-i-propoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium, di-sec-butoxy bis (acetylacetonato) ziru Ni, di-t-butoxy bis (acetylacetonato) zirconium, monoethoxy tris (acetylacetonato) zirconium, mono-n-propoxytris (acetylacetonato) zirconium, mono-i-propoxytris (acetyl) Acetonato) zirconium, mono-n-butoxy-tris (acetylacetonato) zirconium, mono-sec-butoxy-tris (acetylacetonato) zirconium, mono-t-butoxy-tris (acetylacetonato) zirconium, tetrakis (acetyl) Acetonato) zirconium, triethoxy mono (ethyl acetoacetate) zirconium, tri-n-propoxy mono (ethyl acetoacetate) zirconium, tri-i-propoxy mono (ethyl acetate) Acetate) zirconium, tri -n- butoxy mono (ethylacetoacetate) zirconium, tri -sec-
Butoxy mono (ethyl acetoacetate) zirconium, tri-t-butoxy mono (ethyl acetoacetate) zirconium, diethoxy bis (ethyl acetoacetate) zirconium, di-n-propoxy bis (ethyl acetoacetate) zirconium, di- i-propoxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-sec-butoxy bis (ethyl acetoacetate) zirconium, di-t-butoxy bis (ethyl aceto) Acetate) zirconium, monoethoxy-tris (ethylacetoacetate) zirconium, mono-n-propoxy-tris (ethylacetoacetate) zirconium, mono-i-propoxy-tris (ethylacetoacetate) Zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-sec-butoxy tris (ethyl acetoacetate) zirconium, mono-t-butoxy tris (ethyl acetoacetate) zirconium, tetrakis (ethyl) Zirconium chelates such as acetoacetate) zirconium, mono (acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetonato) mono (ethylacetoacetate) zirconium Compound;

Examples thereof include aluminum chelate compounds such as tris (acetylacetonate) aluminum and tris (ethylacetoacetate) aluminum.
Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, and gallic acid. Acid, butyric acid, meritic acid, arachidonic acid, mikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfone Examples include acids, 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, monomethyldiethanolamine, triethanolamine, diazabicycloocrane, diazabicyclo. Nonane, diazabicycloundecene, tetramethylammonium hydroxide and the like can be mentioned.

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

  Of 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 to be used is preferably 0.001 to 10 parts by mass, more preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the raw material silane compound.

  The catalyst may be added in advance to a raw material silane compound or a solution in which a silane compound is dissolved in an organic solvent, or may be dissolved or dispersed in added water.

Water added in the synthesis of another polyorganosiloxane can be added intermittently or continuously in the raw material silane compound or in a solution obtained by dissolving the silane compound in an organic solvent.

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

  When the liquid crystal aligning agent contains another polymer together with the [A] polyorganosiloxane compound, the content of the other polymer is 10 with respect to 100 parts by mass of the [A] polyorganosiloxane compound. 000 parts by mass or less is preferable. The more preferable content of the other polymer varies depending on the type of the other polymer.

  When the liquid crystal aligning agent contains the [A] polyorganosiloxane compound and the [B] polymer, the preferred use ratio of both is [B] the polymer with respect to 100 parts by mass of the [A] polyorganosiloxane compound. The total amount of is preferably 100 to 5,000 parts by mass, more preferably 200 to 3,000 parts by mass.

  On the other hand, when the liquid crystal aligning agent contains [A] a polyorganosiloxane compound and another polyorganosiloxane, the preferred use ratio of both is the ratio of the other polyorganosiloxane compound to 100 parts by weight of the other polyorganosiloxane compound. The amount of the organosiloxane is 100 to 2,000 parts by mass.

  When the liquid crystal aligning agent contains another polymer together with the [A] polyorganosiloxane compound, the other polymer is preferably a [B] polymer or another polyorganosiloxane.

[Curing agent, curing catalyst and curing accelerator]
The curing agent and the curing catalyst can be included in the liquid crystal aligning agent for the purpose of strengthening the crosslinking reaction of the [A] polyorganosiloxane compound. The curing accelerator can be included in the liquid crystal aligning agent for the purpose of accelerating the curing reaction controlled by the curing agent.

  As the curing agent, a curing agent generally used for curing a curable compound having an epoxy group or a curable composition containing a compound having an epoxy group can be used. Examples of such curing agents include polyvalent amines, polyvalent carboxylic acid anhydrides, and polyvalent carboxylic acids.

  Examples of the polyvalent carboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and other polyvalent carboxylic acid anhydrides.

  Examples of the cyclohexanetricarboxylic acid anhydride include, for example, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, cyclohexane-1,3,5-tricarboxylic acid-3,5-anhydride, cyclohexane-1,2 and the like. , 3-tricarboxylic acid-2,3-acid anhydride and the like. Examples of other polyvalent carboxylic acid anhydrides include 4-methyltetrahydrophthalic anhydride, methylnadic acid anhydride, dodecenyl succinic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, Compound of formula (6), tetracarboxylic dianhydride generally used for the synthesis of polyamic acid, alicyclic compound having conjugated double bond such as α-terpinene, allocymene and maleic anhydride Examples include Diels-Alder reaction products and hydrogenated products thereof.

（式（６）中、ｘは１〜２０の整数である。）

(In Formula (6), x is an integer of 1-20.)

  As the curing catalyst, for example, an antimony hexafluoride compound, a phosphorus hexafluoride compound, aluminum trisacetylacetonate, or the like can be used. These catalysts can catalyze the cationic polymerization of epoxy groups by heating.

  Examples of the curing accelerator include imidazole compounds; quaternary phosphorus compounds; quaternary amine compounds; diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; octylic acid Organometallic compounds such as zinc, tin octylate and aluminum acetylacetone complexes; Boron compounds such as boron trifluoride and triphenylborate; Metal halide compounds such as zinc chloride and stannic chloride; Dicyandiamide, amines and epoxy resins High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as adducts; Microcapsule type latent curing accelerators whose surface is covered with a polymer such as quaternary phosphonium salt; Amine salt type latent curing Accelerators: high temperature dissociation type thermal cationic polymerization latent curing accelerators such as Lewis acid salts and Bronsted acid salts.

[Epoxy compound]
The said epoxy compound can be included in the said liquid crystal aligning agent from a viewpoint of improving the adhesiveness with respect to the substrate surface of the liquid crystal aligning film formed.

  Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexanediol diester. Glycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N′-tetraglycidyl -M-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodi Enirumetan, N, N, - diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane are preferred.

  When the liquid crystal aligning agent contains an epoxy compound, the content is preferably 100 parts by mass with respect to a total of 100 parts by mass of the above-mentioned [A] polyorganosiloxane compound and other polymer optionally used. 0.01-40 mass parts or less, More preferably, it is 0.1-30 mass parts.

  In addition, when the said liquid crystal aligning agent contains an epoxy compound, you may use together basic catalysts, such as 1-benzyl-2-methylimidazole, in order to raise | generate the crosslinking reaction efficiently.

[Functional silane compounds]
The functional silane compound can be used for the purpose of improving the adhesion of the resulting liquid crystal alignment film to the substrate. Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl) -3. -Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltri Methoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7 Triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl- 3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene ) -3-Aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane In addition, JP-A 63-2 The reaction products of the silane compound having a tetracarboxylic dianhydride and an amino group described in 1922 JP thereof.

  When the liquid crystal aligning agent contains a functional silane compound, the content ratio thereof is a total of 100 parts by mass of the above-mentioned [A] polyorganosiloxane compound and other polymer optionally used, 50 parts by mass or less is preferable, and 20 parts by mass or less is more preferable.

[Surfactant]
Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, and fluorine-containing surfactants.

  When the liquid crystal aligning agent contains a surfactant, the content is preferably 10 parts by mass or less, more preferably 1 part by mass or less, with respect to 100 parts by mass as a whole of the liquid crystal aligning agent.

<Method for preparing liquid crystal aligning agent>
As described above, the liquid crystal aligning agent contains [A] a polyorganosiloxane compound as an essential component, and may contain other optional components as necessary. Preferably, each component is dissolved in an organic solvent. It is prepared as a composition.

  As the organic solvent that can be used for preparing the liquid crystal aligning agent, those that dissolve the specific polyorganosiloxane and other components optionally used and do not react with these are preferable. The organic solvent that can be preferably used for the liquid crystal aligning agent varies depending on the type of other polymer that is optionally added.

  Preferred organic solvents in the case where the liquid crystal aligning agent contains a [A] polyorganosiloxane compound and a [B] polymer include the organic solvents exemplified above as those used for the synthesis of polyamic acid. At this time, you may use together the poor solvent illustrated as what is used for the synthesis | combination of the polyamic acid of this invention. These organic solvents may be used alone or in combination of two or more.

  On the other hand, when the liquid crystal aligning agent contains only the [A] polyorganosiloxane compound as a polymer, or when it contains the [A] polyorganosiloxane compound and another polyorganosiloxane, a preferable organic solvent is, 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 ethyl ether, dipropylene glycol propyl ether, di Propylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether Ter, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monoamyl 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, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, n-hexyl acetate, cyclohexyl acetate, octyl acetate, amyl acetate, isoacetate Mill and the like. Of these, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, and sec-pentyl acetate are preferred.

  A preferable solvent used for the preparation of the liquid crystal aligning agent can be obtained by combining one or more of the above-described organic solvents in accordance with the presence or absence of other polymers and their types. Such a solvent is one in which each component contained in the liquid crystal aligning agent does not precipitate at the following preferable solid content concentration, and the surface tension of the liquid crystal aligning agent is in the range of 25 to 40 mN / m.

  The solid content concentration of the liquid crystal aligning agent, that is, the ratio of the weight of all components other than the solvent in the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent is selected in consideration of viscosity, volatility, etc. It is the range of 1-10 mass%. The liquid crystal aligning agent is applied to the substrate surface to form a coating film that becomes a liquid crystal aligning film. When the solid content concentration is 1% by mass or more, the film thickness of the coating film is less likely to be too small. A good liquid crystal alignment film can be obtained. On the other hand, when the solid content concentration is 10% by mass or less, it is possible to obtain an excellent liquid crystal alignment film by suppressing the film thickness of the coating film from becoming excessive, and the viscosity of the liquid crystal alignment agent increases. This can be prevented and the coating properties can be improved. The particularly preferable range of the solid content concentration varies depending on the method employed when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the range of 1.5 to 4.5% by mass is particularly preferable. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by mass, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the ink jet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by mass, and thereby the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 40 ° C.

<Liquid crystal display element>
The driving method of the liquid crystal display element of the present invention is not particularly limited, and the present technology is applied to various known methods such as TN, STN, IPS, VA (including VA-MVA method, VA-PVA method, etc.). The liquid crystal alignment film is formed from the liquid crystal alignment agent. In general, a liquid crystal display element includes a pair of substrates on the surface of which a transparent electrode and a liquid crystal alignment film are laminated in this order. The pair of substrates are disposed to face each other, and a liquid crystal is interposed between the pair of substrates. Filled and the periphery is sealed with a sealant.

<Method for manufacturing liquid crystal display element>
The liquid crystal display element formed using the said liquid crystal aligning agent can be manufactured as follows, for example. The liquid crystal alignment film used in the present invention is formed on a substrate by applying the liquid crystal aligning agent on the substrate and then heating the coated surface. As the substrate, for example, glass such as float glass or soda glass; a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, alicyclic polyolefin, or the like can be used. A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.

  The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.

  The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.

  In any case, it is desirable to remove the flow alignment at the time of injection by heating to a temperature at which the liquid crystal using the liquid crystal cell takes an isotropic phase and then gradually cooling to room temperature. And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

  As the sealing agent, for example, an aluminum oxide sphere as a spacer and an epoxy resin containing a curing agent can be used.

  As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of a TN liquid crystal cell or an STN liquid crystal cell, those having positive dielectric anisotropy for forming a nematic liquid crystal are preferable. Examples of such liquid crystals include biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, and cubane liquid crystals. It is done. In addition, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, cholesteryl carbonate; chiral agents such as those sold under the trade names C-15 and CB-15 (Merck); p-decyloxybenzylidene- Ferroelectric liquid crystals such as p-amino-2-methylbutyl cinnamate can be further added and used.

  On the other hand, in the case of a vertical alignment type liquid crystal cell, a cell having negative dielectric anisotropy that forms a nematic liquid crystal is preferable. As such a liquid crystal, for example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, a Schiff base liquid crystal, an azoxy liquid crystal, a biphenyl liquid crystal, and a phenylcyclohexane liquid crystal are used.

  The polarizing plate used outside the liquid crystal cell is not particularly limited, but is a polarizing plate in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning a polyvinyl alcohol film is sandwiched between cellulose acetate protective films, Or the polarizing plate etc. which consist of H film | membrane itself are mentioned.

  The liquid crystal display element of the present invention thus produced is excellent in various performances such as orientation, voltage holding ratio, and afterimage characteristics in addition to the response speed and display characteristics of the liquid crystal.

<Liquid crystal display element having two or more regions having different orientation directions>
The liquid crystal display element has two or more regions in which the liquid crystal alignment mode is vertical and the alignment directions are different, and the basic structure is the same as that of the liquid crystal display element. The means having two or more regions having different alignment methods is not particularly limited, and examples thereof include a means using a patterned transparent electrode and an alignment dividing means by a rubbing treatment of a liquid crystal alignment film. Such a liquid crystal display device can be suitably applied in drive modes such as TN, STN, IPS, and VA (including VA-MVA method, VA-PVA method, etc.), further improves contrast, and has high-speed response. More improved.

As a method for producing the patterned transparent electrode, the liquid crystal aligning agent is preferably applied by an offset printing method, a spin coating method, or an ink jet printing method, and then each coated surface is heated to form a coating film. As a transparent conductive film provided on one surface of a substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. Next, for example, a pattern is formed by a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a method using a mask having a desired pattern when forming the transparent conductive film, and the like.

  Specific examples of the patterned transparent electrode include those shown in FIGS. The patterned transparent electrode will be described with reference to FIG. Referring to FIG. 1B, the transparent substrate 3 has an ITO film 1 partitioned into a plurality of regions, and a plurality of slits 2 are provided and patterned. The width w1 of the slit 2 is, for example, about 10 μm, and the distance w2 between the slits 2 is, for example, about 35 μm. In this case, the ITO line W1 shown in FIG. 1A is about 9 mm (200 lines with a width of 35 μm). Examples of the material for the transparent substrate include glass. In the case of manufacturing a liquid crystal display element using the patterned transparent electrode shown in FIG. 1, two substrates provided with the patterned transparent electrode are prepared, and the slit 2 is formed when the two substrates are opposed to each other. It is necessary to arrange them so that they do not overlap each other (so that the slits 2 are displaced from each other and are in contact with the ITO film 1).

  As the alignment dividing means of the liquid crystal alignment film, for example, a pair (two sheets) of substrates having the liquid crystal alignment film is prepared by operating in the same manner as in the above-mentioned “Liquid Crystal Display Device Manufacturing Method”. A method of rubbing through a mask so as to have regions having different orientation directions as described above can be mentioned. As a form of the mask, a mask that divides a pixel having a hole corresponding to the size of one area into four (a matrix of 1/4 of the pixel size, every other hole is provided, and the hole is Masks arranged in a diagonal line).

  It is preferable that the liquid crystal aligning agent used for manufacture of the liquid crystal display element which has two or more area | regions from which the orientation orientation differs of this invention contains the compound which has group represented by the said Formula (3).

In Formula (3), R ² is a linking group containing any of a double bond, a triple bond, an ether bond, an ester bond, or an oxygen atom. R ³ is a group having at least two monocyclic structures. a is an integer of 0-1. Detailed explanations of these symbols are omitted in the description of [A] polyorganosiloxane compound, and are omitted here.

<Polyorganosiloxane compound>
The polyorganosiloxane compound of the present invention is a compound derived from a polyorganosiloxane having an epoxy group and a compound having a carboxyl group represented by the following formula (1), or R ^{3 of the} formula (1) is represented by the following formula (2 And a portion derived from a compound having a carboxyl group represented by: Since the detailed description of the polyorganosiloxane compound is given in the description of [A] polyorganosiloxane compound contained in the liquid crystal aligning agent, it is omitted here. The polyorganosiloxane compound can be suitably used as a liquid crystal aligning agent for constituting a liquid crystal display device having various properties such as alignment characteristics, high-speed response, voltage characteristics, and afterimage characteristics.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

The weight average molecular weight (Mw) of the polyorganosiloxane having an epoxy group and the [A] polyorganosiloxane compound obtained in the following examples is a polystyrene conversion value measured by GPC having the following specifications.
Column: Tosoh Corporation, 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 was ensured by repeating the synthesis of the raw material compound and the polymer on the synthetic scale shown in the following synthesis examples as necessary.

<Synthesis of polyorganosiloxane having epoxy group>
[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were added. Charged and mixed at room temperature. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out and washed with a 0.2% by mass aqueous ammonium nitrate solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to give a polyorgano having an epoxy group. Siloxane was obtained as a viscous transparent liquid.
As a result of ¹ H-NMR analysis of the polyorganosiloxane having an epoxy group, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity. It was confirmed that no side reaction occurred.

[Synthesis Examples 2-3]
A polyorganosiloxane having an epoxy group was obtained as a viscous transparent liquid in the same manner as in Synthesis Example 1 except that the raw materials used were as shown in Table 1 below. Table 1 shows the Mw and epoxy equivalent of the polyorganosiloxane having an epoxy group obtained in Synthesis Examples 1 to 3. In addition, the abbreviation of the raw material silane compound in Table 1 has the following meaning.
ECETS: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane MTMS: methyltrimethoxysilane PTMS: phenyltrimethoxysilane

<Synthesis of specific carboxylic acid>
Specific carboxylic acid 1 was synthesized according to the following reaction scheme.

[Synthesis Example 4]
To a 500 mL three-necked flask equipped with a condenser tube was added 6.3 g of 4-cyano-4′-hydroxybiphenyl, 10 g of methyl 11-bromoundecanoate, 14.2 g of potassium carbonate, and 200 mL of N, N-dimethylformamide at 160 ° C. The mixture was heated and stirred for 5 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was put into 500 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with water. The obtained solid was vacuum dried at 80 ° C. to obtain 11 g of Compound 1.

[Synthesis Example 5]
Next, 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 condenser, and the mixture was heated and stirred at 80 ° C. for 4 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. While stirring the reaction solution, dilute hydrochloric acid was slowly added dropwise to the reaction solution. The precipitated solid was filtered and washed with water and ethanol in this order. The obtained solid was vacuum dried at 80 ° C. to obtain 8 g of the specific carboxylic acid 1.

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

[Synthesis Example 6]
To a 500 mL three-necked flask equipped with a condenser tube was added 15 g of 4-cyano-4′-hydroxybiphenyl, 13.5 g of ethylene carbonate, 2.5 g of tetrabutylammonium bromide (TBAB), and 300 mL of N, N-dimethylformamide, and 150 ° C. And stirred for 9 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. The reaction solution was separated and washed with a mixed solution of 300 mL of ethyl acetate and 100 mL of 1N sodium hydroxide aqueous solution. After extracting the organic layer, it was further separated and washed in the order of 100 mL of 1N sodium hydroxide aqueous solution and 100 mL of water. The organic layer was dried over magnesium sulfate, and then the organic solvent was distilled off. The obtained solid was vacuum-dried and then recrystallized with 100 mL of ethanol / 250 mL of hexane to obtain 13.1 g of Compound 2.

[Synthesis Example 7]
To a 200 mL three-necked flask equipped with a condenser and a dropping funnel, 12 g of Compound 2, 12.7 g of 4-chlorobenzenesulfonyl chloride, and 60 mL of dehydrated methylene chloride were added and mixed. While the reaction solution was cooled in an ice bath, a solution of triethylamine (6.6 g) in dehydrated methylene chloride (10 mL) was added dropwise over 10 minutes. The mixture was stirred for 30 minutes in the ice bath state, returned to room temperature, and further stirred for 6 hours. Chloroform 150mL was added to the reaction solution, and liquid separation washing | cleaning was performed 4 times with water 100mL. The extracted organic layer was dried over magnesium sulfate, and the organic solvent was distilled off. 16.1g of compound 3 was obtained by wash | cleaning the obtained solid with ethanol.

[Synthesis Example 8]
15 g of compound 3, 11 g of methyl 4-hydroxybenzoate, 12.5 g of potassium carbonate, and 180 mL of N, N-dimethylformamide were added to a 300 mL three-necked flask equipped with a condenser, and the mixture was heated and stirred at 80 ° 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 poured into 500 mL of water and mixed and stirred. The precipitated white solid was filtered off and further washed with ethanol. The obtained solid was vacuum-dried at 80 ° C. to obtain 10 g of Compound 4.

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

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

[Synthesis Example 10]
In Synthesis Example 4, 13.7 g of Compound 5 was obtained by using 10.7 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol instead of 4-cyano-4′-hydroxybiphenyl. It was.

[Synthesis Example 11]
In Synthesis Example 5, 13.5 g of the specific carboxylic acid 3 was obtained by using 13.5 g of the compound 5 instead of the compound 1.

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

[Synthesis Example 12]
In Synthesis Example 6, 25.5 g of 2,3,5,6-tetrafluoro-4- (pentafluorophenyl) phenol was used in place of 4-cyano-4′-hydroxybiphenyl to obtain 23.1 g of compound 6. Obtained.

[Synthesis Example 13]
In Synthesis Example 7, 18.9 g of Compound 6 was used instead of Compound 2 to obtain 24.1 g of Compound 7.

[Synthesis Example 14]
By using 20 g of compound 7 instead of compound 3 in Synthesis Example 8, 15.4 g of compound 8 was obtained.

[Synthesis Example 15]
In Synthesis Example 9, 11.4 g of the specific carboxylic acid 4 was obtained by using 13 g of the compound 8 instead of the compound 4.

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

[Synthesis Example 16]
15 g of the specific carboxylic acid 5 in which the number of methylene groups was changed from 10 to 5 was synthesized in the same manner as the synthesis of the specific carboxylic acid 1.

<[A] Synthesis of polyorganosiloxane compound>
[Example 1]
In a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 5.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 5 above, the above formula (5) 80 g of 4-octyloxybenzoic acid represented by the formula (5-5) and 0.20 g of UCAT 18X (quaternary amine salt of San Apro) exemplified as one of the compounds represented by For 12 hours. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to remove [A] polyorganosiloxane compound A- 14.5 g of 1 was obtained as a white powder. [A] Mw of the polyorganosiloxane compound A-1 was 6,500.

[Example 2]
Except that 4 g of the specific carboxylic acid 2 obtained in Synthesis Example 9 was used in place of the specific carboxylic acid 1, the same operation as in Example 1 was carried out to obtain [A] a white powder of the polyorganosiloxane compound A-2. 8 g was obtained. The Mw of A-2 was 6,000.

[Example 3]
A white powder of [A] polyorganosiloxane compound A-3 was prepared in the same manner as in Example 1 except that 6.8 g of the specific carboxylic acid 3 obtained in Synthesis Example 11 was used instead of the specific carboxylic acid 1. 14.7 g was obtained. The Mw of A-3 was 8,100.

[Example 4]
[A] The polyorganosiloxane compound was synthesized in the same manner as in Example 1 except that 5.6 g of the specific carboxylic acid 4 obtained in Synthesis Example 15 was used instead of the specific carboxylic acid 1. As a result, 15.0 g of white powder of [A] polyorganosiloxane compound A-4 was obtained. The Mw of A-4 was 7,500.

[Example 5]
In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 10 g of the specific carboxylic acid 1 obtained in Synthesis Example 5 above, and UCAT 18X (San Apro 4) Secondary amine salt) 0.20 g was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and then the solvent was distilled off to obtain [A] polyorganosiloxane compound A-5 in white. 16.0 g was obtained as a powder. The Mw of A-5 was 8,500.

[Example 6]
A white powder of [A] polyorganosiloxane compound A-6 was prepared in the same manner as in Example 1 except that 4.1 g of the specific carboxylic acid 5 obtained in Synthesis Example 16 was used instead of the specific carboxylic acid 1. .4 g was obtained. The Mw of A-6 was 6,200.

[Example 7]
For 3.6 g of 4- (4-pentylcyclohexyl) benzoic acid represented by the formula (5-7) exemplified as one of the compounds represented by the above formula (5) instead of 4-octyloxybenzoic acid 13.4 g of a white powder of [A] polyorganosiloxane compound A-7 was obtained in the same manner as in Example 1 except for the above. The Mw of A-7 was 7,900.

[Example 8]
In a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 8.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 5 above, 7) 4- (4-pentylcyclohexyl) benzoic acid represented by 1.4 g and UCAT 18X (quaternary amine salt of San Apro) 0.20 g were charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and the solvent was distilled off to obtain [A] polyorganosiloxane compound A-8 in white. 13.9 g was obtained as a powder. The Mw of A-8 was 8,900.

[Example 9]
In a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 2.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 5 above, 7) 4- (4-pentylcyclohexyl) benzoic acid represented by 5.8 g and UCAT 18X (quaternary amine salt of San Apro) 0.20 g were charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation with methanol was performed, and the precipitate was dissolved in ethyl acetate to obtain a solution. The solution was washed with water three times, and then the solvent was distilled off to remove [A] polyorganosiloxane compound A- 13.4 g of 9 was obtained as white powder. The Mw of A-9 was 7,600.

[Example 10]
In a 100 mL three-necked flask, 9.8 g of the polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 8.0 g of the specific carboxylic acid 1 obtained in Synthesis Example 5 above, 6 g of carboxylic acid derivative represented by 6) and 0.20 g of UCAT 18X (quaternary amine salt of San Apro) were charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and then the solvent was distilled off to obtain [A] polyorganosiloxane compound A-10 in white. 15.5 g was obtained as a powder. The Mw of A-10 was 9,200.

[Comparative Synthesis Example 1]
In a 100 mL three-necked flask, 9.8 g of polyorganosiloxane having an epoxy group obtained in Synthesis Example 1 above, 28 g of methyl isobutyl ketone, 3.3 g of 4-octyloxybenzoic acid, and UCAT 18X (quaternary amine salt of San Apro) 0.10 g was charged and stirred at 80 ° C. for 12 hours. After completion of the reaction, reprecipitation was carried out with methanol, the precipitate was dissolved in ethyl acetate, this solution was washed with water three times, and then the solvent was distilled off to obtain [A] polyorganosiloxane compound CA-1 in white. As a powder, 9.6 g was obtained. The Mw of CA-1 was 6,000.
<Synthesis of polyamic acid>
[Synthesis Example 17]
19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mol) of 4,4′-diamino-2,2′-dimethylbiphenyl It was dissolved in 367.6 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 35 g of polyamic acid PA-1.

[Synthesis Example 18]
2,3,5-tricarboxycyclopentylacetic acid dianhydride (22.4 g, 0.1 mol) and cyclohexanebis (methylamine) (14.23 g, 0.1 mol) were mixed with N-methyl-2-pyrrolidone (329.3 g). And reacted at 60 ° C. for 6 hours. The reaction was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 32 g of polyamic acid PA-2.

<Synthesis of polyimide>
[Synthesis Example 19]
17.5 g of the polyamic acid PA-2 obtained in Synthesis Example 18 was taken, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto, and the mixture was heated at 120 ° C. for 4 hours. It was made to react and imidation was performed. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide PI-1.

[Synthesis Example 20]
As tetracarboxylic dianhydride 19.88 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, diamine compound 6.83 g of p-phenylenediamine, 3.58 g of diaminodiphenylmethane and the above formula (G-4) The diamine 4.72 g was dissolved in N-methyl-2-pyrrolidone 140 g and reacted at 60 ° C. for 4 hours. The reaction solution was then poured into a large excess of methyl alcohol to precipitate the reaction product. Thereafter, it was washed with methyl alcohol and dried at 40 ° C. under reduced pressure for 24 hours to obtain 32.8 g of polyamic acid. 30 g of the resulting polyamic was dissolved in 400 g of N-methyl-2-pyrrolidone, 12.0 g of pyridine and 15.5 g of acetic anhydride were added, and dehydration was carried out at 110 ° C. for 4 hours. Drying was performed to obtain 25 g of polyimide PI-2 having Mw = 92,000, Mw / Mn = 4.19, and an imidization ratio of 79%.

<Preparation of liquid crystal aligning agent>
[Example 11]
The solution containing the polyamic acid PA-1 obtained in Synthesis Example 17 was converted to the polyamic acid PA-1 contained therein, and an amount corresponding to 1,000 parts by mass was taken. [A] Polyorganosiloxane compound A-1 (100 parts by mass) was added, N-methyl-2-pyrrolidone and butyl cellosolve were added, the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 50: 50 (mass ratio), and the solid content concentration was A 3.0 mass% solution was obtained. Liquid crystal aligning agent S-1 was prepared by filtering this solution with a filter having a pore diameter of 10.2 μm.

[Examples 12 to 24 and Comparative Example 1]
[B] A combination of polyamic acid or polyimide as a polymer and a polyorganosiloxane compound as a component [A] is as shown in Table 2, and the same operation as in Example 11 was performed. S-14 and CS-1 were prepared.

[Comparative Example 2]
N-methyl-2-pyrrolidone and butyl cellosolve were added to the polyimide PI-2 obtained in Synthesis Example 20 so that the solvent composition was N-methyl-2-pyrrolidone: butyl cellosolve = 70: 30 (mass ratio). A solution having a solid content concentration of 3.0% by mass was obtained. Liquid crystal aligning agent CS-2 was prepared by filtering this solution with a filter having a pore size of 0.2 μm. In addition, “-” in the table indicates that the corresponding component was not used.

<Manufacture of liquid crystal display elements>
After apply | coating the liquid crystal aligning agent S-1 prepared in the said Example 11 on the transparent electrode surface of the glass substrate with a transparent electrode which consists of an ITO film | membrane using a spinner, and prebaking for 1 minute with an 80 degreeC hotplate. Then, the coating film (liquid crystal alignment film) having a film thickness of 0.08 μm was formed by removing the solvent by heating at 200 ° C. for 1 hour in an oven substituted with nitrogen. This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film.

  After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer periphery of the surface having one liquid crystal alignment film of the above substrates by screen printing, the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. The adhesive was heat cured by heating at 150 ° C. for 1 hour. Next, after filling the liquid crystal injection hole into the gap between the substrates with negative type liquid crystal (Merck, MLC-6608), the liquid crystal injection hole is sealed with an epoxy adhesive, and the flow alignment at the time of liquid crystal injection is removed. This was heated at 150 ° C. for 10 minutes and then gradually cooled to room temperature.

  Furthermore, a liquid crystal display element was manufactured by bonding a polarizing plate on both outer surfaces of the substrate so that the polarization directions of the two polarizing plates were orthogonal to each other. Using the liquid crystal aligning agent prepared as Examples 12-24 and Comparative Examples 1-2, it operated similarly and manufactured the liquid crystal display element.

<Liquid crystal display element having two or more regions having different orientation directions>
[Example 25]
A liquid crystal display element having two or more regions having different orientation directions was produced in the same manner as in the production of the liquid crystal display element except that the patterned transparent electrode shown in FIG. 1 was used.

[Example 26]
The liquid crystal aligning agent A-1 prepared in Example 11 was applied on a substrate provided with a transparent electrode, pre-baked for 1 minute on a hot plate at 80 ° C., and then replaced with nitrogen in an oven. A coating film (liquid crystal alignment film) having a film thickness of 0.08 μm was formed by heating at 0 ° C. for 1 hour to remove the solvent. This operation was repeated to produce a pair (two) of substrates having a liquid crystal alignment film. These substrates were rubbed through a mask that divides one pixel into four. As described above, except that the rubbing process is performed so that one pixel has regions having different orientation directions, two or more different orientation directions are operated in the same manner as in the manufacture of the vertical liquid crystal display element. A liquid crystal display element having a region was manufactured.

<Evaluation>
The manufactured liquid crystal display element was evaluated as follows. The results are shown in Table 2.
[Orientation]
For the liquid crystal display device manufactured above, the presence or absence of light leakage / alignment disturbance in the absence of applied voltage was visually observed under backlight illumination. A case where leakage / alignment disorder was present was indicated by “Δ”, and a case where no vertical alignment state was obtained was indicated by “X”.

[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display device manufactured above for 60 microseconds with a 167 millisecond span, and then the voltage holding ratio (%) after 167 milliseconds from the release of application was measured. The measuring device used was Toyo Technica VHR-1.

[Afterimage characteristics]
For the liquid crystal display device manufactured in the same manner as described above, a voltage of 17 V DC was applied for 20 hours at an environmental temperature of 100 ° C., and the voltage remaining in the liquid crystal cell immediately after the DC voltage was turned off (residual DC voltage) was flickered. -Determined by the elimination method.

[Response speed (electro-optical response at startup)]
The rise time of the liquid crystal response was measured with an apparatus including a polarizing microscope, a photodetector, and a pulse generator. Here, the liquid crystal response speed is the time (msec) required to change from 10% transmittance to 90% transmittance when a voltage of 5 V is applied to the manufactured liquid crystal display element from a state where no voltage is applied for a maximum of 1 second. .)

[contrast]
The contrast was evaluated for the liquid crystal display device produced in Example 11 and the liquid crystal display device produced in Examples 25 and 26 and having two or more regions having different orientation directions. The liquid crystal cell produced as described above was placed between two polarizing plates and fixed on a light box. One polarizing plate was rotated, and the minimum intensity of transmitted light was measured to obtain the minimum transmittance. In addition, the same polarizing plate was rotated, the maximum intensity of the transmitted light was measured, and the maximum transmittance was obtained. The maximum transmittance-minimum transmittance was defined as the relative transmittance, and the relative transmittance was used as a substitute index for contrast. When the relative transmittance is 40 or more, it can be determined to be good.

  As a result, the relative transmittance of the liquid crystal display device produced in Example 11 was 20. The relative transmittance of the liquid crystal display element having two or more regions having different orientation directions produced in Examples 25 and 26 was 49. Further, when the liquid crystal display element having two or more regions having different orientation directions was manufactured using the patterned transparent electrode shown in FIGS. 2 and 3, the same relative transmittance was obtained.

  As is clear from the results in Table 2, the liquid crystal display device including the liquid crystal alignment film prepared using the liquid crystal alignment agents of Examples 11 to 24 has generally required alignment properties, voltage holding ratios, and afterimage characteristics. I found out that I have it. As for the response speed of the liquid crystal, even when the difference is the smallest, it was found that the response speed was increased by about 24% or more compared to the liquid crystal display element of Comparative Example 1. Moreover, it turned out that the liquid crystal display element which has two or more area | regions from which the orientation orientation differs manufactured using the said composition is excellent in contrast.

  ADVANTAGE OF THE INVENTION According to this invention, the liquid crystal aligning agent which can form the liquid crystal display element which is excellent in various orientations, such as an orientation property and high-speed response, and excellent in various performances, such as a voltage characteristic and an afterimage characteristic, can be provided. Therefore, the liquid crystal display element can be suitably applied in a drive mode such as TN, STN, IPS, and VA (including MVA, PVA, optical vertical alignment, PSA, and the like).

1 ITO film 2 Slit 3 Transparent substrate

Claims (9)

[A] containing a polyorganosiloxane compound,
This [A] polyorganosiloxane compound is
A portion derived from a polyorganosiloxane having an epoxy group;
The liquid crystal aligning agent which has a part derived from the compound which has a carboxyl group represented by following formula (1).

(In Formula (1), R ¹ is a methylene group or an alkylene group having 2 to 30 carbon atoms, a phenylene group, or a cyclohexylene group. These groups may have a substituent. R ² is double. R ³ is a linking group containing any one of a bond, a triple bond, an ether bond, an ester bond and an oxygen atom, and R ³ is a group having at least two monocyclic structures and represented by the following formula (2). It is an integer from 0 to 1.)

(In formula (2), R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring, and these further have a substituent. R ⁵ is a linking group containing any one of an optionally substituted alkylene group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring. R ⁷ 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, and includes at least a cyano group or a fluorine atom, and R ⁶ In the case where has a plurality of substituents, the same or different ones may be combined, b is an integer of 0 to 1, and c is an integer of 1 to 9. In is.) The liquid crystal aligning agent according to claim 1, 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 an oxygen atom or a single bond. H is an integer of 1 to 3. i is an integer of 0 to 6. However, when i is 0, A is (It is a single bond. “*” Indicates a bond.)   [B] The liquid crystal aligning agent according to claim 1 or 2, further comprising at least one polymer selected from the group consisting of polyamic acid and polyimide.   A liquid crystal display element provided with the liquid crystal aligning film formed from the liquid crystal aligning agent of any one of Claims 1-3. A transparent electrode;
The liquid crystal alignment film laminated on the transparent electrode,
The liquid crystal display element according to claim 4, wherein the liquid crystal alignment mode is a vertical type and has two or more regions having different alignment directions.   6. The liquid crystal display element according to claim 5, wherein the means having two or more regions having different orientation directions is a means using a transparent electrode patterned as the transparent electrode or a means for imparting an alignment division function to the liquid crystal alignment film. A transparent electrode;
A liquid crystal alignment film laminated on the transparent electrode,
A liquid crystal alignment agent for forming the liquid crystal alignment film in a liquid crystal display element having a liquid crystal alignment mode of a vertical type and having two or more regions having different alignment directions,
A liquid crystal aligning agent comprising a polyorganosiloxane compound having a group represented by the following formula (3).

(In Formula (3), R ² is a linking group containing any one of a double bond, a triple bond, an ether bond, an ester bond or an oxygen atom. R ³ has at least two monocyclic structures and has the following formula ( 2) a is an integer of 0 to 1. “*” represents a bond.)

(In formula (2), R ⁴ and R ⁶ are each a phenylene group, a biphenylene group, a naphthalene group, a cyclohexylene group, a bicyclohexylene group, a cyclohexylenephenylene group, or a heterocyclic ring, and these further have a substituent. R ⁵ is a linking group containing any one of an optionally substituted alkylene group having 1 to 10 carbon atoms, a double bond, a triple bond, an ether bond, an ester bond and a heterocyclic ring. R ⁷ 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, and includes at least a cyano group or a fluorine atom, and R ⁶ In the case where has a plurality of substituents, the same or different ones may be combined, b is an integer of 0 to 1, and c is an integer of 1 to 9. In is.)   The liquid crystal aligning agent according to claim 7, wherein a patterned transparent electrode or a liquid crystal alignment film having an alignment division function is used as a means having two or more regions having different alignment directions.   A liquid crystal display element having a liquid crystal alignment mode of a vertical type and having two or more regions having different alignment directions, comprising a liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 7 or 8. A characteristic liquid crystal display element.

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